JP2002285017A - Resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition excellent in a permanent antistatic effect, mechanical strengths and moldability. SOLUTION: This resin composition consists of a thermoplastic resin (A) having an ester linkage and polyetheresteramide (B) and contains an acidic phosphoric ester (C) and a salt (D) of an alkali metal and/or an alkaline earth metal wherein the weight ratio of (C)/(D) is 1-50 and the total weight of (C) and (D) is 0.001-5.0 wt.% of the total weight of the thermoplastic resins.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a resin composition. More specifically, the present invention relates to a thermoplastic resin composition useful as a molding material for various plastic molded articles and the like.

[0002]

2. Description of the Related Art Heretofore, as a method for imparting permanent antistatic properties to a thermoplastic resin having an ester bond, a method of adding a polyetheresteramide has been known. However, this method causes a reduction in the molecular weight of the thermoplastic resin and the polyetheresteramide due to the interaction between the polyetheresteramide and the thermoplastic resin having an ester bond. There was a problem. To solve this problem, a method of blending and adding a phosphite compound and / or a phenol compound to a polycarbonate resin has been proposed, but a sufficient effect has not been obtained. (JP-A-5-437
No. 87)

[0003]

An object of the present invention is to provide a thermoplastic resin composition having permanent antistatic properties and having an ester bond having excellent mechanical strength.

[0004]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above problems, and as a result, have found that a resin composition comprising a thermoplastic resin (A) having an ester bond and a polyetheresteramide (B). The acid phosphate (C) and the salt of an alkali metal and / or an alkaline earth metal (D) have a weight ratio of (C) / (D) of 1
And a resin composition characterized in that it is contained in an amount of 0.001 to 5% by weight based on the total weight of the thermoplastic resin. The molded article and the molded article thereof were found to have permanent antistatic properties and excellent mechanical strength, and reached the present invention.

The polyetheresteramide (B) includes at least one selected from the group consisting of the following i) to iv). i) at least one component selected from the group consisting of a polyamide-forming monomer and a polyamide, at least one component selected from the group consisting of a polyester-forming monomer and a polyester, and, if necessary, a group consisting of a diol and a diamine; A polyetheresteramide obtained by reacting at least one selected component; ii) reacting at least one component selected from the group consisting of a polyamide-forming monomer and a carboxyl group-containing polyamide with a diol. Iii) a polyetheresteramide obtained by reacting a component comprising a carboxyl group-containing polyester with a diamine; and iv) a dicarboxylic acid, an ester-forming derivative thereof, a lactone and a hydrocarbyl group. Polyetheresteramide a component and a diol and a diamine obtained by reacting selected from the group consisting of Shikarubon acid.

[0006] As the polyester-forming monomer, at least one selected from the group consisting of the following (1) to (3):
Seeds can be used. (1) Carbonic acid or dicarboxylic acid and / or its ester-forming derivative, and diol (2) lactone (3) hydroxycarboxylic acid

The dicarboxylic acids include, for example, those having 2 carbon atoms.
~ 48 dicarboxylic acids can be used, including aliphatic dicarboxylic acids, aromatic dicarboxylic acids and alicyclic dicarboxylic acids.

The aliphatic dicarboxylic acids include saturated aliphatic dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, methylsuccinic acid, dimethylmalonic acid,
β-methylglutaric acid, ethylsuccinic acid, isopropylmalonic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, decandic acid, undecandioic acid,
Examples thereof include dodecandioic acid, tridecandioic acid, tetradecandioic acid, hexadecandioic acid, octadecandioic acid, and icosandioic acid, and unsaturated aliphatic dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, and mesaconic acid.

Examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, phthalic acid, tetrabromophthalic acid, methyl isophthalic acid, phenylmalonic acid, homophthalic acid, phenylsuccinic acid, β-phenylglutaric acid, α-phenyl Adipic acid, β-phenyladipic acid, biphenyl-2,2′-dicarboxylic acid, biphenyl-4,4′-dicarboxylic acid, naphthalenedicarboxylic acid,
Examples thereof include sodium 5-sulfoisophthalate and potassium 5-sulfoisophthalate.

As the alicyclic dicarboxylic acid, for example,
1,3-cyclopentanedicarboxylic acid, 1,2-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3
-Cyclohexanedicarboxylic acid, 1,4-cyclohexanediacetic acid, 1,3-cyclohexanediacetic acid, 1,2-cyclohexanediacetic acid, dicyclohexyl-4,4-dicarboxylic acid and the like. In addition, dimer acids [fatty acids (8 to 24 carbon atoms such as oleic acid, linoleic acid,
Dimer of linolenic acid)].

The ester-forming derivatives include esters of dicarboxylic acids, acid anhydrides and acid halides. Examples thereof include dialkyl (C1-4) esters of carbonic acid and the above-mentioned dicarboxylic acids (dimethyl ester, diethyl ester, dibutyl ester) and diphenyl esters, and acid anhydrides (phthalic anhydride and the like).

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

As the glycol, aliphatic glycols having 2 to 20 carbon atoms, alicyclic glycols having 5 to 12 carbon atoms, and araliphatic glycols having 8 to 26 carbon atoms can be used.

As the aliphatic glycol, alkylene glycols such as ethylene glycol, 1,2-propylene glycol, 1,2-butanediol, 1,3-
Butanediol, 1,4-butanediol, 1,3-hexanediol, 1,4-hexanediol, 1,6-
Hexanediol, 2,5-hexanediol, 1,2
-Octanediol, 1,8-octanediol, 1,
10-decanediol, 1,18-octadecanediol, and 1,20-eicosanediol; and di (thio) alkylene glycols such as diethylene glycol, thiodiethylene glycol and the like.

As the alicyclic glycol, a cycloalkylene glycol such as 1-hydroxymethyl-1-
Cyclobutanol, 1,2-cyclohexanediol,
1,3-cyclohexanediol, 1,4-cyclohexanediol, 1-methyl-3,4-cyclohexanediol, 2-hydroxymethylcyclohexanol,
-Hydroxymethylcyclohexanol, 1,4-cyclohexanedimethanol, and bicycloalkylene glycols such as 1,1'-dihydroxy-1,1'-
Dicyclohexylmethane and the like.

As the araliphatic glycol, for example,
1,4-dihydroxymethylbenzene, 2-phenyl-1,3-propanediol, 2-phenyl-1,4-butanediol, 2-benzyl-1,3-propanediol,
Triphenylethylene glycol, tetraphenylethylene glycol, benzopinacol and the like.

As the dihydric phenol, C6 to C30 is used.
Can be used. Specifically, monocyclic dihydric phenols, for example, catechol, resorcinol, hydroquinone; condensed ring dihydric phenols, for example, dihydroxynaphthalene; bisphenols, for example, bisphenol A, bisphenol F, bisphenol S, dihydroxydiphenyl ether, dihydroxydiphenylthioether; And binaphthol; and their alkyl (C1-10) or halogen (chlorine, bromine, etc.)
Substitutes (eg, brominated bisphenol A) and the like.

As the polyoxyalkylene diol,
Compounds having a structure in which an alkylene oxide (hereinafter referred to as AO) is added to a compound containing two active hydrogen atoms, for example, glycol, amine, dicarboxylic acid, dihydric phenol or the like (AO addition mole number; usually 2 to 100 moles) ) As well as mixtures of two or more of these. As AO, AO having 2 to 30 (preferably 2 to 4) carbon atoms, for example, ethylene oxide (EO), propylene oxide (PO), 1,2-, 2,3- and 1,3-butylene oxide, tetrahydrofuran (THF), styrene oxide, α-olefin oxide having 5 to 30 carbon atoms, epichlorohydrin and the like. AO,
A single type may be used alone or two or more types may be used in combination. In the latter case, block addition (chip type, balance type, active secondary type, etc.), random addition, or a mixed system thereof may be used.

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

The amine includes an aliphatic or aromatic primary monoamine having 1 to 20 carbon atoms, an aliphatic 2 monoamine having 4 to 18 carbon atoms.
Primary diamines, heterocyclic primary (or secondary di) amines having 4 to 13 carbon atoms, alicyclic secondary polyamines having 6 to 14 carbon atoms,
And an aromatic secondary diamine having 8 to 14 carbon atoms can be used.

Examples of the aliphatic or aromatic primary monoamine include alkyl or alkenyl amines, for example, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, s-butylamine,
Isobutylamine, n-amylamine, isoamylamine, n-hexylamine, n-heptylamine, n-octylamine, n-decylamine, n-octadecylamine, n-icosylamine and oleylamine; arylamines such as aniline and toluidine; , N '
-Dialkyl (C 1-4) aminoalkyl (C 2-10) amines, such as dimethylaminoethylamine.

As the aliphatic secondary diamine, N, N'-
Dialkyl (C1-4) alkylene (C2-1
0) Diamines, for example, N, N'-dimethylethylenediamine, N, N'-diethylethylenediamine, N, N
N′-dibutylethylenediamine, N, N′-dimethylpropylenediamine, N, N′-diethylpropylenediamine, N, N′-dibutylpropylenediamine,
N, N'-dimethyltetramethylenediamine, N, N '
-Diethyltetramethylenediamine, N, N'-dibutyltetramethylenediamine, N, N'-dimethylhexamethylenediamine, N, N'-diethylhexamethylenediamine, N, N'-dibutylhexamethylenediamine, N, N ' Dimethyldecamethylenediamine, N,
N'-diethyldecamethylenediamine and N, N'-dibutyldecamethylenediamine are exemplified.

The heterocyclic primary (or secondary di) amine includes, for example, piperazine, 1-aminopiperidine, 1
-Amino homopiperidine, 2-aminothiazole, 2-
Aminobenzothiazole, 3-aminotriazine, 3-
Examples thereof include amino-9-methylcarbazole, 9-aminofluorene, and alkyl (1 to 10 carbon atoms) or halogen-substituted products thereof.

As the alicyclic secondary diamine, for example,
N, N′-dimethyl-1,2-cyclobutanediamine,
N, N′-diethyl-1,2-cyclobutanediamine,
N, N′-dibutyl-1,2-cyclobutanediamine,
N, N′-dimethyl-1,4-cyclohexanediamine, N, N′-diethyl-1,4-cyclohexanediamine, N, N′-dibutyl-1,4-cyclohexanediamine, N, N′-dimethyl-1 , 3-Cyclohexanediamine, N, N'-diethyl-1,3-cyclohexanediamine, N, N'-dibutyl-1,3-cyclohexanediamine and alkyls thereof (1 to 10 carbon atoms)
Or a halogen-substituted product.

As the aromatic secondary diamine, for example,
N, N'-dimethyl-phenylenediamine, N, N'-
Dimethyl-xylylenediamine, N, N'-dimethyl-
Examples include diphenylmethanediamine, N, N′-dimethyl-diphenyletherdiamine, N, N′-dimethyl-benzidine and N, N′-dimethyl-1,4-naphthalenediamine.

As the lactone, a lactone having 4 to 20 carbon atoms can be used, for example, γ-butyrolactone, γ-valerolactone, δ-valerolactone, ε-caprolactone, γ-pimelolactone, γ-caprylolactone, γ-caprolactone.
Decanolactone, enantholactone, laurolactone,
Undecanolactone, eicosanolactone and the like.

The hydroxycarboxylic acid includes 2 carbon atoms.
-20 hydroxycarboxylic acids, such as hydroxyacetic acid, lactic acid, ω-hydroxycaproic acid, ω-
Hydroxyenanthate, ω-hydroxycaprylic acid, ω
-Hydroxypergonic acid, ω-hydroxycapric acid,
Examples include 11-hydroxyundecanoic acid, 12-hydroxydodecanoic acid, and 20-hydroxyeicosanoic acid.

The polyester is prepared by using the above-mentioned polyester-forming monomer and a known polyester-forming method [a method of reacting a diol with a dicarboxylic acid or its ester-forming derivative or a dicarboxylic anhydride and AO, a lactone using a diol or a dicarboxylic acid as an initiator. Alternatively, it can be produced by a method of reacting a hydroxycarboxylic acid or a method combining these. For example, the method described in JP-B-58-19696 can be mentioned.
Further, the polyester includes a carboxyl group-containing polyester and a hydroxyl group-containing polyester.

As the polyamide-forming monomer, at least one selected from the group consisting of the following (1) to (3) can be used. (1) Aminocarboxylic acid (2) Lactam (3) Nylon salt obtained from diamine and dicarboxylic acid

As the aminocarboxylic acid, a compound having 2 to 2 carbon atoms is used.
0 aminocarboxylic acids can be used, for example, glycine,
Alanine, ω-aminocaproic acid, ω-aminoenanthic acid, ω-aminocaprylic acid, ω-aminopergonic acid, ω
-Aminocapric acid, 11-aminoundecanoic acid, 12
-Aminododecanoic acid and 20-aminoeicosanoic acid.

As the lactam, a lactam having 4 to 20 carbon atoms can be used. For example, γ-butyrolactam, γ-valerolactam, ε-caprolactam, γ-pimelolactam, γ-capryloractam, γ-decanolactam, enantholactam, Laurolactam, undecanolactam,
Eicosanolactam and 5-phenyl-2-piperidone.

As the diamine, a diamine having 2 to 20 carbon atoms can be used, and includes aliphatic, alicyclic, and aromatic diamines. For example, ethylenediamine, tetramethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, decamethylenediamine, eicosandiamine, xylylenediamine, cyclohexyldiamine and the like can be mentioned.

As the dicarboxylic acid, those described above can be used. Nylon salts obtained from diamine and dicarboxylic acid include nylon salts of ethylenediamine and adipic acid, nylon salts of tetramethylenediamine and adipic acid, nylon salts of hexamethylenediamine and adipic acid, nylon salts of xylylenediamine and adipic acid, Nylon salt of decamethylenediamine and adipic acid, nylon salt of hexamethylenediamine and decandioic acid, nylon salt of xylylenediamine and decandioic acid, nylon salt of hexamethylenediamine and dodecanediacid, and hexamethylenediamine and 1,4-cyclohexanedicarboxylic acid Nylon salts of acids.

Examples of the polyamide include those obtained by subjecting a polyamide-forming monomer to ring-opening polymerization or dehydration polycondensation by a known method. Polyamide includes
Carboxyl group-containing polyamides and amino group-containing polyamides are included. Specific examples of polyamide include nylon 6,6, nylon 6,9, nylon 6,12, nylon 6, nylon 11, nylon 12, nylon 4,
6, alone or 2 such as a copolymer of nylon 6 and nylon 6,6, a copolymer of nylon 6 and nylon 12, and a copolymer of nylon 6 and nylon 6,6 and nylon 12.
More than one kind, copolymers of these with diamines and / or dicarboxylic acids can be mentioned.

As the carboxyl group-containing polyamide,
Those obtained by adding a dicarboxylic acid as a molecular weight modifier to a polyamide-forming monomer and subjecting it to ring-opening polymerization or polycondensation, and those obtained by depolymerizing a polyamide by adding a dicarboxylic acid as a molecular weight modifier to the polyamide can be used.

The carboxyl group-containing polyamide can be easily produced by a known method. In the former case, for example, the method described in Japanese Patent Publication No. 4-72855, and in the latter case, for example, the Japanese Patent Publication No. It can be manufactured by the method described in JP-A-91526 and the like.

Preferred among the above polyetheresteramides (B) are the polyetheresteramides belonging to the group ii) and having a number average molecular weight (hereinafter referred to as Mn).
It is written. ) Having a carboxyl group-containing polyamide (b1) of 200 to 5,000 and a polyhydric phenol having an Mn of 300 to 5,000 (B2) and / or a polyoxyalkylene glycol (b3). Ether ester amides, particularly preferred are polyether ester amides derived from (b1) and an EO adduct of a dihydric phenol having a Mn of 300 to 5,000. The above and below number average molecular weights (M
n) and the weight average molecular weight (Mw) are values determined by gel permeation chromatography (GPC) using polystyrene as a standard.

The polyetheresteramide (B) can be easily produced from the above-mentioned components (i) to (iv) by a known polyesterification reaction, polyamide reaction, or amide-ester exchange reaction. The temperature for these reactions is usually between 200 and 280 ° C. Generally, the polyesterification and the transamidation reaction are carried out in the presence of an inert gas or under reduced pressure. Polyamidation is carried out under normal pressure to pressurized conditions in the presence of an inert gas. Specifically, it can be manufactured by the method described in Japanese Patent Publication No. 4-72855.

In the above-mentioned polyamide conversion reaction, a known esterification catalyst is usually used. Examples of the catalyst include antimony-based catalysts such as antimony trioxide; tin-based catalysts such as monobutyltin oxide; titanium-based catalysts such as tetrabutyltitanate; tetraalkyl zirconates (eg, tetrabutyl zirconate and the like); zirconium organic acid salts (For example, zirconyl acetate and the like); a metal acetate catalyst such as zinc acetate; and a combination of two or more thereof. Of these, preferred are zirconium-based catalysts and metal acetate-based catalysts, and particularly preferred is zirconyl acetate. The amount of catalyst used is usually 0.1 to 5% by weight based on the total weight of the reactants.

The reduced viscosity of (B) (η _{SP /} C, C = 0.5
The weight% m-cresol solution, 25 ° C .; the same applies hereinafter) is not particularly limited, but is preferably 0.5 or more from the viewpoint of heat resistance and 4.0 or less from the viewpoint of moldability. More preferably, it is 0.6 to 3.0.

In the present invention, examples of the thermoplastic resin (A) having an ester bond include a thermoplastic polyester resin (A1), a polycarbonate resin (A2), a polyester-based thermoplastic polyurethane resin (A3), and an ester group-containing vinyl monomer. (A) polymer (A4).

(A1) includes condensed polyesters and polylactones. As the condensation polyester,
For example, the above-mentioned dicarboxylic acids or their ester-forming derivative components and the above-mentioned diol components (of these, polyoxyalkylenediols have a degree of polymerization of 1 to 10)
And condensates of the above-mentioned hydroxycarboxylic acids. Examples of the polylactone include a ring-opened polymer of the above-described lactone using the above-mentioned diol or dicarboxylic acid as an initiator. Further, these (A1) include a branched component, for example, a trivalent or tetravalent carboxylic acid such as tricarballylic acid, trimesic acid, trimellitic acid, and pyromellitic acid, and / or glycerin, trimethylolpropane, pentaerythritol and the like. The polyhydric (tri- or tetrahydric) alcohol may be copolymerized in a small amount, for example, 1 mol% or less, more preferably 0.5 mol%, as long as the thermoplasticity is not impaired. Specifically, polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate, poly (cyclohexane-1,4-dimethylene) terephthalate, cyclohexane dimethanol / ethylene glycol / terephthalic acid copolymer, polyneopenthylene terephthalate Polybutylene adipate, polyethylene adipate, poly-ε-caprolactone and the like can be mentioned. Preferred among the above are polybutylene terephthalate and cyclohexanedimethanol / ethylene glycol / terephthalic acid copolymer.

(A2) includes a polymer having a structural unit represented by the general formula (6), for example, a polymer having a structure derived from dihydric phenol and phosgene or a derivative thereof.

Embedded image (Wherein, R ₅ and R ₆ are each H, Cl, Br or an alkyl group having 1 to 8 carbon atoms, which may be the same or different, and s and t are each 1 to
When s is 2 to 4, R ₅ may be different from each other, and when t is 2 to 4, they may be different from each other. And Z has 1 to 1 carbon atoms.
8 alkylene groups, alkylene groups having 2 to 8 carbon atoms, cycloalkylene groups having 5 to 15 carbon atoms, cycloalkylidene groups having 5 to 15 carbon atoms, or SO ₂ , SO, S, O, C
O is shown. As specific examples of the dihydric phenol constituting (A2),
For example, bisphenol A, bisphenol F, bisphenol S, and alkyls thereof (having 1 to 1 carbon atoms)
8) or a halogen (chlorine, bromine, etc.)-Substituted product (eg, brominated bisphenol A). These dihydric phenols may be used alone or in combination of two or more. Further, the above-mentioned aliphatic diols may be used in combination. Among these dihydric phenols, bisphenol A is particularly preferred.

As (A3), for example, an organic diisocyanate and a polyester diol [molecular weight of 500 to 5]
000 or more polyester diols, polymer polyols obtained by polymerizing vinyl monomers (eg, acrylonitrile and / or styrene) in the diols, etc., and chain extenders (diols such as 1,4
-Butylene glycol and / or a diamine such as ethylene diamine) and, if necessary, a reaction terminator (monohydric alcohol, primary or secondary monoamine, or mono- or di-alkanolamine) by a one-shot method or a prepolymer method. And the resulting polyurethane. As organic diisocyanate, carbon number (excluding carbon in NCO group, the same applies hereinafter) 6 to
An aromatic diisocyanate having 20; an aliphatic diisocyanate having 2 to 18 carbon atoms; an alicyclic diisocyanate having 4 to 15 carbon atoms; an araliphatic diisocyanate having 8 to 15 carbon atoms;
Mixtures of more than one species can be used. Specific examples include those described in the specification of International Publication WO00 / 47652.

The polyester diol is obtained by reacting a diol (low molecular diol and / or polyoxyalkylene diol having a molecular weight of 1,000 or less) with a dicarboxylic acid or an ester-forming derivative thereof, or a dicarboxylic anhydride and an alkylene oxide. Condensed polyester diols, polylactone diols obtained by ring-opening polymerization of the above lactones using the above diols as initiators, low molecular weight diols and lower alcohols (C 1
And 4) a polycarbonate diol obtained by reacting with a carbonic acid diester. Examples of the low molecular diol include the above-mentioned glycols. Examples of the polyoxyalkylene diol include those described above. As the dicarboxylic acid and lactone, those mentioned as the raw materials for the above (A1) can be used. Specific examples of these polyester diols include polyethylene adipate diol, polyhexamethylene adipate diol, polycaprolactonediol, and polyhexamethylene carbonate diol. Preferred among the above are adipate-based thermoplastic polyurethanes.

(A4) includes a (co) polymer of an ester group-containing vinyl monomer and a copolymer of an ester group-containing vinyl monomer and another vinyl monomer. Examples of the ester group-containing vinyl monomer include an ester of a carboxyl group-containing vinyl monomer and an ester of an unsaturated alcohol. Esters of carboxyl group-containing vinyl monomers include unsaturated carboxylic acids [monocarboxylic acids; for example, (meth) acrylic acid, crotonic acid, oleic acid, 4-vinylbenzoic acid, cinnamic acid; polycarboxylic acids such as (Anhydride) maleic acid, fumaric acid, itaconic acid, citraconic acid] and an alcohol having 1 to 50 carbon atoms [alkanol, cycloalkanol, benzyl alcohol, diol (the above-mentioned glycol, polyoxyalkylene diol) and alcohol containing a tertiary amino group For example, dialkyl (C 1-4 alkanol)
4) amine, N-hydroxyalkyl (2-4 carbon atoms)
Morpholine, epoxy-containing alcohols (such as glycidol)]. Specifically, carbon number 1
Alkyl (meth) acrylate having an alkyl group of 50 to 50, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) ) Acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, eicosyl (meth) acrylate and the like. As esters of unsaturated alcohols, unsaturated alcohols (vinyl alcohol, (meth) allyl alcohol, isopropenyl alcohol, etc.) and carboxylic acids having 2 to 18 carbon atoms [monocarboxylic acid, benzoic acid,
Esters of the aforementioned dicarboxylic acids and the like], for example, vinyl acetate, vinyl butyrate, vinyl propionate, vinyl butyrate, diallyl phthalate, diallyl adipate, isopropenyl acetate, vinyl (meth) acrylate, methyl 4-vinylbenzoate, cyclohexyl (meth) )
Acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, vinyl methoxyacetate,
Vinyl benzoate and the like. Other vinyl monomers include vinyl hydrocarbons [aromatic vinyl hydrocarbons (styrene, α-methylstyrene, etc.), aliphatic vinyl hydrocarbons (ethylene, propylene, butadiene, etc.)], nitrogen-containing vinyl monomers [ Examples thereof include amide group-containing vinyl monomers {such as (meth) acrylamide), nitrile group-containing vinyl monomers {such as (meth) acrylonitrile}, and halogen element-containing vinyl monomers [such as vinyl chloride and chloroprene]. Specific examples of (A4) include polymethyl methacrylate, styrene / methyl methacrylate / acrylonitrile copolymer, methyl methacrylate / butadiene / styrene copolymer (MBS resin), ethylene / glycidyl methacrylate copolymer,
Examples include an ethylene / vinyl acetate / glycidyl methacrylate copolymer.

The Mw of (A) is 20,000 to 500,
000 or more, more preferably 2
5,000 to 45,000 or more.

Further, in the present invention, other thermoplastic resins may be blended with the thermoplastic resin (A) having an ester bond. Such other thermoplastic resins include styrene (co) polymers such as styrene / acrylonitrile copolymer (AS resin), acrylonitrile / butadiene /
Styrene copolymer (ABS resin), styrene / butadiene copolymer; olefin (C2-8) (co) polymer, for example, polyethylene, polypropylene, ethylene / propylene copolymer, ethylene / 4-methylpentene copolymer Polymers, ethylene / butene-1 copolymers, polyacetals [e.g., formaldehyde homopolymers and copolymers of trioxane and alkylene oxides (e.g., ethylene oxide, propylene oxide, etc.)] and maleic anhydride modified products thereof can give.

The mixing ratio of the thermoplastic resin (A) to the total weight of the thermoplastic resin is preferably 30 to 97% by weight, more preferably 40 to 97% by weight.
90% by weight is particularly preferred. The blending ratio with respect to the total weight of the thermoplastic resin (B) is preferably 3 to 50% by weight, and particularly preferably 5 to 40% by weight. The mixing ratio of the “other thermoplastic resin” to the total weight of the thermoplastic resin is preferably 0 to 67% by weight, particularly preferably 0 to 50% by weight. The “total weight of thermoplastic resin” in the present invention refers to the total weight of (A), (B) and the above “other thermoplastic resin”.

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

Embedded image (N is 1 or 2. R ₁ represents a monovalent hydrocarbon group having 1 to 30 carbon atoms, and when n is 2, they may be the same or different.) In the general formula (1) , R ₁ represented by 1 to 1 carbon atoms
Examples of the 30 alkyl groups include methyl, ethyl, n- and i-propyl, n-, i-, sec- and t-butyl, amyl, tertiary amyl, hexyl, octyl, isooctyl, 2-ethylhexyl and tertiary octyl , Nonyl,
Tertiary nonyl, isononyl, decyl, isodecyl, dodecyl, tridecyl, isotridecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, triancontyl and the like. When n is 2, two R ₁ may be the same or different. More preferred acidic phosphate esters are the above-mentioned acidic phosphate esters in which R ₁ has 8 to 30 carbon atoms, and particularly preferred are monostearyl phosphate and distearyl phosphate.

The above-mentioned acidic phosphoric acid ester can be obtained, for example, by hydrolyzing the corresponding trialkyl phosphate or the corresponding triester or tetraester of phosphoric acid, or by hydrolyzing phosphorus oxychloride with the corresponding alkanol. Or a method of reacting phosphorus pentoxide with the corresponding alkanol.

The alkali metal and / or alkaline earth metal salt (D) of the present invention includes alkali metal (such as lithium, sodium and potassium) and / or alkaline earth metal (such as magnesium and calcium).
Organic acids (mono- or dicarboxylic acids having 1 to 12 carbon atoms such as formic acid, acetic acid, propionic acid, oxalic acid, succinic acid and the like; sulfonic acids having 1 to 20 carbon atoms such as methanesulfonic acid and p-toluenesulfonic acid; Thiocyanic acid and the like, and inorganic acids (hydrohalic acid such as hydrochloric acid, hydrobromic acid, perchloric acid, sulfuric acid, phosphoric acid and the like). Specific examples include lithium acetate, magnesium chloride, calcium chloride, sodium bromide, potassium bromide, magnesium bromide, potassium perchlorate, potassium sulfate, potassium phosphate, potassium thiocyanate, and the like. Preferred among these are halides (especially lithium chloride, sodium chloride, potassium chloride) and acetates (especially potassium acetate).

(C) and (D) have a weight ratio of (C) / (D) of 1 to 50, and the total weight of (C) and (D) is 0 to the total weight of the thermoplastic resin. 0.001 to 5% by weight
It is contained so that The weight ratio of (C) / (D) is 1
If it is less than 50 or more than 50, the antistatic property and the physical properties of the resin decrease. When the total weight of (C) and (D) is less than 0.001% by weight or more than 5.0% by weight with respect to the total weight of the thermoplastic resin, the antistatic property and the resin properties are reduced. The weight ratio of (C) / (D) is particularly preferably 2 to 30, and more preferably 5 to 25. (C) and (D)
Is 0.00% of the total weight of the thermoplastic resin.
1-3 are especially preferable, and 0.01-2 are more preferable.

Further, a phosphite can be added to the resin composition of the present invention, if necessary. The phosphite is represented by the general formulas (2), (3), (4) and (5).

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

Embedded image (M is an integer of 2 to 4. R ₃ is a hydrocarbon group having 1 to 40 carbon atoms. When m is 2, divalent, and when m is 3, 3
If m is 4, it is tetravalent. R ₃ ′ and R ₃ ″ are monovalent hydrocarbon groups having 1 to 25 carbon atoms, and may be the same or different.)

Embedded image (K is 1 or 2. R ₄ is a hydrocarbon group having 1 to 40 carbon atoms. When k is 1, it is divalent, and when k is 2, it is tetravalent. R ₄ ′ is 1 to ₄ carbon atoms. 25 monovalent hydrocarbon groups, and when k is 2, they may be the same or different.)

Embedded image (P is an integer of 1 to 4. R ₇ is a hydrocarbon group having 1 to 40 carbon atoms. When p is 1 to 4, each is monovalent to tetravalent.
R ₇ ′ and R ₇ ″ are monovalent hydrocarbon groups having 1 to 25 carbon atoms, and when p is 2 to 4, they may be the same or different.)

Examples of the phosphite represented by the general formula (2) include trilauryl phosphite, triisooctyl phosphite, trioleyl phosphite, triphenyl phosphite, trioctadecyl phosphite, and triisophosphite. Decyl phosphite, tri-normal butyl phosphite, tris-2-ethylhexyl-phosphite, tristearyl phosphite, tris-2,4-di-tert-butylphenyl phosphite, tristridecyl phosphite, tris-4-
Phenylphenol-phosphite, trisnonylphenylphosphite, phenyldiisodecylphosphite, phenyldioctylphosphite, diphenylnonylphenylphosphite, diphenylisodecylphosphite, diphenylisooctylphosphite, diphenyldecylphosphite, diphenyltridecylphosphite And the like.

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

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

Examples of the phosphite represented by the general formula (5) include tetrakis (2,4-di-tert-butylphenol) 4,4′-biphenylenediphosphonite (P-EPQ). Can be Preferred as the phosphite are bis (2,6-di-t-
Butyl-4-methylphenyl) pentaerythritol-
Diphosphite. The phosphite is (C)
Is preferably 0 to 100% by weight, more preferably 0 to 80% by weight, based on the weight of

The resin composition of the present invention can be obtained by kneading the components (A) to (D) using various known mixers. Examples of the mixer include an extruder, a Brabender, a kneader, and a Banbury mixer.

The order of addition of each component at the time of kneading is not particularly limited. For example, a method of blending and kneading (A) to (D); kneading a small amount of (A) and (B) to (D) After blending and kneading, a method of kneading the remaining (A); and blending and kneading (B) to (D), (A)
Is kneaded. Of these, the method is a method called master batch or master pellet. The method is particularly preferable as a method for producing the resin composition of the present invention, since a composition having good dispersibility and excellent permanent antistatic properties and mechanical strength can be obtained. When manufacturing the above resin composition, the method of adding (D) is preferably preliminarily dispersed in polyetheresteramide (B) from the viewpoint of easy dispersion in the composition. . When (D) is dispersed in (B),
It is particularly preferable to add and disperse (D) in advance during the production (polymerization) of (B).

Further, the resin composition of the present invention may contain a nonionic, anionic, cationic or amphoteric surfactant to further improve the antistatic property. Non-ionic surfactants include higher alcohols (C 1
0-30) EO adducts, fatty acid EO adducts, polyethylene glycol type nonionic surfactants such as higher alkylamine (10-30 carbon atoms) EO adducts, and polypropylene glycol (polymerization degree 3-17) EO adducts; Polyethylene oxide (degree of polymerization 4 to 20), fatty acid ester of glycerin, fatty acid ester of pentaerythrit, fatty acid ester of sorbit and sorbitan, polyvalent (3 to 20)
Polyhydric (trivalent to hexavalent) alcohol-type nonionic surfactants such as alkyl ethers of (hexavalent) alcohols and aliphatic amides of alkanolamines are exemplified. Examples of the anionic surfactant include carboxylate salts such as alkali metal salts of higher fatty acids (C10 to C30); higher alcohols (C10 to C30) sulfates and higher alkyl ethers (C10 to C30). Sulfates such as sulfates, alkyl (C8-30) benzenesulfonate, alkane (C8-30) sulfonate,
Sulfonates such as paraffin sulfonate; Examples of the cationic surfactant include quaternary ammonium salts such as an alkyl (8 to 30 carbon atoms) trimethylammonium salt. Examples of the amphoteric surfactant include amino acid-type amphoteric surfactants such as higher alkyl (8 to 30 carbon atoms) aminopropionate, higher alkyl (8 to 30 carbon atoms) dimethyl betaine, and higher alkyl (8 to 30 carbon atoms). Betaine-type amphoteric surfactants such as dihydroxyethyl betaine are exemplified. These may be used alone or in combination of two or more. Of these, preferred are anionic surfactants, and particularly preferred are sulfonates such as alkylbenzene sulfonates, alkane sulfonates and paraffin sulfonates. The amount of the surfactant added is not particularly limited, but is preferably 0.1 to 5% by weight based on the total weight of the resin composition. There is no limitation on the method of addition, but it may be added at the time of polyetheresteramide synthesis or at the time of melt-kneading.

Further, other resin additives can be optionally added to the resin composition of the present invention within a range that does not impair the properties of the composition according to various uses. Examples of the additives include pigments, dyes, fillers (eg, talc, mica, calcium carbonate), nucleating agents (eg, sorbitol, metal benzoate), glass fibers, lubricants (eg, calcium stearate, butyl stearate, olein). Acid amide, polyolefin wax, paraffin wax), plasticizer (for example, phthalate ester, phosphate ester, toluene sulfonamide), release agent [for example, (carboxyl, hydroxyl) modified silicone oil, paraffin wax, polyolefin wax], Antioxidants (eg, hindered phenols), flame retardants (eg, halogen-based flame retardants, phosphorus-based flame retardants, antimony-based flame retardants, metal hydroxide-based flame retardants), ultraviolet absorbers (eg, hindered amine, benzotriazole) ) And the like.

The amount of the additive is not particularly limited, but is preferably 1 to 80% by weight based on the total weight of the resin composition in the case of a filler and a plasticizer. On the other hand, in the case of pigments, dyes, nucleating agents, lubricants, release agents, antioxidants, ultraviolet absorbers and flame retardants, 0.0
1-10% by weight is preferred.

The resin composition of the present invention is useful as a molding material. Examples of the molding method include injection molding, compression molding, calendar molding, slash molding, rotational molding, extrusion molding, blow molding, and film molding (casting, tentering). Method, an inflation method, etc.), and can be formed by any method according to the purpose.

A molded article formed by using the resin composition of the present invention has excellent mechanical strength and permanent antistatic properties, as well as good paintability and printability. Examples of the method for coating the molded article include, but are not limited to, air spray coating, airless spray coating, electrostatic spray coating, dip coating, roller coating, brush coating, and the like. Examples of the paint include paints generally used for plastic coating, such as polyester melamine resin paint, epoxy melamine resin paint, acrylic melamine resin paint, and acrylic urethane resin paint. The coating film thickness (dry film thickness) can be appropriately selected depending on the purpose, but is usually 10 to 50 μm. As a method for printing on the molded article, any printing method generally used for printing plastics can be used, and examples thereof include gravure printing, flexographic printing, screen printing, and offset printing. Can be As the printing ink, those commonly used for printing on plastics can be used.

The resin composition of the present invention can be used for home appliances, OA equipment,
It is extremely useful as a housing product for game machines and office equipment, various plastic containers, various packaging films, flooring sheets, mats, automobile parts, and other various molding materials requiring antistatic properties.

[0067]

EXAMPLES The present invention will be further described with reference to the following examples, but the present invention is not limited to these examples. In the examples, "parts" indicates parts by weight, and "%" indicates% by weight. The physical properties of the molded articles described in the examples and comparative examples were evaluated by the following methods.

[Production of Polyetheresteramide] Production Example 1 ε-caprolactam 1 was placed in a stainless steel autoclave.
05 parts, adipic acid 17.1 parts, "Irganox 10
10 "(Antioxidant, Ciba-Geigy) 0.3 parts and water 7 parts were charged, and after purging with nitrogen, the mixture was heated and stirred at 220 ° C. for 4 hours while being pressurized and sealed to obtain an acid value of 100 having a carboxyl group at both terminals. 117 parts of a polyamide oligomer were obtained. Next, 225 parts of an EO adduct of bisphenol A having a number average molecular weight of 2,000 and 0.5 part of zirconyl acetate were added, and 245 parts were added.
Polymerization was performed for 5 hours at a temperature of 1 ° C. and a reduced pressure of 1 mmHg or less to obtain a viscous polymer. The polymer was taken out in a strand form on a belt and pelletized to obtain a polyetheresteramide [B-1]. Its reduced viscosity was 2.10.

Production Example 2 In a stainless steel autoclave, ε-caprolactam 8 was added.
3.5 parts, 16.5 parts of terephthalic acid, 0.3 part of “Irganox 1010” and 6 parts of water were charged, and after purging with nitrogen, the mixture was heated and stirred at 220 ° C. for 4 hours while being pressurized and sealed. 96 parts of a polyamide oligomer having an acid value of 112 and having the following formula: Next, 192 parts of an EO adduct of bisphenol A having a number average molecular weight of 2,000 and 0.5 part of zirconyl acetate were added, and the mixture was polymerized at 245 ° C. under a reduced pressure of 1 mmHg or less for 5 hours to obtain a viscous polymer. . Less than,
The same operation as in Production Example 1 was performed to obtain polyetheresteramide [B-2]. Its reduced viscosity is 2.10
Met.

Examples 1 to 6, Comparative Examples 1 to 5 Thermoplastic resin having ester bond (A) {[A-2]
Contains (A) and another thermoplastic resin. The following were used as｝. [A-1]: cyclohexane dimethanol / ethylene glycol / terephthalic acid copolymer [trade name: EASTE
R PETG6763 manufactured by Eastman Chemical Japan Co., Ltd.] [A-2]: Polycarbonate and acrylonitrile / styrene / butadiene copolymer (ABS resin) mixture (polycarbonate / ABS resin weight ratio = 70/30)
[Product name Iupilon GP-1 Mitsubishi Gas Chemical Co., Ltd.
[A-3]: Polybutylene terephthalate [trade name: Barox 310 Nippon GE Plastics Co., Ltd.]
[A-4]: Polyester thermoplastic polyurethane [trade name: Pandex T-5165 manufactured by Dainippon Ink & Chemicals, Inc.] [A-5]: Polymethyl methacrylate [trade name: Acrypet VH Mitsubishi Rayon Co., Ltd.] The following were used as acidic phosphate (C). [C-1]: A mixture of monostearyl phosphate and distearyl phosphate [trade name: ADK STAB AX-71 manufactured by Adeka Argus Co., Ltd.] [C-2]: Monolauryl phosphate [manufactured by Nippon Chemical Co., Ltd. The following were used as salts of alkali metals and / or alkaline earth metals. [D-1]: Lithium chloride (added when producing polyetheresteramide) [D-2]: Potassium acetate (added when producing polyetheresteramide) [D-3]: Magnesium chloride (added when producing polyetheresteramide) According to the formulation shown in Table 1 (the numbers indicate the parts to be blended), the above (A) to (C) [(D) was added at the time of manufacturing (B)] was blended for 3 minutes with a Henschel mixer. After that, in a twin-screw extruder with a vent, each temperature as follows,
The mixture was melt-kneaded under the conditions of 100 rpm and a residence time of 5 minutes to obtain a resin composition of the present invention and a resin composition of a comparative example. Kneading temperature; in the case of using [A-1], [A-3] and [A-5]; 230 ° C in the case of using [A-2]; 240 ° C in the case of using [A-4];

[0071]

[Table 1]

Performance Tests For the resin composition of the present invention and the resin composition of the comparative example, test pieces were prepared using an injection molding machine, and the appearance, surface resistivity, IZOD impact strength and tensile yield point strength were evaluated. . Test pieces were prepared at the following cylinder temperatures of the injection molding machine and at a mold temperature of 50 ° C. The results are shown in Table 2. The appearance, surface resistivity, IZOD impact strength and tensile yield point strength were evaluated by the following methods. Cylinder temperature; [A-1] used; 230 ° C [A-2] used; 200 ° C [A-3] and [A-5] used; 160 ° C [A-4] used 240 ° C., (1) Appearance: The surface of the injection molded plate was visually evaluated. Evaluation criteria ○: No appearance defect ×: Appearance defect such as flow mark (2) Surface specific resistance value: (a) Before rinsing; The test specimen after molding was left for 48 hours in an atmosphere of 23 ° C. and a humidity of 50% RH. After that, the measurement was performed according to ASTM D257-78 (Reapproved 1983). (B) After washing with water; after molding, the test piece is washed with an aqueous solution of a detergent (Mama Lemon; manufactured by Rion Co., Ltd.), and then sufficiently washed with ion-exchanged water. After standing for 24 hours in an atmosphere of 50 ° C. and a relative humidity of 50%, the measurement was carried out in accordance with ASTM D257-78 (Reapproved 1983). (3) IZOD impact strength: based on JIS K7110-1984 (notched, 3.2 mm thick). (4) Tensile yield point strength: based on JIS K7113-1981.

[0073]

[Table 2]

As is clear from Table 2, the resin composition of the present invention has excellent permanent antistatic properties and excellent mechanical properties as compared with Comparative Examples. That is, it is a resin composition having both excellent permanent antistatic properties and mechanical properties that could not be achieved conventionally.

[0075]

The polyolefin resin composition of the present invention has an excellent permanent antistatic property which cannot be attained by conventional techniques, and also has excellent mechanical properties and moldability. Because of the above effects, the resin composition of the present invention
Housing products for OA equipment, various plastic containers,
It is extremely useful as various molding materials that require antistatic properties of automobile parts and the like.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 77/12 C08L 77/12 101/00 101/00 F term (Reference) 4F071 AA43 AA50 AA53 AA57 AB18 AB19 AB25 AC09 AC15 AF38 BA01 BB02 BB03 BB04 BB05 BB06 BB09 BC01 BC07 4J002 BE02W BF01W BF02W BG02W CF03W CF05W CF09X CF19W CG01W CK02W CL08X DD067 DD087 DE187 DH026 DH047 EG027 FD0160 FD 01030 FD0160

Claims (8)

[Claims] 1. A resin composition comprising a thermoplastic resin (A) having an ester bond and a polyetherester amide (B), comprising: an acid phosphate (C); and an alkali metal and / or an alkaline earth metal. Has a weight ratio of (C) / (D) of 1 to 50, and
A resin composition comprising (C) and (D) in a total weight of 0.001 to 5% by weight based on the total weight of the thermoplastic resin. 2. The resin composition according to claim 1, wherein (C) is represented by the following general formula (1). Embedded image (N is 1 or 2. R ₁ represents a monovalent hydrocarbon group having 1 to 30 carbon atoms, and when n is 2, they may be the same or different.) 3. The method according to claim 1, wherein (B) has a number average molecular weight of 200 to 5,000.
3. The resin composition according to claim 1, which is a polyetheresteramide derived from a carboxyl group-containing polyamide (b1) of 0 and an alkylene oxide adduct of a dihydric phenol having a number average molecular weight of 300 to 5,000 (b2). 4. object. 4. The resin composition according to claim 1, wherein (B) is a polyetheresteramide produced using a zirconium organic acid salt as a catalyst. 5. The following general formulas (2), (3),
The resin composition according to any one of claims 1 to 4, further comprising a phosphite represented by (4) or (5). Embedded image (R ₂ , R ₂ ′, and R ₂ ″ are monovalent hydrocarbon groups having 1 to 25 carbon atoms, and may be the same or different.) (M is an integer of 2 to 4. R ₃ is a hydrocarbon group having 1 to 40 carbon atoms. When m is 2, divalent, and when m is 3, 3
If m is 4, it is tetravalent. R ₃ ′ and R ₃ ″ are monovalent hydrocarbon groups having 1 to 25 carbon atoms, and may be the same or different from each other.) (K is 1 or 2. R ₄ is a hydrocarbon group having 1 to 40 carbon atoms. When k is 1, it is divalent, and when k is 2, it is tetravalent. R ₄ ′ is 1 to ₄ carbon atoms. 25 monovalent hydrocarbon groups, and when k is 2, they may be the same or different.) (P is an integer of 1 to 4. R ₇ is a hydrocarbon group having 1 to 40 carbon atoms. When p is 1 to 4, each is monovalent to tetravalent.
R ₇ ′ and R ₇ ″ are monovalent hydrocarbon groups having 1 to 25 carbon atoms, and when p is 2 to 4, they may be the same or different.) 6. The (A) is a thermoplastic polyester resin (A1), a thermoplastic polyurethane resin (A2), a polycarbonate resin (A3) or a (co) polymer (A4) of an ester group-containing vinyl monomer. 6. The resin composition according to any one of 1 to 5. 7. A molded article obtained by molding the resin composition according to claim 1. 8. A molded article obtained by applying painting or printing to the molded article according to claim 7.