JP2862326B2 - Polyolefin resin composition - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a resin composition comprising a crystalline polyolefin resin and a polyamide.

Technical Background of the Invention Various resins have conventionally been used to form resin molded articles such as automobile parts.

Various characteristics are required for the resin forming such a resin molded article according to the use of the molded article.

For example, a resin for preparing an automobile part has a high impact strength of a molded body, an excellent heat resistance,
Characteristics corresponding to the intended use, such as high surface hardness, good surface properties of the molded body, and good paintability, are required.

Conventionally, polyolefins and the like have been used as such resins, but few of the conventionally used resins are well-balanced in the above characteristics.

Object of the Invention The present invention has been made based on the above demands, and has an object to provide a polypropylene resin composition having a good balance of properties such as rigidity, strength, heat resistance, and surface hardness. .

SUMMARY OF THE INVENTION A polyolefin resin composition of the present invention comprises a crystalline polyolefin polymer particle, a crystalline polyolefin polymer particle, and a crystalline polyolefin polymer particle 100 under a gas-phase condition capable of substantially maintaining the particle shape. 1 to 99 parts by weight of a graft-modified polyolefin resin (a) formed by contacting 0.01 to 10 parts by weight of an unsaturated carboxylic acid and / or a derivative thereof per part by weight, and polyamide (b) 99 to 1 part by weight And a weight part.

In the resin composition of the present invention, the total of the graft-modified polyolefin resin (a) and the polyamide (b) is 100 parts by weight.

Since the polyolefin resin composition of the present invention comprises the graft-modified polyolefin resin (a) prepared from the crystalline polyolefin polymer particles and the polyamide (B), the balance of properties such as rigidity, strength, heat resistance, and surface hardness. Is good.

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

The polyolefin resin composition of the present invention comprises a graft-modified polyolefin polymer particle (a) prepared from crystalline polyolefin polymer particles, and a polyamide (b).

In the present invention, crystalline polyolefin polymer particles are used when preparing the graft-modified polyolefin resin (a).

The crystalline polyolefin polymer particles having the above characteristics can be obtained by, for example, 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,
Ethylpentene-1, octene-1, methylpentene
1, dimethylhexene-1, trimethylpentene-1,
Ethylhexene-1, methylethylpentene-1, diethylbutene-1, propylpentene-1, decene-1,
Examples thereof include α-olefins such as methylnonene-1, dimethyloctene-1, trimethylheptene-1, ethyloctene-1, methylethylheptene-1, diethylhexene-1, dodecene-1, and hexadodecene-1.

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 carried out in a suspended state so that the produced polymer particles 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; fats such as cyclopentane, methylcyclopentane, cyclohexane and methylcyclohexane Cyclic hydrocarbons; aromatic hydrocarbons such as benzene, toluene and xylene; and halogenated hydrocarbon compounds such as methylene chloride, ethylene chloride and chlorobenzene.

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 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.

In the crystalline polyolefin polymer particles produced by employing the multi-stage polymerization method as described above, the transition metal component in the ash content is usually 100 ppm or less, preferably 10 ppm or less, particularly preferably 5 ppm or less, and the halogen content. , Usually 300 ppm or less, preferably 100 ppm or less, particularly preferably 50 ppm or less.

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) hexyne-
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. in accordance with ASTM D 1238 is usually 0.1 to 100 g / 10 minutes, preferably 1 to 50.
g / 10 minutes.

The graft-modified polyolefin polymer particles (a) used in the present invention can be prepared by modifying the above-mentioned crystalline polyolefin polymer particles with an unsaturated carboxylic acid and / or a derivative thereof.

Preparation of graft-modified polyolefin polymer particles (a)
Examples of unsaturated carboxylic acids used in
Lylic acid, methacrylic acid, maleic acid, fumaric acid, tet
Lahydrophthalic acid, itaconic acid, citraconic acid, clot
Acid, isocrotonic acid, nadic acid (Endos-B
Cyclo [2,2,1] hept-5-ene-2,3-dicarboxylic
Acid). In addition, the above unsaturated cal
Derivatives of boric acid include unsaturated carboxylic anhydrides and unsaturated carboxylic acids.
Saturated carboxylic acid hydride, unsaturated carboxylic acid amide,
S of unsaturated carboxylic imides and unsaturated carboxylic acids
Tell compounds can be mentioned. Of such derivatives
Specific examples include maleenyl chloride, maleimide, anhydrous
Maleic acid, citraconic anhydride, maleic maleic acid
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
Water products are particularly preferred.

The unsaturated carboxylic acid and / or derivative thereof is added to the crystalline polyolefin polymer particles in an amount of 0.01 to 0.01%.
To 10 parts by weight, preferably 0.1 to 5 parts by weight, more preferably 0.2 to 3 parts by weight.

The graft-modified polyolefin polymer particles (a) used in the present invention are prepared by mixing the above-mentioned unsaturated carboxylic acid and / or a derivative thereof with the above-mentioned crystalline polyolefin polymer particles in a gas-phase condition capable of substantially maintaining the particle shape. Below, it can be obtained by grafting together the crystalline polyolefin polymer particles.

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.

In this graft polymerization reaction, for example, a predetermined amount of crystalline polyolefin polymer particles, an unsaturated carboxylic acid and / or a derivative thereof, and, if necessary, a radical initiator are charged into a reaction vessel. A temperature below the melting point of the particles, preferably 50-140
C., more preferably by mixing while heating to a temperature of 60 to 120.degree. Under the above-mentioned temperature conditions, the time for the graft 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.

The thus obtained graft-modified polyolefin polymer particles (a) contain unsaturated carboxylic acid and / or unsaturated carboxylic acid.
Alternatively, the graft ratio of the derivative thereof is usually in the range of 0.01 to 5% by weight, preferably 0.1 to 4% by weight.

The intrinsic viscosity [η] of the thus-obtained graft-modified polyolefin polymer particles (a) measured in decalin at 135 ° C. is usually 0.1 to 10 dl / g, preferably
It is 0.5 to 7 dl / g. Furthermore, 23 according to ASTM-D-1238
The melt flow rate measured at 0 ° C is usually 0.1-200 g / 1
It is in the range of 0 minutes, preferably 0.1-100 g / 10 minutes.

The polyolefin resin composition of the present invention comprises the above-mentioned crystalline polyolefin polymer particles (a) and polyamide (b).

The polyamide (b) used in the present invention is obtained by 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 ring-opening polymerization of a functional derivative thereof. be able to.

Examples of the diamine component used for preparing the polyamide (b) include ethylenediamine, propylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, iminobispropylamine, and bis (hexamethylene) triamine. Aliphatic amines such as 1,3,6-trisaminomethylhexane, trimethylhexamethylenediamine, diethylene glycol, bispropylenediamine, diethylaminopropylamine; mensendiamine, 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; and bisspirocyclic diamines such as 3,9-bis (3-aminopropyl) -2,4,8,10-tetraspiro [5,5] undecane.

Examples of the dicarboxylic acid component include aliphatic dicarboxylic acids such as adipic acid, sebacic acid, dodecane dibasic acid, glutaric acid, and succinic acid, terephthalic acid, isophthalic acid, 1,3-naphthalenedicarboxylic acid, 1,4 And alicyclic dicarboxylic acids such as aromatic dicarboxylic acids such as -naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, and 2,7-naphthalenedicarboxylic acid.

The polyamide (b) used in the present invention has an ε-
Ring opening polymers of caprolactam such as aminoundecanoic acid and ε-aminocaprolactam may be used.

Specific examples of the polyamide (b) used in the present invention include nylon-6, nylon-66, nylon-610, nylon-11, nylon-612, nylon-12,
Copolymer nylon formed from caprolactam and an aqueous solution of nylon salt, copolymer nylon formed from meta-xylene diamine and adipic acid, nylon MXD6 formed from meta-xylene diamine and adipic acid, nylon-46 and methoxymethyl And polyamide formed from terephthalic acid, isophthalic acid, adipic acid and hexamethylenediamine.

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

In the present invention, the graft-modified polyolefin polymer particles (a) and the polyamide (b) have a weight ratio of the graft-modified polyolefin polymer particles (a) to the polyamide (b) of from 99: 1 to 1:99. It is blended in a ratio. By blending them in such a ratio, a resin composition having improved mechanical properties such as impact resistance can be obtained without impairing the excellent properties of the graft-modified polyolefin polymer particles (a). Further, both are preferably 90:10 to 10:
By blending at a weight ratio of 90, more preferably 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 prepared by kneading a mixture of the graft-modified polyolefin polymer particles (a) and the polyamide (b) in the amounts described above.

The polyolefin resin composition of the present invention contains, in addition to the graft-modified polyolefin polymer particles (a) and the polyamide (b), an inorganic filler, an organic filler, a heat stabilizer,
Additives such as weathering stabilizers, antistatic agents, antislip agents, antiblocking agents, antifogging agents, lubricants, pigments, dyes, natural oils, synthetic oils and waxes may be incorporated. For example, as the inorganic filler that can be used in the present invention, various forms of filler such as fibrous, plate-like, granular, and powdery forms can be used, and specifically, silica, diatomaceous earth, and the like. , Titanium oxide, magnesium oxide, pumice powder, pumice balloon, aluminum hydroxide, magnesium hydroxide,
Basic magnesium carbonate, dolomite, calcium sulfate, potassium titanate, barium sulfate, calcium sulfite, talc, clay, mica, asbestos, glass fiber, glass flake, glass beads, calcium silicate, montmorillonite, bentonite, graphite,
Examples thereof include aluminum powder, molybdenum sulfate, boron fiber and silicon carbide fiber.

Since the polyolefin resin composition of the present invention contains the graft-modified polyolefin 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. In addition, 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.

Further, the molded article formed from the polyolefin resin composition of the present invention has excellent coatability.

Effects of the Invention Since the polypropylene resin composition according to the present invention is formed from the graft-modified polyolefin polymer and the polyamide as described above, impact resistance, mechanical properties such as rigidity and heat resistance, and surface hardness are improved. It can be molded. Moreover, a molded article having a good appearance and an improved balance of various properties can be obtained.

Further, the molded article formed from the resin composition of the present invention has very good coatability.

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, properties of the crystalline ethylene propylene block copolymer, the graft-modified crystalline ethylene propylene block copolymer, and 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 strength (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-K7202.

Examples 1-4 and 1-2 [Preparation of Modified Polyolefin A] In a stainless steel autoclave equipped with a helical double ribbon blade, an ethylene component unit content of 25 mol% and n of 23 ° C were added.
Propylene / ethylene block copolymer particles prepared by a two-stage polymerization method and having a decane soluble content of 25% by weight
100 parts by weight were charged, and the inside of the system was completely replaced with nitrogen gas.

Next, a solution of 1 part by weight of maleic anhydride (MAH) and 0.4 part by weight of benzoyl peroxide (BPO) dissolved in 15 parts by weight of toluene was added dropwise while stirring the system. Thereafter, the mixture was further stirred at room temperature for 1 hour, and then the temperature in the system was raised to 100 ° C. over 1 hour. The reaction was carried out by stirring at this temperature for 4 hours to obtain modified polyolefin A particles (unpurified material). As described above, in this method, the maximum heating temperature when preparing the modified polyolefin A particles is 100.
Since it is ° C, the particle shape of the polyolefin particles is not impaired during the modification.

Next, the obtained modified polyolefin A particles (unproduct) are dissolved in xylene at 130 ° C., and the solution is poured into a large amount of acetone to precipitate a polymer. The precipitated polymer is filtered and washed. A purified polymer was obtained.

Next, a press film was prepared using the obtained purified polymer, and the absorbance at 1790 cm ^{−1 was} measured from the measurement result of the IR spectrum of the film.

The amount of graft was determined from the absorbance measured as described above based on a previously prepared calibration curve.

The graft amount of the modified polyolefin A was 0.7% by weight. MFR measured at 230 ° C and 2160g
Was 5 g / 10 minutes.

[Preparation of Modified Polyolefin B] A modified polyolefin B was obtained by performing the same reaction except that the amount of MAH was changed to 0.7 parts by weight and the amount of BOP was changed to 0.06 parts by weight in the production of the modified polyolefin A.

The MAH graft ratio of this modified polyolefin B was 0.22% by weight, and the MFR was 7.9 g / 10 minutes.

[Preparation of Modified Polyolefin C] 100 parts by weight of the ethylene / propylene block copolymer particles used in the production of the modified polyolefin A and M
After mixing 1.15 parts by weight of AH and 0.03 parts by weight of 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3 with a Henschel mixer, the mixture was set at 44 ° C. at 200 ° C.
The modified polymer C was obtained by supplying to a twin screw extruder with φ and L / D = 30 and melt-kneading. In this method, since the melt kneading is performed during the modification, the form of the particulate ethylene propylene block copolymer used as a raw material is impaired during the graft modification.

The graft ratio of this modified polymer C was 0.45% by weight, MFR
Was 41 g / 10 minutes.

[Preparation of Modified Polyolefin D] Modified polyolefin D was obtained in the same manner as above, except that the amount of MAH was changed to 0.5 part by weight and the amount of BPO was changed to 0.02 part by weight.

The MAH graft ratio of this modified polyolefin D was 0.29% by weight, and the MFR was 40 g / 10 minutes.

[Preparation of Composition] 6-nylon (A1020BRL, manufactured by Unitika Ltd.) and Table 1
Was mixed with the modified polyolefin described in Table 1 in an amount shown in Table 1, and the mixture was subjected to 44 mmφ, L / D =
The mixture was supplied to 30 twin-screw extruders and melt-kneaded to prepare a composition.

Next, the composition prepared as described above is supplied to an injection molding machine (manufactured by Toshiba Corporation, IS-50EP), and the temperature of the cylinder of the injection molding machine is set to 270 ° C. and the temperature of the mold is set to 60 ° C. to obtain a molded product. Was prepared.

 The properties of the obtained injection molded article are also shown in Table 1.

Claims (2)

(57) [Claims] (1) Under a gas phase condition under which the crystalline polyolefin polymer particles can substantially maintain the particle shape, the crystalline polyolefin polymer particles and 0.01 to 100 parts by weight of the crystalline polyolefin polymer particles are used. Formed from 1 to 99 parts by weight of graft-modified polyolefin polymer particles (a) formed by contacting 10 parts by weight of unsaturated carboxylic acid and / or a derivative thereof, and 99 to 1 part by weight of polyamide (b) A polyolefin resin composition characterized in that: 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.