JPH03285936A - Polyolefin resin composition - Google Patents

Abstract

PURPOSE:To obtain a composition having excellent impact resistance, rigidity, etc., suitable as engineering plastic, etc., by co-grafting a styrene-based monomer, etc., onto particles of crystalline polyolefin polymer to give particles of graft polymer and blending the particles of co-graft polymer with a polyamide. CONSTITUTION:(A) 1-99 pts wt., preferably 20-80 pts.wt. co-graft polymer particles obtained by co-grafting 1-200 pts.wt., preferably 10-100 pts.wt. styrene- based monomer and 1-200 pts.wt., preferably 10-100 pts.wt. unsaturated carboxylic acid and/or derivative thereof onto 100 pts.wt. particles of crystalline polyolefin polymer which are particles of oxidized crystalline polyolefin polymer having crystal part composed of preferably polypropylene resin and amorphous part composed of ethylene propylene random copolymer rubber and at least partially oxidized with an organic per oxide, under a vapor phase condition of the co-grafting capable of making the particles maintain a particulate shape, are blended with (B) 99-1 pts.wt., preferably 80-20 pts.wt. polyamide (e.g. nylon 6).

Description

[Detailed Description of the Invention] 1. More details regarding the polyolefin resin composition of the present invention. In particular, the balance of properties such as impact resistance, rigidity, heat resistance, surface hardness, and appearance has been improved. The present invention relates to a polyolefin resin composition that can be made into a molded article.

BACKGROUND ART Compositions of hard and soft polymers have traditionally been used in molded articles that require impact resistance, such as automobile exterior parts.

This composition 11 injection adult pig By extrusion molding etc.
Although it is possible to make molded products with excellent properties such as heat resistance, tensile properties, weather resistance, flexibility, and impact resistance, such compositions are not satisfactory in all properties, such as The current situation is that there is a desire for a resin with an improved balance of mechanical properties such as impact resistance, rigidity, heat resistance, surface hardness, and appearance.

The present invention was made based on the above circumstances,
The purpose is to provide a novel polyolefin resin composition. The object of the present invention is to provide a polyolefin resin composition that can be made into a molded article with an improved balance of mechanical properties such as impact resistance, rigidity, heat resistance, surface hardness, and appearance.

1. Under gas phase conditions in which the condensable polyolefin polymer particles of the polyolefin resin composition according to the present invention can substantially maintain the particle shape, based on 100 parts by weight of the crystalline polyolefin polymer particles. , 1 to 2001g of styrenic monomer, and 1 to 20g of styrenic monomer
1 to 99 parts by weight of cograft polymer particles (a) formed by cografting 0 parts by weight of an unsaturated carboxylic acid and/or its derivative onto crystalline polyolefin polymer particles; and 99 to 99 parts by weight of polyamide (b). 1 part by weight.

The total amount of cograft polymer particles (a) and 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 explained.

The primary crystalline polyolefin polymer particles of the polyolefin resin composition according to the present invention are prepared by adding a specific amount of a styrenic monomer, an unsaturated carboxylic acid and It is formed from co-grafted polymer particles (a) formed by co-grafting with/or a derivative thereof, and polyamide (b).

There are no particular limitations on the method for producing the crystalline polyolefin polymer particles used in the present invention.It is preferable to use the method described below.

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

Examples of such σ-olefins include Jj ethylene, propylene, butene-L pentene-1,2-methylbutene-1,3-methylbutene-L hexene-1
,3-methylbentene-L4-methylpentene-3.
3-dimethylpentene-L hebutene-L to methylhexene dimethylpentene-L trimethylbutene to ethylpentene-1, octene-L methylpentene,
L Dimethylhexene-L Trimethylpentene-L
Ethylhexene-L Methylethylpentene-L Diethylbutene-k Propylpentene-L Decene-octamethylnonene-L Dimethyloctene-1, trimethylheptene-k Ethyloctene-L Methylethylhebutene-L Diethylhexene-L Dodecene-1 and Mention may be made of a-olefins such as hexadodecene-1.

Among these, it is preferable to use a-olefins having 2 to 8 carbon atoms alone or in combination, and it is particularly preferable to use ethylene and propylene in combination.

The crystalline polyolefin polymer particles used in the present invention generally contain repeating units derived from the above-mentioned α-olefin in an amount of 50 mol% or more, preferably 80 mol% or more, and particularly preferably 100 mol%.

Other compounds that can be used in addition to the above a-olefins include, for example, linear polyene compounds and cyclic polyene compounds.

These polyene compounds are polyenes having two or more conjugated or non-conjugated olefinic double bonds, and examples of such linear polyene compounds include 1,4-hexadiene, 1,5-hexadiene, 1 .7-octadiene, 1.9-decadiene, 2.4.6-octatriene, 1,3.7-octatriene, 1.5.9-
Examples include decatriene and divinylbenzene.

Also, as an example of a cyclic polyene compound, G! 1.3-
Cyclopentadiene, 1,3-cyclohexadiene, 5
-Ethyl-1,3-cyclohexadiene, 1,3-cycloheptadiene, dicyclopentadiene, dicyclohexadiene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-vinyl-2- norbornene, 5-impropylidene-2-norbornene, methylhydroindene, 2,3-diisopropylidene-5-
Examples include norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, and 2-propenyl-2,5-norbornadiene.

Furthermore, IL cyclic monoenes can also be used in producing the above crystalline polyolefin polymer particles, and examples of such cyclic monoenes include IL cyclopropene, cyclobutene, cyclopentene, cyclohexene, 3-methylcyclohexene, cycloheptene, cyclo Monocycloalkenes such as octene, cyclodecene, cyclododecene, tetracyclodecene, octacyclodecene and cycloeicosene; norbornene, 5-methyl-2-norbornene, 5-ethyl-2-norbornene, 5-inbutyl-2-norbornene, 5 , 6-dimethyl-2-norbornene, 5.5
．． 6-) Bicycloalkenes such as trimethyl-2-norbornene and 2-bornene; 2.3.3a, 'IB
-tetrahydro-4,7-methano-IH-indene and 3a, 5.6.7a-tricycloalkenes such as -tetrahydro-4,7-methano-IH-indene, 1.4
．． 5.8-dimethano-1,2,3,4,4a, 5.8
．． 8a-octahydronaphthalene, as well as these compounds &mi-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 2.3-
Dichloro-1,4,5,8-dimethano-1,2,3,4
, 4a.

5,8.8a-Tetracycloalkenes such as octahydronaphthalene; hexacyclo[6,6,1,1'.@, 111.13.
Q2・7.09・+4] Hebutadecene Azaki Pentacyclo cs, s, i2・9.14・7111・I a,
Q, 03..., O12/17] Henei Kosen kite
Naphthalene t:I [8, 8, 12, @, 14. ”,I
Examples include cyclic monoene compounds such as polycycloalkenes such as Il, 1s, 1'','', 0.0''012.17]tococene-5.

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

Crystalline polyolefin polymer particles L used in the present invention
L Obtained by polymerizing or copolymerizing at least the above a-olefins in the presence of a catalyst. This polymerization reaction or copolymerization reaction can be carried out in the gas phase (gas phase method) or in the liquid phase (
liquid phase method).

The polymerization reaction or copolymerization reaction by the liquid phase method is
Preferably, the reaction is carried out in suspension so that the resulting polymer particles are obtained in a solid state.

An inert hydrocarbon can be used as the solvent used in this polymerization reaction or copolymerization reaction. Furthermore, a-olefin, which is a oxidant, may be used as a reaction solvent.

In producing the crystalline polyolefin polymer particles used in the present invention, a gas phase method is employed during the above polymerization or copolymerization, or a gas phase method is employed after the reaction is performed in a liquid phase using a-olefin as a solvent. It is preferable to adopt a method that combines the following.

iL is a method that combines a liquid phase method and a gas phase method. After prepolymerizing an a-olefin in the presence of a specific catalyst, an inert hydrocarbon or a thick a-olefin is used as a reaction solvent. In the phase, further σ-olefins are polymerized.

Here, jL is an example of an inert hydrocarbon used as a solvent.
Propane, butane, n-pentane, 1-pentane,
n-hexane, 1-hexane, n-heptus n
- Aliphatic hydrocarbons such as octane, 1-octane, n-decane, n-dodecane, and kerosene; Alicyclic hydrocarbons such as cyclopentane, methylcyclopentane, cyclohexane, and methylcyclohexane; Aromatics such as benzene, toluene, and xylene Group hydrocarbons include halogenated hydrocarbon compounds such as methylene chloride, ethylene chloride, and chlorobenzene.

In addition, as a catalyst for the above, it is preferable to use the periodic table of elements rvA! vA & vxA & wA family member
A catalyst component [A] containing, for example, titanium, zirconium, hafnium, vanadium, and an organoaluminium compound having at least one An-carbon bond in the molecule, for example, Group 1 Ln of the Periodic Table of Elements and a group m organometallic compound catalyst component [B].

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

The above catalyst component [A] is preferably a catalyst containing a transition metal atom of group yA storm vA of the periodic table of the elements, and among these, at least one selected from the group consisting of titanium, zirconium, hafnium, and vanadium. Catalyst components containing different types of atoms are particularly preferred.

Other preferred catalyst components [A] include catalyst components containing halogen atoms and magnesium atoms in addition to the above-mentioned transition metal atoms, groups having conjugated electrons to transition metal atoms in groups WA and VA of the periodic table. Catalyst components containing catalyzed compounds are mentioned.

The above catalyst component [A] used in the production of crystalline polyolefin polymer particles in the present invention is present in the reaction system in a solid state during the polymerization reaction or copolymerization reaction as described above, 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.

Regarding such catalyst component [A] +3 JP-A-1987
-135102, 55-135103, 56-
Publication No. 67311 and Japanese Patent Application No. 181019/1983,
It is described in the specification of No. 61-21109.

The above-mentioned organometallic compound catalyst component [B] used together with the above-mentioned catalyst component [A] in producing the crystalline polyolefin polymer particles in the present invention, for example, aluminooxas obtained by the reaction of an organoaluminum compound and water. It is possible to use an organoaluminum compound, or an organoaluminum compound obtained by reacting a solution of aluminoxane with water or an active hydrogen-containing compound.

In addition, IL is added to the organometallic compound catalyst component [B].
In addition to the above components, an electron donor [C] (outside donor) can also be blended.

In preparing the crystalline polyolefin polymer particles in the present invention, one step is to carry out prepolymerization using the above-mentioned catalyst prior to main polymerization.

After the preliminary polymerization, the above crystalline polyolefin polymer particles can be prepared by performing main polymerization in a gas phase. The polymerization temperature during prepolymerization is usually -40 to 80°C, and the polymerization temperature during main polymerization using the above catalyst is usually -50 to 200°C, and the pressure is normal pressure to 100 kg/F2.
Polymerization is carried out by setting within the range of .

In the method for producing such crystalline polyolefin polymer particles, the technique described in Japanese Patent Application No. 1983-294066 can be used.

For example, polymer particles IL produced as described above
It is preferable that the crystalline portion and the amorphous portion have a seabird-like distribution. To obtain a composition with excellent impact resistance by using polymer particles in which the crystalline part is made of crystalline polyolefin, especially polypropylene resin, and the amorphous part is made of ethylene propylene random copolymer rubber. I can do it.

In addition, in this crystalline polyolefin polymer particle, "
"Polymer" includes both polymers and copolymers.

Furthermore, the crystalline polyolefin polymer particles used in the present invention may be oxidized crystalline polyolefin polymer particles in which at least a portion of the crystalline polyolefin polymer particles obtained as described above have been oxidized.

Oxidized crystalline polyolefin polymer particle version as above
Example E: The crystalline polyolefin polymer particles are prepared in the gas phase in the presence of an organic peroxide at a temperature at which the crystalline polyolefin polymer particles are not damaged, that is, at a temperature below the melting point of the crystalline polyolefin polymer, usually from 50 to 140℃,
Preferably, it can be obtained by heating to a temperature of 60 to 120°C.

Examples of organic peroxides used here include IL 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-al, 3-bis(tert-butylperoxyisopropyl)benzene, 1,1-bis(
tert-butylberoxy)-3,3,5-)limethylcyclohexane, n-butyl-4,4-bis(te
rt-butylperoxy)valerate, dibenzoylperoxide, tart-butylperoxybenzony)
, tert-butylperoxy-2-ethylhexanoate, cyclohexanone peroxide, 2,5-dimethyl-2,5-dibenzoylperoxyhexane, tert
Examples include t-butyl peroxybenzoate, di-tert-butyl oxyphthalate, and methyl ethyl ketone peroxide.

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

Melt flow rate i1 of the crystalline polyolefin polymer particles used in the present invention measured at 230°C according to ASTM D 1238 Usually 0.1 to 100g710
minutes, preferably within the range of 1 to 50g710 minutes.

Crystalline polyolefin polymer particles I used in the present invention
L The average particle diameter is usually 10 to 5000 p m.

More preferably, it is within the range of 300 to 3000 pm. In addition, the geometric standard deviation I which indicates the particle size distribution of the crystalline polyolefin polymer particles is usually 1.0 to 2.0.
1 Preferably 1.0 to 1.5, particularly preferably 1.
It is within the range of 0 to 1.5, particularly preferably 1.0 to 1.3.

In addition, the apparent bulk density of the crystalline polyolefin polymer particles due to natural fall is 1, which is usually 0.20 g/33 or more.
It is preferably in the range of 0.30 to 0.70 g/cm', particularly preferably 0.35 to 0.60 g/cm'.

Then, the transition metal component force f1 is applied to the crystalline polyolefin polymer particles produced by adopting the above method.
Usually 1100 ppm or less, preferably 10 ppm or less, particularly preferably 5 ppm or less, halogen component - usually 30 ppm or less
It is contained in a proportion of 0 ppm or less, preferably 1100 ppm or less, particularly preferably 50 ppm or less.

The above cograft polymer particles (a) used in the present invention
IL 1 to 100 parts by weight of the above-mentioned crystalline polyolefin polymer particles are added to the above-mentioned crystalline polyolefin polymer particles under gas phase conditions in which the crystalline polyolefin polymer particles can substantially maintain the particle shape. 200 parts by weight of styrenic monomer and 1 to 200 parts by weight
It is prepared by copolymerizing parts by weight of unsaturated carboxylic acids and/or derivatives thereof.

The styrenic monomer used in the present invention has the 14th order formula [
In the above formula [IIl] which can be expressed in ml, R1 and R2 are G
l Each independently a hydrogen atom or 1 to 3 carbon atoms
represents an alkyl group, specifically 1 methyl pentaethyl penta
Propyl group Isopropyl group can be mentioned. Further, R'IL represents a hydrocarbon group having 1 to 3 carbon atoms or a halogen atom. Specific examples include methyl group, ethyl group, propyl group, isopropyl group, salt fish, odor milk, iodine, and the like.

Moreover, nL represents an integer from 1 to 5.

This styrene monomer! They can be used alone or in combination.

Examples of such styrenic monomers include E styrene, a-methylstyrene, 0-methylstyrene, p
-Methylstyrene, m-methylstyrene, 〇-chlorostyrene, p-chlorostyrene, m-chlorostyrene p
Among the styrene monomers represented by the above formula [ml, styrene and a-methylstyrene are particularly preferred in the present invention.

1 to 200 parts by weight per 100 parts by weight of the crystalline polyolefin polymer particles, preferably 5 to 150 parts by weight, particularly preferably 10 to 10 parts by weight of the styrene monomer.
It is used in an amount of 0 parts by weight.

As an example of the unsaturated carboxylic acid used in the present invention,
Acrylic acid, methacrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid,
Crotonic acid, incrotonic acid, nadic acid (endocys-bicyclo[2,2,11hept-5-ene-2,
3-dicarboxylic acid). Further, examples of the above-mentioned unsaturated carboxylic acid derivatives include IL unsaturated carboxylic anhydrides, unsaturated carboxylic acid halides, unsaturated carboxylic amides, unsaturated carboxylic imides, and unsaturated carboxylic acid ester compounds. Specific examples of such derivatives include maleyl chloride,
Mention may be made of maleimide, maleic anhydride, citraconic anhydride, monomethyl maleate, dimethyl maleate and glycidyl maleate.

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

Among the unsaturated carboxylic acids and derivatives thereof, unsaturated dicarboxylic acids and their acid anhydrides are preferred, and maleic acid, nadic acid, and their acid anhydrides are particularly preferred.

The above unsaturated carboxylic acid and/or its derivative melon
1 to 20 for the above crystalline polyolefin polymer particles
0 weight clothing preferably in an amount of 5 to 150 parts by weight, more preferably 10 to 100 parts by weight.

Co-graft polymer particles (a) used in the present invention The above-mentioned styrenic monomer and unsaturated carboxylic acid and/or its derivative are combined so that the above-mentioned crystalline polyolefin polymer particles can substantially maintain their particle shape. Under gas phase conditions,
It can be obtained by co-grafting onto crystalline polyolefin polymer particles.

At Uni, "a gas phase condition 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 and the gas phase is This means that the reaction is carried out under phase conditions, and that the reaction is carried out under gas phase conditions in which the crystalline polyolefin is not dissolved in a solvent or the like.

For this co-graft polymerization reaction, for example, predetermined amounts of crystalline polyolefin polymer particles, a styrene monomer, an unsaturated carboxylic acid and/or its derivative, and, if necessary, a radical initiator are charged into a reaction vessel.
A temperature lower than the melting point of the crystalline polyolefin polymer particles, preferably 50 to 140°C, more preferably 60 to 140°C.
This is done by mixing while heating to a temperature of 120°C. The cografting reaction time under the above temperature conditions is usually 0.5 to 15 hours, preferably 1 to 10 hours.
Set within a time range.

When using a radical initiator in the above reaction! Examples of the mira-radical initiator include the organic peroxides, organic bersesters, azo compounds, etc. that can be used in the production of the oxidized crystalline polyolefin polymer particles described above.

The radical initiator is generally used in an amount of 01 to 10 parts by weight per 100 parts by weight of the crystalline polymer particles.

The melt fluorate IL of the thus obtained cograft polymer particles (a) measured at 230°C according to ASTM-D-1238 is usually 0.1 to 100 g.
710 minutes, preferably within the range of 1 to 50 g/10 minutes.

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

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

Examples of polyamides (b) that can be used here include iL Nylon-Low Nylon-61
to nylon-ul nylon-632, nylon-
copolymerized nylon formed from caprolactam and a nylon salt aqueous solution, copolymerized nylon formed from metaxylene diamine and adipic acid, nylon MXD6, nylon-46 and methoxymethyl formed from metaxylene diamine and adipic acid. polyamides.

Such polyamides (b) il Example 1 Ethylenediamine, propylene diamine, hexamethylene diamine, diethylene triamine, triethylenetetramine, tetraethylenepentamine, iminobispropylamine, bis(hexamethylene)triamine, 1.3.
6-) Aliphatic amines such as risaminomethylhexane, trimethylhexamethylenediamine, diethylene glycol, bispropylenediamine, diethylaminopropylamine; menzendiamine, isophoronamine,
Alicyclic amines such as bis(4-amino-3-methylcyclohexyl)methane, N-aminoethylbiverazine, and 1,3-diaminocyclohexane; Fatty aromatic amines such as metaxylylene diamine; 0-1J p- Phenylene diamine, diaminodiphenylmethane, diaminodiphenylsulfone, 2.4-diaminoanisole, 2.4-)luenediamine, 2.4
- Aromatic amines such as diaminodiphenylamine, 4,4'-methylene dianiline, diaminodiphenylsulfone; 3,9-bis(3-aminopropyl)-2,4°8
．． Diamine components such as bisspirocyclic diamines such as 10-tetraspiro[5,5]undecane, aliphatic dicarboxylic acids such as adipic acid, sebacic acid, dodecane dibasic acid, geltaric acid, terephthalic acid, isophthalic acid,
1,3-naphthalene dicarboxylic acid, 1,4-naphthalene dicarboxylic acid, 1,5-naphthalene dicarboxylic acid, 2,
It can be produced by polycondensing an aromatic dicarboxylic acid such as 7-naphthalene dicarboxylic acid with a dicarboxylic acid component such as an alicyclic dicarboxylic acid.

In the present invention, the above polyamides (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 blended in a weight ratio of 99:1 to 1:99. Ru. By blending both in such a ratio, a resin composition with improved mechanical properties such as impact resistance can be obtained without impairing the excellent properties of the cograft polymer particles (a). Exposure 2 Both preferably 9
0:10-10:90. More preferably 80:2
By blending in a weight ratio within the range of 0 to 20:80, the mechanical properties of the resulting polyolefin resin composition can be further improved.

Cograft polymer particles blended in the proportions shown above (
The polyolefin resin composition of the present invention can be obtained by cross-mixing a) and polyamide (b).

Polyolefin resin composition 6 of the present invention Other stains of the above-mentioned cograft polymer particles (a) and polyamide (b) Before inorganic filling Before organic filling Thermal stability Ship Weather resistance stability L
Anti-static Shelf Anti-Slip Agent L Anti-Blocking Shelf Anti-fog Qi K Slipper Pigments, dyes, natural sources, additives such as synthetic oils and waxes may be blended.

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

Therefore, the polyolefin resin composition of the present invention can be preferably used in applications requiring particularly high mechanical strength, such as filler-reinforced PPS ABSWJIII and modified polyphenylene oxide, which are contrary to the usual uses of polyolefins. Specifically, IL Engineering Plastics, Vehicle Department
It can be suitably used as a home appliance housing, an OA equipment housing, etc.

In addition, since the polyolefin resin composition of the present invention is formed from co-graft polymer particles (a) and polyamide (b), it has excellent mechanical properties such as impact resistance and rigidity, heat resistance, and surface hardness. It is possible to obtain a molded product with improved appearance.Moreover, it is possible to obtain a molded product with a good appearance and an improved balance of mechanical properties.

Next, the present invention will be explained by showing examples. However, present invention 1
Dai: These examples should not be construed as limiting.

[Evaluation method] In the present invention, the properties of the polypropylene resin composition were measured as follows: & Tuning FS JIS-7203 quasi 1. ．． Measured under the same conditions as FM! ! 1I JIS-7110, 2, measured using a 3.2-thick test piece HDT JIS-7207, 3-2 measured using a 3.2-thick test piece Regarding the surface appearance of the injection molded product of 12 aa X 0, 32 as, which was measured using a test piece with a thickness of 3.2 mm according to 7202 in accordance with JIS-7202, the following was determined by visual observation. It was evaluated in two stages.

O: No flow mark ×: 70-marked cold crystalline propylene homopolymer particles (MFR=0, 3
g/10 minutes) to 100 parts by weight, add a solution of 0.05 parts by weight of benzoyl peroxide dissolved in 5 parts by weight of toluene, mix thoroughly, and then heat in a gear oven set at a temperature of 90°C. MFRiL after oxidation treatment was heated for 3 hours and oxidized at 36 g/10 minutes.Next, 100 parts by weight of the above oxidized propylene homopolymer was placed in a stainless steel autoclave equipped with spiral double ribbon blades. After completely replacing the air in the system with nitrogen gas, while stirring the oxidized propylene homopolymer at room temperature, 53 parts by weight of styrene and 1 part by weight of maleic anhydride were added.
A mixed solution consisting of 3 parts by weight was gradually added dropwise at t4. After the dropwise addition, 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 at this temperature for another 6 hours. Stirring is performed to complete the reaction to obtain co-graft polymer particles A. As mentioned above, the maximum temperature of the reaction system is 100°C, and this temperature is lower than the melting point of propylene homopolymer, This co-grafted polymer particle AI was able to carry out the co-grafting reaction without damaging the morphology of the homopolymer particle.The styrene grafting rate was 9.8% by weight and the maleic anhydride grafting rate was 1.5%.
In the present invention, the graft ratio was 1. The co-grafted polymer particles were dissolved in xylene at 130°C, this solution was poured into a large amount of acetone to precipitate the polymer, and the unprecipitated polymer was filtered. The purified polymer was then washed and a press film was prepared using the obtained purified polymer. From the measurement results of the IR spectrum of this film, 1790 cm-1 and 1600 cm-1, -
40 parts by weight of the co-grafted polymer particles A obtained as above and 6-nylon (manufactured by Unitika) determined from the absorbance measured as above based on a calibration curve prepared in advance. , A1020BRL) 6
A polyolefin resin composition was obtained by supplying and kneading 0 parts by weight to a twin screw extruder (L/D = 30) with a temperature of 240 tons and a temperature of 240 tons. was supplied to an injection molding machine (1S-50EP manufactured by Toshiba ■) and injection molded under 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 this test piece.

Base layer 1" In Example 1, crystalline propylene/ethylene block copolymer (ethylene component unit content 25% by weight, 23°C Cograft polymer particles B were obtained by the same procedure as in Example 1 except that n-decane soluble content (25% by weight) was used.Styrene graft ratio IL of the cograft polymer particles B
A test piece was prepared in the same manner as in Example 1 using this cograft polymer particle B with a maleic anhydride graft ratio of 10.2% by weight and a maleic anhydride graft ratio of 12.0% by weight. The physical properties of this test piece are shown in Table 1. Describe it.

In Example 1, in addition to 40 parts by weight of co-graft polymer particles A and 60 parts by weight of 6-nylon, a total of 1
A composition was prepared in the same manner except that 20 parts by weight of talc was added to 00 parts by weight, and a test piece was made using this composition. The physical properties of this test piece are listed in Table 1.

1jA In Example 2, in addition to 840 parts by weight of cograft polymer particles and 60 parts by weight of 6-nylon, a total of 1
A composition was prepared in the same manner except that 20 parts by weight of talc was added to 00 parts by weight, and a test piece was prepared using this composition. Table 1 shows the physical properties of this test piece.

Comparative Example I Stainless Steel Autoclave Prem Equipped with Helical Double Ribbon Wings Crystalline ethylene-propylene block copolymer used in Example 2 (ethylene component unit content 25% by weight, n-decane soluble content at 23°C 25%) Weight%) 10
Next, the air in the system was completely replaced with nitrogen gas. Next, while stirring, a solution of 1 part by weight of maleic anhydride dissolved in 15 parts by weight of toluene was added dropwise. Then, the mixture was further heated at room temperature. Stirring was carried out for 1 hour, and then the temperature was raised to 100° C. over 1 hour. Stirring was carried out at this temperature for 4 hours to complete the reaction to obtain graft polymer particles C. Maleic anhydride in this graft polymer particle C The olefin was produced in the same manner as in Example 2, in which the grafting rate was 0.067% by weight and the MFR was 5g710 min, except that graft polymer particles C prepared as described above were used instead of graft polymer particles B. Preparation of Resin Composition A test piece was prepared using this olefin resin composition, and the physical properties of this test piece are listed in Table 1.

As is clear from the results shown in Table 1, the molded product formed from this composition had low rigidity, impact strength, hardness, and heat distortion temperature, poor appearance, and poor balance of physical properties. Crystalline propylene/ethylene block copolymer used in Example 2 (ethylene component unit content 25% by weight, 23°C
100 parts by weight of n-decane soluble content (25% by weight) 3 parts by weight of maleic anhydride and 2,5-tert-
This graft polymer was obtained by mixing 30.03 parts of butylperoxy)hexyne and feeding it into a 44-diameter twin-screw extruder (L/D=30) set at a temperature of 230°C. Polymer D14 Maleic anhydride grafting rate is 0.5% by weight, MFR is 36g/
In Example 2 where the time was 10 minutes, instead of graft polymer particles B
A composition was prepared in the same manner except that this graft copolymer was used. A test piece was prepared using this composition. The physical properties of this test piece are listed in Table 1.

Claims (3)

[Claims] (1) Under gas phase conditions in which the crystalline polyolefin polymer particles can substantially maintain the particle shape, 1 to 200 parts by weight of a styrene monomer per 100 parts by weight of the crystalline polyolefin polymer particles; 1-200
1 to 99 parts by weight of cograft polymer particles (a) formed by cografting parts by weight of an unsaturated carboxylic acid and/or its derivative onto crystalline polyolefin polymer particles; and 99 to 1 parts by weight of polyamide (b). A polyolefin resin composition characterized in that it is formed from parts by weight. (2) The polyolefin resin composition according to claim 1, wherein the crystalline polyolefin polymer particles have a crystalline part made of polypropylene resin and an amorphous part made of ethylene propylene random copolymer rubber. . (3) The polyolefin resin according to claim 1 or 2, wherein at least a portion of the crystalline polyolefin polymer particles are oxidized crystalline polyolefin polymer particles oxidized with an organic peroxide. Composition.