JP2862323B2 - Polyolefin resin composition - Google Patents

Description

Description: TECHNICAL FIELD OF THE INVENTION The present invention relates to a polyolefin resin composition, and more particularly to a molding having improved balance among various properties such as impact resistance, rigidity, heat resistance, surface hardness and appearance. The present invention relates to a polyolefin resin composition that can be made into a body.

Technical Background of the Invention Conventionally, a composition of a hard polymer and a soft polymer has been used for a molded article requiring impact resistance such as an automobile exterior part.

This composition can be formed into a molded article having excellent properties such as heat resistance, tensile properties, weather resistance, flexibility and impact resistance by injection molding, extrusion molding, or the like.

However, such a composition is not satisfactory in all the properties. For example, there is a demand for a resin having an improved balance of various properties such as impact resistance, rigidity, heat resistance, surface hardness and appearance. This is the actual situation.

Object of the Invention The present invention has been made based on the above-mentioned circumstances, and has an object to provide a novel polyolefin resin composition. More specifically, an object of the present invention is to provide a polyolefin resin composition which can be formed into a molded article having an improved balance among various properties such as impact resistance, rigidity, heat resistance, surface hardness and appearance.

SUMMARY OF THE INVENTION The polyolefin resin composition according to the present invention is characterized in that, under the gas phase conditions under which the crystalline polyolefin polymer particles can substantially maintain the particle shape, 1 part by weight of the crystalline polyolefin polymer particles Co-grafted polymer particles (a) 1 formed by co-grafting a crystalline polyolefin polymer particle with 1 to 200 parts by weight of a styrene monomer and 1 to 200 parts by weight of an unsaturated carboxylic acid and / or a derivative thereof ~ 99
It is characterized by being formed from 99 parts by weight of polyamide (b) and 99 to 1 part by weight of polyamide (b).

The total of the co-graft polymer particles (a) and the polyamide (b) in the resin composition of the present invention is 100 parts by weight.

Next, the polyolefin resin composition of the present invention will be specifically described.

The polyolefin resin composition according to the present invention is characterized in that the crystalline polyolefin polymer particles have a specific amount of a styrene-based monomer and an unsaturated polymer under a gas phase condition under which the crystalline polyolefin polymer particles can substantially maintain the particle shape. It is formed from a co-graft polymer particle (a) formed by co-grafting a carboxylic acid and / or a derivative thereof, and a polyamide (b).

The method for producing the crystalline polyolefin polymer particles used in the present invention is not particularly limited, but it is preferable to employ the method described below.

The crystalline polyolefin polymer particles used in the present invention can be obtained, for example, by polymerizing or copolymerizing an α-olefin having 2 to 20 carbon atoms.

Examples of such α-olefins include ethylene,
Propylene, butene-1, pentene-1, 2-methylbutene-1, 3-methylbutene-1, hexene-1, 3-
Methylpentene-1,4-methylpentene-1,3,3-
Dimethylpentene-1, heptene-1, methylhexene-1, dimethylpentene-1, trimethylbutene-1,
Ethylenepentene-1, octene-1, methylpentene-1, dimethylhexene-1, trimethylpentene
1, ethylhexene-1, methylethylpentene-1,
Diethylbutene-1, propylpentene-1, decene-
1, α-olefins such as methylnonene-1, dimethyloctene-1, trimethylheptene-1, ethyloctene-1, methylethylheptene-1, diethylhexene-1, dodecene-1, and hexadodecene-1. it can.

Among these, it is preferable to use an α-olefin having 2 to 8 carbon atoms alone or in combination,
It is particularly preferred to use a combination of ethylene and propylene.

The crystalline polyolefin polymer particles used in the present invention contain repeating units derived from the above α-olefin, usually at least 50 mol%, preferably at least 80 mol%,
Particularly preferably, it contains 100 mol%.

Other compounds that can be used other than the above-mentioned α-olefin include, for example, a chain polyene compound and a cyclic polyene compound.

These polyene compounds are polyenes having two or more conjugated or non-conjugated olefinic double bonds,
Examples of such chain polyene compounds include 1,4-hexadiene, 1,5-hexadiene, 1,7-octadiene,
Examples thereof include 1,9-decadiene, 2,4,6-octatriene, 1,3,7-octatriene, 1,5,9-decatriene and divinylbenzene.

Examples of the cyclic polyene compound include 1,3-cyclopentadiene, 1,3-cyclohexadiene, 5-ethyl-1,3-cyclohexadiene, 1,3-cycloheptadiene, dicyclopentadiene, and dicyclohexadiene. , 5
-Ethylidene-2-norbornene, 5-methylene-2-
Norbornene, 5-vinyl-2-norbornene, 5-isopropylidene-2-norbornene, methylhydroindene, 2,3-diisopropylidene-5-norbornene,
2-ethylidene-3-isopropylidene-5-norbornene, 2-propenyl-2,5-norbornadiene and the like can be mentioned.

Further, in producing the above-mentioned crystalline polyolefin polymer particles, a cyclic monoene can be used. Examples of such a cyclic monoene include cyclopropene, cyclobutene, cyclopentene, cyclohexene, 3-methylcyclohexene, and cycloheptene. Monocycloalkenes such as, cyclooctene, cyclodecene, cyclododecene, tetracyclodecene, octacyclodecene and cycloeicosene; norbornene, 5-methyl-2-norbornene,
Ethyl-2-norbornene, 5-isobutyl-2-norbornene, 5,6-dimethyl-2-norbornene, 5,5,6-
Bicycloalkenes such as trimethyl-2-norbornene and 2-bornene; 2,3,3a, 7a-tetrahydro-4,7-methano-1H-indene and 3a, 5,6,7a-tetrahydro-
Tricycloalkenes such as 4,7-methano-1H-indene;
1,4,5,8-Dimethano-1,2,3,4,4a, 5,8,8a-Octahydronaphthalene and, in addition to these compounds, 2-methyl-1,4,5,8- Dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-ethyl-1,4,5,8-dimethano-1,2,
3,4,4a, 5,8,8a-octahydronaphthalene, 2-propyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-hexyl-1,4,5,8-dimethano-
1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-stearyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a- Octahydronaphthalene, 2,3-dimethyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene,
2-methyl-3-ethyl-1,4,5,8-dimethano-1,2,3,
4,4a, 5,8,8a-octahydronaphthalene, 2-chloro-
1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-bromo-1,4,5,8-dimethano-1,2,3,
4,4a, 5,8,8a-octahydronaphthalene, 2-fluoro-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene and 2, Tetracycloalkenes such as 3-dichloro-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene; hexacyclo [6,6,1,1 ^3.6 , 1 ^10.13 , 0 ^2.7 , 0 ^9.14 ]
Heptadecene -4, pentacyclo [8,8,1 ^2.9, 1 ^4.7, 1
^11.18, 0,0 ^3.8, 0 ^12.17] heneicosene -5, octacyclo [8,8,1 ^2.9, 1 ^4.7, 1 ^11.18, 1 ^13.16, 0,0 ^3.8, 0
^12.17 ] Cyclic monoene compounds such as polycycloalkenes such as dococene-5.

Furthermore, in producing the above-mentioned crystalline polyolefin polymer particles, styrene and substituted styrene can be used.

The crystalline polyolefin polymer particles used in the present invention are obtained by polymerizing or copolymerizing at least the above-mentioned α-olefin in the presence of a catalyst.
This polymerization reaction or copolymerization reaction can be carried out in a gas phase (gas phase method) or in a liquid phase (liquid phase method).

The polymerization reaction or copolymerization reaction by the liquid phase method is preferably performed in a suspended state so that the polymer particles to be produced can be obtained in a solid state.

As a solvent used in the polymerization reaction or the copolymerization reaction, an inert hydrocarbon can be used. Further, an α-olefin as a raw material may be used as a reaction solvent.

In producing the crystalline polyolefin polymer particles used in the present invention, the above polymerization or copolymerization employs a gas phase method, or a reaction in a liquid phase using an α-olefin as a solvent, followed by a gas phase reaction. It is preferable to adopt a method of combining methods.

In the method in which the liquid phase method and the gas phase method are combined, an inert hydrocarbon or an α-olefin as a raw material is used as a reaction solvent, and after the α-olefin is prepolymerized in the presence of a specific catalyst, the gas is vaporized. The α-olefin is further polymerized in the phase.

Examples of the inert hydrocarbon used in the solvent include propane, butane, n-pentane, i-pentane,
Aliphatic hydrocarbons such as n-hexane, i-hexane, n-heptane, n-octane, i-octane, n-decane, n-dodecane and kerosene; alicycles such as cyclopentane, methylcyclopentane, cyclohexane and methylcyclohexane Aromatic hydrocarbons such as benzene, toluene and xylene; methylene chloride, ethylene chloride,
Halogenated hydrocarbon compounds such as chlorobenzene can be mentioned.

Further, the catalyst Examples of the catalyst, preferably, the _IV A group elements of the periodic table, _V A, Group _VI A group, containing _VII A and VIII transition metals, such as titanium, zirconium, hafnium, vanadium Component [A] and a catalyst component [B] of an organometallic compound of Groups I, II and III of the Periodic Table of the Elements such as an organoaluminum compound having at least one Al-carbon bond in the molecule. Use a catalyst.

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

Examples of the catalyst component [A] include Periodic Table _IVA
A catalyst containing a transition metal atom of Group _{V or} Group VA is preferred, and among these, a catalyst component containing at least one atom selected from the group consisting of titanium, zirconium, hafnium and vanadium is particularly preferred.

As another preferred catalyst component [A], the catalyst component containing a halogen atom and a magnesium atom in addition to the transition metal atom of the above, the _IV A group of the periodic table, the transition metal atom of _V A, Group conjugated electrons And a catalyst component containing a compound in which a group having the formula is coordinated.

The catalyst component [A] used in the production of the crystalline polyolefin polymer particles according to the present invention may be present in a solid state in the reaction system during the above polymerization reaction or copolymerization reaction, or It is preferable to use a catalyst prepared so that it can exist in a solid state by being supported on a carrier or the like.

Such a catalyst component [A] is disclosed in JP-A-55-13.
Nos. 5102, 55-135103, 56-67311 and Japanese Patent Application Nos. 56-18119 and 61-21109.

The organometallic compound catalyst component [B] used together with the catalyst component [A] in producing the crystalline polyolefin polymer particles in the present invention includes, for example, an aluminoxane, an organic aluminum compound and a reaction of water. The obtained organoaluminum compound or the organoaluminum compound obtained by reacting an aluminoxane solution with water or an active hydrogen-containing compound can be used.

The organometallic compound catalyst component [B] may further contain an electron donor [C] (outside donor) in addition to the above components.

In preparing the crystalline polyolefin polymer particles in the present invention, preliminary polymerization is carried out prior to the main polymerization using the catalyst as described above.

After the preliminary polymerization, the above-mentioned crystalline polyolefin polymer particles can be prepared by performing main polymerization in a gas phase. The polymerization temperature in the prepolymerization is usually -40 to 80 ° C., the polymerization temperature during the polymerization using a catalyst as described above is usually -50 to 200 ° C., the pressure of normal pressure to 100 kg / cm ² Polymerization is performed with the setting within the range.

In the method for producing such crystalline polyolefin polymer particles, the technique described in Japanese Patent Application No. 63-294066 can be used.

For example, polymer particles produced as described above,
It is preferable that the crystal part and the amorphous part have a form distributed in a sea-island shape. Further, the crystal part is made of a crystalline polyolefin, particularly a polypropylene resin,
By using polymer particles whose amorphous part is made of ethylene propylene random copolymer rubber, a composition excellent in impact resistance can be obtained.

The “polymer” in the crystalline polyolefin polymer particles includes both a polymer and a copolymer.

Furthermore, the crystalline polyolefin polymer particles used in the present invention may be oxidized crystalline polyolefin polymer particles obtained by oxidizing at least a part of the crystalline polyolefin polymer particles obtained as described above. .

Oxidized crystalline polyolefin polymer particles as described above, for example, in the presence of an organic peroxide, the crystalline polyolefin polymer particles in the gas phase, the temperature at which the crystalline polyolefin polymer particles are not damaged, that is, the crystal It can be obtained by heating to a temperature below the melting point of the reactive polyolefin polymer, usually from 50 to 140 ° C, preferably from 60 to 120 ° C.

Examples of organic peroxides used herein include dichlorobenzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-bis (tert-butylperoxy) hexane, 2 , 5-Dimethyl-2,5-bis (tert-butylperoxy) hexane-
3,1,3-bis (tert-butylperoxyisopropyl) benzene, 1,1-bis (tert-butylperoxy)
-3,3,5-trimethylcyclohexane, n-butyl-4,4
-Bis (tert-butylperoxy) bararate, dibenzoyl peroxide, tert-butylperoxybenzoate, tert-butylperoxy-2-ethylhexanoate, cyclohexanone peroxide, 2,5-dimethyl-2,5-dibenzoylperoxide Oxyhexane, tert-butyl peroxybenzoate, di-tert-butyl-diperoxyphthalate, methyl ethyl ketone peroxide and the like are included.

When the crystalline polyolefin polymer particles used in the present invention are the oxidized crystalline polyolefin polymer particles as described above, it is possible to obtain a resin composition in which mechanical properties such as impact resistance are further improved.

The melt flow rate of the crystalline polyolefin polymer particles used in the present invention, measured at 230 ° C. according to ASTM D 1238, is generally in the range of 0.1 to 100 g / 10 minutes, preferably 1 to 50 g / 10 minutes.

The crystalline polyolefin polymer particles used in the present invention have an average particle diameter of usually 10 to 5000 μm, preferably
It is in the range of 100 to 4000 μm, more preferably 300 to 3000 μm. Further, the geometric standard deviation indicating the particle size distribution of the crystalline polyolefin polymer particles is usually 1.0 to 2.0,
It is preferably in the range from 1.0 to 1.5, particularly preferably from 1.0 to 1.5, particularly preferably from 1.0 to 1.3.

Also, an apparent bulk density due to gravity of the crystalline polyolefin polymer particles, usually 0.20 g / cm ³ or more, preferably 0.30~0.70g / cm ^3, particularly preferably 0.35~0.60g / cm ³
Within the range.

And, in the crystalline polyolefin polymer particles produced by employing the above method, the transition metal component is usually
100 ppm or less, preferably 10 ppm or less, particularly preferably 5 pp
m or less, the halogen content is usually 300 ppm or less, preferably 100 ppm
It is contained at a ratio of at most ppm, particularly preferably at most 50 ppm.

The co-graft polymer particles (a) used in the present invention are the same as the above-mentioned crystalline polyolefin polymer particles,
Under a gas phase condition under which the crystalline polyolefin polymer particles can substantially maintain the particle shape, based on 100 parts by weight of the crystalline polyolefin polymer particles, 1 to 200 parts by weight of a styrene-based monomer, It is prepared by copolymerizing 200 parts by weight of an unsaturated carboxylic acid and / or a derivative thereof.

The styrenic monomer used in the present invention has the following formula [II
I].

In the above formula [III], R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and specifically, a methyl group, an ethyl group, a propyl group, and an isopropyl group Can be mentioned. Also, R ³
Represents a hydrocarbon group having 1 to 3 carbon atoms or a halogen atom, and specific examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, chlorine, bromine, and iodine.

 N represents an integer of 1 to 5.

The styrene monomers can be used alone or in combination.

Examples of such a styrene-based monomer include styrene, α-methylstyrene, o-methylstyrene, and p-methylstyrene.
-Methylstyrene, m-methylstyrene, o-chlorostyrene, p-chlorostyrene, m-chlorostyrene, p
-Chloromethylstyrene and the like. In the present invention, among the styrene-based monomers represented by the formula [III], styrene and α-methylstyrene are particularly preferred.

The styrene monomer is used in an amount of 1 to 200 parts by weight, preferably 5 to 150 parts by weight, particularly preferably 10 to 100 parts by weight, based on 100 parts by weight of the crystalline polyolefin polymer particles.

 Examples of unsaturated carboxylic acids used in the present invention include:
Acrylic acid, methacrylic acid, maleic acid, fumaric acid,
Tetrahydrophthalic acid, itaconic acid, citraconic acid,
Rotonic acid, isocrotonic acid, nadic acid (Endosys
-Bicyclo [2,2,1] hept-5-ene-2,3-dicarbo
Acid). In addition, the above unsaturated
Derivatives of rubonic acid include unsaturated carboxylic anhydrides,
Unsaturated carboxylic acid halide, unsaturated carboxylic acid amide
Of unsaturated carboxylic imides and unsaturated carboxylic acids
Ester compounds can be mentioned. Such induction
Specific examples of the body include maleenyl chloride, maleimide,
Maleic anhydride, citraconic anhydride, maleic acid monomer
Chill, dimethyl maleate and glycidyl maleate
Can be mentioned.

These unsaturated carboxylic acids and derivatives thereof can be used alone or in combination.

 Among the above unsaturated carboxylic acids and their derivatives
In this case, unsaturated carboxylic acids or their anhydrides are preferred.
And maleic acid and nadic acid Or these acids
Anhydrides are particularly preferred.

The unsaturated carboxylic acid and / or derivative thereof is 1 to 1 with respect to the crystalline polyolefin polymer particles.
It is used in an amount of 200 parts by weight, preferably 5 to 150 parts by weight, more preferably 10 to 100 parts by weight.

The co-graft polymer particles (a) used in the present invention are:
The styrenic monomer and the unsaturated carboxylic acid and / or a derivative thereof are combined with the crystalline polyolefin polymer particles under a gas phase condition under which the crystalline polyolefin polymer particles can substantially maintain the particle shape. It can be obtained by grafting.

Here, "gas phase conditions under which the crystalline polyolefin polymer particles can substantially maintain their particle shape" means that the heating temperature is set to a temperature lower than the melting point of the crystalline polyolefin polymer particles. This means that the reaction is carried out under a phase condition, and that the reaction is carried out under a gas phase condition in which the crystalline polyolefin is not dissolved in a solvent or the like.

This co-graft polymerization reaction includes, for example, a predetermined amount of crystalline polyolefin polymer particles, a styrene-based monomer, an unsaturated carboxylic acid and / or a derivative thereof,
Further, if necessary, a radical initiator is charged into the reaction vessel, and a temperature lower than the melting point of the crystalline polyolefin polymer particles, preferably 50 to 140 ° C., more preferably 60 to 120 ° C.
It is performed by mixing while heating to a temperature of ° C.
Under the above-mentioned temperature conditions, the time of the cografting reaction is usually set in the range of 0.5 to 15 hours, preferably 1 to 10 hours.

In the above reaction, when a radical initiator is used, examples of the radical initiator include the organic peroxides listed as usable in the production of the above-mentioned oxidized crystalline polyolefin polymer particles, or an organic peroxide. Peresters, azo compounds and the like can be mentioned.

Such a radical initiator may be used as the crystalline polymer particles.
It is generally used in a proportion of 0.01 to 10 parts by weight based on 100 parts by weight.

Co-graft polymer particles (a) thus obtained
The melt flow rate measured at 230 ° C. according to ASTM-D-1238 is usually 0.1 to 100 g / 10 min, preferably 1 to 100 g / 10 min.
Within the range of ~ 50g / 10min.

The polyolefin resin composition of the present invention is formed from the above-mentioned co-graft polymer particles (a) and polyamide (b).

The polyamide (b) used in the present invention is obtained by subjecting a polycondensation reaction between a diamine component and a dicarboxylic acid component or a compound capable of forming an amino group and a carboxyl group such as caprolactam or a functional derivative thereof to ring-opening polymerization. Obtainable.

Examples of the polyamide (b) that can be used here include nylon-6, nylon-66, and nylon-61.
0, nylon-11, nylon-612, nylon-12, copolymer nylon formed from caprolactam and aqueous solution of nylon salt, copolymer nylon formed from meta-xylene diamine and adipic acid, meta-xylene diamine and adipic acid Nylon MXD6, nylon-46 formed from
And methoxymethylated polyamides.

Such polyamide (b) is, for example, ethylenediamine, propylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine,
Aliphatic amines such as tetraethylenepentamine, iminobispropylamine, bis (hexamethylene) triamine, 1,3,6-trisaminomethylhexane, trimethylhexamethylenediamine, diethylene glycol, bispropylenediamine, diethylaminopropylamine; Mensen Diamine, isophoroneamine, bis (4-
Alicyclic amines such as amino-3-methylcyclohexyl) methane, N-aminoethylpiperazine, 1,3-diaminocyclohexane; aliphatic aromatic amines such as meta-xylylenediamine; o-, m-, p-phenylenediamine; Diaminodiphenylmethane, diaminodiphenylsulfone, 2,4-diaminoanisole, 2,4-trienediamine, 2,4-diaminodiphenylamine, 4,4′-methylenedianiline,
Aromatic amines such as diaminodixylsulfone; diamine components such as bisspirocyclic diamines such as 3,9-bis (3-aminopropyl) -2,4,8,10-tetraspiro [5,5] undecane; and adipic acid , Sebacic acid, dodecane dibasic acid, aliphatic dicarboxylic acids such as glutaric acid, terephthalic acid, isophthalic acid, 1,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, It can be produced by condensation polymerization of a dicarboxylic acid component such as an alicyclic dicarboxylic acid such as an aromatic dicarboxylic acid such as 7-naphthalenedicarboxylic acid.

In the present invention, the above-mentioned polyamide (b) can be used alone or in combination of two or more.

In the present invention, the co-graft polymer particles (a) and the polyamide (b) are used in a weight ratio of the graft polymer particles (a) and the polyamide (b) of 99: 1 to 1:99. Be blended. By blending both at such a ratio,
A resin composition having improved mechanical properties such as impact resistance can be obtained without impairing the excellent properties of the co-graft polymer particles (a). Furthermore, both preferably 90: 10-1
By blending at a weight ratio of 0:90, more preferably within the range of 80:20 to 20:80, the mechanical properties of the resulting polyolefin resin composition can be further improved.

The polyolefin resin composition of the present invention can be obtained by kneading the co-graft polymer particles (a) and the polyamide (b) compounded in the above ratio.

The polyolefin resin composition of the present invention comprises, in addition to the above-mentioned co-grafted polymer particles (a) and polyamide (b),
Additives such as inorganic fillers, organic fillers, heat stabilizers, weathering stabilizers, antistatic agents, antislip agents, antiblocking agents, antifogging agents, lubricants, pigments, dyes, natural oils, synthetic oils and waxes May be blended.

Since the polyolefin resin composition of the present invention is formed from the co-graft polymer particles (a) and the polyamide (b), the polyolefin resin composition has excellent mechanical properties such as impact resistance and rigidity, and has a good appearance, Moreover, it is possible to form a molded body having an improved balance of various properties.

Therefore, the polyolefin resin composition of the present invention,
In addition to the usual applications of polyolefins, for example, filler-reinforced PP, ABS resin, modified polyphenylene oxide can be preferably used in applications that require particularly high mechanical strength such as is used, specifically, engineering Plastic, vehicle parts, home appliance housing, OA
It can be suitably used as an equipment housing or the like.

Effect of the Invention Since the polyolefin resin composition of the present invention is formed from the co-graft polymer particles (a) and the polyamide (b), the mechanical properties such as impact resistance and rigidity, the heat resistance, and the surface hardness are improved. A molded article can be obtained. In addition, a molded article having a good appearance and an improved balance with various properties can be obtained.

Next, the present invention will be described with reference to examples. However, the present invention should not be construed as being limited by these examples.

[Evaluation Method] In the present invention, characteristics of the polypropylene resin composition were measured as follows.

Initial flexural modulus (FM) According to JIS-K7203, using a 3.2 mm thick test piece, 23
Measured at ° C.

Flexural yield stress (FS) Measured under the same conditions as FM according to JIS-K7203.

IZ impact strength Measured using a 3.2 mm thick test piece according to JIS-K7110.

Heat distortion temperature (HDT) Measured using a 3.2 mm thick test piece according to JIS-K-7207.

Rockwell hardness: Measured using a 3.2 mm thick test piece according to JIS-K7207.

Appearance of Molded Article The surface appearance of the injection molded article of 12 cm × 12 cm × 0.32 cm was evaluated by visual observation in two steps.

：: No flow mark ×: With flow mark Example 1 Crystalline propylene copolymer particles (MFR = 0.3 g / 10 min)
Benzoyl peroxide 0.05 parts by weight to 100 parts by weight
The solution dissolved in toluene was added to the parts by weight, and the mixture was mixed well, and then heated for 3 hours in a gear oven set at a temperature of 90 ° C. to perform an oxidation treatment.

 The MFR after the oxidation treatment was 36 g / 10 minutes.

Next, 100 parts by weight of the above-mentioned oxidized propylene homopolymer was charged into a stainless steel autoclave provided with a spiral double ribbon blade, and the air in the system was completely replaced with nitrogen gas.

Then, while stirring the oxidized propylene homopolymer at room temperature, 53 parts by weight of styrene, maleic anhydride 13
A mixed solution consisting of parts by weight was gradually dropped. After dropping, the mixture was stirred at room temperature for 1 hour, and then the temperature in the system was raised to 100 ° C. over 1 hour, and the reaction was further stirred for 6 hours at this temperature to complete the co-graft polymer. Particle A was obtained. As described above, the maximum temperature of the reaction system is 100 ° C., and since this temperature is lower than the melting point of the propylene homopolymer, the co-grafting reaction can be performed without impairing the form of the co-propylene homopolymer particles. Was.

The cografted polymer particles A had a styrene graft ratio of 9.8% by weight and a maleic anhydride graft ratio of 1.5% by weight.

In the present invention, the graft ratio is determined by dissolving the co-grafted polymer particles in xylene at 130 ° C., throwing this solution into a large amount of acetone to precipitate a polymer, filtering the precipitated polymer, and washing the polymer. obtain purified polymer, then resulting pressed film was prepared using the purified polymer was measured 1790 cm ^-1 and the absorbance of 1600 cm ^-1 from the measurement results of IR spectrum of the film,
It was determined from the absorbance measured as described above based on a previously prepared calibration curve.

Co-grafted polymer particles A 40 obtained as described above
Parts by weight and 60 parts by weight of 6-nylon (Unitika, A1020BRL) at a temperature of 240 ° C. and a 44 mmφ twin screw extruder (L / D
= 30) and kneaded to obtain a polyolefin resin composition.

Next, the obtained polyolefin resin composition was supplied to an injection molding machine (IS-50EP manufactured by Toshiba Corporation) and injection molded under the conditions of a cylinder temperature of 270 ° C and a mold temperature of 60 ° C to obtain a test piece.

 Table 1 shows the physical properties of the test piece.

Example 2 In Example 1, the crystalline polypropylene homopolymer particles (MFR = 0.3 g / 10 minutes) were replaced with crystalline propylene
Cograft polymer particles B were obtained in the same manner as in Example 1, except that an ethylene block copolymer (ethylene component unit content: 25% by weight, n-decane soluble content at 23 ° C: 25% by weight) was used.

The styrene graft ratio of the cografted polymer particles B was 10.2% by weight, and the maleic anhydride graft ratio was 2.0% by weight.

A test piece was prepared in the same manner as in Example 1 using the co-grafted polymer particles B.

 Table 1 shows the physical properties of the test piece.

Example 3 In Example 1, in addition to 40 parts by weight of the co-grafted polymer particles A and 60 parts by weight of 6-nylon, a total of 100 parts
A composition was prepared in the same manner except that 20 parts by weight of talc was blended with respect to parts by weight, and a test piece was prepared using this composition. Table 1 shows the physical properties of the test piece.

Example 4 In Example 2, in addition to 40 parts by weight of the cografted polymer particles B and 60 parts by weight of 6-nylon, a total of 100 parts of both was added.
A composition was prepared in the same manner except that 20 parts by weight of talc was blended with respect to parts by weight, and a test piece was prepared using this composition.

 Table 1 shows the physical properties of the test piece.

Comparative Example 1 In a stainless steel autoclave equipped with a helical double ribbon blade, the crystalline ethylene / propylene block copolymer used in Example 2 (ethylene component unit content: 25% by weight, n-decane soluble content at 23 ° C of 25%) was used. 100% by weight), and air in the system was completely replaced with nitrogen gas.

Next, a solution prepared by dissolving 1 part by weight of maleic anhydride in 15 parts by weight of toluene was added dropwise to this system with stirring.

Thereafter, stirring was further performed at room temperature for 1 hour, and then the temperature was raised to 100 ° C. over 1 hour, and stirring was performed at this temperature for 4 hours to complete the reaction, thereby obtaining graft polymer particles C.

The graft ratio of maleic anhydride in the graft polymer particles C was 0.7% by weight, and the MFR was 5 g / 10 minutes.

An olefin resin composition was prepared in the same manner as in Example 2, except that the graft polymer particles C prepared as described above were used instead of the graft polymer particles B,
A test piece was prepared using this olefin resin composition.

 Table 1 shows the physical properties of the test piece.

As is evident from the results shown in Table 1, the molded article formed from this composition had low rigidity, impact strength, hardness and heat deformation temperature, was inferior in appearance, and had a poor balance of various physical properties. .

Comparative Example 2 100 parts by weight of the crystalline propylene / ethylene block copolymer (ethylene component unit content 25% by weight, n-decane soluble content at 23 ° C. 25% by weight) used in Example 2, 3 parts by weight of maleic anhydride, Graft weight was obtained by mixing 30.03 parts by weight of 2,5-di- (tert-butylperoxy) hexyne and feeding it to a 44 mm diameter twin screw extruder (L / D = 30) set at a temperature of 230 ° C. Combined D was obtained.

The graft polymer D had a maleic anhydride graft ratio of 0.5% by weight and an MFR of 36 g / 10 minutes.

A composition was prepared in the same manner as in Example 2 except that the graft copolymer D was used instead of the graft polymer particles B, and a test piece was prepared using the composition.

 Table 1 shows the physical properties of the test piece.

As is evident from the results shown in Table 1, the molded article formed from this composition had low rigidity, impact strength, hardness and heat deformation temperature, was inferior in appearance, and had a poor balance of various physical properties. .

Claims (3)

(57) [Claims] 1. A styrene-based monomer in an amount of 1 to 200 parts by weight based on 100 parts by weight of a crystalline polyolefin polymer particle under a gas phase condition under which the crystalline polyolefin polymer particles can substantially maintain the particle shape. 1 to 99 parts by weight of a co-grafted polymer particle (a) formed by co-grafting 1 to 200 parts by weight of an unsaturated carboxylic acid and / or a derivative thereof to a crystalline polyolefin polymer particle; b) 99-1 part by weight of the polyolefin resin composition. 2. The polyolefin resin according to claim 1, wherein the crystalline polyolefin polymer particles have a crystal part composed of a polypropylene resin and an amorphous part composed of an ethylene propylene random copolymer rubber. Composition. 3. The method according to claim 1, wherein at least a part of the crystalline polyolefin polymer particles is oxidized crystalline polyolefin polymer particles oxidized with an organic peroxide. Polyolefin resin composition.