JPS62184040A - Impact-resistant polyolefin resin composition - Google Patents

Abstract

PURPOSE:To improve greatly the impact resistance and to improve also the strength and heat resistance of a polyolefin resin compsn. contg. an ethylene/ propylene rubber, by adding a compd. having a cyanato group thereto. CONSTITUTION:A polyolefin resin compsn. contg. 5-30wt% ethylene/propylene rubber is blended with 0.3-10wt% cyanic ester compd. having at least one cyanato group as a modifier and a catalyst for crosslinking said ethylene/ propylene rubber or a catalyst for said cyanic ester compd. Pref. not more than 30wt% (based on the amount of said cyanic ester compd.) mono- or polyfunctional maleimide compd. is used as a modifying aid. Examples of both catalysts are org. peroxides such as dicumyl peroxide, sulfur or melamine.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a polyolefin resin composition that has significantly improved impact resistance, and further has improved mechanical properties and heat deterioration resistance. , molded articles, etc.

[Conventional technology and its problems]

Polyolefin resins are widely used in industry, and polyolefins mixed with ethylene-propylene rubber are also known as impact-resistant grades, but they do not necessarily have sufficient impact resistance compared to BS resins etc. does not have
Poor impact resistance, especially at low temperatures. Also, a large amount of ethylene
By mixing propylene rubber, the impact resistance at room temperature is significantly improved, but there is a drawback that the heat distortion temperature is significantly lowered.

[Means for solving problems]

As a result of various studies on the utilization of the unique properties of cyanato groups in compounds having a cyanato group (-0-C=N), the present invention was developed by first adding a compound having a cyanato group to ethylene-propylene rubber. It is possible to significantly improve the mechanical properties, thermal properties, etc. of ethylene-propylene rubber (Japanese Patent Application No. 6O-183409)
, and that by adding a small amount of a compound having a cyanato group to polyolefin, the thermal stability etc. of polyolefin can be improved (Japanese Patent Application No. 60-0489)
54, Japanese Patent Application No. 6O-194044). As a result of further studies, it was discovered that impact resistance could be significantly improved by blending a compound having a cyanato group into a polyolefin resin composition containing polyolefin and ethylene-propylene rubber, and the present invention was completed. It is.

That is, in the present invention, ethylene-propylene rubber is
A polyolefin resin composition containing 30% by weight, 0.3 to 10% by weight of a cyanate ester compound containing one or more cyanato groups in the molecule as a modifier, and the ethylene-propylene rubber crosslinking catalyst or the cyanate ester. It is an impact-resistant polyolefin resin composition prepared by adding a catalyst compound, and in a preferred embodiment, a monofunctional or polyfunctional maleimide compound is added as a modifying aid in an amount of 30% by weight based on the cyanate ester compound. m below %
The object of the present invention is to provide a reinforced impact-resistant polyolefin resin composition which is further blended with a reinforcing agent such as glass fiber.

The present invention will be explained below.

The polyolefin resin (hereinafter referred to as PO) of the present invention includes polyethylene (PE), polypropylene (PP), polybutene-1, ethylene-propylene copolymer resin, etc.
and compositions of two or more of these polyolefins.

The ethylene-propylene rubber (hereinafter referred to as EPR) of the present invention is obtained by copolymerizing ethylene, propylene, or these with ethylidene, norbornene, dicyclopentadiene, other diene compounds, etc. as raw materials, and is usually ethylene propylene copolymer (= BPM)
, rubbery copolymers such as ethylene-propylene-diene monomer copolymers (=EPDM).

Suitable cyanate ester compounds containing one or more cyanato groups in the molecule of the present invention to be used as a modifier for the PO composition obtained by blending EPR with the above-mentioned PO are as follows:
It is a compound represented by the following general formula (1).

General formula (1): R(OCN)m...
(1) (m in the formula is an integer of 1 or more and usually 5 or less,
(R is an aromatic organic group, and the cyanato group is bonded to the aromatic ring of the organic group) Specific examples include alkyl groups such as monocyanatobenzene and pt-butylcyanatobenzene. Cyanatobenzene, monocyanatonaphthalene, 1.3-or 1゜4-dicyanatobenzene, 1.3.5-) lycyanatobenzene,
1.3-, 1.4-, 1.6-, 1.8-, 2.6- or 2.7-dicyanatonaphthalene, 1.3.6-dicyanatonaphthalene, 4.4'-dicyanato biphenyl,
Bis(4-dicyanatophenyl)methane, 2.2-bis(4-cyanatophenyl)propane, 2.2-bis(3
,5-dichloro-4-cyanatophenyl)propane, 2
．． 2-bis(3,5-dibromo-4-cyanatophenyl)propane, bis(4-cyanatophenyl)ether,
Bis(4-cyanatophenyl)thioether, bis(4
-cyanatophenyl) sulfone, tris(4-cyanatophenyl) phosphite, tris(4-cyanatophenyl) phosphate, and a cyanate ester obtained by the reaction of a polycarbonate oligomer having a hydroxyl group at the end with cyanogen halide ( USP-4,026,91
3), cyanic acid ester (IIsP-4,022,75) obtained by the reaction of novolac and cyanogen halide
5, 3.448.079), etc. In addition to these, Special Publications No. 41-1928, No. 43-18468, No. 44
-4791, 45-11712, 46-4111
2, 47-26853, JP-A-51-63149, U
SP-3,553,244, 3.755.402, 3.740.348, 3.595.900, 3.6
Cyanic acid esters described in 94.410 and 4.116.946 may also be used.

In addition, the above-mentioned polyfunctional cyanate ester can be used as it is, or in the presence of salts such as mineral acids, Lewis acids, carbonates, lithium chloride, phosphate esters such as tributylphosphine, organic metal salts, etc. Alternatively, it can be used simply as a prepolymer having a cyanato group in the molecule obtained by polymerization under heating, or as a prepolymer with a monofunctional or polyfunctional maleimide compound (described later) or as a prereactant (=prepolymer). It can also be used as a prepolymer with amines.

The amount of the cyanate ester compound of the present invention described above is not particularly limited, but is appropriately selected from the range of 0.3 to 10% by weight. If the amount added is less than 0.3% or more than 10% by weight, the effect of improving impact resistance will be insufficient.

The EPR crosslinking catalyst or cyanate ester compound catalyst of the present invention is a catalyst known as a reaction accelerator for a cyanate ester compound or a crosslinking catalyst known as an EPR crosslinking agent, such as dicumyl peroxide. Examples include known organic peroxides such as sulfur, melamine, metal salts such as aluminum acetylacetonate, and metal chelates, which may be used alone or in combination. The amount used is a catalytic amount, usually in the range of 0.05 to 5% by weight.

In a preferred embodiment of the present invention, as a modification aid,
30% by weight based on the above cyanate ester compound
Hereinafter, a monofunctional or polyfunctional maleimide compound is usually used in an amount of 1% by weight or more. When the blend m of the monofunctional or polyfunctional maleimide compound exceeds 30% by weight, the heat resistance such as the heat distortion temperature of the resulting PO resin composition is improved, but the impact resistance becomes insufficient. A preferred compound as such a monofunctional or polyfunctional maleimide compound is the following general formula (2).

(General formula): (In the formula, R1 is an aromatic or alicyclic organic group having a valence of 1 or more and usually 5 or less, x' and x'' are hydrogen, halogen, or an alkyl group, and n is usually 1 (It is an integer of ~5.) The maleimide represented by the above formula is prepared by reacting maleic anhydride with a polyamine containing 1 to 5 amino groups to prepare maleamic acid, and then cyclodehydrating the maleamic acid. It can be produced by a method known per se.Specific examples include N-phenylmaleimide, N-phenylmaleimide,
-Carboxyphenylmaleimide, N-chlorophenylmaleimide, N-methoxyphenylmaleimide, 1.3
- or 1,4-bismaleimidobenzene, 1,3- or 1,4-bismaleimidocyclohexane, 4,4°-bismaleimidobiphenyl, bis(4-maleimidophenyl)methane, bis(4-maleimidophenyl)ether, Bis(4-maleimidophenyl)sulfone, bis(4
-maleimido-3-methylphenyl)methane, bis(4
-maleimido-3,5-dimethylphenyl)methane, bis(4-maleimido-3,5-dichlorophenyl)methane, 2,2-bis(4-maleimidophenyl)propane, 2,2-bis(4-maleimido-3) -methylphenyl)propane, 2,2-bis(4-maleimido-3,5-
dimethylphenyl)propane, 2.2-bis(4-maleimido-3-chlorophenyl)propane, 2.2-bis(4-maleimido-3,5-dichlorophenyl)propane, 2.2-bis(4-maleimido-3) , 5-dibromophenyl)propane, 1.1-bis(4-maleimidophenyl)cyclohexane, 3.4-bismaleimidophenyl-4°-maleimidophenylmethane, 1. l-bis(4-maleimidophenyl)-1-phenylmethane, S
Examples include polymaleimides made from melamines having a -triazine ring, and polymaleimides made from polyamines in which benzene rings are linked with methylene bonds by a reaction between aniline and formaldehyde.

Furthermore, the PO composition of the present invention can of course contain a reinforcing material to form a reinforced composition.

The reinforcing material is a weakly alkaline to weakly acidic reinforcing base material such as glass fiber, and the amount of the reinforcing material is not particularly limited, but it is usually used in the range of 5 to 40% by weight based on the resin composition of the present invention. By doing so, it is possible to improve the heat distortion temperature and the impact resistance at low temperatures. Specific examples include glass fiber, talc, mica, wollastate, calcium carbonate, etc. In the case of weakly alkaline or weakly acidic materials, materials pretreated with a known surface treatment agent or cyanic acid of the present invention may be used. A surface treatment with an ester compound may be used beforehand.

The components described above are used to produce the impact resistant PO resin composition of the present invention.

The preparation method is not particularly limited as long as the added components are uniformly dispersed, but it is usually mixed at a temperature of 140 to 200°C for 1 minute to 1 hour using a roll, niegoo, rougu, extruder, or other means. by.

The impact-resistant PO resin composition of the present invention is as described above, but it also contains dyes, pigments, inorganic fillers, metal fibers, powders, flakes, etc., plasticizers, flame retardants, ultraviolet absorbers, stabilizers, etc. Known additives, thermoplastic resins, and thermosetting resins can be added as appropriate.

〔Example〕

The present invention will be explained below with reference to Examples. Note that the amounts added in Examples and the like are based on weight.

Example-1 The following components were blended into PP resin in the amounts shown in Table 1, and the temperature was 190°C.
℃ for 30 minutes, and this mixture was press-molded at a temperature of 190℃ and a pressure of 20 kg/cot to obtain a flat plate with a thickness of 3M, and a test piece for measuring physical properties was prepared.The results are shown in Table 1. Indicated.

Note that the description in Table 1 is as follows.

Example-2 PE resin (high-density PB, manufactured by Showa Denko Q@, product name: 620
0v) with the ingredients listed in Table 2 and heated at 150°C.
Knead with a Nigu for 0 minutes, and then mix this mixture at a temperature of 1.
Press molded at 50℃ and pressure 20kg/cat to a thickness of 3
A flat plate of mm was obtained and used as a test piece for measuring physical properties.

The results are shown in Table 2.

The description in Table 2 above was the same as the description in Table 1 except that the measurement load for jlDT Book 1 (heat distortion temperature) was 4.6 kg.

[Operation and effects of the invention]

As is clear from the above detailed description and examples, the polyolefin resin composition of the present invention has significantly improved impact strength, especially at low temperatures, and also has improved strength, heat resistance, etc. This is clear, and it can be seen that it is a practically excellent molding material.

Claims (1)

[Scope of Claims] 1. A cyanate ester compound containing one or more cyanato groups in the molecule is added to a polyolefin resin composition containing 5 to 30% by weight of ethylene-propylene rubber as a modifier.
An impact-resistant polyolefin resin composition comprising 3 to 10% by weight of the ethylene-propylene rubber crosslinking catalyst or the cyanate ester compound catalyst. 2. The modification aid is a monofunctional or polyfunctional maleimide compound, which is used in combination in an amount of 30% by weight or less based on the cyanate ester compound (c). The impact-resistant polyolefin resin composition described in . 3. The impact-resistant polyolefin resin composition according to claim 1, which contains a reinforcing material.