JPH0848823A - Resin composition - Google Patents

Abstract

PURPOSE:To provide a resin composition composed of a polyolefinbased resin, a polyether ester amide, a crystal nucleating agent and a specified modified low-molecular polyolefin, excellent in permanent antistatic properties, mechanical strength and moldability and useful as, e.g. a housing material for OA machine. CONSTITUTION:This resin composition is composed of (A) 55 to 95wt.% polyolefin resin, (B) 3 to 40wt.% polyether ester amide, (C) 0.01 to 5wt.% crystal nucleating agent and (D) 0.2 to 10wt.% alpha,beta-unsaturated carboxylic acid (anhydride)-modified polyolefin (D1) having 800 to 25000 number-average molecular weight (Mn) and 5 to 150mg KOH/g acid value, modified polyolefin synthesized by conducting secondary modification of D1 with aminoalcohol and having 800 to 25000Mn and 5 to 150mg KOH/g OH value or low molecular modified polyolefin synthesized by partly or wholly esterifying the carboxylic acid (anhydride) units of D1 and having 1000 to 28000Mn.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a resin composition.
More specifically, it relates to a polyolefin resin composition excellent in permanent antistatic property and mechanical strength.

[0002]

2. Description of the Related Art Conventionally, as a method of imparting permanent antistatic property to polyolefin, (1) a method of adding a polyetheresteramide to polypropylene has been proposed (Japanese Patent Publication No. 4-5691). However, this method has a problem that the polypropylene and the polyether ester amide have poor compatibility with each other, so that phase separation occurs and the resin strength decreases. Furthermore, since polypropylene is a crystalline resin, during molding, the surface of the molded product preferentially becomes a polypropylene phase, and since polyetheresteramide does not easily appear on the surface, in order to impart substantial antistatic properties, It was necessary to add large amounts of polyetheresteramide. In order to improve this, for the purpose of improving the compatibility between the polyolefin and the polyether ester amide,
(2) A method in which a modified polyolefin is used in combination has been proposed (JP-A-1-163234 and JP-A-3-29).
No. 0464 publication). However, in this method, the problem of phase separation is solved by using a modified polyolefin in combination, but the problem that polyether ester amide hardly appears on the surface of a crystalline molded polyolefin product has not been solved.

[0003]

Therefore, there is a strong demand for a polyolefin resin composition having good permanent antistatic properties and excellent mechanical strength.

[0004]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that a crystal nucleating agent and a modified low molecular weight polyolefin are added to a mixture of a polyolefin resin and a polyetheresteramide. By
Since the crystallization rate of the polyether ester amide is high and it is easy to be immobilized on the surface of the composition, addition of a small amount of the polyether ester amide has a permanent antistatic property, and since the compatibility is good, the mechanical strength is improved. It was found that an excellent polyolefin resin composition can be obtained, and the present invention has been achieved.

That is, according to the present invention, the polyolefin resin (A) is 55 to 95% by weight, the polyether ester amide (B) is 3 to 40% by weight, the crystal nucleating agent (C) is 0.01 to 5% by weight, and the following (D1 ) To (D3), a resin composition comprising 0.2 to 10% by weight of one or more modified low molecular weight polyolefin (D). (D1); modified with an α, β-unsaturated carboxylic acid and / or its anhydride, and has a number average molecular weight of 800 to 2
Modified low molecular weight polyolefin having an acid value of 5,000 and an acid value of 5 to 150 mgKOH / g. (D2); (D1) is secondarily modified with amino alcohol, and has a number average molecular weight of 800 to 25,000 and a hydroxyl value of 5
~ 150 mg KOH / g modified low molecular weight polyolefin. (D3): A modified low molecular weight polyolefin having a number average molecular weight of 1,000 to 28,000, which is obtained by esterifying a part or all of the (anhydrous) carboxylic acid unit of (D1) with a polyoxyalkylene compound.

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. The melt flow rate (MFR) of (A) is usually 0.5 to 150, preferably 1 to 100. The melt flow rate is JIS K6758 (for polypropylene resin; temperature 230 ° C., load 2.16 kgf,
In case of polyethylene resin; temperature 190 ℃, load 2.1
It can be measured according to 6 kgf). The crystallinity of (A) is usually 25% or more, preferably 30% or more. The crystallinity can be measured by a method such as X-ray diffraction and infrared absorption spectrum.

The amount of (A) in the resin composition of the present invention is 5
It is 5 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 5% by weight, the antistatic property deteriorates.

In the present invention, examples of the polyether ester amide (B) include the polyether ester amides described in Japanese Patent Application No. 6-95888 and Japanese Patent Publication No. 4-5691. Among these, preferred is a number average molecular weight of 200 having a carboxyl group.
Up to 5,000 polyamides (b1) and a number average molecular weight of 3
Polyether ester amides derived from alkylene oxide adducts (b2) of bisphenols of 0 to 5,000 and / or polyoxyalkylene glycols (b3), and particularly preferred are (b1) and (b2). It is a polyether ester amide derived from

(B1) is (1) a lactam ring-opening polymer,
(2) A polycondensation product of aminocarboxylic acid or (3) a polycondensation product of dicarboxylic acid and diamine. Examples of the lactam of (1) include caprolactam, enanthlactam, laurolactam, and undecanolactam.
Examples of the aminocarboxylic acid of (2) include ω-aminocaproic acid, ω-aminoenanthic acid, ω-aminocaprylic acid,
ω-aminopergonic acid, ω-aminocapric acid, 11-
Examples include aminoundecanoic acid and 12-aminododecanoic acid. As the dicarboxylic acid of (3), adipic acid,
Examples thereof include azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, and isophthalic acid, and examples of the diamine include hexamethylenediamine, heptamethylenediamine, octamethylenediamine, decamethylenediamine, and the like. Two or more of the above-mentioned polyamide-forming monomers may be used in combination. Of these, preferred are caprolactam, 12-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. . As the dicarboxylic acid having 4 to 20 carbon atoms, aliphatic dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid and dodecanedioic acid; terephthalic acid, isophthalic acid, Aromatic dicarboxylic acids such as phthalic acid and naphthalenedicarboxylic acid; 1,4-
Cyclohexanedicarboxylic acid, dicyclohexyl-4,
Alicyclic dicarboxylic acids such as 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 thereof. Of 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 the above (b1) is usually 20.
It is 0 to 5,000, preferably 500 to 3,000. When the number average molecular weight is less than 200, 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 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. Among these, preferred is bisphenol A. 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, preferred is ethylene oxide.

Polyoxyalkylene glycol (b3)
Include polyoxyethylene glycol, polyoxypropylene glycol and polyoxybutylene glycol, and of these, 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.
3,000, particularly preferably 1,600 to 3,000. If the number average molecular weight is less than 300, the antistatic property will be insufficient, and if it exceeds 5,000, the reactivity will decrease, and therefore a great amount of time will be required during the production of the polyetheresteramide.

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

Examples of the production method of (B) include the following production methods or production methods, but are not particularly limited. Production method: a method of reacting an amide-forming monomer and a dicarboxylic acid to form (b1), adding (b2) and / or (b3) thereto, and performing a polymerization reaction at high temperature and reduced pressure. Production method: An amide-forming monomer and a dicarboxylic acid and (b2) and / or (b3) are simultaneously charged in a reaction vessel, and pressure-reacted at high temperature in the presence or absence of water to give an intermediate (b1). ) Is then produced under reduced pressure with (b1), (b2) and / or (b
3) A method of carrying out a polymerization reaction with.

Known esterification catalysts are usually used in the above polymerization reaction. Examples of the catalyst include antimony-based catalysts such as antimony trioxide, tin-based catalysts such as monobutyltin oxide, titanium-based catalysts such as tetrabutyl titanate, zirconium-based catalysts such as tetrabutylzirconate, and metal acetate-based catalysts such as zinc acetate. Examples include catalysts. The amount of these used is usually 0.1 to the total weight of (b1) and (b2) and / or (b3).
It is 5% by weight.

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.
When it exceeds, the moldability of the resin composition is deteriorated.

The amount of (B) in the resin composition of the present invention is usually 3 to 40% by weight, preferably 3 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 moldability may decrease.

In the present invention, the crystal nucleating agent (C) is (B)
Promotes crystallization (that is, raises crystallization temperature)
Used for. Examples of the (C) include dibenzylidene sorbitol-based crystal nucleating agents such as dibenzylidene sorbitol, bis (p-methyldibenzylidene) sorbitol, and bis (p-ethyldibenzylidene) sorbitol; disodium hydrogen phosphate, dihydrogen phosphate. Sodium, magnesium oxide, titanium oxide, zinc oxide, calcium carbonate,
Inorganic crystal nucleating agents such as sodium carbonate, calcium silicate, magnesium silicate, magnesium sulfate, barium sulfate, talc, kaolin, alumina, silica, clay; sodium acetate, sodium benzoate, sodium p-t-butylbenzoate, Organic carboxylic acid salt type crystal nucleating agents such as sodium hydrogen phthalate, sodium stearate, calcium stearate, magnesium stearate, sodium palmitate; bis (4-t-butylphenyl) sodium phosphate, phosphoric acid 2,2′- Examples include phosphoric acid ester sodium salt-based crystal nucleating agents such as methylenebis (4,6-di-t-butylphenyl) sodium,
Two or more kinds of those exemplified as these crystal nucleating agents may be used in combination. Of these, preferred are dibenzylidene sorbitol-based crystal nucleating agents, inorganic-based crystal nucleating agents, and combinations thereof. When an inorganic crystal nucleating agent is used, the particle size is 0.01 to 10 because it is easily dispersed in the resin composition.
It is preferably used in the form of fine particles of 0 μm.

The amount of (C) in the resin composition of the present invention is usually 0.01 to 5% by weight, preferably 0.1 to 2% by weight.
Is. When the amount of (C) is less than 0.01% by weight, (B)
The effect of increasing the crystallization temperature of is insufficient, and as a result, the antistatic property may be insufficient.
If it exceeds, mechanical strength may decrease.

The modified low molecular weight polyolefin (D) in the present invention is at least one selected from the following (D1) to (D3). (D1); modified with an α, β-unsaturated carboxylic acid and / or its anhydride, and has a number average molecular weight of 800 to 2
Modified low molecular weight polyolefin having an acid value of 5,000 and an acid value of 5 to 150 mgKOH / g. (D2); (D1) is secondarily modified with amino alcohol, and has a number average molecular weight of 800 to 25,000 and a hydroxyl value of 5
~ 150 mg KOH / g modified low molecular weight polyolefin. (D3): A modified low molecular weight polyolefin having a number average molecular weight of 1,000 to 28,000, which is obtained by esterifying a part or all of the (anhydrous) carboxylic acid unit of (D1) with a polyoxyalkylene compound.

(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 or ethylene or a thermal degradation method of high molecular weight polypropylene or high molecular weight polyethylene, and α, β- It can be obtained by reacting an unsaturated carboxylic acid and / or its anhydride in the presence of an organic peroxide, if necessary, by a solution method or a melting method to modify. As the low-molecular-weight polyolefin used for the modification, a low-molecular-weight polyolefin obtained by a thermal degradation method, which has a large number of double bonds in the molecule and is easily modified, 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.

Examples of the α, β-unsaturated carboxylic acid or its anhydride used for modification include (meth) acrylic acid, (anhydrous) maleic acid, fumaric acid, (anhydrous) itaconic acid, and citraconic anhydride. Can be mentioned. Among these, (anhydrous) maleic acid is preferable. These amounts used during modification are usually 1 to 25% by weight, preferably 3 to 20% by weight, based on the weight of the low molecular weight polyolefin. The number average molecular weight of (D1) obtained by the above method is usually 800 to 25,000, preferably 1,000 to 20,000. Number average molecular weight is 80
If it is less than 0, the heat resistance is poor, and if it exceeds 25,000, the effect as a compatibilizer becomes poor, and the mechanical properties of the resin composition deteriorate. Also, the acid value of (D1) (mgKOH / g)
Is usually 5 to 150, preferably 10 to 100.
If the acid value is less than 5, the effect as a compatibilizer is poor, and
When it exceeds 0, the hue deteriorates, which causes coloring of the resin composition.

(D2) can be obtained by secondarily modifying the above (D1) with an alkanolamine or the like. Examples of the alkanolamine include monoethanolamine, monoisopropanolamine, diethanolamine, diisopropanolamine and the like. Of these, particularly preferred is monoethanolamine. The hydroxyl value (mgKOH / g) of the (D2) is usually 5 to 150, preferably 10 to 100.

(D3) can be obtained by esterifying a part or all of the (anhydrous) carboxylic acid unit of the above (D1) with a polyoxyalkylene compound.
Examples of the polyoxyalkylene compound used for esterification include compounds having hydroxyl groups at both ends such as polyethylene glycol and polypropylene glycol; compounds in which the above hydroxyl groups are replaced with amino groups or epoxy groups; alcohols (methanol, ethanol, butanol, Alkylene oxide is added to compounds having active hydrogen such as octanol, lauryl alcohol, 2-ethylhexyl alcohol, etc.) and phenols (phenol, alkylphenol, naphthol, phenylphenol, benzylphenol, etc.), and basically a hydroxyl group is added to one end. Examples thereof include polyoxyalkylene compounds. The number average molecular weight of these polyoxyalkylene compounds is usually 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 the (D3) is usually 100
0-28,000, preferably 1,200-25,000
0. If the number average molecular weight is less than 1,000, the heat resistance is poor, and if it exceeds 28,000, the effect as a compatibilizer becomes poor.

The modified low molecular weight polyolefins (D1) to (D3) exemplified above may be used in combination of two or more kinds. A modified low molecular weight polyolefin having any 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 0.2 to 10% by weight, preferably 0.5 to 5% by weight. When the amount of (D) is less than 0.2% by weight, the compatibilizing effect becomes small and the problem of phase separation of the resin composition easily occurs.
If it exceeds 0% by weight, the mechanical strength decreases.

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

As an example of the method for obtaining the composition of the present invention via a masterbatch, for example, (A) 0 to 50 parts by weight, preferably 10 to 40 parts by weight, and (B) 3 to 40 parts by weight, (C) 0.01 to 5 parts by weight and (D) 0.2 to
A method may be mentioned in which 10 parts by weight are blended and kneaded to form a masterbatch, and the masterbatch and the remaining (A) are blended and kneaded. This method has an advantage that a small amount of (B) to (D) can be uniformly dispersed in a large amount of (A), so that the resin composition of the present invention must be passed through the masterbatch. Is preferred.

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 the (E) include lithium chloride, sodium chloride, potassium chloride, magnesium chloride, calcium chloride, sodium bromide, potassium bromide, magnesium bromide and the like. Preferred among these are sodium chloride and potassium chloride.

The amount of (E) used is usually 0.01 to 3% by weight, preferably 0.05 to 2% by weight, based on the weight of (B). If it is less than 0.01% by weight, the effect is not exhibited and 3
If it exceeds 5% by weight, it may be deposited on the surface of the resin and impair the appearance of the resin.

The method of adding (E) is not particularly limited, but from the viewpoint of effective dispersibility in the composition,
It is preferably dispersed in the polyether ester amide (B) in advance. When (E) is dispersed in (B), it is particularly preferable to add (E) in advance during the polymerization of (B) and disperse it.

The resin composition of the present invention may optionally contain a known nonionic, anionic, cationic or amphoteric surfactant (F). These may be used alone or in combination of two or more, and preferred ones among them are anionic surfactants (carboxylic acid salts such as alkali metal salts of higher fatty acids, higher alcohol sulfuric acid ester salts, higher alkyl ether sulfuric acid esters). Sulfate salts such as salts, alkylbenzene sulfonates, alkyl sulfonates, sulfonates such as paraffin sulfonates, phosphoric acid ester salts such as higher alcohol phosphoric acid ester salts, etc.), and particularly preferred are alkylbenzene sulfone Sulfonates such as acid salts, alkyl sulfonates, and paraffin sulfonates.

The amount of (F) used is (A), (B),
Usually 0.1 to 5 relative to the total weight of (C) and (D)
%, Preferably 0.4-3% by weight. If the amount of (F) is less than 0.1% by weight, the effect is not exhibited, and if it exceeds 5% by weight, it may be deposited on the resin surface to impair the appearance of the resin or the physical properties of the resin may be deteriorated, which is not preferable. .

When (F) is used, the addition method is not particularly limited, but in order to effectively disperse it in the composition, it should be dispersed in (A) or (B) in advance. Is preferred.

Further, other known resin additives may be optionally added to the resin composition of the present invention in a range that does not impair the characteristics of the composition, according to various uses. Examples of the additives include pigments, dyes, fillers, glass fibers, lubricants, plasticizers, release agents, antioxidants, flame retardants, and ultraviolet absorbers.

[0039]

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 based on the following test methods. (1) Impact strength: ASTM D256 (with notch) (2) Bending elastic modulus: ASTM D790 (3) Surface specific resistance value: 20 by a super insulation meter (manufactured by Advantest) using injection-molded test pieces with a thickness of 2 mm
The measurement was carried out in an atmosphere of RH and 65% RH. (4) Compatibility: Evaluated by bending the molded product and observing the fracture surface. Evaluation criteria ○: Good, ×: Poor compatibility, delamination.

[Production of Polyether Ester Amide (B)] Production Example 1 3L stainless steel autoclave was charged with 42.3 parts of ε-caprolactam, 5.6 parts of terephthalic acid, and "Irganox 1010" (antioxidant, Ciba-Gaiki Co., Ltd.). Made) 0.2
And 3 parts of water were charged, and after nitrogen substitution, the mixture was heated and stirred at 220 ° C. under pressure and sealing for 4 hours to obtain 47.0 parts of a polyamide oligomer having a carboxyl group at both ends and a number average molecular weight of 1,400. Next, 53.8 parts of bisphenol A ethylene oxide adduct having a number average molecular weight of 1,600 and 0.5 part of zirconyl acetate were added, and the temperature was 230 ° C. and 1 mmHg.
Polymerization was performed for 5 hours under the following reduced pressure conditions 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. The reduced viscosity of this product was 1.90 (m-cresol, 25 ° C., C = 0.5% by weight). This polyetheresteramide is abbreviated as [B-1] below.

Production Example 2 A 3L stainless steel autoclave was charged with 40.5 parts of ε-caprolactam, 5.1 parts of adipic acid, 0.2 parts of "Irganox 1010" and 2 parts of water, and after substitution with nitrogen, at 220 ° C. The mixture was heated and stirred for 4 hours under pressure and closed to obtain 45.2 parts of a polyamide oligomer having a carboxyl group at both ends and a number average molecular weight of 1,300. Next, 55.6 parts of a bisphenol A ethylene oxide adduct having a number average molecular weight of 1,600 and 0.5 part of zirconyl acetate were added to obtain 230
Polymerization was carried out for 5 hours under reduced pressure of 1 ° C. or less and 1 mmHg to obtain a viscous polymer. Thereafter, the same operation as in Production Example 1 was performed to obtain a polyetheresteramide. The reduced viscosity of this product was 2.00 (m-cresol, 25 ° C., C = 0.
5% by weight). This polyether ester amide is abbreviated as [B-2] below.

[Production of Modified Low Molecular Weight Polyolefin (D)] Production Example 3 95 parts of low molecular weight polypropylene having a number average molecular weight of 12,000 and a density of 0.89 obtained by thermal degradation and 5 parts of maleic anhydride were nitrogenated. 50% xylene with 1.5 parts dicumyl peroxide
The solution was added dropwise over 15 minutes, and after the reaction was carried out for 1 hour, the solvent was distilled off to obtain an acid-modified low molecular weight polypropylene. This product has an acid value of 25.7 and a number average molecular weight of 15,
It was 000. This modified product is abbreviated as [D-1] below.

Production Example 4 Acid-modified low molecular weight polypropylene 95 obtained in Production Example 3
Parts were dissolved in 100 parts of xylene under nitrogen at 120 ° C., and then 5 parts of monoethanolamine was added dropwise over 15 minutes, and after the reaction was carried out for 1 hour, the solvent and unreacted monoethanolamine were distilled off. Thus, a modified low molecular weight polypropylene having a hydroxyl group was obtained. The hydroxyl value of this product is 2
It was 5.2 and the number average molecular weight was 16,000.
This modified product is abbreviated as [D-2] below.

Production Example 5 Number average molecular weight 3,000 obtained by thermal degradation, density of 0.
92 low molecular weight polyethylene 95 parts, maleic anhydride 5
And 60 parts of xylene were melted under nitrogen at 140 ° C., and then a 50% xylene solution containing 1.5 parts of tertiary butyl peroxide was added dropwise over 15 minutes.
Then, the reaction was carried out for 2 hours, and then the solvent was distilled off to obtain an acid-modified low molecular weight polyethylene. 95 parts of this acid-modified low-molecular-weight polyethylene and 50 parts of an ethylene oxide 24 mol adduct of lauryl alcohol are melted under nitrogen at 180 ° C., and then subjected to an esterification reaction under a reduced pressure of 10 mmHg for 5 hours to give a polyoxyalkylene-modified low-molecular-weight polyethylene. Got This product had a hydroxyl value of 0.5 and a number average molecular weight of 7,000. Moreover, from the analysis by NMR,
It was confirmed that the esterification reaction was performed quantitatively.
This modified product is abbreviated as [D-3] below.

Production Example 6 (A) to (D) in the proportions shown in Table 1 were blended in a Henschel mixer for 3 minutes, and then in a twin-screw extruder with a vent, conditions of 230 ° C., 50 rpm, and residence time of 5 minutes. And melt-kneaded to obtain master batches (M-1) to (M-3).

[0046]

[Table 1] (Note) [A-1]: Polypropylene "UBE Polypro J609H" manufactured by Ube Industries, Ltd. [A-2]: Polyethylene "Stafflen E750 (C)" manufactured by Nippon Petrochemical Co., Ltd. [C-1]: Dibenzylidene Sorbitol-based crystal nucleating agent "Gel All MD" manufactured by Shin Nippon Rika Co., Ltd. [C-2]: disodium hydrogen phosphate

Examples 1 to 3 Masterbatches (M-1) to (M-3) obtained in Production Example 6
Polypropylene resins [A-1] and [A-2] were blended and kneaded under the same conditions as in Production Example 6 to obtain a composition of the present invention. Table 2 shows the final ratio of each of the components (A) to (D) in the composition of the present invention via the masterbatch.

[0048]

[Table 2]

Examples 4 to 7 and Comparative Examples 1 to 4 (A) to (E) or (A) to (D) shown in Table 3.
Were blended and kneaded under the same conditions as in Production Example 6 to obtain a composition of the present invention and a comparative composition.

[0050] (Note) [E-1]: Sodium chloride (added when kneading with a twin-screw extruder) [E-2]: Potassium chloride (added when producing polyetheresteramide) * 1): The ratio of the metal salt (E) is ( Ratio of B) to weight

Performance Evaluation A test piece was prepared from the composition of the present invention and the comparative composition using an injection molding machine at a cylinder temperature of 220 ° C. and a mold temperature of 50 ° C., and the resin physical properties and antistatic properties were evaluated. The measurement results are shown in Table 4. The antistatic property was evaluated by subjecting the test piece to the treatment and conditioning shown below and measuring the surface resistivity. (A) After molding, the test piece is kept at 20 ° C. and humidity 50% R
Leave in H atmosphere for 24 hours. (B) After molding, the test piece was washed with a detergent (Mama Lemon; Lion).
(Manufactured by K.K.), followed by washing with an aqueous solution, followed by thorough washing with ion-exchanged water, and after removing water on the surface by drying, at 20 ° C.
Leave for 24 hours in an atmosphere of 50% humidity RH.

[0052]

[Table 4]

[0053]

EFFECT OF THE INVENTION The resin composition of the present invention has an excellent permanent antistatic property that cannot be achieved by the conventional techniques, and is excellent in mechanical properties and moldability. Since it has the above-mentioned effects, the resin composition of the present invention is extremely useful as a molding material that requires various antistatic properties such as housing products for home electric appliances and OA equipment, various plastic containers, packaging materials, and automobile parts. .

Claims (4)

[Claims] 1. Polyolefin resin (A) 55 to 95
% By weight, 3 to 40% by weight of polyetheresteramide (B), 0.01 to 5% by weight of crystal nucleating agent (C), and one or more modified low molecular weight polyolefins (D) selected from the following (D1) to (D3). ) A resin composition comprising 0.2 to 10% by weight. (D1); modified with an α, β-unsaturated carboxylic acid and / or its anhydride, and has a number average molecular weight of 800 to 2
Modified low molecular weight polyolefin having an acid value of 5,000 and an acid value of 5 to 150 mgKOH / g. (D2); (D1) is secondarily modified with amino alcohol, and has a number average molecular weight of 800 to 25,000 and a hydroxyl value of 5
~ 150 mg KOH / g modified low molecular weight polyolefin. (D3): A modified low molecular weight polyolefin having a number average molecular weight of 1,000 to 28,000, which is obtained by esterifying a part or all of the (anhydrous) carboxylic acid unit of (D1) with a polyoxyalkylene compound. 2. Further, it is 0.01 with respect to the weight of (B).
The resin composition according to claim 1, which comprises -3 wt% of an alkali metal and / or alkaline earth metal halide (E). 3. The resin composition according to claim 1, wherein (C) is a dibenzylidene sorbitol type crystal nucleating agent and / or an inorganic type crystal nucleating agent. 4. (B) is derived from a polyamide (b1) having a carboxyl group and a number average molecular weight of 200 to 5,000 and an alkylene oxide adduct (b2) of a bisphenol having a number average molecular weight of 300 to 5,000. The resin composition according to any one of claims 1 to 3, which is a polyetheresteramide.