WO2016027670A1 - 帯電防止剤、帯電防止剤組成物、帯電防止性樹脂組成物および成形体 - Google Patents
帯電防止剤、帯電防止剤組成物、帯電防止性樹脂組成物および成形体 Download PDFInfo
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- WO2016027670A1 WO2016027670A1 PCT/JP2015/072192 JP2015072192W WO2016027670A1 WO 2016027670 A1 WO2016027670 A1 WO 2016027670A1 JP 2015072192 W JP2015072192 W JP 2015072192W WO 2016027670 A1 WO2016027670 A1 WO 2016027670A1
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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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/199—Acids or hydroxy compounds containing cycloaliphatic rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/20—Polyesters having been prepared in the presence of compounds having one reactive group or more than two reactive groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/672—Dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/04—Antistatic
Definitions
- the present invention relates to an improvement of an antistatic agent, an antistatic agent composition, an antistatic resin composition (hereinafter also simply referred to as “resin composition”) and a molded article.
- Thermoplastic resin is not only lightweight and easy to process, but also has excellent properties such as the ability to design the substrate according to the application, so it is an important material indispensable in modern times. is there.
- thermoplastic resins have the property of being excellent in electrical insulation, they are frequently used for components of electrical products. However, since the thermoplastic resin is too insulating, there is a problem that it is easily charged by friction or the like.
- thermoplastic resin attracts surrounding dust and dust, which causes a problem that the appearance of the resin molded product is impaired.
- a precision device such as a computer may not be able to operate normally due to charging.
- electric shock there are problems caused by electric shock. When an electric shock occurs from the resin to the human body, it not only makes the person uncomfortable, but may also cause an explosion accident where there is flammable gas or dust.
- the most common antistatic treatment method is a method of adding an antistatic agent to the synthetic resin.
- antistatic agents include a coating type that is applied to the surface of the 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 the material touching the surface is contaminated.
- Patent Documents 1 and 2 polyether ester amides have been proposed for imparting antistatic properties to polyolefin resins.
- Patent Document 3 a block polymer having a structure in which a polyolefin block and a hydrophilic polymer block are repeatedly and alternately bonded has been proposed.
- an object of the present invention is to provide an antistatic agent and an antistatic agent composition that can provide an excellent antistatic effect with a small addition amount, and have sufficient durability and wiping resistance.
- Another object of the present invention is to provide an antistatic resin composition having sufficient durability and wiping resistance and excellent in antistatic properties.
- Still another object of the present invention is to provide a molded body made of a thermoplastic resin, which is less likely to cause a decline in commercial value due to surface contamination due to static electricity or adhesion of dust.
- the antistatic agent of the present invention comprises a diol, a dicarboxylic acid, a compound (B) having one or more groups represented by the following general formula (1) and having hydroxyl groups at both ends, and a polycarboxylic acid compound (D ) Comprises a polymer compound (E) having a structure formed by bonding via an ester bond.
- the polymer compound (E) is a polyester (A) composed of a diol and a dicarboxylic acid, the compound (B), and the polycarboxylic acid compound (D). It preferably has a structure formed by bonding via an ester bond.
- the polymer compound (E) has a block composed of the polyester (A) and a block composed of the compound (B) alternately and alternately via an ester bond. It is preferable that the block polymer (C) having a hydroxyl group at both ends formed by bonding and the polycarboxylic acid compound (D) have a structure formed by bonding via an ester bond.
- the polyester (A) has a structure having a carboxyl group at one end or both ends.
- the number average molecular weight of the block composed of the polyester (A) is 800 to 8,000 in terms of polystyrene, and the number of blocks composed of the compound (B).
- the average molecular weight is preferably 400 to 6,000 in terms of polystyrene, and the number average molecular weight of the block polymer (C) is preferably 5,000 to 25,000 in terms of polystyrene.
- the compound (B) is preferably polyethylene glycol.
- the polycarboxylic acid compound (D) is preferably a carboxylic acid having 3 or more carboxyl groups.
- the antistatic agent composition of the present invention further comprises one or more selected from the group consisting of alkali metal salts and Group 2 element salts to the antistatic agent of the present invention. It is characterized by this.
- the antistatic resin composition of the present invention is characterized in that the antistatic agent of the present invention or the antistatic agent composition of the present invention is blended with a thermoplastic resin. is there.
- the thermoplastic resin is preferably at least one selected from the group consisting of polyolefin resins, polystyrene resins and copolymers thereof.
- the mass ratio of the thermoplastic resin to the antistatic agent or the antistatic agent composition may be in the range of 99/1 to 40/60. preferable.
- the molded article of the present invention is characterized by comprising the antistatic resin composition of the present invention.
- an antistatic agent and an antistatic agent composition that can provide an excellent antistatic effect with a small addition amount, and have sufficient durability and wiping resistance.
- an antistatic resin composition having sufficient durability and wiping resistance and excellent in antistatic properties can be provided.
- the polymer compound (E) according to the present invention includes a diol, a dicarboxylic acid, a compound (B) having one or more groups represented by the following general formula (1) and having hydroxyl groups at both ends, and a polycarboxylic acid compound (D) has a structure formed by bonding via an ester bond.
- the polymer compound (E) includes a diol, a dicarboxylic acid, a compound (B) having at least one group represented by the following general formula (1) and a hydroxyl group at both ends, and a polycarboxylic acid compound (D). Can be obtained by esterification reaction.
- diol used in the present invention examples include aliphatic diols and aromatic group-containing diols.
- the diol may be a mixture of two or more.
- 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 and hydrogenated bisphenol A are preferable from the viewpoint of compatibility with thermoplastic resins and antistatic properties, and 1,4-cyclohexanedimethanol is more preferable.
- the aliphatic diol preferably has hydrophobicity, among the aliphatic diols, polyethylene glycol having hydrophilicity is not preferable. However, this is not the case when used with other diols.
- aromatic group-containing diol examples include bisphenol A, 1,2-hydroxybenzene, 1,3-hydroxybenzene, 1,4-hydroxybenzene, 1,4-benzenedimethanol, an ethylene oxide adduct of bisphenol A, Examples thereof include propylene oxide adducts of bisphenol A, polyhydroxyethyl adducts of mononuclear dihydric phenol compounds such as 1,4-bis (2-hydroxyethoxy) benzene, resorcin, and pyrocatechol.
- diols having an aromatic group ethylene oxide adduct of bisphenol A, 1,4-bis ( ⁇ -hydroxyethoxy) benzene is preferable.
- dicarboxylic acid used in the present invention examples include aliphatic dicarboxylic acids and aromatic dicarboxylic acids, and a mixture of an aliphatic dicarboxylic acid and an aromatic dicarboxylic acid may be used.
- the aliphatic dicarboxylic acid may be a derivative of an aliphatic dicarboxylic acid (for example, acid anhydride, alkyl ester, alkali metal salt, acid halide, etc.).
- the aliphatic dicarboxylic acid and its derivative may be a mixture of two or more.
- the aliphatic dicarboxylic acid is preferably an aliphatic dicarboxylic acid having 2 to 20 carbon atoms, such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, Examples include sebacic acid, 1,10-decanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, dimer acid, maleic acid, and fumaric acid.
- oxalic acid such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid
- Examples include sebacic acid, 1,10-decanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, dimer acid, maleic acid, and fumaric acid.
- 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 melting point and heat resistance.
- the aromatic dicarboxylic acid may be a derivative of an aromatic dicarboxylic acid (for example, acid anhydride, alkyl ester, alkali metal salt, acid halide, etc.). Moreover, 2 or more types of mixtures may be sufficient as aromatic dicarboxylic acid and its derivative (s).
- the aromatic dicarboxylic acid is preferably an aromatic dicarboxylic acid having 8 to 20 carbon atoms.
- a hydrophilic compound is preferable, and a polysiloxane having a group represented by the general formula (1) is preferable.
- Ether is more preferable, and polyethylene glycol represented by the following general formula (2) is particularly preferable.
- m represents a number of 5 to 250. m is preferably 20 to 150 from the viewpoint of heat resistance and compatibility.
- the compound (B) in addition to polyethylene glycol obtained by addition reaction of ethylene oxide, ethylene oxide and other alkylene oxides (for example, propylene oxide, 1,2-, 1,4-, 2,3- or And a polyether obtained by addition reaction with one or more of 1,3-butylene oxide and the like.
- the polyether may be random or block.
- compound (B) examples include compounds 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-, 2,3- or 1,3-butylene oxide, etc.). These may be either random addition or block addition.
- Examples of the active hydrogen atom-containing compound include glycol, dihydric phenol, primary monoamine, secondary diamine and dicarboxylic acid.
- glycol aliphatic glycols having 2 to 20 carbon atoms, alicyclic glycols having 5 to 12 carbon atoms, aromatic glycols 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, 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 diol, 1,20-eicosanediol, diethylene glycol, triethylene glycol, and thiodiethylene glycol.
- Examples of the alicyclic glycol include 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, 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.
- phenol having 6 to 30 carbon atoms can be used.
- alkyls (having 1 to 10 carbon atoms) or halogen-substituted products thereof can be used.
- Examples of primary monoamines include aliphatic primary monoamines having 1 to 20 carbon atoms, such as methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, s-butylamine, isobutylamine, n- Examples thereof include amylamine, isoamylamine, n-hexylamine, n-heptylamine, n-octylamine, n-decylamine, n-octadecylamine and n-icosylamine.
- Secondary diamines include aliphatic secondary diamines having 4 to 18 carbon atoms, heterocyclic secondary diamines having 4 to 13 carbon atoms, alicyclic secondary diamines having 6 to 14 carbon atoms, and carbon numbers 8 -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, and 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 Etc.
- 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, N, N′-dibutyl-1,2- Cyclobutanediamine, N, N'-dimethyl-1,4-cyclohexanediamine, N, N'-diethyl-1,4-cyclohexanediamine, N, N'-dibutyl-1,4-cyclohexanediamine, N, N'- Examples thereof include dimethyl-1,3-cyclohexanediamine, N, N′-diethyl-1,3-cyclohexanediamine, and N, N′-dibutyl-1,3-cyclohexanediamine.
- aromatic secondary diamines include N, N′-dimethyl-phenylenediamine, N, N′-dimethyl-xylylenediamine, N, N′-dimethyl-diphenylmethanediamine, and N, N′-dimethyl-diphenyletherdiamine.
- Examples of the secondary alkanoldiamine include N-methyldiethanolamine, N-octyldiethanolamine, N-stearyldiethanolamine, and N-methyldipropanolamine.
- dicarboxylic acids having 2 to 20 carbon atoms can be used.
- dicarboxylic acids having 2 to 20 carbon atoms can be used.
- aliphatic dicarboxylic acids, aromatic dicarboxylic acids, and alicyclic dicarboxylic acids are used.
- Examples of the aliphatic dicarboxylic acid include oxalic acid, malonic acid, succinic acid, glutaric acid, methyl succinic acid, dimethyl malonic acid, ⁇ -methyl glutaric acid, ethyl succinic acid, isopropyl malonic acid, adipic acid, pimelic acid, suberic acid, Azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanediic acid, tetradecanediic acid, hexadecanediic acid, octadecanediic acid and icosandiic acid.
- aromatic dicarboxylic acid examples include terephthalic acid, isophthalic acid, phthalic acid, phenylmalonic acid, homophthalic acid, phenylsuccinic acid, ⁇ -phenylglutaric acid, ⁇ -phenyladipic acid, ⁇ -phenyladipic acid, biphenyl-2 2,2'-dicarboxylic acid, biphenyl-4,4'-dicarboxylic acid, naphthalenedicarboxylic acid, sodium 3-sulfoisophthalate and potassium 3-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 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 singly or in a mixture of two or more.
- Examples of the polycarboxylic acid compound (D) include carboxylic acids having 3 or more carboxyl groups, and carboxylic acids having 2 or more carboxyl groups and 1 or more hydroxyl groups, and are compatible with and charged with a thermoplastic resin. From the viewpoint of prevention, a carboxylic acid having 3 or more carboxyl groups is preferred.
- the polycarboxylic acid compound (D) may be a mixture thereof.
- the carboxylic acid having 3 or more carboxyl groups may be a derivative thereof (eg, acid anhydride, alkyl ester, alkali metal salt, acid halide, etc.).
- the carboxylic acid having 3 or more carboxyl groups and derivatives thereof may be a mixture of two or more.
- carboxylic acid having 3 or more carboxyl groups examples include aconitic acid, 1,2,3-propanetricarboxylic acid, butane-1,2,3,4-tetracarboxylic acid, 3-butene-1,2,3. -Tricarboxylic acid, trimellitic acid, pyromellitic acid, mellitic acid, cyclohexanetricarboxylic acid, naphthalene-1,2,5-tricarboxylic acid, naphthalene-2,6,7-tricarboxylic acid, 1,3,5-pentanetricarboxylic acid , Trimesic acid, 3,3 ′, 4-diphenyltricarboxylic acid, benzophenone-3,3 ′, 4-tricarboxylic acid, diphenylsulfone-3,3 ′, 4-tricarboxylic acid, diphenylether-3,3 ′, 4-tricarboxylic acid Acid, diphenyl-2,2 ′, 3,3′-te
- the carboxylic acid having two or more carboxyl groups and one or more hydroxyl groups may be a derivative thereof (for example, acid anhydride, alkyl ester, alkali metal salt, acid halide, etc.).
- the carboxylic acid having two or more carboxyl groups and one or more hydroxyl groups and derivatives thereof may be a mixture of two or more.
- carboxylic acid having two or more carboxyl groups and one or more hydroxyl groups examples include tartaric acid, malic acid, citric acid, isocitric acid, citramalic acid, and tartronic acid.
- the polymer compound (E) includes a polyester (A) composed of a diol and a dicarboxylic acid, the compound (B), and the polycarboxylic acid from the viewpoint of compatibility with a thermoplastic resin and antistatic properties.
- the acid compound (D) preferably has a structure formed by bonding via an ester bond.
- the polymer compound (E) is composed of a block composed of a polyester (A) composed of a diol and a dicarboxylic acid and the above compound (B) from the viewpoint of compatibility with a thermoplastic resin and antistatic properties.
- the block polymer (C) having a hydroxyl group at both ends formed by alternately and alternately connecting the constituted blocks via ester bonds and the polycarboxylic acid compound (D) are bonded via ester bonds. It preferably has a structure.
- the polyester (A) of the present invention is only required to be composed of a diol and a dicarboxylic acid.
- a residue obtained by removing the hydroxyl group of the diol and a residue obtained by removing the carboxyl group of the dicarboxylic acid are ester bonds. It has a structure which couples via.
- the polyester (A) preferably has a structure having a carboxyl group at one end or both ends, and more preferably has a structure having a carboxyl group at both ends. Further, the degree of polymerization of the polyester (A) is preferably in the range of 2-50.
- polyester (A) has a carboxyl group at one or both ends
- an ester bond is formed by a reaction between the carboxyl group and the hydroxyl group of the compound (B) to form the structure of the polymer compound (E). It is preferable.
- polyester (A) has a hydroxyl group at both ends, it is preferable that an ester bond is formed by a reaction between the hydroxyl group and the carboxyl group of the compound (D) to form the structure of the polymer compound (E). .
- the polyester (A) can be obtained, for example, by subjecting the dicarboxylic acid and the diol to a polycondensation reaction.
- the dicarboxylic acid may be a derivative of a dicarboxylic acid (for example, an acid anhydride, an alkyl ester, an alkali metal salt, an acid halide, etc.).
- a dicarboxylic acid for example, an acid anhydride, an alkyl ester, an alkali metal salt, an acid halide, etc.
- the polyester (A) is obtained using the derivative, the state is left as it is. Then, it may proceed to the reaction for obtaining the next block polymer (C) having a structure having hydroxyl groups at both ends, or may proceed to the reaction with the polycarboxylic acid (D).
- the dicarboxylic acid and its derivative may be a mixture of two or more.
- the polyester (A) having a carboxyl group at both ends can be obtained, for example, by subjecting the dicarboxylic acid or a derivative thereof and the diol to a polycondensation reaction.
- the reaction ratio of the dicarboxylic acid or derivative thereof to the diol is preferably such that the dicarboxylic acid or derivative thereof is used excessively so that both ends are carboxyl groups, and the molar ratio is 1 mole relative to the diol. It is preferable to use in excess.
- the polyester (A) having a carboxyl group at one end can be obtained, for example, by polycondensation reaction of the dicarboxylic acid or a derivative thereof and the diol.
- the reaction ratio of the dicarboxylic acid or derivative thereof to the diol is preferably used in an equimolar amount of the dicarboxylic acid or derivative thereof and the diol so that one end is a carboxyl group.
- the polyester (A) having a hydroxyl group at both ends can be obtained, for example, by subjecting the dicarboxylic acid or a derivative thereof and the diol to a polycondensation reaction.
- the reaction ratio between the dicarboxylic acid or derivative thereof and the diol is preferably such that the diol is used excessively so that both ends are hydroxyl groups, and the molar ratio is used in an excess of 1 mol with respect to the dicarboxylic acid. It is preferable.
- the polyester (A) may be a mixture.
- a catalyst that promotes the esterification reaction may be used.
- the catalyst conventionally known ones such as dibutyltin oxide, tetraalkyl titanate, zirconium acetate, and zinc acetate can be used.
- both ends may be treated to form a dicarboxylic acid after the reaction with the diol, In the state as it is, you may progress to the next reaction for obtaining the block polymer (C) which has a structure which has a carboxyl group in both ends.
- a suitable polyester (A) comprising a diol and a dicarboxylic acid and having a carboxyl group at both ends forms an ester bond by reacting with the component (B) to form the structure of the block polymer (C).
- the carboxyl groups at both ends may be protected, modified, or in the form of a precursor.
- antioxidants such as a phenolic antioxidant
- the compound (B) having hydroxyl groups at both ends only needs to form an ester bond by reacting with the component (A) to form the structure of the block polymer (C), and the hydroxyl groups at both ends are protected. It may be modified, modified, or in the form of a precursor.
- the block polymer (C) having a structure having a hydroxyl group at both ends has a block composed of the polyester (A) and a block composed of the compound (B). Have a structure in which they are repeatedly and alternately bonded through ester bonds formed by carboxyl groups and hydroxyl groups.
- An example of such a block polymer (C) is, for example, one having a structure represented by the following general formula (3).
- (A) represents a block composed of the polyester (A) having carboxyl groups at both ends
- (B) is from the compound (B) having hydroxyl groups at both ends.
- t is the number of repeating units, and preferably represents a number of 1 to 10.
- t is more preferably a number of 1 to 7, and most preferably a number of 1 to 5.
- the block polymer (C) having a structure having hydroxyl groups at both ends is obtained by polycondensation reaction of the polyester (A) having carboxyl groups at both ends and the compound (B) having hydroxyl groups at both ends.
- a structure equivalent to that having a structure in which the polyester (A) and the compound (B) are alternately and repeatedly bonded through an ester bond formed by a carboxyl group and a hydroxyl group can be obtained. If it has, it is not always necessary to synthesize from the polyester (A) and the compound (B).
- the block polymer (C) which has can be obtained preferably.
- 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.
- the catalyst conventionally known ones such as dibutyltin oxide, tetraalkyl titanate, zirconium acetate, and zinc acetate can be used.
- antioxidants such as a phenolic antioxidant
- the block polymer (C) having a structure having hydroxyl groups at both ends and the polycarboxylic acid (D) preferably have a hydroxyl group at the end of the block polymer (C). It has a structure formed by bonding via an ester bond formed with a carboxyl group of the polycarboxylic acid compound (D).
- the polymer compound (E) may further contain an ester bond formed by the hydroxyl group of the polyester (A) and the carboxyl group of the polycarboxylic acid compound (D).
- the hydroxyl group of the block polymer (C) may be reacted with the carboxyl group of the polycarboxylic acid compound (D).
- the number of carboxyl groups in the polycarboxylic acid compound is preferably 0.5 to 5 equivalents, more preferably 0.5 to 1.5 equivalents, of the number of hydroxyl groups in the block polymer (C) to be reacted.
- the said reaction may be performed in various solvents and may be performed in a molten state.
- the polycarboxylic acid compound (D) to be reacted is preferably 0.1 to 2.0 equivalents, more preferably 0.2 to 1.5 equivalents, of the number of hydroxyl groups of the block polymer (C) to be reacted.
- the polycarboxylic acid compound (D) may be added to the reaction system without isolation of the block polymer (C) and reacted as it is.
- the hydroxyl group of the unreacted polyester (A) used excessively when synthesizing the block polymer (C) reacts with a part of the carboxyl groups of the polycarboxylic acid compound (D) to form an ester bond. It may be formed.
- a preferred polymer compound (E) of the present invention is an ester bond in which a block polymer (C) having a structure having hydroxyl groups at both ends and a polycarboxylic acid compound (D) are formed by respective hydroxyl groups and carboxyl groups. It is not always necessary to synthesize from the block polymer (C) and the polycarboxylic acid compound (D) as long as it has a structure equivalent to that having a structure bonded via the.
- the number average molecular weight of the block composed of the polyester (A) in the polymer compound (E) is preferably 800 to 8,000, more preferably 1,000 to 6,000 in terms of polystyrene. More preferably, it is 2,000 to 4,000.
- the number average molecular weight of the block composed of the compound (B) having hydroxyl groups at both ends in the polymer compound (E) is preferably 400 to 6,000, more preferably 1,000 in terms of polystyrene. 5,000 to 5,000, more preferably 2,000 to 4,000.
- the number average molecular weight of the block composed of the block polymer (C) having a structure having hydroxyl groups at both ends in the polymer compound (E) is preferably 5,000 to 25,000 in terms of polystyrene, More preferably, it is 7,000 to 17,000, and more preferably 9,000 to 13,000.
- the antistatic agent of the present invention is also preferably an antistatic agent composition comprising one or more selected from the group consisting of alkali metal salts and Group 2 element salts.
- alkali metal salts and Group 2 element salts include organic acid or inorganic acid salts.
- alkali metals include lithium, sodium, potassium, cesium, rubidium, and the like.
- the acid include beryllium, magnesium, calcium, strontium, barium and the like, and examples of the organic acid include aliphatic monocarboxylic acids having 1 to 18 carbon atoms such as formic acid, acetic acid, propionic acid, butyric acid, and lactic acid.
- Aliphatic carboxylic acids having 1 to 12 carbon atoms such as oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid and adipic acid; aromatic carboxylic acids such as benzoic acid, phthalic acid, isophthalic acid, terephthalic acid and salicylic acid Acid; charcoal such as methanesulfonic acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, trifluoromethanesulfonic acid, etc.
- Examples of the inorganic acid include hydrochloric acid, hydrobromic acid, sulfuric acid, sulfurous acid, phosphoric acid, phosphorous acid, polyphosphoric acid, nitric acid, perchloric acid, and the like. .
- alkali metal salts are preferable, lithium, sodium and potassium are more preferable, and lithium is most preferable.
- acetic acid salts, perchloric acid salts, p-toluenesulfonic acid salts, and dodecylbenzenesulfonic acid salts are preferred.
- alkali metal salt and the group 2 element salt include, for example, lithium acetate, sodium acetate, potassium acetate, lithium chloride, sodium chloride, potassium chloride, magnesium chloride, calcium chloride, lithium phosphate, and sodium phosphate.
- the alkali metal salt and / or the Group 2 element salt may be added to the polymer compound (E) used in the antistatic agent of the present invention, or may be added to the thermoplastic resin together with the polymer compound (E). May be used.
- the blending amount of the alkali metal salt and / or the Group 2 element salt is preferably 0.01 to 20 parts by mass, and 0.1 to 15 parts by mass with respect to 100 parts by mass of the polymer compound (E). More preferred is 1 to 10 parts by mass.
- the antistatic agent of the present invention may be used as an antistatic agent composition by blending a surfactant.
- a surfactant nonionic, anionic, cationic or amphoteric surfactants can be used.
- Nonionic surfactants include polyethylene glycol type nonionic surfactants such as higher alcohol ethylene oxide adducts, fatty acid ethylene oxide adducts, higher alkylamine ethylene oxide adducts, and polypropylene glycol ethylene oxide adducts; polyethylene oxide, fatty acid esters of glycerin Polyanhydric alcohol type nonionic surfactants such as fatty acid ester of pentaerythritol, fatty acid ester of sorbit or sorbitan, alkyl ether of polyhydric alcohol, aliphatic amide of alkanolamine, etc.
- Is for example, carboxylates such as alkali metal salts of higher fatty acids; sulfate esters such as higher alcohol sulfates, higher alkyl ether sulfates, alkylbenzes Sulfonates such as sulfonates, alkyl sulfonates, and paraffin sulfonates; and phosphate ester salts such as higher alcohol phosphates.
- cationic surfactants include alkyltrimethylammonium salts. And quaternary ammonium salts.
- amphoteric surfactants include amino acid-type amphoteric surfactants such as higher alkylaminopropionates, and betaine-type amphoteric surfactants such as higher alkyldimethylbetaines and higher alkyldihydroxyethylbetaines, which can be used alone or Two or more types can be used in combination.
- anionic surfactants are preferable, and sulfonates such as alkylbenzene sulfonate, alkyl sulfonate, and paraffin sulfonate are particularly preferable.
- the surfactant may be blended in the polymer compound (E) used in the antistatic agent of the present invention, or may be blended in a thermoplastic resin together with the polymer compound (E).
- the compounding 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 polymer compound (E). preferable.
- the antistatic agent of the present invention may be used as an antistatic agent composition by blending a polymer antistatic agent.
- a polymer antistatic agent for example, a polymer type antistatic agent such as a known polyether ester amide can be used. Examples of the known polyether ester amide include those described in JP-A-7-10989. And polyether ester amides comprising the polyoxyalkylene adducts of bisphenol A described.
- a block polymer having a repeating structure having 2 to 50 bonding units between a polyolefin block and a hydrophilic polymer block can be used, and examples thereof include a block polymer described in US Pat. No. 6,552,131.
- the polymer type antistatic agent may be blended in the polymer compound (E) used in the antistatic agent of the present invention, or may be blended in a thermoplastic resin together with the polymer compound (E).
- the blending amount of the polymer antistatic agent is preferably 0 to 50 parts by mass, more preferably 5 to 20 parts by mass with respect to 100 parts by mass of the polymer compound (E).
- the antistatic agent of the present invention may be used as an antistatic agent composition by blending an ionic liquid.
- the ionic liquid are those having a melting point of room temperature or lower, at least one of cations or anions constituting the ionic liquid is an organic ion, and an initial conductivity of 1 to 200 ms / cm, preferably 10 to 200 ms.
- a room temperature molten salt that is / cm for example, a room temperature molten salt described in International Publication No. 95/15572.
- Examples of cations constituting the ionic liquid include cations selected from the group consisting of amidinium, pyridinium, pyrazolium and guanidinium cations.
- Imidazolinium cation Examples include those having 5 to 15 carbon atoms, such as 1,2,3,4-tetramethylimidazolinium and 1,3-dimethylimidazolinium;
- Imidazolium cation Examples include those having 5 to 15 carbon atoms, such as 1,3-dimethylimidazolium, 1-ethyl-3-methylimidazolium;
- Tetrahydropyrimidinium cation Examples include those having 6 to 15 carbon atoms, such as 1,3-dimethyl-1,4,5,6-tetrahydropyrimidinium, 1,2,3,4-tetra.
- Methyl-1,4,5,6-tetrahydropyrimidinium (4) Dihydropyrimidinium cation C6-20, for example, 1,3-dimethyl-1,4-dihydropyrimidinium, 1,3-dimethyl-1,6-dihydropyrimidi Ni, 8-methyl-1,8-diazabicyclo [5,4,0] -7,9-undecadienium, 8-methyl-1,8-diazabicyclo [5,4,0] -7,10-un Decadienium.
- 1,3-dimethyl-1,4-dihydropyrimidinium 1,3-dimethyl-1,6-dihydropyrimidi Ni
- 8-methyl-1,8-diazabicyclo [5,4,0] -7,9-undecadienium 8-methyl-1,8-diazabicyclo [5,4,0] -7,10-un Decadienium.
- Examples of the pyridinium cation include those having 6 to 20 carbon atoms, such as 3-methyl-1-propylpyridinium and 1-butyl-3,4-dimethylpyridinium.
- Examples of the pyrazolium cation include those having 5 to 15 carbon atoms, such as 1,2-dimethylpyrazolium and 1-n-butyl-2-methylpyrazolium.
- Guanidinium cation having an imidazolinium skeleton One having 8 to 15 carbon atoms includes, for example, 2-dimethylamino-1,3,4-trimethylimidazolinium, 2-diethylamino-1,3 , 4-trimethylimidazolinium;
- the above cations may be used alone or in combination of two or more. Of these, from the viewpoint of antistatic properties, 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 inorganic acid constituting the anion include the following.
- examples of the organic acid include carboxylic acid, sulfuric acid ester, sulfonic acid and phosphoric acid ester;
- examples of the inorganic acid include super strong acid (for example, borofluoric acid, tetrafluoroboric acid, perchloric acid, phosphorus hexafluoride). Acid, hexafluoroantimonic acid and hexafluoroarsenic acid), phosphoric acid and boric acid.
- the organic acid and inorganic acid may be used singly or in combination of two or more.
- a super strong acid conjugate in which the Hammett acidity function ( ⁇ H 0 ) of the anion constituting the ionic liquid is 12 to 100 is preferable.
- Bases acids that form anions other than conjugate bases of super strong acids, and mixtures thereof.
- halogen eg, fluorine, chlorine and bromine
- alkyl having 1 to 12 carbon atoms
- benzenesulfonic acid eg, p-toluenesulfonic acid and dodecylbenzenesulfonic acid.
- examples of super strong acids include those derived from proton acids, combinations of proton acids and Lewis acids, and mixtures thereof.
- borofluoric acid trifluoromethanesulfonic acid, bis (trifluoromethanesulfonyl) imidic acid and bis (pentafluoroethylsulfonyl) imidic acid are preferable from the viewpoint of ease of synthesis.
- Examples of the protonic acid used in combination with the Lewis acid include hydrogen halide (for example, hydrogen fluoride, hydrogen chloride, hydrogen bromide and hydrogen iodide), perchloric acid, fluorosulfonic acid, methanesulfonic acid, and trifluoromethane.
- Examples include sulfonic acid, pentafluoroethanesulfonic acid, nonafluorobutanesulfonic acid, undecafluoropentanesulfonic acid, tridecafluorohexanesulfonic acid, and mixtures thereof.
- hydrogen fluoride is preferred 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.
- 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 composed of these combinations include tetrafluoroboric acid, hexafluorophosphoric acid, hexafluorotantalic acid, hexafluoroantimonic acid, hexafluoride. Tantalum sulfonate, tetrafluoroboronic acid, hexafluorophosphoric acid, chloroboron trifluoride, arsenic hexafluoride and mixtures thereof.
- a conjugate base of a super strong acid (a super strong acid comprising a proton acid and a super strong acid comprising a combination of a proton acid and a Lewis acid), and more preferred.
- a conjugate base of a super strong acid composed of a proton acid and a super strong acid composed of a proton acid and boron trifluoride and / or phosphorus pentafluoride is particularly preferred.
- the ionic liquid having an amidinium cation is preferable from the viewpoint of antistatic properties, the ionic liquid having a 1-ethyl-3-methylimidazolium cation is more preferable, and particularly preferable.
- 1-ethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide is more preferable, and particularly preferable.
- the compounding amount of the ionic liquid 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 polymer compound (E). preferable.
- the antistatic agent of the present invention may be blended with a compatibilizing agent to form an antistatic agent composition.
- blending a compatibilizing agent 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, for example, Examples include a polymer described in JP-A-3-258850, a modified vinyl polymer having a sulfonyl group described in JP-A-6-345927, or a block polymer having a polyolefin part and an aromatic vinyl polymer part. It is done.
- the compatibilizing agent may be blended in the polymer compound (E) used in the antistatic agent of the present invention, or may be blended in a thermoplastic resin together with the polymer compound (E).
- the compounding amount of the compatibilizer is preferably 0.1 to 15 parts by mass, more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the polymer compound (E).
- the antistatic agent and antistatic agent composition of the present invention are particularly preferably used as an antistatic resin composition by blending with a thermoplastic resin.
- 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, etc.
- ⁇ -olefin polymers or polyolefin resins such as ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, ethylene-propylene copolymer and their copolymers; polyvinyl chloride, polyvinylidene chloride, chlorine Polyethylene, chlorinated polypropylene, polyvinylidene fluoride, rubber chloride, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-vinylidene chloride-vinyl acetate ternary Copolymer, vinyl chloride-acrylic Halogen-containing resins such as acid ester copolymers, vinyl chloride-maleic acid ester copolymers, vinyl chloride-cyclohexyl maleimide copolymers; petroleum resins, coumarone resins, polystyrene, polyvinyl acetate,
- Thermoplastic resins are isoprene rubber, butadiene rubber, acrylonitrile-butadiene copolymer rubber, styrene-butadiene copolymer rubber, fluorine rubber, silicone rubber, olefin elastomer, styrene elastomer, polyester elastomer, nitrile elastomer, nylon. It may be an elastomer such as a base elastomer, a vinyl chloride elastomer, a polyamide elastomer, or a polyurethane elastomer. In the present invention, these thermoplastic resins may be used alone or in combination of two or more. Further, the thermoplastic resin may be alloyed.
- thermoplastic resins include molecular weight, degree of polymerization, density, softening point, proportion of insoluble matter in solvent, degree of stereoregularity, presence or absence of catalyst residue, type and blending ratio of monomer as raw material, type of polymerization catalyst (For example, Ziegler catalyst, metallocene catalyst, etc.) can be used.
- type of polymerization catalyst for example, Ziegler catalyst, metallocene catalyst, etc.
- at least one selected from the group consisting of polyolefin resins, polystyrene resins and copolymers thereof is preferable from the viewpoint of antistatic properties.
- the mass ratio of the thermoplastic resin and the antistatic agent or antistatic agent composition in the antistatic resin composition of the present invention is preferably in the range of 99/1 to 40/60.
- the blending method of the polymer compound (E) into the thermoplastic resin is not particularly limited, and any commonly used method can be used. For example, by roll kneading, bumper kneading, an extruder, a kneader, etc. What is necessary is just to mix and knead
- a high molecular compound (E) may be added to a thermoplastic resin as it is, you may add after impregnating a support
- a carrier those known as fillers and fillers of synthetic resins, or flame retardants and light stabilizers that are solid at room temperature can be used.
- titanium oxide powder those obtained by chemically modifying the surface of these carriers, solid materials among the flame retardants and antioxidants listed below, and the like can be mentioned.
- these carriers those obtained by chemically modifying the surface of the carrier are preferred, and those obtained by chemically modifying the surface of the silica powder are more preferred.
- These carriers preferably have an average particle size of 0.1 to 100 ⁇ m, more preferably 0.5 to 50 ⁇ m.
- the polymer compound (E) As a method of blending the polymer compound (E) into the thermoplastic resin, the polymer compound (E) is synthesized while kneading the block polymer (C) and the polycarboxylic acid compound (D) simultaneously with the thermoplastic resin.
- the polymer compound (E) and a thermoplastic resin may be mixed at the time of molding such as injection molding, and may be blended by a method of obtaining a molded product.
- a master batch may be manufactured and this master batch may be blended.
- the antistatic resin composition of the present invention may contain various additives such as phenolic antioxidants, phosphorus antioxidants, thioether antioxidants, ultraviolet absorbers, hindered amine light stabilizers, etc., as necessary. Further, it can be added, whereby the resin composition of the present invention can be stabilized.
- phenolic antioxidant examples include 2,6-ditert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, distearyl (3,5-ditert-butyl-4). -Hydroxybenzyl) phosphonate, 1,6-hexamethylenebis [(3,5-ditert-butyl-4-hydroxyphenyl) propionic acid amide], 4,4'-thiobis (6-tert-butyl-m-cresol ), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), 4,4′-butylidenebis (6-tert-butyl) -M-cresol), 2,2′-ethylidenebis (4,6-ditert-butylphenol), 2,2′-ethylidenebis (4-secondarybutyl-6-tert-butyl) Eno
- Examples of the phosphorus antioxidant include trisnonylphenyl phosphite, tris [2-tert-butyl-4- (3-tert-butyl-4-hydroxy-5-methylphenylthio) -5-methylphenyl].
- Phosphite tridecyl phosphite, octyl diphenyl phosphite, di (decyl) monophenyl phosphite, di (tridecyl) pentaerythritol diphosphite, di (nonylphenyl) pentaerythritol diphosphite, bis (2,4-di Tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-ditert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,4,6-tritert-butylphenyl) pentaerythritol diphosphite Phosphite, bis (2,4-dicumylphenyl) pe Taerythritol diphosphite, tetra (tridecyl) isopropylidene diphenol diphosphit
- thioether-based antioxidant examples include dialkylthiodipropionates such as dilauryl thiodipropionate, dimyristyl thiodipropionate, distearyl thiodipropionate, and pentaerythritol tetra ( ⁇ -alkylthiopropionic acid). Examples include esters.
- the addition amount of these thioether-based antioxidants 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 thermoplastic resin.
- Examples of the ultraviolet absorber 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′-ditert-butylphenyl) -5-chloro Benzotriazole, 2- (2′-hydroxy-3′-tert-butyl-5′-methylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-5′-tert.
- Octylphenyl) benzotriazole 2- (2′-hydroxy-3 ′, 5′-dicumylphenyl) benzotriazole, 2 2- (methylenebis (4-tert-octyl-6- (benzotriazolyl) phenol), 2- (2′-hydroxy-3′-tert-butyl-5′-carboxyphenyl) benzotriazole and the like 2- ( 2'-hydroxyphenyl) benzotriazoles; phenyl salicylate, resorcinol monobenzoate, 2,4-ditertiarybutylphenyl-3,5-ditertiarybutyl-4-hydroxybenzoate, 2,4-ditertiary amylphenyl Benzoates such as 3,5-ditert-butyl-4-hydroxybenzoate and hexadecyl-3,5-ditert-butyl-4-hydroxybenzoate; 2-ethyl-2′-ethoxyoxanilide, 2-ethoxy Substitute
- hindered amine light stabilizer 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-tetramethyl-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 -Butanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, bis (2, , 6,6-tetramethyl-4-piperidyl) -di (tridecyl
- a known neutralizing agent as necessary in order to neutralize the residual catalyst in the polyolefin resin.
- 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 (stearamide), ethylene bis (12-hydroxystearamide), and stearic acid amide. Compounds, and these neutralizing agents may be used in combination.
- the antistatic resin composition of the present invention further includes an aromatic carboxylic acid metal salt, an alicyclic alkyl carboxylic acid metal salt, an aluminum p-tert-butylbenzoate, an aromatic phosphate metal salt, if necessary.
- Nucleating agents such as dibenzylidene sorbitol, metal soap, hydrotalcite, triazine ring-containing compound, metal hydroxide, phosphate ester flame retardant, condensed phosphate ester flame retardant, phosphate flame retardant, inorganic phosphorus Flame retardants, (poly) phosphate flame retardants, halogen flame retardants, silicon flame retardants, antimony oxides such as antimony trioxide, other inorganic flame retardant aids, other organic flame retardant aids, Fillers, pigments, lubricants, foaming agents and the like may be added.
- triazine ring-containing compound examples include melamine, ammelin, benzguanamine, acetoguanamine, phthalodiguanamine, melamine cyanurate, melamine pyrophosphate, butylenediguanamine, norbornene diguanamine, methylene diguanamine, ethylene dimelamine, trimethylene Dimelamine, tetramethylene dimelamine, hexamethylene dimelamine, 1,3-hexylene dimelamine and the like can be mentioned.
- 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.
- phosphate ester flame retardant examples include, for example, trimethyl phosphate, triethyl phosphate, tributyl phosphate, tributoxyethyl phosphate, trischloroethyl phosphate, trisdichloropropyl phosphate, triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, Trixylenyl phosphate, octyl diphenyl phosphate, xylenyl diphenyl phosphate, trisisopropylphenyl phosphate, 2-ethylhexyl diphenyl phosphate, t-butylphenyl diphenyl phosphate, bis- (t-butylphenyl) phenyl phosphate, tris- (t-butyl Phenyl) phosphate, isopropylphenyldiphenylphosphate, bis- ( Isopropy
- 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 the (poly) phosphate flame retardant include ammonium salts and amine salts of (poly) phosphoric acid such as ammonium polyphosphate, melamine polyphosphate, piperazine polyphosphate, melamine pyrophosphate, and piperazine pyrophosphate. .
- Examples of other inorganic flame retardant aids include inorganic compounds such as titanium oxide, aluminum oxide, magnesium oxide, hydrotalcite, talc, montmorillonite, and surface-treated products thereof.
- inorganic compounds such as titanium oxide, aluminum oxide, magnesium oxide, hydrotalcite, talc, montmorillonite, and surface-treated products thereof.
- TIPAQUE R-680 Titanium oxide: manufactured by Ishihara Sangyo Co., Ltd.
- Kyowa Mag 150 magnesium oxide: manufactured by Kyowa Chemical Industry Co., Ltd.
- DHT-4A hydrotalcite: manufactured by Kyowa Chemical Industry Co., Ltd.
- Alkamizer 4 zinc modified hydro
- talcite manufactured by Kyowa Chemical Industry Co., Ltd.
- examples of other organic flame retardant aids include pentaerythritol.
- additives usually used in synthetic resins such as a crosslinking agent, an antifogging agent, a plate-out preventing agent, a surface treatment agent, a plasticizer, Lubricants, flame retardants, fluorescent agents, antifungal agents, bactericides, foaming agents, metal deactivators, release agents, pigments, processing aids, antioxidants, light stabilizers, etc., do not impair the effects of the present invention. It can mix
- the additive blended in the antistatic resin composition of the present invention may be added directly to the thermoplastic resin, or blended into the antistatic agent or antistatic composition of the present invention and then added to the thermoplastic resin. It may be added.
- An antistatic resin molded product can be obtained by molding the antistatic resin composition of the present invention.
- the molding method is not particularly limited, and examples thereof include extrusion processing, calendar processing, injection molding, roll, compression molding, blow molding, rotational molding, and the like. Resin plate, sheet, film, bottle, fiber, irregular shape product Various shaped products such as these can be manufactured.
- the molded product obtained from the antistatic resin composition of the present invention is excellent in antistatic performance and sustainability. It also has resistance to wiping.
- the antistatic resin composition of the present invention and a molded body using the same are electric, electronic, communication, agriculture, forestry and fisheries, mining, construction, food, textile, clothing, medical, coal, petroleum, rubber, leather, automobile, precision It can be used in a wide range of industrial fields such as equipment, wood, building materials, civil engineering, furniture, printing, and musical instruments.
- the antistatic resin composition of the present invention and the molded product thereof are printers, personal computers, word processors, keyboards, PDAs (small information terminals), telephones, copiers, facsimiles, ECRs (electronic money registers).
- the antistatic resin composition of the present invention and the molded product thereof are a seat (filling, outer material, etc.), belt, ceiling, compatible top, armrest, door trim, rear package tray, carpet, mat, sun visor, foil cover. , Mattress cover, air bag, insulation material, suspension hand, suspension band, electric wire coating material, electrical insulation material, paint, coating material, upholstery material, flooring, corner wall, carpet, wallpaper, wall covering material, exterior material , Interior materials, roofing materials, deck materials, wall materials, pillar materials, floorboards, fence materials, frames and repetitive shapes, window and door shapes, slabs, siding, terraces, balconies, soundproofing plates, heat insulating plates, windows Automobiles such as materials, vehicles, ships, aircraft, buildings, housing and construction materials and civil engineering materials, clothing, curtains, sheets, nonwoven fabrics, plywood, synthetic fiber boards, carpets, doormats, sheets, buckets Hose, can be container, glasses, bags, cases, goggles, skis, rackets, tents, household goods of musical instruments, etc., can be
- An antistatic agent was produced according to the following production example.
- the number average molecular weight was measured by the following molecular weight measurement method.
- Mn The number average molecular weight (hereinafter referred to as “Mn”) was measured by a gel permeation chromatography (GPC) method.
- GPC gel permeation chromatography
- the measurement conditions for Mn are as follows. Apparatus: GPC apparatus manufactured by JASCO Corporation, Solvent: tetrahydrofuran, Reference material: Polystyrene, Detector: differential refractometer (RI detector), Column stationary phase: Shodex KF-804L manufactured by Showa Denko KK Column temperature: 40 ° C Sample concentration: 1 mg / 1 mL, Flow rate: 0.8 mL / min. , Injection volume: 100 ⁇ L
- the obtained polyester was charged with 150 g of polyethylene glycol having a number average molecular weight of 4,000, 0.45 g of an antioxidant (ADK STAB AO-60) and 0.45 g of zirconium acetate, and at 200 ° C. for 5 hours. Polymerization was performed under reduced pressure to obtain a polyether ester having hydroxyl groups at both ends.
- the polyether ester had a hydroxyl value of 9, and a number average molecular weight Mn of 12,200 in terms of polystyrene.
- the obtained polyester was charged with 150 g of polyethylene glycol having a number average molecular weight of 4,000, 0.45 g of an antioxidant (ADK STAB AO-60) and 0.45 g of zirconium acetate, and at 200 ° C. for 5 hours. Polymerization was performed under reduced pressure to obtain a polyether ester having hydroxyl groups at both ends.
- the polyether ester had a hydroxyl value of 9, and a number average molecular weight Mn of 12,200 in terms of polystyrene.
- the obtained polyester was charged with 150 g of polyethylene glycol having a number average molecular weight of 2,000, 0.45 g of an antioxidant (ADK STAB AO-60) and 0.45 g of zirconium acetate, and at 210 ° C. for 6 hours. Polymerization was performed under reduced pressure to obtain a polyether ester having hydroxyl groups at both ends.
- the polyether ester had a hydroxyl value of 4.5 and a number average molecular weight Mn of 6,100 in terms of polystyrene.
- the obtained polyester was charged with 200 g of polyethylene glycol having a number average molecular weight of 2,000, 0.4 g of an antioxidant (ADK STAB AO-60) and 0.4 g of zirconium acetate, and at 210 ° C. for 6 hours. Polymerization was performed under reduced pressure to obtain a polyether ester having hydroxyl groups at both ends.
- the polyether ester had a hydroxyl value of 9, and a number average molecular weight Mn of 12,100 in terms of polystyrene.
- 200 g of the obtained polyester was 200 g of polyethylene glycol having a number average molecular weight of 4,000, 22 g of pyromellitic anhydride as a polycarboxylic acid, 0.4 g of an antioxidant (ADK STAB AO-60), and zirconium acetate.
- An antistatic agent (E) -6 of the present invention was obtained by adding 0.4 g and polymerizing under reduced pressure for 6 hours while gradually raising the temperature from 200 ° C to 240 ° C.
- an antistatic agent (E) -7 of the present invention 150 g was charged with 100 g of polyethylene glycol having a number average molecular weight of 2,000, 0.2 g of an antioxidant (ADK STAB AO-60) and 0.25 g of zirconium acetate, and at 240 ° C. for 6 hours. Polymerization was carried out under reduced pressure to obtain an antistatic agent (E) -7 of the present invention.
- Examples 1 to 17, Comparative Examples 1 to 8 Using the antistatic resin composition blended based on the blending amounts shown in Tables 1 to 3 below, test pieces were obtained according to the test piece preparation conditions shown below. Using the obtained test piece, the surface resistivity (SR value) measurement and the water wiping resistance evaluation test were performed according to the following. Similarly, the resin composition of the comparative example was prepared with the formulation shown in Table 4 below, and evaluated.
- ⁇ Impact copolymer polypropylene resin composition test piece preparation conditions The antistatic resin composition blended based on the blending amount shown in the following table was subjected to conditions of 200 ° C. and 6 kg / hour using a twin screw extruder (PCM30, 60 mesh included) manufactured by Ikegai Co., Ltd. Granulation gave pellets. The obtained pellets were molded using a horizontal injection molding machine (NEX80: manufactured by Nissei Plastic Industry Co., Ltd.) under processing conditions of a resin temperature of 200 ° C. and a mold temperature of 40 ° C., and a 100 mm ⁇ 100 mm ⁇ 3 mm test piece was formed. Obtained.
- NEX80 manufactured by Nissei Plastic Industry Co., Ltd.
- ⁇ Homopolypropylene resin composition test piece preparation conditions An antistatic resin composition blended based on the blending amount shown in the following table was produced under the conditions of 230 ° C. and 6 kg / hour using a Ikegai twin screw extruder (PCM30, 60 mesh included). Granulated to obtain pellets. The obtained pellets were molded using a horizontal injection molding machine (NEX80: manufactured by Nissei Plastic Industry Co., Ltd.) under processing conditions of a resin temperature of 230 ° C. and a mold temperature of 40 ° C., and a 100 mm ⁇ 100 mm ⁇ 3 mm test piece was formed. Obtained.
- NEX80 manufactured by Nissei Plastic Industry Co., Ltd.
- ⁇ ABS resin composition test piece preparation conditions An antistatic resin composition blended based on the blending amount shown in the following table was produced under the conditions of 230 ° C. and 6 kg / hour using a Ikegai twin screw extruder (PCM30, 60 mesh included). Granulated to obtain pellets. The obtained pellets were molded using a horizontal injection molding machine (NEX80: manufactured by Nissei Plastic Industry Co., Ltd.) under processing conditions of a resin temperature of 230 ° C. and a mold temperature of 50 ° C., and a 100 mm ⁇ 100 mm ⁇ 3 mm test piece was formed. Obtained.
- NEX80 manufactured by Nissei Plastic Industry Co., Ltd.
- SR value ⁇ Method for measuring surface resistivity (SR value)>
- the obtained test piece was stored under conditions of a temperature of 25 ° C. and a humidity of 60% RH. After storage for 1 day and 30 days of molding, the R8340 resistance meter manufactured by Advantest was used in the same atmosphere. The surface specific resistance value ( ⁇ / ⁇ ) was measured under the conditions of an applied voltage of 100 V and an applied time of 1 minute. The measurement was performed for 5 points, and the average value was obtained.
- ⁇ Water wiping resistance evaluation test> The surface of the obtained test piece was wiped 50 times with a waste water cloth and then stored for 2 hours under conditions of a temperature of 25 ° C. and a humidity of 60%, and then an R8340 resistance meter manufactured by Advantest was used in the same atmosphere. The surface resistivity ( ⁇ / ⁇ ) was measured under the conditions of an applied voltage of 100 V and an applied time of 1 minute. The measurement was performed for 5 points, and the average value was obtained.
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Abstract
Description
すなわち、本発明の帯電防止剤は、ジオール、ジカルボン酸、下記一般式(1)で示される基を一つ以上有し両末端に水酸基を有する化合物(B)、および、ポリカルボン酸化合物(D)が、エステル結合を介して結合してなる構造を有する高分子化合物(E)からなることを特徴とするものである。
本発明に係る高分子化合物(E)は、ジオール、ジカルボン酸、下記一般式(1)で示される基を一つ以上有し両末端に水酸基を有する化合物(B)、および、ポリカルボン酸化合物(D)が、エステル結合を介して結合してなる構造を有する。
本発明で用いられるジオールとしては、脂肪族ジオール、芳香族基含有ジオールが挙げられる。また、ジオールは、2種以上の混合物でもよい。脂肪族ジオールとしては、例えば、1,2-エタンジオール(エチレングリコール)、1,2-プロパンジオール(プロピレングリコール)、1,3-プロパンジオール、1,2-ブタンジオール、1,3-ブタンジオール、2-メチル-1,3-プロパンジオール、1,4-ブタンジオール、1,5-ペンタンジオール、2,2-ジメチル-1,3-プロパンジオール(ネオペンチルグリコール)、2,2-ジエチル-1,3-プロパンジオール(3,3-ジメチロールペンタン)、2-n-ブチル-2-エチル-1,3プロパンジオール(3,3-ジメチロールヘプタン)、3-メチル-1,5-ペンタンジオール、1,6-ヘキサンジオール、2,2,4-トリメチル-1,3-ペンタンジオール、2-エチル-1,3-ヘキサンジオール、2-メチル-1,8-オクタンジオール、1,9-ノナンジオール、1,10-デカンジオール、1,12-オクタデカンジオール、1,4-シクロヘキサンジメタノール、水添ビスフェノールA、1,2-、1,3-または1,4-シクロヘキサンジオール、シクロドデカンジオール、ダイマージオール、水添ダイマージオール、ジエチレングリコール、ジプロピレングリコール、トリエチレングリコール、ポリエチレングリコール等が挙げられる。これら脂肪族ジオールの中でも、1,4-シクロヘキサンジメタノール、水添ビスフェノールAが、熱可塑性樹脂との相溶性および帯電防止性の点から好ましく、1,4-シクロヘキサンジメタノールがより好ましい。
本発明で用いられるジカルボン酸としては、脂肪族ジカルボン酸および芳香族ジカルボン酸が挙げられ、脂肪族ジカルボン酸と芳香族ジカルボン酸との混合物でもよい。
上記一般式(2)中、mは5~250の数を表す。mは、耐熱性や相溶性の点から、好ましくは20~150である。
上記一般式(3)中、(A)は、上記両末端にカルボキシル基を有するポリエステル(A)から構成されたブロックを表し、(B)は、上記両末端に水酸基を有する化合物(B)から構成されたブロックを表し、tは繰り返し単位の繰り返しの数であり、好ましくは1~10の数を表す。tは、より好ましくは1~7の数であり、最も好ましくは1~5の数である。
(1)イミダゾリニウムカチオン
炭素原子数5~15のものが挙げられ、例えば、1,2,3,4-テトラメチルイミダゾリニウム、1,3-ジメチルイミダゾリニウム;
(2)イミダゾリウムカチオン
炭素原子数5~15のものが挙げられ、例えば、1,3-ジメチルイミダゾリウム、1-エチル-3-メチルイミダゾリウム;
(3)テトラヒドロピリミジニウムカチオン
炭素原子数6~15のものが挙げられ、例えば、1,3-ジメチル-1,4,5,6-テトラヒドロピリミジニウム、1,2,3,4-テトラメチル-1,4,5,6-テトラヒドロピリミジニウム;
(4)ジヒドロピリミジニウムカチオン
炭素原子数6~20のものが挙げられ、例えば、1,3-ジメチル-1,4-ジヒドロピリミジニウム、1,3-ジメチル-1,6-ジヒドロピリミジニウム、8-メチル-1,8-ジアザビシクロ[5,4,0]-7,9-ウンデカジエニウム、8-メチル-1,8-ジアザビシクロ[5,4,0]-7,10-ウンデカジエニウム。
(1)イミダゾリニウム骨格を有するグアニジニウムカチオン
炭素原子数8~15のものが挙げられ、例えば、2-ジメチルアミノ-1,3,4-トリメチルイミダゾリニウム、2-ジエチルアミノ-1,3,4-トリメチルイミダゾリニウム;
(2)イミダゾリウム骨格を有するグアニジニウムカチオン
炭素原子数8~15のものが挙げられ、例えば、2-ジメチルアミノ-1,3,4-トリメチルイミダゾリウム、2-ジエチルアミノ-1,3,4-トリメチルイミダゾリウム;
(3)テトラヒドロピリミジニウム骨格を有するグアニジニウムカチオン
炭素原子数10~20のものが挙げられ、例えば、2-ジメチルアミノ-1,3,4-トリメチル-1,4,5,6-テトラヒドロピリミジニウム、2-ジエチルアミノ-1,3-ジメチル-4-エチル-1,4,5,6-テトラヒドロピリミジニウム;
(4)ジヒドロピリミジニウム骨格を有するグアニジニウムカチオン
炭素原子数10~20のものが挙げられ、例えば、2-ジメチルアミノ-1,3,4-トリメチル-1,4-ジヒドロピリミジニウム、2-ジメチルアミノ-1,3,4-トリメチル-1,6-ジヒドロピリミジニウム、2-ジエチルアミノ-1,3-ジメチル-4-エチル-1,4-ジヒドロピリミジニウム、2-ジエチルアミノ-1,3-ジメチル-4-エチル-1,6-ジヒドロピリミジニウム。
数平均分子量(以下、「Mn」と称する)は、ゲルパーミエーションクロマトグラフィー(GPC)法によって測定した。Mnの測定条件は以下の通りである。
装置 :日本分光(株)製GPC装置,
溶媒 :テトラヒドロフラン,
基準物質 :ポリスチレン,
検出器 :示差屈折計(RI検出器),
カラム固定相 :昭和電工(株)製Shodex KF-804L,
カラム温度 :40℃,
サンプル濃度 :1mg/1mL,
流量 :0.8mL/min.,
注入量 :100μL
セパラブルフラスコに、1,4-シクロヘキサンジメタノールを228g、アジピン酸を230g、酸化防止剤(アデカスタブAO-60)を0.4g仕込み、160℃から200℃まで徐々に昇温しながら常圧で4時間重合した。その後、酢酸ジルコニウムを0.2g添加し、200℃、減圧下で3時間重合して、ポリエステルを得た。ポリエステルの酸価は14、数平均分子量Mnはポリスチレン換算で5,200であった。
セパラブルフラスコに、1,4-シクロヘキサンジメタノールを228g、アジピン酸230g、酸化防止剤(アデカスタブAO-60)を0.4g仕込み、160℃から200℃まで徐々に昇温しながら常圧で4時間重合した。その後、酢酸ジルコニウムを0.2g添加し、200℃、減圧下で3時間重合してポリエステルを得た。ポリエステルの酸価は14、数平均分子量Mnはポリスチレン換算で5,200であった。
セパラブルフラスコに、水添ビスフェノールAを275g、アジピン酸を166g、酸化防止剤(アデカスタブAO-60)を0.4g仕込み、170℃から200℃まで徐々に昇温しながら常圧で5時間重合した。その後、酢酸ジルコニウムを0.2g添加し、210℃、減圧下で4時間重合して、ポリエステルを得た。ポリエステルの酸価は28、数平均分子量Mnはポリスチレン換算で2,800であった。
セパラブルフラスコに、1,4-シクロヘキサンジメタノールを225g、セバシン酸を209g、酸化防止剤(アデカスタブAO-60)を0.4g仕込み、160℃から200℃まで徐々に昇温しながら常圧で4時間重合した。その後、酢酸ジルコニウムを0.4g添加し、200℃、減圧下で4時間重合して、ポリエステルを得た。ポリエステルの酸価は28、数平均分子量Mnはポリスチレン換算で5,200であった。
セパラブルフラスコに、1,4-シクロヘキサンジメタノールを99g、1,4-シクロヘキサンジカルボン酸を126g、数平均分子量2,000のポリエチレングリコールを150g、酸化防止剤(アデカスタブAO-60)を0.35g仕込み、160℃から200℃まで徐々に昇温しながら常圧で6時間重合した。その後、酢酸ジルコニウムを0.35g添加し、210℃、減圧下で5時間重合して、両末端に水酸基を有するポリエーテルエステルを得た。このポリエーテルエステルの水酸基価は8、数平均分子量Mnはポリスチレン換算で13,100であった。
セパラブルフラスコに、水添ビスフェノールAを312g、アジピン酸を175g、酸化防止剤(アデカスタブAO-60)を0.4g仕込み、160℃から210℃まで徐々に昇温しながら常圧で6時間重合した。その後、酢酸ジルコニウムを0.2g添加し、210℃、減圧下で5時間重合してポリエステルを得た。ポリエステルの水酸基価は28、数平均分子量Mnはポリスチレン換算で4700であった。
セパラブルフラスコに、1,4-シクロヘキサンジメタノールを186g、セバシン酸を261g、ポリカルボン酸として無水トリメリット酸を12.8g、酸化防止剤(アデカスタブAO-60)を0.4g仕込み、160℃から210℃まで徐々に昇温しながら常圧で5時間重合した。その後、酢酸ジルコニウムを0.4g添加し、210℃、減圧下で4時間重合してポリエステルを得た。ポリエステルの酸価は28、数平均分子量Mnはポリスチレン換算で7,600であった。
セパラブルフラスコに、1,4-シクロヘキサンジメタノールを103g、1,4-シクロヘキサンジカルボン酸を123g、数平均分子量4,000のポリエチレングリコールを100g、ポリカルボン酸としてクエン酸を3.3g、酸化防止剤(アデカスタブAO-60)を0.3g仕込み、160℃から210℃まで徐々に昇温しながら常圧で5時間重合した。その後、酢酸ジルコニウムを0.3g添加し、210℃から240℃まで徐々に昇温しながら減圧下で4時間重合して、本発明の帯電防止剤(E)-8を得た。
製造例1記載の方法で、両末端に水酸基を有するポリエーテルエステルを合成した。これを、比較帯電防止剤(1)として比較例に用いた。
セパラブルフラスコに、製造例1記載の方法で得られたポリエーテルエステルを200g、モノカルボン酸として安息香酸を4.1g、酸化防止剤(アデカスタブAO-60)を0.2g、酢酸ジルコニウムを0.2g仕込み、240℃で5時間、減圧下で重合した。これを、比較帯電防止剤(2)として比較例に用いた。
セパラブルフラスコに、製造例1記載の方法で得られたポリエーテルエステルを200g、ジカルボン酸としてテレフタル酸を2.8g、酸化防止剤(アデカスタブAO-60)を0.2g、酢酸ジルコニウムを0.2g仕込み、240℃で5時間、減圧下で重合した。これを、比較帯電防止剤(3)として比較例に用いた。
下記の表1~3に記載した配合量に基づいてブレンドした帯電防止性樹脂組成物を用いて、下記に示す試験片作製条件に従い、試験片を得た。得られた試験片を用いて、下記に従い、表面固有抵抗値(SR値)の測定および耐水拭き性評価試験を行った。同様にして、下記の表4に示す配合で、比較例の樹脂組成物を調製し、それぞれ評価を行った。
下記の表中に示す配合量に基づいてブレンドした帯電防止性樹脂組成物を、(株)池貝製の2軸押出機(PCM30,60mesh入り)を用いて、200℃、6kg/時間の条件で造粒し、ペレットを得た。得られたペレットを、横型射出成形機(NEX80:日精樹脂工業(株)製)を用い、樹脂温度200℃、金型温度40℃の加工条件で成形し、100mm×100mm×3mmの試験片を得た。
下記の表中に示す配合量に基づいてブレンドした帯電防止性樹脂組成物を、(株)池貝製2軸押出機(PCM30,60mesh入り)を用いて、230℃、6kg/時間の条件で造粒し、ペレットを得た。得られたペレットを、横型射出成形機(NEX80:日精樹脂工業(株)製)を用い、樹脂温度230℃、金型温度40℃の加工条件で成形し、100mm×100mm×3mmの試験片を得た。
下記の表中に示す配合量に基づいてブレンドした帯電防止性樹脂組成物を、(株)池貝製2軸押出機(PCM30,60mesh入り)を用いて、230℃、6kg/時間の条件で造粒し、ペレットを得た。得られたペレットを、横型射出成形機(NEX80:日精樹脂工業(株)製)を用い、樹脂温度230℃、金型温度50℃の加工条件で成形し、100mm×100mm×3mmの試験片を得た。
得られた試験片を、成形加工後直ちに、温度25℃、湿度60%RHの条件下に保存し、成形加工の1日および30日保存後に、同雰囲気下で、アドバンテスト社製のR8340抵抗計を用いて、印加電圧100V、印加時間1分の条件で、表面固有抵抗値(Ω/□)を測定した。測定は5点について行い、その平均値を求めた。
得られた試験片の表面を流水中ウエスで50回拭いた後、温度25℃、湿度60%の条件下で2時間保存し、その後、同雰囲気下にて、アドバンテスト社製、R8340抵抗計を用いて、印加電圧100V、印加時間1分の条件で、表面固有抵抗値(Ω/□)を測定した。測定は5点について行い、その平均値を求めた。
*2:ドデシルベンゼンスルホン酸ナトリウム
*3:p-トルエンスルホン酸リチウム
*4:1-エチル-3-メチルイミダゾリウムビス(トリフルオロメタンスルホニル)イミド
*5:インパクトコポリマーポリプロピレン、日本ポリプロ株式会社製、商品名 BC03B
*6:ホモポリプロピレン、日本ポリプロ株式会社製、商品名 MA3
*7:ABS樹脂、テクノポリマー株式会社製、商品名 テクノABS110
Claims (13)
- 前記高分子化合物(E)が、ジオールとジカルボン酸とから構成されるポリエステル(A)、前記化合物(B)、および、前記ポリカルボン酸化合物(D)が、エステル結合を介して結合してなる構造を有する請求項1記載の帯電防止剤。
- 前記高分子化合物(E)が、前記ポリエステル(A)から構成されたブロックおよび前記化合物(B)から構成されたブロックがエステル結合を介して繰り返し交互に結合してなる両末端に水酸基を有するブロックポリマー(C)と、前記ポリカルボン酸化合物(D)とが、エステル結合を介して結合してなる構造を有する請求項2記載の帯電防止剤。
- 前記ポリエステル(A)が、片末端または両末端にカルボキシル基を有する構造を有する請求項3記載の帯電防止剤。
- 前記ポリエステル(A)から構成されたブロックの数平均分子量がポリスチレン換算で800~8,000であり、前記化合物(B)から構成されたブロックの数平均分子量がポリスチレン換算で400~6,000であり、かつ、前記ブロックポリマー(C)の数平均分子量が、ポリスチレン換算で5,000~25,000である請求項3記載の帯電防止剤。
- 前記化合物(B)がポリエチレングリコールである請求項1記載の帯電防止剤。
- 前記ポリカルボン酸化合物(D)が、カルボキシル基を3個以上有するカルボン酸である請求項1記載の帯電防止剤。
- 請求項1記載の帯電防止剤に対し、さらに、アルカリ金属の塩および第2族元素の塩からなる群から選択される1種以上が配合されてなることを特徴とする帯電防止剤組成物。
- 熱可塑性樹脂に対し、請求項1記載の帯電防止剤、または、請求項8記載の帯電防止剤組成物が配合されてなることを特徴とする帯電防止性樹脂組成物。
- 前記熱可塑性樹脂が、ポリオレフィン系樹脂、ポリスチレン系樹脂およびそれらの共重合体からなる群から選ばれる1種以上である請求項9記載の帯電防止性樹脂組成物。
- 前記熱可塑性樹脂と、前記帯電防止剤との質量比が、99/1~40/60の範囲である請求項9記載の帯電防止性樹脂組成物。
- 前記熱可塑性樹脂と、前記帯電防止剤組成物との質量比が、99/1~40/60の範囲である請求項9記載の帯電防止性樹脂組成物。
- 請求項9記載の帯電防止性樹脂組成物からなることを特徴とする成形体。
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US15/505,429 US10301519B2 (en) | 2014-08-22 | 2015-08-05 | Anti-static agent, anti-static agent composition, anti-static resin composition, and molding |
KR1020177007776A KR20170045283A (ko) | 2014-08-22 | 2015-08-05 | 대전 방지제, 대전 방지제 조성물, 대전 방지성 수지 조성물 및 성형체 |
CN201580045236.XA CN106661435B (zh) | 2014-08-22 | 2015-08-05 | 抗静电剂、抗静电剂组合物、抗静电性树脂组合物及成型体 |
EP15833531.5A EP3184598A4 (en) | 2014-08-22 | 2015-08-05 | Anti-static agent, anti-static agent composition, anti-static resin composition, and molding |
BR112017003340A BR112017003340A2 (pt) | 2014-08-22 | 2015-08-05 | agente antiestático, composição do agente antiestático, composição de resina antiestática e moldagem |
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CN107653672B (zh) * | 2017-10-13 | 2020-06-09 | 浙江真爱毯业科技有限公司 | 一种丝胶改性涤纶拉舍尔毛毯 |
US10829634B2 (en) * | 2017-12-05 | 2020-11-10 | Ticona Llc | Aromatic polymer composition for use in a camera module |
JP7101522B2 (ja) * | 2018-04-17 | 2022-07-15 | 株式会社Adeka | 制電性熱可塑性樹脂組成物およびその成形体 |
TW202035647A (zh) * | 2019-01-17 | 2020-10-01 | 美商陶氏有機矽公司 | 抗靜電聚矽氧橡膠組成物 |
US20220177757A1 (en) * | 2019-03-29 | 2022-06-09 | Adeka Corporation | Antistatic agent, antistatic composition comprising same, antistatic resin composition comprising same, and molded article thereof |
EP3992227A1 (en) * | 2020-07-20 | 2022-05-04 | Bio Bond ApS | Bio-based plasticiser for resins and blends containing said plasticiser |
WO2023062820A1 (ja) * | 2021-10-15 | 2023-04-20 | 株式会社秋本製作所 | 高分子型帯電防止剤含有樹脂組成物および成形体 |
CN117888225B (zh) * | 2024-01-17 | 2024-08-02 | 深圳市又一服饰设计有限公司 | 一种防静电涤纶纺织面料及其制备方法 |
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EP3184598A4 (en) | 2018-01-24 |
KR20170045283A (ko) | 2017-04-26 |
TW201623560A (zh) | 2016-07-01 |
JP2016044225A (ja) | 2016-04-04 |
CN106661435B (zh) | 2018-09-11 |
BR112017003340A2 (pt) | 2018-01-23 |
EP3184598A1 (en) | 2017-06-28 |
US20170267905A1 (en) | 2017-09-21 |
TWI657131B (zh) | 2019-04-21 |
JP6452993B2 (ja) | 2019-01-16 |
US10301519B2 (en) | 2019-05-28 |
CN106661435A (zh) | 2017-05-10 |
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