JP2631965B2 - Resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a resin composition.
More specifically, the present invention relates to a polyolefin resin composition having excellent permanent antistatic properties and mechanical strength.

[0002]

2. Description of the Related Art Hitherto, as a method for imparting permanent antistatic properties to a polyolefin, there has been proposed (1) a method of adding a polyetheresteramide to a polyolefin (Japanese Patent Publication No. 4-5691 and the like). However, this method has a problem that phase separation occurs due to poor compatibility between the polyolefin and the polyetheresteramide, and the resin strength is reduced. Furthermore, because the polyolefin is a crystalline resin, during molding, the surface of the molded product is preferentially a polyolefin phase, and the polyetheresteramide is unlikely to appear on the surface. A large amount of polyetheresteramide needs to be added, and as a result, there has been a problem that mechanical strength, moldability and the like are reduced. In order to improve this, (2) a method of using a high-molecular-weight modified polyolefin in combination for the purpose of improving the compatibility between the polyolefin and the polyetheresteramide has been proposed (JP-A-1-163234, JP-A-1-163234). JP-A-3-29064). However, this method has solved the problem of phase separation, but has not yet solved the problem that polyetheresteramide does not easily appear on the surface of a crystalline polyolefin molded product.

[0003]

Accordingly, there is a strong need for a polyolefin resin composition having permanent antistatic properties and excellent mechanical strength.

[0004]

Means for Solving the Problems The inventors of the present invention have made intensive studies to solve the above-mentioned problems, and as a result, a mixture of a polyolefin resin and a polyetheresteramide was mixed with a polyester resin and / or a polyacetal resin and a modified low molecular weight resin. Addition of polyolefin makes polyetheresteramide easily appear on the surface. Addition of a small amount of polyetheresteramide has permanent antistatic properties and good compatibility, so polyolefin resin with excellent mechanical strength We have found that a composition is obtained and arrived at the present invention.

That is, the present invention relates to 55 to 95% by weight of a polyolefin resin (A), 3 to 40% by weight of a polyetheresteramide (B), 1 to 20% by weight of a polyester resin and / or a polyacetal resin (C). A resin composition comprising 0.2 to 20% by weight of one or more modified low molecular weight polyolefins (D) selected from the following (D1) to (D3). (D1): a number average molecular weight of 800 to 25,000,
Modified low molecular weight polyolefin having an acid value of 5-150. (D2): a number average molecular weight of 800 to 25,000,
A modified low molecular weight polyolefin having a hydroxyl value of 5 to 150. (D3); a part or all of (D1) is esterified with a polyoxyalkylene compound, and has a number average molecular weight of 1,
2,000 to 28,000 modified low molecular weight polyolefins.

In the present invention, the polyolefin resin (A) may be a (co) polymer of propylene and / or ethylene, or a copolymer of propylene and / or ethylene with at least one other α-olefin (random or block). Is mentioned. Examples of other α-olefins include 1-butene, 4-methyl-1-pentene, 1
-Pentene, 1-octene, 1-decene, 1-dodecene and the like. (A) Melt flow rate (MF
R) is usually 0.5 to 150, preferably 1 to 100. Melt flow rate is JIS K6758 (in the case of polypropylene resin; temperature 230 ° C, load 2.16)
kgf, polyethylene-based resin; temperature 190 ° C., load 2.16 kgf).
The crystallinity of (A) is usually 25% or more, preferably 30%
That is all. The crystallinity can be measured by a method such as X-ray diffraction and infrared absorption spectrum.

[0007] The amount of (A) in the resin composition of the present invention is usually 55 to 95% by weight, preferably 60 to 90% by weight. If the amount of (A) is less than 55% by weight, the mechanical strength will be poor, and if it exceeds 95% by weight, the antistatic property will be reduced.

In the present invention, examples of the polyetheresteramide (B) include the polyetheresteramides described in Japanese Patent Application No. 4-152538 and Japanese Patent Publication No. 4-5691. Of these, preferred are polyamides (b1) having carboxyl groups at both ends and having a number average molecular weight of 200 to 5,000, and alkylene oxide adducts (b2) of bisphenols having a number average molecular weight of 300 to 5,000 and / or Or a polyetheresteramide derived from polyoxyalkylene glycol (b3), and particularly preferred are:
It is a polyetheresteramide derived from (b1) and (b2).

The polyamide (b1) constituting (B) is
(1) a lactam ring-opening polymer, (2) 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, enantholactam, laurolactam, And undecanolactam. As the aminocarboxylic acid (2), ω-aminocaproic acid, ω-aminoenanthic acid,
ω-aminocaprylic acid, ω-aminopergonic acid, ω-aminocapric acid, 11-aminoundecanoic acid, 12-aminododecanoic acid and the like. Examples of the dicarboxylic acid (3) include adipic acid, azelaic acid, sebacic acid, undecandioic acid, dodecandioic acid, isophthalic acid, and the like.
Heptamethylenediamine, octamethylenediamine, decamethylenediamine, and the like. Two or more of the above-mentioned amide-forming monomers may be used in combination. Of these, preferred are caprolactam, 1
2-Aminododecanoic acid and adipic acid-hexamethylenediamine, particularly preferred is caprolactam.

(B1) can be obtained by using a dicarboxylic acid component having 4 to 20 carbon atoms as a molecular weight regulator and subjecting the amide-forming monomer to ring-opening polymerization or polycondensation in the presence of the dicarboxylic acid component in a conventional manner. . The carbon number of 4 to 20
Examples of the dicarboxylic acids include aliphatic carboxylic acids such as succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecandioic acid and dodecanediacid; terephthalic acid, isophthalic acid, phthalic acid, naphthalenedicarboxylic acid Aromatic dicarboxylic acids such as acids; 1,4
-Cyclohexanedicarboxylic acid, dicyclohexyl-
Alicyclic dicarboxylic acids such as 4,4-dicarboxylic acid; alkali metal salts of 3-sulfoisophthalic acid such as sodium 3-sulfoisophthalate and potassium 3-sulfoisophthalate;
And mixtures of two or more of these. 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.

The number average molecular weight of (b1) is usually from 200 to
It is 5,000, preferably 500-3,000. When the number average molecular weight is less than 200, the heat resistance of the polyetheresteramide itself decreases, and when the number average molecular weight exceeds 5,000, the reactivity decreases, so that much time is required for producing the polyetheresteramide.

The bisphenols of the alkylene oxide adduct (b2) of bisphenols include bisphenol A (4,4'-dihydroxydiphenyl-2,2-
Propane), bisphenol F (4,4'-dihydroxydiphenylmethane), bisphenol S (4,4'-
Dihydroxydiphenylsulfone), 4,4′-dihydroxydiphenyl-2,2-butane, and the like, of which bisphenol A is preferred. As the alkylene oxide of (b2), ethylene oxide, propylene oxide, 1,2- or 1,4
-Butylene oxide and mixtures of two or more thereof. Of these, particularly preferred is ethylene oxide.

Polyoxyalkylene glycol (b3)
Examples thereof include polyoxyethylene glycol, polyoxypropylene glycol and polyoxybutylene glycol, and among them, preferred is polyoxyethylene glycol.

The number average molecular weight of the above (b2) and (b3) is usually from 300 to 5,000, preferably from 1,000 to 5,000.
It is 3,000, more preferably 1,600-3,000. When the number average molecular weight is less than 300, the antistatic property becomes insufficient, and when the number average molecular weight exceeds 5,000, the reactivity decreases, so that a great amount of time is required in producing the polyetheresteramide.

(B2) and / or (b3) constituting (B) are usually in the range of 20 to 80% by weight based on the total weight of (b1) and (b2) and / or (b3). Used. If the amount of (b2) and / or (b3) is less than 20% by weight, the antistatic property is poor, and if it exceeds 80% by weight, the heat resistance decreases.

Examples of the method for producing the polyetheresteramide (B) include, but are not particularly limited to, the following methods and methods. Production method: A method in which (b1) is formed by reacting an amide-forming monomer and a dicarboxylic acid, and (b2) and / or (b3) are added thereto, and a polymerization reaction is performed at high temperature and reduced pressure. Production method: An amide-forming monomer and a dicarboxylic acid and (b2) and / or (b3) are simultaneously charged into a reaction vessel, and pressure-reacted at a high temperature in the presence or absence of water to give an intermediate (b1). And then (b1), (b2) and / or (b) under reduced pressure
3) A method of performing a polymerization reaction with 3).

In the above-mentioned polymerization 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, zirconium-based catalysts such as tetrabutylzirconate, and metal acetate-based catalysts such as zinc acetate. Catalysts and the like. These amounts are (b1) and (b1)
It is usually 0.1 to 5% by weight based on the total weight of 2) and / or (b3).

The reduced viscosity of (B) (η _{SP /} C, C = 0.5
(% By weight m-cresol solution, 25 ° C.) is not particularly limited, but is usually 0.5 to 4.0, preferably 0.6 to 3.0. If the reduced viscosity is less than 0.5, heat resistance is poor, and 4.0.
If it exceeds 300, the moldability will decrease.

The amount of (B) in the resin composition of the present invention is usually 3 to 40% by weight, preferably 5 to 30% by weight.
If the amount of (B) is less than 3% by weight, the antistatic property is insufficient, and if it exceeds 40% by weight, the mechanical strength may be reduced.

In the present invention, a polyester resin and / or
Examples of the polyacetal resin (C) include aromatic polyesters such as polybutylene terephthalate, polyethylene terephthalate and polycyclohexane dimethylene terephthalate; aliphatic polyesters such as polybutylene adipate and polyethylene adipate; polyacetals (homopolymers, copolymers) and the like. Can be Preferred among these are polybutylene terephthalate, polyethylene terephthalate and polyacetal.

The melting peak temperature (melting point) determined from DSC (differential scanning calorimetry) of (C) is usually from 140 to 270.
° C, preferably 150 to 260 ° C, particularly preferably 16 ° C.
0 to 240 degrees. When the melting point is lower than 140 ° C., the polyetheresteramide (B) hardly comes out to the surface of the resin molded product, so that the antistatic property is reduced. When the melting point exceeds 270 ° C., kneading may be difficult.

Intrinsic viscosity [η] of (C) (in the case of polyacetal resin; 6% in a 0.5% parachlorophenol solution)
0 ° C., in the case of a polyester resin; 25 ° C. in a 0.5% solution of orthochlorophenol) is not particularly limited, but is usually 0.1 to 4.

The amount of (C) in the resin composition of the present invention is usually 1 to 20% by weight, preferably 3 to 15% by weight.
If the amount of (C) is less than 1% by weight, the antistatic property becomes insufficient, and if it exceeds 20% by weight, the moldability decreases.

The modified low molecular weight polyolefin (D) in the present invention is at least one selected from the following (D1) to (D3). (D1): a number average molecular weight of 800 to 25,000,
Modified low molecular weight polyolefin having an acid value of 5-150. (D2): a number average molecular weight of 800 to 25,000,
A modified low molecular weight polyolefin having a hydroxyl value of 5 to 150. (D3); a part or all of (D1) is esterified with a polyoxyalkylene compound, and has a number average molecular weight of 1,
2,000 to 28,000 modified low molecular weight polyolefins.

[0025] (D1) is a low molecular weight polyolefin having a number average molecular weight of 700 to 20,000 obtained by a polymerization method of propylene and / or ethylene or a thermal degradation method of high molecular weight polypropylene and / or polyethylene, and α, β -It can be obtained by reacting an unsaturated carboxylic acid and / or an anhydride thereof, if necessary, in the presence of an organic peroxide by a solution method or a melting method to modify. From the viewpoint of easy modification, a low molecular weight polyolefin obtained by a thermal degradation method is preferable. The low-molecular-weight polyolefin obtained by the thermal degradation method can be obtained, for example, by the method described in JP-A-3-62804.

The α, β-unsaturated carboxylic acid and / or its anhydride used for the modification include (meth) acrylic acid, (maleic anhydride) maleic acid, fumaric acid, (anhydride) itaconic acid and citraconic anhydride. And the like. Among these, maleic acid (anhydride) is preferred. These amounts used during the modification are usually 1 to 25% by weight, preferably 3 to 2% by weight, based on the weight of the low molecular weight polyolefin.
0% by weight. (D1) obtained by the above method
Has a number average molecular weight of usually 800 to 25,000, preferably 1,000 to 20,000. If the number average molecular weight is less than 800, the heat resistance is poor, and if it exceeds 25,000, the effect as a compatibilizer is poor, and the mechanical properties of the resin composition deteriorate. The acid value of (D1) is usually 5 to 15
0, preferably 10 to 100. If the acid value is less than 5, the effect as a compatibilizer is poor, and if it exceeds 150, the hue deteriorates, which causes coloring of the resin composition.

(D2) can be obtained by subjecting the above (D1) to secondary modification with an alkanolamine or the like. Alkanolamines include, for example, monoethanolamine, monoisopropanolamine, diethanolamine and diisopropanolamine.
Of these, particularly preferred is monoethanolamine. The hydroxyl value of (D1) is usually from 5 to 150, preferably from 10 to 100. If the hydroxyl value is less than 5, the effect of introducing the hydroxyl group is small, and if it exceeds 150, the hue deteriorates, which causes coloring of the resin composition.

(D3) can be obtained by esterifying a part or all of the (anhydride) carboxylic acid unit of the above (D1) with a polyoxyalkylene compound.
Examples of the polyoxyalkylene compound used for the esterification include compounds having hydroxyl groups at both ends, such as polyethylene glycol and polypropylene glycol, and compounds in which the above hydroxyl groups are replaced with amino groups or epoxy groups. Further, alcohols (methanol, ethanol, butanol, octanol, lauryl alcohol,
Polyoxyalkylene compounds having an alkylene oxide added to a compound having active hydrogen such as 2-ethylhexyl alcohol, phenols (phenol, alkylphenol, naphthol, phenylphenol, benzylphenol, etc.) and having a hydroxyl group at one end basically. And the like. The number average molecular weight of these polyoxyalkylene compounds is usually from 300 to 5,000. The esterification rate is not particularly limited, but it is preferable that 10 to 100 mol% of the (anhydrous) carboxylic acid unit of (D1) is esterified. The number average molecular weight of (D3) is usually 1,000 to 28,000, preferably 1,2.
00 to 25,000. If it is less than 1,000, heat resistance is poor, and if it exceeds 28,000, the effect as a compatibilizer is poor.

The modified low molecular weight polyolefins (D1) to (D3) exemplified above may be used in combination of two or more. A modified low-molecular-weight polyolefin having all of a carboxyl group, a hydroxyl group and a polyoxyalkylene group in the molecule may be used.

The amount of (D) in the resin composition of the present invention is usually from 0.2 to 20% by weight, preferably from 0.5 to 10% by weight.
It is. When the amount of (D) is less than 0.2% by weight, the effect as a compatibilizing agent is reduced, so that a problem of phase separation is likely to occur. When it exceeds 20% by weight, the mechanical strength decreases.

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), a method of blending a small amount of (A) and (B) to (D) After kneading, a method of kneading the remaining (A) and a method of blending and kneading (B) to (D) and then kneading (A) can be mentioned. 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.

As a method for obtaining the composition of the present invention via a master batch, (A) 0 to 50 parts by weight, preferably 5 to 20 parts by weight, (B) 3 to 40 parts by weight,
A method of blending and kneading (C) 1 to 20 parts by weight and (D) 0.2 to 20 parts by weight to form a master batch, and blending and kneading the master batch with the remaining amount of (A) is exemplified. it can. In particular, this method has an advantage of uniformly dispersing a small amount of (B) to (D) in a large amount of (A), and the composition of the present invention is preferably formed via the masterbatch.

The resin composition of the present invention may contain a halide (E) of an alkali metal and / or an alkaline earth metal for the purpose of further improving the antistatic property. Examples of (E) include lithium chloride, sodium chloride, potassium chloride, magnesium chloride, calcium chloride, sodium bromide, potassium bromide, and magnesium bromide. Preferred among these are sodium chloride and potassium chloride.

When (E) is used, the amount used is (B)
0.01 to 3% by weight, preferably 0.01%
~ 2% by weight. If the amount is less than 0.01% by weight, no effect is exhibited, and if it exceeds 3% by weight, it may precipitate on the resin surface and impair the appearance of the resin.

There is no particular limitation on the method of adding (E), but from the viewpoint of easy dispersion in the composition,
It is preferable to disperse in advance in the polyetheresteramide (B). When (E) is dispersed in (B), a method of adding (E) and dispersing it during polymerization of (B) is particularly preferable.

The resin composition of the present invention may contain a nonionic, anionic, cationic or amphoteric surfactant (F) to further improve the antistatic property. As nonionic surfactants, higher alcohol ethylene oxide adducts, fatty acid ethylene oxide adducts, higher alkylamine ethylene oxide adducts, polyethylene glycol type nonionic surfactants such as polypropylene glycol ethylene oxide adducts, polyethylene oxide, Glycerin fatty acid ester, pentaerythrit fatty acid ester, sorbit and sorbitan fatty acid ester, polyhydric alcohol alkyl ether,
Examples include polyhydric alcohol type nonionic surfactants such as aliphatic amides of alkanolamines. Examples of the anionic surfactant include carboxylate salts such as alkali metal salts of higher fatty acids, sulfate salts such as higher alcohol sulfate salts and higher alkyl ether sulfate salts, alkylbenzene sulfonates, alkyl sulfonates, and paraffin sulfones. Sulfonates such as acid salts, and phosphate salts such as higher alcohol phosphates, and the like. Examples of the cationic surfactant include quaternary ammonium salts such as an alkyltrimethylammonium 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 sulfonates, alkyl sulfonates, and paraffin sulfonates.

The amount of (F) used is (A), (B),
Usually 0.1 to 5 based on the total weight of (C) and (D)
%, Preferably 0.4 to 3% by weight.

The method of adding (F) 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 may optionally contain other resin additives according to various uses, as long as the properties 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.

[0041]

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. (1) Impact strength: ASTM D256 (notched, 3.2 mm thickness) (2) Flexural modulus: ASTM D790 (3) Surface specific resistance value: A super-insulation meter using a 3 mm-thick injection-molded disk specimen. (Advantest) 2
The measurement was performed in an atmosphere of 0 ° C. and a humidity of 50% RH. (4) Compatibility: Evaluated by bending the molded product and observing the fracture surface. Evaluation criteria ○: good, ×: poor compatibility, delamination.

[Production of Polyetheresteramide] Production Example 1 In a 3 L stainless steel autoclave, 105 parts of ε-caprolactam, 17.1 parts of adipic acid, “Irganox 1010” (antioxidant, manufactured by Ciba-Gaiky) 0.3 And 7 parts of water, and after purging with nitrogen, the mixture was heated and stirred at 220 ° C. for 4 hours while being pressurized and sealed to obtain 117 parts of a polyamide oligomer having an acid value of 100 and having carboxyl groups at both ends.
Next, 225 parts of a bisphenol A ethylene oxide adduct having a number average molecular weight of 2,000 and 0.5 part of zirconyl acetate were added, and the mixture was added at 245 ° C. under a reduced pressure of 1 mmHg or less.
Polymerization was carried out for a time to obtain a viscous polymer. The polymer was taken out in a strand form on a belt and pelletized to obtain a polyetheresteramide. The reduced viscosity (η _SP / C, m-cresol solvent, 25 ° C., C
= 0.5% by weight, the same applies hereinafter) was 2.10. This polyetheresteramide is abbreviated as [B-1] below.

Production Example 2 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. The mixture was heated and stirred for 4 hours in a sealed state to obtain 117 parts of a polyamide oligomer having an acid value of 110 and having carboxyl groups at both ends. Then, 175 parts of polyoxyethylene glycol having a number average molecular weight of 1,500 and 0.5 parts 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. Hereinafter, the same operation as in Production Example 1 was performed to obtain a polyetheresteramide. This had a reduced viscosity of 2.30. This polyether ester amide is referred to below as [B-2]
Abbreviated.

Production Example 3 A 3 L stainless steel autoclave was charged with 83.5 parts of ε-caprolactam, 16.5 parts of terephthalic acid, 0.3 parts of “Irganox 1010” and 6 parts of water. The mixture was heated and stirred for 4 hours while sealing under pressure to obtain 96 parts of oxidized 112 polyamide oligomer having carboxyl groups at both ends. Next, 192 parts of a bisphenol A ethylene oxide adduct having a number average molecular weight of 2,000 and 0.5 part of zirconyl acetate were added, and the mixture was added at 245 ° C. and 1 mmH
Polymerization was performed for 5 hours under a reduced pressure of not more than g to obtain a viscous polymer. Hereinafter, the same operation as in Production Example 1 was performed to obtain a polyetheresteramide. Its reduced viscosity is 2.
It was 10. This polyetheresteramide is abbreviated as [B-3] below.

[Production of modified low-molecular-weight polyolefin] Production Example 4 95 parts of low-molecular-weight polypropylene having a number average molecular weight of 12,000 and a density of 0.89 obtained by a thermal degradation method and 5 parts of maleic anhydride were heated at 180 ° C. under nitrogen. And then 1.5% of dicumyl peroxide dissolved in xylene 50%
The solution was added dropwise over 15 minutes, and after the reaction was performed for 1 hour, the solvent was distilled off to obtain an acid-modified low molecular weight polypropylene. Its acid value is 25.7, number average molecular weight is 15,
000. This modified product is abbreviated as [D-1] below.

Production Example 5 95 parts of [D-1] obtained in Production Example 3 was used in xylene 100
Was dissolved under nitrogen at 120 ° C., and then 5 parts of monoethanolamine was added dropwise over 15 minutes, and the mixture was reacted for 1 hour. Thereafter, the solvent and unreacted monoethanolamine were distilled off to remove hydroxyl groups. To obtain a modified low molecular weight polypropylene. This had a hydroxyl value of 25.2 and a number average molecular weight of 16,000. This modified product is abbreviated as [D-2] below.

Production Example 6 95 parts of [D-1] obtained in Production Example 4 and 50 parts of a 24 mol adduct of lauryl alcohol with ethylene oxide were melted at 180 ° C. under nitrogen, and then esterified under reduced pressure of 10 mmHg for 5 hours. The reaction was carried out to obtain the desired polyoxyalkylene-modified low molecular weight polypropylene. This has a hydroxyl value of 0.5 and a number average molecular weight of 18,000.
Met. In addition, NMR analysis confirmed that the esterification reaction was performed quantitatively. This modified product is abbreviated as [D-3] below.

Production Example 7 A number average molecular weight of 3,000 and a density of 0.
38 parts of low molecular weight polyethylene of 93 and maleic anhydride 2
Of xylene and 140 parts of xylene were dissolved at 140 ° C. under xylene reflux, and then a 50% solution of xylene in which 0.3 part of ditertiary butyl peroxide was dissolved was added dropwise over 15 minutes, and the reaction was continued for 2 hours. After the operation, the solvent was distilled off to obtain an acid-modified low molecular weight polyethylene. This had an acid value of 28.0 and a number average molecular weight of 3,800.
This modified product is abbreviated as [D-4] below.

[Preparation of Masterbatch] Production Example 8 After blending the components (A) to (D) in the proportions shown in Table 1 for 3 minutes using a Henschel mixer, the mixture was heated at 240 ° C. using a vented twin-screw extruder. The mixture was melt-kneaded under the conditions of 100 rpm and a residence time of 5 minutes to obtain master batches (M-1) to (M-3).

[0050]

[Table 1] (Note) [A-1]; polypropylene [trade name Ube Polypro J
609, manufactured by Ube Industries, Ltd.] [A-2]; polyethylene [trade name: Staphrene E75]
0 (C), manufactured by Nippon Petrochemical Co., Ltd.] [C-1]; polybutylene terephthalate [trade name: Duranex 2000, manufactured by Polyplastics Co., Ltd.]

Examples 1 to 5 Masterbatches (M-1) to (M-4), polyolefin resin (A) and alkali metal salt (E) shown in Table 2
Was blended and kneaded under the same conditions as in Production Example 8 to obtain a composition of the present invention. Table 2 shows the composition of the resin composition of the present invention via the masterbatch and the final ratio of each component.

[0052]

[Table 2]

Examples 6 to 12 and Comparative Examples 1 to 4 The ratios (A) to (D) shown in Table 3 were blended and kneaded under the same conditions as in Production Example 8 to obtain the composition of the present invention and the comparative composition. I got something.

[0054]

[Table 3] (Note) [C-2]: Polyacetal [Product name DURACON M9
0 Polyplastics Co., Ltd.] [E-1]: Potassium chloride (added during production of polyetheresteramide) * 1): The ratio of metal salt (E) is the ratio (%) to the weight of (B). .

Performance Test A test piece was prepared from the composition of the present invention and a comparative composition using an injection molding machine at a cylinder temperature of 240 ° C. and a mold temperature of 50 ° C., and the resin properties and antistatic properties were evaluated. Table 4 shows the results. The antistatic property was evaluated by subjecting the test piece to the treatment and conditioning described below and measuring the surface specific resistance. (A) After molding, the test piece is kept at 20 ° C. and humidity 50% R
Leave for 24 hours under H atmosphere. (B) After molding, test specimens were washed with detergent (mama lemon; lion
After washing with an aqueous solution and then sufficiently washing with ion-exchanged water, the water on the surface was dried and removed, and then at 20 ° C.
Left in a 50% RH atmosphere for 24 hours.

[0056]

[Table 4]

As is apparent from Table 4, the resin composition of the present invention is superior in permanent antistatic properties as compared with Comparative Examples 1 and 2, and superior in mechanical properties as compared with Comparative Examples 2, 3 and 4. . That is, it is a polyolefin-based resin composition having both excellent permanent antistatic properties and mechanical properties that could not be achieved conventionally. In particular, the composition via the masterbatch (Examples 1 to 5) is the composition without the corresponding masterbatch (Examples 6, 7, 8, 10 and 1).
It is superior to the performance of 2). This indicates that the small components are uniformly dispersed and contribute to the performance. Further, by adding a metal salt, particularly excellent performance (permanent antistatic property) is exhibited.

[0058]

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 is extremely useful as various molding materials requiring antistatic properties of housing products for home appliances and OA equipment, various plastic containers, automobile parts, and the like.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical display location C08L77 / 12 LQS C08L 77/12 LQS LQT LQT // C08J 5/00 CES C08J 5/00 CES

Claims (4)

(57) [Claims] 1. Polyolefin resin (A) 55 to 95
% By weight, 3 to 40% by weight of a polyetheresteramide (B), 1 to 20% by weight of a polyester resin and / or a polyacetal resin (C), and (D1) to
(D3) A resin composition comprising one or more modified low-molecular-weight polyolefins (D) selected from the group consisting of 0.2 to 20% by weight. (D1): a number average molecular weight of 800 to 25,000,
Modified low molecular weight polyolefin having an acid value of 5-150. (D2): a number average molecular weight of 800 to 25,000,
A modified low molecular weight polyolefin having a hydroxyl value of 5 to 150. (D3); a part or all of (D1) is esterified with a polyoxyalkylene compound, and has a number average molecular weight of 1,
2,000 to 28,000 modified low molecular weight polyolefins. 2. A polyamide (b) having a carboxyl group at both terminals and having a number average molecular weight of 200 to 5,000.
The resin composition according to claim 1, which is a polyetheresteramide derived from 1) and an alkylene oxide adduct (b2) of a bisphenol having a number average molecular weight of 300 to 5,000. 3. The method according to claim 1, wherein (C) is at least one selected from a polybutylene terephthalate resin, a polyethylene terephthalate resin and a polyacetal resin.
Or the resin composition according to 2. 4. A small amount of polyolefin resin (A), polyetheresteramide (B), polyester resin and / or polyacetal resin (C) and modified low molecular weight polyolefin (D) or polyetheresteramide (B) The resin composition according to any one of claims 1 to 3, which is obtained via a master batch comprising a) a) a polyester resin and / or a polyacetal resin (C) and a modified low-molecular-weight polyolefin (D).