JPH0848768A - Polyetheresteramide and resin composition - Google Patents

Abstract

PURPOSE:To obtain a resin compsn. excellent in heat resistance and permanent antistatic properties by compounding a specific polyetheresteramide derived from a polyamide having a specified mol.wt. and an arom. polyether with a thermoplastic resin. CONSTITUTION:A resin compsn. is prepd. by compounding a polyetheresteramide (C) derived from a polyamide (A) having carboxyl groups at both molecular ends and a number-average mol.wt. of 500-5,000 and an arom. polyether (B) represented by the formula [wherein Z is a residue of a dihydric phenol (e.g. a bisphenol); Q is 2-4C oxyalkylene; X is an alkylene residue of a 1-18C alkylene dihalide; m is 1-30; and n is 1-25] with a thermoplastic resin (D) (e.g. a styrenic resin) in a wt. ratio of C to D of (5:95)-(40:60). Polymer A is obtd., e.g. by the ring-opening polymn. of a lactam (esp. epsilon-caprolactam), and polymer B, e.g. from bisphenol A, ethylene oxide, and methylene chloride.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyether ester amide having excellent heat resistance and permanent antistatic property and further excellent compatibility with various thermoplastic resins, and a resin composition using the polyether ester amide. Is.

[0002]

2. Description of the Related Art Conventionally, polyether ester amides have been known to impart excellent antistatic properties as an antistatic agent for some thermoplastic resins. (1) Polyoxyalkylene glycol is used as the polyether component. Since it uses (for example, polyethylene glycol), it has low heat resistance,
There is a problem that molding cannot be performed at high temperature; (2) Degradation of the layered structure or poor impact strength due to poor compatibility between the polyether ester amide and other thermoplastic resins,
There is a problem that a resin composition having desirable mechanical properties cannot be obtained. In order to solve the problem of (2), a method of using a modified vinyl polymer having a carboxyl group in a polyether ester amide as a compatibilizing agent (Japanese Patent Publication No. 4-72855), and a vinyl monomer having a hydroxyl group There is known a method (JP-A-2-70739) in which a rubber-modified styrene-based thermoplastic resin having a body as a copolymerization component is used as a compatibilizer. However, although the compatibility is improved by these methods, there is a drawback that the antistatic property is deteriorated because it is necessary to add a large amount of the compatibilizing agent. Further, by using a polyether ester amide using a polyoxyalkylene glycol having a specific molecular weight (for example, polyethylene glycol) and an alkylene oxide adduct of bisphenol as a polyether component, a resin composition which is transparent and has excellent permanent chargeability However, the problem of heat resistance in the above (1) has not been solved yet.

[0003]

Therefore, polystyrene, polymethylmethacrylate, styrene / acrylonitrile copolymer (SAN resin), acrylonitrile / butadiene / styrene copolymer (ABS) are excellent in heat resistance.
Resin), methyl methacrylate / butadiene / styrene copolymer (MBS resin), styrene / methyl methacrylate / acrylonitrile copolymer, polyethylene, polypropylene, polyethylene terephthalate (PET resin),
There is a demand for a polyetheresteramide having good compatibility with various thermoplastic resins such as polybutylene terephthalate (PBT resin), thermoplastic polyurethane and polyvinyl chloride.

[0004]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that a high-viscosity polyether ester amide derived from a polyamide having a specific molecular weight and an aromatic ring-containing polyether, It has been found that it is superior in heat resistance and antistatic properties to conventional polyetheresteramides; and that a resin composition comprising this polyetheresteramide and a thermoplastic resin is superior in heat resistance, permanent antistatic properties and mechanical properties. Has reached the present invention.

That is, the present invention comprises a polyamide (a1) having a carboxyl group at both ends and a number average molecular weight of 500 to 5,000, and an aromatic ring having a number average molecular weight of 500 to 5,000 represented by the following general formula (1). Polyether (a2)
And a resin composition comprising the polyether ester amide (A) and a thermoplastic resin (B). H-{(Q) _m- O-Z-O- (Q) _m- X} _n- (Q) _m
-O-Z-O- (Q) _m- H (1) (In the formula, Z is a dihydric phenol selected from bisphenols, monocyclic dihydric phenols, dihydroxybiphenyls, dihydroxynaphthalene, and binaphthols. Residue, Q is an oxyalkylene group having 2 to 4 carbon atoms, X is an alkylene residue of an alkylene dihalide having 1 to 18 carbon atoms, m is an integer of 1 to 30, and n is an integer of 1 to 25.)

The polyamide (a1) having carboxyl groups at both ends constituting the polyether ester amide (A) of the present invention is (1) a lactam ring-opening polymer, (2)
It is a polycondensate of an aminocarboxylic acid or (3) a polycondensate of a dicarboxylic acid and a diamine. Examples of the lactam of (1) include caprolactam, enanthlactam, laurolactam, and undecanolactam. As the aminocarboxylic acid of (2), ω-aminocaproic acid, ω-
Examples thereof include aminoenanthic acid, ω-aminocaprylic acid, ω-aminopergonic acid, ω-aminocapric acid, 11-aminoundecanoic acid and 12-aminododecanoic acid.
Examples of the dicarboxylic acid (3) include adipic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid and isophthalic acid, and examples of the diamine include hexamethylenediamine, heptamethylenediamine, octamethylenediamine and decamethylene. Diamine and the like can be mentioned. Two or more of the amide-forming monomers exemplified above may be used in combination. Among these, preferred are caprolactam, 12-aminododecanoic acid and adipic acid-hexamethylenediamine, and particularly preferred is caprolactam.

The polyamide (a1) having a carboxyl group at both ends uses a dicarboxylic acid having 4 to 20 carbon atoms as a molecular weight regulator, and in the presence of this, the above amide-forming monomer is subjected to ring-opening polymerization or a conventional method. Obtained by polycondensation. Examples of the dicarboxylic acid having 4 to 20 carbon atoms include aliphatic dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid and dodecanedioic acid;
Aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid and naphthalenedicarboxylic acid; alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid and dicyclohexyl-4,4-dicarboxylic acid; sodium 3-sulfoisophthalate 3-sulfoisophthalic acid alkali metal salts such as potassium 3-sulfoisophthalate; and mixtures of two or more thereof. Among these, preferred are aliphatic dicarboxylic acids, aromatic dicarboxylic acids and alkali metal salts of 3-sulfoisophthalic acid, and particularly preferred are adipic acid, sebacic acid, terephthalic acid, isophthalic acid and sodium 3-sulfoisophthalate. is there.

The number average molecular weight of the above (a1) is usually 50.
It is 0 to 5,000, preferably 500 to 3,000. When the number average molecular weight is less than 500, the heat resistance of the polyether ester amide itself is lowered, and when it exceeds 5,000, the reactivity is lowered, so that a large amount of time is required for producing the polyether ester amide.

The aromatic ring-containing polyether (a2) is a compound represented by the above general formula (1), in which Z is the residue of the dihydric phenol (b1) and Q is 2 carbon atoms. To oxyalkylene group derived from alkylene oxide (b2), X is a residue of the polyfunctional halogen compound (c2).

As the dihydric phenols (b1), monocyclic phenols such as hydroquinone, catechol, resorcin, orcin and urushiol; bisphenol A
(4,4'-dihydroxydiphenyl-2,2-propane), bisphenol F (4,4'-dihydroxydiphenylmethane), bisphenol S (4,4'-dihydroxydiphenylsulfone), 4,4'-dihydroxydiphenyl-2. , Bisphenols such as 2-butane;
Dihydroxybiphenyls; those having a naphthalene nucleus such as dihydroxynaphthalene and binaphthol, and the like. Among these, bisphenols are preferable, and bisphenol A is particularly preferable.

As the alkylene oxide (b2),
For example, ethylene oxide, propylene oxide,
1,2- or 1,4-butylene oxide and mixtures of two or more thereof are mentioned. Of these, preferred is ethylene oxide.

The aromatic ring-containing polyether diol (c1) constituting the aromatic ring-containing polyether (a2) in the present invention can be prepared by subjecting (b1) to (b2) to a known method such as 100 to 200 in the presence of an alkali catalyst. It can be produced by addition reaction at a temperature of ° C. (B
The addition mole number of 2) is usually 1 to 30 moles, and preferably 2 for each.
~ 20 moles.

As the polyfunctional halogen compound (c2),
Examples thereof include polyhalogenated aliphatic hydrocarbons, polyhalogenated aromatic ring-containing hydrocarbons, polyhalogenated ethers, and polyhalogenated ketones.

The polyhalogenated aliphatic hydrocarbons include
Methylene dihalides such as methylene chloride, methylene bromide, methylene iodide and monobromomonochloromethane; 1,
Examples include alkylene dihalides such as 1-dichloroethane and 1,2-dichloroethane; and chloroform and carbon tetrachloride.

The polyhalogenated aromatic ring-containing hydrocarbons include benzal chloride, benzal bromide, bis (chloromethyl) benzene and the like. Polyhalogenated ethers include bis (chloromethyl) ether and 2,2 '
-Polyhalogenated aliphatic ethers such as dichloroethyl ether; polyhalogenated aromatic ethers such as 4,4'-bis (chloromethyl) diphenyl ether; bis (chloromethoxy) benzene, tris (chloromethoxy) benzene and the like Examples include polyhalogenated araliphatic ethers. Examples of polyhalogenated ketones include bis (chloromethyl) ketone and bis (chloromethoxy) benzene. Others, bis (chloromethyl)
Examples thereof include polyhalogenated alcohols such as formal, acid halides such as dichlorochloroacetyl chloride, and phosgene.

These may be used alone or in combination of two or more kinds. Of these, preferred are polyhalogenated aliphatic hydrocarbons, polyhalogenated aromatic ring-containing hydrocarbons and polyhalogenated ethers, and particularly preferred are methylenes among polyhalogenated aliphatic hydrocarbons. Dihalides (methylene chloride, methylene bromide, methylene iodide and bromochloromethane).

The manufacturing method of (a2) is not particularly limited,
Usually, (c1) and (c2) are replaced with an alkali metal compound (c
It can be produced by a method of reacting in the presence of 3) at a temperature of 40 ° C to 150 ° C. Alkali metal compound (c
Examples of 3) include caustic alkalis such as sodium hydroxide and potassium hydroxide; metal alcoholates of lower alcohols such as sodium methylate and sodium ethylate.

The number average molecular weight of (a2) is usually 500.
˜5,000, preferably 500 to 3,000.
If it is less than 500, the antistatic property becomes insufficient, and 5,000
If it exceeds the range, the reactivity is lowered, so that a great amount of time is required at the time of producing the polyetheresteramide.

The amount of (a2) constituting the polyether ester amide (A) of the present invention is usually 20 to 80% by weight based on the total weight of (a1) and (a2),
It is preferably in the range of 25 to 75% by weight. If the amount of (a2) is less than 20%, the antistatic property of (A) will be poor, and if it exceeds 80% by weight, the heat resistance of (A) will be reduced, such being undesirable. If necessary, a polyalkylene oxide (polyethylene oxide or the like) or an aromatic ring-containing polyether diol (c1) may be used together with (a2). When used in combination, the amount used is not particularly limited, but is usually 30% by weight or less with respect to (a2) from the viewpoint of heat resistance.

The production method of (A) is not particularly limited, but the following production method or production method can be exemplified. Production method: A method of reacting an amide-forming monomer and a dicarboxylic acid to form (a1), adding (a2) thereto, and performing a polymerization reaction at high temperature and reduced pressure. Production method: An amide-forming monomer and a dicarboxylic acid and (a2) are simultaneously charged into a reaction vessel, and pressure reaction is performed at high temperature in the presence or absence of water to produce (a1) as an intermediate, and then decompression. A method of performing a polymerization reaction of (a1) and (a2) below.

In the above polymerization reaction, a known esterification catalyst is usually used. Examples of the catalyst include antimony catalysts such as antimony trioxide, tin catalysts such as monobutyltin oxide, titanium catalysts such as tetrabutyl titanate; zirconium catalysts such as tetrabutyl zirconate; zirconyl acetate and zinc acetate. Examples thereof include organic acid metal salt-based catalysts. The amount of catalyst used is
It is usually 0.1 to 5 relative to the total weight of (a1) and (a2).
% By weight.

The relative viscosity of (A) (0.5 wt% m-cresol solution, 25 ° C.) is usually 1.2 to 3.0, preferably 1.3 to 2.5. When the relative viscosity is less than 1.2, the heat resistance is poor, and when it exceeds 3.0, the moldability is deteriorated.

In the resin composition of the present invention, the thermoplastic resin (B) contains at least one selected from the group consisting of styrenes, (meth) acrylic acid esters, (meth) acrylonitrile, and butadiene as a structural unit (copolymer). )
Polymer (polystyrene, styrene / acrylonitrile copolymer, acrylonitrile / butadiene / styrene copolymer, methyl methacrylate / butadiene / styrene copolymer, methyl methacrylate / ethyl methacrylate / butadiene / styrene copolymer and styrene / methacryl Methyl acid / acrylonitrile copolymer, etc.); Polyolefin resins such as polypropylene and polyethylene; Polyester resins such as polyethylene terephthalate (PET resin) and polybutylene terephthalate (PBT resin);
Polycarbonate resin; acrylic resin; thermoplastic polyurethane resin; polyvinyl chloride resin and the like. Of these, preferred are polystyrene, polymethylmethacrylate, styrene / acrylonitrile copolymer, acrylonitrile / butadiene / styrene copolymer, methyl methacrylate / butadiene / styrene copolymer, styrene / methyl methacrylate / acrylonitrile copolymer. Coalesced, polypropylene, polyethylene, PET resin and PBT resin.

In the resin composition of the present invention, the weight ratio of (A) and (B) is usually (5-40) :( 95-6).
0), preferably (10-35) :( 90-65). If the ratio of (A) is less than 5, the antistatic effect becomes insufficient, and if it exceeds 40, the physical properties of the resin may be impaired.

The resin composition of the present invention may contain a compatibilizing agent (C) for the purpose of further improving the compatibility between (A) and (B). Examples of the compatibilizer (C) include JP-A-3-258850 and Japanese Patent Application No. 5-856.
No. 16, etc., a modified vinyl polymer having at least one functional group selected from the group consisting of a carboxyl group, an epoxy group, an amino group, a hydroxyl group, a polyalkylene oxide group, a sulfonic acid group and derivatives thereof ( C1); modified low molecular weight polyolefin (C2) described in Japanese Patent Application No. 3-321308, etc .;
Examples thereof include block polymers (C3) having a polyolefin moiety and an aromatic vinyl polymer moiety described in Japanese Patent Application No. 9129 and Japanese Patent Application No. 5-85616. These may be used alone or in combination of two or more.

Of these, (B) is styrene, (meth) acrylic acid ester, (meth) acrylonitrile,
(C) in the case of a (co) polymer having a constitutional unit of at least one selected from the group consisting of butadiene,
(C1) (for example, styrene / acrylonitrile / maleic anhydride copolymer, acrylonitrile / butadiene /
Styrene / acrylic acid copolymer, styrene / glycidyl methacrylate / methyl methacrylate copolymer, etc.) are preferred. (C) when (B) is a polyolefin resin
(C2) (for example, the number average molecular weight is 1,00
Maleic anhydride modified low molecular weight polypropylene of 0 to 25,000 and (C3) (for example, polypropylene / polystyrene block polymer having a number average molecular weight of 1,000 to 25,000) are preferable.

When (C) is contained, the amount of (C) is
It is usually 0.1 to 15% by weight, preferably 1 to 10% by weight, based on the total weight of (A) and (B). If the amount of (C) is less than 0.1% by weight, the effect of improving compatibility is not sufficiently exhibited, and if it exceeds 15% by weight, the physical properties of the resin are impaired.

Further, for the purpose of further improving the antistatic effect, a metal salt (D) comprising a halide of an alkali metal and / or an alkaline earth metal may be contained.
Examples of the (D) include lithium chloride, sodium chloride, potassium chloride, magnesium chloride, calcium chloride, sodium bromide, potassium bromide, magnesium bromide and the like. Of these, particularly preferred are:
Sodium chloride and potassium chloride.

The amount of (D) used is usually 0.01 to 5% by weight, preferably 0.05 to 3% by weight, based on the total weight of (A), (B) and (C). The amount of (D) is 0.
If it is less than 01% by weight, the effect is not exhibited, and if it exceeds 5% by weight, it is deposited on the resin surface and the appearance of the resin molded product is impaired.

The method of adding (D) is not particularly limited, but in order to effectively disperse it in the composition, it is preferable to disperse it in the polyether ester amide (A) in advance. When (D) is dispersed in (A), a method of adding (D) and dispersing it during the polymerization of (A) is particularly preferable.

The resin composition of the present invention may contain a nonionic, anionic, cationic or amphoteric surfactant (E) to further improve the antistatic property. As the nonionic surfactant, higher alcohol ethylene oxide adduct, fatty acid ethylene oxide adduct, higher alkylamine ethylene oxide adduct, polyethylene glycol type nonionic surfactant such as polypropylene glycol ethylene oxide adduct, polyethylene oxide, Glycerin fatty acid ester, pentaerythritol fatty acid ester, sorbit and sorbitan fatty acid ester, polyhydric alcohol alkyl ether,
Examples thereof include polyhydric alcohol type nonionic surfactants such as aliphatic amides of alkanolamines. Examples of the anionic surfactant include carboxylic acid salts such as alkali metal salts of higher fatty acids, sulfuric acid ester salts such as higher alcohol sulfuric acid ester salts and higher alkyl ether sulfuric acid ester salts, alkylbenzene sulfonates, alkyl sulfonates, paraffin sulfone. Examples thereof include sulfonates such as acid salts, and phosphate ester salts such as higher alcohol phosphate ester salts. Examples of the cationic surfactant include quaternary ammonium salts such as alkyl trimethyl ammonium salt. Examples of the amphoteric surfactant include amino acid-type amphoteric surfactants such as higher alkylaminopropionate and betaine-type amphoteric surfactants such as higher alkyldimethylbetaine and higher alkyldihydroxyethylbetaine. 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 sulfonate, alkyl sulfonate, and paraffin sulfonate.

The amount of (E) used is usually 0.1 to 5% by weight, preferably 0.4 to 3% by weight, based on the total weight of (A), (B) and (C). If the amount of (E) is less than 0.1% by weight, the effect is not exhibited, and if it exceeds 5% by weight, it is deposited on the surface of the resin to impair the appearance of the resin and the physical properties of the resin are impaired, which is not preferable.

The method of adding (E) is not particularly limited, but in order to effectively disperse it in the composition,
It is preferable to disperse in (A) or (B) in advance.

The resin composition of the present invention can be obtained by kneading the above components using various known mixers. Mixers include, for example, extruders, Brabenders, kneaders and Banbury mixers.

The order of addition of the respective components at the time of kneading is not particularly limited, but for example, a method of blending and kneading (A) to (C) at once, and a small amount of (B) and (A) and (C). Examples include a method of kneading the remaining (B) after blending and kneading, a method of previously blending and kneading (A) and (C), and then kneading (B). The above methods and are methods called master batch or master pellet. Among these, the method of obtaining a resin having good dispersibility and being excellent in permanent antistatic property and mechanical strength is particularly preferable.

As a method for obtaining the composition of the present invention via a masterbatch, for example, (A) 40 to 90 parts by weight, (B) 50 to 10 parts by weight and (C) 0 to 30 parts by weight are blended. Examples thereof include a method of kneading to form a masterbatch, and the masterbatch and (B) are blended and kneaded to obtain the composition of the present invention. This method is particularly preferable as a method for producing the resin composition of the present invention, since a small amount of (A) can be uniformly dispersed in a large amount of (B).

According to various uses, other known additives for resins can be optionally added to the resin composition of the present invention as long as the characteristics of the composition are not impaired.
Examples of the additives include pigments, dyes, fillers, nucleating agents, glass fibers, lubricants, plasticizers, release agents, antioxidants, flame retardants, and ultraviolet absorbers.

[0038]

EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited thereto. In the examples, "part" means part by weight and "%" means% by weight. The finally obtained resin composition was molded by an injection molding method, and then various physical properties were measured by the following test methods.

Surface specific resistance value: A super insulation meter (manufactured by Advantest) using a square test piece having a thickness of 2 mm.
Was measured in an atmosphere of 20 ° C. and a humidity of 65% RH. Izod impact strength: According to ASTM D256-56A. Tensile strength: According to ASTM D638. Thermal loss onset temperature: Measured by TG-DTA under nitrogen (heat resistance index).

[Production of aromatic ring-containing polyether (a2)] Production Example 1 341 parts of bisphenol A and ethylene oxide 659
A part was reacted in the presence of a potassium hydroxide catalyst to obtain an aromatic ring-containing polyether diol having a number average molecular weight of 668 and a hydroxyl value of 168 (mgKOH / g, the same hereinafter). 500 parts of this aromatic ring-containing polyether diol and 170 parts of a 25% sodium methylate methanol solution were placed in a closed container, and methanol was distilled off under reduced pressure at 120 ° C. with stirring to perform alcoholation. Then, 40 parts of methylene chloride was added over about 30 minutes, and the reaction was carried out at 100 ° C. for about 3 hours. The reaction product was diluted with 500 parts of toluene, sodium chloride was filtered off, and the volatile matter was removed under reduced pressure for purification. Thus, 460 parts (a-1) of a viscous liquid polyether was obtained. The hydroxyl value of this polyether was 84, and the number average molecular weight was 1335.

Production Example 2 564 parts of bisphenol A and ethylene oxide 436
Parts were reacted in the presence of a potassium hydroxide catalyst to obtain an aromatic ring-containing polyether diol having a number average molecular weight of 404 and a hydroxyl value of 278. 500 parts of this aromatic ring-containing polyether diol and 377 parts of a 25% sodium methylate methanol solution were placed in a closed container, and methanol was distilled off under reduced pressure at 120 ° C. under stirring to perform alcoholation. Then, 167 parts of methylene bromide was added over about 60 minutes and 10
The reaction was carried out at 0 ° C for about 2 hours. This reaction product was mixed with toluene 50
Diluted with 0 parts, filtered off sodium bromide and purified by removing volatiles under reduced pressure. Thus, about 450 parts (a-2) of a viscous liquid polyether was obtained.
This polyether has a hydroxyl value of 82 and a number average molecular weight of 1
It was 370.

[Production of Polyether Esteramide (A)] Production Example 3 105 parts of ε-caprolactam, 17.1 parts of adipic acid and "Irganox 1010"(antioxidant; manufactured by Ciba-Gaiki) in a 3 L stainless steel autoclave. After charging 0.3 part and 6 parts of water, the mixture was replaced with nitrogen, and the mixture was heated and stirred at 220 ° C. under pressure and sealing for 4 hours, and a polyamide oligomer 117 having a carboxyl group at both ends and an acid value of 110 (mgKOH / g, the same applies hereinafter). I got a part. Next, 153 parts of (a-1) obtained in Production Example 1, 0.5 part of zirconyl acetate and 0.1 part of potassium chloride were added, and the mixture was polymerized at 245 ° C. under a reduced pressure of 1 mmHg or less for 5 hours to give a viscous product. A polymer was obtained. This polymer was taken out in a strand form on a belt and pelletized to obtain a polyether ester amide. The relative viscosity of this product is 2.15 (0.5
Wt% m-cresol solution, 25 ° C., the same below). This polyether ester amide is referred to below as [A-1]
Abbreviated.

Production Example 4 105 parts of ε-caprolactam, 17.1 parts of adipic acid, 0.3 parts of "Irganox 1010" and 6 parts of water were charged into a 3 L stainless steel autoclave, and after nitrogen substitution, pressure was applied at 220 ° C. The mixture was heated and stirred for 4 hours in a sealed state to obtain 117 parts of a polyamide oligomer having a carboxyl group at both ends and an acid value of 110. Then obtained in Production Example 2 (a-2)
142 parts, 16 parts of polyoxyethylene glycol having a number average molecular weight of 1,500 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. This polymer was taken out in a strand form on a belt and pelletized to obtain a polyether ester amide. This product had a relative viscosity of 2.10. This polyetheresteramide is abbreviated as [A-1] below.

[Production of Comparative Polyetheresteramide] Production Example 5 A 3 L stainless steel autoclave was charged with 105 parts of ε-caprolactam, 17.1 parts of adipic acid, 0.3 parts of "Irganox 1010" and 6 parts of water. After nitrogen substitution, the mixture was heated and stirred at 220 ° C. under pressure and closed for 4 hours to obtain 117 parts of a polyamide oligomer having a carboxyl group at both ends and an acid value of 110. Next, 175 parts of polyoxyethylene glycol having a number average molecular weight of 1,500 and 0.5 part of zirconyl acetate were added, and the mixture was polymerized for 5 hours at 245 ° C. under a reduced pressure of 1 mmHg or less to obtain a viscous polymer. This polymer was taken out in a strand form on a belt and pelletized to obtain a comparative polyether ester amide. This product had a relative viscosity of 2.20.
This polyetheresteramide is abbreviated as [A-3] below.

[Production of Compatibilizer (C)] Production Example 6 A unit amount consisting of 68% by weight of methyl methacrylate, 24% by weight of styrene, 4% by weight of acrylonitrile and 4% by weight of acrylic acid in the presence of 40 parts of polybutadiene latex. 60 parts of the body mixture was emulsion polymerized. The resulting graft copolymer latex is coagulated with sulfuric acid, neutralized with caustic soda, washed,
After filtration and drying, a powdery graft copolymerization reaction product [C-1] was obtained.

Production Example 7 Number average molecular weight 5,000 obtained by thermal degradation, density of 0.
950 parts of low molecular weight polypropylene No. 92 and 50 parts of maleic anhydride were melted at 180 ° C. under a nitrogen gas atmosphere, and then 30 parts of 50% xylene solution in which 15 parts of dicumyl peroxide were dissolved was added dropwise over 15 minutes. Then one
After reacting for a period of time, xylene was distilled off to obtain acid-modified low molecular weight polypropylene [C-2].

[Manufacture of Masterbatch] Manufacturing Example 8 The components (A) to (C) in the proportions shown in Table 1 were blended in a Henschel mixer for 3 minutes, and then mixed in a vented twin-screw extruder as shown in Table 1. Master batches (M-1) to (M-) were melt-kneaded under the conditions of the temperature shown, 30 rpm, and a residence time of 5 minutes.
3) was obtained.

[0048]

[Table 1] (Note) [B-1]: manufactured by Japan Synthetic Rubber Co., Ltd. "JSR-ABS 10" [B-2]: manufactured by Ube Industries, Ltd. "UBE Polypro J609H" [B-3]: manufactured by Toray Co., Ltd. "Toray PBT 1401-X07"

Examples 1 to 3 Masterbatches (M-1) to (M-3) obtained in Production Example 8
And thermoplastic resins [B-1] to [B-3] were blended and kneaded in the combinations shown in Table 2 under the same conditions as in Production Example 8 to obtain a resin composition of the present invention. Table 2 shows the final proportions of the components (A) to (C) in the resin composition of the present invention via the masterbatch.

[0050]

[Table 2]

Examples 4 to 9 and Comparative Examples 1 to 7 The components (A) to (C) shown in Table 3 were blended and kneaded under the same conditions as in Production Example 8 to obtain a resin composition of the present invention and a comparative example. A resin composition was obtained.

[0052]

[Table 3]

Each of these resin compositions was subjected to an injection molding machine, and the cylinder temperature was the same as the kneading temperature.
A test piece was molded at ℃ and each physical property was measured. The results are shown in Table 4. The surface resistivity was measured on the test piece treated under the following conditions. (A) After molding, the square test piece is kept at 20 ° C. and the humidity is 65%
Leave for 24 hours in RH atmosphere. (B) After molding, the corner test piece was washed with an aqueous solution of a detergent [Mama Lemon; manufactured by Lion Co., Ltd.], and then sufficiently washed with ion-exchanged water, and then the surface water was dried to remove the water.
Leave for 24 hours in an atmosphere of 65 ° C and 65% RH.

[0054]

[Table 4] NB: Not broken

As is clear from the results of Examples 4 and 5 and Comparative Example 1 shown in Table 3, the polyetheresteramide of the present invention is superior in heat resistance and antistatic property to the conventional polyetheresteramide. Further, as is clear from the results of Example 8 and Comparative Example 6, the resin composition obtained by kneading the polyether ester amide of the present invention and the thermoplastic resin has a compatibilizing agent addition amount in comparison with the conventional one. It is possible to reduce the amount, and therefore, even if a compatibilizer is used as compared with the prior art, there is almost no deterioration in antistatic property, and the compatibility is good, so that a resin composition having excellent mechanical strength can be obtained. It was From the comparison between Example 1 and Example 6, it is preferable that the composition of the present invention is prepared via a masterbatch.

[0056]

The polyetheresteramide of the present invention is superior in heat resistance and antistatic property to the conventional polyetheresteramide. A resin composition comprising this polyether ester amide and a thermoplastic resin is excellent in heat resistance, permanent antistatic property and mechanical properties, and is useful as various molding materials.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical indication C08L 47/00 LKK 53/00 LLY LLZ 67/02 LPG 77/12 LQR 101/00 LTA 101/02 LSY

Claims (9)

[Claims] 1. A polyamide (a1) having a carboxyl group at both ends and having a number average molecular weight of 500 to 5,000 and a number average molecular weight of 500 to 5,000 represented by the following general formula (1).
A polyether ester amide derived from a 0-containing aromatic ring-containing polyether (a2). H-{(Q) _m- O-Z-O- (Q) _m- X} _n- (Q) _m
-O-Z-O- (Q) _m- H (1) (In the formula, Z is a dihydric phenol selected from bisphenols, monocyclic dihydric phenols, dihydroxybiphenyls, dihydroxynaphthalene and binaphthols. Residue, Q is an oxyalkylene group having 2 to 4 carbon atoms, X
Represents an alkylene residue of an alkylene dihalide having 1 to 18 carbon atoms, m represents an integer of 1 to 30, and n represents an integer of 1 to 25. ) 2. The polyetheresteramide according to claim 1, which has a relative viscosity of 1.2 to 3.0 (0.5% by weight m-cresol solution, 25 ° C.). 3. The polyetheresteramide according to claim 1, wherein Q is an oxyethylene group. 4. A resin composition comprising the polyetheresteramide (A) according to any one of claims 1 to 3 and a thermoplastic resin (B). 5. The (B) is a (co) polymer having a constitutional unit of at least one selected from the group consisting of styrenes, (meth) acrylic acid esters, (meth) acrylonitrile and butadiene. The resin composition described. 6. The resin composition according to claim 4, wherein (B) is a polyolefin resin. 7. The resin composition according to claim 4, wherein (B) is a polyester resin. 8. The weight ratio of (A) and (B) is (5-4).
0): (95-60), The resin composition according to any one of claims 4 to 7. 9. The composition according to claim 4, further comprising at least one compatibilizing agent (C) selected from the following (C1) to (C3).
The resin composition according to any one of to 8. (C1); Modified vinyl polymer having at least one functional group selected from the group consisting of carboxyl group, epoxy group, amino group, hydroxyl group, polyalkylene oxide group, sulfonic acid group and derivatives thereof (C2) A modified low molecular weight polyolefin (C3); a block polymer having a polyolefin part and an aromatic vinyl polymer part