JPH0222349A - Polyolefin resin composition - Google Patents

Abstract

PURPOSE:To obtain a polyolefin resin composition improved in impact resistance and tensile elongation without impairing stiffness and heat resistance and suitable for injection molding, extrusion molding, etc., by blending a polyolefin resin with an inorganic filler and cyclic phosphorus compound having a specific structure at specific amounts. CONSTITUTION:The aimed composition obtained by blending total amount (100 pts.wt.) of (A) 70-90 pts.wt. polyolefin resin (e.g., crystalline propylene homopolymer) and (B) 30-10 pts.wt. inorganic filler (e.g. talc) with (C) 0.05-1 pts.wt., preferably 0.1-0.5 pts.wt. cyclic phosphorus compound and (D) 0.1-1 pts.wt., preferably 0.1-0.5 pts.wt. fatty acid metal salt expressed by formula II (M1 is Ca, Mg, etc.; R4 is 16-22C alkyl) or alkyl phosphoric acid metal salt which is mixture of compounds expressed by formula III and formula IV (R5 and R6 are 10-22C alkyl; M2 is Zn, etc.; R7 is 10-22C alkyl, etc.).

Description

[Detailed description of the invention] (Industrial application field) The present invention relates to polyolefin resin compositions.

More specifically, the present invention relates to a polyolefin resin composition in which specific amounts of an inorganic filler, a cyclic phosphorus compound having a specific structure, and a fatty acid metal salt or an alkyl phosphate metal salt having a specific structure are blended into a polyolefin resin.

Polyolefin resin compositions containing inorganic fillers have excellent rigidity, heat resistance, and dimensional stability, and are therefore used in the production of various molded products in the fields of injection molding, extrusion molding, and vacuum (pressure) molding.

(Prior art) Although inorganic filler polyolefin resin compositions have excellent rigidity, heat resistance, and dimensional stability, they have drawbacks such as decreased impact resistance and tensile elongation. And how to improve tensile elongation of ethylene-propylene rubber (ERR)? Methods of adding rubbery substances such as ethylene-propylene-genterpolymers are generally known. However, there is a contradiction in that when a rubbery substance is added, although impact strength and tensile elongation are significantly improved, rigidity and heat resistance are reduced.

In addition, polyolefin resin compositions usually contain inorganic fillers and thioether antioxidants as stabilizers.

A formulation containing a phenolic antioxidant, a neutralizing agent, a metal soap, etc. as a pigment dispersant is often used. The flexibility of the material decreases, leading to problems such as a decrease in tensile elongation and impact strength.

(Problems to be Solved by the Invention) The present inventors have solved the above-mentioned problems regarding the inorganic filler polyolefin resin composition, namely, the rigidity and heat resistance of the molded product when the composition is made into a molded product. We have conducted intensive research to obtain an inorganic filler polyolefin resin composition that can improve impact resistance and tensile elongation without impairing dimensional stability. As a result, a composition obtained by blending a polyolefin resin with specific amounts of an inorganic filler, a cyclic phosphorus compound having a specific structure, and a fatty acid metal salt or an alkyl phosphate metal salt having a specific structure can solve the above-mentioned problems. The present invention was completed based on this knowledge.

As is clear from the above description, the present invention provides a polyolefin resin composition that can improve impact resistance and tensile elongation without impairing the rigidity, heat resistance, and dimensional stability of the molded product. It is about providing something.

(Means for solving problems) The present invention has the following structure.

(1) (al polyolefin resin 70 to 90 parts by weight (
bll non-optical filler 30-10 parts by weight (c) above (a
) and (b) in a total of 100 parts by weight, 0.05 to 1.0 parts by weight of a cyclic phosphorus compound represented by the following general formula [I] and a fatty acid metal salt represented by the maximum (It) below or the following - 0.1 to 1 alkyl phosphate metal salt, which is a mixture of compounds represented by maximum (nl) and (IV).
．． A polyolefin resin composition containing 0 parts by weight.

(However, R, R, and R each represent a different or similar alkyl group having 1 to 6 carbon atoms or a hydrogen atom.) R4C00M.

(If) represents a different or similar alkyl group having 16 to 22 carbon atoms. ) (It!I, R6 represents a different or similar alkyl group having 10 to 22 carbon atoms, M represents Zn, Ba, M
g, indicates Ca or Sr. ) (R? represents an alkyl group or alkenyl group having 10 to 22 carbon atoms, M represents Zn, Ba, Mg, Ca or Sr.) As the polyolefin resin used in the present invention, α-based resins such as ethylene, propylene, butene, etc. - Crystalline homopolymers of olefins, crystalline random polymers of the α-olefin and other α-olefins, and crystalline block polymers.

Particularly preferred are polypropylene resins such as crystalline propylene homopolymer, crystalline ethylene 7-propylene random polymer, and crystalline propylene-hexene-bute 7s original copolymer.

Examples of inorganic fillers include calcium charcoal, talc, mica, clay, magnesium hydroxide, wollastonite, calcium silicate, and glass fiber, but talc with an average particle size of 2 to 10 μm is preferred.

The blending ratio of the inorganic filler is polyolefin resin 70-9
The blending ratio is 0 parts by weight and 30 to 10 parts by weight of the inorganic filler, for a total of 100 parts by weight.

If the blending ratio is more than 30 parts, the impact resistance and tensile elongation of the molded product when molded using the obtained composition will decrease;
This is not preferred because no improvement in dimensional stability is achieved.

The cyclic phosphorus compound represented by the general formula [1] used in the present invention is 9,10-di-hydro-9-oxa-10
-7 osulfur aphenanthrene-10-oxide (hereinafter referred to as HCA-P), and fatty acid metal salts represented by the maximum (n) include zinc stearate, magnesium stearate, calcium stearate, aluminum Stearate, barium stearate, etc.

- Alkyl phosphoric acid metal salts which are mixtures of compounds of maximum (lu) or (IV) are stearic acid metal salts (Z as metals).
rl, Ca, Mg, Sr or Ba), lauryl phosphate metal salt (Zn%Ca%Mg, Sr as metal)
or Ba), 2-ethylhexyl phosphate metal salt (Zn%Ca, Mg, Sr or Bi as metal)
etc. can be mentioned.

The ratio of the cyclic phosphorus compound represented by the general formula [I] to 100 parts by weight of the inorganic filler polyolefin resin is 0.05 to 1.0, preferably 0.05 to 1.0.
05 to 0.5 parts by weight. If it is less than 0.05 parts by weight, the effect of improving impact resistance and tensile elongation will not be sufficiently exhibited, and on the other hand, if it exceeds 1 part by weight, it is possible, but no further improvement in the above-mentioned effects can be expected and in practice. Not on point.

The addition ratio of the monofatty acid metal salt shown in [■] above is 0.1 to 1.0 parts by weight, preferably 0.1 to 0.51 parts by weight.
It is a quantity part.

The addition ratio of the alkyl phosphate metal salt, which is a mixture of the compounds represented by the general formula Cl1l) and [■], is 0.1 to 1.
．． 0 parts by weight, preferably 0.1 to 0.5 parts by weight.

Furthermore, if the amount added is less than 0.1 part by weight, the effect of improving impact resistance and tensile elongation will not be sufficiently exhibited, while if it exceeds 1 part by weight, the above-mentioned effects will not be improved further. It is hopeless, impractical, foolish, and uneconomical. Furthermore, in the present invention, additives that are normally added to inorganic fillers and olefin resins, such as phenol-based, thioether-based and phosphite-based antioxidants, light stabilizers, antistatic agents, pigments, A filler containing a heavy metal deactivator (copper damage inhibitor), a flame retardant, a neutralizing agent, the above-mentioned commonly used additives, a cyclic phosphorus compound represented by the general formula [I], and the -maximum [■ ] or the above-mentioned -maximum (II) and [■
] A predetermined amount of each alkyl phosphate metal salt, which is a mixture of the compounds represented by the above, is put into a stirring mixer and stirred and mixed for 1 to 10 minutes, and then the mixture is melt-kneaded in an extruder and pelletized. It can be carried out.

As for mixing equipment, it is sufficient to use ordinary mixing equipment such as Henschel Mixer (trade name) Super Mixer with a high-speed stirrer, ribbon blender, tumbler mixer, Banbury mixer, etc. For melt kneading, use an ordinary single-screw extruder. A twin-screw extruder is used in maku.

The melt mixing temperature was 190 to 300° C. Preferably, prescribed test pieces were molded from acid pellets to evaluate the composition of the present invention.

As a method for evaluating the test piece, tensile elongation measurement (JIS
K 7113) and Izod impact strength measurement (JI
SK 7110) (with notch).

(Examples) The present invention will be specifically described below with reference to Examples and Comparative Examples, but the scope of the present invention is not limited thereby.

Examples 1 to 8, Comparative Examples 1 to 3 As Examples 1 to 5, the melt flow rate of the polyolefin resin was 9.8.9/10 minutes (10 minutes when 9 was added to the load 2.16 at 230°C To 80 parts by weight of propylene homopolymer (discharge amount of molten resin), to 20'f (11 parts in total) of talc with an average particle size of 6 to 8 μm, to a total of 100 parts by weight, HCA as a cyclic phosphorus compound listed in Table 1 below.
-2,5-di-t-butyl-P-cresol with 0.05 to 0.5 parts by weight of P and 0.1 to 0.5 parts of zinc stearate as a fatty acid metal salt and other additives. 0.05 parts by weight, tetrakis[methyl-3-(
0.1 part by weight of 3,5-di-t-butylhydroxyphenylpropionate]methane and 00.5 parts by weight of similistilthiopropionate were added and stirred and mixed for 3 minutes using a Henschel mixer, and then the mixture was 2 of 30n
The mixture was melt-kneaded using a screw extruder at a melt mixing temperature of 250°C and pelletized to obtain pellets.

Further, as Example 6.7, the amounts of polyolefin resin and inorganic filler added were the same as in Examples 1 to 5, and the general formula [
! ] As a cyclic phosphorus compound, the amount of HCA-P added was 0.2 parts by weight, and fatty acid metal salts of magnesium stearate and calcium stearate were each added in an amount of 0.2 parts by weight or 0.3 parts by weight, etc. The additives were the same as in Examples 1 to 5, and pellets were obtained in accordance with Examples 1 to 51C.

As Example 8, the amounts of polyolefin resin and inorganic filler added were the same as Examples 1 to 5, and the amount of HCA-P added as the cyclic phosphorus compound represented by formula (I) was 0.
Example 1: 2 parts by weight, 0.2 parts by weight of zinc stearyl phosphate was added as an alkyl phosphate metal salt which is a mixture of compounds represented by the general formulas (I[l) and (It/), and other additives were added. -5 were added in the same amount to obtain pellets according to Examples 1-5.

In addition, as Comparative Examples 1 to 3, 80 parts by weight of the same propylene homopolymer as used in Examples 1 to 5 was added to
In Comparative Example 1, HC was added as a cyclic phosphorus compound represented by the general formula (1) to a total of 100 parts by weight of 20 parts by weight of 8μ talc.
In Comparative Example 2, 0.2 parts by weight of A-P was added and 0.2 parts by weight of zinc stearate were added to obtain pellets according to Examples 1 to 5.

The pellets obtained from each experimental side and each comparison side were put into an injection molding machine, and a predetermined test piece was molded at a resin temperature of 250 ° C.
Using this test piece, tensile elongation and Izod impact strength were measured. The results are shown in Table 1.

As shown in Table 1, 0.2 parts by weight of HCA-P and 0.1.0.2.0.51 parts of zinc stearate, respectively.
Examples 1 to 3, in which particulate addition was used, showed an improvement of approximately 2 to 5 times in flat tensile and female elongation and 1.3 to 1.5 times in isot impact strength compared to Comparative Example 1. , the effects of the present invention were confirmed.

In Examples 2.4 and 5, the same amount of zinc stearate as in Comparative Example 2 was added, and HC-P was O12, 0, and 05, respectively.
, 0.5 parts by weight, but when each was used in combination, Comparative Example 2
It can be seen that the improvement is from just over 3 times to just under 3 times, and the Izot impact strength is also improved by over 1.3 times.

In Examples 1 to 5, in which 0.1 parts by weight or more of zinc stearate was added in a combined system of HCA-P and zinc stearate, the improvement in tensile elongation and Izot impact strength was remarkable compared to Comparative Example 3K. 3, Example 6.7 shows that H
Addition amount of C and A-P: 0.2 % by weight: (I f'ζ 0.2 parts by weight of magnesium stearate ↓ and 0.3 parts by weight of calcium stearate are used together, but the effect is shown in the example. 2.3, the tensile elongation and Izod impact strength of the zinc stearate combination system and it F'J
Equivalent effects are observed.

Example 8 HCA-PO, 2 parts in 1 part - up to Cl11
Zinc stearyl phosphate as an alkyl phosphate metal salt, which is a mixture of compounds represented by ') and (IV), is
．． When 2 parts by weight were added together, compared to Comparative Example 1, the tensile elongation was 1.8 times, and the Izot impact strength was 1.
It was confirmed that the effect was improved by more than 5 times.

(Effects of the Invention) The composition of the present invention has excellent tensile elongation and isot impact strength, and is used to manufacture various molded products in various molding fields such as injection molding, extrusion molding, and vacuum (pressure) molding. It can be suitably used for.

that's all

Claims (1)

[Claims] (1) (a) 70 to 90 parts by weight of polyolefin resin (b
) 30 to 10 parts by weight of an inorganic filler (c) 0.0 to 10 parts by weight of a cyclic phosphorus compound represented by the following general formula [I] based on a total of 100 parts by weight of the above (a) and (b).
05 to 1.0 parts by weight and a fatty acid metal salt represented by the following general formula [II] or the following general formulas [III] and [IV]
A polyolefin resin composition containing 0.1 to 1.0 parts by weight of an alkyl phosphate metal salt, which is a mixture of compounds represented by the formula. ▲There are mathematical formulas, chemical formulas, tables, etc.▼〔I〕 (However, R_1, R_2, and R_3 each have 1 carbon number.
~6 different or similar alkyl groups or hydrogen atoms. ) R_4COOM_1 [II] (M_1 is Ca, Mg, Al, Zn, Pb, or S
Indicates n. R_4 represents a different or similar alkyl group having 16 to 22 carbon atoms. ) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [III] (R_5 and R_6 represent different or similar alkyl groups having 10 to 22 carbon atoms, and M_2 represents Zn, Ba, Mg, C
a or Sr. ) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [IV] (However, R_7 represents an alkyl group or alkenyl group having 10 to 22 carbon atoms, and M_3 represents Zn, Ba, Mg, Ca, or Sr.)