JP2009221287A - Thermoplastic resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition which hardly causes molding defects and substantially avoids deterioration in the resin strength of a molding, even when an antistatic agent is used in a large amount. <P>SOLUTION: The thermoplastic resin composition contains the following (A) to (D) in a weight ratio (C)/(D) of 0.02-30 and a weight ratio [(C)+(D)]/[(A)+(B)] of 0.00001-0.03, (A): a thermoplastic resin having an ester bond, (B): a block copolymer having a structure in which a block of a polyolefin (b1) and a block of a polyoxyalkylene chain-containing compound (b2) bond to each other through at least one bond selected from the group consisting of an ester bond, an amide bond, an ether bond, an imide bond and a urethane bond, (C): an alkyl acid phosphate, and (D): an antistatic property improver. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a thermoplastic resin composition. More specifically, the present invention relates to a thermoplastic resin composition containing an acidic phosphate ester and an antistatic property improver at a specific content.

  Conventionally, as a method for imparting permanent antistatic property to a thermoplastic resin having an ester bond, a method of adding a polyether ester amide as an antistatic agent is known. Due to the interaction of the thermoplastic resin having the above, there is a problem that the thermoplastic resin and the polyether ester amide are likely to be lowered in molecular weight, the resin strength is lowered, and molding defects are caused. As a countermeasure, when the thermoplastic resin having an ester bond is a polycarbonate resin, a method of blending and adding, for example, a phosphite compound and / or a phenolic compound in addition to the polyether ester amide has been proposed ( For example, see Patent Document 1).

JP-A-5-43787

  However, even with the conventional method described above, when the amount of the antistatic agent used is increased for the purpose of further improving the antistatic property, problems such as a decrease in resin strength and a defective molding occur. When the amount of the antistatic agent used is large, a sufficient effect is not obtained. An object of the present invention is to provide a thermoplastic resin composition that is less likely to cause molding defects and less likely to lower the resin strength of a molded product even when the amount of an antistatic agent used is large.

The inventors of the present invention have arrived at the present invention as a result of intensive studies to solve the above problems. That is, this invention is a thermoplastic resin composition containing the following (A)-(D), Comprising: Weight ratio (C) / (D) is 0.02-30, and weight ratio [( C) + (D)] / [(A) + (B)] is a thermoplastic resin composition in which 0.00001 to 0.03; a molded article formed by molding the composition; It is a molded article formed by painting and / or printing.
(A): Thermoplastic resin having ester bond (B): Block of polyolefin (b1) and block of polyoxyalkylene chain-containing compound (b2) are formed from ester bond, amide bond, ether bond, imide bond and urethane bond. Block polymer (C) having a structure bonded through at least one bond selected from the group consisting of: Acid phosphate ester (D): Antistatic property improver

The thermoplastic resin composition of the present invention and a molded product formed by molding the composition have the following effects.
(1) The thermoplastic resin composition is excellent in moldability.
(2) A molded product formed by molding the composition has excellent antistatic properties and excellent mechanical strength.

  Examples of the thermoplastic resin (A) having an ester bond in the present invention include a thermoplastic polyester resin (A1), a thermoplastic polyurethane resin (A2), a polycarbonate resin (A3), and an ester group-containing vinyl (co) polymer ( A4) and the like, and a combination of two or more of these may be used.

  (A1) includes condensed polyesters and polylactones. Examples of the condensed polyester include a condensate of dicarboxylic acid or an ester-forming derivative component thereof and a diol component (of which the degree of polymerization of polyoxyalkylene diol is 1 to 10) and a condensate of hydroxycarboxylic acid.

  As the dicarboxylic acid, for example, a dicarboxylic acid having 2 to 48 carbon atoms can be used, and examples thereof include aliphatic dicarboxylic acids, aromatic dicarboxylic acids, and alicyclic dicarboxylic acids.

  Aliphatic dicarboxylic acids include saturated aliphatic dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, methyl succinic acid, dimethyl malonic acid, β-methyl glutaric acid, ethyl succinic acid, isopropyl malonic acid, adipic acid, pimelin. Acids, suberic acid, azelaic acid, sebacic acid, decanediic acid, undecanediic acid, dodecanediic acid, tridecanediic acid, tetradecanediic acid, hexadecanediic acid, octadecanediic acid and icosandiic acid, etc., and unsaturated aliphatic dicarboxylic acids such as malein Examples include acid, fumaric acid, citraconic acid, and mesaconic acid.

  Examples of aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, phthalic acid, tetrabromophthalic acid, methyl isophthalic acid, phenylmalonic acid, homophthalic acid, phenylsuccinic acid, β-phenylglutaric acid, α-phenyladipic acid, β -Phenyladipic acid, biphenyl-2,2'-dicarboxylic acid, biphenyl-4,4'-dicarboxylic acid, naphthalenedicarboxylic acid, sodium 5-sulfoisophthalate and potassium 5-sulfoisophthalate.

  Examples of the alicyclic dicarboxylic acid include 1,3-cyclopentanedicarboxylic acid, 1,2-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, and 1,3-cyclohexanedicarboxylic acid. Examples include acid, 1,4-cyclohexanediacetic acid, 1,3-cyclohexanediacetic acid, 1,2-cyclohexanediacetic acid, and dicyclohexyl-4,4-dicarboxylic acid. In addition, dimer acid [a dimer of fatty acid (having 8 to 24 carbon atoms, such as oleic acid, linoleic acid and linolenic acid)] can also be used.

  Ester-forming derivatives include esters of dicarboxylic acids, acid anhydrides and acid halides. Examples thereof include carbonic acid or dialkyl (carbon number 1 to 4) ester (dimethyl ester, diethyl ester and dibutyl ester) and diphenyl ester of the above dicarboxylic acid, and acid anhydrides (phthalic anhydride and the like).

  As the diol, glycol, polyoxyalkylene diol, and dihydric phenol can be used.

  As glycol, C2-C20 aliphatic glycol, C5-C12 alicyclic glycol, C8-C26 araliphatic glycol, etc. can be used.

  Aliphatic glycols include alkylene glycols such as ethylene glycol, 1,2-propylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,3-hexanediol, 1, 4-hexanediol, 1,6-hexanediol, 2,5-hexanediol, 1,2-octanediol, 1,8-octanediol, 1,10-decanediol, 1,18-octadecanediol and 1,20 -Eicosanediol; and di (thio) alkylene glycols such as diethylene glycol and thiodiethylene glycol.

  Examples of alicyclic glycols include cycloalkylene glycols such as 1-hydroxymethyl-1-cyclobutanol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, and 1-methyl-3,4. -Cyclohexanediol, 2-hydroxymethylcyclohexanol, 4-hydroxymethylcyclohexanol, 1,4-cyclohexanedimethanol and bicycloalkylene glycol such as 1,1'-dihydroxy-1,1'-dicyclohexylmethane.

  Examples of the araliphatic glycol include 1,4-dihydroxymethylbenzene, 2-phenyl 1,3-propanediol, 2-phenyl 1,4-butanediol, 2-benzyl 1,3-propanediol, and triphenylethylene glycol. , Tetraphenylethylene glycol, benzopinacol and the like.

  The polyoxyalkylene diol includes a compound having two active hydrogen atoms, for example, a compound having a structure in which alkylene oxide (hereinafter referred to as AO) is added to a glycol, amine, dicarboxylic acid, dihydric phenol or the like (AO addition mole). Number; usually 2 to 10 moles) and mixtures of two or more thereof. As AO, AO having 2 to 30 (preferably 2 to 4) carbon atoms such as ethylene oxide (EO), propylene oxide (PO), 1,2-, 2,3- and 1,3-butylene oxide, tetrahydrofuran (THF), styrene oxide, α-olefin oxide having 5 to 30 carbon atoms, epichlorohydrin, and the like. AO may be used alone or in combination of two or more. In the latter case, block addition (chip type, balance type, active secondary type, etc.), random addition, or a mixed system thereof may be used.

  As the dihydric phenol, phenol having 6 to 30 carbon atoms can be used. Specifically monocyclic dihydric phenols such as catechol, resorcinol and hydroquinone; condensed ring dihydric phenols such as dihydroxynaphthalene; bisphenols such as bisphenol A, bisphenol F, bisphenol S, dihydroxydiphenyl ether and dihydroxydiphenyl thioether; and binaphthol; These alkyl (C1-C10) or halogen (chlorine, bromine, etc.) substitution products (for example, brominated bisphenol A) etc. are mentioned.

  As the glycol, dihydric phenol and dicarboxylic acid to which AO is added, those exemplified above can be used.

  As the hydroxycarboxylic acid, a hydroxycarboxylic acid having 2 to 20 carbon atoms can be used. For example, hydroxyacetic acid, lactic acid, ω-hydroxycaproic acid, ω-hydroxyenanthic acid, ω-hydroxycaprylic acid, ω-hydroxypergonic acid, Examples include ω-hydroxycapric acid, 11-hydroxyundecanoic acid, 12-hydroxydodecanoic acid, and 20-hydroxyeicosanoic acid.

  Examples of the polylactone include a ring-opening polymerization product of a lactone using the above diol or dicarboxylic acid as an initiator.

  As the lactone, a lactone having 4 to 20 carbon atoms can be used. For example, γ-butyrolactone, γ-valerolactone, δ-valerolactone, ε-caprolactone, γ-pimerolactone, γ-caprolactone, γ-decanolactone, enanthate. Examples include lactone, laurolactone, undecanolactone, and eicosanolactone. In addition, these (A1) include branched components, for example, trivalent or tetravalent carboxylic acids such as tricarballylic acid, trimesic acid, trimellitic acid, pyromellitic acid and / or glycerin, trimethylolpropane, pentaerythritol, etc. The polyhydric (tri- or tetrahydric) alcohol may be copolymerized in a small amount, for example, 1 mol% or less, more preferably 0.5 mol% within a range not inhibiting the thermoplasticity. Specifically, polyethylene terephthalate, polybutylene terephthalate, polycyclohexamethylene dimethylene terephthalate, cyclohexanedimethanol / ethylene glycol / terephthalic acid copolymer, polybutylene adipate, polyethylene adipate, poly-ε-caprolactone, polylactic acid, etc. Can be mentioned. Of these, preferred are polybutylene terephthalate and cyclohexanedimethanol / ethylene glycol / terephthalic acid copolymer.

  Examples of (A2) include organic diisocyanates and polyester diols (polyester diols having a molecular weight of 500 to 5000 or more, polymer polyols obtained by polymerizing vinyl monomers (for example, acrylonitrile and styrene) in the diols, etc.), chains Elongating agent (diol, such as 1,4-butylene glycol and / or diamine, such as ethylenediamine) and, if necessary, reaction terminator (monohydric alcohol, primary or secondary monoamine or mono- or di-alkanolamine), one-shot method Or the polyurethane obtained by making it react by a prepolymer method is mentioned. As organic diisocyanate, C6-C20 aromatic diisocyanate, C2-C18 aliphatic diisocyanate, C4-C15 alicyclic diisocyanate, carbon number (excluding carbon in NCO group, the same applies hereinafter) 8-15 araliphatic diisocyanates, modified products of these diisocyanates and mixtures of two or more of these can be used. Specific examples include those described in International Publication No. WO 00/47652.

  Polyester diol is reacted with diol (low molecular diol and / or polyoxyalkylene diol having a molecular weight of 1,000 or less) and dicarboxylic acid (or an ester-forming derivative thereof) or dicarboxylic acid anhydride (if necessary, further alkylene A condensed polyester diol obtained by reacting with an oxide), a polylactone diol obtained by ring-opening polymerization of the above lactone using the above diol as an initiator, and a low molecular diol and a lower alcohol (1 carbon number) To 4) polycarbonate diol obtained by reacting with carbonic acid diester. Examples of the low molecular diol include the above-described glycols. Examples of the polyoxyalkylene diol include those described above. As the dicarboxylic acid and lactone, those mentioned above as the raw material of (A1) can be used. Specific examples of these polyester diols include polyethylene adipate diol, polyhexamethylene adipate diol, polycaprolactone diol, and polyhexamethylene carbonate diol. Of these, preferred are adipate thermoplastic polyurethanes.

(A3) includes bisphenol (C12-20 (hereinafter C represents carbon number), such as bisphenol A, bisphenol F, bisphenol S, and 4,4′-dihydroxydiphenyl-2,2-butane) -based polycarbonate, such as The condensate of the said bisphenol and phosgene or a carbonic acid diester is mentioned.
Examples of the bisphenol include C12-20, such as bisphenol A, bisphenol F, bisphenol S, and 4,4′-dihydroxydiphenyl-2,2-butane. Among these, bisphenol A is more preferable from the viewpoint of dispersibility. is there.

(A4) includes (co) polymers of ester group-containing vinyl monomers, and copolymers of ester group-containing vinyl monomers and other vinyl monomers. Examples of the ester group-containing vinyl monomer include esters of carboxyl group-containing vinyl monomers and esters of unsaturated alcohols.
Esters of carboxyl group-containing vinyl monomers include C2-30 (preferably 3-20, more preferably 4-15) unsaturated mono- and dicarboxylic acids [crotonic acid, maleic acid, fumaric acid and itaconic acid] and carbon. Alcohol having 1 to 50 [alkanol, cycloalkanol, benzyl alcohol, diol (glycol and polyoxyalkylene diol), tertiary amino group-containing alcohol such as dialkyl (1 to 4 carbon) alkanol (2 to 4 carbon) amine , N-hydroxyalkyl (2 to 4 carbon atoms) morpholine and epoxy-containing alcohols (such as glycidol)].
Specifically, an alkyl (meth) acrylate having an alkyl group having 1 to 50 carbon atoms such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl ( Examples include meth) acrylate, dodecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, and eicosyl (meth) acrylate.
Examples of the unsaturated alcohol ester include unsaturated alcohols [vinyl alcohol, (meth) allyl alcohol, isopropenyl alcohol, etc.] and carboxylic acids having 2 to 18 carbon atoms [monocarboxylic acid, benzoic acid, and the aforementioned dicarboxylic acid, etc.]. Esters such as vinyl acetate, vinyl butyrate, vinyl propionate, vinyl butyrate, diallyl phthalate, diallyl adipate, isopropenyl acetate, vinyl (meth) acrylate, methyl 4-vinylbenzoate, cyclohexyl (meth) acrylate, benzyl (meth) Examples include acrylate, phenyl (meth) acrylate, vinyl methoxyacetate and vinyl benzoate. Other vinyl monomers include vinyl hydrocarbons [aromatic vinyl hydrocarbons (such as styrene and α-methylstyrene), aliphatic vinyl hydrocarbons (such as ethylene, propylene, and butadiene)], nitrogen-containing vinyl monomers [ Examples thereof include amide group-containing vinyl monomers {(meth) acrylamide and the like}, nitrile group-containing vinyl monomers {(meth) acrylonitrile and the like}, and halogen element-containing vinyl monomers [vinyl chloride, chloroprene and the like].
Specific examples of (A4) include polymethyl methacrylate, styrene / methyl methacrylate / acrylonitrile copolymer, methyl methacrylate / butadiene / styrene copolymer (MBS resin), ethylene / glycidyl methacrylate copolymer, and ethylene / acetic acid. Examples include vinyl / glycidyl methacrylate copolymer.

  The block polymer (B) in the present invention is selected from the group consisting of a block of the polyolefin (b1) and a block of the polyoxyalkylene chain-containing compound (b2) consisting of an ester bond, an amide bond, an ether bond, an imide bond and a urethane bond. And having a structure bonded through at least one bond. As (B), the block polymer described in the international publication WO00 / 47652 specification can be used. The proportion of (b2) based on the total weight of (b1) and (b2) is preferably 20 to 80%, more preferably 30 to 70%, from the viewpoint of the antistatic property and heat resistance of (B). (B1) constituting (B) includes a polyolefin (b11) having carbonyl groups at both ends of the polymer, a polyolefin (b12) having hydroxyl groups at both ends of the polymer, and a polyolefin having amino groups at both ends of the polymer ( b13) and the like can be used.

  As (b11), those in which a carbonyl group is introduced into both ends of polyolefin (b10) whose main component is a polyolefin that can be modified at both ends are used. As (b12), those having hydroxyl groups introduced at both ends of (b10) are used. As (b13), those in which amino groups are introduced at both ends of (b10) are used. (B10) is usually a mixture of a polyolefin that can be modified at both ends, a polyolefin that can be modified at one end, and a polyolefin that does not have a modifiable end group, but contains a polyolefin that can be modified at both ends as a main component. You can use it if you do. Based on the weight of (b10), the content of the polyolefin that can be modified at both ends as the main component of (b10) is preferably 50 to 100%, more preferably 75 to 100%, and particularly preferably 80 to 100%. It is.

  (B10) means (co) polymerization (polymerization or copolymerization) of one or a mixture of two or more C2-30 (preferably 2-12, more preferably 2-10) olefins. )) And a degraded polyolefin [a product obtained by mechanically, thermally or chemically degrading a high molecular weight polyolefin (preferably Mn 50,000 to 150,000)] (reduced) Method). From the viewpoint of ease of modification and availability of introduction of a carbonyl group, a hydroxyl group or an amino group, a degraded polyolefin, particularly a thermally degraded polyolefin is preferred. The heat-degraded polyolefin is not particularly limited, but is heat-degraded by heating a high molecular weight polyolefin in an inert gas (usually at 300 to 450 ° C. for 0.5 to 10 hours) (for example, JP-A-3 -62804). According to the thermal degradation, a low molecular weight polyolefin having an average terminal double bond amount per molecule of 1.5 to 2 can be easily obtained as described later. Examples of the high molecular weight polyolefin used in the thermal degradation method include (co) polymers of one or a mixture of two or more C2-30 (preferably 2-12, more preferably 2-10) olefins. Can be used. As the C2-30 olefin, the same ones as those used in the production of the polyolefin (polymerization method) described later can be used, and among these, ethylene, propylene and C4-12 α-olefins are preferred, and ethylene is more preferred. , Propylene and C4-10 α-olefins, particularly preferred are ethylene and propylene.

  Examples of the C2-30 olefin used in the production of the polyolefin (polymerization method) include ethylene, propylene, C4-30 (preferably 4-12, more preferably 4-10) α-olefin and C4-30. A diene of (preferably 4-18, more preferably 4-8) is used. Examples of the α-olefin include 1-butene, 4-methyl-1-pentene, 1-pentene, 1-octene, 1-decene and 1-dodecene. Examples of the diene include butadiene, isoprene, cyclopentadiene, 1,11-dodecadiene, and the like. Of these, ethylene, propylene, C4-12 α-olefin, butadiene and isoprene are preferred, ethylene, propylene, C4-10 α-olefin and butadiene are more preferred, and ethylene, propylene and butadiene are particularly preferred. is there.

The polyolefin obtained by the polymerization method can be produced by various methods. For example, it can be easily obtained by a (co) polymerization reaction in the presence of a radical catalyst, a metal oxide catalyst, a Ziegler catalyst, or a Ziegler-Natta catalyst. Various radical catalysts can be used, such as organic peroxides (di-t-butyl peroxide, t-butyl peroxybenzoate, decanol peroxide, lauryl peroxide, peroxydicarbonate ester, etc.), Examples include azo compounds (azonitrile, azoamidine and azoamide compounds) and γ-alumina carriers with molybdenum oxide attached thereto.
Examples of the metal oxide catalyst include those obtained by attaching chromium oxide to a silica-alumina support. Examples of the Ziegler catalyst or Ziegler-Natta catalyst include (C ₂ H ₅ ) ₃ Al—TiCl ₄ .

  Mn of (b10) is preferably 800 to 20,000, more preferably 1,000 to 10,000, and particularly preferably 1,200 to 6,000. When Mn is within this range, the antistatic property is further improved. The amount of double bonds in (b10) is preferably 1-40 per 1,000 C, more preferably 2-30, and particularly preferably 4-20. When the amount of the double bond is within this range, the antistatic property is further improved. The average number of double bonds per molecule is preferably 1.1 to 5.0, more preferably 1.3 to 3.0, particularly preferably 1.5 to 2.5, and most preferably 1.8. ~ 2.2. When the average number of double bonds is within this range, it becomes easier to take a repeating structure, and the antistatic property is further improved. According to the thermal degradation method, a low-molecular-weight polyolefin having an average terminal double bond amount of 1.5 to 2 per molecule in the range of 800 to 6,000 can be easily obtained [Katsuhide Murata, Tadahiko Makino. , Journal of Chemical Society of Japan, page 192 (1975)].

  As the polyolefin (b11) having carbonyl groups at both ends of the polymer, the end of (b10) is α, β unsaturated carboxylic acid (anhydride) (α, β-unsaturated carboxylic acid, C1-4 alkyl ester thereof) Or an anhydride thereof. The same applies hereinafter.) Polyolefin (b11-1) having a structure modified with (b11-1) and polyolefin (b11-2) having a structure obtained by secondary modification of (b11-1) with lactam or aminocarboxylic acid. ), Polyolefin (b11-3) having a structure modified by oxidation or hydroformylation of (210), polyolefin (b11-4) having a structure of (b11-3) secondarily modified with lactam or aminocarboxylic acid, and A mixture of two or more of these can be used.

  (B11-1) can be obtained by modifying (b10) with an α, β-unsaturated carboxylic acid (anhydride). As α, β-unsaturated carboxylic acid (anhydride) used for modification, monocarboxylic acid, dicarboxylic acid, alkyl (C1-4) ester thereof and anhydride thereof can be used, for example, (meth) acrylic acid (Means acrylic acid or methacrylic acid; the same shall apply hereinafter), methyl (meth) acrylate, butyl (meth) acrylate, maleic acid (anhydride), dimethyl maleate, fumaric acid, itaconic acid (anhydride) , Diethyl itaconate and citraconic acid (anhydride). Of these, dicarboxylic acids, their alkyl esters and their anhydrides are preferred, maleic acid (anhydride) and fumaric acid are more preferred, and maleic acid (anhydride) is particularly preferred.

  The amount of α, β-unsaturated carboxylic acid (anhydride) used for modification is preferably 0.5 to 40%, more preferably 1 to 30%, particularly preferably 2 based on the weight of the polyolefin (b210). ~ 20%. When the amount of α, β-unsaturated carboxylic acid (anhydride) is within this range, it becomes easier to take a repeating structure, and filler dispersibility and antistatic properties are further improved. The modification with α, β-unsaturated carboxylic acid (anhydride) can be performed by various methods. For example, the terminal double bond of (b10) can be modified by either solution method or melt method. , Β-unsaturated carboxylic acid (anhydride) can be thermally added (ene reaction). The temperature at which (b10) is reacted with the α, β-unsaturated carboxylic acid (anhydride) is usually 170 to 230 ° C.

  (B11-2) can be obtained by secondarily modifying (b11-1) with a lactam or an aminocarboxylic acid. As the lactam used for the secondary modification, C6-12 (preferably 6-8, more preferably 6) lactam and the like can be used, and examples thereof include caprolactam, enantolactam, laurolactam, and undecanolactam. Moreover, as aminocarboxylic acid, C2-12 (preferably 4-12, more preferably 6-12) aminocarboxylic acid etc. can be used, for example, amino acids (glycine, alanine, valine, leucine, isoleucine, phenylalanine, etc. ), Ω-aminocaproic acid, ω-aminoenanthic acid, ω-aminocaprylic acid, ω-aminopergonic acid, ω-aminocapric acid, 11-aminoundecanoic acid and 12-aminododecanoic acid. Among these, caprolactam, laurolactam, glycine, leucine, ω-aminocaprylic acid, 11-aminoundecanoic acid and 12-aminododecanoic acid are preferable, and caprolactam, laurolactam, ω-aminocaprylic acid, 11-amino are more preferable. Undecanoic acid and 12-aminododecanoic acid, particularly preferably caprolactam, laurolactam and 12-aminododecanoic acid. The amount of lactam or aminocarboxylic acid used for secondary modification is preferably 0.1 to 50, more preferably 0.3 to 20 per carboxyl group of α, β unsaturated carboxylic acid (anhydride). The number is particularly preferably 0.5 to 10, most preferably 1 to 2. When this amount is within this range, it becomes easier to take a repeating structure, and filler dispersibility and antistatic properties are further improved.

(B11-3) can be obtained by introducing (b10) a carbonyl group by oxidation with oxygen and / or ozone or hydroformylation with an oxo method. The introduction of the carbonyl group by the oxidation method can be performed by a known method, for example, the method described in US Pat. No. 3,692,877. The introduction of a carbonyl group by hydroformylation can be performed by a known method, for example, see Macromolecules, Vol. 31, 5943 page. (B11-4) can be obtained by secondarily modifying (b11-3) with a lactam or an aminocarboxylic acid.
The lactam and aminocarboxylic acid and preferred ranges thereof are the same as those which can be used in the production of (b11-2). The amount of lactam and aminocarboxylic acid used is the same.

  Mn of the polyolefin (b11) having carbonyl groups at both ends of the polymer is preferably 800 to 25,000, more preferably from the viewpoint of heat resistance and reactivity with the polyoxyalkylene chain-containing compound (b2) described later. 1,000 to 20,000, particularly preferably 2,500 to 10,000. The acid value of (b11) is preferably 4 to 280 (mg KOH / g. In the following, only numerical values are described), more preferably 4 to 100, particularly from the viewpoint of reactivity with (b2). Preferably it is 5-50.

  As the polyolefin (b12) having a hydroxyl group at both ends of the polymer, a polyolefin having a hydroxyl group obtained by modifying (b11) with hydroxylamine and a mixture of two or more of these can be used. Examples of hydroxylamine that can be used for the modification include C2-10 (preferably 2-6, more preferably 2-4) hydroxylamine, and the like. For example, 2-aminoethanol, 3-aminopropanol, 1-amino- Examples include 2-propanol, 4-aminobutanol, 5-aminopentanol, 6-aminohexanol, and 3-aminomethyl-3,5,5-trimethylcyclohexanol. Of these, 2-aminoethanol, 3-aminopropanol, 4-aminobutanol, 5-aminopentanol and 6-aminohexanol are preferred, 2-aminoethanol and 4-aminobutanol are particularly preferred. Is 2-aminoethanol. The modification with hydroxylamine can be performed by various methods, for example, by directly reacting (b211) with hydroxylamine. The reaction temperature is usually 120 ° C to 230 ° C.

  The amount of hydroxylamine used for modification is preferably 0.1 to 2, more preferably 0.3 to 1.5, particularly preferably per residue of α, β unsaturated carboxylic acid (anhydride). Is 0.5 to 1.2, most preferably 1. When the amount of hydroxylamine is within this range, it becomes easier to take a repeating structure, and the antistatic property is further improved. Mn of (b12) is preferably 800 to 25,000, more preferably 1,000 to 20,000, particularly preferably from the viewpoint of heat resistance and reactivity with the polyoxyalkylene chain-containing compound (b2) described later. Is 2,500 to 10,000. The hydroxyl value of (b12) is preferably 4 to 280 (mg KOH / g. In the following, only numerical values are described), more preferably 4 to 100, particularly from the viewpoint of reactivity with (b2). Preferably it is 5-50.

  As the polyolefin (b13) having an amino group at both ends of the polymer, a polyolefin having an amino group obtained by modifying (b11) with a diamine (Q1) and a mixture of two or more of these can be used. As the diamine (Q1) used for this modification, C2-12 (preferably 2-8, more preferably 2-6) diamines can be used, for example, ethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine. And decamethylenediamine. Among these, ethylenediamine, hexamethylenediamine, heptamethylenediamine and octamethylenediamine are preferable, ethylenediamine and hexamethylenediamine are more preferable, and ethylenediamine is particularly preferable. The modification with diamine can be performed by a known method, for example, by reacting (b11) and diamine (Q1) directly. The reaction temperature is usually 120 ° C to 230 ° C.

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

  Mn of (b13) is preferably 800 to 25,000, more preferably 1,000 to 20,000, particularly preferably from the viewpoint of heat resistance and reactivity with the polyoxyalkylene chain-containing compound (b2) described later. Is 2,500 to 10,000. Further, the amine value of (b13) is preferably 4 to 280 (mg KOH / g, hereinafter, only numerical values are described) from the viewpoint of reactivity with (b2), more preferably 4 to 100, and particularly preferably. Is 5-50.

As the polyoxyalkylene chain-containing compound (b2) constituting the block polymer (B), polyether diol (b21), polyether diamine (b22), and modified products thereof (b23) can be used. The upper limit of the volume resistivity of (b2) is preferably 10 ¹¹ Ω · cm, more preferably 10 ¹⁰ Ω · cm, particularly preferably 10 ⁹ Ω · cm, from the viewpoint of antistatic properties, and the lower limit preferable from the viewpoint of mechanical properties. Is 10 ⁵ Ω · cm, more preferably 10 ⁶ Ω · cm, and particularly preferably 10 ⁷ Ω · cm. Further, Mn of (b2) is preferably 150 to 20,000, more preferably 300 to 20,000, particularly preferably 1,000 to 15,000, from the viewpoint of heat resistance and reactivity with (b1). Most preferably, it is 1,200 to 8,000.

As the polyether diol (b21), one having a structure obtained by addition reaction of AO to the diol (b20) or dihydric phenol can be used.
^{H- (OA 1) m-O} -E 1 -O- (A 1 O) m'-H
The thing shown by is mentioned. In the formula, E ¹ is a residue obtained by removing a hydroxyl group from a diol or a dihydric phenol; A ¹ is a C2-12 (preferably 2-8, more preferably 2-4) alkylene which may contain a halogen atom. Group; m and m ′ are integers of 1 to 300, preferably 2 to 250, and more preferably 8 to 150. M and m ′ may be the same or different. m (OA ¹ ) and m ′ (A ¹ O) may be the same or different, and the bond form in the case where they are composed of two or more oxyalkylene groups is a block or Either random or a combination thereof may be used.

  Of these diols (b20) and dihydric phenols, dihydric alcohols and dihydric phenols are preferable from the viewpoint of reactivity, aliphatic dihydric alcohols and bisphenols are more preferable, and ethylene glycol and bisphenol A are particularly preferable. It is.

  The polyether diol (b21) can be produced, for example, by subjecting the diol (b20) or dihydric phenol to AO addition reaction. As AO, C2-4 AO (EO, PO, 1,2-, 1,4-, 2,3- and 1,3-butylene oxide and a mixture of two or more thereof) and the like are used. If necessary, other AO or substituted AO may be used in combination (in the present invention, these are collectively referred to as AO). Examples of other AO or substituted AO include epoxidized C5-12 α-olefin, styrene oxide and epihalohydrin (such as epichlorohydrin and epibromohydrin). The amount of other AO or substituted AO is preferably 30% or less, more preferably 0 to 25%, particularly preferably 0 to 20%, based on the weight of total AO.

  When two or more kinds of AO are used in combination, the binding form may be either block and / or random. Preferred as AO is EO alone or a combination of EO and another AO (block and / or random addition), more preferred is a combination of EO and EO / PO, and particularly preferred is EO alone. The number of moles of AO added is preferably 1 to 300 moles, more preferably 2 to 250 moles, and particularly preferably 10 to 100 moles per hydroxyl group of (b20) or dihydric phenol. When the added mole number of AO is within this range, the volume resistivity value of (b2) tends to be more preferable.

  AO can be added by a known method, for example, at a temperature of 100 to 200 ° C. in the presence of an alkali catalyst. The content of the C2-4 oxyalkylene unit in the polyether diol (b21) is preferably 5 to 99.8%, more preferably 8 to 99.6%, particularly preferably based on the weight of (b21). 10 to 98%. The content of oxyethylene units in the polyoxyalkylene chain is preferably 5 to 100%, more preferably 10 to 100%, particularly preferably 50 to 100%, most preferably 60, based on the weight of the polyoxyalkylene chain. ~ 100%. When the content of the oxyethylene unit is within this range, the volume resistivity value of (b2) tends to be more preferable.

As the polyether diamine (b22), one having a structure in which the hydroxyl group of (b21) is modified to an amino group can be used.
^{R "NH-A 2 - (} OA 1) m-O-E 1 -O- (A 1 O) m'-A 2 -NHR"
The thing shown by is mentioned. The symbols E ¹ , A ¹ , m and m ′ in the formula are the same as those in the formula (b21), and A ² may contain a halogen atom, C 2-12 (preferably 2-8, more preferably Represents an alkylene group of 2 to 4), and A ¹ and A ² may be the same or different. R ″ represents H or a C1-4 (preferably 1 or 2) alkyl group. (B22) can be easily obtained by changing the hydroxyl group of (b21) to an amino group by a known method. Various methods can be used as a method for changing a hydroxyl group to an amino group. For example, a method in which a terminal cyanoalkyl group obtained by cyanoalkylating a hydroxyl group in (b21) is reduced to form an amino group [for example, (b21) and Examples include a method of reacting acrylonitrile and hydrogenating the resulting cyanoethylated product], a method of reacting (b21) with an aminocarboxylic acid or lactam, and a method of reacting a halogenated amine under alkaline conditions.

  Examples of the modified product (b23) of (b21) or (b22) include the isocyanate modified product (terminal isocyanate group) of (b21) or (b22) and the epoxy modified product (terminal epoxy group). The isocyanate-modified product can be obtained by reacting (b21) or (b22) with an organic diisocyanate or reacting (b22) with phosgene. The epoxy-modified product is obtained by reacting (b21) or (b22) with diepoxide (epoxy resin such as diglycidyl ether, diglycidyl ester, alicyclic diepoxide: epoxy equivalent 85 to 600), or (b21) and epihalohydrin. It can be obtained by reacting with (e.g. epichlorohydrin).

  Examples of the organic diisocyanate include those described above. Of the organic diisocyanates, aromatic and aliphatic diisocyanates are preferable from the viewpoint of reactivity, TDI, MDI and HDI are more preferable, and HDI is particularly preferable.

  In order to accelerate the polyurethane-forming reaction, a commonly used catalyst may be used if necessary. As such a catalyst, a metal catalyst, an amine catalyst and a mixture of two or more thereof can be used.

(B) in the present invention includes a block polymer represented by the general formula (6). In the general formula (6), — (CH (R ⁶ ) —CH (R ⁷ ) _y — is a polyolefin segment, and (OA ¹ ) _m —O—E ¹ —O— (A ¹ O) _m ′ is poly It is a segment of an oxyalkylene chain-containing compound

In the general formula (6), A ¹ , E ¹ , m and m ′ are the same as described above, one of R ⁶ and R ⁷ is H, and the other is H or C 1-10 (preferably 1-8, Preferably 1-6) alkyl group; h is an integer of 2-50, preferably 3-40, more preferably 4-30; y is 15-800, preferably 20-500, more preferably 30 ~ 400) represents an integer. X and X ′ are groups selected from groups selected from the groups represented by the general formulas (7) to (13) and corresponding groups represented by (7 ′) to (13 ′), that is, X is represented by the general formula In the group represented by (7), X ′ is a group represented by the general formula (7 ′), and the same relationship applies to the general formulas (8) to (13) and (8 ′) to (13 ′). It is.

In the general formulas (7) to (13) and (7 ′) to (13 ′), R is a C1-24 monovalent hydrocarbon group, specifically, aliphatic, aromatic and alicyclic carbonization. It includes hydrogen radicals, a ² may be the same or different and a ¹ and a ² is as defined above. R ⁸ and R ^{8 'is} a trivalent C2~3 hydrocarbon group; divalent hydrocarbon group R ⁹ is C1～11 (preferably 1-8, more preferably 1 to 6); R ¹⁰ is H or C1-10 (preferably 1 to 8, more preferably 1-6) alkyl group; R ¹¹ is C2～22 (preferably 4 to 18, more preferably 6 to 12) carbon atoms of; E ² is Organic diisocyanate residue; r is an integer of 1 to 10 (preferably 1 to 8, more preferably 1 to 6), and u and v represent 0 or 1. Q, Q ′, T, and T ′ are groups represented by the following formula.

However, R ¹⁰ is H or C1-10 (preferably 1 to 8, more preferably 1-6) alkyl group; when t is 1 when R ⁷ is a methyl group, H; R ¹² is H or methyl 0 or 1.
The polyether segment {(OA ¹ ) m —O—E ¹ —O— (A ¹ O) m ′} in {} in the repeating unit represented by the general formula (6) is represented by the polyether diol (b21). In the formula, E ¹ , A ¹ , m and m ′ are the same as described above.

In the general formula (6), the block polymer (B1) in which X is a group represented by the general formula (7) and X ′ is a group represented by the general formula (7 ′) is a polyolefin (b11 -1) and polyether diol (b21) can be obtained. R ⁸ and R ⁸ ′ in general formulas (7) and (7 ′) are formulas formed from unsaturated dicarboxylic acids

(R ′ is H or methyl group; t is 1 or 0 when R ′ is H, and 1 when R ′ is methyl group.)
For example, when maleic acid or fumaric acid is used for carbonyl modification of polyolefin, R ³ is —CH ₂ —CH <and R ^{3 ′} is> CH—CH ₂ —.

  (B1) can be produced by various methods. For example, polyether diol (b21) is added to polyolefin (b11-1) having a carbonyl group, and polymerization (polycondensation) reaction is usually performed at 200 to 250 ° C. under reduced pressure. It can be manufactured by the method to be performed. It can also be produced using a single or twin screw extruder. Usually, it can manufacture by the method of superposing | polymerizing with 160-250 degreeC and residence time 0.1-20 minutes. Various catalysts can be used for the above polymerization reaction. Catalysts include antimony catalysts (such as antimony trioxide), tin catalysts (such as monobutyltin oxide), titanium catalysts (such as tetrabutyl titanate), zirconium catalysts (such as tetrabutylzirconate), organic acid metal salts [zirconium organic acid salts (Such as zirconyl acetate) and zinc acetate], and mixtures of two or more thereof. Of these, preferred are a zirconium catalyst and an organic acid metal salt, and more preferred is zirconyl acetate. The usage-amount of a catalyst is 0.001 to 5% normally with respect to the total weight of (b11-1) and (b21).

  In the general formula (6), the block polymer (B2) in which X is a group represented by the general formula (8) and X ′ is a group represented by the general formula (8 ′) is a polyolefin having a carbonyl group (b11-1 ) And polyether diamine (b22). The polymerization reaction of (b11-1) and (b22) can be performed by the same method as the polymerization reaction of (b11-1) and (b21).

  In the general formula (6), the block polymer (B3) in which X is a group represented by the general formula (9) and X ′ is a group represented by the general formula (9 ′) is represented by (b11-2) and (b21 ). The polymerization reaction of (b11-2) and (b21) can be performed by the same method as the polymerization reaction of (b11-1) and (b21).

  In the general formula (6), the block polymer (B4) in which X is a group represented by the general formula (10) and X ′ is a group represented by the general formula (10 ′) includes (b11-2) and (b22 ). Alternatively, (b22) may be secondarily modified with the lactam or aminocarboxylic acid, and then reacted with (b11-1). These polymerization reactions can be carried out in the same manner as the polymerization reaction of (b11-1) and (b21).

  In the general formula (6), the block polymer (B5) in which X is a group represented by the general formula (11) and X ′ is a group represented by the general formula (11 ′) is (b11-3) (r = 1) or (b11-4) (when r ≧ 2) and (b21) (when u = 0) or polyetherdiamine (b22) (when u = 1). be able to. The polymerization reaction between (b11-3) or (b11-4) and (b21) or (b22) can be carried out in the same manner as the polymerization reaction between (b11-1) and (b21).

  In the general formula (6), the block polymer (B6) in which X is a group represented by the general formula (12) and X ′ is a group represented by the general formula (12 ′) has hydroxyl groups at both ends of the polymer. Polyolefin (b12) and polyether diol (b21) (when u = 0) or polyether diamine (b22) (when u = 1) are bonded via an organic diisocyanate. It can be obtained by reacting simultaneously or sequentially. For example, (b12) can be obtained by reacting (b21) with (b22) after reacting (b12) with organic diisocyanate to obtain an isocyanate-modified polyolefin.

  In the general formula (6), the block polymer (B6) in which X is a group represented by the general formula (13) and X ′ is a group represented by the general formula (13 ′) is represented by (b11-3) (v = 0) or (b12) (when v = 1) and (b21) or (b22) are bonded via an organic diisocyanate, and these are reacted simultaneously or sequentially. Obtainable. For example, (b11-3) or (b12) can be reacted with an organic diisocyanate to obtain an isocyanate-modified polyolefin, and then reacted with (b21) or (b22). it can. The reaction between (b12) and an organic diisocyanate, the reaction between (b21) or (b22) and an organic diisocyanate, and the reaction between an isocyanate-modified polyolefin and (b21) or (b22) are the same as the usual urethanization or urea reaction. Can be done by the method.

  When forming the isocyanate-modified polyolefin, the equivalent ratio (NCO / OH ratio) of the organic diisocyanate and (b12) and the equivalent ratio of the isocyanate-modified polyolefin and (b21) or (b22) (NCO / OH ratio) are: The ratio is preferably 1.8 / 1 to 3/1, more preferably 1.9 / 1 to 2.5 / 1, and particularly preferably 2/1. When the equivalent ratio is within this range, it becomes easier to take a repeating structure, and filler dispersibility and antistatic properties are further improved. As the organic diisocyanate and the catalyst for promoting the reaction, those described above can be used.

Of the block polymers (B), (B1), (B2), (B3) and (B4) are preferable, (B1) and (B3) are more preferable, and (B3) is particularly preferable.
The amount of the polyoxyalkylene chain-containing compound (b2) constituting the block polymer (B) is preferably 20 to 90% based on the total weight of (b1) and (b2) from the viewpoint of antistatic properties. More preferably, it is 25 to 90%, and particularly preferably 30 to 70%. Further, Mn in (B) is preferably 2,000 to 60,000, more preferably 5,000 to 40,000, and particularly preferably 8,000 to 30,000 from the viewpoint of antistatic properties.

In the structure of the block polymer (B), the average number of repeating units (Nn) of the block of the polyolefin (b1) and the block of the polyoxyalkylene chain-containing compound (b2) is preferably from the viewpoint of antistatic properties. It is 2 to 50, more preferably 2.3 to 30, particularly preferably 2.7 to 20, and most preferably 3 to 10. Nn can be determined by Mn and ¹ H-NMR analysis of (B). For example, the case of (B1) having a structure in which the blocks of (b11) and (b21) are alternately and repeatedly bonded will be described. In ¹ H-NMR analysis, 4.0 to 4.1 ppm of ester bonds { A signal attributed to a proton of —C (C═O) —OCH ₂ —} and a signal attributed to a proton of polyethylene glycol of 3.2 to 3.7 ppm can be observed. The ratio of these proton integral values is obtained, and Nn can be obtained from this ratio and Mn.

  Both ends of (B) have a carbonyl group, amino group, hydroxyl group and / or unmodified polyolefin end derived from (b1), and a hydroxyl group, amino group, isocyanate group and / or epoxy group derived from (b2). The non-modified polyolefin means a polyolefin terminal that is not modified at all, that is, an alkyl group or an alkenyl group.

The blending ratio of (B) to (A) is preferably 3 to 50% by weight, particularly preferably 5 to 40% by weight.

  As the acidic phosphate ester (C) in the present invention, any acidic phosphate ester generally used as an additive for plastics can be used. For example, what substituted 1 to 3 or more of the active hydrogen of phosphoric acid is mentioned. Examples of phosphoric acids include phosphoric acid, metaphosphoric acid, orthophosphoric acid, phosphorous acid, phosphonic acid, pyrophosphoric acid, diphosphinic acid, diphosphoric acid, and diphosphonic acid. Examples of the group that substitutes active hydrogen include an alkyl group, an aryl group, an alkenyl group, and a hydroxyalkyl group (all having 1 to 30 carbon atoms). Examples of the above include monoalkyl esters, monoaryl esters, dialkyl esters, diaryl esters, monoalkyl esters of phosphorous acid, and trialkyl esters of pyrophosphoric acid. Of these, preferred are those represented by the general formula (1).

(R ₁ is a monovalent hydrocarbon group having 1 to 30 carbon atoms, n is 1 or 2, and R ₁ when n is 2 may be the same or different.) In the formula (1), examples of the alkyl group having 1 to 30 carbon atoms represented by R ₁ include methyl, ethyl, n- and i-propyl, n-, i-, sec- and t-butyl, amyl, Tertiary amyl, hexyl, octyl, isooctyl, 2-ethylhexyl, tertiary octyl, nonyl, tertiary nonyl, isononyl, decyl, isodecyl, dodecyl, tridecyl, isotridecyl, tetradecyl, hexadecyl, octadecyl, eicosyl and triancontyl groups, etc. can give. When n is 2, two R _{1 s} may be the same or different. More preferable as the acidic phosphate ester is an acidic phosphate ester in which R ₁ has 8 to 30 carbon atoms, and particularly preferable are a monostearyl ester of phosphoric acid and a distearyl ester of phosphoric acid.

  The acidic phosphate ester is, for example, a method of hydrolyzing a corresponding trialkyl phosphate or a corresponding triester or tetraester of phosphoric acid, a method of hydrolyzing after reacting phosphorus oxychloride with a corresponding alkanol, or It can be synthesized by a known method such as a method of reacting phosphorus pentoxide with the corresponding alkanol.

  The antistatic property improver (D) in the present invention is added for the purpose of further improving the antistatic property of the thermoplastic resin composition. Examples of (D) include alkali metal salts or alkaline earth metal salts (D1), surfactants (D2), ionic liquids (D3), and conductive substances (D4).

  As (D1), alkali metal (lithium, sodium, potassium, etc.) and / or alkaline earth metal (magnesium, calcium, etc.) organic acids [C1-12 mono- and di-carboxylic acids (formic acid, acetic acid, propion) Acid, oxalic acid and succinic acid), salts of C1-20 sulfonic acids (such as methanesulfonic acid, p-toluenesulfonic acid and trifluoromethanesulfonic acid) and thiocyanic acid, and inorganic acids [hydrohalic acid ( Hydrochloric acid, hydrobromic acid, etc.), perchloric acid, sulfuric acid, nitric acid, phosphoric acid, etc.].

  Specific examples of (D1) include halide [fluoride (lithium fluoride, -sodium, -potassium, -magnesium, -calcium, etc.), chloride (lithium chloride, -sodium, -potassium, -magnesium, -calcium, etc.) ), Bromides (such as lithium bromide, -sodium, -potassium, -magnesium and -calcium) and iodides (such as lithium iodide, -sodium, -potassium, -magnesium and -calcium)], perchlorates ( Lithium perchlorate, -sodium, -potassium, -magnesium and -calcium), fluorinated sulfonates (lithium fluorosulfonate, -sodium, -potassium, -magnesium and -calcium), methanesulfonate (methane) Lithium sulfonate, -sodium, -potassium, -mag Cium and -calcium etc.), trifluoromethanesulfonate (lithium trifluoromethanesulfonate, -sodium, -potassium, -magnesium and -calcium etc.), pentafluoroethanesulfonate (lithium pentafluoroethanesulfonate, -sodium, -Potassium,-magnesium and-calcium, etc.), bis (trifluoromethylsulfonyl) imidoate [lithium bis (trifluoromethylsulfonyl) imidoate, -sodium, -potassium, -magnesium and -calcium etc.], bis (penta Fluoroethylsulfonyl) imidate [lithium bis (pentafluoroethylsulfonyl) imidate, -sodium, -potassium, -magnesium, -calcium, etc.], nonafluorobutanesulfonate ( Lithium nafluorobutanesulfonate, -sodium, -potassium, -magnesium and -calcium), undecafluoropentanesulfonate (lithium undecafluoropentanesulfonate, -sodium, -potassium, -magnesium and -calcium) , Tridecafluorohexanesulfonate (lithium tridecafluorohexanesulfonate, -sodium, -potassium, -magnesium, -calcium, etc.), acetate (lithium acetate, -sodium, -potassium, -magnesium, -calcium, etc.) , Sulfates (sodium sulfate, -potassium, -magnesium, -calcium, etc.), phosphates (sodium phosphate, -potassium, -magnesium, -calcium, etc.), and thiocyanates (potassium thiocyanate, etc.). It is done. Of these, from the viewpoint of antistatic properties, preferred are chloride, perchlorate, trifluoromethanesulfonate, bis (trifluoromethylsulfonyl) imidate and acetate, and more preferred are lithium chloride and -potassium. And -sodium, lithium perchlorate, -potassium and -sodium, lithium trifluoromethanesulfonate, -potassium and -sodium, lithium bis (trifluoromethylsulfonyl) imidate, -sodium and -potassium, and potassium acetate.

  Examples of the surfactant (D2) include nonionic, anionic, cationic and amphoteric surfactants. Nonionic surfactants include polyethylene glycol type [higher alcohols (C8-18, such as stearyl alcohol, lauryl alcohol and myristyl alcohol, the same shall apply hereinafter) EO (2-50 mol) adducts, higher fatty acids (C8-24 , E.g. stearic acid, lauric acid and myristic acid, hereafter the same) EO (2-50 mol) adduct, higher alkylamine (C8-24, e.g. stearylamine, laurylamine and myristylamine, hereafter the same) EO (2 -50 mol) adduct, polypropylene glycol (Mn 800-4,000) EO (2-50 mol) adduct, etc.], and polyhydric alcohol type [polyoxyethylene (Mn 200-3,000), higher fatty acid ester of glycerin , Pentaerislit higher fatty acid ester, Sol Or higher fatty acid esters of sorbitan, alkyl (C3-60) ethers of polyhydric (divalent to pentavalent or higher) alcohols (C3-60, such as glycerin, pentaerythritol, sorbit and glucose), alkanolamines ( C2-24) higher fatty acid amides, etc.].

  Examples of the anionic surfactant include compounds other than the above (D1), such as carboxylates [alkali metal salts of higher fatty acids (above)], sulfate esters [higher alcohol sulfate esters, higher alkyl ethers (C8-24). ) Sulfate ester salt, etc.], sulfonate [alkyl (C8-24) benzene sulfonate, alkyl (C8-18) sulfonate, paraffin (C25-60) sulfonate, etc.], phosphate ester salt [higher grade Alcohol phosphate ester salts, etc.). Examples of the cationic surfactant include quaternary ammonium salts [alkyl (C8-24) trimethylammonium salts and the like]. Examples of amphoteric surfactants include amino acid types (such as higher alkylaminopropionates), betaine types [higher alkyl (C8-24) dimethylbetaine, higher alkyl (C8-24) dihydroxyethyl betaine, etc.] and the like. These surfactants may be used alone or in combination of two or more. Of these, anionic surfactants are preferred from the viewpoint of heat resistance and antistatic properties, more preferred are sulfonates, and particularly preferred are alkylbenzene sulfonates, alkyl sulfonates, and paraffin sulfonates. .

  The ionic liquid (D3) is a compound other than the above (D1) and (D2), has a melting point of room temperature or lower, and at least one of cations or anions constituting (D3) is an organic ion, and has an initial conductivity. Is a room temperature molten salt of 1 to 200 ms / cm (preferably 10 to 200 ms / cm), for example, a room temperature molten salt described in WO95 / 15572.

  Examples of the cation constituting (D3) include an amidinium cation, a guanidinium cation, and a tertiary ammonium cation.

  Examples of the amidinium cation include imidazolinium cation [1,2,3,4-tetramethylimidazolinium, 1,3,4-trimethyl-2-ethylimidazolinium, 1,3-dimethylimidazolinium. And 1,3-dimethyl-2,4-diethylimidazolinium and the like]; imidazolium cation [1,3-dimethylimidazolium, 1,3-diethylimidazolium, 1-ethyl-3-methylimidazolium and 1, 2,3-trimethylimidazolium, etc.]; tetrahydropyrimidinium cation [1,3-dimethyl-1,4,5,6-tetrahydropyrimidinium, 1,2,3-trimethyl-1,4,5,6 -Tetrahydropyrimidinium, 1,2,3,4-tetramethyl-1,4,5,6-tetrahydropyrimidinium and 1,2,3,5-tetramethyl-1,4,5,6-tetrahydropyrimidinium and the like]; and dihydropyrimidinium cation [1,3-dimethyl-1,4- or -1,6-dihydro Pyrimidinium, 1,2,3-trimethyl-1,4- or -1,6-dihydropyrimidinium and 1,2,3,4-tetramethyl-1,4- or -1,6-dihydropyri Midinium etc.].

Examples of the guanidinium cation include a guanidinium cation having an imidazolinium skeleton [2-dimethylamino-1,3,4-trimethylimidazolinium, 2-diethylamino-1,3,4-trimethylimidazolinium, 2-diethylamino-1,3-dimethyl-4-ethylimidazolinium, 2-dimethylamino-1-methyl-3,4-diethylimidazolinium, etc.]; guanidinium cation having an imidazolium skeleton [2-dimethyl Amino-1,3,4-trimethylimidazolium, 2-diethylamino-1,3,4-trimethylimidazolium, 2-diethylamino-1,3-dimethyl-4-ethylimidazolium and 2-dimethylamino-1-methyl -3,4-diethylimidazolium etc.]; tetrahydropyri Guanidinium cation having a midinium skeleton [2-dimethylamino-1,3,4-trimethyl-1,4,5,6-tetrahydropyrimidinium, 2-diethylamino-1,3,4-trimethyl-1,4 , 5,6-tetrahydropyrimidinium and 2-diethylamino-1,3-dimethyl-4-ethyl-1,4,5,6-tetrahydropyrimidinium, etc.]; and guanidinium having a dihydropyrimidinium skeleton Cation [2-dimethylamino-1,3,4-trimethyl-1,4- or -1,6-dihydropyrimidinium, 2-diethylamino-1,3,4-trimethyl-1,4- or -1, 6-dihydropyrimidinium and 2-diethylamino-1,3-dimethyl-4-ethyl-1,4- or -1,6-dihydropyrimimi Bromide, etc.] and the like.

  Examples of the tertiary ammonium cation include methyl dilauryl ammonium.

The amidinium cation, guanidinium cation and tertiary ammonium cation may be used alone or in combination of two or more.
Of these, from the viewpoint of initial conductivity, an amidinium cation is preferable, an imidazolium cation is more preferable, and a 1-ethyl-3-methylimidazolium cation is particularly preferable.

In (D3), the following are mentioned as an organic acid and / or an inorganic acid which comprise an anion. Examples of the organic acid include carboxylic acid, sulfate ester, higher alkyl ether sulfate ester, sulfonic acid, and phosphate ester. Examples of inorganic acids include super strong acids (for example, borofluoric acid, tetrafluoroboric acid, perchloric acid, hexafluorophosphoric acid, hexafluoroantimonic acid and hexafluoroarsenic acid), phosphoric acid and boric acid. It is done. The organic acid and inorganic acid may be used alone or in combination of two or more. Among the organic and inorganic acids, the initial conductivity of the aspect preferably from the anion Hamett acidity function constituting the (D3) (-H ₀₎ is 12 to 100 in (D3), superacid, superacid These are acids that form anions other than the conjugated bases, and mixtures thereof.

  Examples of the anion other than the conjugate base of the super strong acid include halogen (for example, fluorine, chlorine and bromine) ions, alkyl (C1-12) benzenesulfonic acid (for example, p-toluenesulfonic acid) ions, and poly (n = 1 to 25). ) Fluoroalkanesulfonic acid (for example, undecafluoropentanesulfonic acid) ion.

  Super strong acids include those derived from protonic acids and combinations of protonic acids and Lewis acids, and mixtures thereof. Examples of the protonic acid as the super strong acid include bis (trifluoromethylsulfonyl) imidic acid, bis (pentafluoroethylsulfonyl) imidic acid, tris (trifluoromethylsulfonyl) methane, perchloric acid, fluorosulfonic acid, alkane (C1 -30) sulfonic acid [eg methane sulfonic acid, dodecane sulfonic acid etc.], poly (n = 1-30) fluoroalkane (C1-30) sulfonic acid (eg trifluoromethane sulfonic acid, pentafluoroethane sulfonic acid, heptafluoropropane) Sulfonic acid, nonafluorobutanesulfonic acid, undecafluoropentanesulfonic acid and tridecafluorohexanesulfonic acid), borofluoric acid and tetrafluoroboric acid. Of these, borofluoric acid, trifluoromethanesulfonic acid and bis (pentafluoroethylsulfonyl) imidic acid are preferred from the viewpoint of ease of synthesis.

  Examples of proton acids used in combination with Lewis acids include hydrogen halides (eg, hydrogen fluoride, hydrogen chloride, hydrogen bromide and hydrogen iodide), perchloric acid, fluorosulfonic acid, methanesulfonic acid, and trifluoromethanesulfonic acid. , Pentafluoroethanesulfonic acid, nonafluorobutanesulfonic acid, undecafluoropentanesulfonic acid, tridecafluorohexanesulfonic acid and mixtures thereof. Of these, hydrogen fluoride is preferred from the viewpoint of the initial conductivity of (D3).

  Examples of the Lewis acid include boron trifluoride, phosphorus pentafluoride, antimony pentafluoride, arsenic pentafluoride, tantalum pentafluoride, and mixtures thereof. Of these, boron trifluoride and phosphorus pentafluoride are preferable from the viewpoint of the initial conductivity of (D3). The combination of the protonic acid and the Lewis acid is arbitrary, but as the super strong acid comprising these combinations, for example, tetrafluoroboric acid, hexafluorophosphoric acid, hexafluorotantalic acid, hexafluoroantimonic acid, tantalum hexafluoride Examples include sulfonic acid, tetrafluoroboric acid, hexafluorophosphoric acid, chloroboron trifluoride, arsenic hexafluoride, and mixtures thereof.

  Of the above anions, (D3) from the viewpoint of the initial conductivity, a super strong acid conjugate base (a super strong acid consisting of a proton acid and a super strong acid consisting of a combination of a proton acid and a Lewis acid), more preferably It is a conjugate base of a super strong acid consisting of a super strong acid consisting of a proton acid and a proton acid and boron trifluoride and / or phosphorus pentafluoride.

  The conductive substance (D4) is a compound other than the (D1) and (D3), and examples thereof include carbon nanotubes, carbon black, and white carbon.

  The method of adding (D) is not particularly limited, but from the viewpoint of effective dispersion in the resin, it is preferable to disperse in (A) in advance, and after the production of (A) (D) More preferably, it is added and dispersed in advance.

  In (C) and (D), the weight ratio of (C) / (D) is 0.02 to 30, and the weight ratio [(C) + (D)] / [(A) + (B)] It is contained so as to be 0.00001 to 0.03. When the weight ratio of (C) / (D) is less than 0.02 or exceeds 30, the antistatic property and the physical properties of the resin are deteriorated. When the weight ratio [(C) + (D)] / [(A) + (B)] is less than 0.00001 or more than 0.03, the antistatic property and the resin physical properties are deteriorated. The weight ratio of (C) / (D) is particularly preferably 0.03 to 20, and more preferably 0.04 to 3. The weight ratio [(C) + (D)] / [(A) + (B)] is particularly preferably 0.00001 to 0.02, more preferably 0.0001 to 0.01.

  In addition, the thermoplastic resin composition of the present invention contains the above (A), (B), (C) and (D) as essential components, but may further contain other components as necessary. . Examples of other components include thermoplastic resins (A ') other than (A), phosphite (C'), compatibilizer (E), and other resin additives (F).

The thermoplastic resin (A ′) other than (A) is a thermoplastic resin having no ester bond, and is a styrene (co) polymer [for example, styrene / acrylonitrile copolymer (AS resin), acrylonitrile / butadiene / styrene. Copolymer (ABS resin) and styrene / butadiene copolymer] Olefin (2 to 8 carbon atoms) (co) polymer [eg, polyethylene, polypropylene, ethylene / propylene copolymer, ethylene / 4-methylpentene copolymer And ethylene / butene-1 copolymers], polyacetals [for example, homopolymers of formaldehyde and copolymers of trioxane and alkylene oxide (for example, ethylene oxide, propylene oxide, etc.), and modified maleic anhydrides thereof. . The blending ratio of (A ′) to (A) is preferably 0 to 200% by weight, particularly preferably 0 to 100% by weight.

  Examples of the phosphite (C ′) include compounds represented by general formulas (2), (3), (4) and (5).

(R ₂ , R ₂ ′ and R ₂ ″ are monovalent hydrocarbon groups having 1 to 25 carbon atoms, which may be the same or different.)

(R ₃ is an m-valent hydrocarbon group having 1 to 40 carbon atoms, and R ₃ ′ and R ₃ ″ are monovalent hydrocarbon groups having 1 to 25 carbon atoms, May be different, and m is an integer from 2 to 4.)

(R ₄ is a 2 × k valent hydrocarbon group having 1 to 40 carbon atoms, R ₄ ′ is a monovalent hydrocarbon group having 1 to 25 carbon atoms, k is 1 or 2, and k R ₄ ′ when is 2 may be the same or different.)

(R ₅ is a p-valent hydrocarbon group having 1 to 40 carbon atoms, R ₅ ′ and R ₅ ″ are monovalent hydrocarbon groups having 1 to 25 carbon atoms, and p is an integer of 1 to 4 And R ₅ ′ and R ₅ ″ when p is 2 to 4 may be the same or different.)

  Examples of the phosphite represented by the general formula (2) include trilauryl phosphite, triisooctyl phosphite, trioleyl phosphite, triphenyl phosphite, trioctadecyl phosphite, triisodecyl phosphite. , Trinormal butyl phosphite, tris-2-ethylhexyl phosphite, tristearyl phosphite, tris-2,4-ditertiary butylphenyl phosphite, tristridecyl phosphite, tris-4-phenylphenol phosphite , Trisnonyl phenyl phosphite, phenyl diisodecyl phosphite, phenyl dioctyl phosphite, diphenyl nonyl phenyl phosphite, diphenyl isodecyl phosphite, diphenyl Seo octyl phosphite, diphenyl decyl phosphite and diphenyl tridecyl phosphite and the like.

  Examples of the phosphite represented by the general formula (3) include tetraphenyl dipropylene glycol diphosphite, tetralauryl bisphenol A-diphosphite, tetratridecyl bisphenol A-diphosphite, and tetraphenyltetra. Examples include tridecylpentaerythritol-tetraphosphite.

  Examples of the phosphite represented by the general formula (4) include diisodecylpentaerythritol-diphosphite, dilaurylpentaerythritol-diphosphite, distearylpentaerythritol-diphosphite, dinonylphenylpentaerythritol. -Diphosphite and bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol-diphosphite.

  Examples of the phosphite represented by the general formula (5) include tetrakis (2,4-ditertiary butylphenol) 4,4'-biphenylene diphosphonite (P-EPQ).

  Preferred as the phosphite is bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol-diphosphite. The phosphite (C ′) is preferably 0 to 100% by weight, more preferably 0 to 80% by weight, based on the weight of (C).

  The compatibilizing agent (E) is added for the purpose of further improving the compatibility of (A) and (B). (E) includes a modified vinyl polymer having at least one polar group selected from the group consisting of a carboxyl group, an epoxy group, an amino group, a hydroxyl group, and a polyoxyalkylene group (for example, in JP-A-3-258850) And a modified vinyl polymer having a sulfonyl group (for example, those described in JP-A-6-345927) and a block copolymer having a polyolefin portion and an aromatic vinyl polymer portion. These (E) s may be used alone or in combination of two or more. The amount of (E) used is usually 20% or less based on the total weight of (A) and (B), preferably 0.1 to 15%, more preferably 1 from the viewpoints of compatibility and mechanical properties of the molded product. -10%, particularly preferably 1.5-8%.

Other additives for resin (F) include colorant (F1), filler (F2), nucleating agent (F3), lubricant (F4), plasticizer (F5), release agent (F6), and antioxidant. And at least one selected from the group consisting of an agent (F7), a flame retardant (F8), an ultraviolet absorber (F9) and an antibacterial agent (F10).

  Examples of the colorant (F1) include ordinary resin pigments and dyes. Examples of the pigment include inorganic pigments and organic pigments.

  Examples of the filler (F2) include fibrous, granular, and plate-like fillers. Examples of the fibrous filler include glass fiber, carbon fiber, silica fiber, silica-alumina fiber, zirconia fiber, aramid fiber, metal (stainless steel, aluminum, titanium, copper, etc.) fiber, and the like. Of these, glass fibers and carbon fibers are preferable from the viewpoint of mechanical properties of the molded product. As granular fillers, carbon black, silica, quartz powder, glass beads, silicates (calcium silicate, aluminum silicate, kaolin, talc, clay, diatomaceous earth, silica powder, etc.), metal oxides (iron oxide, titanium oxide, Zinc oxide, alumina, etc.), metal carbonates (calcium carbonate, magnesium carbonate, etc.), metal (sulfur) sulfates (calcium sulfate, barium sulfate, aluminum sulfate, calcium sulfite, etc.), metal sulfides (molybdenum disulfide) Etc.), silicon carbide, silicon nitride, boron nitride and various metal (magnesium, silicon, aluminum, titanium, copper, silver, gold, etc.) powders. Examples of the plate-like filler include mica, glass flakes, and various metal (aluminum, copper, silver, gold, etc.) foils. These fillers may be used alone or in combination of two or more. Of the above fillers, a fibrous filler is preferable from the viewpoint of mechanical properties of a molded product, and a glass fiber is more preferable.

  Examples of the nucleating agent (F3) include polyvalent organic acids and / or metal salts thereof, aryl phosphate compounds, cyclic polyvalent metal aryl phosphate compounds and dibenzylidene sorbitol compounds, for example, compounds described in JP-A-2008-31461. It is done.

  Examples of the lubricant (F4) include waxes (such as carnauba wax), higher fatty acids (such as stearic acid), higher alcohols (such as stearyl alcohol), and higher fatty acid amides (such as stearic acid amide), for example, as described in JP-A-2008-31461. The compound of this is mentioned.

Examples of the plasticizer (F5) include aromatic carboxylic acid ester type, aliphatic monocarboxylic acid ester type, aliphatic dicarboxylic acid ester type, aliphatic tricarboxylic acid ester type and phosphoric acid triester type. And the compounds described in the Japanese Patent Publication.
Examples of the release agent (F6) include lower alcohol esters of higher fatty acids, polyhydric alcohol esters of fatty acids, glycol esters of fatty acids, liquid paraffin, and hydrogenated products having unsaturated double bonds that can be hydrogenated therein. And the like, for example, compounds described in JP-A-2008-31461.

  Examples of the antioxidant (F7) include phenol-based, sulfur-based, phosphorus-based, and amine-based compounds such as compounds described in JP-A-2008-31461.

  Examples of the flame retardant (F8) include organic flame retardants and inorganic flame retardants, for example, compounds described in JP-A-2008-31461.

  Examples of the ultraviolet absorber (F9) include benzotriazole-based, benzophenone-based, salicylate-based, and acrylate-based compounds such as compounds described in JP-A-2008-31461.

  Examples of the antibacterial agent (F10) include benzoic acid, paraoxybenzoic acid ester, sorbic acid, halogenated phenol and the like, for example, compounds described in JP-A-2008-31461.

The total use amount of (F) is usually 170% or less based on the total weight of (A) and (B), and preferably 0.1 to 100% from the viewpoint of the additive effect and mechanical properties of the molded product. . The amount of each (F) used is based on the total weight of (A) and (B), (F1) is usually 5% or less, preferably 0.1 to 3%; (F2) is usually 150% or less, Preferably 5 to 100%; (F3) is usually 20% or less, preferably 1 to 10%; (F4) is usually 20% or less, preferably 1 to 10%; (F5) is usually 20% or less, preferably 1 to 10%; (F6) is usually 10% or less, preferably 0.1 to 5%; (F7) is usually 5% or less, preferably 0.1 to 3%; (F8) is usually 20% or less, Preferably, it is 1 to 10%; (F9) is usually 5% or less, preferably 0.1 to 3%; (F10) is usually 3% or less, preferably 0.05 to 1%.
When the additive is the same between (F1) to (F10) above, the amount of each additive effect is not used regardless of other effects, but the amount used is adjusted according to the purpose of use. It shall be.

  As a manufacturing method of the thermoplastic resin composition of the present invention, (A) to (F) [[D] is previously contained in (A) from the viewpoint of effective dispersion as described above. Also good. It is manufactured by melt mixing. As a method of melt-mixing, a normal method, for example, pellets or powdery components are mixed with an appropriate mixer (Henschel mixer, etc.) and then melt-mixed with an extruder (temperature 150 to 260 ° C.) to form pellets. The method of making it. The order of addition of each component during mixing is not particularly limited. For example, a normal master batch method or a master pellet method may be used, and these methods include a small amount of (C), (D), and (E). And / or (F) is a preferable method from the viewpoint of uniformly dispersing the resin in the resin.

  Examples of the molding method of the thermoplastic resin composition of the present invention include injection molding, compression molding, calendar molding, slush molding, rotational molding, extrusion molding, blow molding, film molding (casting method, tenter method, inflation method, etc.) and the like. Depending on the purpose, it can be molded by any method that incorporates means such as single layer molding, multilayer molding (the thermoplastic resin composition of the present invention may be a surface layer portion or a core layer) or foam molding.

The molded product obtained from the thermoplastic resin composition of the present invention has excellent mechanical properties, water resistance and permanent antistatic properties, as well as good paintability and printability. Examples of the method for coating the molded product include, but are not limited to, an air spray method, an airless spray method, an electrostatic spray method, a dipping method, a roller method, and a brush coating method. Examples of the paint include paints generally used for plastic coating such as polyester melamine resin paint, epoxy melamine resin paint, acrylic melamine resin paint, and acrylic urethane resin paint. Although a coating film thickness (film thickness after drying) can be appropriately selected according to the purpose, it is preferably 10 to 50 μm, more preferably 15 to 40 μm from the viewpoint of coating film properties and drying efficiency. In addition, examples of the method of printing after coating the molded product or the molded product include printing methods generally used for plastic printing, such as gravure printing, flexographic printing, screen printing, and offset printing. . Examples of the printing ink include those usually used for printing plastics.

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

Production Example 1 [Production of acid-modified polypropylene (b1-1)]
Thermal degradation method [Thermal degradation of ethylene / propylene (random addition) copolymer (ethylene content 2%) at a density of 0.90 g / cm ^{3 at} 23 ° C. and MFR 6.0 g / 10 min at 410 ± 0.1 ° C. Low molecular weight ethylene / propylene random copolymer (Mn 3,500, density 0.89 g / cm ³ , 7.1 double bond amount per 1,000 C, average double bond per molecule) (Number 1.8, content of polyolefin which can be modified at both ends 90%) 95 parts, maleic anhydride 10 parts and xylene 30 parts were melted at 200 ° C. in a nitrogen gas atmosphere (sealed), Time reaction was performed. Then, excess maleic anhydride and xylene were distilled off under reduced pressure at 200 ° C. for 3 hours to obtain acid-modified polypropylene (b1-1). The acid value of (b1-1) was 27.2, and Mn was 3,700.

Production Example 2 [Production of secondary modified polypropylene (b1-2)]
(B1-1) 66 parts and 34 parts of 12-aminododecanoic acid were melted at 200 ° C. in a nitrogen gas atmosphere, reacted at 200 ° C. for 3 hours under reduced pressure of 1.3 kPa or less, and secondary modified polypropylene ( b1-2) was obtained. The acid value of (b1-2) was 17.7, and Mn was 5,700.

Production Example 3 [Production of Block Polymer (B-1)]
In a stainless steel autoclave, 76.0 parts of (b1-2), Mn 2,000, 24.0 parts of polyethylene glycol having a volume resistivity of 1 × 10 ⁷ Ω · cm, 0.3 part of an antioxidant, and 0.3% of zirconyl acetate. 5 parts were charged and polymerized for 4 hours under the conditions of 230 ° C. and reduced pressure of 0.13 kPa or less to obtain a viscous polymer. The polymer was taken out as a strand on a belt and pelletized to obtain a block polymer (B-1).

Production Example 4 [Production of Block Polymer (B-2)]
In Production Example 3, instead of 76.0 parts of the charged amount of (b1-2), 86.0 parts, and 24.0 parts of polyethylene glycol having a Mn of 2,000 and a volume resistivity of 1 × 10 ⁷ Ω · cm The block polymer (B-2) was prepared in the same manner as in Production Example 3, except that 33.5 parts of an EO adduct of bisphenol A having a Mn of 1,000 and a volume resistivity of 2 × 10 ⁸ Ω · cm was used. Obtained.

Production Example 5 [Production of block polymer (B-3)]
A terminal cyanoalkyl group obtained by cyanoalkylating the hydroxyl groups at both ends of polyethylene glycol having (b1-2) 75.8 parts, Mn 2,000, and a volume resistivity of 1 × 10 ⁷ Ω · cm was added to a stainless steel autoclave. 24.2 parts of hydrophilic polymer (volume resistivity 2 × 10 ⁸ Ω · cm) reduced to primary amino group by reduction and 0.3 part of antioxidant were charged, and the temperature was 220 ° C. and 0.13 kPa or less. Polymerization was performed for 6 hours under reduced pressure to obtain a viscous polymer. The polymer was taken out as a strand on a belt and pelletized to obtain a block polymer (B2-3).

Production Example 6 [Production of block polymer (B-4)]
In a stainless steel autoclave, 73.3 parts of (b1-1) and the terminal cyanoalkyl group obtained by cyanoalkylating the hydroxyl groups at both ends of the EO adduct (Mn1,500) of bisphenol A are reduced to a primary amino group. 26.7 parts of a hydrophilic polymer modified with a base (volume resistivity 2 × 10 ⁸ Ω · cm) was charged and polymerized for 3 hours at 200 ° C. under reduced pressure of 1.3 kPa or less to form a viscous polymer. Obtained. The polymer was taken out as a strand on the belt and pelletized to obtain a block polymer (B-4).

Production Example 7 [Production of ionic liquid (D-1)]
A polytetrafluoroethylene reaction vessel was charged with 128 parts of methanol, and then 20 parts by weight of anhydrous HF was blown and absorbed under normal pressure at a temperature of 20 to 30 ° C. in about 30 minutes. Next, 131.9 parts of BF ₃ 2 methanol complex (BF ₃ content 51.4%) was added dropwise at 30 to 40 ° C. in about 30 minutes, and then a methanol solution of 1-ethyl-3-methylimidazolium methyl carbonate. (Concentration 50%) 372 parts were dropped over about 30 minutes. The reaction was carried out while generating carbon dioxide gas by the reaction, and after the generation of carbon dioxide gas was stopped, all the solvent and the like were removed at a temperature of 60 to 70 ° C. over about 1 hour under reduced pressure. A colorless and transparent liquid was obtained in the reaction vessel. As a result of NMR analysis, the obtained liquid was 1-ethyl-3-methylimidazolium tetrafluoroborate (D-1). The yield was 99%.

Comparative Production Example 1 [Production of polyetheresteramide]
In a 3 L stainless steel autoclave, 66.9 parts of ε-caprolactam, 33.1 parts of adipic acid, antioxidant [trade name: Irganox 1010, manufactured by Ciba Specialty Chemicals Co., Ltd., hereinafter the same] 0.3 part and water 6 parts were charged and the autoclave was purged with nitrogen, and then heated and stirred at 220 ° C. under pressure (0.3 to 0.5 MPa) for 4 hours to obtain 96 parts of polyamide having an acid value of 374 having carboxyl groups at both ends. It was. Next, 160 parts of polyethylene glycol of Mn500 and 0.5 part of zirconyl acetate were added and polymerized at 245 ° C. under reduced pressure of 0.13 kPa or less for 5 hours to obtain a viscous polymer. This polymer was taken out in a strand form on a belt and pelletized to obtain a polyether ester amide.

Examples 1-8, Comparative Examples 1-5
According to the composition shown in Table 1, after blending the above (A) to (D) [(D) added during the production of (B)] for 3 minutes with a Henschel mixer, Were melt-kneaded under the conditions as described above, 100 rpm, and residence time of 5 minutes to obtain resin compositions and (Examples 1 to 8 and Comparative Examples 1 to 5), respectively.
Kneading temperature: When using [A-1], [A-3] or [A-5]; 230 ° C.
[A-2] When used: 240 ° C
[A-4] When used: 200 ° C

(note)
[A-1]: Cyclohexanedimethanol / ethylene glycol / terephthalic acid copolymer [trade name EASTER PETG6763 manufactured by Eastman Chemical Japan Co., Ltd.]
[A-2]: Polycarbonate and acrylonitrile / styrene / butadiene copolymer (ABS resin) mixture (polycarbonate / ABS resin weight ratio = 70/30) [trade name Iupilon GP-1 manufactured by Mitsubishi Gas Chemical Co., Ltd.]
[A-3]: Polybutylene terephthalate [trade name Baroques 310 made by Nippon GE Plastics Co., Ltd.]
[A-4]: Polyester-based thermoplastic polyurethane [trade name: Pandex T-5165 manufactured by Dainippon Ink & Chemicals, Inc.]
[A-5]: Polymethyl methacrylate [Brand name Acripet VH manufactured by Mitsubishi Rayon Co., Ltd.]
The following were used as acidic phosphoric acid ester (C).
[C-1]: Monostearyl phosphate and distearyl phosphate mixture [trade name; ADK STAB AX-71 manufactured by ADEKA Corporation]
[C-2]: Monolauryl phosphate [manufactured by Daihachi Chemical Industry Co., Ltd.]
[D-2]: Lithium chloride (added when producing block polymer)
[D-3]: Sodium dodecylbenzenesulfonate (added when producing block polymer)
([A-2] contains (A) and another thermoplastic resin (A ′).)
Phosphite compound [trade name; ADK STAB PEP-36 manufactured by ADEKA Corporation]
Phenolic compounds [trade name; Irganox 1076 manufactured by Nippon Ciba-Geigy Co., Ltd.]

performance test;
About the resin composition of this invention and the resin composition of the comparative example, the test piece was created using the injection molding machine, and the external appearance, the surface specific resistance value, IZOD impact strength, and the tensile yield point strength were evaluated. Test cylinders were prepared at the cylinder temperatures of the injection molding machine as shown below and at a mold temperature of 50 ° C. The results are shown in Table 2. Appearance, surface resistivity, IZOD impact strength, and tensile yield strength were evaluated by the following methods.
Cylinder temperature: When using [A-1], [A-3] or [A-5]: 230 ° C.
[A-2] When used: 240 ° C
[A-4] When used: 200 ° C
(1) Appearance: The surface of the injection-molded plate was visually evaluated.
Evaluation criteria ○: No appearance defects
X: Appearance defects such as a flow mark (2) Surface resistivity value: After the molded specimen is left in an atmosphere of 23 ° C. and 50% humidity for 48 hours, it conforms to ASTM D257-78 (Reapproved 1983) And measured.
(3) IZOD impact strength: compliant with JIS K7110-1984 (with notch, 3.2 mm thickness).
(4) Tensile yield point strength: Conforms to JIS K7113-1981.

  As is apparent from Table 2, the resin compositions of the present invention (Examples 1 to 7) are more compact than the comparative resin compositions (Comparative Examples 1 to 4). It turns out that it is excellent in strength.

  Since the antistatic resin composition of the present invention is excellent in moldability and gives a molded product having excellent antistatic properties and mechanical strength, various molding methods [injection molding, compression molding, calendar molding, slush molding, rotation Molding, extrusion molding, blow molding, film molding (casting method, tenter method, inflation method, etc.)], and any various molding methods that incorporate means such as single layer molding, multilayer molding or foam molding depending on the purpose. Molded and required antistatic properties, housing products for home appliances / OA equipment, game equipment and office equipment, various plastic containers such as IC trays, various packaging films, flooring sheets, artificial grass, mats, and It is extremely useful as various molding materials for automobile parts.

Claims (7)

A thermoplastic resin composition containing the following (A) to (D), wherein the weight ratio (C) / (D) is 0.02 to 30, and the weight ratio [(C) + (D) ] / [(A) + (B)] is a thermoplastic resin composition of 0.00001 to 0.03.
(A): Thermoplastic resin having ester bond (B): Block of polyolefin (b1) and block of polyoxyalkylene chain-containing compound (b2) are formed from ester bond, amide bond, ether bond, imide bond and urethane bond. Block polymer (C) having a structure bonded through at least one bond selected from the group consisting of: Acid phosphate ester (D): Antistatic property improver   The antistatic property improver (D) is at least one selected from the group consisting of an alkali metal salt and / or alkaline earth metal salt (D1), a surfactant (D2) and an ionic liquid (D3). Item 2. The thermoplastic resin composition according to Item 1. The thermoplastic resin composition according to claim 1 or 2, wherein the acidic phosphate ester (C) is an acidic phosphate ester represented by the following general formula (1).
(R ₁ is a monovalent hydrocarbon group having 1 to 30 carbon atoms, n is 1 or 2, and R ₁ when n is 2 may be the same or different.) Furthermore, the thermoplastic resin composition in any one of Claims 1-3 containing the phosphite shown by following General formula (2), (3), (4) or (5).
(R ₂ , R ₂ ′ and R ₂ ″ are monovalent hydrocarbon groups having 1 to 25 carbon atoms, which may be the same or different.)
(R ₃ is an m-valent hydrocarbon group having 1 to 40 carbon atoms, and R ₃ ′ and R ₃ ″ are monovalent hydrocarbon groups having 1 to 25 carbon atoms, May be different, and m is an integer from 2 to 4.)
(R ₄ is a 2 × k valent hydrocarbon group having 1 to 40 carbon atoms, R ₄ ′ is a monovalent hydrocarbon group having 1 to 25 carbon atoms, k is 1 or 2, and k R ₄ ′ when is 2 may be the same or different.)
(R ₅ is a p-valent hydrocarbon group having 1 to 40 carbon atoms, R ₅ ′ and R ₅ ″ are monovalent hydrocarbon groups having 1 to 25 carbon atoms, and p is an integer of 1 to 4 And R ₅ ′ and R ₅ ″ when p is 2 to 4 may be the same or different.)   The thermoplastic resin (A) having an ester bond is composed of a thermoplastic polyester resin (A1), a thermoplastic polyurethane resin (A2), a polycarbonate resin (A3), and an ester group-containing vinyl (co) polymer (A4). The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition is one or more selected from the group consisting of:   The molded object formed by shape | molding the thermoplastic resin composition in any one of Claims 1-5.   A molded article obtained by coating and / or printing the molded body according to claim 6.