JP2022086164A - Antistatic polycarbonate resin composition, and molded body of the same - Google Patents

Abstract

To provide a polycarbonate resin composition from which a molded body excellent in antistatic performance and its durability, and transparency can be provided, and a molded body of the same.SOLUTION: There are provided an antistatic polycarbonate resin composition that contains 3-40 pts.mass of one or more polymer compounds (E) with respect to 100 pts.mass of a polycarbonate resin, in which the polymer compound (E) is a polymer compound obtained by reaction of polyester (a) obtained by reaction of diol (a1) and a dicarboxylic acid (a2), a compound (b) having one or more ethyleneoxy groups and hydroxyl groups at both terminals, and an epoxy compound (D) having two or more epoxy groups; and a molded body of the same.SELECTED DRAWING: None

Description

The present invention relates to an antistatic polycarbonate resin composition (hereinafter, also simply referred to as “resin composition”), which has excellent long-lasting antistatic properties and transparency, and a molded product thereof.

Polycarbonate resin is excellent in impact resistance, heat resistance, transparency and the like, and is widely used in various fields such as electricity, electronics, optics, building materials, medical care, foods, and vehicles. However, products using plastics such as polycarbonate resin generally have a feature that charged static electricity is difficult to dissipate due to their high electrical insulation. Therefore, during the use of the product, there is a possibility that it may lead to problems such as adhesion of dust, destruction due to static electricity, and malfunction, and it has been required to impart continuous antistatic performance to the polycarbonate resin. In particular, films that require transparency, such as packaging films for electrical and electronic components, are required to have transparency and sustained antistatic performance.

As a conventional method for imparting antistatic performance to a polycarbonate resin while maintaining transparency, a method of blending a diglycerin fatty acid ester with a polycarbonate resin (Patent Document 1) and a method of blending a phosphonium sulfonate (Patent Document 2). ) Has been proposed. However, these methods have a problem that the antistatic property is lowered by washing or wiping the product because the diglycerin fatty acid ester or the phosphonium sulfonate develops the antistatic property by migrating to the product surface. ..

Further, as a method for exhibiting antistatic performance without being affected by washing or wiping of a product, a method using a polymer-type antistatic agent such as a polyether ester amide has been proposed (Patent Document 3).

Japanese Unexamined Patent Publication No. 02-196852 Japanese Patent Application Laid-Open No. 62-230835 Japanese Unexamined Patent Publication No. 62-273252

However, these conventional methods are not sufficient in antistatic performance and their sustainability, and further improvement is desired at present. Further, there is also a problem that the transparency of the molded product is adversely affected.
In particular, when it is used for a film, there is a problem that sufficient antistatic property cannot be exhibited, and its durability is not sufficient. Further, since sufficient performance cannot be obtained unless a large amount is added to the resin, there is a problem that the transparency of the film is adversely affected.
Therefore, an object of the present invention is to provide a polycarbonate resin composition having excellent antistatic properties and further having excellent transparency, and a molded product thereof.

As a result of diligent studies to solve the above problems, the present inventors have found that the above problems can be solved by adopting the following configuration, and have completed the present invention.
That is, the present invention is an antistatic polycarbonate resin composition containing 3 to 40 parts by mass of one or more kinds of the polymer compound (E) with respect to 100 parts by mass of the polycarbonate resin, wherein the polymer compound (E) is contained. However, it has a polyester (a) obtained by the reaction of a diol (a1) and a dicarboxylic acid (a2), a compound (b) having one or more ethyleneoxy groups and having hydroxyl groups at both ends, and two or more epoxy groups. It provides an antistatic polycarbonate resin composition which is a polymer compound obtained by the reaction with an epoxy compound (D).

Further, in the present invention, the polymer compound (E) comprises a polyester block (A) composed of the polyester (a) and a polyether block (B) composed of the compound (b). A hydroxyl group or a carboxyl group having a hydroxyl group or a carboxyl group at the end of the polyester (a), a hydroxyl group having a hydroxyl group at the end of the compound (b), and a hydroxyl group formed by the reaction of the epoxy group or the epoxy group of the epoxy compound (D). The present invention provides the antistatic polycarbonate resin composition having a structure formed by the reaction of the above, which is bonded via an ester bond or an ether bond.

Further, in the present invention, the polymer compound (E) has carboxyl groups at both ends formed by repeatedly and alternately bonding the polyester block (A) and the polyether block (B) via an ester bond. The present invention provides the antistatic polycarbonate resin composition having a structure in which a block polymer (C) and the epoxy compound (D) are bonded via an ester bond.

The present invention also provides the antistatic polycarbonate resin composition having a structure in which the polyester (a) constituting the polymer compound (E) has a carboxyl group at both ends.
The present invention also provides the antistatic polycarbonate resin composition in which the compound (b) constituting the polymer compound (E) is polyethylene glycol.
The present invention further provides the antistatic polycarbonate resin composition containing 0.01 to 8 parts by mass of one or more selected from the group consisting of alkali metal salts and ionic liquids. be.
The present invention also provides a molded product obtained from the antistatic polycarbonate resin composition.
The present invention also provides the molded product which is a film.

According to the present invention, it is possible to provide a polycarbonate resin composition having excellent antistatic property continuously and further having excellent transparency, and a molded product thereof. The molded product of the present invention has excellent transparency, is less likely to generate static electricity, and is less likely to cause surface contamination due to static electricity or deterioration of commercial value due to adhesion of dust. The present invention is particularly suitable for application to films.

Hereinafter, embodiments of the present invention will be described in detail.
The resin composition of the present invention is an antistatic polycarbonate resin composition containing 3 to 40 parts by mass of one or more polymer compounds (E) with respect to 100 parts by mass of the polycarbonate resin, and the polymer compound. (E) comprises a polyester (a) obtained by reacting a diol (a1) with a dicarboxylic acid (a2), a compound (b) having one or more ethyleneoxy groups and having hydroxyl groups at both ends, and an epoxy group. It is a polymer compound obtained by the reaction with the epoxy compound (D) having two or more.

First, the polycarbonate resin used in the resin composition of the present invention will be described.
The polycarbonate resin is a polymer obtained by a phosgene method in which various dihydroxydiaryl compounds are reacted with phosgene, or an ester exchange method in which a dihydroxydiaryl compound is reacted with a carbonic acid ester such as diphenyl carbonate, and is a typical example. Examples include polycarbonate resins made from 2,2-bis (4-hydroxyphenyl) propane (bisphenol A).

Examples of the dihydroxydiaryl compound include bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, and 2,2-bis (4-hydroxyphenyl) butane, in addition to bisphenol A. 2,2-Bis (4-hydroxyphenyl) octane, bis (4-hydroxyphenyl) phenylmethane, 2,2-bis (4-hydroxyphenyl-3-methylphenyl) propane, 1,1-bis (4-hydroxy) -3-3rd butylphenyl) propane, 2,2-bis (4-hydroxy-3-bromophenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2- Bis (hydroxyaryl) alkanes such as bis (4-hydroxy-3,5-dichlorophenyl) propane; 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclohexane and the like. Bis (hydroxyaryl) cycloalkhans; dihydroxydiaryl ethers such as 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dimethyldiphenyl ether; dihydroxy such as 4,4'-dihydroxydiphenylsulfide Diaryl sulfides; dihydroxydiaryl sulfoxides such as 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide; 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxy Examples thereof include dihydroxydiarylsulfones such as −3,3′-dimethyldiphenylsulfone. These may be used alone or in admixture of two or more. In addition to these, piperazine, dipiperidyl hydroquinone, resorcin, 4,4'-dihydroxydiphenyl and the like may be mixed and used.

Further, the dihydroxydiaryl compound and, for example, a phenol compound having a valence of 3 or more shown below may be mixed and used. Examples of the trivalent or higher phenol compound include fluoroglucolcin, 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) -heptene, 2,4,6-dimethyl-2,4,6-. Tri- (4-hydroxyphenyl) -heptane, 1,3,5-tri- (4-hydroxyphenyl) -benzol, 1,1,1-tri- (4-hydroxyphenyl) -ethane and 2,2-bis -[4,4- (4,4'-dihydroxydiphenyl) -cyclohexyl] -propane and the like can be mentioned.

The viscosity average molecular weight of the polycarbonate resin is usually 10,000 to 100,000, preferably 15,000 to 35,000, and more preferably 17,000 to 28,000. When producing the polycarbonate resin, a molecular weight modifier, a catalyst, or the like can be used as needed.
The refractive index of the polycarbonate resin is usually in the range of about 1.584 to 1.586.

Next, the polymer compound (E) will be described. The polymer compound (E) is blended to impart antistatic properties to the polycarbonate resin composition. The polymer compound (E) used in the present invention is a polyester (a) obtained by reacting a diol (a1) with a dicarboxylic acid (a2), and a compound having one or more ethyleneoxy groups and hydroxyl groups at both ends. It is a polymer compound obtained by reacting (b) with an epoxy compound (D) having two or more epoxy groups. Here, the ethyleneoxy group is a group represented by the following general formula (1).

The polymer compound (E) is a block of polyester composed of polyester (a) and a block of polyether composed of a compound (b) having one or more ethyleneoxy groups and hydroxyl groups at both ends. By reacting the hydroxyl group or carboxyl group having (B) at the end of the polyester (a) with the hydroxyl group having at the end of the compound (b) with the epoxy group or epoxy group of the epoxy compound (D). It is preferable to have a structure formed by a reaction with the formed hydroxyl group via an ester bond or an ether bond from the viewpoint of antistatic property, its durability, and transparency of the molded product.

The polyester block (A) of the polymer compound (E) is composed of the polyester (a) obtained by reacting the diol (a1) with the dicarboxylic acid (a2). The polyester (a) can be obtained by subjecting a diol to a dicarboxylic acid in an esterification reaction.

Examples of the diol (a1) used in the polymer compound (E) according to the present invention include an aliphatic diol and an aromatic group-containing diol. The diol (a1) 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. , 2-Methyl-1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 2,2-dimethyl-1,3-propanediol (neopentyl glycol), 2,2-diethyl- 1,3-Propanediol (3,3-dimethylolpentane), 2-n-butyl-2-ethyl-1,3propanediol (3,3-dimethylolheptan), 3-methyl-1,5-pentane Glycol, 1,6-hexanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2-methyl-1,8-octanediol, 1,9- Nonanediol, 1,10-decanediol, 1,12-octadecanediol, 1,4-cyclohexanedimethanol, hydrogenated bisphenol A, 1,2-, 1,3- or 1,4-cyclohexanediol, cyclododecanediol , Dimerdiol, hydrogenated dimerdiol, diethylene glycol, dipropylene glycol, triethylene glycol and the like. Among these aliphatic diols, 1,4-cyclohexanedimethanol and hydrogenated bisphenol A are preferable, and 1,4-cyclohexanedimethanol is more preferable from the viewpoint of antistatic property, its durability, and transparency of the molded product. Since the aliphatic diol is preferably hydrophobic from the viewpoint of antistatic property, its durability, and transparency of the molded product, it is not preferable to use polyethylene glycol having hydrophilicity.

Examples of the aromatic group-containing diol 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. Among these diols having an aromatic group, ethylene oxide adduct of bisphenol A and 1,4-bis (β-hydroxyethoxy) benzene are preferable. The aromatic diol is preferably hydrophobic from the viewpoint of antistatic property, its durability, and transparency of the molded product.

Among these diols, 1,4-cyclohexanedimethanol is particularly preferable from the viewpoint of antistatic property, its durability, and the transparency of the molded product.

Examples of the dicarboxylic acid (a2) used in the polymer compound (E) according to the present invention include aliphatic dicarboxylic acids and aromatic dicarboxylic acids. The dicarboxylic acid (a2) may be a mixture of two or more kinds.

The aliphatic dicarboxylic acid used in the polymer compound (E) according to the present invention may be a derivative of the 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 kinds.

The aliphatic dicarboxylic acid preferably includes an aliphatic dicarboxylic acid having 2 to 20 carbon atoms, and examples thereof include oxalic acid, malonic acid, glutamic acid, methylsuccinic acid, dimethylmalonic acid, 3-methylglutaric acid and ethylsuccinic acid. , Isopropylalonic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid (1,10-decandicarboxylic acid), tridecanedioic acid, tetradecanedioic acid, hexadecanedioic acid, octadecane Diacid, Eikosandioic acid, 1,3-cyclopentanedicarboxylic acid, 1,2-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1 , 4-Cyclohexanedioacetic acid, 1,3-cyclohexanedioacetic acid, 1,2-cyclohexanedioacetic acid, 1,1-cyclohexanedioacetic acid, dimeric acid, maleic acid, fumaric acid and the like. Among these aliphatic dicarboxylic acids, a dicarboxylic acid having 4 to 12 carbon atoms is more preferable, and an adipic acid is even more preferable, from the viewpoints of antistatic property, its durability, and transparency of a molded product.

The aromatic dicarboxylic acid used in the polymer compound (E) according to the present invention may be a derivative of the aromatic dicarboxylic acid (for example, acid anhydride, alkyl ester, alkali metal salt, acid halide, etc.). Further, the aromatic dicarboxylic acid and its derivative may be a mixture of two or more kinds.

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 β-phenylglutal. Acid, α-phenyladipic acid, β-phenyladipic acid, biphenyl-2,2'-dicarboxylic acid, biphenyl-4,4'-dicarboxylic acid, naphthalenedicarboxylic acid, sodium 3-sulfoisophthalate and 3-sulfoisophthalic acid Examples include potassium. Among these aromatic dicarboxylic acids, terephthalic acid, isophthalic acid, and phthalic acid (including phthalic anhydride) are preferable, and phthalic acid (phthalic anhydride is used. Including) is more preferable.

As the dicarboxylic acid (a2), both an aliphatic dicarboxylic acid and an aromatic dicarboxylic acid are preferably used in combination, and adipic acid is used as the aliphatic dicarboxylic acid and phthalic acid (including phthalic anhydride) is used as the aromatic dicarboxylic acid. It is particularly preferable to use them together.

Next, the block of the compound (b) and the polyether (B) of the polymer compound (E) will be described. The block of the polyether (B) 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.

As the compound (b) having one or more ethyleneoxy groups represented by the general formula (1) and having hydroxyl groups at both ends, a hydrophilic compound is preferable, and the compound (b) has an ethyleneoxy group represented by the general formula (1). Polyether is more preferable, polyethylene glycol is even more preferable from the viewpoint of antistatic property, its durability, and transparency of the molded product, and polyethylene glycol represented by the following general formula (2) is particularly preferable.

In the general formula (2), m represents a number of 5 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 molded product.

As 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 Examples thereof include a polyether obtained by addition-reacting with one or more of (1,3-butylene oxide, etc.), and the polyether may be either random or blocked.

Further examples of the compound (b) 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-, Examples thereof include compounds having a structure in which one or more of (2,3- or 1,3-butylene oxide, etc.) are added. These may be either random addition or block addition.

Examples of the active hydrogen atom-containing compound include glycols, divalent phenols, primary monoamines, secondary diamines and dicarboxylic acids.
As the 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-. Hexylenediol, 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, and 1-methyl-3,4-cyclohexanediol. , 2-Hydroxymethylcyclohexanol, 4-hydroxymethylcyclohexanol, 1,4-cyclohexanedimethanol, 1,1'-dihydroxy-1,1'-dicyclohexyl and the like.

Examples of the aromatic glycol include dihydroxymethylbenzene, 1,4-bis (β-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.

As the dihydric phenol, phenol having 6 to 30 carbon atoms can be used, for example, catechol, resorcinol, 1,4-dihydroxybenzene, hydroquinone, bisphenol A, bisphenol F, bisphenol S, dihydroxydiphenyl ether, dihydroxydiphenylthioether, binaphthol. And these alkyl (1 to 10 carbon atoms) or halogen-substituted products and the like can be mentioned.

Examples of the primary monoamine include aliphatic primary monoamines having 1 to 20 carbon atoms, for example, 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.

The secondary diamine includes 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. Diamine, N, N'-dibutylpropylene diamine, 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.

Examples of the heterocyclic secondary diamine 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-. 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, N, N'-dibutyl-1,3-cyclohexanediamine and the like.

Examples of the aromatic secondary diamine 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.

As the 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, β-methylglutaric acid, ethylsuccinic acid, isopropylmalonic acid, adipic acid, pimelic acid, and sveric acid. Examples thereof include azelaic acid, sebacic acid, undecandic acid, dodecandic acid, tridecandic acid, tetradecandic acid, hexadecandic acid, octadecandic acid and icosandic acid.

Examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, phthalic acid, phenylmalonic acid, homophthalic acid, phenylsuccinic acid, β-phenylglutaric acid, α-phenyladipic acid, β-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. Acids, 1,4-cyclohexanediacetic acid, 1,3-cyclohexanediacetic acid, 1,2-cyclohexanediacetic acid and dicyclohexyl-4,4'-dicarboxylic acid and the like can be mentioned.
These active hydrogen atom-containing compounds can be used alone or in a mixture of two or more.

Next, the epoxy compound (D) having two or more epoxy groups constituting the polymer compound (E) will be described. The epoxy compound (D) used in the present invention is not particularly limited as long as it has two or more epoxy groups, and is, for example, a poly of a mononuclear polyvalent phenol compound such as hydroquinone, resorcin, pyrocatechol, and fluoroglucosinol. Glycidyl ether compounds; dihydroxynaphthalene, biphenol, methylenebisphenol (bisphenol F), methylenebis (orthocresol), etylidenebisphenol, isopropyridenebisphenol (bisphenol A), isopropyridenebis (orthocresol), tetrabromobisphenol A, 1,3- Bis (4-hydroxycumylbenzene), 1,4-bis (4-hydroxycumylbenzene), 1,1,3-tris (4-hydroxyphenyl) butane, 1,1,2,2-tetra (4) -Hydroxyphenyl) Polyglycyl ether compounds of polynuclear polyvalent phenol compounds such as ethane, thiobisphenol, sulfobisphenol, oxybisphenol, phenol novolac, orthocresol novolak, ethylphenol novolak, butylphenol novolak, octylphenol novolak, resorcinnovolac, terpenphenol. ; Ethylene glycol, propylene glycol, butylene glycol, hexanediol, diethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycol, polyglycol, thiodiglycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, bisphenol A-ethylene oxide adduct, Polyglycidyl ethers of polyhydric alcohols such as dicyclopentadiene dimethanol; maleic acid, fumaric acid, itaconic acid, succinic acid, glutaric acid, suberic acid, adipic acid, azelaic acid, sebacic acid, dimer acid, trimeric acid, phthalic acid. Glycidyl esters of aliphatic, aromatic or alicyclic polybasic acids such as acids, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, pyromellitic acid, tetrahydrophthalic acid, hexahydrophthalic acid, endomethylenetetrahydrophthalic acid And homopolymers or copolymers of glycidyl methacrylate; having glycidylamino groups such as N, N-diglycidylaniline, bis (4- (N-methyl-N-glycidylamino) phenyl) methane, diglycidyl orthotoluidine. Epoxy compounds; vinyl cyclohexene diepoki Sid, dicyclopentadiene diepoxiside, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-6-methylcyclohexanecarboxylate, bis (3,4-) Epoxides of cyclic olefin compounds such as epoxy-6-methylcyclohexylmethyl) adipates; epoxidized conjugated diene polymers such as epoxidized polybutadienes and epoxidized styrene-butadiene copolymers, heterocyclic compounds such as triglycidyl isocyanurate, epoxys. Examples include epoxide oil. In addition, these epoxy compounds are internally crosslinked with a prepolymer of terminal isocyanate, or polyvalent active hydrogen compounds (polyhydric phenol, polyamine, carbonyl group-containing compound, polyphosphate ester, etc.) are used to increase the molecular weight. It may be the one that has been used. Two or more kinds of the epoxy compound (D) may be used.

The epoxy compound (D) has bisphenol F diglycidyl ether, dicyclopentadiene dimethanol diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, and hexanediol di from the viewpoints of antistatic property, its durability, and transparency of the molded product. Glycidyl ether is preferable, and bisphenol F diglycidyl ether is more preferable.
The epoxy equivalent of the epoxy compound (D) is preferably 70 to 2,000, more preferably 100 to 1,000, and even more preferably 150 to 600, from the viewpoints of antistatic property, its durability, and transparency of the molded product. preferable.

The polymer compound (E) of the present invention is a polyester (a) obtained by reacting a diol (a1) with a dicarboxylic acid (a2), and a compound having one or more ethyleneoxy groups and having hydroxyl groups at both ends (b). ) And the epoxy compound (D) having two or more epoxy groups react with each other, and are composed of a polyester block (A) composed of the polyester (a) and the compound (b). An epoxy group of an epoxy compound having a polyether block (B), a hydroxyl group or a carboxyl group at the end of the polyester (a), a hydroxyl group at the end of the compound (b), and two or more epoxy groups. Alternatively, a compound having a structure formed by the reaction of the hydroxyl group formed by the reaction of the epoxy group and bonded via an ester bond or an ether bond is antistatic and its durability, and a molded product. It is preferable from the viewpoint of transparency.

Further, the polymer compound (E) is composed of a block (A) of a polyester composed of a polyester (a) and a compound (b) from the viewpoint of antistatic property, its durability, and transparency of a molded product. The block polymer (C) having a carboxyl group at both ends formed by repeatedly and alternately bonding the polyether block (B) via an ester bond, and the epoxy compound (D) are the carboxyl groups of the block polymer (C). And, those having a structure formed by bonding via an ester bond formed by the epoxy group of the epoxy compound (D) are preferable, and further, a hydroxyl group formed by opening the ring of the epoxy group by a reaction with a carboxyl group. It is also preferable to have a structure in which the bond is formed through an ester bond formed by a reaction with a carboxyl group.

The polyester (a) constituting the block of the polyester (A) according to the present invention may be composed of a diol (a1) and a dicarboxylic acid (a2), and has antistatic properties and its durability, and the transparency of the molded product. From the viewpoint of sex, it is preferable that the residue of the diol (a1) excluding the hydroxyl group and the residue of the dicarboxylic acid (a2) excluding the carboxyl group are bonded via an ester bond. The polyester (a) constituting the polyester block (A) according to the present invention, which is more preferable, is made of a diol, an aliphatic dicarboxylic acid and an aromatic dicarboxylic acid in terms of antistatic property, its durability, and transparency of a molded product. From the viewpoint of antistatic property, its durability, and the transparency of the molded product, preferably, the residue excluding the hydroxyl group of the diol and the residue excluding the carboxyl group of the aliphatic dicarboxylic acid are It has a structure that is bonded via an ester bond, and has a structure in which a residue excluding a hydroxyl group of a diol and a residue excluding a carboxyl group of an aromatic dicarboxylic acid are bonded via an ester bond.

Further, the polyester (a) preferably has a structure having carboxyl groups at both ends from the viewpoints of antistatic property, its durability, and transparency of the molded product. 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 molded product.

The polyester (a) having a carboxyl group at both ends is obtained, for example, by subjecting the diol (a1) to an esterification reaction of the dicarboxylic acid (a2) (preferably an aliphatic dicarboxylic acid and an aromatic dicarboxylic acid). be able to.

The aliphatic dicarboxylic acid may be a derivative of the aliphatic dicarboxylic acid (for example, acid anhydride, alkyl ester, alkali metal salt, acid halide, etc.), and when the derivative is used to obtain the polyester (a). 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. Further, the aliphatic dicarboxylic acid and its derivative may be a mixture of two or more kinds.

The aromatic dicarboxylic acid may be a derivative of the aromatic dicarboxylic acid (eg, acid anhydride, alkyl ester, alkali metal salt, acid halide, etc.), and when the derivative is used to obtain polyester, the final product is obtained. 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. Further, the aromatic dicarboxylic acid and its derivative may be a mixture of two or more kinds.

When using an aliphatic dicarboxylic acid and an aromatic dicarboxylic acid, the ratio of the residue of the aliphatic dicarboxylic acid excluding the carboxyl group to the residue of the aromatic dicarboxylic acid excluding the carboxyl group in the polyester (a). Is preferably 90:10 to 99.9: 0.1, and more preferably 93: 7 to 99.9: 0.1 in terms of molar ratio from the viewpoint of antistatic property, its durability, and transparency of the molded product.

The polyester (a) having a carboxyl group at both ends comprises, for example, the above dicarboxylic acid or a derivative thereof (preferably the above aliphatic dicarboxylic acid or a derivative thereof, and the above aromatic dicarboxylic acid or a derivative thereof) and the above diol. It can be obtained by subjecting it to an esterification reaction.

The reaction ratio of the dicarboxylic acid or its derivative (preferably an aliphatic dicarboxylic acid or its derivative, and the aromatic dicarboxylic acid or its derivative) to the diol is such that both ends are carboxyl groups, and the dicarboxylic acid or its derivative is used. (Preferably, an aliphatic dicarboxylic acid or a derivative thereof, and an aromatic dicarboxylic acid or a derivative thereof) are preferably used in excess, and it is preferable to use an excess of 1 mol with respect to the diol in terms of molar ratio.
The compounding ratio of the aliphatic dicarboxylic acid or its derivative at the time of the esterification reaction and the aromatic dicarboxylic acid or its derivative is preferably 90:10 to 99.9: 0.1 in terms of molar ratio, and 93: 7 to 99.9. : 0.1 is more preferable.

Further, depending on the compounding ratio and reaction conditions, a polyester composed only of a diol and an aliphatic dicarboxylic acid or a polyester composed only of a diol and an aromatic dicarboxylic acid may be produced. They may be mixed in a), or they may be reacted with the compound (b) as they are to obtain a block polymer (C).

For the esterification reaction, a catalyst that promotes the reaction may be used, and as the catalyst, conventionally known catalysts such as dibutyltin oxide, tetraalkyl titanate, zirconium acetate, and zinc acetate can be used.

Further, the dicarboxylic acid (preferably an aliphatic dicarboxylic acid and an aromatic dicarboxylic acid) can be used with derivatives such as a carboxylic acid ester, a carboxylic acid metal salt, and a carboxylic acid halide instead of the dicarboxylic acid. After the reaction with the diol, both ends may be treated to form a dicarboxylic acid, or 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 suitable polyester (a) consisting of a diol and a dicarboxylic acid (preferably an aliphatic dicarboxylic acid and an aromatic dicarboxylic acid) and having a carboxyl group at both ends forms an ester bond by reacting with the compound (b). , Anything that forms the structure of the block polymer (C), and the carboxyl groups at both ends may be protected, modified, or in the form of a precursor. Further, in order to suppress the oxidation of the product during the reaction, an antioxidant such as a phenolic antioxidant may be added to the reaction system.
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 or an ether bond, preferably an ester bond to form a block polymer (C). It forms a structure, and 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 of the polymer compound (E) according to the present invention is composed of the block (A) composed of the polyester (a) and the compound (b). It has a block (B) formed therein, 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. Examples of the block polymer (C) include those having a structure represented by the following general formula (3).

In the general formula (3), (A) represents a block composed of the polyester (a) having a carboxyl group at both ends, and (B) is composed of a compound (b) having a hydroxyl group at both ends. The block is represented, and t is the number of repetitions in the repeating unit, and preferably represents 1 to 10 in terms of antistatic property, its durability, and storage stability. 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. However, 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 it is, it is not always necessary to synthesize it from the polyester (a) and the compound (b).

The reaction ratio between the polyester (a) and the compound (b) is adjusted so that the compound (b) has an X mol and the polyester (a) has an X + 1 mol, and carboxyl groups are grouped at both ends. The block polymer (C) having the above can be preferably obtained.
In the reaction, after the synthesis reaction of the polyester (a) is completed, the compound (b) may be added to the reaction system and reacted as it is without isolating the polyester (a).

For the polycondensation reaction, a catalyst that promotes the esterification reaction may be used, and as the catalyst, conventionally known catalysts such as dibutyltin oxide, tetraalkyl titanate, zirconium acetate, and zinc acetate can be used. Further, in order to suppress the oxidation of the product during the reaction, an antioxidant such as a phenolic antioxidant may be added to the reaction system.

The polymer compound (E) according to the present invention preferably has a block polymer (C) having a structure having carboxyl groups at both ends, and 2 It has a structure in which the above-mentioned epoxy compound (D) having an epoxy group is bonded via an ester bond. The ester bond was formed by an ester bond formed by the reaction of the carboxyl group at the end of the block polymer (C) with the epoxy group of the epoxy compound (D), and further by this reaction (reaction between the carboxyl group and the epoxy group). Any of the ester bonds formed by the reaction of the hydroxyl group and the carboxyl group may be used, and the presence of both ester bonds is preferable from the viewpoint of antistatic property, its durability, and the transparency of the molded product.

Further, the polymer compound (E) may further contain an ester bond formed by the carboxyl group of the polyester (a) and the epoxy group of the epoxy compound (D).

Further, the polymer compound (E) may contain an ester bond formed by the carboxyl group of the polyester (a) and the hydroxyl group formed by the reaction of the epoxy group of the epoxy compound.

Furthermore, the polymer compound (E) further contains an ether bond formed by the hydroxyl group of the polyester (a) or the hydroxyl group of the compound (b) and the epoxy group of the epoxy compound (D). You may.

In order to obtain a preferable polymer compound (E), the block polymer (C) may be reacted with the epoxy compound (D). That is, the carboxyl group of the block polymer (C) may be reacted with the epoxy group of the epoxy compound (D). More preferably, the hydroxyl group formed from the reacted epoxy group may be reacted with the carboxyl group. The number of epoxy groups in the epoxy compound (D) is preferably 0.5 to 5 equivalents, more preferably 0.5 to 1.5 equivalents of the number of carboxyl groups in the block polymer (C) to be reacted. Further, the above reaction may be carried out in various solvents or in a molten state.

The epoxy compound (D) having two or more epoxy groups to be reacted is preferably 0.1 to 2.0 equivalents, more preferably 0.2 to 1.5 equivalents of the number of carboxyl groups of the block polymer (C) to be reacted. preferable.

In the reaction, after the synthesis reaction of the block polymer (C) is completed, the epoxy compound (D) may be added to the reaction system and reacted as it is without isolating the block polymer (C). In that case, the carboxyl group of the unreacted polyester (a) used excessively when synthesizing the block polymer (C) reacts with a part of the epoxy group of the epoxy compound (D) to form an ester bond. You may.

The preferred polymer compound (E) according to the present invention is a block polymer (C) having a structure having a carboxyl group at both ends and an epoxy compound (D) having two or more epoxy groups, respectively, having a carboxyl group and an epoxy group. It is not always necessary to synthesize the block polymer (C) and the epoxy compound (D) as long as they have a structure equivalent to that having a structure bonded via an ester bond formed by. The ester bond formed by the carboxyl group and the epoxy group referred to here also includes an ester bond formed by the carboxyl group and the hydroxyl group formed from the epoxy group by reacting with the carboxyl group.

Further, in the polymer compound (E) of the present invention, after obtaining the polyester (a) from the diol (a1) and the dicarboxylic acid (a2), the compound (b) and / or the compound (b) and / or the compound (b) are obtained without isolating the polyester (a). It may be reacted with the epoxy compound (D).

In the present invention, the number average molecular weight of the compound (b) constituting the block (B) composed of the compound (b) having hydroxyl groups at both ends in the polymer compound (E) is calculated from the measured value of the hydroxyl value. However, from the viewpoint of antistatic property, its durability, and the transparency of the molded product, it is preferably 400 to 10,000, more preferably 1,000 to 8,000, and further preferably 2,000 to 8. It is 000. The method for measuring the hydroxyl value and the method for calculating the number average molecular weight from the hydroxyl value are described below.

<Calculation method of number average molecular weight from hydroxyl value>
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

<Measurement method of hydroxyl value>
・ Reagent A (acetylating agent)
(1) 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.

First, weigh 2 g of a sample into a 200 mL Erlenmeyer flask, add 10 mL of triethyl phosphate, and heat to dissolve. Add 15 mL of Reagent A, plug and shake vigorously. Add 20 mL of Reagent B, plug and shake vigorously. Add 50 mL of Reagent C. Titrate with 1N-KOH aqueous solution and calculate by the following formula.
Hydroxy group value [mgKOH / g] = 56.11 × f × (TB) / S
factor of 1N-KOH aqueous solution
B: Empty test titration [mL]
T: Quantitative test titration [mL]
S: Sample amount [g]

Further, in the present invention, the number average molecular weight of the polyester (a) constituting the block (A) composed of the polyester (a) in the polymer compound (E) is antistatic property and its durability in terms of polystyrene. From the viewpoint of transparency of the molded product, it is preferably 1,000 to 10,000, more preferably 1,500 to 8,000, and further preferably 2,500 to 7,500. If the number average molecular weight is less than 1,000, the storage stability may be inferior, and if it exceeds 10,000, the reaction for obtaining the polymer compound (E) may take a long time and the economic efficiency may be inferior. The molecular compound may be colored by a long-term reaction.
As a method for measuring the number average molecular weight in terms of polystyrene, a gel permeation chromatograph (GPC) method is preferable, and the measuring method is shown below.

<Measurement method of number average molecular weight by polystyrene conversion>
The number average molecular weight (hereinafter, also referred to as “Mn”) was measured by a gel permeation chromatography (GPC) method. The measurement conditions for Mn are as follows.

Equipment: GPC equipment manufactured by JASCO Corporation Solvent: Chloroform standard substance: Polystyrene detector: Differential refractometer (RI detector)
Column stationary phase: Showa Denko Corporation Shodex LF-804
Column temperature: 40 ° C
Sample concentration: 1 mg / 1 mL
Flow rate: 0.8 mL / min.
Injection volume: 100 μL

Further, the number average molecular weight of the block polymer (C) having a structure having carboxyl groups at both ends in the polymer compound (E) is the point of antistatic property and its durability, and transparency of the molded product in terms of polystyrene. Therefore, it is preferably 5,000 to 50,000, and more preferably 10,000 to 4,5,000. If the number average molecular weight is less than 5,000, the storage stability may be inferior, and if it exceeds 50,000, the reaction for obtaining the polymer compound (E) may take a long time and the economic efficiency may be inferior. The molecular compound may be colored by a long-term reaction. As a method for measuring the number average molecular weight in terms of polystyrene, a gel permeation chromatograph (GPC) method is preferable, and the measuring method is as described above.

In the resin composition of the present invention, the content of the polymer compound (E) is 3 to 40 parts by mass with respect to 100 parts by mass of the polycarbonate resin, and the antistatic property, its durability, and the transparency of the molded product are exhibited. From the point of view, 5 to 35 parts by mass is preferable, and 7 to 30 parts by mass is more preferable. If it is less than 3 parts by mass, sufficient antistatic property may not be obtained, and if it exceeds 40 parts by mass, the transparency of the molded product may be adversely affected.

The resin composition of the present invention further contains one or more selected from the group of alkali metal salts and ionic liquids in terms of antistatic property and its durability, water wiping resistance, and appearance of the molded body. Is preferable.

Hereinafter, the alkali metal salt will be described first. Examples of the alkali metal salt include organic acid or inorganic acid salt, and examples of the alkali metal include lithium, sodium, potassium, cesium, rubidium and the like. Examples of 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 and the like. Aromatic carboxylic acids such as benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, salicylic acid; methanesulfonic acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, trifluoromethane. Examples thereof include sulfonic acid having 1 to 20 carbon atoms such as sulfonic acid and nonafluorobutane sulfonic acid. Examples of the inorganic acid include hydrochloric acid, hydrobromic acid, sulfuric acid, sulfite, phosphoric acid, phosphoric acid, polyphosphoric acid, nitric acid, perchloric acid and the like. Among them, salts of lithium, sodium and potassium are preferable, and sodium is more preferable, from the viewpoints of antistatic property and its durability, water wiping resistance, and safety to living organisms and the environment. Further, from the viewpoint of antistatic property, its durability, and transparency of the molded product, 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 dodecylbenzenesulfonic acid is preferable. Salt is more preferred. Two or more kinds of alkali metal salts may be used.

Specific examples of 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. Lithium acid, sodium perchlorate, potassium perchlorate, lithium p-toluenesulfonate, sodium p-toluenesulfonate, potassium p-toluenesulfonate, lithium dodecylbenzenesulfonate, sodium dodecylbenzenesulfonate, dodecylbenzenesulfonic acid Examples thereof include potassium, potassium trifluoromethanesulfonate, potassium nonafluorobutane sulfonate, sodium trifluoromethanesulfonate, sodium nonafluorobutane sulfonate, lithium trifluoromethanesulfonate, lithium nonafluorobutane sulfonate and the like. Among these, lithium p-toluenesulfonate, sodium p-toluenesulfonate, and dodecylbenzenesulfonate are preferable from the viewpoints of antistatic property and its durability, transparency of the molded product, and safety to the living body and the environment. Lithium acid, sodium dodecylbenzenesulfonate and the like, and most preferably sodium dodecylbenzenesulfonate.

In the resin composition of the present invention, the content of the alkali metal salt is 0.01 to 8.0 with respect to 100 parts by mass of the polycarbonate resin from the viewpoint of antistatic property, its durability, and transparency of the molded product. By mass is preferable, 0.1 to 5.0 parts by mass is more preferable, and 0.3 to 4.0 parts by mass is more preferable. If the amount of the alkali metal salt is less than 0.01 parts by mass, the effect of adding the alkali metal salt may not be sufficient, and if it exceeds 8.0 parts by mass, the transparency of the molded product may be adversely affected. be.

Next, the ionic liquid will be described.
Examples of 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 the initial conductivity is 1 to 200 ms / cm, preferably 10 to 10 to. A room temperature molten salt having a temperature of 200 ms / cm, for example, the room temperature molten salt described in International Publication No. 95/15572.

Examples of the cations constituting the ionic liquid include cations selected from the group consisting of amidinium, pyridinium, pyrazolium and guanidinium cations. Among these, examples of the amidinium cation include the following.

(1) Imidazolinium cations Examples thereof include those having 5 to 15 carbon atoms, for example, 1,2,3,4-tetramethylimidazolinium, 1,3-dimethylimidazolinium;
(2) Imidazole cation Examples thereof include those having 5 to 15 carbon atoms, for example, 1,3-dimethylimidazolium, 1-ethyl-3-methylimidazolium;
(3) Tetrahydropyrimidinium cations 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;

(4) Dihydropyrimidinium cations 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.

Examples of the guanidinium cation include the following.
(1) 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;
(2) 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;
(3) 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;
(4) 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. 2-Dimethylamino-1,3,4-trimethyl-1,6-dihydropyrimidinium, 2-diethylamino-1,3-dimethyl-4-ethyl-1,4-dihydropyrimidinium, 2-diethylamino-1 , 3-Dimethyl-4-ethyl-1,6-dihydropyrimidinium.

One type of cation may be used alone, or two or more types may be used in combination. Of these, from the viewpoint of antistatic property and its durability, preferably an amidinium cation, more preferably an imidazolium cation, particularly preferably 1-ethyl-3-methylimidazolium cation, 1-ethyl-3 methylimidazole. Rumdodecylbenzene sulfonate.

Examples of the organic acid or the inorganic acid constituting the anion in the ionic liquid include the following. Organic acids include, for example, carboxylic acids, sulfate 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.

Among the organic acid and the inorganic acid, the ionic liquid is preferable from the viewpoint of antistatic property and its durability, in which the Hamett acidity function (-H0) of the anion constituting the ionic liquid is 12 to 100. Acids that form anions other than the conjugated bases of strong acids, the conjugated bases of superacids, and mixtures thereof.

Examples of anions other than the conjugated base of the super strong acid include halogen (eg, fluorine, chlorine and bromine) ions, alkyl (1 to 12 carbon atoms) benzenesulfonic acid (eg, p-toluenesulfonic acid and dodecylbenzenesulfonic acid). ) Ions and poly (n = 1-25) fluoroalcan sulfonic acid (eg, undecafluoropentane sulfonic acid) ions.

Examples of superacids include protonic acids and those derived from a combination of protonic acid and Lewis acid, and mixtures thereof. Examples of the protonic acid as a super strong acid include bis (trifluoromethylsulfonyl) imide acid, bis (pentafluoroethylsulfonyl) imide acid, tris (trifluoromethylsulfonyl) methane, perchloric acid, fluorosulfonic acid, and alkane ( 1 to 30 carbon atoms) sulfonic acid (eg, methane sulfonic acid, dodecane sulfonic acid, etc.), poly (n = 1 to 30) fluoroalkane (1 to 30 carbon atoms) sulfonic acid (eg, trifluoromethane sulfonic acid, etc.) Pentafluoroethane sulfonic acid, heptafluoropropane sulfonic acid, nonafluorobutane sulfonic acid, undecafluoropentane sulfonic acid and tridecafluorohexane sulfonic acid), borofluoric acid and boron tetrafluorofluoric acid. Of these, borofluoric acid, trifluoromethanesulfonic acid, bis (trifluoromethanesulfonyl) imide acid and bis (pentafluoroethylsulfonyl) imide acid are preferable from the viewpoint of ease of synthesis.

Proton acids used in combination with Lewis acid include, for example, hydrogen halide (eg, hydrogen fluoride, hydrogen chloride, hydrogen bromide and hydrogen iodide), perchloric acid, fluorosulfonic acid, methanesulfonic acid, trifluoromethane. Examples thereof include sulfonic acid, pentafluoroethanesulfonic acid, nonafluorobutanesulfonic acid, undecafluoropentanesulfonic acid, tridecafluorohexanesulfonic acid and mixtures thereof. Of these, hydrogen fluoride is preferable from the viewpoint of the initial conductivity of the ionic liquid.

Lewis acids include, for example, 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, tantalum hexafluorofluoride, antimonic acid hexafluoride, and hexafluoric acid. Examples thereof include tantalum sulphonic acid, boron tetrafluoroacid, phosphoric acid hexafluoride, boron trifluoride chloride, arsenic hexafluoride and mixtures thereof.

Of these anions, the conjugated base of superstrong acid (superacid consisting of protonic acid and superstrong acid consisting of a combination of protonic acid and Lewis acid) is preferable from the viewpoint of antistatic property of ionic liquid and its durability. More preferred are superacids and protonic acids consisting of protonic acids and conjugated bases of superacids consisting of boron trifluoride and / or phosphorus pentafluoride.

Among the ionic liquids, the ionic liquid having an amidinium cation is preferable, and the 1-ethyl-3-methylimidazolium cation is more preferable in terms of antistatic property, its durability, and the transparency of the molded product. Ionic liquids with, particularly preferred are 1-ethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide.

In the resin composition of the present invention, the content of the ionic liquid is 0.01 to 8.0 mass with respect to 100 parts by mass of the polycarbonate resin from the viewpoint of antistatic property, its durability, and transparency of the molded body. Parts are preferable, 0.1 to 5.0 parts by mass are more preferable, and 0.3 to 4.0 parts by mass are more preferable. If the amount of the ionic liquid is less than 0.01 parts by mass, the effect of adding the ionic liquid may not be sufficient, and if it exceeds 8.0 parts by mass, the transparency of the molded product may be adversely affected. be.

In the resin composition of the present invention, an alkali metal salt and an ionic liquid may be used in combination.
When the alkali metal salt and the ionic liquid are blended with the polycarbonate resin, they may be blended directly, or during the synthesis reaction of the polymer compound (E), the alkali metal salt and the ionic liquid are added to the reaction system. May be blended with the addition of one or more selected from the group of.

The resin composition of the present invention may further contain a salt of a Group 2 element as long as the effects of the present invention are not impaired.
Examples of the salt of the group 2 element include salts of organic acid or inorganic acid, and examples of the group 2 element include beryllium, magnesium, calcium, strontium, barium and the like. Examples of 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 and the like. Aromatic carboxylic acids such as benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, salicylic acid; methanesulfonic acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, trifluoromethane. Examples thereof include sulfonic acid having 1 to 20 carbon atoms such as sulfonic acid. Examples of the inorganic acid include hydrochloric acid, hydrobromic acid, sulfuric acid, sulfite, phosphoric acid, phosphoric acid, polyphosphoric acid, nitric acid, perchloric acid and the like.

Further, the resin composition of the present invention may contain a surfactant as long as the effects of the present invention are not impaired. As the surfactant, a nonionic, anionic, cationic or amphoteric surfactant can be used.

Examples of 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 esters of polyethylene oxide and glycerin. , Pentaerislit fatty acid ester, sorbit or sorbitan fatty acid ester, polyhydric alcohol alkyl ether, polyhydric alcohol type nonionic surfactant such as alkanolamine aliphatic amide and the like.

Examples of the anionic surfactant include carboxylates such as alkali metal salts of higher fatty acids; sulfate esters such as higher alcohol sulfates and higher alkyl ether sulfates, alkylbenzene sulfonates and alkyl sulfonates. Sulfates such as paraffin sulfonates; phosphate ester salts such as higher alcohol phosphates and the like can be mentioned.

Examples of the cationic surfactant include quaternary ammonium salts such as alkyltrimethylammonium salts.
Examples of the amphoteric tenside include amino acid-type amphoteric surfactants such as higher alkylaminopropionate, higher alkyldimethylbetaine, and betaine-type amphoteric surfactants such as higher alkyldihydroxyethylbetaine, which may be used alone or. Two or more types can be used in combination.
When the surfactant is blended, the blending amount is preferably 0.1 to 5 parts by mass, more preferably 0.3 to 4 parts by mass with respect to 100 parts by mass of the polycarbonate resin.

Further, the resin composition of the present invention may contain a polymer-type antistatic agent as long as the effects of the present invention are not impaired. As the polymer antistatic agent, for example, a known polymer type antistatic agent such as a polyether ester amide can be used, and as a known polyether ester amide, for example, JP-A-7-10989 can be used. Examples thereof include the polyether ester amides comprising the polyoxyalkylene adducts of Bisphenol A described above. Further, 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.
When the polymer type antistatic agent is blended, the blending amount is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the polycarbonate resin.

Furthermore, the resin composition of the present invention may contain a compatibilizer, if necessary, as long as the effects of the present invention are not impaired. By blending a compatibilizer, the compatibility between the antistatic component and other components or resin components can be improved. As the compatibilizer, 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, JP-A-3. Examples thereof include the polymer described in JP-A-258850, the modified vinyl polymer having a sulfonyl group described in JP-A-6-345927, and the block polymer having a polyolefin moiety and an aromatic vinyl polymer moiety. ..
When the compatibilizer is blended, the blending amount is preferably 0.01 to 5 parts by mass, more preferably 0.1 to 3 parts by mass with respect to 100 parts by mass of the polycarbonate resin.

Further, the resin composition of the present invention contains a phenol-based antioxidant, a phosphorus-based antioxidant, a thioether-based antioxidant, a hindered amine-based light stabilizer, an ultraviolet absorber, etc., as long as the effects of the present invention are not impaired. Various additives can be further added, whereby the resin composition of the present invention can be stabilized.

Examples of the phenolic antioxidant include 2,6-ditertiary butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, and distearyl (3,5-ditritiary butyl-4-4). Hydroxybenzyl) phosphonate, 1,6-hexamethylenebis [(3,5-ditritiarybutyl-4-hydroxyphenyl) propionic acid amide], 4,4'-thiobis (6-thibutyl-m-cresol) , 2,2'-Methylenebis (4-methyl-6-tertiary butylphenol), 2,2'-Methylenebis (4-ethyl-6-third butylphenol), 4,4'-butylidenebis (6-third butyl-) m-cresol), 2,2'-etylidenebis (4,6-ditriadibylphenol), 2,2'-ethylidenebis (4-second butyl-6-third butylphenol), 1,1,3- Tris (2-methyl-4-hydroxy-5-third butylphenyl) butane, 1,3,5-tris (2,6-dimethyl-3-hydroxy-4-third butylbenzyl) isocyanurate, 1,3 , 5-Tris (3,5-ditritiary butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-Tris (3,5-ditritiary butyl-4-hydroxybenzyl) -2,4,6 -Trimethylbenzene, 2-third butyl-4-methyl-6- (2-acryloyloxy-3-third butyl-5-methylbenzyl) phenol, stearyl (3,5-ditritiary butyl-4-hydroxyphenyl) ) Propionate, tetrakis [3- (3,5-ditertiary butyl-4-hydroxyphenyl) methyl propionate] methane, thiodiethylene glycolbis [(3,5-ditritiary butyl-4-hydroxyphenyl) propionate], 1,6-Hexamethylenebis [(3,5-dithiary butyl-4-hydroxyphenyl) propionate], bis [3,3-bis (4-hydroxy-3-third butylphenyl) butyric acid] glycol Ester, Bis [2-3rd butyl-4-methyl-6- (2-hydroxy-3-3rd butyl-5-methylbenzyl) phenyl] terephthalate, 1,3,5-tris [(3,5-di) Tertiary butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate, 3,9-bis [1,1-dimethyl-2-{(3-tertiary butyl-4-hydroxy-5-methylphenyl) propionyloxy} Ethyl] -2,4,8,10-tetraoxaspiro [5,5] unde Can, triethylene glycol bis [(3-tertiary butyl-4-hydroxy-5-methylphenyl) propionate] and the like can be mentioned. The amount of these phenolic antioxidants added is preferably 0.001 to 10 parts by mass, more preferably 0.05 to 5 parts by mass with respect to 100 parts by mass of the polycarbonate resin.

Examples of the phosphorus antioxidant include trisnonylphenyl phosphite and tris [2-third butyl-4- (3-third butyl-4-hydroxy-5-methylphenylthio) -5-methylphenyl] phos. Fight, Tridecylphosphite, Octyldiphenylphosphite, Di (decyl) monophenylphosphite, Di (tridecyl) pentaerythritol diphosphite, Di (nonylphenyl) pentaerythritol diphosphite, Bis (2,4-dith) Tributylphenyl) Pentaerythritol diphosphite, bis (2,6-ditrimeric butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,4,6-tritrithbutylphenyl) pentaerythritol diphos Fight, bis (2,4-dicumylphenyl) pentaerythritol diphosphite, tetra (tridecyl) isopropyridene diphenol diphosphite, tetra (tridecyl) -4,4'-n-butylidenebis (2-third butyl- 5-Methylphenol) diphosphite, hexa (tridecyl) -1,1,3-tris (2-methyl-4-hydroxy-5-third butylphenyl) butanetriphosphite, tetrakis (2,4-ditertiary butylphenyl) ) Biphenylenediphosphonite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2,2'-methylenebis (4,6-tertiary butylphenyl) -2-ethylhexylphosphite , 2,2'-Methylenebis (4,6-3rd Butylphenyl) -Octadecylphosphite, 2,2'-Echilidenebis (4,6-di3rd Butylphenyl) Fluorophosphite, Tris (2-[( 2,4,8,10-Tetrakiss tertiary butyldibenzo [d, f] [1,3,2] dioxaphosphepine-6-yl) oxy] ethyl) amine, 2-ethyl-2-butylpropylene glycol And 2,4,6-tritriary butylphenol phosphite and the like. The amount of these phosphorus-based antioxidants added is preferably 0.001 to 10 parts by mass, more preferably 0.05 to 5 parts by mass with respect to 100 parts by mass of the polycarbonate resin.

Examples of the thioether-based antioxidant include dialkylthiodipropionates such as dilauryl thiodipropionate, dimyristyl thiodipropionate, and distearyl thiodipropionate, and pentaerythritol tetra (β-alkylthiopropionic acid) esters. Kind is mentioned. The amount of these thioether-based antioxidants added is preferably 0.001 to 10 parts by mass, more preferably 0.05 to 5 parts by mass with respect to 100 parts by mass of the polycarbonate resin.

Examples of the hindered amine-based light stabilizer 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) Sevacate, Tetrakiss (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-piperidyl) di (tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) di (tridecyl) -1,2 , 3,4-Butanetetracarboxylate, Bis (1,2,2,4,4-pentamethyl-4-piperidyl) -2-butyl-2- (3,5-ditritiary butyl-4-hydroxybenzyl) Maronate, 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-piperidinol / diethyl polycondensate succinate, 1,6-bis (2,2,6,6-tetra Methyl-4-piperidylamino) hexane / 2,4-dichloro-6-morpholino-s-triazine polycondensate, 1,6-bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane / 2,4-Dichloro-6-3 octylamino-s-triazine polycondensate, 1,5,8,12-tetrakis [2,4-bis (N-butyl-N- (2,2,6,6) -Tetramethyl-4-piperidyl) amino) -s-triazine-6-yl] -1,5,8,12-tetraazadodecane, 1,5,8,12-tetrakis [2,4-bis (N-) Butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino) -s-triazine-6-yl] -1,5,8-12-tetraazadodecane, 1,6,11 -Tris [2,4-bis (N-butyl-N- (2,2,6,6-tetramethyl-4-piperidyl) amino) -s-triazine-6-yl] aminoundecane, 1,6,11 -Tris [2,4-bis (N-butyl-N- (1,2,2,6) , 6-Pentamethyl-4-piperidyl) amino) -s-triazine-6-yl] Amino undecane and other hindered amine compounds can be mentioned. The amount of these hindered amine-based light stabilizers added is preferably 0.001 to 30 parts by mass, more preferably 0.05 to 10 parts by mass with respect to 100 parts by mass of the polycarbonate 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'-ditertiary butylphenyl) -5-chlorobenzo Triazol, 2- (2'-hydroxy-3'-third butyl-5'-methylphenyl) -5-chlorobenzotriazol, 2- (2'-hydroxy-5'-third octyl) Phenyl) benzotriazol, 2- (2'-hydroxy-3', 5'-dicumylphenyl) benzotriazol, 2,2'-methylenebis (4-thioctyl-6- (benzotriazolyl) phenol ), 2- (2'-Hydroxyphenyl) benzotriazoles such as 2- (2'-hydroxy-3'-third butyl-5'-carboxyphenyl) benzotriazole; phenylsalicylate, resorcinol monobenzoate, 2,4 -Di-tertiary butyl phenyl-3,5-di-tertiary butyl-4-hydroxybenzoate, 2,4-di-three-amylphenyl-3,5-di-tertiary butyl-4-hydroxybenzoate, hexadecyl-3,5 -Phenylates such as di-tertiary butyl-4-hydroxybenzoate; substituted oxanilides such as 2-ethyl-2'-ethoxyoxide and 2-ethoxy-4'-dodecyloxanilide; ethyl-α-cyano- Cyano acrylates such as β, β-diphenyl acrylate, methyl-2-cyano-3-methyl-3- (p-methoxyphenyl) acrylate; 2- (2-hydroxy-4-octoxyphenyl) -4,6- Bis (2,4-ditertiary butylphenyl) -s-triazine, 2- (2-hydroxy-4-methoxyphenyl) -4,6-diphenyl-s-triazine, 2- (2-hydroxy-4-propoxy) Examples thereof include triaryltriazines such as -5-methylphenyl) -4,6-bis (2,4-ditertiary butylphenyl) -s-triazine. The amount of these ultraviolet absorbers added is preferably 0.001 to 30 parts by mass, more preferably 0.05 to 10 parts by mass with respect to 100 parts by mass of the polycarbonate resin.

Further, if necessary, it is preferable to add a known neutralizing agent in order to neutralize the residual catalyst in the synthetic resin. Examples of 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 may be mentioned, and these neutralizing agents may be mixed and used.

Furthermore, the resin composition of the present invention further comprises, if necessary, sodium-2,2'-methylenebis (4,6-di-tert-butylphenyl) phosphate, lithium-2,2'-methylenebis (4). , 6-di-tert-butylphenyl) phosphate, aluminum hydroxybis [2,2'methylenebis (4,6-di-tert-butylphenyl) phosphate], sodium benzoate, 4-tert-butyl benzoate aluminum salt, Sodium adipate and carboxylic acid metal salts such as 2-sodium bicyclo [2.2.1] heptane-2,3-dicarboxylate, dibenzylene sorbitol, bis (methylbenzylene) sorbitol, bis (3,4-dimethylbenzylene) Polyol derivatives such as sorbitol, bis (p-ethylbenzylene) sorbitol, and bis (dimethylbenzylene) sorbitol, N, N', N "-tris [2-methylcyclohexyl] -1,2,3-propanetricarboxamide, N , N', N "-tricyclohexyl-1,3,5-benzenetricarboxamide, N, N'-dicyclohexylnaphthalenedicarboxamide, amide compounds such as 1,3,5-tri (dimethylisopropoilamino) benzene, etc. May be blended with a nucleating agent such as aromatic carboxylic acid metal salt, alicyclic alkyl carboxylic acid metal salt, p-tertiary butyl benzoate metal salt, aromatic phosphate metal salt, dibenzylene sorbitol and the like. ..

Furthermore, the resin composition of the present invention further contains, if necessary, a metal soap, a triazine ring-containing compound, a metal hydroxide, a phosphoric acid ester-based flame retardant, a condensed phosphoric acid ester-based flame retardant, and a phosphate-based flame retardant. , Inorganic phosphorus-based flame retardant, (poly) phosphate-based flame retardant, silicon-based flame retardant, filler, pigment, lubricant, foaming agent and the like may be added.

Examples of triazine ring-containing compounds include melamine, ammeline, benzguanamine, acetoguanamine, phthalodiguanamine, melamine cyanurate, melamine pyrophosphate, butyreneguanamine, norbornenediguanamine, methylenediguanamine, ethylenedimelamine, trimethylenedi. Examples thereof include melamine, tetramethylene dimelamine, hexamethylene dimelamine, 1,3-hexylene melamine and the like.
Examples of the metal hydroxide 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 phosphoric acid ester flame retardants 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.

Examples of the condensed phosphoric acid ester flame retardant 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-based flame retardant include ammonium salts and amine salts of (poly) phosphate such as ammonium polyphosphate, melamine polyphosphate, piperazine polyphosphate, melamine pyrophosphate, and piperazine pyrophosphate.

If necessary, the resin composition of the present invention includes additives usually used for synthetic resins, such as cross-linking agents, anti-fog agents, anti-plate-out agents, surface treatment agents, plasticizers, lubricants, and fluorescent agents. Antifungal agents, bactericidal agents, foaming agents, metal deactivators, mold release agents, pigments, dyes, processing aids, fillers, foaming agents and the like can be blended within a range that does not impair the effects of the present invention.

Further, the resin composition of the present invention may contain a synthetic resin other than the polycarbonate resin as long as the effects of the present invention are not impaired.
Examples of synthetic resins other than the polycarbonate resin include thermoplastic resins such as polypropylene, high density polyethylene, low density polyethylene, linear low density polyethylene, crosslinked polyethylene, ultrahigh molecular weight polyethylene, polybutene-1, Α-olefin polymers such as poly-3-methylpentene and poly-4-methylpentene or polyolefin resins such as ethylene-vinyl acetate copolymers and ethylene-propylene copolymers and copolymers thereof; polyvinyl chloride , Polyvinylidene chloride, chlorinated polyethylene, chlorinated polypropylene, polyvinylidene fluoride, rubber chloride, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-chloride Halogen-containing resins such as vinylidene-vinyl acetate ternary copolymer, vinyl chloride-acrylic acid ester copolymer, vinyl chloride-maleic acid ester copolymer, vinyl chloride-cyclohexylmaleimide copolymer; petroleum resin, kumaron resin, Co-production of acrylic resins such as polystyrene, polyvinyl acetate, polymethylmethacrylate, styrene and / or α-methylstyrene with other monomers (eg, maleic anhydride, phenylmaleimide, methyl methacrylate, butadiene, acrylonitrile, etc.) Polymers (eg, AS resin, ABS (acrylonitrile butadiene styrene copolymer) resin, ACS resin, SBS resin, MBS resin, heat resistant ABS resin, etc.); polyvinyl alcohol, polyvinylformal, polyvinylbutyral; polyethylene terephthalate, polybutylene terephthalate, Aromatic polyesters such as polyalkylene terephthalates such as polycyclohexanedimethylene terephthalate, polyalkylene naphthalates such as polyethylene naphthalate and polybutylene naphthalate, and linear polyesters such as polytetramethylene terephthalate; polyhydroxybutyrate, polycaprolactone, poly. Degradable aliphatic polyesters such as butylene succinate, polyethylene succinate, polylactic acid, polyapple acid, polyglycolic acid, polydioxane, poly (2-oxetanone); polyamides such as polyphenylene oxide, polycaprolactam and polyhexamethylene adipamide. , Polyacetal, Polyphenylene sulfide, Polyurethane, Fiber element resin, Polymer resin, Polysulfone, Polyphenylene ether, Po Examples thereof include thermoplastic resins such as etherketones, polyetheretherketones, and liquid crystal polymers, and blends thereof. The thermoplastic resin includes isoprene rubber, butadiene rubber, acrylonitrile-butadiene copolymer rubber, styrene-butadiene copolymer rubber, fluororubber, silicone rubber, polyolefin-based thermoplastic elastomer, styrene-based thermoplastic elastomer, and polyester-based thermoplastic elastomer. , A nitrile-based thermoplastic elastomer, a nylon-based thermoplastic elastomer, a vinyl chloride-based thermoplastic elastomer, a polyamide-based thermoplastic elastomer, a polyurethane-based thermoplastic elastomer, or the like may be used. These thermoplastic resins may be used alone or in combination of two or more. Further, the thermoplastic resin may be alloyed.

The method for producing the resin composition of the present invention is not particularly limited, and the polymer compound (E),, if necessary, one or more of an alkali metal salt and an ionic liquid, and other optional components may be added to the polycarbonate resin. As the method may be used, any commonly used method can be used. For example, it may be mixed and kneaded by a roll kneading, a bumper kneading, an extruder, a kneader or the like.

Further, the polymer compound (E) may be added 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. As such 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 above-mentioned flame retardant agents and antioxidants, and the like. Among these carriers, the one in which the surface of the carrier is chemically modified is preferable, and the one in which the surface of the silica powder is chemically modified is more preferable. These carriers preferably have an average particle size of 0.1 to 100 μm, more preferably 0.5 to 50 μm.

Further, as a method of blending the polymer compound (E) into the polycarbonate resin, the polymer compound (E) is kneaded with the block polymer (C) and the epoxy compound (D) having two or more epoxy groups at the same time as the polycarbonate resin. 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 a polymer compound (high molecular weight compound (during injection molding or the like) may be kneaded at the same time. E) may be blended by a method of mixing a thermoplastic resin 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. Further, a master batch of the polymer compound (E) and the polycarbonate resin may be produced in advance, and this master batch may be blended, at which time the master batch is selected from the group of alkali metal salts and ionic liquids. One or more may be blended.

Next, the molded product of the present invention will be described.
By molding the resin composition of the present invention, it is possible to obtain a molded product having excellent antistatic properties and durability thereof and excellent transparency. 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 from the resin composition of the present invention is a molded product that does not easily generate static electricity and does not easily cause a decrease in commercial value due to surface contamination due to static electricity or adhesion of dust. In addition, the molded product obtained from the resin composition of the present invention has excellent antistatic properties and durability thereof, and has excellent transparency.

Among the molded products obtained from the resin composition of the present invention, the film is particularly preferable because it has excellent antistatic properties and durability thereof, and has excellent 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 cause a decrease in 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 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. Can be used in a wide range of industrial fields such as building materials, civil engineering, furniture, printing, and musical instruments.

More specifically, 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, household appliances such as kotatsu, TVs, VTRs, video cameras, radio cassette recorders. , Tape recorders, mini discs, CD players, speakers, AV equipment such as liquid crystal displays, connectors, relays, condensers, switches, printed boards, coil bobbins, semiconductor encapsulation materials, LED encapsulation materials, electric wires, cables, transformers, deflection yokes. , Distribution boards, electric / electronic parts such as watches and communication equipment, interior / exterior materials for automobiles, electric parts containers, electronic parts containers, plate-making films, adhesive films, bottles, food containers, food packaging films, pharmaceuticals / Pharmaceutical wrapping film, product packaging film, agricultural film, agricultural sheet, greenhouse film, electronic component packaging film, electrical component packaging film, electronic device packaging film, electrical product packaging film, precision component packaging film , Used for applications such as packaging films for precision equipment.

Further, the resin composition of the present invention and a molded body 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. , Airbag, Insulation material, Hanging hand, Hanging hand band, Wire covering material, Electrical insulation material, Paint, Coating material, Overlaying material, Floor material, Corner wall, Carpet, Wallpaper, Wall covering material, Exterior material, Interior material , Roofing materials, deck materials, wall materials, pillar materials, floorboards, fence materials, skeletons and plywood, windows and door profiles, shavings, siding, terraces, balconies, soundproofing boards, heat insulating boards, windowing materials, etc. Cars, vehicles, ships, aircraft, buildings, housing and building materials and civil engineering materials, clothing, curtains, sheets, non-woven fabrics, plywood, synthetic fiber boards, rugs, entrance mats, sheets, buckets, hoses, containers, glasses, bags, cases. , Goggles, ski boards, rackets, tents, daily necessities such as musical instruments, sporting goods, etc.

Among these, the resin composition of the present invention and the film using the same are: electronic parts packaging film, electric parts packaging film, electronic equipment packaging film, electric product packaging film, precision parts packaging film, precision equipment. It is preferably used for packaging films and the like.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto. In the following examples and the like, "%", "ppm" and "part" are based on mass unless otherwise specified.

The polymer compound (E) used in the present invention was produced according to the following production example. In the following production example, the number average molecular weight of the compound (b) is calculated by the following <method for calculating the number average molecular weight from the hydroxyl value>, and the number average molecular weights other than the compound (b) are calculated by the following <polystyrene conversion]. It was calculated by the method for measuring the number average molecular weight according to>.

<Calculation method of number average molecular weight from hydroxyl value>
The hydroxyl value was measured by the following method for measuring the hydroxyl value, and the number average molecular weight was determined by the following formula.
Number average molecular weight = (56110 × 2) / hydroxyl value

<Measurement method of hydroxyl value>
・ Reagent A (acetylating agent)
(1) 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.

First, weigh 2 g of a sample into a 200 mL Erlenmeyer flask, add 10 mL of triethyl phosphate, and heat to dissolve. Add 15 mL of Reagent A, plug and shake vigorously. Add 20 mL of Reagent B, plug and shake vigorously. Add 50 mL of Reagent C. Titrate with 1N-KOH aqueous solution and calculate by the following formula.

Hydroxy group value [mgKOH / g] = 56.11 × f × (TB) / S
factor of 1N-KOH aqueous solution
B: Empty test titration [mL]
T: Quantitative test titration [mL]
S: Sample amount [g]

<Measurement method of number average molecular weight by polystyrene conversion>
The number average molecular weight was measured by gel permeation chromatography (GPC) method. The measurement conditions for Mn are as follows.
Equipment: GPC equipment manufactured by JASCO Corporation Solvent: Chloroform standard substance: Polystyrene detector: Differential refractometer (RI detector)
Column stationary phase: Showa Denko Corporation Shodex LF-804
Column temperature: 40 ° C
Sample concentration: 1 mg / 1 mL
Flow rate: 0.8 mL / min.
Injection volume: 100 μL

[Manufacturing Example 1]
In a separable flask, 656 g of 1,4-cyclohexanedimethanol, 708 g of adipic acid, 0.7 g of phthalic anhydride, and an antioxidant (tetrakis [3- (3,5-dithiary butyl-4-hydroxyphenyl)] ) Propionyloxymethyl] Methane, ADEKA STAB AO-60, manufactured by ADEKA Co., Ltd.) was charged in 0.7 g, and the temperature was gradually increased from 160 ° C to 210 ° C for 4 hours at normal pressure, then 210 ° C under reduced pressure for 3 hours. Time polymerization was performed to obtain polyester (a) -1. The number average molecular weight Mn of the obtained polyester (a) -1 was 5,400.

Next, 600 g of the obtained polyester (a) -1, a number average molecular weight of 4000 as the compound (b) -1 having hydroxyl groups at both ends, and 300 g of polyethylene glycol having the number of repeating units of ethyleneoxy groups = 80, A block polymer (C) having a structure having a carboxyl group at both ends is charged with 0.5 g of an antioxidant (Adecastab AO-60) and 0.8 g of zirconium octylate and polymerized at 210 ° C. for 7 hours under reduced pressure. ) -1 was obtained. The number average molecular weight Mn of the block polymer (C) -1 having a structure having a carboxyl group at both ends was 12,000.
To 360 g of the obtained block polymer (C) -1 having a structure having carboxyl groups at both ends, 6 g of bisphenol F diglycidyl ether (epoxy equivalent 170 g / eq) as the epoxy compound (D) -1 was charged and 240. Polymerization at ° C. for 3 hours under reduced pressure gave the polymer compound (E) -1 used in the resin composition of the present invention.

<Examples 1 to 11 and Comparative Examples 1 to 6>
Using the resin compositions of Examples and Comparative Examples prepared based on the blending amounts (parts by mass) shown in Tables 1 to 3 below, a test film was obtained according to the method for producing a test film shown below. rice field. Using the obtained test film, the surface resistivity (SR value), Haze value, and total light transmittance were measured and evaluated according to the following measurement methods. The results are shown in Tables 1 to 3.

<Method for producing test film for resin composition>
Each resin composition was granulated using a single-screw extruder (D1220B) manufactured by Toyo Seiki Seisakusho Co., Ltd. at 280 ° C. and 1 kg / hour to obtain pellets. Using the obtained pellets, a cast film for testing with a thickness of 50 μm, 100 μm, and 200 μm was used in a T-die cast film forming machine (extruder: single-screw D1220B; T-die: MT60B) manufactured by Toyo Seiki Seisakusho Co., Ltd. Was produced.

<Measurement of surface resistivity (SR value)>
Immediately after molding, the obtained test film was stored under the conditions of temperature 25 ° C. and humidity 50% RH, and after 1 day and 30 days storage of molding processing, under the same atmosphere, Mitsubishi Chemical Analytical Co., Ltd. The surface resistivity (Ω / □) was measured using a high-restor-UX (MCP-HT800) resistance meter manufactured by Tech under the conditions of an applied voltage of 500 V and an applied time of 1 minute. The measurement was performed on 5 test films at 5 points per film, and the average value was calculated.

<Measurement of Haze value>
The Haze value of the test film was measured according to ISO14782.
<Measurement of total light transmittance>
The total light transmittance of the test film was measured according to ISO 14782.

* 1: Polycarbonate resin, melt volume flow rate = 14 cm ^3/10 min (ISO1133, 300 ° C x 1.2 kg)
* 2: Sodium dodecylbenzene sulfonate * 3: Polyether ester amide antistatic agent (manufactured by BASF, trade name Irgastat P-18)

* 1: Polycarbonate resin, melt volume flow rate = 14 cm ^3/10 min (ISO1133, 300 ° C x 1.2 kg)
* 2: Sodium dodecylbenzene sulfonate * 3: Polyether ester amide antistatic agent (manufactured by BASF, trade name Irgastat P-18)

* 1: Polycarbonate resin, melt volume flow rate = 14 cm ^3/10 min (ISO1133, 300 ° C x 1.2 kg)
* 2: Sodium dodecylbenzene sulfonate * 3: Polyether ester amide antistatic agent (manufactured by BASF, trade name Irgasstat P-18)
From the above, it is clear that the resin composition of the present invention can provide a molded product having excellent antistatic properties, durability thereof, and transparency. Especially suitable for films.

Claims (8)

An epoxide-resistant polycarbonate resin composition containing 3 to 40 parts by mass of one or more polymer compounds (E) with respect to 100 parts by mass of the polycarbonate resin, wherein the polymer compound (E) is a diol (a1). ) And the polyester (a) obtained by the reaction of the dicarboxylic acid (a2), the compound (b) having one or more ethyleneoxy groups and having hydroxyl groups at both ends, and the epoxy compound (D) having two or more epoxy groups. An epoxide-resistant polycarbonate resin composition which is a polymer compound obtained by the reaction of and. The polymer compound (E) has a polyester block (A) composed of the polyester (a) and a polyether block (B) composed of the compound (b), and the polyester. Formed by the reaction of the hydroxyl group or carboxyl group at the end of (a), the hydroxyl group at the end of the compound (b), and the epoxy group or the hydroxyl group formed by the reaction of the epoxy group of the epoxy compound (D). The antistatic polycarbonate resin composition according to claim 1, which has a structure formed by bonding via an ester bond or an ether bond. The block polymer (C) having a carboxyl group at both ends is formed by repeatedly and alternately bonding the polymer compound (E) to the polyester block (A) and the polyether block (B) via an ester bond. The antistatic polycarbonate resin composition according to claim 1 or 2, which has a structure in which the epoxy compound (D) is bonded to the epoxy compound (D) via an ester bond. The antistatic polycarbonate resin composition according to any one of claims 1 to 3, wherein the polyester (a) constituting the polymer compound (E) has a structure having carboxyl groups at both ends. The antistatic polycarbonate resin composition according to any one of claims 1 to 4, wherein the compound (b) constituting the polymer compound (E) is polyethylene glycol. The antistatic polycarbonate resin according to any one of claims 1 to 5, further comprising 0.01 to 8 parts by mass of one or more selected from the group consisting of alkali metal salts and ionic liquids. Composition. A molded product obtained from the antistatic polycarbonate resin composition according to any one of claims 1 to 6. The molded product according to claim 7, which is a film.