JPH03281646A - Polyolefin resin composition and its preparation - Google Patents

Abstract

PURPOSE:To prepare the title compsn. excellent in impact resistance esp. at room temp. by crosslinking, in a specific manner, a compsn. contg. a crystalline polyolefin resin and an unsatd. carboxylic acid-modified soft polymer in a specified ratio. CONSTITUTION:A resin compsn. contg. a crystalline polyolefin resin (e.g. a PP) and a soft polymer grafted with an unsatd. carboxylic acid (deriv.) (e.g. a maleic anhydride-grafted ethylene-propylene random copolymer) in a wt. ratio of the resin to the polymer of (99:1) to (50:50) is crosslinked by an amine (e.g. hexamethylenediamine) in an amt. of 0.01-10 pts.wt. based on 100 pts.wt. the sum of the resin and the polymer.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a polyolefin resin composition.

BACKGROUND ART Conventionally, thermoplastic rubber-like elastic bodies have been used as molded bodies that require impact resistance, such as automobile parts. This rubber-like elastic body has thermoplasticity and elasticity, and can be molded into molded products with excellent properties such as heat resistance, tensile properties, weather resistance, flexibility, and elasticity by injection molding or other methods. I can do it.

However, such rubber-like elastic bodies are not satisfactory in all properties. The present invention aims to provide a novel polyolefin resin composition and a method for producing this polyolefin resin composition.Further details J& Particularly improved impact resistance at normal and low temperatures It is an object of the present invention to provide a novel polyolefin resin composition and a method for producing this polyolefin resin composition.

i Ashiri 1 The first polyolefin resin composition according to the present invention (Dai) A crystalline polyolefin resin (a) and a soft polymer (b) graft-modified with an unsaturated carboxylic acid and/or its derivative are combined at 99% :1 to 50:50, and the resin composition comprises the crystalline polyolefin resin (a) and the soft polymer (b).
It is characterized by having a crosslinked structure formed by 0.01 to 10 parts by weight of the amino group-containing compound (c) based on a total of 100 parts by weight.

The second polyolefin resin composition according to the present invention comprises a crystalline polyolefin resin (a) and a soft polymer (b) graft-modified with an unsaturated carboxylic acid and/or its derivative in a ratio of 99=1 to 50: 50, and the resin composition contains 0.01 to 10 parts by weight based on a total of 100 parts by weight of the crystalline polyolefin resin (a) and the soft polymer (b). It has a crosslinked structure formed by parts by weight of the amino group-containing compound (c), and the crystalline polyolefin resin (a)
For a total of 100 parts by weight of and soft polymer (h+),
It is characterized by containing 1 to 100 parts by weight of an inorganic filler (d).

First polyolefin resin composition storage according to the present invention A crystalline polyolefin resin (a) and a soft polymer (b) graft-modified with an unsaturated carboxylic acid and/or its derivative are mixed in a ratio of 99:1 to 50:50. and the above crystalline polyolefin resin (a) and the soft polymer (
It can be produced by heating a mixture containing 0.01 to 10 parts by weight of the amino group-containing compound (c) based on a total of 100 parts by weight with b) to form a crosslinked structure.

The second polyolefin resin composition according to the present invention comprises a crystalline polyolefin resin (a) and a soft polymer (b) graft-modified with an unsaturated carboxylic acid and/or its derivative in a ratio of 99:I to 50:1. The crystalline polyolefin resin (a) and the soft polymer (
For a total of 100 parts by weight of b), 0.01 to 10
It can be produced by heating a mixture containing 3i parts of an amino group-containing compound and 1 to 100 parts by weight of an inorganic filler (d) to form a crosslinked structure.

The polyolefin resin composition of the present invention is composed of a crystalline polyolefin resin (a) and a soft polymer (b), and has a crosslinked structure formed by an amino group-containing compound, so it has particularly high resistance at room temperature. Impact resistance is improved.

, a. Dislocation Next, the polyolefin resin composition of the present invention will be specifically explained.

The polyolefin resin composition according to the present invention contains a binding polyolefin resin (a) and a soft polymer (b).

Polyolefin blended in the resin composition of the present invention A polyolefin formed from an α-olefin having 2 to 2 carbon atoms. Examples of such a-olefins include iL ethylene, propylene, 1-butene, 1-
Mention may be made of pentene, 1-hexene, 4-methyl-1-pentene, 1-octene and 1-decene. The polyolefin used in the present invention may be a polymer prepared by using the above α-olefin alone, or a copolymer prepared by combining multiple α-olefins. It may be a combination.

The polyolefin used in the present invention is crystalline, and the crystallinity power (usually 10 to 95%, preferably 30 to 95%) determined by X-ray diffraction method (measured at 23°C)
is within the range of

1J13 as a polyolefin resin used in the present invention
A polyolefin whose intrinsic viscosity [V] measured in decalin at 5° C. is usually in the range of 0.1 to 10 dl/wide, preferably 1 to 5 dl/g is used.

In addition, this polyolefin conforms to ASTM-D-1238
The melt flow rate measured at 230°C according to
It is within the range of 50g/10 minutes.

In particular, in the present invention, as a polyolefin resin,
Preference is given to using polypropylene, which may be a homopolymer or a copolymer. When using a polypropylene copolymer as the polyolefin resin, monomers to be copolymerized with propylene include ethylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-
Mention may be made of octene and 1-decene. These monomers can be used alone or in combination. When using polypropylene copolymer
The content of repeating units derived from propylene in the copolymer is usually 1 to 50 mol% or more, preferably 80 mol% or more.

Further, in the present invention, it is particularly preferable to use a polypropylene homopolymer and/or a polypropylene copolymer having a melt flow rate (MFR) of 0.5 to 45 g/10 minutes.

Such a crystalline polyolefin resin can be produced by homopolymerizing or copolymerizing olefins according to known techniques.

Furthermore, as the crystalline polyolefin resin, it is possible to use polymer particles obtained by polymerizing or copolymerizing the above α-olefin in the presence of a catalyst in liquid phase, gas phase, or a combination of both. .

A method that combines liquid phase method and gas phase method. , further polymerize the a-olefin in the gas phase.

The catalyst used here preferably includes transitions of groups AaLvA, vyA, and A of the periodic table of elements, such as titanium, zirconium, hafnium,
Catalyst component [A] containing vanadium, for example, an organoaluminum compound having at least one AQ-carbon bond in the molecule, and elements from groups I & II of the periodic system and m
A catalyst consisting of an organometallic compound catalyst component [B] having a metal of the above group is used.

Note that the catalyst component [A] can be prepared by further blending an electron donor (inside donor) in addition to the above components.

Regarding such catalyst components, Japanese Patent Application Laid-Open No. 55-1351
No. 02, No. 55-135103, No. 56-811
No. 56-67311 and patent application No. 56-1
No. 81019 and No. 61-21109.

Further, as the organometallic compound catalyst component [B], for example, an organoaluminum compound obtained by a reaction between an organoaluminum compound and water, or a reaction between an aluminoxane solution and water or an active hydrogen-containing compound may be used. I can do it.

This kind of organometallic compound catalyst component [B] GL
In addition to the above component [B], an electron donor (outside donor) can also be blended.

Using the catalyst as described above, a small amount of olefin is prepolymerized in a liquid phase prior to main polymerization.

After preliminary polymerization, polymer particles can be prepared by performing main polymerization in a gas phase. The polymerization temperature during prepolymerization is -40 to 80°C.

Polymerization temperature jL during main polymerization using the above catalyst
Normally -50 to 200℃, pressure is normal pressure to 100kg/c
Polymerization is carried out within the range of ar.

Regarding the manufacturing method of such polymer particles, a patent application issued in 1983
The technique described in Japanese Patent No. 3-294066 can be used.

The soft polymer (b) used in the present invention is a polymer that exhibits rubber-like elasticity due to the formation of a crosslinked structure.

The tensile modulus (YM) of a 2-thick test piece of such a polymer measured according to ASTM-D-638 is usually 0.1 to 20.0 OOh/crr! , preferably within the range of 10 to 15,000 kg/cm.

Furthermore, the glass transition temperature (Tg) of such a soft polymer (b) is usually -150 to +50°C, preferably -
It is within the range of 60 to -35°C. Furthermore, the intrinsic viscosity [V] of this soft polymer measured in decalin at 135° C. is 0.2 to 0.2 Odl/c, preferably 1 to 5 dl/c.
It is g. In addition, its density is 0.82 to 0.96 g/e
/, preferably 0.84 to 0.92 g/sl. Furthermore, the crystallinity of this soft polymer measured by X-ray diffraction is usually 90% or less, preferably 25% or less, and more preferably 10% or less. That is, this soft polymer preferably has low crystallinity or poor quality.

By kneading with the above-mentioned crystalline polyolefin resin (a), the above-mentioned soft polymer (b) has the property that at least a part thereof is dispersed in the crystalline polyolefin resin in the form of fine particles.

IL as a soft polymer (b) having the above properties
Graft modified meolefin copolymers are preferably used.

Specifically, such graft-modified α-olefin copolymers include (a) graft-modified ethylene/α-olefin copolymer rubber, and (b) graft-modified propylene/a-olefin copolymer rubber. can be mentioned.

The above-mentioned graft-modified ethylene/α-olefin copolymer rubber (a) and graft-modified propylene/a-olefin copolymer rubber (b) can be used alone or in combination. .

As the a-olefin constituting the above-mentioned graft-modified ethylene/a-olefin copolymer rubber (a), usually an a-olefin having 3 to 20 carbon atoms, such as propylene, 1-buteth, 1-pentene, 1-hexene. , 4-methyl-1-pentene, 1-octene, 1-decene and mixtures thereof.

Among these, propylene and/or 1-butene are particularly preferred.

Also, as the a-olefin constituting the graft-modified propylene/a-olefin copolymer rubber (b), usually,
Mention may be made of α-olefins having 4 to 20 carbon atoms, such as 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene and mixtures thereof. Among these, 1-butene is particularly preferred.

The a-olefin copolymer used in the present invention is
Within a range that does not impair the properties of the a-olefin copolymer,
It may also contain component units other than those derived from α-olefins, such as component units derived from diene compounds.

For example, the component units allowed to be included in the a-olefin copolymer used in the present invention include 1.4-
Hexadieth 1,6-octadiene, 2-methyl-
Chained non-conjugated dienes such as 1,5-hexadiene, 6-methyl-1,5-hebutadiene, 7-methyl-1,6-octadiene: cyclohexadiene, dicyclopentadiene, methyltetrahydroindene, 5- Vinylnorbornene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2-norbornene,
Cyclic non-conjugated dienes such as 6-chloromethyl-5-isopropenyl-2-norbornene.

2.3-diisopropylidene-5-norbornene, 2-
Examples include component units derived from diene compounds such as ethylidene-3-inpropylidene-5-norbornene and 2-propenyl-2,2-norbornadiene. The content of such diene components is usually 10 mol% or less, preferably 5 mol% or less.

In the graft-modified ethylene/a-olefin copolymer (a) used in the present invention, the molar ratio of repeating units derived from ethylene and repeating units derived from a-olefin (ethylene/me-olefin) is as follows: a
-It varies depending on the type of olefin, but generally 1/
99 to 99/1, preferably 50,150 to 9,515. The above molar ratio number is preferably from 50,150 to 90/10 when the σ-olefin is propylene, and from 80/20 to 9,515 when the a-olefin is an a-olefin having 4 or more carbon atoms. It is preferable that there be.

In addition, the graft-modified propylene used in the present invention, a-
In the olefin copolymer (b), the molar ratio between repeating units derived from propylene and repeating units derived from a-olefin (propylene/mie olefin) varies depending on the type of a-olefin, but generally It is preferable that it is 50150-9515. When the α-olefin is 1-butene, the above molar ratio is preferably from 50150 to 90/10, and α
-80/20 if the olefin has 5 or more carbon atoms
It is preferable that it is 9515-9515.

Among the above-mentioned graft-modified α-olefin copolymers, those with an ethylene content of 35 to 50 mol% and a crystallinity of 10
% or less of an ethylene/propylene random copolymer or an ethylene/a-olefin random copolymer that is graft-modified with a graft monomer is preferable because it has an excellent effect of improving mechanical properties such as impact strength.

Graft modified α-olefin copolymer (b
) It is preferable to use a, β-unsaturated carboxylic acid and its derivatives as the grafting monomer used for preparing . Examples of such unsaturated carboxylic acids include acrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, incrotonic acid, nadic acid (endocys-bicyclo[2,2, 1] hept-5-ene-2,3-dicarboxylic acid). Furthermore, the above three unsaturated carboxylic acid derivatives include unsaturated carboxylic anhydrides, unsaturated carboxylic acid halides, unsaturated carboxylic amides, unsaturated carboxylic imides, and unsaturated carboxylic acid ester compounds. I can do it. Specific examples of such derivatives include maleyl chloride, maleimide,
Mention may be made of maleic anhydride, citraconic anhydride, monomethyl maleate, dimethyl maleate and glycidyl maleate.

These graft monomers can be used alone or in combination.

Among the above-mentioned graft monomers, unsaturated dicarboxylic acids or their acid anhydrides are preferred, and maleic acid, nadic acid, or their acid anhydrides are particularly preferred.

The graft-modified α-olefin copolymer used in the present invention can be produced, for example, by modifying the above-mentioned graft monomer and α-olefin copolymer using various conventionally known methods. I can do it. For example, there is a method of melting the a-olefin copolymer and adding a graft monomer to carry out graft polymerization, or a method of dissolving the a-olefin copolymer in a solvent and adding a graft monomer to carry out graft copolymerization. Furthermore, as a method for producing a graft-modified olefin copolymer, a method of modifying an unreacted σ-olefin copolymer by blending a graft monomer to a desired graft modification rate, A modified M-olefin copolymer is prepared, and this highly modified a-olefin copolymer is converted into an unmodified σ-olefin copolymer.
- There is a method of diluting with an olefin copolymer to produce a graft-modified α-olefin copolymer having a desired modification rate.

In the present invention, graft-modified olefin copolymers produced by any method can also be used. The graft-modified meolefin copolymer used in the present invention has a modification rate of usually 1 to 0.01 to 5.
Weight List The copolymer is preferably in a range of 0.1 to 4% by weight.

In such a reaction, it is preferable to carry out the reaction in the presence of a radical initiator in order to efficiently graft copolymerize the graft monomer. The graft reaction is usually carried out at a temperature of 60 to 350°C. Proportion of radical initiator used: Usually in the range of 0.001 to 5 parts by weight per 100 parts by weight of the unmodified α-olefin elastomeric copolymer.

As the radical initiator, organic peroxides and organic peresters are preferably used. Specific examples of the radical initiators include benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, 2,5-dimethyl-2 , 5-di(peroxidebenzoate)hexyne-al. 4-bis(te
rt-butylperoxyisopropyl]benzene, lauroyl peroxide, tert-butyl peracetate, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-&2,5-dimethyl-2,5-
di(tert-butylperoxy)hexane, tert
-butyl perbenzoate, tert-butyl perphenylacetate, tert-butyl perisobutyrate, tert-butylperusee-octoate,
Mention may be made of tert-butyl perpivalate, cumyl perpivalate and tert-butyl perdiethyl acetate. Furthermore, in the present invention, an azo compound can also be used as a radical initiator, and specific examples of this azo compound include azobisisobutyronitrile and dimethylazoisobutyrate.

Among these, as radical initiators, benzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-25-di(
tert-butylperoxy)hexyne-a 2.5
Dialkyl peroxides such as -dimethyl-2,5-di(tert-butylperoxy)hexane and 1,4-bis(tert-butylperoxyisoprobyl)benzene are preferably used.

For the graft-modified olefin copolymer used in the present invention, the above-mentioned graft-modified ethylene/α-olefin copolymer (a) and graft-modified propylene/α-olefin copolymer (a) are used alone or The above-mentioned graft-modified elastic copolymer may not contain other polymers or copolymers or other soft polymers to the extent that the properties of the graft-modified σ-olefin elastic copolymer used in combination are not impaired. It's okay to stay.

In the present invention, examples of such other polymers or copolymers include tall. , an aromatic vinyl hydrocarbon/conjugated diene copolymer or a hydride thereof. Specifically, as such an aromatic vinyl hydrocarbon/conjugated diene copolymer or its hydride, it is
Styrene-butadiene copolymer rubber, styrene-butadiene-styrene copolymer rubber, styrene-isoprene block copolymer rubber, styrene-isoprene-styrene block copolymer rubber, hydrogenated styrene-butadiene-styrene block copolymer rubber and hydrogenated styrene
Isoprene/styrene block copolymer rubber can be mentioned.

In the present invention, the crystalline polyolefin resin (a) and the soft polymer (b) as described above are blended in a weight ratio within the range of 99.1 to 1.99. By blending the two in such a ratio, the excellent properties of the crystalline polyolefin resin (a) are not impaired, and the impact! A resin composition with improved mechanical properties such as strength can be obtained. Furthermore, by blending both in a weight ratio within the range of 95.5 to 80.20, the rigidity of the resulting polyolefin resin composition can be maintained appropriately while the impact strength is particularly improved.

When the soft polymer (b) is blended with the crystalline polyolefin resin (a) in this way, the crystalline polyolefin resin (a)
) The soft polymer (b) is not uniformly dissolved in
At least a portion of the soft polymer (b) is dispersed in the crystalline polyolefin resin (a) in the form of fine particles.

In the polyolefin resin composition of the present invention, a crosslinked structure formed by the amino group-containing compound (c) is formed.

In the present invention, a compound having at least two amino groups in the molecule can be used as the amino group-containing compound (c).

Examples of such amino group-containing compounds (c) include ethylenediamine, propylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, iminobispropylamine, bis(hexamethylene)triamine, 1.3
．． 6-) Aliphatic amines such as risaminomethylhexane, trimethylhexamethylene diamine, diethylene glycol, bispropylene diamine and diethylaminoprobylamine, menzendiamine, isophorone diamine, bis(4-)
Alicyclic amines such as amino-3-methylcyclohexyl)methane, N-aminoethylpiperazine and 1,3-diaminocyclohexane, fatty aromatic amines such as metaxylylene diamine, rlp-phenylenediamine, diaminodiphenylmethane , diaminodiphenylsulfone, 2,4-diaminoanisole, 2,4-toluenediamine, 2,4-diaminodiphenylamine, 4,4'-methylene dianiline and diaminodiphenylsulfone, and 3.9 -bis(3-aminopropyl) -2,4,8,
Examples include bisspiro ring diamines such as 10-tetraspiro[5,5]undecane.

Such amino group-containing compounds (c) can be used alone or in combination.

Among such amino group-containing compounds (c), aliphatic amines are preferably used, and hexamethylene diamine is particularly preferably used.

In the present invention, the amino group-containing compound (c) IL
The crystalline polyolefin resin (a) and the soft polymer (b)
), 0.01 to 10% by weight, preferably 0.2 to 2% by weight, and more preferably 0.01 to 10% by weight.
It is used in a proportion of 2 to 0.5 parts by weight.

By blending the amino group-containing compound (c) to form a crosslinked structure in this way, the dispersed particle size of the soft polymer (b) tends to become small. By doing so, the mechanical properties such as impact strength of the polyolefin resin composition of the present invention are improved.

The polyolefin resin composition of the present invention can be produced, for example, by separately producing a crystalline polyolefin resin (a) and a soft polymer (b), and then melting a mixture of the crystalline polyolefin resin and the graft-modified elastic copolymer (b). A method of kneading and further blending the amino group-containing compound (c) with this mixed wire and heating and kneading to form a crosslinked structure, or a method of forming a crosslinked structure by mixing the crystalline polyolefin resin (a) and the soft polymer (b).
) in a suitable hot arc, saturated hydrocarbon solvent such as heptane, decane and cyclohexane, or an aromatic hydrocarbon solvent such as toluene, benzene and xylene, and the 7-mino group-containing compound (c) is added to this solution. It can be produced by forming a crosslinked structure by blending, mixing and heating, and then removing the solvent by a conventional method.

In particular, in the present invention, crystalline polyolefin resin (a
), a soft polymer (b), and an amino group-containing compound (c)
It is preferable to adopt a method of heating a mixture containing the above to form a crosslinked structure.

At this time, the crystalline polyolefin resin (a) and the soft polymer (b) are mixed in advance, and then the amino group-containing compound (
Although it is also possible to prepare a mixture by adding c), the crystalline polyolefin resin (a) and the soft polymer (b) are melt-kneaded in advance so that the soft polymer (b) becomes the crystalline polyolefin resin (a). Particularly preferred is a method in which a pellet having a seabird structure dispersed in a seabird is prepared, the pellet is mixed with an amino group-containing compound, and then the resulting mixture is heated to form a crosslinked structure.

In the above method, when preparing pellets, a melt kneading device is used to feed the soft polymer (b) as the main feed, and the crystalline polyolefin resin (
A method of supplying a) to this melt-kneading apparatus as a side feed can be adopted.

Crystalline polyolefin resin (a) and soft polymer (b).

Heating temperature cost when melting and kneading the crystalline polyolefin resin (a) and the soft polymer (b),
The temperature is set to be higher than the melting point on the high temperature side, preferably 0 to 80° C. higher than the melting point.

The amino group-containing compound (c
) to prepare a mixture consisting of pellets and an amino group-containing compound.

Next, by heating this mixture, a crosslinked structure formed by the amino group-containing compound is formed.

Crosslinked structure using amino group-containing compound It can be formed by heating a mixture of the above pellets and the amine group-containing compound and kneading the pellets while melting them. The heating temperature in this case may be at least the melting temperature of the pellets, but it is usually set within the range of 150 to 300°C, preferably 150 to 250°C. The crosslinked structure is usually formed by applying shear stress to the melted resin by heating as described above. Specifically, a method is preferably employed in which a mixture of pellets and an amino group-containing compound as described above is melt-kneaded using a device capable of imparting shear stress to the melt, such as a melt-blending device.

In addition, in the present invention, crystalline polyolefin resin (
The step of dispersing the soft polymer (b) in a) and the step of forming a crosslinked structure may be performed in stages.

By carrying out the crosslinking reaction using the amino group-containing compound in this manner, at least a portion of the graft groups introduced into the soft polymer (b) are crosslinked by residues from which hydrogen atoms have been removed from the amino group-containing compound. It is thought that an intermolecular crosslinked structure is formed. Since the soft polymer (b) in which the crosslinked structure is formed has excellent rubber-like elasticity, the molded article formed from the polyolefin resin composition of the present invention has good impact resistance as a whole. come to have.

The polyolefin resin composition of the present invention can be prepared as described above.
Generally speaking, a soft polymer (b) in which a crosslinked structure is formed by a crystalline polyolefin resin (a) and an amino group-containing compound.
), and an inorganic filler can be further added thereto.

In the present invention, as the inorganic filler (d), fillers in various forms such as fiberboard, granule, and powder can be used.

Specific examples of inorganic fillers include IL silica, diatomaceous earth, titanium oxide, magnesium oxide, pumice particles, pumice balloons, aluminum hydroxide, magnesium hydroxide, basic magnesium carbonate, dolomite, calcium sulfate,
Potassium titanate, barium sulfate, calcium sulfite,
Mention may be made of talc, clay, mica, asbestos, glass fibers, glass flakes, glass peas, calcium silicate, montmorillonite, bentonite, graphite, aluminum powder, molybdenum sulfate, boron fibers and silicon carbide fibers. Inorganic fillers can be used alone or in combination.

For example, among such inorganic fillers, fibrous inorganic fillers are particularly preferred in order to improve the impact strength of the molded article, and specifically, glass fibers and poron fibers are particularly preferred.

In the present invention, the inorganic filler has a total weight of 100% of the crystalline polyolefin resin (a) and the soft polymer (b).
1 to 100 parts by weight, preferably 5 to 100 parts by weight
It is used in an amount of 50 parts by weight.

By blending the above-mentioned inorganic fillers, the impact resistance of the molded product can be improved! In addition to improving the mechanical properties, the water absorption rate of the molded body also decreases.

Such inorganic fillers are used in crystalline polyolefin resins (
It can be blended when a) and the soft polymer (b) are kneaded to prepare pellets, or it can be blended when an amino group-containing compound is blended into pellets and heated and kneaded to form a crosslinked structure. Alternatively, it can be added after the crosslinked structure is formed and mixed by kneading if necessary.

In addition to the above-mentioned components, the polyolefin resin composition of the present invention also contains inorganic filling material, organic filling material, thermal stability material, weatherability stability material, antistatic material, anti-static material, anti-slip material, anti-fog pigment, Additives such as dyes, natural sources, synthetic oils and waxes may also be included.

Since the resin composition of the present invention has a crosslinked structure formed by an amino group-containing compound, it does not impair the excellent properties of the molded product formed from the crystalline polyolefin resin and the soft polymer, and is particularly resistant to room temperature. Impact resistance is significantly improved.

Accordingly, the polyolefin resin composition of the present invention is suitable for use in conventional applications of polyolefins, such as filler-reinforced P
PS Can be preferably used in applications where mechanical strength is particularly required, such as those in which ABS resin and modified polyphenylene oxide are used, and specifically used in 11 engineering plastics, vehicle parts, construction, civil engineering, etc. be able to.

The polyolefin resin composition of the present invention contains a crystalline polyolefin resin (a) and a soft polymer (b) in a predetermined ratio, and is formed by using an amino group-containing compound (c). Because it has a crosslinked structure, it has excellent impact resistance, especially at room temperature. Further, there is hardly any deterioration in other properties accompanying the development of such properties.

Next, the present invention will be explained by showing examples. Just L original Fi
Aid These examples should not be construed as limiting.

[Evaluation method] In the present invention, the properties of the polyolefin resin, soft polymer (also referred to as graft-modified elastic copolymer), and polyolefin resin composition were measured as follows. Class evolution 1 measured at ℃ Flockwell measured by X-ray diffraction method at 23℃ <R scale> HRASTM D
Tensile modulus (YM) measured at 23°C using two square plates with a thickness of 1m based on ASTM-D-638 Measured at 23°C using a press test piece with a thickness of 2m based on ASTM-D-638 The initial flexural modulus (FM) was measured at 23'C using a 1/8-inch notched injection test piece with an L flow source ASTM D 256. Using a 1/8 inch thick injection test piece, crosshead speed 20 m/min, 2
Measured at 3° C. and in accordance with ASTM D 790 in the same manner as FM.

Melt Flow Rate (MFR) ASTM D-785, measured at 230°C
J) 85 weight suit Maleic anhydride grafted ethylene/propylene random copolymer in which the amount of maleic anhydride grafted is 1% by weight (ethylene component unit content 8
0 mol%, crystallinity 4.5%, [η] 2.2 dl/g
, YM=80kg/cd, tri-blend 15 parts by weight [hereinafter referred to as M-EPRJ] and L/D=4
2. Diameter 30. II twin screw extruder (set temperature 170℃)
After kneading with PP-a/M-EPR blend 100
Hexamethylene diamine (HMDA) 0 parts by weight
．． Add 2 parts by weight and use the twin screw extruder again (set temperature 170
℃) to obtain a polyolefin resin composition. This composition was mixed at a cylinder temperature of 200℃ and a mold temperature of 40℃.
Table 1 shows the physical properties of test pieces and square plates obtained by injection molding under the following conditions.

As is clear from the results shown in Table 1, the molded article having the above composition is excellent in impact strength, rigidity, and hardness at room and low temperatures.

Comparative Example 1 In Example 1, hexamethylene diamine (HMDA
) without &:, 85 parts by weight of PP-a and M-EP
A polyolefin resin composition was prepared in the same manner except that a blend consisting of 15 parts by weight of R was kneaded twice under the same conditions as in Example 1. A test piece and a square plate were obtained using this composition. The physical properties of this composition are shown in Table 1. Shown below.

As is clear from the results listed in Table 1, the molded product with the above composition has excellent rigidity and hardness, but
In Example 1, the amount of PP-a was changed to 80 parts by weight and M
A polyolefin resin composition was prepared in the same manner except that the amount of -EPH was changed to 20 parts by weight, and test pieces and square plates were obtained using this composition. Table 1 shows the physical properties of the test pieces and square plates.

From the results listed in Table 1, it is clear that the molded product with the above composition has a high impact strength at room temperature and low temperature.
Excellent rigidity and hardness.

In Example 2, hexamethylene diamine (HMDA)
) without using PP-a 80 parts by weight and M-EPR
A polyolefin resin composition was prepared in the same manner except that a blend consisting of 20 parts by weight was kneaded twice under the same conditions as in Example 2, and the physical properties of test pieces and square plates obtained using this composition are shown below. Shown in 1.

As is clear from the results listed in Table 1, the molded body with the above composition has a force f1 that is excellent in rigidity and hardness.
In Example 2, the impact strength at both room temperature and low temperature was low (in Example 2, MFR was 9.
A polyolefin resin composition was prepared in the same manner except that the polypropylene homopolymer of No. 2 (hereinafter referred to as PP-bJ) was used. Test pieces and square plates were obtained using this composition. The physical properties of the test pieces and square plates are shown in Table 1. Shown below.

As is clear from the results shown in Table 1, the molded article having the above composition is excellent in impact strength, rigidity, and hardness at room and low temperatures.

In Example 3, hexamethylene diamine (HMDA)
) is not used; pp-bso parts by weight and M-EPR
A polyolefin resin composition was prepared in the same manner except that a blend consisting of 20 parts by weight was kneaded twice under the same conditions as in Example 3. Test pieces and square plates were obtained using this composition. The physical properties are shown in Table 1. Shown below.

As is clear from the results listed in Table 1, the molded product with the above composition has excellent rigidity and hardness, and
HRFM FS IZ(23'C) IZ(
−℃）■bamboo→)(kg/cd) (kg/cgo)(-
Example 1 Comparative Example 1 Example 2 Comparative Example 2 Example 3 Comparative Example 3 13.800 14.200 12, Yanagi 13.3CX) 12.9) 0

Claims (4)

[Claims] (1) A polyolefin resin composition containing a crystalline polyolefin resin (a) and a soft polymer (b) graft-modified with an unsaturated carboxylic acid and/or its derivative in a weight ratio of 99:1 to 50:50. and the resin composition contains 0.01 to 1 part by weight based on a total of 100 parts by weight of the crystalline polyolefin resin (a) and the soft polymer (b).
A polyolefin resin composition having a crosslinked structure formed by 0 parts by weight of an amino group-containing compound (c). (2) Contains the crystalline polyolefin resin (a) and the soft polymer (b) graft-modified with an unsaturated carboxylic acid and/or its derivative in a weight ratio of 99:1 to 50:50, and 0.0 parts by weight for a total of 100 parts by weight of the crystalline polyolefin resin (a) and the soft polymer (b)
A method for producing a polyolefin resin composition, which comprises heating a mixture containing 1 to 10 parts by weight of an amino group-containing compound (c) to form a crosslinked structure. (3) A polyolefin resin composition containing a crystalline polyolefin resin (a) and a soft polymer (b) graft-modified with an unsaturated carboxylic acid and/or its derivative in a weight ratio of 99:1 to 50:50. and the resin composition contains 0.01 to 1 part by weight based on a total of 100 parts by weight of the crystalline polyolefin resin (a) and the soft polymer (b).
It has a crosslinked structure formed by 0 parts by weight of the amino group-containing compound (c), and 1 to 100 parts by weight based on a total of 100 parts by weight of the crystalline polyolefin resin (a) and the soft polymer (b). 1. A polyolefin resin composition comprising: (d) an inorganic filler. (4) Contains the crystalline polyolefin resin (a) and the soft polymer (b) graft-modified with an unsaturated carboxylic acid and/or its derivative in a weight ratio of 99:1 to 50:50, and the above-mentioned 0.0 parts by weight for a total of 100 parts by weight of the crystalline polyolefin resin (a) and the soft polymer (b)
1 to 10 parts by weight of an amino group-containing compound and 1 to 100 parts by weight
A method for producing a polyolefin resin composition, which comprises heating a mixture containing part by weight of an inorganic filler (d) to form a crosslinked structure.