JPH03285938A - Polyolefin resin composition - Google Patents

Abstract

PURPOSE:To obtain a composition having excellent impact resistance, rigidity, heat resistance, 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 polyester. 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 polypropylnen resin and amorphous part composed of ethylene propylene random copolymer rubber and at least partially oxidized with an organic peroxide, under a vapor phase condition of the co grafting capable of making the particles maintain a particulate state, are blended with (B) 99-1 pts.wt., preferably 80-20 pts.wt. polyester (e.g. polybutylene terephthalate).

Description

[Detailed Description of the Invention] I Hadada Kuzuhagi Goko 1 The present invention 1 More details regarding the polyolefin resin composition Special number Mi Improved balance of 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 molded article.

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

By extrusion molding, etc., this composition can be made into molded products with excellent properties such as heat resistance, tensile properties, weather resistance, flexibility, and impact resistance. The current situation is that the properties are not satisfactory, and there is a desire for a resin with an improved balance of physical properties such as impact resistance, rigidity, heat resistance, surface hardness, and appearance.

The present invention has been made based on the above circumstances and aims 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 Satomi 1 Polyolefin resin composition according to the present invention Under gas phase conditions in which the primary crystalline polyolefin polymer particles can substantially maintain the particle shape, 1 to 1 parts by weight are added to 100 parts by weight of the crystalline polyolefin polymer particles. -200 parts by weight of styrenic monomer and 1 to 20 parts by weight 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 polyester (b). 1 part by weight.

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

In the polyolefin resin composition according to the present invention, crystalline polyolefin polymer particles are treated with a specific amount of a styrenic monomer and unsaturated under gas phase conditions in which the crystalline polyolefin polymer particles can substantially maintain the particle shape. It is formed from cograft polymer particles (a) formed by cografting a carboxylic acid and/or a derivative thereof, and a polyester (b).

Although 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.

Crystalline polyolefin polymer particles having the above characteristics can be obtained, for example, by polymerizing or copolymerizing a-olefins having 2 to 20 carbon atoms.

Examples of such a-olefins (Table Ethylene,
Propylene, butene-L Pentene-1,2-methylbutene-1,3-methylbutene-L Hexene-1,3-
Methylpentene-L4-Methylpentene-3,3-dimethylpentene-1, heptene-1, methylhexene-
k Dimethylpentene-L Trimethylbutene-L Ethylpentene-1, Octene-1, Methylpentene-L
Dimethylhexene-1, trimethylpentene-Ethylhexene-L Methylethylpentene-L Diethylbutene-L Propylpentene-L Decene-L Methylnonene-L Dimethyloctene-L Trimethylhebutene-L Ethyloctene-k Methylethylhebutene- L
Mention may be made of a-olefins such as diethylhexene-L dodecene-1 and 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.

1 crystalline polyolefin polymer particle used in the present invention contains repeating units derived from the above a-olefin, usually 50 mol% or more, preferably 80 mol% or more, particularly preferably 100 mol%.

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

These polyene compounds are polyenes having two or more conjugated or non-conjugated olefinic double bonds,
Examples of such linear polyene compounds include IL1.
4-hexadiene, 1.5-hexadiene, 1.7-octadiene, 1,9-decadiene, 2.4.6-octatriene, 1.3.7-octatriene, 1.5
．． Examples include 9-decatriene and divinylbenzene.
can be done.

Examples of cyclic polyene compounds include 1,3-cyclopentadiene, 1,3-cyclohexadiene, 5-ethyl-1,3-cyclohexadiene, 1,3-cycloheptadiene, dicyclopentadiene, and dicyclohexadiene. xadiene, 5-ethylidene-2-norbornene, 5-methylene-
2-norbornene, 5-vinyl-2-norbornene, 5
-Impropylidene-2-norbornene, methylhydroindene, 2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-impropylidene-5-norbornene, 2-propenyl-2,5-norbornadiene, etc. Can be mentioned.

Furthermore, when producing the above crystalline polyolefin polymer particles, a cyclic monoene can also be used,
Examples of such cyclic monoenes include +3 monocycloalkenes such as cyclopropene, cyclobutene, cyclopentene, cyclohexene, 3-methylcyclohexene, cycloheptene, cyclooctene, cyclodecene, cyclododecene, tetracyclodecene, octacyclodecene and cycloeicosene; norbornene , 5-methyl-2-norbornene, 5-ethyl-2-norbornene, 5-isobutyl-2-norbornene 5,6-simethyl-2-norbornene 5.5
．． Bicycloalkenes such as 6-trimethyl-2-norbornene and 2-bornene + 2+ 3+ 3a, 7
Tricycloalkenes such as a-tetrahydro-4,7-methano-IH-indene and 3a, 5.6.7a-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 &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, s, 8+ 8a-octahydronaphthalene, 2-propyl-1,4,5,8-dimethano-1,2,3,4,4a, 5.8゜8a-octahydro Naphthalene, 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, 5.8.8
a-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-
Bromo1,4.5.8-dimethano-1,2,3,4,4
a, 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.

Tetracycloalkenes such as 5,8.8a-octahydronaphthalene; hexacyclo[5,5,l, 13.1.11@, +3
．． Q2.7. Q9. +4] Hebutadecene box pentacyclo [8, 8, 12, @, 1', ? 111.1@
, (J(p, e, Q10.+?) Henei Kosen nail octacyclo [8, 8, 12-9, 14, 7, 1st, +1
1. lI3.18. Q, Q31Q12.1)] Cyclic monoene compounds such as polycycloalkenes such as tococene-5 can be mentioned.

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

Crystalline polyolefin polymer particles used in the present invention 1
It can be 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 a liquid phase method is preferably carried out in a suspended state so that the resulting polymer particles can be obtained in a solid state.

An inert hydrocarbon can be used as the solvent used in this polymerization reaction or copolymerization reaction. Furthermore, the 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-mentioned polymerization or copolymerization method may be employed, or the reaction may be carried out in the liquid phase using an α-olefin as a solvent, followed by a reaction in the vapor phase. It is preferable to adopt a method that combines methods.

This is a method that combines a liquid phase method and a gas phase method. After prepolymerizing the a-olefin in the presence of a specific catalyst using an inert hydrocarbon or a-olefin as a raw material as a reaction solvent, the a-olefin is polymerized in the gas phase. Then, a-olefin is further polymerized.

Here, iL is an example of an inert hydrocarbon used as a solvent.
Propane, butane, n-pentane, i-pentane,
n-hexane, i-hexane, n-hebutane, n-
Aliphatic hydrocarbons such as octane, i-octane, n-decane, n-dodecane, and kerosene; Alicyclic hydrocarbons such as cyclopentane, methylcyclopentane, cyclohexane, and methylcyclohexane; Aromatics such as benzene, toluene, and xylene Hydrocarbon: Mention may be made of halogenated hydrocarbon compounds such as methylene chloride, ethylene chloride, and chlorobenzene.

In addition, as the above catalyst, 2 Preferably IL Periodic Table of Elements rvlL vA2fL VTA & ■
Catalyst components containing Group A and Group II transition metals, such as titanium, zirconium, hafnium, and vanadium [A]
and an organometallic compound catalyst component [B
] is used.

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

As the catalyst component [A] above, 1. Element ■A of the periodic table!
Catalysts containing transition metal atoms of the vA group are preferred, and among these, catalyst components containing at least one type of atom selected from the group consisting of titanium, zirconium, hafnium and vanadium are particularly preferred.

In addition, other preferred catalyst components [A] include catalyst components containing halogen atoms and magnesium atoms in addition to the transition metal atoms listed above, and groups having conjugated electrons coordinating with transition metal atoms in group IVA of the periodic table. Catalyst components containing such compounds are mentioned.

The 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 or as a carrier during the polymerization reaction or copolymerization reaction as described above. It is preferable to use a catalyst prepared so that it can exist in a solid state by being supported on a catalyst such as a catalyst.

About such a catalyst component [A] G1 JP-A-1983
-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] when producing the crystalline polyolefin polymer particles in the present invention: For example, by the reaction of aluminoxane, an organoaluminum compound and water. Alternatively, an organoaluminum compound obtained by reacting a solution of aluminoxane with water or an active hydrogen-containing compound can be used.

Further, in addition to the above-mentioned organometallic compound catalyst component [B]lL, an electron donor [C] (outside donor) can also be blended.

In preparing the crystalline polyolefin polymer particles in the present invention, JL uses the above-mentioned catalyst to prepolymerize 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 preliminary polymerization 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/Cx.
Polymerization is carried out by setting n2 within the range.

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

For example, polymer particles jL produced as described above
It is preferable that the crystalline portion and the amorphous portion have a seabird-like distribution. A composition with excellent impact resistance is obtained 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 lydum copolymer rubber. be able to.

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.

Around the oxidized crystalline polyolefin polymer particles as above
For example, 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 It can be obtained by heating to a temperature of 140°C, preferably 60 to 120°C.

Examples of organic peroxides used herein include dichlorobenzoyl peroxide, dicumyl peroxide, and dichlorobenzoyl peroxide.
ert-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(t
ert-butylperoxy)-3,3,5-)limethylcyclohexane, n-butyl-4,4-bis(tert-butylperoxy)-3,3,5-)limethylcyclohexane,
tert-butylperoxy) valerate, dibenzoyl peroxide, tert-butylperoxybenzoate,
tert-butyl peroxy-2-ethylhexanoate, cyclohexanone peroxide, 2,5-dimethyl-2,5-dibenzoyl peroxyhexane, tert
-butyl peroxybenzoate, di-tert-butyl-cibar oxyphthalate, methyl ethyl ketone peroxide and the like.

Crystalline Polyolefin Polymer Particles Used in the Present Invention With the oxidized crystalline polyolefin polymer particles as described above, it is possible to obtain a resin composition with further improved mechanical properties, particularly impact resistance.

Furthermore, 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 usually 0.1 to 100g71
0 minutes, preferably within the range of 1 to 50g710 minutes.

Crystalline polyolefin polymer particles used in the present invention 1
The average particle diameter is usually lO~5000μ, preferably 100~4000μ, more preferably 300~
It is within the range of 3000pm. In addition, the geometric standard deviation that indicates the particle size distribution of the crystalline polyolefin polymer particles is usually 1.0 to 2.0, preferably 1.0 to 1.5.
, particularly preferably 1.0-1.5, particularly preferably 1.
It is within the range of 0 to 1.3.

The apparent bulk density of the crystalline polyolefin polymer particles due to natural fall is usually 0.20 g/d3 or less, preferably 0.30 to 0.70 g/as, particularly preferably 0.35 to 0.60 g/cm'.

The crystalline polyolefin polymer particles produced using the above method have a transition metal content of 25 tons.

Usually 100 ppm or less, preferably 10 ppm or less,
Particularly preferably 5 ppm or less, the halogen component is 1
It is usually contained in a proportion of 300 ppm or less, preferably 100 ppm or less, particularly preferably 50 ppm or less.

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

The above cograft polymer particles (an
t, to the above-mentioned crystalline polyolefin polymer particles. Under gas phase conditions in which the crystalline polyolefin polymer particles can substantially maintain their particle shape, 1 to 1 parts by weight are added to 100 parts by weight of the above-mentioned crystalline polyolefin polymer particles. 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 following formula [ml] [In the above formula [ml], R1 and R214 hydrogen atoms or alkyl groups having 1 to 3 carbon atoms are expressed as
Methyl group Ethyl group Propyl hog isopropyl group can be mentioned. In addition, Ri 11 A hydrocarbon group having 1 to 3 carbon atoms or a halogen atom can be specifically mentioned as shown in Table 1.

Moreover, n131 represents an integer of 5.

This styrenic monomer 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 [m], styrene and a-methylstyrene are particularly preferred in the present invention.

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

Examples of unsaturated carboxylic acids used in the present invention include myacrylic acid, methacrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, incrotonic acid, nadic acid, (endocys-bicyclo[ 2,2,1]hept-5-ene-2,3-
dicarboxylic acids). Further, as derivatives of the above unsaturated carboxylic acids, there may be mentioned unsaturated carboxylic acid anhydrides, unsaturated carboxylic acid halides, unsaturated carboxylic amides, unsaturated carboxylic imides, and ester compounds of unsaturated carboxylic acids. . 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.

1 of the above unsaturated carboxylic acids and/or derivatives thereof 1 to 2 for the above crystalline polyolefin polymer particles
00 weight clothing, preferably 5 to 150 weight clothing, and more preferably 10 to 100 parts by weight.

Cograft polymer particles used in the present invention (a month!

The above-mentioned styrenic monomer and unsaturated carboxylic acid and/or its derivative are added to the crystalline polyolefin polymer particles under gas phase conditions such that the crystalline polyolefin polymer particles can substantially maintain their particle shape. It can be obtained by grafting.

Here, "under gas phase conditions under which the crystalline polyolefin polymer particles can substantially maintain their particle shape" is defined as IL. This means that the reaction is carried out under such 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.

This co-graft polymerization reaction is similar to example 1! , a predetermined amount of crystalline polyolefin polymer particles, a styrenic monomer, an unsaturated carboxylic acid and/or a derivative thereof,
Furthermore, if necessary, a radical initiator is added to the reaction vessel at a temperature lower than the melting point of the crystalline polyolefin polymer particles, preferably 50 to 140°C, more preferably 60°C.
This is done by mixing while heating to a temperature of ~120°C. Under the above temperature conditions, the cografting reaction time +L is usually 0.5 to 15 hours, preferably 1
It is set within the range of ~10 hours.

In the above reaction, when using a radical initiator,
Examples of the 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 0.01 to 10 parts by weight per 100 parts by weight of the crystalline polymer particles.

The melt fluorate of the thus obtained cograft polymer particles (a) measured at 230°C according to ASTM-D-1238 is usually 001 to 100 g71
0 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 polyester (b).

Polyester (b) used in the present invention is a resin produced by condensation of polyhydric alcohol and polybasic acid,
Such resins may include alkyd resins, maleic acid resins and unsaturated polyester resins.

Examples of such polyhydric alcohols include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, butylene glycol,
trimethylene glycol, tetramethylene glycol,
Examples include glycerin, trimethylolpropane, diglycerin, triglycerin, pentaerythritol, mannitol, and sorbitol.

Examples of such polybasic acids and acid anhydrides include
Phthalic anhydride, maleic anhydride, fumaric acid, adipine terephthalic acid, naphthalene dicarboxylic acid, succinic acid, sebacic acid, itaconic acid, citraconic anhydride, cyclopentadiene-maleic anhydride adduct and terpene.
Maleic anhydride adducts, rosin-maleic anhydride adducts, and the like.

Examples of polyesters (b) produced by polycondensation of polyhydric alcohols and polybasic acids include polyethylene fumarate, polyethylene terephthalate, polyethylene naphthalate, polyethylene sebacate, polypropylene fumarate, polypropylene adibate, and polyester (b). Examples include butylene fumarate, polybutylene terephthalate, polybutylene adipate, and the like.

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

In addition, in the present invention, among the various polyesters (b) as described above, polybutylene terephthalate,
Polyethylene terephthalate is preferred, and polybutylene terephthalate is particularly preferred.

In the present invention, the cograft polymer particles (a) and the polyester (b) are blended in a weight ratio of 99:1 to 1:99. Ru. By blending both in such a ratio, mechanical properties such as impact resistance are improved without impairing the excellent properties of the cograft polymer particles (a). Furthermore, both are preferably 90:10 to 10:90,
More preferably, by blending in a weight ratio within the range of 80:20 to 20:80, the mechanical strength 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 kneading a) and polyamide (b).

Initial velocity of the polyolefin resin composition of the present invention Land number of the above cograft polymer particles (a) and polyester (b) Inorganic filling berth Organic filling berth Before thermal stabilization Weatherability stability L
Antistatic Lift Anti-Slip Shelf Anti-Blocking Shelf Anti-Fog Shelf Slippery Additives such as pigments, dyes, natural sources, synthetic oils and waxes may be blended.

For example, as the inorganic filler, powdered fillers such as talc and titanium oxide are preferably used.

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

Therefore, polyolefin resin composition 1 of the present invention! Normal usage momme of polyolefin For example, filler M strong PP,
It can be preferably used in applications where mechanical strength is required, such as ABS resin, modified polyphenylene oxide, etc. Specifically, it is suitable for engineering plastics, vehicle parts & home appliance housings, OA equipment housings, etc. It can be used for.

i Rijiko J First edition of the polyolefin resin composition of the present invention Contains co-graft polymer particles (a) and polyester (b) in a predetermined ratio, resulting in improved mechanical properties such as impact resistance and rigidity, and heat resistance. Further, by using this resin composition, a molded article with high surface hardness can be obtained.

Molded object IL formed from the composition of the present invention
It has a good appearance and a good balance of properties.

Next, the present invention will be explained by showing examples. However, 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: FM JIS-7203 or higher; measured at 23°C using a 3.2-thick test piece. Geq response (FS) JIS-7203 quasi 1. Measured under the same conditions as FM - LA" 1st class 1 JIS - 7110 or higher Measured using a test piece with a thickness of 3.21 / temperature HDT JIS - 7207 or higher The thickness was measured using a test piece with a thickness of 3.2+*s according to JIS-7202. The surface appearance of the injection molded articles from 32 countries was evaluated using the following two stages by visual observation.

0: No flow mark ×: With flow mark 1 todoro 1 unit 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. MFRG4 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, the oxidized propylene homopolymer was mixed with 53% styrene and 13% maleic anhydride while stirring at room temperature.
A mixed solution consisting of parts by weight was gradually added dropwise. After the addition, the mixture was stirred at room temperature for 1 hour, and the temperature inside the system was raised to 100°C over 1 hour.
The reaction was completed by stirring for a period of time to obtain cograft polymer particles A. As mentioned above, the maximum temperature of the reaction system was 100°C.
Since this temperature is lower than the melting point of the propylene homopolymer, the cograft reaction can be carried out without damaging the morphology of the copropylene homopolymer particles. The grafting rate was 9.8% by weight, and the grafting rate of maleic anhydride was 1.5% by weight. In the present invention, the grafting rate was determined by dissolving the cograft polymer particles in xylene at 130°C and dissolving this solution in a large amount of acetone. The precipitated polymer is filtered and washed to ice the purified polymer.Next, a press film is prepared using the obtained purified polymer, and the IR spectrum of this film is measured. From the results, 1790cm-1 and 1600cm-1
40 parts by weight of the co-graft polymer particles A obtained as described above, determined from the absorbance measured as above based on a calibration curve prepared in advance;
Polybutylene terephthalate (PBT, 1
A polyolefin resin composition was obtained by supplying and kneading parts of 401-XO4) and 601i to a 44 m twin-screw extruder CL/D=30) set at a temperature of 240°C. The composition was supplied to an injection molding machine (Toshiba 1S-50EP) and injection molded under conditions of a cylinder temperature of 270°C and a mold temperature of 60°C to obtain a test piece. The physical properties of this test piece are listed in Table 1. do.

X1j1 In Example 1, crystalline propylene/ethylene block copolymer (ethylene component unit content 25% by weight, n- Cograft polymer particles B were obtained in the same manner as in Example 1 except that decane soluble portion (25% by weight) was used.Styrene graft ratio 1f of this cograft polymer particle B
, 10.2% by weight, maleic anhydride graft ratio 2.
A test piece was prepared in the same manner as in Example 1 using this cograft polymer particle B which was 0% by weight. The physical properties of this test piece are listed in Table 1.

Cold ILu In Example 1, in addition to 40 parts by weight of cograft polymer particles A and 60 parts by weight of polyester, 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.

X1IA In Example 2, in addition to 840 parts by weight of cograft polymer particles and 60 parts by weight of polyester, 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. The physical properties of this test piece are listed in Table 1.

A stainless steel autoclave equipped with spiral double ribbon blades & - Crystalline ethylene-propylene block copolymer used in Example 2 (ethylene component unit content 25% by weight, n-decane soluble content at 23°C 25% by weight) 100
Parts by weight are charged. After the air in the system is completely replaced with nitrogen gas, a solution of 1 part by weight of maleic anhydride dissolved in 15 parts by weight of toluene is added dropwise while stirring. Stirring was carried out at room temperature for 1 hour, then the temperature was raised to 100°C over 1 hour, and stirring was carried out at this temperature for 4 hours to complete the reaction to obtain graft polymer particles C. The maleic acid grafting rate was 0.7% by weight, and the MFR was 5g710min. In Example 2, the graft polymer particles C prepared as described above were used instead of the cograft polymer particles B. prepared an olefin resin composition in the same manner.
A test piece was prepared using this olefin resin composition. 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 has low rigidity, impact strength, hardness, and heat distortion temperature, poor appearance, poor balance of physical properties, and Crystalline propylene/ethylene block copolymer used in Example 2 (ethylene component unit content 25% by weight, 23°C
(Total decane soluble content: 25% by weight) 10,000 parts by weight, water, 3 parts by weight of maleic acid, and 30.03 parts by weight of 2,5-di(tert-butylperoxy)hexyne were mixed, and a diameter of 44° was set at a temperature of 230°C. Twin screw extruder (L
/D=30) to obtain a graft polymer.The maleic anhydride grafting rate was 0.5% by weight, and the MFR was 36g/10.
A composition was prepared in the same manner as in Example 2, except that this graft copolymer was used instead of cograft polymer particles B. A test piece was prepared using this composition. Table 1 shows the physical properties of the prepared test piece.

As is clear from the results shown in Table 1, the molded article 14 formed from this composition had low rigidity, impact strength, hardness, and heat distortion temperature, and was poor in appearance and had a poor balance of physical properties.

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 polyester (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.