JPH01104637A - Propylene based polymer composition - Google Patents

Abstract

PURPOSE:To obtain the titled lightweight composition, containing silica.alumina hollow bodies in a specific proportion, having a modified propylene based polymer in a specific proportion based on the above-mentioned hollow bodies with excellent scuff resistance and improved mechanical characteristics and useful as automotive parts. CONSTITUTION:The aimed composition which is a composition consisting of (A) a crystalline propylene based polymer having 0.01-100g/10min melt flow index, (B) silica.alumina hollow bodies having 5-400mum average particle diameter and 0.70-1.00g/cm<3> density and (C) a modified propylene based polymer obtained by treating (i) 100pts.wt. propylene based polymer with (ii) 0.01-10pts. wt. organic compound having at least one unsaturated bond and carboxylic acid group or anhydride group thereof in the molecule and (iii) 0.01-10pts.wt. organic peroxide. The composition ratio of the component (B) based on the total composition accounts for 3-50wt.% and the amount of the component (iii) based on 100pts.wt. component (B) is 7-75pts.wt.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to propylene-based polymer compositions.

More specifically, the present invention relates to a propylene polymer composition that is lightweight, has good scratch resistance, and has excellent mechanical properties, as well as good appearance of molded products and prevention of sink marks.

[Conventional technology]

As is well known, propylene polymers not only have excellent moldability, but also have other properties such as mechanical properties, heat resistance, solvent resistance, oil resistance, and chemical resistance.

Because of its good quality, it is widely manufactured industrially and used in many fields as parts of automobiles, electrical appliances, electronic appliances, and daily necessities. However, mechanical properties (especially
The flexural modulus and tensile strength) are not necessarily satisfactory, the heat resistance is not sufficient, and the scratch resistance of the molded product is also poor. For this purpose, inorganic fillers such as glass beads, talc, and calcium carbonate are blended, molded into various shapes, and used in many directions.

However, when relatively large amounts of these inorganic fillers are blended to improve the mechanical properties, heat resistance, and scratch resistance, there is a drawback that the density (specific gravity) increases, resulting in increased costs. The current situation is that

These problems will be explained by way of example with respect to automobile instrument panels. There are two types of Insulmen Docknel fl: a regular mat-attached type and a padless type, but the padless type will be explained here.

Acrylonitrile-butadiene-styrene terpolymer resin (ABS resin) has conventionally been used as a material for padless type instrument panels. In recent years, in an effort to reduce the cost of automobiles, polyzolopyrene resins containing inorganic fillers have come into use.

Inorganic fillers used in inorganic filler-containing polypropylene resins include Merck, calcium carbonate,
Glass fiber etc. are used.

When using Merck, there is a problem that the scale does not have good scratch resistance and the strength of the weld decreases. Further, when calcium carbonate is used, there is a problem that not only the rigidity (flexural modulus) is not improved, but also the scratch resistance cannot be solved. Furthermore, when glass fiber is used, there are problems in terms of impact resistance and appearance, as well as cost. Moreover, compositions containing these inorganic fillers have a high density, and when used as the instrument panel, they generally have a density of 1.04 to 1.04.
1.20 fl/cm3, which results in a problem of increased weight of the product.

[Problem to be solved by the invention 3 From the above, the present invention solves the problems that cannot be solved by inorganic filler-filled polypropylene resins containing these inorganic fillers, namely, mechanical properties ( The molded product has good scratch resistance, has no sink marks, is lightweight, and has a good appearance when made into a molded product. The object of the present invention is to obtain a certain propylene-based polymer composition.

[Means for solving problems]

According to the present invention, these problems can be solved by using a flow index [according to JIS K7210,
Measured under condition 14, hereinafter referred to as rMFRj] is 0.0
(B) Silica-7/l having an average particle size of 5 to 400 μm and a density of 0.70 to 1.0097 cm3;
/ Mina hollow body □ and (Q (1) 100 parts by weight of propylene-based 1 combined (2)
"Organic compounds that have at least one unsaturated group in the molecule and contain a carboxylic acid group or its anhydride group" (
(hereinafter referred to as "carboxylic acid compounds") o, oi ~ IOM
A modified propylene polymer obtained by treating 0.01 to 10 parts by weight of an organic peroxide (hereinafter referred to as "
The proportion of silica/alumina hollow bodies in the total composition is 3 to 50 parts by weight, and the proportion of silica/alumina hollow bodies in the total composition is 3 to 50 parts by weight. The composition ratio of the modified propylene polymer can be determined by a propylene polymer composition containing 7 to 7 SiiE parts. Hereinafter, the present invention will be fully explained in detail.

(A) Crystalline propylene polymer The crystalline propylene polymer used in the present invention is a monopolymer mainly composed of propylene, including propylene homopolymer and propylene combined with ethylene and/or other α-olefins. Random and block copolymers of are preferably used.

Ethylene and α in random and block copolymers
- The copolymerization ratio of olefins is at most 20, with a total of 1.
The quantity is i. Further, as other α-olefins, α-olefins having 4 to 12 carbon atoms are desirable, and α-olefins having 4 to 8 carbon atoms are particularly preferred. Suitable α-
As olefins, butene-1, heptene-1,4-
Mention may be made of methylpentene-1 and hexene-1.

The MFR of the propylene polymer is 0.01 to 100g7
10 minutes and 0.01 to 80. ! A 9/10 minute amount is preferred, and a 0.1 to 70 g/LO amount is particularly preferred. If a propylene-based polymer having an MFR of less than 0.01 g and 710 minutes is used, the kneading properties will be poor.

On the other hand, if a propylene polymer with a hardness exceeding 100.9/10 minutes is used, the impact resistance of the composition will be poor.

(B) Silica/Alumina Hollow Body The average particle diameter of the silica/alumina hollow body used in the present invention is 5 to 400 μm, preferably 5 to 300 μm, and preferably 5 to 200 μm. Silica-alumina hollow bodies having an average particle diameter of less than 5 μm are difficult to produce, and even if they are obtained, it is difficult to obtain hollow bodies having the density described below. On the other hand, 400 μm
If it exceeds i, the resulting product will not only have a poor appearance, but will also have a large drop in impact strength.

In addition, the silica/alumina hollow body with is 0.70 to 1.0
0 ji/cm” and 0.70 to O195 ji/c
m3 is preferred, especially 0.70 to 0.90 g/cm3
is suitable.

If the density is less than 0.70 &/cm3, the damage rate during crosstalk is high. On the other hand, if it exceeds 1.001/cm3, the effect of reducing the weight of the product is low.

The proportion of silica in the silica-alumina hollow body of the present invention is 5
0 to 75% by weight, preferably 55 to 75i,
A preferable amount is 55 to 70% by weight. The silica-alumina hollow body contains oxides of other metals as impurities. Examples of the metal oxide include iron oxide (for example, triiron tetroxide). The proportion of impurities is usually at most 4% by weight.

This silica-alumina hollow body is a hollow spherical ceramic balloon, and its external shape and hollow structure are close to a perfect sphere.

Further, the wall thickness of the hollow body is generally 1/12 to IA relative to the particle size from the viewpoint of breakage resistance and weight.

The surface of the silica-alumina hollow body may be untreated or may be surface-treated using acrylic silane, aminosilane, glycidylsilane, or the like. Further, metals such as iron, copper, aluminum, zinc, etc., which are fully open and surface-treated, can also be used. This surface treatment improves the dispersibility of the silica-alumina hollow body.

(C) Modified zolopyrene polymer The modified zolopyrene polymer of the present invention is obtained by treating the propylene polymer described below with a carboxylic acid compound and an organic peracid compound.

(1) Zolopylene polymers Examples of the zolopylene polymers include propylene homopolymers, block copolymers of ethylene and propylene, and block copolymers of propylene and other α-olefins having at most 12 carbon atoms. Examples include copolymerization (copolymerization ratio of α-olefin is at most 20% by weight). The MFRI of this zolopyrene polymer is usually 0.01 to 10 min, preferably 0.01 to 50 g/10 min, particularly 0
．． 02 to 5 ON/10 minutes is suitable.

(2) Carboxylic acid compound The carboxylic acid compound used for producing the entire modified propylene polymer of the present invention is an α,β-unsaturated carboxylic acid and its anhydride. The number of carbon atoms in the unsaturated carboxylic acid compound is usually at most 30, preferably 25 or less.

The unsaturated carboxylic acid compounds are broadly classified into monobasic unsaturated carboxylic acids, dibasic unsaturated carboxylic acids, and anhydrides thereof. - Representative examples of basic unsaturated carboxyl acids include acrylic acid and methacrylic acid. Also, dibasic unsaturated Cal? Typical examples of phosphoric acids include maleic acid, 7-malic acid, itaconic acid, citraconic acid, and 3-malic acid.
, 6-nindomethylene-1,2,3,6-tetrahydrosis-phthalic acid. Further, the anhydride is an anhydride of the dibasic unsaturated cargonic acid, and includes maleic anhydride, citraconic anhydride, citraconic anhydride and 3.6-
Examples include endomethylene-1,2,3,6-titrahydrosis-phthalic anhydride.

(3) Organic peroxide Furthermore, organic peroxides are generally used as initiators in radical polymerization and crosslinking agents for polymers, and those with a half-life of 1 minute of 100°C or more are preferable.
A temperature of 130° C. or higher is preferable. If the above-mentioned temperature is 100° C. or lower, the scale is not difficult to handle, and the effect of using it is not very noticeable, so it is not desirable.

(A) Mixing ratio In producing the modified propylene polymer of the present invention,
100! The mixing ratio of the hydroxyl compound to the propylene polymer is 0.01 to 10 parts by weight,
0.05 to 10 parts by weight is preferred, particularly 0.1 to 7.0 parts by weight.
Parts by weight are preferred. 100 property improvement effect is insufficient. On the other hand, even if it is used in an amount exceeding 10 parts by weight, the stiffness improvement effect corresponding to the amount used will not be observed, and rather the original properties of the propylene polymer will be impaired, which is not preferable.

The mixing ratio of organic peroxide to 100 parts by weight of propylene polymer is 0.01 to 10 parts by weight, and 0.01 to 10 parts by weight.
．． 05 to 7.0 parts by weight is desirable, especially 0.1 to 5 parts by weight.
．． 0 parts by weight is preferred. If the mixing ratio of the organic peroxide to 100 parts by weight of the propylene polymer is less than 0.01 parts by weight, not only the effect of improving adhesion is low, but also the durability of the adhesion strength of the mixture is reduced. On the other hand, exceeding 103 parts is undesirable in any case, since the future good mechanical properties of the polymer are reduced.

(5) Method for producing modified propylene polymer In order to produce the modified propylene polymer of the present invention, the above propylene polymer, Cal. It can be produced by treating (heating) the oxidized metal and the organic peroxide at the above mixing ratio. At this time, the propylene polymer, carboxylic acid compound, and organic peroxide may be mixed together during the treatment, but they must be mixed in advance in a triblend, or at a relatively low temperature (where the hydroxyl compound reacts). It can be obtained by kneading the mixture at a temperature that does not exceed 100°C, and then heating the resulting mixture as described below.

If the treatment is carried out at high temperatures, the propylene-based polymer may deteriorate. However, it must be carried out at a temperature at which the organic peroxide used for graft polymerization between the propylene polymer and the carboxylic acid compound decomposes. Based on the above, this treatment generally has a 180 to 3
It is carried out at 00°C (preferably 200-280°C).

(Composition ratio) In the composition of the present invention, silica and
The composition ratio of the alumina hollow body is 3 to 50% by weight, 5
-45% by weight is desirable, and wrinkles and wrinkles are preferably 7-40% by weight. If the proportion of the silica-alumina hollow bodies in the total composition is less than 3% by weight, the resulting composition will not have good rigidity.

On the other hand, if it exceeds 50 weight eIb, the impact resistance will be significantly reduced.

The composition ratio of the modified propylene polymer to 100 parts by weight of the silica-alumina hollow body is 7 to 75% by weight, preferably 10 to 70% by weight, particularly 10 to 6% by weight.
0% by weight is preferred.

If the composition ratio of the modified propylene polymer to the silica-alumina hollow body of 100 parts is less than 7% by weight, the effect of improving rigidity will be small. On the other hand, even if more than 75 parts by weight is added, there is no effect of improving rigidity depending on the amount added.

Further, the composition ratio Fi of the propylene polymer in the entire composition is preferably 40% by weight or more, and particularly preferably 50% by weight or more. If the proportion of the propylene polymer in the entire composition is less than 40% by weight, the resulting composition will have poor mechanical strength (particularly impact strength).

(6) Production and molding method of composition To produce the composition of the present invention, the above-mentioned polymeric substance or polymeric substance and filler may be uniformly blended. At this time, if necessary, all additives such as oxygen, light or heat stabilizers, flame retardants, processability improvers, lubricants, antistatic agents and pigments commonly used in olefinic polymers may be added. Of course, it may be added.

The compositions may be obtained by tri-blending using mixers such as tumblers, ribbon grinders, and Hensel mixers, or by using batch kneaders (e.g.
The mixture can be kneaded by using a continuous mixer (Banbury mixer) or a continuous kneader (for example, an extruder), but it is also possible to knead continuously by using a continuous mixer as described above. Further, by using these methods in combination (for example, triblending and then continuously kneading), more uniform mixing can be achieved.

The composition thus obtained is usually molded into a pellet shape and produced into a desired molded article by a molding method such as injection molding or extrusion molding, which is commonly used in the respective fields of thermoplastic resins.

Even when melt-kneading is performed when producing the above composition,
Even when molding, the temperature is higher than the melting point of the polymer used, but at a temperature that does not cause thermal decomposition. For these reasons, the temperature is generally 180-280°C (preferably 200-280°C).
60°C).

[Effect]

In the propylene polymer composition of the present invention, the modified propylene polymer improves the compatibility at the interface between the silica-alumina hollow bodies uniformly dispersed in the composition and the crystalline propylene polymer as the main component. As a result, it acts as an action to
It is believed to improve the mechanical strength of the composition.

[Examples and comparative examples]

Hereinafter, the present invention will be explained in more detail with reference to Examples.

In addition, in the examples and comparative examples, the flexural modulus is AS
Measured according to TM D790. Also, the density i
Measured according to JIS K6758. Furthermore, pencil hardness was measured according to JIS K5401.

The physical properties, manufacturing method, etc. of the crystalline propylene polymer, silica/alumina hollow body, and modified propylene polymer used in the Examples and Comparative Examples are shown below.

[(a) Crystalline globylene polymer]

As a crystalline propylene polymer, MFR is 1091L
An ethylene-propylene block comonomer having an O content and an ethylene copolymerization ratio of 15% by weight [hereinafter referred to as rp
p(A)], a propylene single polymer with an MFR of 13 g/10 min [hereinafter referred to as rPP(B)J], and a copolymerization ratio of ethylene with an MFR of 10.9/10 min. An ethylene-propylene random copolymer (hereinafter referred to as rpp ('IJ)) having a concentration of 2.0% by weight was used.

[(B) Silica/alumina hollow body] Also, silica/alumina hollow body
As an alumina hollow body, a spherical hollow body having an average particle diameter of 57 μm, a density of 0.75 ji 7 cm3, and a silica content of 61% by weight [hereinafter referred to as "hollow body"
1), the average particle size is 90 μm, and the density is 0.
．． 72, lit 7cm3, and silica content is 59% by weight [hereinafter referred to as "hollow body (2
)” and the average particle size is 57 μm, the density is 0.75 filα3, and the silica content is 6
A spherical hollow body (hereinafter referred to as "hollow body (3)") whose surface was treated with aminosilane was used.

[(C) Modified propylene polymer] Furthermore, as a modified propylene polymer, 100 parts by weight of a propylene homopolymer having a weight of 0.6 g/10 min was added with o, sox, part water maleic acid and 0.4 parts by weight. Part by weight of penzoylno-4-oxide was previously triblended for 5 minutes using a Henschel mixer. The resulting mixture was passed through an extruder (
Pellets (hereinafter referred to as "modified PPJ") were prepared by kneading using a cylinder with a diameter of 40 tm and a cylinder temperature of 180 to 230 DEG C. (hereinafter referred to as "modified PPJ").

[(ヰヰ　Inorganic filler〕

In addition, for comparison with the silica-alumina hollow body, talc has an average particle size of 10 μm and an aspect ratio of 4.0, light calcium carbonate (hereinafter referred to as rCaCO5J) has an average particle size of 2.5 μm, Average particle size is 30μm
A glass piece having a diameter of 13 μm (hereinafter referred to as ``GF'') and a glass fiber having an average length of 3 m (hereinafter referred to as ``GF'') were used.

Examples 1 to 10, Comparative Examples 1 to 8 Crystalline propylene polymer (hereinafter referred to as rPPJ), silica-alumina hollow body (
A modified propylene polymer (hereinafter referred to as "modified PPJ") and an inorganic filler were tri-blended for 5 minutes using a Henschel mixer.The resulting mixture was transferred to a vented extruder ( The pellets (m-acid) were added to Zen-no-do while kneading at a resin temperature of 210°C using a diameter of 4 ox).The MFR and density of the pellets thus obtained were measured. The results are shown in Table 2.

Each pellet was injection molded using an injection molding machine with a total of 5 ounces at a resin temperature of 230° C. to produce specimens. The flexural modulus and pencil hardness of each specimen obtained were measured. The results obtained are shown in Table 2.

Table 2 (Part 1) Table 2 (Part 2) In Comparative Example 4, the appearance of the molded product was not good (there were considerable welds on the surface).

The results of the above Examples and Comparative Examples show that the propylene thread 1 composite composition of the present invention is not only lightweight, has high rigidity, and has excellent scratch resistance, but also has various other physical properties and It is clear that the mechanical properties are also good.

〔Effect of the invention〕

The propylene polymer composition of the present invention exhibits the following effects.

(1) @Quantity.

(2) The surface of the molded product has excellent scratch resistance.

(3) Good moldability as well.

(A) The appearance of the molded product is excellent (no welds or sink marks occur).

The propylene polymer composition of the present invention can be used in a wide variety of ways in order to exhibit the above-mentioned effects. Typical examples include automobile parts such as instrument panels, and housings for electrical and electronic equipment such as housings for various office automation equipment.

Claims (1)

[Claims] (A) Melt flow index is 0.01 to 100g
/10 minutes, (B) an average particle size of 5 to 400 μm, and a density of 0.70 to 1
．． 00 g/cm^3 of silica-alumina hollow body and (C) (1) 100 parts by weight of propylene polymer (2)
0.01 to 10 parts by weight of an organic compound having at least one unsaturated bond in the molecule and containing a carboxylic acid group or its anhydride group; and (3) 0.01 to 10 parts by weight of an organic peroxide. It is a composition consisting of a modified propylene-based polymer obtained by processing, and the composition ratio of silica/alumina hollow bodies in the whole composition is 3 to 50% by weight, and 100 parts by weight of silica/alumina hollow bodies. A propylene polymer composition in which the composition ratio of the modified propylene polymer to the body is 7 to 75 parts by weight.