WO2020203619A1 - Agent antistatique, composition d'agent antistatique en contenant, composition de résine antistatique en contenant, corps moulé et film à base de ceux-ci - Google Patents

Agent antistatique, composition d'agent antistatique en contenant, composition de résine antistatique en contenant, corps moulé et film à base de ceux-ci Download PDF

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Publication number
WO2020203619A1
WO2020203619A1 PCT/JP2020/013574 JP2020013574W WO2020203619A1 WO 2020203619 A1 WO2020203619 A1 WO 2020203619A1 JP 2020013574 W JP2020013574 W JP 2020013574W WO 2020203619 A1 WO2020203619 A1 WO 2020203619A1
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acid
antistatic agent
block
compound
polyester
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PCT/JP2020/013574
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English (en)
Japanese (ja)
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景佑 清水
直樹 圓城
和清 野村
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株式会社Adeka
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Publication of WO2020203619A1 publication Critical patent/WO2020203619A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/16—Anti-static materials

Definitions

  • the present invention relates to an antistatic agent, an antistatic agent composition containing the antistatic agent, an antistatic resin composition containing these (hereinafter, also simply referred to as “resin composition”), a molded product thereof, and a film thereof.
  • the present invention relates to an antistatic agent capable of continuously imparting an excellent antistatic effect to a resin, an antistatic agent composition containing the same, an antistatic resin composition containing these, a molded product and a film thereof.
  • thermoplastic resins are indispensable in modern times because they are not only lightweight and easy to process, but also have excellent properties such as the ability to design a base material according to the application. It is an important material. Further, since the thermoplastic resin has a property of being excellent in electrical insulation, it is frequently used for components of electric products and the like. However, since the thermoplastic resin has too high an insulating property, there is a problem that it is easily charged by friction or the like.
  • thermoplastic resin attracts dust and dirt around it, which causes a problem of spoiling the appearance of the resin molded product.
  • precision instruments such as computers may not be able to operate normally due to charging.
  • electric shock When an electric shock is generated from the resin to the human body, it not only causes discomfort to the human body, but also may induce an explosion accident in the presence of flammable gas or dust.
  • synthetic resin films used for packaging materials for electrical and electronic equipment and electrical and electronic parts the generation of static electricity due to charging causes electric shocks and fine dust, which causes damage to the parts and equipment, which is large. It becomes a problem.
  • the synthetic resin has been conventionally treated to prevent charging.
  • the most common antistatic treatment method is to add an antistatic agent to the synthetic resin.
  • antistatic agents include a coating type that is applied to the surface of a resin molded body and a kneading type that is added when the resin is processed and molded, but the coating type is inferior in sustainability.
  • a large amount of organic matter is applied to the surface, there is a problem that those touching the surface are contaminated.
  • Patent Documents 1 and 2 a polyether is used to impart antistatic properties to a polyolefin resin. Esteramides have been proposed. Further, Patent Document 3 proposes a block polymer having a structure in which a block of polyolefin and a block of hydrophilic polymer are repeatedly and alternately bonded. Further, Patent Document 4 proposes a polymer-type antistatic agent having a polyester block.
  • an object of the present invention is an antistatic agent capable of continuously imparting an excellent antistatic effect to a synthetic resin, an antistatic agent composition containing the antistatic agent, and an antistatic resin composition containing these. , The molded article and the film.
  • the present inventors can impart excellent antistatic performance to the synthetic resin, and the polymer compound having a predetermined structure can be compatible with the synthetic resin. Since it is excellent in quality, it does not adversely affect the transparency, and it has been found that the above-mentioned problems can be solved by using this, and the present invention has been completed.
  • the antistatic agent of the present invention contains a polyester block (A) composed of a polyester (a) obtained by reacting a diol (a1) and a dicarboxylic acid (a2), and one or more ethyleneoxy groups.
  • a block (B) of a polyester composed of a compound (b) having a hydroxyl group at both ends and a polyhydric alcohol compound (D) having three or more hydroxyl groups are bonded via an ester bond or an ether bond.
  • the number average molecular weight of the polyester (a) calculated by the acid value measurement method is 1,600 to 10,000, and the number average molecular weight of the compound (b) calculated by the hydroxyl value measurement method is 1,000 to 6. It is characterized by being 000.
  • the polymer compound (E) has a polyester block (A) and a polyether block (B), and has a hydroxyl group or a carboxyl group at the end of the polyester (a).
  • a polymer having a structure formed by the reaction of the hydroxyl group at the terminal of the compound (b) and the hydroxyl group of the polyhydric alcohol compound (D) via an ester bond or an ether bond is preferable.
  • the compound (E) is a block polymer (C) having a carboxyl group at both ends, in which a block (A) and a block (B) are repeatedly and alternately bonded via an ester bond, and a polyhydric alcohol compound (D).
  • the block polymer (C) of the polymer compound (E) has a number average molecular weight of 8,000 to 50,000 calculated by the acid value measurement method.
  • the polyester (a) of the polymer compound (E) has carboxyl groups at both ends.
  • the compound (b) of the polymer compound (E) is preferably polyethylene glycol.
  • the ratio of the block (B) of the polyether to the total mass of the block (A) and the block (B) of the polymer compound (E) is 20 to 50% by mass. Those within the range are preferable.
  • the antistatic agent composition of the present invention is characterized in that the antistatic agent of the present invention is further blended with one or more selected from the group consisting of alkali metal salts and ionic liquids. Is.
  • the antistatic resin composition of the present invention is characterized in that the antistatic agent of the present invention is blended with a synthetic resin. Further, the other antistatic resin composition of the present invention is characterized in that the antistatic agent composition of the present invention is blended with the synthetic resin.
  • the synthetic resin is preferably at least one selected from the group consisting of polyolefin-based resins, polystyrene-based resins and copolymers thereof.
  • the molded product of the present invention is characterized by being obtained from the antistatic resin composition of the present invention.
  • the molded product of the present invention is suitable for a film.
  • the film of the present invention preferably has a Haze value of 0% or more and 40.0% or less at a thickness of 50 ⁇ m.
  • an antistatic agent capable of continuously imparting an excellent antistatic effect to a synthetic resin, an antistatic agent composition containing the antistatic agent, an antistatic resin composition containing these, and the like thereof. Molds and films can be provided.
  • the molded product of the present invention is suitable for a film having excellent transparency because static electricity is less likely to be generated, surface contamination due to static electricity and deterioration of commercial value due to adhesion of dust are less likely to occur.
  • the antistatic agent of the present invention has both a polyester block (A) composed of a polyester (a) obtained by reacting a diol (a1) and a dicarboxylic acid (a2) and a block (A) having one or more ethyleneoxy groups.
  • a block (B) of a polyester composed of a compound (b) having a hydroxyl group at the terminal and a polyhydric alcohol compound (D) having three or more hydroxyl groups are formed via an ester bond or an ether bond, preferably an ester bond. It contains one or more of the polymer compounds (E) having a structure formed by bonding with an ester.
  • the ethyleneoxy group is a group represented by the following general formula (1).
  • the polymer compound (E) has a number average molecular weight of 1,600 to 10,000 calculated by the acid value measurement method of the polyester (a) constituting the polyester block (A).
  • the number average molecular weight of the compound (b) constituting the block (B) of the polyether is 1,000 to 6,000 calculated by the method for measuring the hydroxyl value.
  • the number average molecular weight calculated by the acid value measurement method of polyester (a) is preferably 2,000 to 8 from the viewpoint of antistatic property, its durability, and film transparency. It is 000, more preferably 3,000 to 8,000.
  • the method for calculating the number average molecular weight of the antistatic agent of the present invention by the acid value measurement method is as follows.
  • one end or both ends of the polyester (a) are hydroxyl groups, treat the hydroxyl groups with maleic anhydride to form a carboxyl group, measure the acid value in the same manner, calculate the number average molecular weight, and then use it for treatment. It may be calculated by making a correction excluding the maleic anhydride.
  • the number average molecular weight of the compound (b) having one or more ethyleneoxy groups and having hydroxyl groups at both ends calculated by the hydroxyl value measurement method is preferably from the viewpoint of antistatic property, its durability, and film transparency. It is 1,500 to 5,000, more preferably 1,800 to 4,000.
  • the method for calculating the number average molecular weight of the antistatic agent of the present invention by the hydroxyl value measurement method is as follows.
  • ⁇ Calculation method of number average molecular weight by hydroxyl value measurement method> The hydroxyl value was measured by the following method for measuring the hydroxyl value, and the number average molecular weight (hereinafter, also referred to as “Mn”) was determined by the following formula.
  • Number average molecular weight (56110 ⁇ 2) / hydroxyl value ⁇ method for measuring hydroxyl value> ⁇
  • Reagent A acetylating agent
  • Triethyl phosphate 1560 mL (2) Acetic anhydride 193 mL (3) Perchloric acid (60%) 16g
  • the above reagents are mixed in the order of (1) ⁇ (2) ⁇ (3).
  • ⁇ Reagent B Pyridine and pure water are mixed in a volume ratio of 3: 1.
  • ⁇ Reagent C Add 2-3 drops of phenolphthalein solution to 500 mL of isopropyl alcohol and neutralize with 1N-KOH aqueous solution.
  • the polymer compound (E) is composed of a polyester block (A) composed of polyester (a) and ethylene from the viewpoint of antistatic property, its durability, and transparency of the film. It has a block (B) of a polyether composed of a compound (b) having one or more oxy groups and having hydroxyl groups at both ends, and has a hydroxyl group or a carboxyl group at the ends of polyester (a) and a compound (b). ) And the hydroxyl group of the polyvalent alcohol compound (D) having three or more hydroxyl groups, formed by an ester bond or an ether bond, preferably a structure formed by bonding via an ester bond. It is preferable to have.
  • the polymer compound (E) contains a polyester block (A), a polyether block (B), and a polyether block (B) from the viewpoints of antistatic property, its durability, and film transparency.
  • a block polymer (C) having a carboxyl group at both ends, which is repeatedly and alternately bonded via an ester bond, and a polyhydric alcohol compound (D) having three or more hydroxyl groups are bonded via an ester bond. It is preferable that
  • Examples of the diol (a1) used in the polymer compound (E) include an aliphatic diol and an aromatic group-containing diol.
  • the diol may be a mixture of two or more kinds.
  • Examples of the aliphatic diol include 1,2-ethanediol (ethylene glycol), 1,2-propanediol (propylene glycol), 1,3-propanediol, 1,2-butanediol, and 1,3-butanediol.
  • 1,4-cyclohexanedimethanol, 1,6-hexanediol, 1,12-dodecanediol, and hydrogenated bisphenol A are used in terms of antistatic properties, their durability, and film transparency.
  • 1,4-cyclohexanedimethanol, 1,6-hexanediol and 1,12-dodecanediol are more preferable, and 1,4-cyclohexanedimethanol is even more preferable.
  • the aliphatic diol is preferably hydrophobic from the viewpoint of antistatic property, its durability, and transparency of the film, it is not preferable to use polyethylene glycol having hydrophilicity.
  • aromatic group-containing diol examples include bisphenol A, 1,2-hydroxybenzene, 1,3-hydroxybenzene, 1,4-hydroxybenzene, 1,4-benzenedimethanol, and an ethylene oxide adduct of bisphenol A.
  • aromatic group-containing diol examples include bisphenol A, 1,2-hydroxybenzene, 1,3-hydroxybenzene, 1,4-hydroxybenzene, 1,4-benzenedimethanol, and an ethylene oxide adduct of bisphenol A.
  • examples thereof include a propylene oxide adduct of bisphenol A, a polyhydroxyethyl adduct of a mononuclear divalent phenol compound such as 1,4-bis (2-hydroxyethoxy) benzene, resorcin, and pyrocatechol.
  • diols having an aromatic group ethylene oxide adduct of bisphenol A and 1,4-bis ( ⁇ -hydroxyethoxy) benzene are preferable.
  • the aromatic diol preferably has hydrophobicity from the viewpoint of antistatic property, its durability, and transparency of the film.
  • diol (a1) 1,4-cyclohexanedimethanol, 1,6-hexanediol, and 1,12-dodecanediol are preferred among the above from the viewpoints of antistatic property, its durability, and film transparency. I'm sorry.
  • examples of the dicarboxylic acid (a2) used in the polymer compound (E) include aliphatic dicarboxylic acids and aromatic dicarboxylic acids.
  • the dicarboxylic acid may be a mixture of two or more kinds.
  • the dicarboxylic acid used in the polymer compound (E) may be a derivative of the dicarboxylic acid (a2).
  • the derivative include carboxylic acid anhydride, carboxylic acid ester (for example, carboxylic acid alkyl ester such as carboxylic acid methyl ester), carboxylic acid alkali metal salt (for example, carboxylic acid sodium salt), and carboxylic acid halide (for example, carboxylic acid). Acid chloride) and the like.
  • the aliphatic dicarboxylic acid preferably includes an aliphatic dicarboxylic acid having 2 to 20 carbon atoms, and examples thereof include oxalic acid, malonic acid, succinic acid, glutaric acid, methylsuccinic acid, dimethylmalonic acid and 3-methylglutaric acid.
  • Ethylsuccinic acid isopropylmalonic acid, adipic acid, pimelli acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid (1,10-decandicarboxylic acid), tridecanedioic acid, tetradecanedioic acid, hexadecanedi Acid, octadecanedioic acid, eikosandioic acid, 1,3-cyclopentanedicarboxylic acid, 1,2-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid Examples thereof include acids, 1,4-cyclohexanedioacetic acid, 1,3-cyclohexanediacetic acid, 1,2-cyclohexanediac
  • a dicarboxylic acid having 4 to 16 carbon atoms is preferable, and a dicarboxylic acid having 6 to 12 carbon atoms is more preferable, from the viewpoint of antistatic property, its durability, and transparency of the film.
  • the aromatic dicarboxylic acid preferably includes an aromatic dicarboxylic acid having 8 to 20 carbon atoms, and examples thereof include terephthalic acid, isophthalic acid, phthalic acid, phenylmalonic acid, homophthalic acid, phenylsuccinic acid and ⁇ -phenylglutal. Acid, ⁇ -Phenyladiponic acid, ⁇ -phenyladipic acid, biphenyl-2,2'-dicarboxylic acid, biphenyl-4,4'-dicarboxylic acid, naphthalenedicarboxylic acid, sodium 3-sulfoisophthalate and 3-sulfoisophthalic acid Examples include potassium.
  • aromatic dicarboxylic acids terephthalic acid, isophthalic acid, and phthalic acid (including phthalic anhydride) are preferable, and phthalic acid (including phthalic anhydride) is preferable from the viewpoint of antistatic property, its durability, and film transparency. ) Is more preferable.
  • adipic acid, sebacic acid, and terephthalic acid are preferable as the dicarboxylic acid (a2) from the viewpoints of antistatic property, its durability, and film transparency.
  • the block (B) of the polyether is composed of the compound (b) having one or more ethyleneoxy groups represented by the following general formula (1) and having hydroxyl groups at both ends.
  • a hydrophilic compound is preferable, and the ethyleneoxy group represented by the general formula (1) is used.
  • the possessed polyether is more preferable, polyethylene glycol is even more preferable from the viewpoint of antistatic property and its durability, and the transparency of the film, and polyethylene glycol represented by the following general formula (2) is particularly preferable.
  • m represents a number from 4 to 250.
  • m is preferably 20 to 200, more preferably 40 to 180, from the viewpoint of antistatic property, its durability, and transparency of the film.
  • Examples of the compound (b) include ethylene oxide and other alkylene oxides such as propylene oxide, 1,2-, 1,4-, 2,3-, in addition to polyethylene glycol obtained by addition reaction of ethylene oxide.
  • ethylene oxide and other alkylene oxides such as propylene oxide, 1,2-, 1,4-, 2,3-, in addition to polyethylene glycol obtained by addition reaction of ethylene oxide.
  • a polyether obtained by addition reaction with one or more kinds of 1,3-butylene oxide and the like can be mentioned, and this polyether may be either random or blocked.
  • a compound having a structure in which ethylene oxide is added to an active hydrogen atom-containing compound ethylene oxide and other alkylene oxides, for example, propylene oxide, 1,2-, 1,4-,
  • examples thereof include compounds having a structure in which one or more kinds such as 2,3- or 1,3-butylene oxide are added. These may be either random addition or block addition.
  • Examples of the active hydrogen atom-containing compound include glycols, dihydric phenols, primary monoamines, secondary diamines and dicarboxylic acids.
  • glycol an aliphatic glycol having 2 to 20 carbon atoms, an alicyclic glycol having 5 to 12 carbon atoms, an aromatic glycol having 8 to 26 carbon atoms, and the like can be used.
  • Examples of the aliphatic glycol include ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, and 1,3-.
  • Hexanediol, 1,4-hexanediol, 1,6-hexanediol, 2,5-hexanediol, 1,2-octanediol, 1,8-octanediol, 1,10-decanediol, 1,18-octadecane examples thereof include diols, 1,20-eicosane diols, diethylene glycols, triethylene glycols and thiodiethylene glycols.
  • Examples of the alicyclic glycol include 1-hydroxymethyl-1-cyclobutanol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1-methyl-3,4-cyclohexanediol. , 2-Hydroxymethylcyclohexanol, 4-hydroxymethylcyclohexanol, 1,4-cyclohexanedimethanol, 1,1'-dihydroxy-1,1'-dicyclohexyl and the like.
  • aromatic glycol examples include dihydroxymethylbenzene, 1,4-bis ( ⁇ -hydroxyethoxy) benzene, 2-phenyl-1,3-propanediol, 2-phenyl-1,4-butanediol, and 2-benzyl.
  • -1,3-Propanediol triphenylethylene glycol, tetraphenylethylene glycol, benzopinacol and the like can be mentioned.
  • phenol having 6 to 30 carbon atoms can be used, for example, catechol, resorcinol, hydroquinone, bisphenol A, bisphenol F, bisphenol S, dihydroxydiphenyl ether, dihydroxydiphenyl thioether, binaphthol and alkyl (carbon atoms) thereof. Numbers 1 to 10) or halogen-substituted products can be mentioned.
  • Examples of the primary monoamine include aliphatic primary monoamines having 1 to 20 carbon atoms.
  • Examples of the secondary diamine include an aliphatic secondary diamine having 4 to 18 carbon atoms, a heterocyclic secondary diamine having 4 to 13 carbon atoms, an alicyclic secondary diamine having 6 to 14 carbon atoms, and a carbon atom number. 8 to 14 aromatic secondary diamines and secondary alkanol diamines having 3 to 22 carbon atoms can be used.
  • Examples of the aliphatic secondary diamine include N, N'-dimethylethylenediamine, N, N'-diethylethylenediamine, N, N'-dibutylethylenediamine, N, N'-dimethylpropylenediamine, N, N'-diethylpropylene.
  • N, N'-dibutylpropylenediamine N, N'-dimethyltetramethylenediamine, N, N'-diethyltetramethylenediamine, N, N'-dibutyltetramethylenediamine, N, N'-dimethylhexamethylenediamine , N, N'-diethylhexamethylenediamine, N, N'-dibutylhexamethylenediamine, N, N'-dimethyldecamethylenediamine, N, N'-diethyldecamethylenediamine and N, N'-dibutyldecamethylenediamine. And so on.
  • heterocyclic secondary diamine examples include piperazine and 1-aminopiperidine.
  • Examples of the alicyclic secondary diamine include N, N'-dimethyl-1,2-cyclobutanediamine, N, N'-diethyl-1,2-cyclobutanediamine, and N, N'-dibutyl-1,2-.
  • aromatic secondary diamine examples include N, N'-dimethyl-phenylenediamine, N, N'-dimethyl-xylylenediamine, N, N'-dimethyl-diphenylmethanediamine, and N, N'-dimethyl-diphenyletherdiamine. , N, N'-dimethyl-benzidine and N, N'-dimethyl-1,4-naphthalenediamine and the like.
  • Examples of the secondary alkanolamine include N-methyldiethanolamine, N-octyldiethanolamine, N-stearyldiethanolamine, N-methyldipropanolamine and the like.
  • dicarboxylic acid a dicarboxylic acid having 2 to 20 carbon atoms can be used, and for example, an aliphatic dicarboxylic acid, an aromatic dicarboxylic acid, an alicyclic dicarboxylic acid and the like are used.
  • Examples of the aliphatic dicarboxylic acid include oxalic acid, malonic acid, succinic acid, glutaric acid, methylsuccinic acid, dimethylmalonic acid, ⁇ -methylglutaric acid, ethylsuccinic acid, isopropylmalonic acid, adipic acid, pimelic acid, and suberic acid.
  • Examples include azelaic acid, suberic acid, undecandic acid, dodecandic acid, tridecandic acid, tetradecandic acid, hexadecandic acid, octadecandic acid and icosandic acid.
  • aromatic dicarboxylic acid examples include terephthalic acid, isophthalic acid, phthalic acid, phenylmalonic acid, homophthalic acid, phenylsuccinic acid, ⁇ -phenylglutaric acid, ⁇ -phenyladipic acid, ⁇ -phenyladipic acid and biphenyl-2. , 2'-Dicarboxylic acid, biphenyl-4,4'-dicarboxylic acid, naphthalenedicarboxylic acid, sodium 3-sulfoisophthalate, potassium 3-sulfoisophthalate and the like.
  • 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 thereof include acids, 1,4-cyclohexanediacetic acid, 1,3-cyclohexanediacetic acid, 1,2-cyclohexanediacetic acid and dicyclohexyl-4,4'-dicarboxylic acid.
  • active hydrogen atom-containing compounds can be used alone or in a mixture of two or more.
  • the polyhydric alcohol compound (D) having three or more hydroxyl groups constituting the polymer compound (E) will be described.
  • the polyhydric alcohol compound (D) used in the antistatic agent of the present invention is not particularly limited as long as it has three or more hydroxyl groups.
  • glycerin 1,2,3-butanetriol, 1,2,4-butanetriol, 2-methyl-1,2,3-propanetriol, 1,2,3-pentanetriol, 1,2,4- Pentantriol, 1,3,5-pentantriol, 2,3,4-pentantriol, 2-methyl-2,3,4-butanetriol, trimethylolethane, 2,3,4-hexanetriol, 2-ethyl -1,2,3-butanetriol, trimethylolpropane, 4-propyl-3,4,5-heptantriol, 2,4-dimethyl-2,3,4-pentanetriol, triethanolamine, triisopropanolamine, Trivalent alcohols such as 1,3,5-tris (2-hydroxyethyl) isocyanurate; pentaerythritol, 1,2,3,4-pentantetrol, 2,3,4,5-hexanetetrol, 1, 2,4,5-Pentantetrol, 1,3,4,5-hexanetetrol, diglycerin, ditrimethyl
  • the molecular weight of the polyhydric alcohol compound is not particularly limited, and high molecular weight polyhydric alcohols such as polypentaerythritol and polyvinyl alcohol can be used, and synthetic polyhydric alcohols such as polyester polyol can also be used. Two or more kinds of the polyhydric alcohol compound (D) may be used.
  • the polyhydric alcohol compound (D) having three or more hydroxyl groups has pentaerythritol, trimethylolpropane, dipentaerythritol, glycerin, diglycerin, and ditrimethylolpropane from the viewpoints of antistatic property, its durability, and film transparency. Is preferable.
  • the phenol compound is not contained in the alcohol compound, the phenol compound having a phenolic hydroxyl group is not contained in the polyhydric alcohol compound (D) in the antistatic agent of the present invention.
  • the polyester (a) constituting the polyester block (A) according to the polymer compound (E) may be composed of a diol (a1) and a dicarboxylic acid (a2).
  • the residue of the diol (a1) excluding the hydroxyl group and the residue of the dicarboxylic acid (a2) excluding the carboxyl group are ester-bonded. It has a structure that binds through.
  • the polyester (a) preferably has a structure having carboxyl groups at both ends from the viewpoint of antistatic property, its durability, and transparency of the film. Further, the degree of polymerization of the polyester (a) is preferably in the range of 2 to 50 from the viewpoint of antistatic property, its durability, and transparency of the film.
  • the polyester (a) having a carboxyl group at both ends can be obtained by subjecting a diol (a1) and a dicarboxylic acid (a2) to an esterification reaction.
  • the dicarboxylic acid (a2) may be a derivative thereof (for example, an acid anhydride, an ester such as an alkyl ester, an alkali metal salt, an acid halide, etc.), and when the polyester (a) is obtained by using the derivative. Finally, both ends may be treated to form a carboxyl group, and the reaction may proceed as it is to obtain the next block polymer (C) having a structure having a carboxyl group at both ends.
  • a derivative thereof for example, an acid anhydride, an ester such as an alkyl ester, an alkali metal salt, an acid halide, etc.
  • reaction ratio of the dicarboxylic acid (a2) and the diol (a1) it is preferable to use an excess of the dicarboxylic acid (a2) so that both ends become carboxyl groups, and the molar ratio of the dicarboxylic acid (a1) is adjusted to the diol (a1). On the other hand, it is preferable to use an excess of 1 mol.
  • a catalyst that promotes the esterification reaction may be used for the esterification reaction, and conventionally known catalysts such as dibutyltin oxide, tetraalkyl titanate, zirconium acetate, and zinc acetate can be used.
  • both ends may be treated as dicarboxylic acids after the reaction between them and diols, and the dicarboxylic acids may be used as they are.
  • the next reaction may proceed to obtain a block polymer (C) having a structure having a carboxyl group at both ends.
  • a suitable polyester (a) composed of a diol (a1) and a dicarboxylic acid (a2) and having a carboxyl group at both ends forms an ester bond by reacting with the compound (b) to form a structure of the block polymer (C).
  • the carboxyl groups at both ends may be protected, modified, or in the form of a precursor.
  • an antioxidant such as a phenolic antioxidant may be added to the reaction system in order to suppress the oxidation of the product during the reaction.
  • the compound (b) having one or more ethyleneoxy groups and having hydroxyl groups at both ends preferably reacts with the polyester (a) to form an ester bond to form the structure of the block polymer (C).
  • the hydroxyl groups at both ends may be protected, modified, or in the form of a precursor.
  • the block polymer (C) having a structure having carboxyl groups at both ends according to the polymer compound (E) is a block (A) composed of the polyester (a) and a compound ( It has a block (B) composed of b), and has a structure in which these blocks are repeatedly and alternately bonded via an ester bond formed by a carboxyl group and a hydroxyl group.
  • a block polymer (C) for example, one having a structure represented by the following general formula (3) can be mentioned.
  • (A) represents a block composed of polyester (a) having a carboxyl group at both ends
  • (B) is composed of a compound (b) having hydroxyl groups at both ends.
  • t is the number of repetitions in a repeating unit, and preferably represents a number of 1 to 10 from the viewpoint of antistatic property, its durability, and transparency of the film. t is more preferably a number from 1 to 7, and most preferably a number from 1 to 5.
  • the block polymer (C) having a structure having a carboxyl group at both ends is obtained by subjecting a polyester (a) having a carboxyl group at both ends and a compound (b) having a hydroxyl group at both ends to undergo a polycondensation reaction.
  • the polyester (a) and the compound (b) have a structure equivalent to that having a structure in which the polyester (a) and the compound (b) are repeatedly and alternately bonded via an ester bond formed by a carboxyl group and a hydroxyl group. If so, it is not always necessary to synthesize the polyester (a) and the compound (b).
  • the reaction ratio of the polyester (a) to the compound (b) is a block polymer having carboxyl groups at both ends if the reaction ratio of the compound (b) is adjusted to be X + 1 mol with respect to X mol.
  • (C) can be preferably obtained.
  • the compound (b) may be added to the reaction system and reacted as it is without isolating the polyester (a).
  • a catalyst that promotes the esterification reaction may be used in the polycondensation reaction, and conventionally known catalysts such as dibutyltin oxide, tetraalkyl titanate, zirconium acetate, and zinc acetate can be used. Further, an antioxidant such as a phenolic antioxidant may be added to the reaction system in order to suppress the oxidation of the product during the reaction.
  • the polymer compound (E) is preferably a block polymer (C) having a structure having carboxyl groups at both ends from the viewpoint of antistatic property, its durability, and transparency of the film.
  • the polyhydric alcohol compound (D) having three or more hydroxyl groups are bonded via an ester bond.
  • This ester bond is an ester bond formed by the reaction of the carboxyl group at the end of the block polymer (C) with the hydroxyl group of the polyhydric alcohol compound (D), which is antistatic property, its durability, and storage stability. , Preferable from the viewpoint of film transparency.
  • polymer compound (E) may further contain an ester bond formed by the carboxyl group of the polyester (a) and the hydroxyl group of the polyhydric alcohol compound (D).
  • the block polymer (C) and the polyhydric alcohol compound (D) may be reacted. That is, the carboxyl group of the block polymer (C) may be reacted with the hydroxyl group of the polyhydric alcohol compound (D).
  • the number of hydroxyl groups of the polyhydric alcohol compound to be reacted is preferably 0.5 to 5.0 equivalents, more preferably 0.5 to 2.0 equivalents of the number of carboxyl groups of the block polymer (C) to be reacted. Further, the above reaction may be carried out in various solvents or in a molten state.
  • the polyhydric alcohol compound (D) having three or more hydroxyl groups to be reacted is preferably 0.1 to 2.0 equivalents, preferably 0.2 to 1.5 equivalents, of the number of carboxyl groups of the block polymer (C) to be reacted. Is more preferable.
  • the polyhydric alcohol compound (D) may be added to the reaction system and reacted as it is without isolating the block polymer (C).
  • the carboxyl group of the unreacted polyester (a) used excessively when synthesizing the block polymer (C) reacts with some hydroxyl groups of the polyhydric alcohol compound (D) to form an ester bond. It may be formed.
  • a block polymer (C) having a structure having a carboxyl group at both ends and a polyhydric alcohol compound (D) having three or more hydroxyl groups are formed by the respective carboxyl groups and hydroxyl groups. It is not always necessary to synthesize the block polymer (C) and the polyhydric alcohol compound (D) as long as they have a structure equivalent to that having a structure bonded via an ester bond.
  • the number average molecular weight of the block polymer (C) having a structure having a carboxyl group at both ends in the polymer compound (E) calculated by the acid value measurement method is the antistatic property and its durability, and the film. From the viewpoint of transparency, it is preferably 8,000 to 50,000, and more preferably 9,000 to 40,000.
  • the method for calculating the number average molecular weight of the block polymer (C) by the acid value measurement method may be as described in ⁇ Method for calculating the number average molecular weight by the acid value measurement method>.
  • the polymer compound (E) is a compound obtained by obtaining a polyester (a) from a diol (a1) and a dicarboxylic acid (a2) without isolating the polyester (a). It may be reacted with (b) and / or the polyhydric alcohol compound (D).
  • the polymer compound (E) is the sum of the polyester block (A) and the polyether block (B) in terms of antistatic property, its durability, and film transparency.
  • the proportion of the block (B) of the polyether is preferably in the range of 20 to 50% by mass, more preferably 24 to 45% by mass, and even more preferably 24 to 40% by mass.
  • the mass of the block (A) and the block (B) may be calculated from the mass of the polyester (a) and the compound (b).
  • the polymer compound (E) in the form of pellets from the viewpoint of handleability.
  • the polymer may be extruded from an extruder and cut into pellets.
  • a machine such as a pelletizer may be used for cutting.
  • the antistatic agent composition of the present invention is obtained by further blending the antistatic agent of the present invention with one or more selected from the group of alkali metal salts and ionic liquids.
  • the antistatic agent of the present invention further contains one or more selected from the group of alkali metal salts and ionic liquids to obtain an antistatic agent composition having excellent antistatic performance and durability thereof. preferable.
  • alkali metal salts include salts of organic acids or inorganic acids, and examples of alkali metals include lithium, sodium, potassium, cesium, rubidium and the like.
  • organic acids include aliphatic monocarboxylic acids having 1 to 18 carbon atoms such as formic acid, acetic acid, propionic acid, butyric acid, and lactic acid; oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid, adipic acid, etc.
  • An aliphatic dicarboxylic acid having 1 to 12 carbon atoms aromatic carboxylic acids such as benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, and salicylic acid; methanesulfonic acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, and trifluoromethane.
  • aromatic carboxylic acids such as benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, and salicylic acid
  • sulfonic acids having 1 to 20 carbon atoms such as sulfonic acids.
  • inorganic acids include hydrochloric acid, hydrobromic acid, sulfuric acid, sulfurous acid, phosphoric acid, phosphorous acid, polyphosphoric acid, nitric acid
  • salts of lithium, sodium, and potassium are preferable, and sodium is more preferable, from the viewpoints of friction band voltage, surface resistivity, and safety to living organisms and the environment. Further, from the viewpoint of antistatic property and its durability, a salt of acetic acid, a salt of perchloric acid, a salt of p-toluenesulfonic acid and a salt of dodecylbenzenesulfonic acid are preferable, and a salt of dodecylbenzenesulfonic acid is more preferable. Two or more kinds of alkali metal salts may be used.
  • alkali metal salts include, for example, lithium acetate, sodium acetate, potassium acetate, lithium chloride, sodium chloride, potassium chloride, lithium phosphate, sodium phosphate, potassium phosphate, lithium sulfate, sodium sulfate, and perchlorine.
  • Examples include potassium.
  • lithium p-toluenesulfonate, sodium p-toluenesulfonate, lithium dodecylbenzenesulfonate, and dodecylbenzenesulfone are preferable from the viewpoints of antistatic property, their sustainability, and safety to living organisms and the environment.
  • the alkali metal salt may be blended with the antistatic agent of the present invention, or may be blended with the synthetic resin together with the antistatic agent of the present invention.
  • the amount of the alkali metal salt to be blended is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the antistatic agent of the present invention from the viewpoint of antistatic property, its durability, and transparency of the film. 1 to 15 parts by mass is more preferable, and 3.0 to 12 parts by mass is most preferable.
  • ionic liquids have a melting point of 100 ° C. or lower, at least one of the cations or anions constituting the ionic liquid is an organic ion, and has an initial conductivity of 1 to 200 mS / cm, preferably 10 to 10 to.
  • Examples of the cations constituting the ionic liquid include cations selected from the group consisting of amidinium, pyridinium, pyrazolium and guanidinium cations.
  • examples of the amidinium cation include the following.
  • Imidazolinium cations examples thereof include those having 5 to 15 carbon atoms, for example, 1,2,3,4-tetramethylimidazolinium, 1,3-dimethylimidazolinium;
  • Imidazole cation examples thereof include those having 5 to 15 carbon atoms, for example, 1,3-dimethylimidazolium, 1-ethyl-3-methylimidazolium;
  • Tetrahydropyrimidinium cation examples thereof include those having 6 to 15 carbon atoms, for example, 1,3-dimethyl-1,4,5,6-tetrahydropyrimidinium, 1,2,3,4-tetra. Methyl-1,4,5,6-tetrahydropyrimidinium;
  • Dihydropyrimidinium cation examples thereof include those having 6 to 20 carbon atoms, for example, 1,3-dimethyl-1,4-dihydropyrimidinium, 1,3-dimethyl-1,6-dihydropyrimidi. Nium, 8-methyl-1,8-diazabicyclo [5,4,0] -7,9-undecagenium, 8-methyl-1,8-diazabicyclo [5,4,0] -7,10-un Decagenium.
  • Examples of the pyridinium cation include those having 6 to 20 carbon atoms, and examples thereof include 3-methyl-1-propylpyridinium and 1-butyl-3,4-dimethylpyridinium.
  • Examples of the pyrazolium cation include those having 5 to 15 carbon atoms, and examples thereof include 1,2-dimethylpyrazolium and 1-n-butyl-2-methylpyrazolium.
  • guanidinium cations examples include the following.
  • Guanidinium cation having an imidazolinium skeleton examples thereof include those having 8 to 15 carbon atoms, for example, 2-dimethylamino-1,3,4-trimethylimidazolinium and 2-diethylamino-1,3. , 4-trimethylimidazolinium;
  • Guanidinium cation having an imidazolium skeleton examples thereof include those having 8 to 15 carbon atoms, for example, 2-dimethylamino-1,3,4-trimethylimidazolium and 2-diethylamino-1,3,4. -Trimethylimidazolium;
  • Guanidinium cation having a tetrahydropyrimidinium skeleton examples thereof include those having 10 to 20 carbon atoms, for example, 2-dimethylamino-1,3,4-trimethyl-1,4,5,6-tetrahydro. Pyrimidinium, 2-diethylamino-1,3-dimethyl-4-ethyl-1,4,5,6-tetrahydropyrimidinium;
  • Guanidinium cation having a dihydropyrimidinium skeleton examples thereof include those having 10 to 20 carbon atoms, for example, 2-dimethylamino-1,3,4-trimethyl-1,4-dihydropyrimidinium.
  • cations may be used alone or in combination of two or more.
  • an amidinium cation is preferable, an imidazolium cation is more preferable, and a 1-ethyl-3-methylimidazolium cation is particularly preferable.
  • examples of the organic acid or the inorganic acid constituting the anion include the following.
  • Organic acids include, for example, carboxylic acids, sulfuric acid esters, sulfonic acids and phosphoric acids; inorganic acids include, for example, super-strong acids (eg, borofluoric acid, boron tetrafluoroacid, perchloric acid, phosphorus hexafluoride). Acids, antimonic acid hexafluoride and arsenic hexafluoride), phosphoric acid and boric acid.
  • the organic acid and the inorganic acid may be used alone or in combination of two or more.
  • the ionic liquid is preferable from the viewpoint of antistatic property and its durability, and the transparency of the film, because the Hamettet acidity function (-H0) of the anion constituting the ionic liquid is 12 to 12 to A conjugate base of a superacid, an acid forming an anion other than the conjugate base of a superacid, and a mixture thereof, which is 100.
  • halogen eg, fluorine, chlorine and bromine
  • alkyl (1-12 carbon atoms alkyl (1-12 carbon atoms
  • benzenesulfonic acid eg, p-toluenesulfonic acid and dodecylbenzenesulfonic acid.
  • Examples of superacids include protonic acids and those derived from a combination of protonic acids and Lewis acids, and mixtures thereof.
  • borofluoric acid trifluoromethanesulfonic acid, bis (trifluoromethanesulfonyl) imide acid and bis (pentafluoroethylsulfonyl) imide acid are preferable from the viewpoint of ease of synthesis.
  • Protonic acids used in combination with Lewis acid include, for example, hydrogen halides (eg, hydrogen fluoride, hydrogen chloride, hydrogen bromide and hydrogen iodide), perchloric acid, fluorosulfonic acid, methanesulfonic acid, trifluoromethane. Included are sulfonic acids, pentafluoroethane sulfonic acids, nonafluorobutane sulfonic acids, undecafluoropentane sulfonic acids, tridecafluorohexane sulfonic acids and mixtures thereof. Of these, hydrogen fluoride is preferable from the viewpoint of the initial conductivity of the ionic liquid.
  • hydrogen fluoride is preferable from the viewpoint of the initial conductivity of the ionic liquid.
  • Lewis acid examples 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 the ionic liquid.
  • the combination of the protonic acid and the Lewis acid is arbitrary, but examples of the super strong acid consisting of these combinations include tetrafluoroboric acid, hexafluorophosphate, tantalic hexafluoride, antimonic hexafluoride, and hexafluoride. Examples thereof include tantalum sulphonic acid, boron tetrafluoride acid, phosphoric acid hexafluoride, boron trifluoride chloride, arsenic hexafluoride and mixtures thereof.
  • a conjugated base of a super strong acid (a super strong acid composed of a protonic acid and a super strong acid composed of a combination of a protonic acid and a Lewis acid) is preferable from the viewpoint of antistatic property of an ionic liquid, and further preferable.
  • an ionic liquid having an amidinium cation is preferable, a ionic liquid having a 1-ethyl-3-methylimidazolium cation is more preferable, and an ionic liquid having a 1-ethyl-3-methylimidazolium cation is particularly preferable.
  • the ionic liquid may be blended with the antistatic agent of the present invention, or may be blended with the synthetic resin together with the antistatic agent of the present invention.
  • the blending amount of the ionic liquid is preferably 0.01 to 20 parts by mass, preferably 0.1 to 100 parts by mass, based on 100 parts by mass of the antistatic agent of the present invention, from the viewpoint of antistatic property, its durability, and transparency of the film. To 15 parts by mass is more preferable, and 1 to 12 parts by mass is most preferable.
  • an alkali metal salt and an ionic liquid may be used in combination.
  • the antistatic agent of the present invention and one or more selected from the group of alkali metal salts and ionic liquids are further optionally added to any other option.
  • the components may be mixed, and various mixers can be used for mixing. It may be heated at the time of mixing. Examples of mixers that can be used include tumbler mixers, Henschel mixers, ribbon blenders, V-type mixers, W-type mixers, super mixers, Nauter mixers, and the like. Further, one or more selected from the group of alkali metal salts and ionic liquids may be added to the reaction system during the synthesis reaction of the polymer compound (E).
  • the antistatic agent of the present invention may be used as an antistatic agent composition having antistatic properties by blending a salt of a Group 2 element as long as the effect of the present invention is not impaired.
  • the salt of the group 2 element include salts of organic acids or inorganic acids, and examples of the group 2 element include beryllium, magnesium, calcium, strontium, barium and the like.
  • organic acids include aliphatic monocarboxylic acids having 1 to 18 carbon atoms such as formic acid, acetic acid, propionic acid, butyric acid, and lactic acid; oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid, adipic acid, etc.
  • An aliphatic dicarboxylic acid having 1 to 12 carbon atoms aromatic carboxylic acids such as benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, and salicylic acid; methanesulfonic acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, and trifluoromethane.
  • aromatic carboxylic acids such as benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, and salicylic acid
  • sulfonic acids having 1 to 20 carbon atoms such as sulfonic acids.
  • inorganic acids include hydrochloric acid, hydrobromic acid, sulfuric acid, sulfurous acid, phosphoric acid, phosphorous acid, polyphosphoric acid, nitric acid
  • the salt of the Group 2 element may be blended with the antistatic agent of the present invention, or may be blended with the synthetic resin together with the antistatic agent of the present invention.
  • the amount of the salt of the Group 2 element is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 15 parts by mass, and 3.0 to 12 parts by mass with respect to 100 parts by mass of the antistatic agent of the present invention. Most preferably by mass.
  • the antistatic agent of the present invention may be used as an antistatic agent composition having antistatic properties by blending a surfactant as long as the effects of the present invention are not impaired.
  • a surfactant a nonionic, anionic, cationic or amphoteric surfactant can be used.
  • the nonionic surfactant include polyethylene glycol-type nonionic surfactants such as higher alcohol ethylene oxide adduct, fatty acid ethylene oxide adduct, higher alkylamine ethylene oxide adduct, and polypropylene glycol ethylene oxide adduct; fatty acid ester of polyethylene oxide and glycerin.
  • carboxylates such as alkali metal salts of higher fatty acids
  • sulfate esters such as higher alcohol sulfates and higher alkyl ether sulfates, alkylbenzene sulfonates, alkyl sulfonates, paraffin sulfonates and the like.
  • Sulfates; Phosphates such as higher alcohol phosphates and the like can be mentioned, and examples of the cationic surfactant include quaternary ammonium salts such as alkyltrimethylammonium salts.
  • examples of the amphoteric surfactant include amino acid-type amphoteric surfactants such as higher alkylaminopropionate, betaine-type amphoteric surfactants such as higher alkyldimethylbetaine and higher alkyldihydroxyethyl betaine, and these may be used alone or. Two or more types can be used in combination.
  • anionic surfactants are preferable, and sulfonates such as alkylbenzene sulfonates, alkyl sulfonates and paraffin sulfonates are particularly preferable.
  • the surfactant may be blended with the antistatic agent of the present invention, or may be blended with the synthetic resin together with the antistatic agent of the present invention.
  • the blending amount of the surfactant is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 15 parts by mass, and most preferably 1 to 10 parts by mass with respect to 100 parts by mass of the antistatic agent of the present invention. ..
  • the antistatic agent of the present invention may be used as an antistatic agent composition having antistatic properties by blending a polymer type antistatic agent as long as the effects of the present invention are not impaired.
  • a polymer type antistatic agent such as a polyether ester amide
  • a known polyether ester amide for example, JP-A-7-10989
  • examples thereof include the polyether ester amide composed of the polyoxyalkylene adduct of bisphenol A described above.
  • a block polymer having a repeating structure in which the bonding unit between the polyolefin block and the hydrophilic polymer block is 2 to 50 can be used, and examples thereof include the block polymer described in US Pat. No. 6,552,131.
  • the polymer-type antistatic agent may be blended with the antistatic agent of the present invention, or may be blended with a synthetic resin together with the antistatic agent of the present invention.
  • the blending amount of the polymer-type antistatic agent is preferably 0 to 50 parts by mass, and more preferably 5 to 20 parts by mass with respect to 100 parts by mass of the antistatic agent of the present invention.
  • the antistatic agent of the present invention may be blended with a compatibilizer as long as the effects of the present invention are not impaired to prepare an antistatic agent composition having antistatic properties.
  • a compatibilizer By blending a compatibilizer, the compatibility between the antistatic agent of the present invention and other components or synthetic resins can be improved.
  • a compatibilizer include a modified vinyl polymer having at least one functional group (polar group) selected from the group consisting of a carboxyl group, an epoxy group, an amino group, a hydroxyl group and a polyoxyalkylene group. Examples thereof include the polymer described in Japanese Patent Application Laid-Open No.
  • More preferable compatibilizers include acid anhydride-modified polyolefins such as maleic anhydride-modified polyethylene, maleic anhydride-modified polypropylene, itaconic anhydride-modified polyethylene, and itaconic anhydride-modified polypropylene.
  • the compatibilizer may be blended with the antistatic agent of the present invention, or may be blended with the antistatic agent of the present invention and used.
  • the blending amount of the compatibilizer is preferably 0.1 to 15 parts by mass, and more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the antistatic agent of the present invention.
  • the antistatic agent composition of the present invention may contain other components as arbitrary components in addition to the antistatic agent of the present invention and the above components as long as the effects of the present invention are not impaired. These other components may be directly blended in the composition, or the antistatic agent of the present invention or the antistatic agent composition of the present invention may be blended in a synthetic resin such as a thermoplastic resin to have antistatic properties. When used as a resin composition, it may be blended with a synthetic resin.
  • the antistatic agent and antistatic agent composition of the present invention can be blended with a synthetic resin, particularly preferably a thermoplastic resin, and used as an antistatic resin composition having antistatic properties.
  • the resin composition of the present invention is obtained by blending the antistatic agent of the present invention and the antistatic agent composition of the present invention with a synthetic resin.
  • a synthetic resin a thermoplastic resin is preferable.
  • thermoplastic resins include polypropylene, high-density polyethylene, low-density polyethylene, linear low-density polyethylene, crosslinked polyethylene, ultrahigh-molecular-weight polyethylene, polybutene-1, poly-3-methylpentene, poly-4-methylpentene, and the like.
  • Copolymers of acrylic resins, styrene and / or ⁇ -methylstyrene with other monomers eg, maleic anhydride, phenylmaleimide, methyl methacrylate, butadiene, acrylonitrile, etc.
  • monomers eg, maleic anhydride, phenylmaleimide, methyl methacrylate, butadiene, acrylonitrile, etc.
  • AS resin eg.
  • ABS acrylonitrile, etc.
  • butadiene-styrene copolymer butadiene-styrene copolymer
  • ACS resin SBS resin
  • MBS resin heat-resistant ABS resin, etc.
  • Polymethylmethacrylate polyvinyl alcohol, polyvinylformal, polyvinylbutyral
  • Aromatic polyesters such as polyalkylene naphthalate such as polyalkylene terephthalate, polyethylene naphthalate, polybutylene naphthalate and linear polyesters such as polytetramethylene terephthalate; polyhydroxybutyrate, polycaprolactone, polybutylene succinate, polyethylene succinate , Polylactic acid, polyappleic acid, polyglycolic acid, polydioxane, poly (2-oxetanone) and other degradable aliphatic polyesters; polyamides such as polyphenylene oxide, polycaprolactam and polyhexamethylene adipamide, polycarbonate, polycarbonate / ABS resin , Branched polymer, polyacetal, polyphenylene sulfide, polyurethane, fibrous resin, polyimide Examples thereof include thermoplastic resins such as resins, polysulfones, polyphenylene ethers, polyetherketones, polyetheretherketones, and liquid crystal polymers, and blend
  • the thermoplastic resin includes isoprene rubber, butadiene rubber, acrylonitrile-butadiene copolymer rubber, styrene-butadiene copolymer rubber, fluororubber, silicone rubber, olefin elastomer, and styrene elastomer. It may be an elastomer such as a polyester-based elastomer, a nitrile-based elastomer, a nylon-based elastomer, a vinyl chloride-based elastomer, a polyamide-based elastomer, or a polyurethane-based elastomer. In the resin composition of the present invention, these thermoplastic resins may be used alone or in combination of two or more. Moreover, the thermoplastic resin may be alloyed.
  • thermoplastic resins have molecular weight, degree of polymerization, density, softening point, ratio of insoluble matter in solvent, degree of stereoregularity, presence or absence of catalyst residue, type and compounding ratio of monomer as raw material, type of polymerization catalyst. It can be used regardless of (for example, Ziegler catalyst, metallocene catalyst, etc.).
  • thermoplastic resins at least one selected from the group consisting of polyolefin-based resins, polystyrene-based resins and copolymers thereof is preferable from the viewpoint of antistatic properties.
  • the mass ratio of the thermoplastic resin to the antistatic agent of the present invention or the antistatic agent composition of the present invention in the resin composition of the present invention is preferably in the range of 99/1 to 40/60.
  • the antistatic agent of the present invention or the antistatic agent composition of the present invention is used for the polyolefin resin to form a film, it is preferable because it is excellent in antistatic property, its durability, and transparency of the film.
  • the polyolefin resin include polypropylene, high-density polyethylene, low-density polyethylene, straight-chain low-density polyethylene, crosslinked polyethylene, ultra-high molecular weight polyethylene, polybutene-1, poly-3-methylpentene, poly-4-methylpentene and the like.
  • polyolefin resins such as ⁇ -olefin polymer or ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, and ethylene-propylene copolymer, and copolymers thereof. These films are suitable for packaging materials for electric / electronic parts, electric / electronic products, precision parts, precision machinery, precision products, and the like.
  • the amount of the antistatic agent of the present invention to be blended with the synthetic resin is preferably 0.9 to 90 parts by mass with respect to 100 parts by mass of the synthetic resin from the viewpoint of antistatic property, its durability, and transparency of the film. .8 to 55 parts by mass is more preferable, and 4.5 to 45 parts by mass is even more preferable.
  • the amount of the antistatic agent composition of the present invention blended with respect to the synthetic resin is such that the antistatic agent composition is added to 100 parts by mass of the synthetic resin from the viewpoint of antistatic property, its durability, and transparency of the film. It is preferably 1.0 to 100 parts by mass, more preferably 2.0 to 60 parts by mass, and even more preferably 5.0 to 50 parts by mass.
  • the method of blending the antistatic agent of the present invention into the synthetic resin is not particularly limited, and any commonly used method can be used, for example, mixing by roll kneading, bumper kneading, extruder, kneader or the like. , Knead and mix.
  • the antistatic agent of the present invention may be added to the synthetic resin as it is, or may be added after impregnating the carrier, if necessary. In order to impregnate the carrier, the mixture may be heated and mixed as it is, or if necessary, the carrier may be impregnated after diluting with an organic solvent, and then the solvent may be removed.
  • a carrier those known as fillers and fillers of synthetic resins, flame retardants and light stabilizers that are solid at room temperature can be used, and for example, calcium silicate powder, silica powder, talc powder, and alumina powder can be used. , Titanium oxide powder, chemically modified surface of these carriers, solid ones among the flame retardant agents and antioxidants listed below.
  • these carriers those in which the surface of the carrier is chemically modified are preferable, and those in which the surface of the silica powder is chemically modified are more preferable.
  • These carriers preferably have an average particle size of 0.1 to 100 ⁇ m, and more preferably 0.5 to 50 ⁇ m.
  • the polymer which is the antistatic agent of the present invention is kneaded with the block polymer (C) and the polyhydric alcohol compound (D) at the same time as the synthetic resin.
  • the compound (E) may be synthesized and blended, and at that time, one or more selected from the group of alkali metal salts and ionic liquids may be kneaded at the same time, and at the time of molding such as injection molding.
  • the antistatic agent of the present invention and the synthetic resin may be mixed to obtain a molded product, and at that time, one or more selected from the group of alkali metal salts and ionic liquids may be further blended.
  • a masterbatch of the antioxidant of the present invention and the synthetic resin may be manufactured in advance, and this masterbatch may be blended. At that time, from the group of alkali metal salts and ionic liquids. One or more selected types may be blended.
  • additives such as phenol-based antioxidants, phosphorus-based antioxidants, thioether-based antioxidants, ultraviolet absorbers, and hindered amine-based light stabilizers are further added to the resin composition of the present invention, if necessary. This allows the resin composition of the present invention to be stabilized.
  • antioxidants such as these antioxidants may be added to the antistatic agent composition of the present invention before being added to the synthetic resin. Further, it may be blended at the time of producing the polymer compound (E) which is the antistatic agent of the present invention.
  • the antioxidant is preferable because it can prevent oxidative deterioration of the polymer compound (E) during production by blending it at the time of producing the polymer compound (E).
  • phenolic antioxidant examples include 2,6-ditertiary butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, and distearyl (3,5-ditertiary butyl-4-4).
  • phosphorus-based antioxidants examples include trisnonylphenyl phosphite and tris [2-tertiary butyl-4- (3-third butyl-4-hydroxy-5-methylphenylthio) -5-methylphenyl] phos.
  • thioether-based antioxidant examples include dialkylthiodipropionates such as dilauryl thiodipropionate, dimyristyl thiodipropionate, and distearyl thiodipropionate, and pentaerythritol tetra ( ⁇ -alkylthiopropionic acid) ester.
  • dialkylthiodipropionates such as dilauryl thiodipropionate, dimyristyl thiodipropionate, and distearyl thiodipropionate
  • pentaerythritol tetra ( ⁇ -alkylthiopropionic acid) ester kind.
  • the amount of these thioether-based antioxidants added is preferably 0.001 to 10 parts by mass, and more preferably 0.05 to 5 parts by mass with respect to 100 parts by mass of the synthetic resin.
  • ultraviolet absorber examples include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 5,5'-methylenebis (2-hydroxy-4-methoxybenzophenone).
  • 2-Hydroxybenzophenones such as 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3', 5'-ditertiary butylphenyl) -5-chlorobenzo Triazol, 2- (2'-hydroxy-3'-tertiary butyl-5'-methylphenyl) -5-chlorobenzotriazol, 2- (2'-hydroxy-5'-tertiary octyl) Phenyl) benzotriazol, 2- (2'-hydroxy-3', 5'-dicumylphenyl) benzotriazol, 2,2'-methylenebis (4-third octyl-6- (benzotriazolyl) phenol ), 2- (2'-Hydroxyphenyl) benzotriazoles such as 2- (2'-hydroxy-3'-tertiary butyl-5'-carboxyphenyl) benzotriazole; phenylsalicylate, resorcinol mono
  • hindered amine-based photostabilizer examples include 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2,6. , 6-Tetramethyl-4-piperidylbenzoate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, Bis (1-octoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butane Tetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butane tetracarboxylate, bis (2,2,6,6-tetramethyl-4) -Piperidil) bis (
  • a known neutralizing agent is added as necessary to further neutralize the residual catalyst in the polyolefin resin as long as the effects of the present invention are not impaired. It is preferable to do so.
  • the neutralizing agent include fatty acid metal salts such as calcium stearate, lithium stearate, and sodium stearate, or fatty acid amides such as ethylene bis (stearoamide), ethylene bis (12-hydroxystearoamide), and stearic acid amide. Compounds are mentioned, and these neutralizing agents may be mixed and used.
  • an aromatic carboxylic acid metal salt an alicyclic alkyl carboxylic acid metal salt, p-th, as long as the effects of the present invention are not impaired.
  • Organic flame retardant aids, fillers, pigments, lubricants, foaming agents and the like may be added.
  • triazine ring-containing compound examples include melamine, ammeline, benzguanamine, acetoguanamine, phthalodiguanamine, melamine cyanurate, melamine pyrophosphate, butylene guanamine, norbornene diguanamine, methylene diguanamine, ethylene dimeramine, and trimethylene di.
  • examples thereof include melamine, tetramethylene dimelamine, hexamethylene dimelamine, and 1,3-hexylene melamine.
  • metal hydroxide examples include magnesium hydroxide, aluminum hydroxide, calcium hydroxide, barium hydroxide, zinc hydroxide, Kismer 5A (magnesium hydroxide: manufactured by Kyowa Chemical Industry Co., Ltd.) and the like.
  • Examples of the phosphoric acid ester flame retardant include trimethyl phosphate, triethyl phosphate, tributyl phosphate, tributoxyethyl phosphate, trischloroethyl phosphate, trisdichloropropyl phosphate, triphenyl phosphate, tricresyl phosphate, cresyldiphenyl phosphate, and triki.
  • Sirenyl phosphate octyldiphenyl phosphate, xylenyldiphenyl phosphate, trisisopropylphenyl phosphate, 2-ethylhexyldiphenyl phosphate, t-butylphenyldiphenyl phosphate, bis- (t-butylphenyl) phenyl phosphate, tris- (t-butylphenyl) ) Phosphate, isopropylphenyldiphenyl phosphate, bis- (isopropylphenyl) diphenyl phosphate, tris- (isopropylphenyl) phosphate and the like.
  • condensed phosphate ester flame retardant examples include 1,3-phenylene bis (diphenyl phosphate), 1,3-phenylene bis (dixylenyl phosphate), bisphenol A bis (diphenyl phosphate) and the like.
  • Examples of (poly) phosphate-based flame retardants include ammonium salts and amine salts of (poly) phosphoric acid such as ammonium polyphosphate, melamine polyphosphate, piperazine polyphosphate, melamine pyrophosphate, and piperazine pyrophosphate.
  • inorganic flame retardant aids include inorganic compounds such as titanium oxide, aluminum oxide, magnesium oxide, hydrotalcite, talcite, and montmorillonite, and surface-treated products thereof.
  • inorganic compounds such as titanium oxide, aluminum oxide, magnesium oxide, hydrotalcite, talcite, and montmorillonite, and surface-treated products thereof.
  • TIPAQUE R-680 Titanium oxide: Ishihara Sangyo Co., Ltd.
  • Kyowa Mag 150 magnesium oxide: Kyowa Chemical Industry Co., Ltd.
  • DHT-4A hydrotalcite: Kyowa Chemical Industry Co., Ltd.
  • Alchemizer 4 zinc-modified hydro
  • Hydrotalcite Various commercially available products such as Kyowa Chemical Industry Co., Ltd. can be used.
  • pentaerythritol can be mentioned.
  • the resin composition of the present invention includes additives usually used for synthetic resins, such as a cross-linking agent, an antifogging agent, and a plate-out inhibitor, as needed, as long as the effects of the present invention are not impaired.
  • additives usually used for synthetic resins such as a cross-linking agent, an antifogging agent, and a plate-out inhibitor, as needed, as long as the effects of the present invention are not impaired.
  • the additive to be blended in the resin composition of the present invention may be added directly to the synthetic resin, and after being blended in the polymer compound (E) which is the antistatic agent of the present invention or the antistatic agent composition, It may be added to the synthetic resin.
  • a resin molded product having antistatic properties By molding the resin composition of the present invention, a resin molded product having antistatic properties can be obtained.
  • the molding method is not particularly limited, and examples thereof include extrusion processing, calendar processing, injection molding, roll, compression molding, blow molding, rotary molding, and the like, and include resin plates, sheets, films, bottles, fibers, and deformed products. It is possible to manufacture molded products having various shapes such as.
  • the molded product obtained by the resin composition of the present invention is excellent in antistatic performance and its durability.
  • the molded product obtained from the resin composition of the present invention is a molded product that does not easily generate static electricity and does not easily cause surface contamination due to static electricity or deterioration of commercial value due to adhesion of dust.
  • the film is particularly preferable because it is excellent in antistatic property, its durability, and the transparency of the film. These films are less likely to generate static electricity, are less likely to cause surface contamination due to static electricity, and are less likely to lose their commercial value due to adhesion of dust, and are also excellent in transparency. Therefore, it is suitable for packaging materials for electric / electronic parts, electric / electronic products, precision parts, precision equipment, and the like.
  • the film obtained by the resin composition of the present invention has excellent transparency.
  • the Haze value (cloudiness) at a thickness of 50 ⁇ m is preferably 0% or more and 40.0% or less, and more preferably 0% or more and 35.0% or less.
  • the Haze value can be measured in accordance with JIS K7136.
  • the resin composition of the present invention and a molded product using the same can be used for electricity / electronics / communication, agriculture, forestry and fisheries, mining, construction, food, textiles, clothing, medical care, coal, petroleum, rubber, leather, automobiles, precision equipment, and wood.
  • the resin composition of the present invention and a molded product thereof include a printer, a personal computer, a word processor, a keyboard, a PDA (small information terminal), a telephone, a copying machine, a facsimile, an ECR (electronic money registration machine), and the like.
  • Office work such as calculators, electronic notebooks, cards, holders, stationery, OA equipment, washing machines, refrigerators, vacuum cleaners, microwave ovens, lighting equipment, game machines, irons, home appliances such as kotatsu, TVs, VTRs, video cameras, radio cassettes , Tape recorder, mini disc, CD player, speaker, AV equipment such as liquid crystal display, connector, relay, condenser, switch, printed board, coil bobbin, semiconductor encapsulation material, LED encapsulation material, electric wire, cable, transformer, deflection yoke , Distribution boards, electrical and electronic parts such as watches and communication equipment, interior and exterior materials for automobiles, plate making films, adhesive films, bottles, food containers, food packaging films, pharmaceutical / pharmaceutical wrap films, product packaging films , Agricultural film, agricultural sheet, greenhouse film, packaging film for electrical and electronic parts, etc.
  • AV equipment such as liquid crystal display, connector, relay, condenser, switch, printed board, coil bobbin, semiconductor encapsulation material, LED encapsulation material, electric
  • the resin composition of the present invention and a molded product thereof are used for seats (filling, outer material, etc.), belts, ceiling coverings, compatible tops, armrests, door trims, rear package trays, carpets, mats, sun visors, foil covers, mattress covers.
  • roofing materials deck materials, wall materials, pillar materials, floor boards, wall materials, skeletons and plywood, window and door shapes, moss boards, siding, terraces, balconies, soundproof boards, heat insulating boards, window materials, etc.
  • the polymer compound (E), which is the antistatic agent of the present invention was produced according to the following production example. Further, in the following production example, the number average molecular weights of the polyester (a) and the block polymer (C) are calculated by the following ⁇ method for calculating the number average molecular weight by the acid value measurement method>, and the number average molecular weight of the compound (b). was calculated by the following ⁇ method for calculating the number average molecular weight by the hydroxyl value measurement method>.
  • polyester (a) -5 165.3 g was used as compound (b) -1 having hydroxyl groups at both ends, the number average molecular weight was 3,300 (hydroxyl value 34), and the number of repeating units of ethyleneoxy groups.
  • 199.6 g of block polymer (C) -6 having a structure having a group was obtained.
  • the block polymer (C) -6 having a structure having a carboxyl group at both ends had an acid value of 3.3 and a number average molecular weight of 34,000.
  • polyester (a) -7 was used as compound (b) -1 having hydroxyl groups at both ends, the number average molecular weight was 3,300 (hydroxyl value 34), and the number of repeating units of ethyleneoxy groups.
  • 165.2 g of block polymer (C) -8 having a structure having a group was obtained.
  • the block polymer (C) -8 having a structure having a carboxyl group at both ends had an acid value of 5.8 and a number average molecular weight of 19,200.
  • polyester (a) -9 was used as compound (b) -1 having hydroxyl groups at both ends, the number average molecular weight was 3,300 (hydroxyl value 34), and the number of repeating units of ethyleneoxy groups.
  • 66.0 g of polyethylene glycol 75, 0.3 g of antioxidant (Adecastab AO-60), 0.4 g of zirconium octylate were charged, polymerized at 200 ° C. for 3 hours under reduced pressure, and carboxyl at both ends.
  • 179.3 g of block polymer (C) -10 having a structure having a group was obtained.
  • the block polymer (C) -10 having a structure having a carboxyl group at both ends had an acid value of 8.5 and a number average molecular weight of 13,300.
  • Examples 1 to 25, Comparative Examples 1 to 9 Using the resin compositions of Examples and Comparative Examples blended based on the blending amounts (parts by mass) shown in Tables 1 to 7 below, test films were obtained according to the test film preparation method shown below. Using the obtained test film, the surface resistivity (SR value) was measured according to the following measurement method, and the antistatic property and its durability were evaluated. Further, the Haze value was measured according to the following measurement method. The results are shown in Tables 1-7.
  • SR value ⁇ Surface resistivity (SR value) measurement method>
  • the obtained test film is stored under the conditions of a temperature of 25 ° C. and a humidity of 50% RH, and after 1 day and 30 days of the molding process, under the same atmosphere, Mitsubishi Chemical Analytech Co., Ltd.
  • the surface resistivity ( ⁇ / ⁇ ) was measured under the conditions of an applied voltage of 100 V and an applied time of 1 minute using a high rester-UX high rester (MCP-HT800) resistor meter manufactured by Nittoseiko Analytical Co., Ltd. The measurement was performed on 5 test films at 5 points per film, and the average value was calculated.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

L'invention concerne : un agent antistatique qui peut conférer de façon durable un excellent effet antistatique à une résine synthétique ; une composition d'agent antistatique en contenant ; une composition de résine antistatique en contenant ; et un corps moulé et un film à base de ceux-ci.　Cet agent antistatique contient au moins un composé polymère (E) présentant une structure obtenue par liaison, de type liaison ester ou liaison éther, d'une séquence de polyester (A) composée d'un polyester (a) obtenu par réaction d'un diol (a1) et d'un acide dicarboxylique (a2), d'une séquence de polyester (B) constituée d'un composé (b) comportant des groupes hydroxyle aux deux extrémités et possédant un ou plusieurs groupes éthylèneoxy, et d'un composé d'alcool multivalent (D) comportant au moins trois groupes hydroxyle, le poids moléculaire moyen en nombre calculé par un procédé de mesure de l'indice d'acide variant de 1 600 à 10 000, et le poids moléculaire moyen en nombre calculé par un procédé de mesure de l'indice d'hydroxyle variant de 1 000 à 6 000.
PCT/JP2020/013574 2019-03-29 2020-03-26 Agent antistatique, composition d'agent antistatique en contenant, composition de résine antistatique en contenant, corps moulé et film à base de ceux-ci WO2020203619A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014148454A1 (fr) * 2013-03-21 2014-09-25 株式会社Adeka Agent antistatique, composition d'agent antistatique, composition de résine antistatique, et article moulé
WO2016042936A1 (fr) * 2014-09-17 2016-03-24 株式会社Adeka Agent antistatique, composition d'agent antistatique, composition de résine antistatique, et article moulé
WO2016117233A1 (fr) * 2015-01-19 2016-07-28 株式会社Adeka Composition de résine antistatique, ainsi que récipient et matériau d'emballage l'employant

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014148454A1 (fr) * 2013-03-21 2014-09-25 株式会社Adeka Agent antistatique, composition d'agent antistatique, composition de résine antistatique, et article moulé
WO2016042936A1 (fr) * 2014-09-17 2016-03-24 株式会社Adeka Agent antistatique, composition d'agent antistatique, composition de résine antistatique, et article moulé
WO2016117233A1 (fr) * 2015-01-19 2016-07-28 株式会社Adeka Composition de résine antistatique, ainsi que récipient et matériau d'emballage l'employant

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