JPH0881595A - Propylene/ethylene random copolymer resin composition - Google Patents

Abstract

PURPOSE: To obtain a resin compsn. excellent in transparency by blending a propylene/ethylene random copolymer with an ammonium organophosphate compd. and a lithium aluminum compd. CONSTITUTION: A resin compsn. comprises (a) 100 pts.wt. propylene/ethylene random copolymer having an ethylene unit content of 0.5 to 7wt.%; (b) 0.01-0.5 pts.wt. (b1 ) ammonium organophosphate compd. of formula I or (b2 ) ammonium organophosphate compd. of formula II; and (c) 0.01-0.5 pt.wt. lithium aluminum double hydroxide salt of formula III. In the formulae, R1 and R2 are each H, 1-12C alkyl, or the like; X is a direct bond, and alkylene group, or the like; A is an ammonium ion or the like; m is l to 6; R3 , R4 and R5 are each H, 1-12C alkyl, or the like; and n is l to 6.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a propylene / ethylene random copolymer resin composition having excellent transparency, which is used for food containers, medical instruments, laboratory instruments and the like.

[0002]

2. Description of the Related Art Polypropylene resin has good heat resistance, chemical resistance and rigidity, and also has excellent electrical properties and processability, so that it can be used for injection molding, film molding and sheeting. Widely used as a material for molding and blow molding. Further, the propylene / ethylene random copolymer in which propylene contains a small amount of ethylene has good impact resistance and transparency in addition to the above properties. However, when the propylene / ethylene random copolymer is used in food containers, medical instruments, physics and chemistry experimental instruments, etc., the transparency is insufficient and there is a problem that the application is limited.

As a method for obtaining a polypropylene resin composition having good transparency, a metal salt of a carboxylic acid, a metal salt of an aromatic sulfonic acid, a metal salt of an aromatic phosphoric acid, a sorbitol compound or the like is used as a nucleating agent. The method of adding as (for example, JP-A-58-25341 and JP-A-56-30449) has been proposed. Of these methods, the addition of a sorbitol-based compound is most effective in improving transparency, but it has problems such as poor heat resistance and rigidity, odor generation, and bleed-out. In addition, since sorbitol compounds are expensive, there is a problem in economic efficiency. Therefore, if these problems are solved, it is expected that the application range of the propylene resin material will be expanded.

Therefore, an object of the present invention is to provide a propylene / ethylene random copolymer resin composition having excellent transparency.

[0005]

As a result of earnest research in view of the above problems, the present inventors have blended a propylene / ethylene random copolymer with an ammonium organic phosphate compound and a lithium aluminum complex hydroxide salt compound. By doing so, they discovered that transparency can be improved, and completed the present invention.

That is, the propylene / ethylene random copolymer resin composition of the present invention comprises (a) 100 parts by weight of a propylene / ethylene random copolymer having an ethylene content of 0.5 to 7% by weight,

(B) (b ₁ ) General formula (I):

[Chemical 4] (However, R ₁ and R ₂ are each a hydrogen atom and a carbon number 1
To 12 alkyl groups, cycloalkyl groups, aryl groups or aralkyl groups, X is a direct bond, an alkylene group or an alkylidene group, A is an ammonium ion or an organic ammonium ion, and m is an integer of 1 to 6. is there. ) Ammonium organophosphate compound represented by

(B ₂ ) General formula (II):

[Chemical 5] (However, R ₃ , R ₄ and R ₅ are each a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group, and X is a direct bond, an alkylene group or an alkylidene group, A is an ammonium ion or an organic ammonium ion, and n is 1 to 6
Is an integer. 0.01 to 0.5 parts by weight of an organic ammonium phosphate compound represented by

(C) General formula (III):

[Chemical 6] (Wherein X is an inorganic or organic anion, n is a valence of the anion (X), and m is an integer of 3 or less.) 0.01 to 0.5 parts by weight of a lithium aluminum complex hydroxide salt compound It consists of and.

The present invention will be described in detail below. [1] Each component of propylene / ethylene random copolymer resin composition (a) Propylene / ethylene random copolymer (1) Ethylene content The ethylene content in the propylene / ethylene random copolymer is 0.5 to 7% by weight. Is. When the ethylene content is less than this range, the impact resistance, which is a characteristic of the propylene / ethylene random copolymer, decreases, and when it exceeds this range, the rigidity and heat resistance decrease. The preferred ethylene content is
It is 2 to 5% by weight.

(2) Melt Flow Rate (MFR) The propylene / ethylene random copolymer used in the present invention has a melt flow rate (MFR, measured at 230 ° C. and 2.16 kg) of 0.2 to 5 g / 10 minutes, preferably Is 0.5-2g / 10
Minutes.

(3) Production method The production method of the propylene / ethylene random copolymer is not particularly limited, but it can be obtained by applying a gas phase polymerization method in which propylene and ethylene are simultaneously supplied in the presence of a stereoregular catalyst. To be

As the stereoregular catalyst, titanium trichloride,
Titanium halides such as titanium tetrachloride and trichloroethoxytitanium, transition metal components such as contact products of the above titanium halides with magnesium compounds represented by magnesium halide, and alkylaluminum compounds or their halides and hydrides. There are two-component catalysts with organometallic components such as alkoxides, and three-component catalysts in which an electron-donating compound containing nitrogen, phosphorus, sulfur, oxygen, silicon, etc. is added to these components.

(B) Ammonium organophosphate salt compound In the present invention, (b ₁ ) general formula (I):

[Chemical 7] (However, R ₁ and R ₂ are each a hydrogen atom and a carbon number of 1 to
12 is an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group, X is a direct bond, an alkylene group or an alkylidene group, A is an ammonium ion or an organic ammonium ion, and m is an integer of 1 to 6. . ) Ammonium organophosphate compound represented by

(B ₂ ) General formula (II):

Embedded image (However, R ₃ , R ₄ and R ₅ are each a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group, and X is a direct bond, an alkylene group or an alkylidene group, A is an ammonium ion or an organic ammonium ion, and n is 1 to 6
Is an integer. ) An organic phosphoric acid ammonium salt compound represented by

Specific examples of the organic ammonium phosphate compound include those described in JP-A-5-9390.

[0017]

[Chemical 9]

[0018]

[Chemical 10]

[0019]

[Chemical 11]

[0020]

[Chemical 12]

[0021]

[Chemical 13]

[0022]

Embedded image

[0023]

[Chemical 15]

[0024]

Embedded image

(C) Lithium-Aluminum Composite Hydroxide Salt Compound The lithium-aluminum composite hydroxide salt compound used in the present invention has the general formula (III):

(Wherein, X is an inorganic or organic anion, n is the valence of the anion (X), and m is an integer of 3 or less).

Specific examples of the lithium-aluminum composite hydroxide salt compound include those described in JP-A-5-179052. That is, the inorganic or organic anion represented by X in the general formula is obtained from carbonic acid, sulfuric acid, chlorine oxyacid (for example, perchloric acid), phosphorus oxyacid (phosphoric acid, phosphorous acid, metaphosphoric acid), or the like. One or a combination of two or more of the above-mentioned anions is preferable, but acetic acid, propionic acid, adipic acid, benzoic acid, phthalic acid, terephthalic acid, maleic acid, fumaric acid,
Examples thereof include anions obtained from succinic acid, p-oxybenzoic acid, salicylic acid, picric acid and the like.

(D) Other Additives The propylene / ethylene random copolymer resin composition of the present invention contains silica, alumina, talc, mica, clay, kaolin, wollastonite, zeolite, silica depending on the application. Alumina, calcium carbonate, aluminum hydroxide, titanium dioxide, zinc oxide, magnesium oxide, zirconium oxide, zinc sulfide, barium sulfate, calcium sulfate, calcium phosphate, magnesium phosphate,
Granular, powdery or scale-like materials such as aluminum silicate, silicon nitride, glass, hydrotalcite, etc., or inorganic materials such as glass fiber, potassium titanate fiber, carbon fiber, carbon black, graphite, mica ceramics fiber, metal fiber, etc. Filler or silane-based, titanate-based, boron-based, aluminate-based, inorganic filler surface-treated with a zircoaluminate-based coupling agent, wood powder, pulp, synthetic fibers, organic fillers such as natural fibers, Phenol-based, thioether-based, phosphorus-based antioxidants, light stabilizers, clarifying agents, nucleating agents such as organic carboxylic acids or metal salts thereof, lubricants, antistatic agents, antifogging agents, antiblocking agents, pigments, A heavy metal deactivator, a radical generator such as a peroxide, a dispersant such as a metal soap, or a neutralizer may be used for the purpose of the present invention. It can be blended in just no range.

[2] Blending ratio The blending ratio of each component is 0.01 to 0.5 parts by weight, preferably 0.01 to 0.5 parts by weight of the organic phosphate ammonium salt compound (b) with respect to 100 parts by weight of the propylene / ethylene random copolymer (a). 0.1 ~
0.3 parts by weight, 0.01 to 0.5 parts by weight of the lithium aluminum complex hydroxide salt compound (c), preferably 0.01 to 0.
2 parts by weight.

If the amount of the organic ammonium phosphate compound is less than 0.01 parts by weight, heat resistance, rigidity and transparency will be deteriorated. On the other hand, if it exceeds 0.5 parts by weight, no substantial effect is observed, and the compound is expensive and costly, which is not preferable.

If the blending amount of the lithium aluminum complex hydroxide salt compound is less than 0.01 parts by weight, rigidity and transparency will be deteriorated. On the other hand, if it exceeds 0.5 parts by weight, no substantial effect is observed, and the compound is expensive and costly, which is not preferable.

[3] Method for Producing Propylene / Ethylene Random Copolymer Resin Composition The propylene / ethylene random copolymer resin composition of the present invention is prepared by mixing the above components using a Henschel mixer, super mixer, ribbon blender or the like. It can be obtained by melt-kneading with a usual single-screw extruder, twin-screw extruder, Banbury mixer, Brabender, roll or the like in the temperature range of 170 to 300 ° C.

[0032]

EXAMPLES The present invention will be described in detail with reference to the following examples and comparative examples, but the present invention is not limited thereto.

Examples 1 to 4 1. Raw material (a) Propylene / ethylene random copolymer (RPP) Ethylene content: 3% by weight Melt flow rate (MFR): 1.5 g / 10 min (230
(B) Organic ammonium phosphate salt compound, Asahi Denka Kogyo Co., Ltd., NA-21 (c) Lithium aluminum complex hydroxide salt compound Mizusawa Chemical Industry Co., Ltd., Mizukarac (d) Antioxidant Phenolic antioxidant: manufactured by Nippon Ciba Geigy Co., Ltd.
Irganox 1010 Phosphorus antioxidant: Irgaph manufactured by Nippon Ciba Geigy Co., Ltd.
os 168

2. Kneading method: With respect to 100 parts by weight of the propylene / ethylene random copolymer (a), the compounding amounts of the organic ammonium phosphate salt compound (b) and the lithium aluminum complex hydroxide salt compound (c) shown in Table 1 below, Each of 0.05 parts by weight of a phenolic antioxidant and a phosphorus antioxidant (d) was mixed in a Henschel mixer, and then melt-kneaded using a 50 mmφ single screw extruder. The die was extruded at a die outlet temperature of 230 ° C. to obtain pellets.

3. Molding method The obtained pellets were heated to 210 ° C using an injection molding machine.
° C., injection pressure 400 kg / cm ² and at a mold temperature of 30 ° C., to prepare a test piece.

4. Physical property measurement Physical property measurement of each test piece was performed by the following methods. The measurement results are shown in Table 1 below. (1) Haze value (%): Using a 1 mm thick test piece, ASTM D10
It was measured according to 03-61. (2) Odor: Existence of odor was examined. (Yes ... No, No ...
○)

Comparative Example 1 In addition to the propylene / ethylene random copolymer (a), the organic phosphate ammonium salt compound (b) and the antioxidant (d), which are the same as those in the examples, according to the blending amounts shown in Table 1 below, Calcium stearate (Nippon Oil & Fats Co., Ltd., CaSt) was mixed, pellets were prepared under the same conditions as in the examples, and the physical properties were measured. The results are shown in Table 1 below.

Comparative Example 2 As an additive, CaSt and 1,3,2,4-di (p-methylbenzylidene) sorbitol (Mitsui Toatsu Chemical Co., Ltd., Gelol MD) used in Comparative Example 1 were used in the following table. Pellets were prepared under the same conditions as in Example, except that they were blended according to the blending amount shown in 1, and their physical properties were measured. The results are shown in Table 1 below.

Comparative Example 3 As an additive, pellets were prepared under the same conditions as in Example except that Gelol MD used in Comparative Example 2 and Mizucarac used in Example were compounded according to the compounding amounts shown in Table 1 below. The physical properties were measured. The results are shown in Table 1 below.

Table 1 Example No. 1 Two Three Four  RPP Blended amount (weight part) 100 100 100 100 Ethylene content (wt%) 3 3 3 3Additive blending amount (parts by weight) NA-21 0.2 0.2 0.2 0.15 Mizucarac 0.05 0.1 0.025 0.05 Gel All MD ─ ─ ─ ─ CaSt ─ ─ ─ ─Properties of the composition Haze value (%) 9.4 9.2 9.3 9.9 Odor ○ ○ ○ ○

Table 1 (continued)Comparative example No. 1 Two Three RPP Blended amount (parts by weight) 100 100 100 Ethylene content (% by weight) 3 3 3 Additive blending amount (parts by weight) NA-21 0.2 ─ mizukarak ─ ─ 0.05 Gelol MD ─ 0.2 0.2 CaSt 0.1 0.1 ─ Properties of the composition Haze value (%) 13.1 11.7 11.1 Odor ○ × ×

As is clear from the above results, the propylene / ethylene random copolymer resin composition of the present invention has a low haze value and excellent transparency. On the other hand, in the case of the propylene / ethylene random copolymer resin composition of the comparative example to which the sorbitol compound was added, the transparency was slightly high, but odor was generated.

[0043]

[Effect] The propylene / ethylene random copolymer resin composition of the present invention is excellent in transparency and can be widely used for applications such as food containers, medical instruments, and physics and chemistry laboratory instruments.

[Chemical 17]

Claims (3)

[Claims] 1. The content of (a) ethylene is 0.5 to 7% by weight.
And 100 parts by weight of the propylene / ethylene random copolymer of (b) (b ₁ ) in the general formula (I): (However, R ₁ and R ₂ are each a hydrogen atom and a carbon number 1
To 12 are an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group, X is a direct bond, an alkylene group or an alkylidene group, A is an ammonium ion or an organic ammonium ion, and m is an integer of 1 to 6. is there. ), Or an organic ammonium phosphate compound represented by the formula (b ₂ ): (However, R ₃ , R ₄ and R ₅ are each a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group, and X is a direct bond, an alkylene group or an alkylidene group, A is an ammonium ion or an organic ammonium ion, and n is 1 to 6
Is an integer. 0.01 to 0.5 parts by weight of an organic ammonium phosphate compound represented by the formula (c), and (c) the general formula (III): (Wherein X is an inorganic or organic anion, n is a valence of the anion (X), and m is an integer of 3 or less) 0.01 to 0.5 parts by weight of a lithium aluminum complex hydroxide salt compound A propylene / ethylene random copolymer resin composition comprising: 2. The propylene / ethylene random copolymer resin composition according to claim 1, wherein propylene /
0.1 parts by weight per 100 parts by weight of ethylene random copolymer (a)
A propylene / ethylene random copolymer resin composition characterized by containing ˜0.3 parts by weight of an organic ammonium phosphate compound (b). 3. The propylene / ethylene random copolymer resin composition according to claim 1 or 2, wherein 0.01 to 0.2 parts by weight of lithium aluminum is added per 100 parts by weight of the propylene / ethylene random copolymer (a). A propylene / ethylene random copolymer resin composition comprising a composite hydroxide salt compound (c).