JPH03247637A - Polyolefin blown hollow molded material - Google Patents

Abstract

PURPOSE:To obtain a polyolefin blown hollow molded material having permanent antistatic properties and excellent surface properties of the molded material by mixing a specific amount of specific polyether ester amide. CONSTITUTION:(A) 60-99wt.%, preferably 60-98wt.% polyolefin (e.g. polyethylene or polypropylene) is mixed with (B) 40-1wt.%, preferably 40-2wt.% polyether ester amide obtained by copolymerization of B1: >=6C aminocarboxylic acid or lactam, or salt of >=6C diamine and dicarboxylic acid (e.g. caprolactam or 12-aminododecanoic acid), B2: poly(alkylene oxide) glycol having 200-6000 number-average molecular weight (e.g. polyethylene glycol) and B3: 4-20C dicarboxylic acid (e.g. terephthalic acid) so as to contain 10-90wt.% polyether ester unit.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a polyolefin blow molded article having permanent antistatic properties.

, [Prior Art] A method of blow molding a resin composition obtained by kneading a nonionic antistatic agent with a polyolefin resin to obtain a hollow molded product with excellent antistatic properties (Japanese Patent Laid-Open No. 56-50942) Publications) are well known.

On the other hand, a resin composition in which a polyolefin resin is mixed with a polyether ester amide is also known (Japanese Patent Application Laid-Open No. 1983-1979-1).
118838).

[Problems to be Solved by the Invention] However, the method of kneading an antistatic agent into a polyolefin resin is not satisfactory because the antistatic effect is lost when the surface of the molded product is wiped with a cloth or washed with water.

In addition, the bleed-out antistatic agent covers the surface of the molded product at a high concentration, causing problems with the surface characteristics of the molded product, such as deterioration of printability.

Therefore, an object of the present invention is to provide a permanently antistatic hollow molded product whose antistatic properties are not impaired by environments such as wiping with a cloth or washing with water, and which has excellent molded product surface characteristics.

[Means for Solving the Problems] It has been found that the above-mentioned problems of the present invention can be achieved by forming a blow molded product from a polyolefin resin containing 1 to 40% by weight of a specific polyether ester amide, and the present invention reached.

That is, the present invention comprises (A) 60 to 99% by weight of polyolefin, (B) (a
) Aminocarboxylic acid or lactam having 6 or more carbon atoms, or salt of diamine and dicarboxylic acid having 6 or more carbon atoms, (b) Poly(alkylene oxide) glycol having a number average molecular weight of 200 to 6000, and (c) Number of carbon atoms. A polyolefin blow molded product made by blow molding a resin composition consisting of 40 to 1% by weight of polyether ester amide, which is copolymerized with 4 to 20 dicarboxylic acids so that the polyether ester units are 10 to 90% by weight. be.

The present invention will be specifically explained below.

The polyolefin (A) used in the present invention includes:
Mention may be made of polyethylene, polypropylene, ethylene/propylene copolymers, ethylene/propylene/genterpolymers, ethylene/butene-1 copolymers, ethylene/vinyl acetate copolymers and mixtures thereof, in particular polyethylene, polypropylene, ethylene/propylene Copolymers are preferably used.

Examples of the (a) aminocarboxylic acid or lactam having 6 or more carbon atoms, or the salt of diamine and dicarboxylic acid having 6 or more carbon atoms, which are the constituent components of the polyether ester amide (B) in the present invention, include ω-aminocaproic acid;
Aminocarboxylic acids such as ω-aminoenantoic acid, ω-aminocaprylic acid, ω-aminopergonic acid, ω-aminocapric acid and 11-aminoundecanoic acid, 12-aminododecanoic acid, or caprolactam, enantholactam, capryllactam and laurolactam Salts of lactams and diamine dicarboxylic acids such as hexamethylenediamine-adipate, hexamethylenediamine-sebacate and hexamethylenediamine-isophthalate are used, in particular caprolactam, 12-aminododecanoic acid, hexamethylenediamine Diamine-adipate is preferably used.

(B) Constituent component of polyether ester amide (
b) As poly(alkylene oxide) glycol,
Polyethylene glycol, poly(1,2-propylene oxide) glycol, poly(1,3-propylene oxide) glycol, poly(tetramethylene oxide) glycol, poly(hexamethylene oxide) glycol,
Block or random copolymers of ethylene oxide and propylene oxide and block or random copolymers of ethylene oxide and tetrahydrofuran are used.

Among these, polyethylene glycol is particularly preferably used because of its excellent antistatic properties.

The number average molecular weight of poly(alkylene oxide) glycol is used in the range of 200 to 6,000, particularly 250 to 4,000. If the number average molecular weight is less than 200, the mechanical properties of the resulting polyether ester amide will be poor, and the number If the average molecular weight exceeds 6.000, antistatic properties will be insufficient, which is not preferable.

Furthermore, within the range that does not impair the effects of the present invention, the general formula (
A diol compound represented by I> can be copolymerized.

H+Rl+-0-A r -0-1-R2→-Hm
n...
(I) (Wherein, Ar represents an aromatic group or alicyclic group having 6 to 20 carbon atoms, R1 and R2 represent an ethylene oxide group or a propylene oxide group, and m and n are each an integer of 1 to 15. ) The diol compound represented by the above formula (I>) has the following formula (
Compounds represented by II) to (IV> and their halogen derivatives are included.

(In the formula, R1 and R2 represent an ethylene oxide group or a propylene oxide group, and Y is a covalent bond, an alkylene group having 1 to 6 carbon atoms, an alkylidene group, a cycloalkylidene group, an arylalkylidene group, 0, so, so
□ indicates CO1S, CF2, C(cF3)2 or NH.

Moreover, m and n each represent an integer of 1 to 15.

Specifically, preferred diol compounds include ethylene oxide adducts of hydroquinone, ethylene oxide adducts of bisphenol A, ethylene oxide adducts of brominated bisphenol A, ethylene oxide adducts of bisphenol S, ethylene oxide adducts of dihydroxynaphthalene, and the like. These include block polymers, and particularly preferred are ethylene oxide adducts of bisphenol A and block polymers thereof.

- The amount of the diol compound represented by formula (I>) is not particularly limited, but it is preferably in the range of 0 to 60% by weight based on the polyether ester unit obtained by copolymerizing with (c).

(B) Constituent component of polyether ester amide (
c) Dicarboxylic acids having 4 to 20 carbon atoms include terephthalic acid, 'isophthalic acid, phthalic acid, naphthalene-2,
Aromatic dicarboxylic acids such as 6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, diphenyl-4,4-monodicarboxylic acid, diphenoxyethanedicarboxylic acid and sodium 3-sulfoisophthalate, 1°4-cyclohexanedicarboxylic acid , 1,2-cyclohexanedicarboxylic acid and dicyclohexyl-4,4-monodicarboxylic acid and fatty acids such as succinic acid, oxalic acid, adipic acid, sebacic acid and dodecanedioic acid (decanedicarboxylic acid). Among them, terephthalic acid, isophthalic acid, 1,4-cyclohexanedicarboxylic acid, adipic acid, sebacic acid and dodecanedioic acid are preferably used from the viewpoint of polymerizability, color tone and physical properties.

(b) poly(alkylene oxide) glycol and/or
Alternatively, the diol compound and (c) dicarboxylic acid are reacted at a molar ratio of 1:1, but the charging ratio is usually changed depending on the type of dicarboxylic acid used.

The (b) poly(alkylene oxide) glycol and/or diol compound and (c) dicarboxylic acid, which are the constituent components of the polyether ester, are constituent units of the polyether ester amide, and are used in an amount of 90 to 10% by weight. If it exceeds 10% by weight, the mechanical properties of the polyether ester amide will be poor, and if it is less than 10% by weight, the resulting resin will have poor antistatic properties, which is not preferred.

(B) The polymerization method for polyether ester amide is not particularly limited, and for example, (a) (a) aminocarboxylic acid or lactam and (c) dicarboxylic acid are reacted to form a polyamide prepolymer having carboxylic acid groups at both ends. Making,
(b) A method in which poly(alkylene oxide) glycol and/or diol compounds are reacted under vacuum; (b) Each of the compounds (a), (b), and (c) above is charged into a reaction tank, and water is A method of producing a carboxylic acid-terminated polyamide prepolymer by carrying out a pressurized reaction at high temperature in the presence or absence, and then proceeding with polymerization under normal pressure or reduced pressure, and (c) the above (a) and (b). ) and (c) may be simultaneously charged into a reaction tank, melt-mixed, and then polymerized all at once under high vacuum.

Furthermore, there are no restrictions on the polymerization angular catalyst, and examples include antimony-based catalysts such as antimony dioxide, tin-based catalysts such as monobutyltin oxide, titanium-based catalysts such as tetrabutyl titanate, and zirconate-based catalysts such as tetrabutyl zirconate. One type or two or more types can also be used.

The polymer thus obtained is (A) polyolefin 60~
99% by weight, preferably 60-98% by weight, (B) polyether ester amide 40-1% by weight, preferably 4
Within the range of 0 to 2% by weight, the total amount of (A) and (B) is 1
00% by weight.

If the polyolefin (A) is less than 60% by weight, the blow moldability will be poor, and if it exceeds 99% by weight, the antistatic properties of the blow hollow molded product will be insufficient.

(B) If the polyether ester amide content is less than 1% by weight, the antistatic properties of the blow hollow molded product will be insufficient, and if it exceeds 40% by weight, the blow moldability will be poor, which is not preferable.

As for the kneading method of polyolefin and polyether ester amide, generally known methods can be adopted.
A kneading method using an axle-screw extruder or a multi-screw extruder with two or more screws may be used 1).

Blow molding is also performed by a known method.

Note that the blown hollow molded product of the present invention also includes a multilayer blow hollow molded product in which at least one layer is formed of a composition containing polyether ester amide.

Compositions that do not contain polyetheresteramide include polyolefins such as polypropylene and polyethylene, polyethylene terephthalate, ionomer resins,
Thermoplastic resins commonly used for blow molded products, such as polyamide and glass fiber reinforced polyamide, are preferably used.

Furthermore, as necessary, various stabilizers such as compatibilizers such as oligomers, antioxidants, and ultraviolet absorbers, pigments, dyes, lubricants, etc.
Glass fibers, inorganic fillers, etc. can also be added.

In this way, a blown hollow molded product is obtained, and the term blown hollow molded product as used in the present invention refers to hollow containers, tanks, bottles, pipes, etc. that are suitable for blow molding.

They are preferably used as small cosmetic containers such as cylindrical, conical, square, rectangular, drum-shaped, and daruma-shaped containers, detergents, liquid medicine containers, and the like.

[Examples] In order to explain the present invention more specifically, Examples and Comparative Examples will be given below.

Note that parts and percentages in the examples indicate parts by weight and percentages by weight, respectively.

Reference Example (1) (A) Preparation of polyolefin A-1: Polypropylene (Mll measured by ASTM D1238, 5 g/10 minutes) (Mitsui Noblen JS-G manufactured by Mitsui Toatsu Chemical Co., Ltd.) was used.

A-2: Polypropylene (MIo measured according to ASTM D1238, 5 g/10 minutes) (Mitsui Noblen EB-G, manufactured by Mitsui Toatsu Chemical Co., Ltd.) was used.

A-3: Polyethylene (Mll measured according to ASTM D1238, 9 g/10 min) (Milason 50, manufactured by Mitsui Petrochemicals Ltd.) was used.

A-4: Polyethylene (MIo measured according to ASTM D1238, 7 g/10 min) (Hizex 3000B manufactured by Mitsui Petrochemicals) was used.

(2) (B) Preparation of polyether ester amide B-1
= 50 parts of caprolactam, 44.2 parts of polyethylene glycol with a number average molecular weight of 1000, and terephthal #7
．． 6 parts of "Irganox" 1098 (# anti-oxidant > 0
．． 2 parts of antimony trioxide and 0.1 parts of antimony trioxide were charged into a reaction vessel equipped with a helical ribbon stirring blade, the atmosphere was replaced with nitrogen, and the mixture was heated and stirred at 260°C for 60 minutes to obtain a transparent homogeneous solution. Polymerization was carried out for 4 hours under conditions of .5 mm) Iq or less to obtain a viscous and transparent polymer.

Pellet-shaped polyether ester amide (B-1) was prepared by discharging the polymer in a glob onto a cooling belt and pelletizing it.The polyether ester unit in (B-1) was 45% by weight. Ta.

BP
E-20, manufactured by Sanyo Chemical Industries, Ltd.) 6.3 parts, 41.9 parts of polyethylene glycol with a number average molecular weight of 1000, and 14.3 parts of dodecadionic acid were added to "Irganox" 10980.
2 parts and 0.02 part of antimony dioxide were charged into the reaction vessel used in A-1, the atmosphere was replaced with nitrogen, the mixture was heated and stirred at 260°C for 60 minutes to form a transparent homogeneous solution, and the mixture was heated to 500 mmH.
The pressure was reduced to p to remove water in the gas phase of the reaction vessel, and 0.08 part of tetrabutyl zirconate was added. then 260'
Polymerization was carried out for 3 hours and 30 minutes under the conditions of C10°5mmt1g or less to obtain a viscous and transparent polymer. Thereafter, polyether ester amide (B-2>) was prepared in the same manner as B-1. The polyether ester unit in (B-2) was 40% by weight.

Examples 1-6. Comparative Examples 1 and 2 Pellets were prepared by mixing (A>polyolefin and (B) polyether ester amide prepared in Reference Example in the blending ratio shown in Table 1).

Using the obtained pellets, the outer diameter was 10 mm at 220 to 240°C using a blow molding machine with a diameter of 40 mmφ extruder.
0 m, a parison with a wall thickness of 4 mm, 1 side of 120 mm,
A square prismatic container with a height of 15 ONn was molded.

In all of Examples 1 to 6, extremely good blow molding was achieved.

The surface resistivity values of these molded products were measured under the following conditions using a 40×4CLm square plate taken from the center of the body of the molded product.

(1) Immediately after molding, wash with detergent "Mama Lemon" (Lion Yushi Kansei) aqueous solution, then thoroughly wash with distilled water to remove surface moisture, and then condition the humidity at 50% RH 123°C for 24 hours. It was measured using

(2) After molding, leave it in a 50% RH 123℃ for 200 days, wash it with a detergent "Mama Lemon'° aqueous solution, then thoroughly wash it with distilled water to remove surface moisture.
Measure the humidity at 0% RH and 123°C for 24 hours.

The measurement results are shown in Table 1.

The shapeability of the molded container was visually determined by determining whether the obtained container was completely shaped, that is, whether or not membrane breakage occurred during blowing.

The thickness of the center of the body of the obtained container was 3 rran.

Comparative Examples 1 to 2 The (A) polyolefin and (B) polyether ester amide prepared in the reference examples were melt-kneaded and blow-molded in the same manner as in the examples at the compounding ratio shown in Table 1 to determine each physical property. It was measured.

The measurement results are shown in Table 1.

The following is clear from the results in Table 1. The blow hollow molded products of the present invention (Examples 1 to 6) all have excellent formability and low surface resistivity values. Moreover, the resistance value hardly changes even after surface cleaning or aging.
Demonstrates excellent permanent antistatic properties.

On the other hand, the blending amount of polyether ester amide (B) is 1
If the amount is less than 40 parts by weight (Comparative Example 1), the antistatic property (resistance value) will be poor, and if the amount exceeds 40 parts by weight (Comparative Example 2), the shapeability will be poor, which is not preferred.

[Effects of the Invention] As seen in the examples, the present invention provides blow hollow molded products with excellent permanent antistatic properties.

Claims (1)

[Scope of Claims] (A) 60 to 99% by weight of polyolefin; (B) (a) an aminocarboxylic acid or lactam having 6 or more carbon atoms; or a salt of a diamine and dicarboxylic acid having 6 or more carbon atoms; (b) Polyether ester amide 40 obtained by copolymerizing poly(alkylene oxide) glycol with a number average molecular weight of 200 to 6,000 and (c) dicarboxylic acid having 4 to 20 carbon atoms so that the polyether ester units are 10 to 90% by weight. A polyolefin blow-molded product made by blow-molding a resin composition containing ~1% by weight.