JP2807493B2 - Polyolefin resin composition - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a polyolefin resin composition comprising a cyclic olefin random copolymer (a) and a graft copolymer (b).

Technical Background of the Invention Polyolefins conventionally used are resins having excellent chemical resistance and solvent resistance, but when the crystallinity is low, it is considered that the polyolefin has sufficient rigidity and heat resistance. I can't say.

For this reason, a method of adding a nucleating agent to improve the heat resistance and rigidity of the polyolefin or a method of gradually cooling the polyolefin in a molten state to increase the crystallinity has been adopted, but the effect is sufficient. It is hard to say.

Apart from such conventional polyolefins, it has been reported that a copolymer obtained by reacting ethylene with a bulky monomer has superior properties such as heat resistance as compared with conventional polyolefins. (See, for example, U.S. Pat. No. 2,883,372 and JP-B-46-14910).

Then, a specific cyclic olefin is used as a bulky monomer, and a cyclic random copolymer obtained by copolymerizing this cyclic olefin and ethylene provides heat resistance, heat aging resistance, solvent resistance, dielectric properties and rigidity. Based on the finding that it is excellent, the present applicant has already filed an application for a random copolymer using a specific cyclic olefin (Japanese Patent Application Laid-Open No. 60-168708 and Japanese Patent Application No. 59-220550). ,same
Nos. 59-236828, 59-236829, 59-242336 and 61-95906).

Object of the invention It is an object of the present invention to further improve mechanical properties such as impact strength of a resin composition containing the above-mentioned cyclic olefin random copolymer.

More specifically, the present invention provides a cyclic olefin random copolymer-containing resin composition in which mechanical properties such as impact strength are particularly improved without impairing the excellent properties of the cyclic olefin random copolymer. The purpose is.

SUMMARY OF THE INVENTION The polyolefin resin composition according to the present invention comprises 52 to 90 mol% of an ethylene component unit and 10 to 48 mol% of a component unit derived from a cyclic olefin represented by the following formula [I] and / or [II] ( However, the total amount of the components in the cyclic olefin random copolymer is 100 mol%) and the intrinsic viscosity [η] measured in decalin at 130 ° C. is
The cyclic olefin random copolymer (a) within the range of 0.05 to 10 dl / g and the amorphous or low-crystalline α-olefin elastic copolymer formed from at least two kinds of α-olefins A graft copolymer (b) in which a saturated carboxylic acid and a derivative thereof are grafted; and an amino group-containing compound (c) having two or more amino groups in the molecule. 0.01 to 1 based on 100 parts by weight of the copolymer (b)
0 parts by weight, and the weight ratio of the component (a) to the component (b) is in the range of 99: 1 to 1:99.

However, in the above formulas [I] and [II], m and n are 0 or a positive integer, l is an integer of 3 or more, and R ^{1 to} R ¹⁰ are each independently a hydrogen atom, a halogen atom and Represents one type of atom or group selected from the group consisting of hydrocarbon groups.

The polyolefin resin composition of the present invention contains a specific cyclic olefin random copolymer (a) and a graft copolymer (b) at a predetermined ratio, and further contains an amino group-containing compound (c). Particularly, mechanical properties such as impact strength can be improved without impairing the excellent properties of the cyclic olefin random copolymer.

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

The polyolefin resin composition according to the present invention is a composition comprising a cyclic olefin random copolymer (a), a graft copolymer (b), and an amino group-containing compound (c).

The cyclic olefin random copolymer (a) used in the present invention comprises an ethylene component unit and a component unit derived from a cyclic olefin represented by the following formula [I] and / or [II]. And such a cyclic olefin random copolymer has an intrinsic viscosity [η] measured in decalin at 135 ° C. within the range of 0.05 to 10 dl / g, preferably 0.1.
It is in the range of 2 to 1.2 dl / g. The softening temperature (TMA) of the cyclic olefin random copolymer measured with a thermal mechanical analyzer is usually in the range of 70 to 200 ° C, preferably in the range of 100 to 180 ° C.
The glass transition temperature (Tg) is usually in the range of 50 to 190 ° C,
It is preferably in the range of 80 to 170 ° C., and the degree of crystallinity measured by X-ray diffraction is usually in the range of 0 to 20%, preferably in the range of 0 to 2%.

The above-mentioned cyclic polyolefin copolymer is obtained, for example, by copolymerizing ethylene and an unsaturated monomer represented by the following formula [I] or [II] in a liquid phase in the presence of a catalyst. Can be obtained.

However, in the above formulas [I] and [II], n and m are each 0 or a positive integer, l is an integer of 3 or more, and R ^{1 to} R ¹⁰ are each independently a hydrogen atom , A halogen atom or a hydrocarbon group.

The cyclic olefin represented by the above formula [I] can be easily produced by condensing a cyclopentadiene and a corresponding olefin using a Diels-Alder reaction. Similarly, the cyclic olefin represented by the formula [II] can be easily produced by condensing a cyclopentadiene and a corresponding cyclic olefin using a Diels-Alder reaction.

Specific examples of the cyclic olefin represented by the formula [I] include, for example, bicyclo [2,2,1] hept-2-ene, 6-methylbicyclo [2,2,1] hept-2-ene, 5 , 6-Dimethylbicyclo [2,2,1] hept-2-ene, 1-methylbicyclo [2,2,1] hept-2-ene, 6-ethylbicyclo [2,2,1] hept-2-ene Ene, 6-n-butylbicyclo [2,2,1] hept-2-ene, 6-isobutylbicyclo [2,2,1] hept-2-ene and 7-methylbicyclo [2,2,1] hept Bicyclo [2,2,1] hept-2-ene derivatives such as -2-ene; 1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene , 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, 2,3-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, 2,3-dichloro-1,4,5,8-dimethano-1,2,3,4,4a, 5,
8,8a-octahydronaphthalene, 2-cyclohexyl-1,4,5,8-dimethano-1,2,3,4,4
a, 5,8,8a-octahydronaphthalene, 2-n-butyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,
8,8a-octahydronaphthalene and 2-isobutyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,
8,8a- octahydronaphthalene such as octahydronaphthalene; tetracyclo [4,4,0,1 ^2.5, 1 ^7.10] -3-dodecene, 5,10-dimethyl-tetracyclo [4,4,0,1 ^{2, 5} , 1 ^7,10 ] −
3-dodecene, 2,10-dimethyl-tetracyclo [4,4,0,1 ^2,5, 1 ^7,10] -
3-dodecene, 11,12-dimethyl-tetracyclo [4,4,0,1 ^2,5, 1 ^7,10]
-3-dodecene, 2,7,9-trimethyltetracyclo [4,4,0,1 ^2,5 ,
1 ^7,10 ] -3-dodecene, 9-ethyl-2,7-dimethyltetracyclo [4,4,0,1
^{2,5,1 7,10} ] -3-dodecene, 9-isobutyl-2,7-dimethyltetracyclo [4,4,
0,1 ^2,5, 1 ^7,10] -3-dodecene, 9,11,12- trimethyl tetracyclo [4,4,0,1 ^2,5, 1
^7,10 ] -3-dodecene, 9-ethyl-11,12-dimethyltetracyclo [4,4,0,1
^2,5, 1 ^7,10] -3-dodecene 9-isobutyl-11,12-dimethyl-tetracyclo [4,
4,0,1 ^2,5 , 1 ^7,10 ] -3-dodecene and 5,8,9,10-tetramethyltetracyclo [4,4,0,1 ^2,5 , 1
^7,10] -3-tetracyclo such dodecene [4,4,0,1 ^2,5, 1
^7,10] -3-dodecene derivatives; hexacyclo [6,6,1,1 ^3,6, 1 ^10,13, 0 ^2,7, 0 ^9,14] -4
- heptadecene, 12-methyl hexa cyclo [6,6,1,1 ^3,6, 1 ^10,13, 0 ^2,7, 0
^9,14] -4-heptadecene, 12-ethylhexanoate cyclo [6,6,1,1 ^3,6, 1 ^10,13, 0 ^2,7, 0
^9,14] -4-heptadecene, 12-isobutyl hexamethylene cyclo [6,6,1,1 ^3,6, 1 ^10,13, 0
^2,7, 0 ^9,14] -4-heptadecene and 1,6,10- trimethyl-12-isobutyl hexamethylene cyclo [6,6,1,1 ^3,6, 1 ^10,13, 0 ^2,7, 0 ^9,14] -4-hexacyclo such heptadecene [6,6,1,1 ^3,6, 1 ^10,13, 0 ^2,7, 0 ^9,14] -
4 heptadecene derivatives; octacyclo [8,8,0,1 ^2,9, 1 ^4,7, 1 ^{11, 18,} 1 ^{13, 16,}
0 ^3,8, 0 ^12,17] -5- dodecene, 15-methyl-octa cyclo [8,8,0,1 ^2,9, 1 ^4,7, 1 ^{11, 18,} 1
^{13 and 16,} 0 ^3,8, 0 ^12,17] -5- dodecene and 15-ethyl-octa cyclo [8,8,0,1 ^2,9, 1 ^4,7, 1 ^{11, 18,} 1
^{13 and 16,} 0 ^3,8, 0 ^12,17] -5-octacyclo such dodecene [8,8,0,1 ^2,9, 1 ^4,7, 1 ^{11, 18,} 1 ^{13, 16,} 0 ^{3 , 8,0 12,17} ] -5
-Dodecene derivatives.

Further, as the cyclic olefin represented by the formula [II],
Specifically, for example, 14,15-dimethyl-penta cyclo [6,5,1,1 ^3,6, 0 ^2,7, 0
^9,13] -4-pentadecene, pentacyclo [6,6,1,1 ^3,6, 0 ^2,7, 0 ^9,13] -4-hexadecene, heptacyclo [8,7,0,1 ^2,9, 1 ^4,7 , 1 ^11,17 , 0 ^3,8 ,
0 ^12,16] -5-icosene and heptacyclo [8,8,0,1 ^2,9, 1 ^4,7, 1 ^{11, 18,} 0 ^3,8,
0 ^12,17] -5 henicosenoic like; tricyclo [4,3,0,1 ^2,5] -3-decene, 2-methyl - tricyclo [4,3,0,1 ^2,5] -3-decene and 5-methyl - tricyclo [4,3,0,1 ^2,5] -3-tricyclo decene [4,3,0,1 ^2,5] -3-decene derivatives; tricyclo [4,4,0 , 1 ^2,5] -3-undecene and 10-methyl - tricyclo [4,4,0,1 ^2,5] -3-undecene and the like of tricyclo [4,4,0,1 ^2,5] -3 undecene derivatives; 1,3-dimethyl - pentacyclo [6,6,1,1 ^3,6, 0 ^2,7, 0
^9,14] -4-hexadecene, 1,6-dimethyl - pentacyclo [6,6,1,1 ^3,6, 0 ^2,7, 0
^9,14] -4-hexadecene and 5,16- dimethyl - pentacyclo [6,6,1,1 ^3,6, 0 ^2,7, 0
^9,14] -4-pentacyclo such as hexadecene [6,6,1,1
^3,6, 0 ^2,7, 0 ^9,14] -4-hexadecene derivatives, pentacyclo [6,5,1,1 ^3,6, 0 ^2,7, 0 ^9,13] -4-pentadecene and 1, 3-dimethyl - pentacyclo [6,5,1,1 ^3,6, 0 ^2,7, 0
^9,13] -4-pentacyclo such as pentadecene [6,5,1,1
^3,6, 0 ^2,7, can be exemplified 0 ^9,13] -4-pentadecene derivatives.

In the present invention, the monomer constituting the cyclic olefin random copolymer (a) by copolymerizing with the cyclic olefin compound represented by the above formula [I] or [II] is ethylene. However, in the cyclic olefin random copolymer used in the present invention, other olefin compounds may be copolymerized in addition to ethylene as the olefin compound.

In the present invention, examples of other olefin compounds that can be copolymerized with ethylene and the cyclic olefin compound represented by the above formula [I] or [II] include propylene, 1-butene, 4-methyl-1- Pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, etc.
Cycloolefins such as cyclopentene, cyclohexene, 3-methylcyclohexene, cyclooctene and 3a, 5,6,7a-tetrahydro-4,7-methano-1H-indene; 1,4-hexadiene; Non-conjugated dienes such as methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 1,7-octadiene, dicyclopentadiene, 5-ethylidene-2-norbornene and 5-vinyl-2-norbornene; Norbornene-2,5-methylnorbornene-2,5
-Ethylnorbornene 2,5-isopropylnorbornene-2,5-n-butylnorbornene-2,5-i-butylnorbornene-2,5,6-dimethylnorbornene-
Examples thereof include norbornenes such as 2,5-chloronorbornene-2, 2-fluoronorbornene-2, and 5,6-dichloronorbornene-2.

The reaction between the above ethylene and the cyclic olefin represented by the formula [I] and / or [II] is usually performed in a hydrocarbon solvent.

Examples of the hydrocarbon solvent used herein include aliphatic hydrocarbons such as hexane, heptane, octane and kerosene; alicyclic hydrocarbons such as cyclohexane and methylcyclohexane; and aromatic hydrocarbons such as benzene, toluene and xylene. be able to. Further, among the polymerizable unsaturated monomers that can be used in preparing the cyclic olefin random copolymer, a compound that is liquid at the reaction temperature can be used as the reaction solvent. These solvents can be used alone or in combination.

The catalyst used in the reaction between the above olefin and the cyclic olefin represented by the formula [I] or [II] includes a catalyst comprising a vanadium compound and an organoaluminum compound which are soluble in a hydrocarbon solvent used as a reaction solvent. Examples of the vanadium compound used as the catalyst here include compounds represented by the formula VO (OR) _{a Vb} or the formula V (OR) _c X _d .

However, in the above formula, R is a hydrocarbon group,
0 ≦ a ≦ 3, 0 ≦ b ≦ 3, 2 ≦ a + b ≦ 3, 0 ≦ c ≦
4, 0 ≦ d ≦ 4, 3 ≦ c + d ≦ 4.

Further, the vanadium compound may be an electron donor adduct of the vanadium compound represented by the above formula.

Examples of these vanadium _{compounds, VOCl 3, VO (OC 2} H 5) Cl 2, VO (OC 2 H 5) 2 Cl, VO (O-iso-C 3 H 7) Cl 2, VO (O- _{n-C 4 H 9) Cl} 2, VO (OC 2 H 5) 3, VOBr 2, VCl 4, VOCl 2, VO (O-n-C 4 H 9) 3, VCl 3 · 2 (OC 8 H 17 OH) and the like. These vanadium compounds can be used alone or in combination.

Examples of electron donors that form adducts with the above-mentioned vanadium compounds include alcohols, phenols, ketones, aldehydes, carboxylic acids, esters of organic or inorganic acids, ethers, acid amides, acid anhydrides, and alkoxy. Examples include oxygen-containing electron donors such as silane, and nitrogen-containing electron donors such as ammonia, amine, nitrile, and isocyanate.

Examples of specific compounds that can be used as such an electron donor include methanol, ethanol, propanol, pentanol, hexanol, octanol, dodecanol, octadecyl alcohol, oleyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl. Alcohols having 1 to 18 carbon atoms such as alcohol, isopropyl alcohol and isopropylbenzyl alcohol; phenols having 6 to 20 carbon atoms such as phenol, cresol, xylenol, ethylphenol, propylphenol, nonylphenol, cumylphenol and naphthol; Phenols may have a lower alkyl group); acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, benzene C3-15 ketones such as zoquinone; C2-15 aldehydes such as acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde and naphthaldehyde; methyl formate, methyl acetate, ethyl acetate, vinyl acetate,
Propyl acetate, octal acetate, cyclohexyl acetate, ethyl propionate, methyl butyrate, ethyl valerate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, ethyl dichloroacetate, methyl methacrylate, ethyl crotonate, ethyl cyclohexanecarboxylate, benzoic Methyl acrylate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, methyl toluate, ethyl toluate, amyl toluate, ethyl ethyl benzoate, anisic acid Methyl, n-butyl maleate, diisobutyl methylmalonate, di-n-hexyl cyclohexenecarboxylate, diethyl nadicate, diisopropyl tetrahydrophthalate, diethyl phthalate, diisobutyl phthalate, Organic acid esters having 2 to 30 carbon atoms such as di-n-butyl luate, di-2-ethylhexyl phthalate, γ-butyrolactone, δ-valerolactone, coumarin, phthalide and ethylene carbonate; acetyl chloride, benzoyl chloride, toluic acid C2 to C15 acid halides such as chloride and anisic acid chloride; C2 to C20 ethers such as methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran and anisole and diphenyl ether; Acid amides such as benzoic acid amide and toluic acid amide; amines such as methylamine, ethylamine, diethylamine, tributylamine, piperidine, tribenzylamine, aniline, pyridine, picoline and tetramethylenediamine Nitriles such as acetonitrile, benzonitrile and tolunitrile; and alkoxysilanes such as ethyl silicate and diphenyldimethoxysilane. These electron donors can be used alone or in combination.

As the organoaluminum compound used here,
A compound having at least one Al-carbon bond in a molecule can be used.

Here, examples of the organoaluminum compound include: (i) a compound represented by the formula R ¹ _m Al (OR ² ) _{n Hp} X _q (where R ¹ and R ^{2 each} have the number of carbon atoms, usually 1 to 15, preferably 1 X is a halogen, m is 0 ≦ m ≦ 3, n
Is an organic aluminum compound represented by 0 ≦ n <3, p is a number of 0 ≦ n <3, and q is a number of 0 ≦ q <3, and m + n + p + q = 3). (Ii) Formula M ¹ AlR ¹ ₄ (where M ¹ is Li, Na, and K, and R ¹ has the same meaning as described above).

Specific examples of the organoaluminum compound represented by the above formula (i) include the compounds described below.

A compound represented by the formula R ¹ _m Al (OR ² ) _3-m, wherein R ¹ and R ² have the same meanings as described above, and m is preferably a number satisfying 1.5 ≦ m <3.

Formula R ¹ _m AlX _3-m (where R ¹ is as defined above, X is halogen, m
Is preferably 0 <m <3).

Formula R ¹ _m AlH _3-m (where R ¹ has the same meaning as described above, and m is preferably 2
≦ m <3).

Formula R ¹ _m Al (OR ² ) _n X _q (where R ¹ and R ² have the same meanings as above. X is a halogen, 0 <m ≦ 3, 0 ≦ n <3, 0 ≦ q <3. , M + n
+ Q = 3).

Specific examples of the organoaluminum compound represented by the above formula (i) include: trialkylaluminums such as triethylaminium and tributylaluminum; trialkylaluminums such as triisopropylaluminum; diethylaluminum ethoxide, dibutylaluminum butoxide and the like. Dialkylaluminum alkoxide; alkylaluminum sesquialkoxide such as ethylaluminum sesquiethoxide and butylaluminum sesquibutoxide; partially alkoxylated alkylaluminum having an average composition represented by formula R ¹ _2.5 Al (OR ² ) _0.5 ; Dialkylaluminum halides such as aluminum chloride, dibutylaluminum chloride and diethylaluminum bromide; Alkyl aluminum sesquihalides such as chloride, butyl aluminum sesquichloride and ethyl aluminum sesquibromide; partially halogenated alkyl aluminum such as alkyl aluminum dihalides such as ethyl aluminum dichloride, propyl aluminum dichloride and butyl aluminum dibromide; diethyl aluminum Partially hydrogenated alkylaluminums such as dialkylaluminum hydrides such as hydride and dibutylaluminum hydride, and alkylaluminum dihydrides such as ethylaluminum dihydride and propylaluminum dihydride; ethylaluminum ethoxycyclolide, butylaluminum butoxycyclolide, and ethylaluminum Partially alkoxylated and halogenated ethoxybromide Alkylaluminum.

The organoaluminum compound may be a compound similar to the compound represented by the formula (i), such as an organoaluminum compound in which two or more aluminum atoms are bonded via an oxygen atom or a nitrogen atom. Specific examples of such compounds include: Can be mentioned.

Examples of the organoaluminum compound represented by the above formula (ii) include LiAl (C ₂ H ₅ ) ₄ and LiAl (C ₇ H ₁₅ ) ₄ .

Of these, alkyl aluminum halides,
It is preferred to use an alkyl aluminum dihalide or a mixture thereof.

The amount of the above-mentioned vanadium compound to be used is usually 0.01 to 5 g atoms / vanadium atom, preferably
In the range of 0.05 to 3 gram atoms /. The amount of the organoaluminum compound used is expressed as a ratio of aluminum atoms to vanadium atoms (Al / V) in the polymerization reaction system (Al / V), 2 or more, preferably 2 to 50, and particularly preferably 3 to 50.
In the range of ~ 20.

The cyclic olefin random polymer (a) obtained by using the catalyst as described above usually has an ethylene component unit of 52
~ 90 mol%, preferably in the range of 55-80 mol%,
It contains a repeating unit derived from a cyclic olefin in the range of 10 to 48 mol%, preferably 20 to 45 mol%.
When the cyclic olefin random copolymer contains α-olefin component units other than the ethylene component unit, the content of the α-olefin component unit in the cyclic olefin random copolymer is usually 20 mol% or less, preferably
10 mol% or less.

In the cyclic olefin random copolymer used in the present invention, the repeating units derived from the ethylene component unit and the cyclic olefin are arranged substantially linearly, and further, these repeating units are randomly arranged. I have.

The cyclic olefin copolymer (a) used in the present invention has a repeating unit constituting an alicyclic structure represented by the following formula [II]
[I] or the following formula [IV].

However, in the above formulas [III] and [IV], m and n are 0 or a positive integer, 1 is an integer of 3 or more, and R ^{1 to} R ¹⁰ are each independently a hydrogen atom, a halogen atom and Represents one type of atom or group selected from the group consisting of hydrocarbon groups.

Amorphous or low-crystalline α-olefin formed from at least two kinds of α-olefins used in the present invention.
The graft copolymer (b) obtained by grafting an unsaturated carboxylic acid and its derivative to an olefin elastic copolymer has a tensile modulus of usually 0.1 kg / cm ^{2 to} 20000 kg / cm ² , preferably 10 kg / cm ^{2 to} 15000 kg. / cm ² range.

Further, the glass transition temperature (Tg) of such a graft copolymer (b) is usually -150 to + 50 ° C, preferably -6.
It is in the range of 0 to -35 ° C. Further, the intrinsic viscosity [η] of the graft-modified α-olefin copolymer measured in decalin at 135 ° C. is 0.2 to 10 dl / g, preferably 1 to 5 dl.
/ g is desirable. The density is 0.82-0.96
g / cm ^3, it is desirable that preferably is 0.84~0.92g / cm ^3. Further, the degree of crystallinity of the graft-modified elastic copolymer measured by an X-ray diffraction method is usually 90% or less, preferably 25% or less, and the graft-modified elastic copolymer has low crystallinity or It is preferably amorphous.

By kneading with the above-mentioned cyclic olefin random copolymer (a), the above-mentioned graft copolymer (b)
Has the property that at least a part thereof is dispersed in the form of fine particles in the random copolymer of cyclic olefin.

When the graft copolymer (b) used in the present invention is a graft-modified α-olefin copolymer, specifically, such a graft-modified α-olefin copolymer includes (a) Examples thereof include a graft-modified ethylene / α-olefin copolymer rubber and (ii) a graft-modified propylene / α-olefin copolymer rubber. The above graft-modified ethylene α
The olefin copolymer rubber (a) and the graft-modified propylene / α-olefin copolymer rubber (b) can be used alone or in combination.

The α-olefin constituting the above-mentioned graft-modified ethylene / α-olefin copolymer rubber (a) is usually an α-olefin having 3 to 20 carbon atoms, for example, propylene, 1-butene, 1-pentene, 1- Hexene, 4-methyl-1-pentene, 1-octene, 1-decene and mixtures thereof can be mentioned. Of these, propylene and / or 1-butene are particularly preferred.

The α-olefin constituting the graft-modified propylene / α-olefin copolymer rubber (b) is usually an α-olefin having 4 to 20 carbon atoms, for example, 1-butene, 1-pentene, 1-hexene, -Methyl-1-pentene, 1-octene, 1-decene and mixtures thereof. Of these, 1-butene is particularly preferred.

Incidentally, the α-olefin copolymer used in the present invention may be an α-olefin copolymer such as a component unit derived from a diene compound, as long as the properties of the α-olefin copolymer are not impaired.
-It may contain a component unit other than a component unit derived from an olefin.

For example, the component units permitted to be contained in the α-olefin copolymer used in the present invention include 1,4-
Hexadiene, 1,6-octadiene, 2-methyl-1,5-
Hexadiene, 6-methyl-1,5-heptadiene, 7-
Chain non-conjugated dienes such as methyl-1,6-octadiene; cyclohexadiene, dicyclopentadiene, methyltetrahydroindene, 5-vinylnorbornene, 5-
Cyclic non-conjugated dienes such as ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2-norbornene, 6-chloromethyl-5-isopropylenyl-2-norbornene; 2,3-diisopropylene Liden-5-norbornene, 2-
Component units derived from diene compounds such as ethylidene-3-isopropylidene-5-norbornene and 2-propenyl-2,2-norbornadiene can be mentioned. The content of such a diene component is usually 10 mol%.
Or less, preferably 5 mol% or less.

In the graft-modified ethylene / α-olefin copolymer (A) used in the present invention, the molar ratio of ethylene to α-olefin (ethylene / α-olefin) is α
-Although it depends on the type of olefin, it is generally 1/99 to
It is 99/1, preferably 50/50 to 95/5. The molar ratio is
When the α-olefin is propylene, 50/50 to 9
Preferably, the α-olefin has 4 carbon atoms.
In the case of the above α-olefin, the ratio is preferably 80/20 to 95/5.

Further, the graft-modified propylene α used in the present invention
-In the olefin copolymer (b), the molar ratio of propylene to α-olefin (propylene / α-olefin) varies depending on the type of α-olefin, but is generally 50/50 to 95/5. Is preferred. The molar ratio is 50/5 when the α-olefin is 1-butene.
It is preferably 0 to 90/10, and when the α-olefin has 5 or more carbon atoms, it is preferably 80/20 to 95/5.

In the present invention, among the above graft-modified α-olefin copolymers, an ethylene / propylene random copolymer or an ethylene / α-olefin random having an ethylene content of 35 to 50 mol% and a crystallinity of 10% or less is used. A copolymer obtained by graft-modifying a copolymer with a graft monomer is preferable because it is excellent in improving mechanical properties such as impact strength.

 Graft-modified α-olefin copolymer used in the present invention
Graft monomer used to produce coalescence (b)
-Unsaturated carboxylic acid or its derivative
It is preferred to use Of such unsaturated carboxylic acids
Examples include acrylic acid, maleic acid, fumaric acid,
Trahydrophthalic acid, itaconic acid, citraconic acid, black
Tonic acid, isocrotonic acid, nadic acid (Endosys-
Bicyclo [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 halide, unsaturated carboxylic amide,
Esters for saturated carboxylic imides and unsaturated carboxylic acids
Compounds. Ingredients for such derivatives
Typical examples are maleenyl chloride, maleimide,
Maleic acid, citraconic anhydride, monomethyl maleate,
Dimethyl maleate, glycidyl maleate
Can be.

These graft monomers can be used alone or in combination.

 Among the above graft monomers, unsaturated monomers
Rubonic acid or its anhydride is preferred,
Acid, nadic acid Or these acid anhydrides are particularly preferred.
New

The graft-modified α-olefin copolymer used in the present invention is produced, for example, by modifying the above-mentioned graft monomer and α-olefin copolymer by employing various conventionally known methods. Can be. For example, there is a method in which the α-olefin copolymer is melted and a graft monomer is added for graft polymerization, or a method in which the α-olefin copolymer is dissolved in a solvent and the graft monomer is added for graft copolymerization. Further, as a method for producing a graft-modified α-olefin copolymer, a method in which an unreacted α-olefin copolymer is modified by blending a graft monomer so as to have a desired graft modification rate, A graft-modified α-olefin copolymer having a desired modification ratio is prepared by diluting the high-modification α-olefin copolymer with an unmodified α-olefin copolymer. There is a method of manufacturing. In the present invention, a graft-modified olefin copolymer produced by any method can be used. And the graft-modified α used in the present invention
-The olefin copolymer has a modification ratio of usually 0.01 to 5
% By weight, preferably in the range of 0.1 to 4% by weight.

Such a reaction is preferably performed in the presence of a radical initiator in order to efficiently graft-copolymerize the graft monomer. The grafting reaction is usually performed at a temperature of 60 to 350 ° C. The usage ratio of the radical initiator is usually in the range of 0.001 to 5 parts by weight based on 100 parts by weight of the unmodified α-olefin elastic copolymer.

As the radical initiator, organic peroxides and organic peresters are preferably used. Specific examples of such radical initiators include benzoyl peroxide,
Dichlorobenzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-
2,5-di (peroxidebenzoate) hexyne-3,
1,4-bis (tert-butylperoxyisopropyl) benzene, lauroyl peroxide, tert-butylperacetate, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3,2,5-dimethyl- 2,5-di (tert
-Butylperoxy) hexane, tert-butylperbenzoate, tert-butylperphenylacetate, tert
-Butyl perisobutyrate, tert-butyl per-sec
-Octoate, tert-butyl perpivalate, cumyl perpivalate and tert-butyl perdiethyl acetate. Furthermore, in the present invention, an azo compound can be used as a radical initiator,
Specific examples of the azo compound include azobisisobutyronitrile and dimethylazoisobutyrate.

Among them, benzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3,2,5-dimethyl are used as radical initiators. −2,5−
Di (tert-butylperoxy) hexane, 1,4-bis (t
Dialkyl peroxides such as (ert-butylperoxyisopropyl) benzene are preferably used.

The graft-modified α-olefin copolymer used in the present invention usually comprises the above-mentioned graft-modified ethylene / α-olefin copolymer (a) and the graft-modified propylene / α-olefin copolymer (b) alone. Or a combination thereof, but the above-mentioned graft-modified elastic copolymer is used as another polymer or copolymer or another graft copolymer within a range not to impair the properties of the graft-modified α-olefin elastic copolymer. May be included.

In the present invention, examples of such another polymer or copolymer include an aromatic vinyl hydrocarbon / conjugated diene copolymer or a hydride thereof.
Specifically, such an aromatic vinyl hydrocarbon / conjugated diene copolymer or its hydride is styrene
Butadiene copolymer rubber, styrene / butadiene / styrene copolymer rubber, styrene / isoprene block copolymer rubber, styrene / isoprene / styrene block copolymer rubber, hydrogenated styrene / butadiene / styrene block copolymer rubber and water A styrene / isoprene / styrene block copolymer rubber can be used.

In the present invention, the cyclic olefin random copolymer (a) and the graft copolymer (b) as described above are 99: 1
It is blended in a weight ratio within the range of ~ 1: 99. By blending both in such a ratio, a resin composition having improved mechanical properties such as impact strength can be obtained without impairing the excellent properties of the cyclic olefin random copolymer (a). Furthermore, by blending both at a weight ratio within the range of 95: 5 to 80:20, the impact strength is particularly improved while appropriately maintaining the rigidity of the obtained polyolefin resin composition.

When the graft copolymer (b) is blended with the cyclic olefin random copolymer (a) in this manner, the graft copolymer (b) is not uniformly dissolved in the cyclic olefin random copolymer (a). At least a part of the graft copolymer (b) is dispersed in the cyclic olefin random copolymer (a) in the form of fine particles.

Further, by blending the amino group-containing compound (c) having two or more amino groups in the molecule, the dispersed particle diameter of the graft copolymer (b) tends to be small. Finely dispersing also improves mechanical properties such as impact strength of the polyolefin resin composition of the present invention.

Examples of such an amino group-containing compound (c) include ethylenediamine, propylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, iminobispropylamine, bis (hexamethylene) triamine, 1,3 ,
Aliphatic amines such as 6-trisaminomethylhexane, trimethylhexamethylenediamine, diethylene glycol, bispropylenediamine, diethylaminopropylamine, mensendiamine, isophoronediamine, bis (4
-Amino-3-methylcyclohexyl) methane, N-aminoethylpiperazine, alicyclic amines such as 1,3-diaminocyclohexane, aliphatic aromatic amines such as meta-xylylenediamine, o-, m-, p-phenylenediamine , Diaminodiphenylmethane, diaminodiphenylsulfone, 2,4-diaminoanisole, 2,4-toluenediamine, 2,4-diaminodiphenylamine, 4,4'-methylenedianiline,
Examples thereof include aromatic amines such as diaminodixylyl sulfone, and bisspirocyclic diamines such as 3,9-bis (3-aminopropyl) -2,4,8,10-tetraspiro [5,5] undecane.

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

Among such amino group-containing compounds (c), hexamethylenediamine is particularly preferably used.

The amount of the amino group-containing compound (c) blended in the polyolefin resin composition of the present invention is appropriately set in consideration of the graft ratio of the graft monomer in the graft copolymer and the amount of the graft copolymer in the composition. The amount is usually 0.01 to 10 parts by weight, preferably 0.2 to 2 parts by weight, per 100 parts by weight of the graft copolymer (b).

Further, the polyolefin resin composition of the present invention, in addition to the above components, an inorganic filler, an organic filler, a heat stabilizer, a weather resistance stabilizer, an antistatic agent, an anti-slip agent, an anti-blocking agent, and an anti-fog agent And additives such as lubricants, pigments, dyes, natural oils, synthetic oils and waxes.

The polyolefin resin composition of the present invention can be produced using a known method. For example, a cyclic olefin random copolymer (a) and a graft copolymer (b)
, A mixture of the cyclic olefin random copolymer and the graft-modified elastic copolymer (b) is melt-kneaded, and the kneaded product is further kneaded with an amino group-containing compound (c). And a cyclic olefin random copolymer (a) and a graft copolymer (b)
Is dissolved in a suitable solvent, for example, a saturated hydrocarbon solvent such as heptane, hexane, decane and cyclohexane, and an aromatic hydrocarbon solvent such as toluene, benzene and xylene, and the amino group-containing compound (c) is added to the solution. It can be produced by mixing, mixing and removing the solvent by a conventional method.

Thus, the polyolefin resin composition of the present invention containing the cyclic olefin random copolymer (a), the graft copolymer (b), and the amino group-containing compound (c) has a softening temperature (TM) measured by a thermal mechanical analyzer.
A) is usually in the range of 50-200 ° C, preferably 100-180 ° C.

The polyolefin resin composition of the present invention may be used for ordinary polyolefins, for example, filler-reinforced PP, ABS
The resin and modified polyphenylene oxide can be preferably used in applications requiring particularly high mechanical strength, such as those in which a modified polyphenylene oxide is used.

Effects of the Invention Since the polyolefin resin composition of the present invention contains the cyclic olefin random copolymer (a) and the graft copolymer (b) at a predetermined ratio, and further contains the amino group-containing compound (c), The properties of the graft copolymer (b) are improved, and the particle size of the graft copolymer (b) in the composition is reduced. And the particles of such a graft copolymer (b) are less likely to be deformed during molding.

Therefore, as compared with the case where the amino group-containing compound (c) is not used, mechanical properties such as impact strength are remarkably improved. Then, such excellent mechanical properties hardly lower other excellent properties.

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] The properties of the cyclic olefin random copolymer and the graft copolymer (also referred to as a graft-modified elastic copolymer) used in the present invention and the properties of the polyolefin resin composition of the present invention were measured as follows.

Intrinsic viscosity [η] Measured in decalin at 135 ° C.

Softening temperature (TMA) Heating rate 5 ° C / min Weight 50g, T is the temperature at which a flat-bottom needle with a diameter of 1mm enters 100μm.
MA.

Graft monomer content in the graft-modified elastic copolymer Measured by ¹³ C-NMR.

Crystallinity Measured by X-ray diffraction at 23 ° C.

Tensile modulus According to ASTM D 638, using a 2 mm thick pressed test piece
Measured at ° C.

IZ Impact Strength Measured at 23 ° C. using a 1/8 inch thick notched injection test piece according to ASTM D256.

Initial flexural modulus (FM) Measured at 23 ° C. at a crosshead speed of 20 mm / min using a 1/8 inch thick injection test specimen according to ASTM D790.

Flexural yield stress (FS) Measured in the same manner as FM according to ASTM D790.

Gloss According to ASTM D 523, a 2 mm thick exit square plate is used, and the incident angle is 60
゜, measured at 23 ° C.

Resin density Measured at 23 ° C. according to ASTM D-1505-67.

Example of Polymerization (Synthesis of Cyclic Olefin Copolymer (A)) Ethylene and 1,4,5,8-dimetano-1,2,3, 4,4a, 5,8,8a
Octahydronaphthalene (structural formula: (Hereinafter abbreviated as DMON)). That is, from the top of the polymerization vessel, a cyclohexane solution of DMON was added to VO (OC ₂ H ₅ ) Cl ₂ with a DMON concentration of 60 g / catalyst in the polymerization vessel.
Are continuously fed into the polymerization reactor such that the vanadium concentration in the polymerization reactor becomes 7.2 mmol /, while the polymerization liquid in the polymerization reactor becomes 1 from the lower part of the polymerization reactor. Extracted continuously. Further, from the top of the polymerization vessel, ethylene was fed at 85 / hour, hydrogen was fed at 6 / hour, and nitrogen was fed at 45 / hour. The copolymerization reaction was performed at 10 ° C. by circulating a refrigerant through a jacket attached to the outside of the polymerization.

When copolymerization was carried out under the above reaction conditions, a polymerization reaction mixture containing an ethylene / DMON random copolymer was obtained. A small amount of isopropyl alcohol was added to the polymerization liquid extracted from the lower part of the polymerization vessel to stop the polymerization reaction. Thereafter, the polymerization liquid is introduced into the household mixer containing about three times the amount of acetone with respect to the polymerization liquid while rotating the mixer,
The resulting copolymer was precipitated. The precipitated copolymer was collected by filtration, dispersed in acetone so that the polymer concentration became about 50 g /, and the copolymer was treated at the boiling point of acetone for about 2 hours. After the treatment described above, the copolymer was collected by filtration and dried under reduced pressure at 120 ° C. for one day.

The ethylene composition of the ethylene / DMON random copolymer (A) obtained as described above was determined by ¹³ C-NMR analysis to be 67 mol%, and the intrinsic viscosity [η] measured in decalin at 135 ° C. ] Was 0.60 dl / g, and softening temperature (TMA) was 111 ° C.

Examples 1 to 5 The ethylene / DMON random copolymer (A) obtained in the polymerization example and the graft-modified elastic copolymer (B) shown in Table 1
Were dry-blended with the weight composition shown in Table 1 and kneaded with a twin-screw extruder (a set temperature of 210 ° C.).
(B) Hexamethylenediamine (HMDA) was added at the ratio shown in Table 1 to 100 parts by weight of the blend, and
The mixture was kneaded and extruded with a screw extruder (set temperature 210 ° C.) to obtain a polyolefin resin composition.

This composition was subjected to injection molding under the conditions of a cylinder temperature of 230 ° C. and a mold temperature of 60 ° C. to obtain a test piece and a square plate. Table 1 shows these physical properties.

By doing so, a polyolefin resin composition excellent in impact strength, rigidity, and gloss was obtained.

Comparative Example 1 The ethylene / DMON random copolymer (A) obtained in the polymerization example and the graft-unmodified elastic copolymer (B) shown in Table 1 were dry-blended at a weight ratio of 95/15, After kneading with a screw extruder (set temperature 210 ° C), (A) /
(B) 0.2 parts by weight of HMDA was added to 100 parts by weight of the blend, and the mixture was kneaded and extruded again with a twin-screw extruder (set temperature: 210 ° C.) to obtain a polyolefin resin composition.

This composition was molded and evaluated in the same manner as in Examples 1 to 5. Table 1 shows the physical properties.

The composition thus obtained was excellent in rigidity and gloss, but had low impact strength.

COMPARATIVE EXAMPLE 2 The ethylene-simolamami random copolymer (A) obtained in the polymerization example and the graft-modified elastic copolymer (B) shown in Table 1 were dry-blended in a weight composition of 85/15, and this was mixed with 2 The mixture was kneaded twice with a screw extruder (set temperature 210 ° C.) to obtain a polyolefin resin composition.

This composition was molded and evaluated in the same manner as in Examples 1 to 5. Table 1 shows the physical properties.

The composition thus obtained was excellent in rigidity and gloss, but had low impact strength.

Examples 6 to 8 Table 1 shows the cyclic olefin random copolymer (A) shown in Table 1 and the graft-modified elastic copolymer (B) shown in Table 1 obtained by a method similar to the polymerization examples. Dry blending at the specified weight composition and this is a twin screw extruder (set temperature 210 ° C)
HMDA was added at a ratio of 0.2 parts by weight to 100 parts by weight of the (A) / (B) blend, and kneaded and extruded with a twin-screw extruder to obtain a polyolefin resin composition.

This composition was molded and evaluated by the methods shown in Examples 1 to 5. Table 1 shows the physical properties.

By doing so, a polyolefin resin composition having excellent impact strength, rigidity, and gloss was obtained.

Examples 9 to 10 Cyclic olefin random copolymer (A) shown in Table 1
And the graft-modified elastic copolymer (B) were dry-blended in a weight composition of 85/15, and this was mixed with a twin-screw extruder (set temperature 21).
After kneading at 0 ° C.), 4,4′-diaminotriphenylmethane was added to 100 parts by weight of the (A) / (B) blend at the ratio shown in Table 1, and again a twin-screw extruder ( Set temperature 21
(0 ° C.), and kneaded and extruded to obtain a polyolefin resin composition.

This composition was molded and evaluated in the same manner as in Examples 1 to 5. Table 1 shows the physical properties.

By doing so, a polyolefin resin composition having excellent impact strength, rigidity, and gloss was obtained.

Comparative Example 3 Cyclic olefin random copolymer (A) shown in Table 1
And the graft-unmodified elastic copolymer (B) are dry-blended in a weight composition of 85/15, and are twin-screw extruder (set temperature 210 ° C)
After kneading, 0.2 parts by weight of HMDA is added to 100 parts by weight of the (A) / (B) blend, and the mixture is kneaded and extruded again with a twin-screw extruder (set temperature 210 ° C.) to obtain a polyolefin resin composition. I got

This composition was molded and evaluated in the same manner as in Examples 1 to 5. Table 1 shows the physical properties.

The composition thus obtained was excellent in rigidity and gloss, but a polyolefin resin composition having low impact strength was obtained.

Comparative Example 4 Cycloolefin random copolymer (A) shown in Table 1
And the graft-unmodified elastic copolymer (A) are dry blended at a weight composition of 85/15, and are twin-screw extruder (set temperature 210 ° C)
And kneaded twice to obtain a polyolefin resin composition.

This composition was molded and evaluated in the same manner as in Examples 1 to 5. Table 1 shows the physical properties.

By doing so, a polyolefin resin composition having excellent rigidity and gloss but low impact strength was obtained.

Examples 11 to 14 The cyclic olefin random copolymers (A) shown in Table 1
And the graft-modified elastic copolymer (B) shown in Table 1
After dry-blending with a weight composition of 5 and kneading it with a twin-screw extruder (set temperature 210 ° C.), this (A) / (B)
HMDA was added to 100 parts by weight of the blend at the ratio shown in Table 1, and the mixture was kneaded again with a twin-screw extruder to obtain a polyolefin resin composition.

This composition was molded and evaluated in the same manner as in Examples 1 to 5. Table 1 shows the physical properties.

By doing so, impact strength, rigidity, gloss,
A polyolefin resin composition having excellent heat resistance was obtained.

Comparative Examples 5 to 6 The cyclic olefin random copolymer (A) shown in Table 1 and the graft-modified elastic copolymer (B) shown in Table 1 were mixed at 85/15.
Dry blend with the weight composition of
The mixture was kneaded to obtain a polyolefin resin composition.

This composition was molded and evaluated in the same manner as in Examples 1 to 5. Table 1 shows the physical properties.

The composition thus obtained was excellent in rigidity, gloss and heat resistance, but had low impact strength.

Examples 15-16 Cyclic olefin random copolymers (A) shown in Table 1
And the graft-modified elastic copolymer (B) shown in Table 1
After dry-blending with a weight composition of 5 and kneading it with a twin-screw extruder (set temperature 210 ° C.), this (A) / (B)
0.2 parts by weight of HMDA was added to 100 parts by weight of the blend, and kneaded again with a twin-screw extruder to obtain a polyolefin resin composition.

This composition was molded and evaluated in the same manner as in Examples 1 to 5. Table 1 shows the physical properties.

By doing so, impact strength, rigidity, gloss,
A polyolefin resin composition having excellent heat resistance was obtained.

Comparative Examples 7 and 8 Cycloolefin random copolymer (A) shown in Table 1
And the graft-modified elastic copolymer (B) were dry-blended at a weight composition of 85/15 and kneaded twice with a twin-screw extruder, and then this composition was treated in the same manner as in Examples 1 to 5. Molded and evaluated. Table 1 shows the physical properties.

The composition obtained in this way has rigidity,
Although excellent in gloss and heat resistance, impact strength was low.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI // (C08L 23/08 23:26) (C08L 23/08 51:06) (C08L 23/26 23:08) (C08L 51 / 06 23:08) (58) Field surveyed (Int.Cl. ⁶ , DB name) C08L 23/08 C08L 23/26 C08L 51/06 C08K 5/17-5/19 C08K 5/41

Claims (2)

(57) [Claims] (A) 52 to 90 mol% of an ethylene component unit and 10 to 48 mol% of a component unit derived from a cyclic olefin represented by the following formula [I] and / or [II] (wherein, cyclic olefin random And the intrinsic viscosity [η] measured in decalin at 130 ° C. is in the range of 0.05 to 10 dl / g. (B) a graft copolymer obtained by grafting an unsaturated carboxylic acid and a derivative thereof to an amorphous or low-crystalline α-olefin elastic copolymer formed from at least two kinds of α-olefins; c) an amino group-containing compound having two or more amino groups in the molecule, the compounding amount of the amino group-containing compound being:
The weight ratio of the component (a) to the component (b) is in the range of 99: 1 to 1:99 with respect to 100 parts by weight of the graft copolymer (b). A polyolefin resin composition; (In the above formulas [I] and [II], m and n are 0 or a positive integer, 1 is an integer of 3 or more, and R ^{1 to} R ¹⁰ are each independently a hydrogen atom, a halogen atom, And one kind of atom or group selected from the group consisting of hydrocarbon groups.) Wherein the graft copolymer (b) a tensile modulus of 0.1 kg / cm ² or more 20000 kg / cm ² polyolefin resin composition of claim 1 wherein claims, characterized in that less.