JPH05125233A - Modified polyolefin resin composition - Google Patents

Abstract

PURPOSE:To obtain the title composition excellent in adhesiveness and mechanical properties even when a high melt flow rate polyolefin is used as a starting material by mixing a polyolefin containing a specified amount of a specified silane-modified diene/olefin copolymer with an inorganic filler. CONSTITUTION:5-50 pts.wt. inorganic filler is added to 100 pts.wt. polyolefin containing at least 5wt.% silane-modified diene/olefin copolymer prepared by modifying a copolymer of an olefin with a nonconjugated diene comonomer of the formula (wherein R1 to R4 are each hydrogen or 1-6C alkyl; and n is an integer of 1-20) with a silane coupling agent.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a modified polyolefin resin composition containing an inorganic filler. More specifically, for interior and exterior parts of automobiles, electrical components, home appliances, molded products such as medical materials, packaging materials such as films, coating of electric wires and cables, compatibilizers and adhesives for various polymer alloys, etc. It relates to a suitable modified polyolefin resin composition.

[0002]

2. Description of the Related Art Polyolefins are lightweight, have excellent moldability, have good mechanical properties such as mechanical strength, insulation properties, chemical resistance, etc., and are used in various applications such as films, fibers, and molded products. However, its properties such as adhesiveness, paintability, printability and hydrophilicity are not sufficient.
Therefore, in order to improve such properties, a modification method using a silane-based compound has been attracting attention. For example, a copolymer of ethylene and vinylsilane (JP-A-55-155039) and a copolymer of propylene and alkenylsilane are noted. Polymers (JP-A 1-158059), graft copolymers of polyethylene and vinyl silane (JP-A 56-11248), graft copolymers of polypropylene and vinyl silane (JP-A 59580).
A large number of silane compound-modified polyolefins have been proposed mainly in the field of electric wire coating, such as JP-A-36115). Modification of a polyolefin with a silane-based compound makes it possible to obtain a polymer by water-crosslinking, and does not require radical formation by irradiation with radiation such as an electron beam or ultraviolet rays during modification,
Also in terms of physical properties, it has a feature that mechanical strength is improved by water-crosslinking and that modification can be performed relatively easily with simple equipment.

However, according to this method, the molecular weight of the raw material polyolefin is remarkably reduced by the cleavage of the polyolefin main chain during the radical formation process during heat modification, and only a low modification rate can be obtained. Therefore, it is necessary to use a high molecular weight material for the modified polyolefin. Especially, in the case of polypropylene, a high molecular weight material having a melt flow rate (MFR) of 0.8 g / 10 minutes or less is required as the raw material polypropylene. There are restrictions (Japanese Patent Laid-Open No. 59-36115). The problem of the decrease in the molecular weight of the polyolefin due to modification is, for example, a propylene random copolymer (PPDM) containing a non-conjugated diene as described in JP-A-2-269109 and JP-A-2-269110. There is a demand for a polyolefin resin, which is partially improved by using it, but is still insufficient, has excellent adhesiveness and mechanical properties, and does not require a primer or the like. Therefore, the object of the present invention is to use a polyolefin having a high melt flow rate as a raw material,
It is intended to provide a modified polyolefin resin composition having excellent adhesiveness and mechanical properties.

[0004]

Means for Solving the Problems As a result of intensive studies by the present inventors, a silane-modified diene-olefin copolymer obtained by modifying a diene-olefin copolymer containing a non-conjugated diene comonomer with a silane coupling agent. The present invention has been accomplished by finding that a modified polyolefin resin composition having excellent adhesiveness and mechanical properties can be obtained by adding an inorganic filler to a polyolefin containing at least a specific amount. That is, the present invention provides (a) the following general formula (1)

[0005]

[Chemical 2]

[In the formula, R _{1 to} R ₄ are a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and n is an integer of 1 to 20. ] 100 parts by weight of a polyolefin containing 5% by weight or more of a silane-modified diene-olefin copolymer obtained by modifying a copolymer of a non-conjugated diene comonomer represented by the following formula and an olefin with a silane coupling agent, and (b) an inorganic filler 5 to The modified polyolefin resin composition is characterized by containing 50 parts by weight.

The modified polyolefin resin composition of the present invention will be described in detail below. The (a) polyolefin of the modified polyolefin resin composition component of the present invention is ethylene,
And α having 3 or more carbon atoms such as propylene, butene-1, hexene-1, 3-methylbutene-1,4-methyl-pentene-1, heptene-1, octene-1, decene-1
-Olefin homopolymers, random, block, graft, etc. copolymers of these two or more monomers, mixtures thereof, ethylene or α-olefins having 3 or more carbon atoms, and a major portion of other unsaturated monomers. Random, block, graft and other copolymers. Further, the silane-modified diene-olefin copolymer contained in the component (a) in an amount of 5% by weight or more is a silane coupling agent of a diene-olefin copolymer such as random, block or graft of the above-mentioned various polyolefins and non-conjugated dienes. It has been modified by. In the present invention, the above-mentioned silane-modified diene-olefin copolymer is used alone or as a mixture with the above-mentioned polyolefin as the component (a).

The diene used in component (a) of the present invention
Examples of the olefin copolymer include a propylene random copolymer (PPDM) containing a non-conjugated diene comonomer represented by the following general formula (1) and an ethylene-propylene-diene copolymer (EPDM). it can.

[0009]

[Chemical 3]

[In the formula, all symbols have the same meanings as described above. ] Specific examples of the non-conjugated diene represented by the general formula (1) include, for example, 2-methyl-1,4-pentadiene,
1,4-hexadiene, 4-methylidene-1-hexene, 4-methyl-1,4-hexadiene, 5-methyl-
1,4-hexadiene, 1,4-heptadiene, 4-ethyl-1,4-hexadiene, 4,5-dimethyl-1,
4-hexadiene, 4-methyl-1,4-heptadiene, 4-ethyl-1,4-heptadiene, 5-methyl-
1,4-heptadiene, 5-methyl-1,4-octadiene, 1,5-heptadiene, 1,5-octadiene,
5-methyl-1,5-heptadiene, 6-methyl-1,
5-heptadiene, 2-methyl-1,5-hexadiene, 1,6-octadiene, 6-methyl-1,6-octadiene, 7-methyl-1,6-octadiene, 2-methyl-1,6-heptadiene, 1,9-decadiene,
1,13-tetradecadiene and the like can be mentioned. Among these, 1,4-hexadiene, 2-methyl-1,5
-Hexadiene, 7-methyl-1,6-octadiene,
1,9-decadiene, 1,13-tetradecadiene and the like are preferable. Two or more kinds of these non-conjugated diene comonomers may be mixed and used.

In the component (a) of the present invention, the preferred diene-olefin copolymer as a raw material for the silane-modified diene-olefin copolymer is a copolymer of propylene and a non-conjugated diene such as random, block or graft. ,
A mixture of these copolymers and polyolefin is also preferable. Particularly preferred is PPDM having a content of the non-conjugated diene comonomer represented by the general formula (1) of about 0.05 to 10 mol%, preferably 0.1 to 3.0 mol%, and 5% by weight or more of the PPDM, more preferably Is 20% by weight
It is the polyolefin contained above. Polyolefin is melt flow rate (MFR, JISK7210, load 2.16kg,
It is preferable that the temperature (230 ° C.) is about 0.1 to 200 g / 10 minutes.

In the component (a) of the present invention, the silane coupling agent used as a modifier is not particularly limited, but preferably a vinyl group having an unsaturated bond in one molecule,
It has a polar group such as a methacrylic group or an acrylic group, and an alkoxy group. These alone or 2
It is also possible to use two or more kinds in combination. Preferred silane coupling agents are shown below with chemical formulas.

Vinyltriethoxysilane: CH ₂ = CHSi (OC ₂ H ₅ ) ₃

Vinyl tris (2-methoxyethoxy) silane: CH ₂ ═CHSi (OC ₂ H ₅ OCH ₃ ) ₃

3-methacryloxypropyltrimethoxysilane:

[Chemical 4]

The mixing ratio of the silane coupling agent as the above-mentioned modifier varies depending on the kind of the raw material diene-olefin copolymer and cannot be generally stated, but it is 0.5 with respect to 100 parts by weight of the diene-olefin copolymer. It is about 20 parts by weight. The silane-modified diene-olefin copolymer preferable as the component (a) in the present invention is the above-mentioned raw material diene-olefin copolymer, especially the above-mentioned general formula (1).
Containing a non-conjugated diene comonomer represented by
A silane coupling agent of 0.5 to 20 parts by weight is added to 100 parts by weight of a polyolefin containing 20% by weight or more of M and modified. Among these, the melt flow rate (MFR, JISK7210, load 2.16kg, 230 ℃)
0.01 to 100 g / 10 minutes, preferably 0.1 to 100
Silane-modified PPDM with g / 10 min is preferred.

Such a preferable silane-modified diene-olefin copolymer can be obtained by utilizing a known modification method such as a solution method or a melt-kneading method. In addition, a commercially available product may be appropriately selected and used. That is,
In the melt-kneading method, a diene-olefin copolymer, the above-mentioned silane coupling agent, and if necessary a catalyst are used, and these components are put into an extruder, a twin-screw kneader, or the like, and the temperature is about 180 to 300 ° C. The silane-modified diene-olefin copolymer is obtained by kneading for about 0.1 to 20 minutes while heating to a temperature and melting. Further, in the case of the solution method, the above-mentioned starting materials are dissolved in an organic solvent such as xylene to prepare 90 to 20
Denaturation is carried out at a temperature of about 0 ° C. with stirring for 0.1 to 100 hours.

In any modification method, a conventional radical polymerization catalyst can be used as a catalyst, for example, benzoyl peroxide, lauroyl peroxide, ditertiary butyl peroxide, acetyl peroxide, tert-butyl peroxybenzoic acid. Peroxides such as acids, dicumyl peroxide, peroxybenzoic acid, peroxyacetic acid, tertiary butyl peroxypivalate, 2,5-dimethyl-2,5-ditertiary butyl peroxyhexyne, and azobisisobutyronitrile Azo compounds and the like are used.
The amount of the catalyst added is about 0.01 to 10.0 parts by weight with respect to 100 parts by weight of the modifying raw material diene-olefin copolymer.

As the inorganic filler (b) of the polyolefin resin composition component of the present invention, powdery, fibrous, spherical,
Various shapes such as flakes can be used.
Examples of the powdered inorganic filler include oxides such as alumina, magnesium oxide and calcium oxide, aluminum hydroxide, magnesium hydroxide, basic magnesium carbonate, calcium hydroxide, tin oxide hydrate, zirconium oxide hydrate. Hydrated metal oxides such as, carbonates such as calcium carbonate, magnesium carbonate, talc, clay,
Silicates such as bentonite, barium borate, borate such as zinc borate, aluminum phosphate, phosphates such as sodium tripolyphosphate, sulfates such as gypsum, sulfites, metals such as copper, iron and lead. Powder, a mixture of two or more of these, and the like can be mentioned. Examples of the fibrous material include glass fiber, potassium titanate fiber, metal-coated glass fiber, ceramic fiber, wollastonite, carbon fiber,
Metal carbide fibers and the like, other, glass beads,
Spherical materials such as glass balloons and shirasu balloons, glass powder, glass flakes, and mica can also be used. Among the above inorganic fillers, glass fiber, talc and mica are preferred. Two or more kinds of these inorganic fillers can be used in combination. Here, as the glass fiber, chopped strands, roving, etc. can be used,
The fiber diameter is preferably about 0.1 to 20 μm. Also,
Talc is a complex salt of magnesium oxide and silicic acid,
The average particle size is preferably about 0.1 to 100 μm. The mica is an aluminosilicate containing an alkali metal, and preferably has an average particle size of about 5 to 500 μm and an aspect ratio of about 10 to 500.

In the modified polyolefin resin composition of the present invention, the compounding ratio of the component (a) polyolefin containing 5% by weight or more of the silane-modified diene-olefin copolymer and the component (b) inorganic filler is 100 parts by weight of the component (a). 5 to 50 parts by weight of component (b), preferably 10 to 4 parts by weight.
0 parts by weight. When the amount of the component (b) is less than 5 parts by weight, the mechanical strength and heat resistance of the modified polyolefin resin composition are insufficient, and the use of more than 50 parts by weight adversely affects the moldability and adhesiveness of the composition. .. In the component (a), the ratio of the unmodified starting diene-olefin copolymer to the silane coupling agent is 0.5 to 20 parts by weight of the silane coupling agent based on 100 parts by weight of the unmodified starting diene-olefin copolymer. Parts by weight, preferably 1.0 to 10 parts by weight. If the amount is less than 0.5 part by weight, the adhesion with the inorganic filler due to the use of the silane coupling agent is insufficient, and if the amount exceeds 20 parts by weight, the mechanical properties of the modified polyolefin resin composition are adversely affected.

In the present invention, in addition to the above-mentioned substances, other fillers and reinforcing materials used in the field of olefinic elastomers and ordinary resin compositions to the extent that the properties of the modified polyolefin resin composition of the present invention are not impaired. , A heat stabilizer, a light stabilizer, a flame retardant, a plasticizer, an antistatic agent, a foaming agent, a nucleating agent and the like can be added. Here, the olefin elastomer means two or more copolymer rubbers of α-olefins such as ethylene, propylene, butene-1, hexene-1, and 4-methyl-pentene-1, or α-olefins. And a monomer of another kind. Specific examples of the copolymer rubber of two or more kinds of the α-olefin include ethylene-propylene copolymer rubber (E
PR) and ethylene-butene copolymer rubber (EBR)
Can be mentioned.

The modified polyolefin resin composition of the present invention is prepared by mixing the above components with a kneader such as a single-screw extruder, a twin-screw extruder, a Banbury mixer, a kneading roll, and a Brabender at 180 to 300 ° C., preferably 190. It can be obtained by melt-kneading at ˜230 ° C. In the present invention, there is no particular limitation on the kneading order of each component, and a method in which the component (a) and the component (b) are put into a kneading machine all at once and kneading, or one of the component (a) and the component (b) is kneaded in advance. After kneading by adding to the machine and kneading by adding the other, the unmodified diene-olefin copolymer and the silane coupling agent are independently used as the component (a), and the unmodified After kneading the diene-olefin copolymer and the component (b), the silane coupling agent may be kneaded, and other kneading orders may be adopted.

[0023]

According to the present invention, a low molecular weight raw material having a melt flow rate (MFR) of 0.8 g / 10 minutes or more, which has hitherto been difficult to obtain with a high modification rate, is used, and adhesion and mechanical properties are It is possible to obtain a modified polyolefin resin composition containing an inorganic filler having excellent physical properties. Although the reason why the present invention produces such an effect is not always clear, the silane-modified diene polyolefin copolymer is suppressed by suppressing the decrease in the molecular weight of the polyolefin main chain during the heat modification through the non-conjugated diene comonomer in the component (a). It is believed that this is because the physical properties of the inorganic filler are improved, and the compatibility dispersibility of the inorganic filler is improved by the silane coupling agent in the silane-modified diene-olefin copolymer.

[0024]

EXAMPLES The present invention will be described in more detail with reference to Examples and Comparative Examples. In each of the examples and comparative examples, the following materials were used as raw materials and additives. Polyolefin (1) Polypropylene homopolymer PP-1: [E200 manufactured by Tonen Kagaku KK, melt flow rate (MFR, 230 ° C, 2.16 kg load) 0.6 g / 1
0 minutes, weight average molecular weight (Mw) 450,000] (for production of silane-modified polyolefin PO-1, PO-2) PP-2: [J-209 manufactured by Tonen Kagaku KK, melt flow rate (MFR, 230 ° C, 2.16) kg load) 9.2 g / 1
0 minutes, weight average molecular weight (Mw) 200,000] (2) Propylene-non-conjugated diene random copolymer (PP
DM) PPDM-1: [1,9-decadiene content 0.45 mol%, melt flow rate (MFR, 230 ° C., 2.16 kg load) 125 g / 10 min, weight average molecular weight (Mw) 10
10,000] PPDM-2: [1,9-decadiene content 0.56 mol%, melt flow rate (MFR, 230 ° C, 2.16 kg load) 17.7 g / 10 minutes, weight average molecular weight (Mw) 170,000] PPDM-3: [7-methyl-1,6-octadiene content 0.49 mol%, melt flow rate (MFR, 23
0 ° C., 2.16 kg load) 8.0 g / 10 min, weight average molecular weight (Mw) 200,000] PPDM-4: [7-methyl-1,6-octadiene content 1.10 mol%, melt flow rate (MFR, 23
0 ° C., 2.16 kg load) 10.4 g / 10 minutes, weight average molecular weight (Mw) 190,000] Radical generator POX: Perhexin 25B [NOF CORPORATION] Silane coupling agent SA: 3-methacryloxypropyltrimethoxysilane [Nippon Unica A-174] Inorganic filler GW: glass fiber [fiber diameter 2 μm, fiber length 3 mm]

Silane-modified diene-olefin copolymer (1) Silane-modified PPDM (Production Example 1) Propylene-non-conjugated diene random copolymer (PPDM
-1) 100 parts by weight and silane coupling agent (SA)
3 parts by weight and 0.1 parts by weight of POX were kneaded with a Labo Plastomill at 200 ° C. for about 5 minutes, and melt flow rate (MFR, 230 ° C., 2.16 kg load) 12.3 g / 10
Min, weight average molecular weight (Mw) 190,000 silane-modified PPD
M (SP-1) was obtained. The silane coupling agent graft ratio of this modified PPDM was 1.6% by weight. In addition,
The graft ratio was calculated by the following method. Silane modified PPD
In the IR spectrum of M (modified PPDM was dissolved in boiling xylene, insoluble matter was removed, dissolved components were precipitated with acetone, and this was pressed to a thickness of about 50 μm, and then measured). Peak related to expansion and contraction of carbonyl (C = O) bond of ring agent (1730 cm
^-1 ) and one of the peaks (840 cm ^-1 ) peculiar to isotactic polypropylene, the graft ratio was calculated. (2) Silane-modified PPDM (Production Example 2) Melt flow rate (MFR, 230 ° C., 2.16 kg) was the same as in Production Example 1 except that POX was 0.2 part by weight.
A silane-modified PPDM (SP-2) having a load of 18.5 g / 10 minutes and a weight average molecular weight (Mw) of 170,000 was obtained. This modified P
The silane coupling agent graft ratio of PDM was 2.0% by weight. (3) Silane-modified PPDM (Manufacturing Example 3) Melt flow rate (MFR, MFR, MFR) was the same as in Manufacturing Example 1 except that SA was 5 parts by weight and POX was 0.5 part by weight.
Silane-modified PPDM (SP-3) having a weight average molecular weight (Mw) of 150,000 was obtained at 230 ° C. and 2.16 kg load) 32.2 g / 10 minutes. The silane coupling agent graft ratio of this modified PPDM was 3.8% by weight.

(4) Silane-modified PPDM (Production Example 4) PPDM-2 was used in place of PPDM-1, and POX was used.
Melt flow rate (MFR, 230 ° C, 2.16kg load) in the same manner as in Production Example 1 except that 0.2 part by weight was used.
Silane-modified PPDM (SP-4) having a weight average molecular weight (Mw) of 220,000 was obtained at 5 g / 10 minutes. The silane coupling agent graft ratio of this modified PPDM was 2.3% by weight. (5) Silane-modified PPDM (Production Example 5) A melt flow rate (MF) was obtained in the same manner as in Production Example 4 except that PPDM-3 was used instead of PPDM-2.
R, 230 ° C., 2.16 kg load) 31.7 g / 10 minutes, weight average molecular weight (Mw) 150,000 silane-modified PPDM (SP-
5) was obtained. The graft ratio of the silane coupling agent of this modified PPDM was 1.5% by weight. (6) Silane-modified PPDM (Production Example 6) Melt flow rate (MF) was the same as in Production Example 4 except that PPDM-4 was used in place of PPDM-2.
R, 230 ° C., 2.16 kg load) 26.5 g / 10 minutes, weight average molecular weight (Mw) 160,000 silane-modified PPDM (SP-
6) was obtained. The silane coupling agent graft ratio of this modified PPDM was 2.3% by weight.

100 parts by weight of silane-modified polyolefin (PO-1) polypropylene homopolymer (PP-1), 3 parts by weight of silane coupling agent (SA) and PO
X0.2 parts by weight using a Labo Plastomill at 200 ° C
Kneading for about 5 minutes, melt flow rate (MFR, 23
A modified product (PO-1) having a weight average molecular weight (Mw) of 100,000 and 113 g / 10 minutes at 0 ° C. and a load of 2.16 kg was obtained. The IR spectrum of this modified product was measured in the same manner as in Production Example 1. As a result, carbonyl (C =
No peak (1730 cm ⁻¹ ) related to the stretching of the (O) bond was observed. From this, the silane coupling agent is PP
Therefore, it was confirmed that the graft reaction did not proceed. Silane-modified polyolefin (PO-2) Melt flow rate (MFR, 230 ° C, 2.16 kg load) 290 g / in the same manner as in the case of PO-1 except that SA was 5 parts by weight and POX was 0.5 part by weight. 10 minutes,
A modified product (PO-2) having a weight average molecular weight (Mw) of 75,000 was obtained. As with PO-1, the modified product did not show a peak (1730 cm ^-1 ) related to the expansion and contraction of the carbonyl (C = O) bond of the silane coupling agent in the IR spectrum, and the silane coupling agent was introduced into PP. It was confirmed that there was not.

Examples 1 to 11 and Comparative Examples 1 to 5 Silane-modified diene-olefin copolymers (SP-1 to S
P-6), silane-modified polyolefin (PO-1 or PO-2), and unmodified polyolefin (PP-2)
And an inorganic filler (GW) were dry-blended with a Henschel mixer at a ratio shown in Table 1, and then 20 with a twin-screw extruder (TEX44 type manufactured by Japan Steel Works, Ltd.).
The mixture was kneaded at 0 ° C. and 50 rpm to obtain pellets of the resin composition. Melt flow rate (MF of each obtained resin composition
R, 230 ° C., 2.16 kg load), bending maximum strength, bending elastic modulus and Izod impact strength of the injection-molded article at 23 ° C., and heat distortion temperature were measured. The results are also shown in Table 1.

[0029]

[Table 1]

[0030]

[Table 2]

The methods for measuring the physical properties shown in Table 1 above are as follows. (1) Melt flow rate: Measured at 230 ° C and a load of 2.16 kg. (2) Maximum bending strength (23 ° C): Measured according to JIS K7203. (3) Flexural modulus (23 ° C): Measured according to JIS K7203. (4) Izod impact strength (23 ° C): Measured according to JIS K7110. (5) Heat distortion temperature (load 18.6 kg / cm ² ): Measured according to JIS K7207.

As is apparent from Table 1, the modified polyolefin resin composition of the present invention is a composition comprising an unmodified polyolefin lacking a silane-modified diene-olefin copolymer and an inorganic filler (Comparative Examples 1 and 5). ), All of the bending maximum strength, bending elastic modulus, Izod impact strength, and heat distortion temperature are better than those of compositions (Comparative Examples 2 to 4) including unmodified polyolefin, silane-modified polyolefin, and inorganic filler. Especially, the maximum bending strength is significantly improved.

[0033]

As described in detail above, the present invention provides a modified polyolefin resin composition containing a silane-modified diene-olefin copolymer and an inorganic filler. According to the present invention, a high melt flow rate is provided. A modified polyolefin resin composition having excellent mechanical properties such as bending strength can be obtained by using a raw material of rate. Such modified polyolefin resin composition of the present invention is used as various engineering plastics, especially for automobile interior and exterior parts and electrical components, home appliances, molded articles such as medical materials, packaging materials such as films, coating of electric wires and cables, etc. It is suitable as a compatibilizing agent for various polymer alloys or as an adhesive.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yuji Fujita 1-3-1 Nishitsurugaoka, Oi-cho, Iruma-gun, Saitama Tonen Research Institute

Claims (1)

[Claims] 1. (a) The following general formula (1): Wherein, R ₁ to R ₄ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, n represents an integer of 1 to 20. ] 100 parts by weight of a polyolefin containing 5% by weight or more of a silane-modified diene-olefin copolymer obtained by modifying a copolymer of a non-conjugated diene comonomer represented by the following formula and an olefin with a silane coupling agent, and (b) an inorganic filler 5 to 50 parts by weight of the modified polyolefin resin composition.