JPH04226147A - Polyolefin resin composition - Google Patents

Abstract

PURPOSE:To obtain the title composition improved in mechanical properties such as impact strengths by mixing a specified cycloolefin resin with an elastomer grafted with an unsaturated carboxylic acid (derivative) and an amino compound. CONSTITUTION:100 pts.wt. title composition is obtained by mixing 50-95 pts.wt. cycloolefin resin which is a random cycloolefin copolymer comprising units of an ethylene component and units derived from a cycloolefin of the formula [wherein (n) and (q) are each H, halogen or a hydrocarbon group; and R<15> to R<18> are bonded to each other to form a double bond-containing monocyclic or polycyclic group; R<15> and R<16> or R<17> and R<18> are bonded to each other to form alkylidene] and/ or a ring opening (co)polymer of a cycloolefin of the formula or a hydrogenation product thereof), 1-50 pts.wt. elastomer grafted with an unsaturated carboxylic acid (derivative) and having a modulus (at 23 deg.C) of 0.1-2000kg/cm<3>, and 0.01-45 pts.wt. amino compound.

Description

[Detailed description of the invention]

0001

TECHNICAL FIELD OF THE INVENTION The present invention relates to a polyolefin resin composition containing a cyclic olefin resin and a graft-modified elastomer and having excellent impact resistance.

0002

Technical Background of the Invention Conventionally used polyolefins are resins with excellent chemical resistance and solvent resistance, but when their crystallinity is low, they do not have sufficient rigidity and heat resistance. I can't say that there is.

[0003] For this reason, in order to improve the heat resistance and rigidity of polyolefin, a method of adding a nucleating agent or a method of gradually cooling the polyolefin in a molten state to increase the degree of crystallinity has been adopted. It is hard to say that the effect is sufficient.

[0004] Apart from such conventional polyolefins, copolymers obtained by reacting ethylene with bulky monomers have superior properties such as heat resistance compared to conventional polyolefins. It has been reported (for example, see US Pat. No. 2,883,372 and Japanese Patent Publication No. 14910/1983).

[0005] A cyclic olefin random copolymer obtained by using a specific cyclic olefin as a bulky monomer and copolymerizing this cyclic olefin with ethylene has excellent heat resistance, heat aging resistance, solvent resistance, and dielectric properties. Based on the knowledge that it has excellent properties and rigidity, the applicant has already filed applications for random copolymers using specific cyclic olefins (Japanese Patent Laid-Open No. 60-168708 and Japanese Patent Application No. No. 59-220550, No. 59-2368
No. 28, No. 59-236829, No. 59-24233
6 and 61-95906).

[0006]

OBJECTS OF THE INVENTION The object of the present invention is to further improve the mechanical properties such as impact strength of a resin composition containing a cyclic olefin resin as described above.

More specifically, it is an object of the present invention to provide a cyclic olefin resin-containing resin composition that has further improved mechanical properties, particularly impact strength, without impairing the excellent properties of the cyclic olefin resin. It is said that

[0008]

SUMMARY OF THE INVENTION The polyolefin resin composition according to the present invention comprises (a) a cyclic olefin random copolymer (a- 1) and/or a ring-opening polymer or ring-opening copolymer of a cyclic olefin represented by the following formula [I], or a hydrogenated product thereof (a-2), and (b) a tensile modulus at 23 ° C. 0.
an elastomer graft-modified with an unsaturated carboxylic acid and its derivatives, the weight of which is 1 to 2000 kg/cm2;
(c) a compound having one amino group in the molecule, and the amount of component (a) in the total of 100 parts by weight of components (a), (b) and (c) is 50 to 9
5 parts by weight, the amount of component (b) is 1 to 50 parts by weight, and (c
) The amount of the component is within the range of 0.01 to 45 parts by weight.

[0009]

[Case 2]

...[I] However, in the above formula [I], n is 0 or 1, m is 0 or a positive integer, q is 0 or 1, and R1 to R18 and Ra and Rb are , each independently represents an atom or group selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group, and R15 to R1
8 may be bonded to each other to form a monocyclic or polycyclic group, and the monocyclic or polycyclic group may have a double bond, and R15 and R16 may , or R1
7 and R18 may form an alkylidene group.

Since the polyolefin resin composition of the present invention is formed from a cyclic olefin resin (a), a graft-modified elastomer (b), and a compound (c) having one amino group in the molecule, A molded article with improved mechanical properties such as impact strength and surface gloss can be obtained without impairing the excellent properties of the cyclic olefin resin.

0012

DETAILED DESCRIPTION OF THE INVENTION Next, the polyolefin resin composition of the present invention will be explained in detail. The polyolefin resin composition according to the present invention is a composition formed from a cyclic olefin resin (a), a graft-modified elastomer (b), and a specific amino group-containing compound (c).

The component (a) used in the present invention, that is, the cyclic olefin resin, is (a-1) a cyclic resin consisting of an ethylene component unit and a component unit derived from a cyclic olefin represented by the following formula [I]. olefin random copolymer and (a-2) a ring-opening polymer or ring-opening copolymer of a cyclic olefin represented by the following formula [I], or a hydrogenated product thereof (these can be combined into a cyclic olefin ring-opening polymer or a ring-opening copolymer thereof) (sometimes referred to as a hydrogenated ring-opening polymer), these can be used alone or in combination with different polymers or copolymers.

[0014]

[Chemical formula 3]

[I] However, in the above formula [I], n is 0 or 1, m is 0 or a positive integer, and q is 0 or 1.

[0016] Furthermore, R1 to R18 and Ra and R
b each independently represents an atom or group selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group. Here, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. In addition, examples of the hydrocarbon group include, each independently, an alkyl group having 1 to 20 carbon atoms and a cycloalkyl group having 3 to 15 carbon atoms. Specific examples of the alkyl group include , methyl group, ethyl group,
Propyl group, isopropyl group, amyl group, hexyl group,
Mention may be made of octyl, decyl, dodecyl and octadecyl groups. Moreover, a cyclohexyl group can be mentioned as a specific example of the cycloalkyl group.

Furthermore, in the above formula [I], R15 and R16, R17 and R18, and further R15 and R1
7, R16 and R18, R15 and R18, or R16 and R17 may each bond (jointly with each other) to form a monocyclic or polycyclic group, and this The monocyclic or polycyclic group thus formed may have a double bond.

[0018] Furthermore, R15 and R16, or R17
and R18 may form an alkylidene group. Such alkylidene groups usually have 2 to 20 carbon atoms.
is an alkylidene group, and specific examples of such alkylidene groups include ethylidene group, propylidene group, and isopropylidene group.

[0019] Such a cyclic olefin resin has 13
The intrinsic viscosity [η] measured in decalin at 5°C is 0.3
~2.0dl/g, preferably 0.4~1.2
It is within the range of dl/g. In addition, the softening temperature (TMA) of this cyclic olefin resin measured with a thermal mechanical analyzer is usually 70 to 200.
℃, preferably within the range of 100 to 180℃, and furthermore, the glass transition temperature (Tg) is usually 50 to 180℃.
within the range of 190°C, preferably within the range of 80 to 170°C, and the crystallinity measured by X-ray diffraction is usually within the range of 0 to 20%, preferably within the range of 0 to 2%. It is in.

The cyclic olefin represented by the above formula [I] can be easily produced by condensing a cyclopentadiene with a corresponding olefin or an equivalent cyclic olefin using a Diels-Alder reaction. can.

Specifically, the cyclic olefin represented by the above formula [I] used in the present invention includes bicyclo[2.2.1]hept-2-ene derivatives, tetracyclo[4.4.0. 12,5.17,10]-3-dodecene derivative, hexacyclo[6.6.1.13,6.1
10,13.02,7.09,14]-4-heptadensene derivative, octacyclo[8.8.0.12,9.1
4, 7.111, 18.113, 16.03, 8.01
2,17]-5-docosene derivative, pentacyclo[6.
6.1.13,6.02,7.09,14]-4-hexadecene derivative, heptacyclo-5-icosene derivative,
Heptacyclo-5-heneicosene derivatives, tricyclo[4.3.0.12,5]-3-decene derivatives, tricyclo[4.3.0.12,5]-3-undecene derivatives, pentacyclo[6.5.1 .13, 6.02, 7.0
9,13]-4-pentadecene derivative, pentacyclopentadecadiene derivative, pentacyclo[4.7.0.1
2,5.08,13.19,12]-3-pentadecene derivative, pentacyclo[7.8.0.13,6.02,
7.110, 17.011, 16.112, 15]-4
- eicosene derivatives, and nonacyclo[9.10.1
．． 1.4.7.03, 8.02, 10.012, 21.
113,20.014,19.115,18]-5-pentacocene derivatives.

Specific examples of such compounds are shown below.

[0023]

[C4]

[0024]

[C5]

[0025]

[C6]

[0026]

[C7]

[0027]

[Chemical formula 8]

[0028]

[Chemical formula 9]

[0029]

[Chemical formula 10]

[0030]

[Chemical formula 11]

[0031]

[Chemical formula 12]

[0032]

[Chemical formula 13]

[0033]

[Chemical formula 14]

[0034]

[Chemical formula 15]

[0035]

[Chemical formula 16]

[0036]

[Chemical formula 17]

[0037]

[Chemical formula 18]

[0038]

[Chemical formula 19]

[0039]

[C20]

[0040]

[C21]

First, in the present invention, a cyclic olefin resin (a
Cyclic olefin random copolymer (
A-1) will be explained. In the present invention, the cyclic olefin random copolymer (a-1) used as the cyclic olefin resin (a) is, for example, mixed with ethylene in the liquid phase in the presence of a catalyst and expressed by the above formula [I]. It can be obtained by copolymerizing with unsaturated monomers.

In the present invention, the monomer copolymerized with the cyclic olefin compound represented by the above formula [I] to constitute the cyclic olefin random copolymerization (a-1) is ethylene. However, in addition to ethylene, other olefin compounds may be copolymerized in the cyclic olefin random copolymer used in the present invention.

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] include propylene, 1-butene, and 4-methyl-1-pentene. ,1
- α-olefins having 3 to 20 carbon atoms such as hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and 1-eicosene; cyclopentene, cyclohexene, 3
-methylcyclohexene, cyclooctene and 3a,
5,6,7a-tetrahydro-4,7-methano-1H-
Cycloolefins such as indene; 1,4-hexadiene, 4-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-2, 5-chloronorbornene-2, 2-fluoronorbornene -2 and 5,6-dichloronorbornene-2
Examples include norbornenes such as

The reaction between ethylene and the cyclic olefin represented by formula [I] is usually carried out in a hydrocarbon solvent. Hydrocarbon solvents used here include, for example, aliphatic hydrocarbons such as hexane, heptane, octane and kerosene; alicyclic hydrocarbons such as cyclohexane and methylcyclohexane; aromatic hydrocarbons such as benzene, toluene and xylene. be able to. Furthermore, among the polymerizable unsaturated monomers that can be used in the preparation of the cyclic olefin random copolymer, compounds that are liquid at the reaction temperature can also be used as the reaction solvent. These solvents can be used alone or in combination.

Examples of the catalyst used in the reaction between the above olefin and the cyclic olefin represented by formula [I] include catalysts comprising a vanadium compound and an organoaluminum compound that are soluble in the hydrocarbon solvent used as the reaction solvent. Examples of the vanadium compound used as a catalyst here include a compound represented by the formula VO(OR)aVb or the formula V(OR)cXd. 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, and 3≦c+d≦4.

Furthermore, the vanadium compound may be an electron donor adduct of the vanadium compound represented by the above formula. Examples of these vanadium compounds include VOCs
l3, VO (OC2H5) Cl2, VO (OC2H5)
2Cl, VO(O-iso-C3H7)Cl2, VO(
O-n-C4H9)Cl2, VO(OC2H5)3, V
OBr2, VCl4, VOCl2, VO(O-n-C4
Examples include vanadium compounds such as H9)3 and VCl3.2 (OC8H17OH). These vanadium compounds can be used alone or in combination.

Examples of electron donors that form adducts with the above vanadium compounds include alcohols, phenols, ketones, aldehydes, carboxylic acids, esters of organic or inorganic acids, ethers, acid amides, and acid anhydrides. thing,
Oxygen-containing electron donors such as alkoxysilane, ammonia,
Nitrogen-containing electron donors such as amines, nitriles, and isocyanates can be mentioned.

Examples of specific compounds used as such electron donors include methanol, ethanol,
Propanol, pentanol, hexanol, octanol, dodecanol, octadecyl alcohol, oleyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol, isopropyl alcohol and isopropylbenzyl alcohol, etc. with 1 or more carbon atoms
18 alcohols; phenols having 6 to 20 carbon atoms such as phenol, cresol, xylenol, ethylphenol, propylphenol, nonylphenol, cumylphenol, and naphthol (these phenols may have a lower alkyl group) ; C3-15 such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, benzoquinone, etc.
Ketones; aldehydes having 2 to 15 carbon atoms such as acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde and naphthaldehyde; methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate , ethyl propionate, methyl butyrate, ethyl valerate,
Methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, ethyl dichloroacetate, methyl methacrylate, ethyl crotonate, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, benzoate Cyclohexyl acid, phenyl benzoate, benzyl benzoate, methyl toluate, ethyl toluate, amyl toluate, ethyl ethylbenzoate, methyl anisate, n-butyl maleate, diisobutyl methylmalonate, di-n-hexyl cyclohexenecarboxylate , diethyl nazic acid, diisopropyl tetrahydrophthalate, diethyl phthalate, diisobutyl phthalate, di-n-butyl phthalate, di-2-ethylhexyl phthalate, γ-butyrolactone, δ-valerolactone, coumarin, phthalide, and carbon such as ethylene carbonate. Organic acid esters having 2 to 30 carbon atoms; acid halides having 2 to 15 carbon atoms such as acetyl chloride, benzoyl chloride, toluyl chloride and anisyl chloride; methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran , anisole, diphenyl ether, etc. with 2 carbon atoms
-20 ethers; acid amides such as acetic acid amide, 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 tolnitrile; Alkoxysilanes such as ethyl silicate and diphenyldimethoxysilane. These electron donors can be used alone or in combination.

As the organic aluminum compound used here, a compound having at least one Al-carbon bond in the molecule can be used. Here, examples of organoaluminum compounds include (i) formula R1mAl(OR2)nHpXq (where R1 and R2 are hydrocarbon groups containing the number of carbon atoms, usually 1 to 15, preferably 1 to 4, These may be the same or different. X is halogen, m is 0≦m
≦3, n is 0≦n<3, p is 0≦n<3, q is 0≦q<
3, and m+n+p+q=3), (ii) an organoaluminum compound represented by the formula M1AlR14 (where M1 is Li, N
a, K, and R1 has the same meaning as above), complex alkylation products of Group 1 metals and aluminum can be mentioned.

Specific examples of the organoaluminum compound represented by the above formula (i) include the compounds described below. Formula R1mAl(OR2)3-m (where R1 and R2 have the same meanings as above, and m is preferably 1.
5≦m<3).

Formula R1mAlX3-m (where R
1 has the same meaning as above, X is halogen, and m preferably satisfies 0<m<3. A compound represented by the formula R1mAlH3-m (wherein R1 has the same meaning as above and m preferably satisfies 2≦m<3).

Formula R1mAl(OR2)nXq (
Here, R1 and R2 have the same meanings as above. X is halogen, 0<m≦3, 0≦n<3, 0≦q<3, m+
n+q=3).

Specific examples of organoaluminum compounds represented by the above formula (ii) include trialkylaluminums such as triethylaluminum and tributylaluminium; trialkylaluminums such as triisopropylaluminum; diethylaluminium ethoxide and dibutylaluminum butoxide. dialkylaluminum alkoxides such as; alkylaluminum sesquialkoxides such as ethylaluminum sesquiethoxide and butylaluminum sesquibutoxide; partially alkoxylated alkylaluminums having an average composition of the formula R12.5Al(OR2)0.5, etc. dialkylaluminum halides such as diethylaluminum chloride, dibutylaluminum chloride and diethylaluminium bromide; alkylaluminum sesquihalides such as ethylaluminum sesquichloride, butylaluminum sesquichloride and ethylaluminum sesquibromide; ethylaluminum dichloride, propylaluminum dichloride and butylaluminum dichloride; partially halogenated alkyl aluminum dihalides such as alkyl aluminum dihalides such as bromide; dialkyl aluminum hydrides such as diethylaluminum hydride and dibutyl aluminum hydride; alkyl aluminum dihydrides such as ethyl aluminum dihydride and propyl aluminum dihydride; Mention may be made of partially hydrogenated alkyl aluminums, such as; partially alkoxylated and halogenated alkyl aluminums, such as ethylaluminum ethoxy chloride, butylaluminum butoxy chloride and ethylaluminum ethoxy bromide.

In addition, organoaluminum compounds have the formula (
It may also be a compound similar to the compound represented by ii). Specific examples of such compounds include (C2
H5)2AlOAl(C2H5)2, (C4H9)2A
IOAl(C4H9)2, (C2H5)2AlN(C6
H5) Al(C2H5)2 can be mentioned.

Further, as an example of the organoaluminum compound represented by the above formula (ii), LiAl(C2H5
)4 and LiAl(C7H15)4. Among these, it is particularly preferable to use alkyl aluminum halides, alkylaluminium dihalides, or mixtures thereof.

The amount of the vanadium compound used is usually in the range of 0.01 to 5 gram atoms/liter, preferably 0.05 to 3 gram atoms/liter, in terms of vanadium atoms. The amount of the organoaluminum compound to be used, expressed as the ratio of aluminum atoms to vanadium atoms in the polymerization reaction system (Al/V), is usually 2 or more, preferably 2 to 50, particularly preferably 3 to 20. It is in.

The cyclic olefin random polymer (a) obtained using the above-mentioned catalyst usually contains ethylene component units in the range of 52 to 90 mol%, preferably 55 to 80 mol%, and contains cyclic olefin units. It contains repeating units derived from olefins in an amount of 10 to 48 mol%, preferably 20 to 45 mol%. In addition, when the cyclic olefin random copolymer contains α-olefin component units other than ethylene component units, the content of this α-olefin component unit in the cyclic olefin random copolymer is usually 20 mol% or less, preferably It is 10 mol% or less.

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

The cyclic olefin resin (a) used in the present invention has a structure in which the repeating units constituting the alicyclic structure are represented by the following formula [II].

[0060]

[C22]

... [II] However, in the above formula [II], n is 0 or 1, m is 0 or a positive integer, q is 0 or 1, and R1 to R18 and Ra and Rb are , each independently represents an atom or group selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group, and R15 and R1
6, or R17 and R18 may each be combined to form a monocyclic or polycyclic group, and the monocyclic or polycyclic group may have a double bond. ,Also,
R15 and R16 or R17 and R18 may form an alkylidene group.

Next, in the present invention, cyclic olefin resin (a
) The cyclic olefin ring-opening polymer and hydrogenated ring-opening polymer (a-2) used as (a-2) will be explained. Among the cyclic olefin resins (a), the cyclic olefin ring-opening polymer (a-2) is, for example, a cyclic olefin represented by the above formula [I] combined with ruthenium, rhodium, palladium, osmium, indium, or platinum. A catalyst consisting of a metal halide, nitrate or acetylacetone compound and a reducing agent; titanium, palladium, zirconium,
Alternatively, it can be produced by (co)polymerizing a metal halide such as molybdenum or an acetylacetone compound with ring opening in the presence of a catalyst consisting of an organic aluminum.

It is considered that at least a part of the cyclic olefin represented by formula [I] in this cyclic olefin ring-opening polymer has a structure represented by [III].

[0064]

[C23]

... [III] In the above formula [III], R1 to R18, Ra
and Rb, and m, n and q have the same meanings as in formula [I].

Further, the hydrogenated product of the ring-opening polymer (hydrogenated ring-opening polymer) (a-2) is obtained by converting the cyclic olefin ring-opening polymer obtained as described above into the hydrogenated ring-opening polymer in the presence of a hydrogenation catalyst. It can be produced by reducing with hydrogen.

In this hydrogenated ring-opening polymer (a-2), at least a part of the cyclic olefin represented by formula [I] has a structure represented by [IV]. It is thought that there are.

[0068]

[C24]

[IV] In the above formula [IV], R1 to R18, Ra and Rb, and m, n and q have the same meanings as in formula [I].

[0070] Such a cyclic olefin resin (a) contains component (a) and component (b) constituting the resin composition of the present invention.
) and (c) in a total of 100 parts by weight, (a
) is blended in such an amount that the amount of the component falls within the range of 60 to 95 parts by weight. In particular, it is preferred that this amount be within the range of 60 to 85 parts by weight.

By blending component (a) in the above amount, a resin composition with improved mechanical properties such as impact strength can be obtained without impairing the excellent properties of the cyclic olefin resin (a). be able to.

The graft-modified elastomer (b) used in the present invention is a modified elastomer having a tensile modulus at 23°C in the range of 0.1 kg/cm2 to 2000 kg/cm2, preferably 1 kg/cm2 to 1500 kg/cm2. It is a polymer.

Further, the glass transition temperature (Tg) of such graft-modified elastomer (b) is usually -150 to
+50°C, preferably in the range of -80 to -20°C. Furthermore, the temperature of this graft-modified elastomer at 135°C,
The intrinsic viscosity [η] measured in decalin is usually 0.2
-10 dl/g, preferably 1-5 dl/g. In addition, its density is usually 0.82 to 0.96 g/cm3,
Preferably it is 0.84 to 0.92 g/cm3. Furthermore, the crystallinity of this graft-modified elastomer measured by X-ray diffraction is usually 30% or less, preferably 25% or less.

Various modified elastomers can be used as the graft-modified elastomer (b) used in the present invention, but this graft-modified elastomer (b) is a graft-modified α-olefin copolymer having the above characteristics. In this case, such graft-modified α-olefin copolymers include (a) graft-modified ethylene/α-olefin copolymer rubber, (b) graft-modified propylene/α-olefin An example is copolymer rubber. The above graft modified ethylene α
-Olefin copolymer rubber (a) and 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, such as propylene, 1-butene, 1-pentene. , 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene and mixtures thereof. Among 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, such as 1-butene, 1-pentene, 1- Mention may be made of hexene, 4-methyl-1-pentene, 1-octene, 1-decene and mixtures thereof. Among these, especially 1-
Butene is preferred.

[0077] The α-olefin copolymer used in the present invention may be made from α-olefins such as component units derived from diene compounds within a range that does not impair the properties of the α-olefin copolymer. It may contain component units other than the derived component units.

For example, the component units allowed to be included 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
- linear non-conjugated dienes such as heptadiene, 7-methyl-1,6-octadiene; cyclohexadiene, dicyclopentadiene, methyltetrahydroindene, 5-vinylnorbornene, 5-ethylidene-2-norbornene, 5-methylene-2 - norbornene, 5-isopropylidene-2-norbornene and 6-chloromethyl-5-
Cyclic non-conjugated dienes such as isopropenyl-2-norbornene; 2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene and 2-propenyl-2,2-norbornadiene; Component units derived from diene compounds; cyclic olefin components as described above can be mentioned. The content of such diene components is usually 10 mol% or less,
Preferably it is 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) varies depending on the type of α-olefin. Generally 10/90 to 90/10, preferably 50/50 to
It's 90/10. When the α-olefin is propylene, the above molar ratio is preferably 50/50 to 90/10, and the α-olefin has 4 or more carbon atoms.
- In the case of an olefin, the ratio is preferably 50/50 to 90/10.

In addition, in the graft-modified propylene/α-olefin copolymer (b) used in the present invention, the molar ratio of propylene to α-olefin (propylene/α-olefin
-olefin) is generally preferably 50/50 to 90/10, although it varies depending on the type of α-olefin. The above molar ratio is preferably 50/50 to 90/10 when the α-olefin is 1-butene, and 50/50 to 90/10 when the α-olefin has 5 or more carbon atoms. Preferably it is 10.

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

[0082] As the graft monomer used to produce the graft-modified elastomer (b) used in the present invention, it is preferable to use an unsaturated carboxylic acid or a derivative thereof. Examples of such unsaturated carboxylic acids include acrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, nadic acid TM (endocys-bicyclo[2,2,1 ] hept-5-ene-2,
3-dicarboxylic acid). Further, the derivatives of the unsaturated carboxylic acids mentioned above include unsaturated carboxylic 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, maleimide, maleic anhydride, citraconic anhydride, monomethyl maleate, dimethyl maleate, glycidyl maleate, glycidyl acrylate and glycidyl methacrylate.

These graft monomers can be used alone or in combination. Among the above-mentioned graft monomers, unsaturated dicarboxylic acids or their acid anhydrides are preferred, and maleic acid, nadic acid TM or their acid anhydrides, glycidyl methacrylate, and glycidyl acrylate are particularly preferred.

The graft-modified elastomer used in the present invention can be produced, for example, by modifying the above-mentioned graft monomer and α-olefin copolymer using various conventionally known methods. . For example, there is a method of melting the elastomer and adding a graft monomer to perform graft polymerization, or a method of dissolving the elastomer in a solvent and adding a graft monomer to perform graft copolymerization. Furthermore, methods for producing a graft-modified elastomer include a method in which an unmodified elastomer is modified by blending a graft monomer to achieve a desired graft modification ratio, and a method in which a graft-modified elastomer with a high graft modification ratio is prepared in advance and the There is a method of diluting an elastomer with a high modification rate with an unmodified elastomer to produce a graft-modified elastomer with a desired modification rate. In the present invention,
Graft-modified elastomers produced by either method can also be used. The graft-modified elastomer used in the present invention is a copolymer with a modification rate usually in the range of 0.01 to 5% by weight, preferably 0.1 to 4% by weight.

[0085] Such a reaction is preferably carried out in the presence of a radical initiator in order to efficiently graft copolymerize the graft monomer. The graft reaction is usually carried out at a temperature of 60 to 350°C. The proportion of the radical initiator used is usually in the range of 0.001 to 5 parts by weight per 100 parts by weight of the unmodified elastomer.

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-butyl peracetate, 2,5-dimethyl-2,5 -di(tert-butylperoxy)hexyne-3,2,5-dimethyl-2,5-di(tert-
butyl peroxy)hexane, tert-butyl perbenzoate, tert-butyl perphenylacetate, tert-butyl perisobutyrate, tert-butyl per-sec-octoate, tert-butyl perpivalate, cumyl perpivalate and tert-
Mention may be made of butyl perdiethyl acetate. Furthermore, in the present invention, an azo compound can also be used as a radical initiator, and specific examples of this azo compound include azobisisobutyronitrile and dimethylazoisobutyrate.

Among these, benzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-
2,5-di(tert-butylperoxy)hexyne-
Dialkyl peroxides such as 3,2,5-dimethyl-2,5-di(tert-butylperoxy)hexane and 1,4-bis(tert-butylperoxyisopropyl)benzene are preferably used.

The graft-modified elastomer used in the present invention usually contains the above-mentioned graft-modified ethylene/α-olefin copolymer (a) and graft-modified propylene/α-olefin copolymer (b) alone or in combination. Although used in combination, the above-mentioned graft-modified elastomer may contain other polymers or copolymers or other graft copolymers within a range that does not impair the properties of the graft-modified elastomer.

In the present invention, examples of such other polymers or copolymers include aromatic vinyl hydrocarbon/conjugated diene copolymers and hydrides thereof. Specifically, such aromatic vinyl hydrocarbon/conjugated diene copolymers or their hydrides include:
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 hydrogenated styrene/isoprene/styrene block copolymer rubber.

Such a graft-modified elastomer (b
) is blended in an amount such that the amount of component (b) is within the range of 1 to 50 parts by weight in a total of 100 parts by weight of components (a), (b), and (c). . In particular, it is preferred that this amount be within the range of 10 to 30 parts by weight.

By blending component (b) in the above amount, a resin composition with improved mechanical properties such as impact strength without impairing the excellent properties of the cyclic olefin random copolymer (a). can be obtained.

The polyolefin resin composition of the present invention includes:
As component (C), a compound having one amino group in the molecule is blended. The concept of "compound" used here includes condensates, ring-opening reactants, and polymeric compounds.

In the present invention, the following compounds are used as the component (C). (C-1) Condensate having one amino group in the molecule, (
C-2) a ring-opening reactant having one amino group in the molecule,
(C-3) A polymer in which one amino group is bonded to a polyolefin having a molecular weight of 20,000 or more; (C-4) A low-molecular-weight amino compound in which one of the molecular ends is an amino group.

That is, the condensate (C-1) used as component (C) in the present invention is formed by a condensation reaction, and mainly means an oligomer or polymer of aminocarboxylic acid. The ring-opening reaction product (C-2) is formed by a ring-opening reaction, and mainly means a ring-opening reaction product of lactams. Furthermore, polymer (C-
3) is a polymer in which one amino group is bonded to a polyolefin having a molecular weight of 20,000 or more. Then, a low molecular weight amino compound (C
-4) means a monomer mainly used when preparing the above condensate (C-1) or ring-opening reaction product (C-2).

In the present invention, component (C) is (
Component C-1), component (C-2), component (C-3), or component (C-4) can be used alone, or two or more can be used in combination.

In the present invention, compounds of formula (C-4a) shown below are particularly effective as the low molecular weight amino compound (C-4) in which one of the molecular terminals is an amino group and used as component (c). Alternatively, a compound represented by (C-4b) can be mentioned.

0097 H2N-R-COOH・
...(C-4a)

[0098]

[C25]

(C-4b) However, in the above formulas (C-4a) and (C-4b), R represents an alkylene group. Specific examples of such low molecular weight amino compounds include ε-aminocaproic acid, 7-aminoheptanoic acid, ω-aminoundecanoic acid, laurolactam, ω-aminononanoic acid, β-propiolactam, 2-piveridone, γ-butyrolactam, 11
-aminoundecanoic acid, α-pyropidone, γ-aminobutyric acid, β-alanine, 8-aminovaleric acid and ε-aminolactam.

The amino group-containing condensate (C-1) or ring-opening reactant (C-2) is usually an amino group-containing condensate (C-1) or a dicarboxylic acid and a diamine, or an amino group-containing compound such as ε-aminocaprolactam. A compound formed by a condensation reaction using an amino group- and carboxyl group-containing compound or a functional derivative thereof, which may have (or has) a carboxyl group, and a ring-opening reaction product thereof (
or condensation polymer).

Typical examples of the amino group-containing condensate (C-1) include polyamide precursors and polyamide resins. Here, the polyamide precursors include ethylenediamine, propylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, iminobispropylamine, bis(hexamethylene)triamine, 1,
Aliphatic amines such as 3,6-trisaminomethylhexane, trimethylhexamethylene diamine, bispropylene diamine, diethylaminopropylamine, menthene diamine, isophorone diamine, bis(4-amino-
Alicyclic amines such as 3-methylcyclohexyl)methane, N-aminoethylpiperazine, 1,3-diaminocyclohexane, fatty aromatic amines such as metaxylylene diamine, o-, m-, p-phenylenediamine, diaminodiphenylmethane , diaminodiphenylsulfone, 2
, 4-diaminoanisole, 2,4-toluenediamine, 2,4-diaminodiphenylamine, 4,4'-methylene dianiline, diaminodixylyl sulfone, etc., 3,9-bis(3-aminopropyl) -2
, 4,8,10-tetraspiro[5,5]undecane and other bisspirocyclic diamines, and adipic acid, sebacic acid, terephthalic acid, isophthalic acid,
Oligomers formed by polycondensation with dicarboxylic acids such as dodecanedioic acid and glutaric acid; ε-caprolactam, aminocaproic acid, enantholactam, 7-
Examples include oligomers formed by ring-opening or condensation of aminoheptanoic acid, 11-aminoundecanoic acid, and the like.

[0102] In the present invention, oligomer means the above-mentioned condensate or ring-opening polymer having a molecular weight of less than 2,000. In addition, examples of the polyamide resin include those having a molecular weight of 2000 or more, which are the above-mentioned diamine components and dicarboxylic acid components, condensates of ε-aminoundecanoic acid, etc., and ring-opening reaction products of the above-mentioned lactams. Specifically, nylon-2, nylon-3, nylon-4, nylon-5, nylon-6, nylon-
7. Copolymerization formed from nylon-8, nylon-9, nylon-10, nylon-11, nylon-12, nylon-13, nylon-66, nylon-610, nylon-612, caprolactam and nylon salt aqueous solution Mention may be made of nylon, nylon MXD6 formed from metaxylene diamine and adipic acid, nylon-46 and methoxymethylated polyamide.

In the present invention, the above oligomers and polyamides can be used alone or in combination. Among these, especially nylon 6,
Preferred are polyamide resins that have an amino group at one end of the molecular chain and are crystalline, such as nylon 11 and nylon 12.

[0104] The polymer (C-3) in which one amino group is bonded to a polyolefin having a molecular weight of 20,000 or more is, for example, a polymer of α-olefin such as ethylene or propylene that has one amino group bonded to it. It is a polymer with Such a polymer (C-3) can be prepared by introducing an amino group into a polyolefin using a known method.

Compound (c) having such an amino group
is blended in an amount within the range of 0.01 to 45 parts by weight in a total of 100 parts by weight of the components (a), (b) and (c). Especially this amount is 0.01
It is preferably within the range of 30 parts by weight.

By blending this amino group-containing compound (c), it becomes possible to form a molded article with particularly excellent impact strength and gloss. That is, such components (C-1), (C-2), and (C-3) have relatively high crystallinity near room temperature, and due to this crystallinity, cyclic olefin-based components Resin properties are improved. In addition, component (C-4) also acts in the same manner as the components (C-1), (C-2), and (C-3) described above in the composition. By blending the compound (c) having an amino group, when the compound (c) is below the melting point of the compound, its crystals act as a crosslinking agent and form a crosslinked structure in the graft-modified elastomer. It is thought that a structure is formed and exhibits a reinforcing effect, and as the temperature rises, the reinforcing effect due to the crosslinked structure decreases, and the composition comes to have good fluidity and exhibits good moldability. It will be done.

[0107] The polyolefin resin composition of the present invention includes:
Furthermore, in addition to the above ingredients, inorganic fillers, organic fillers, heat stabilizers, weathering stabilizers, antistatic agents, anti-slip agents,
Additives such as anti-blocking agents, anti-fogging agents, lubricants, pigments, dyes, natural oils, synthetic oils and waxes may be included.

[0108] The polyolefin resin composition of the present invention can be obtained by, for example, separately producing a cyclic olefin resin (a) and a graft-modified elastomer (b), and then melting a mixture of the cyclic olefin resin and the graft-modified elastomer (b). A method of kneading and further blending and kneading a compound (c) having an amino group in the kneaded product, and a method of kneading a cyclic olefin random copolymer (a), a graft-modified elastomer (b), and a compound having an amino group (c) A method in which the graft-modified elastomer (b) and the compound having an amino group (c) are melt-kneaded all at once, and the resulting kneaded product is blended with the cyclic olefin resin (a) and kneaded. be.

As described above, the polyolefin resin composition of the present invention containing the cyclic olefin resin (a), the graft-modified elastomer (b), and the amino group-containing compound (c) has a softening temperature ( TMA) is usually in the range of 50-200°C, preferably 100-180°C.

[0110] The polyolefin resin composition of the present invention is suitable not only for ordinary polyolefin applications but also for applications where mechanical strength is particularly required, such as when filler-reinforced PP, ABS resin, and modified polyphenylene oxide are used. can be used.

[0111]

[Effect of the invention] The polyolefin resin composition of the present invention has
It has a structure in which a graft-modified elastomer (b) is dispersed in a cyclic olefin random copolymer (a). It is thought that by blending the compound (c) having an amino group with this, a crosslinked structure is formed inside the graft-modified elastomer (b), and molding using such a polyolefin resin composition is possible. The body has excellent impact properties. In particular, by using a compound having one amino group in the molecule as component (c), the contribution of this crosslinked structure is reduced during melting, and such a polyolefin resin composition has excellent fluidity. With,
The moldings will have excellent impact strength and gloss.

[0112]

EXAMPLES Next, the present invention will be explained by showing examples. However, the present invention should not be construed as limited by these Examples.

[Evaluation Method] The properties of the cyclic olefin random copolymer and graft-modified elastomer used in the present invention, the compound having an amino group, and the polyolefin resin composition of the present invention were measured as follows. Intrinsic viscosity [η] Measured in decalin at 135°C. Softening Temperature (TMA) TMA was defined as the temperature at which a flat-bottomed needle with a diameter of 1 mm penetrated 100 μm under a heating rate of 5° C./min and a load of 50 g. Graft monomer amount in graft modified elastomer 13
Measured by C-NMR. Tensile modulus was measured at 23°C using a 2 mm thick press test piece according to ASTM-D-638. Crystallinity was measured at 23°C by X-ray diffraction. IZ impact strength was measured at 23° C. according to ASTM D 256 using a 1/8 inch thick injection test piece with a notch. Initial flexural modulus (FM) According to ASTM D 790, using a 1/8 inch thick injection test piece, crosshead speed 20 mm/min,
Measured at 23°C. Bending yield point stress (FS) Measured in accordance with ASTM D 790 in the same manner as FM. Gloss Measured according to ASTM D 523 using a 2 mm thick exit angle plate at an incident angle of 60 degrees and 23 degrees Celsius. Melt index (MI) According to JIS-K-6760, 260℃, 2.16Kg
It was done with a load.

[0114]

[Production Example 1] (Cyclic olefin random copolymer (a)
Preparation example) Using a 1 liter polymerization vessel equipped with stirring blades,
Continuously ethylene and tetracyclo [4.4.0.12,
5.17,10] dodecene-3 (hereinafter referred to as “TCD-3”)
A copolymerization reaction was carried out with (sometimes abbreviated as). That is, a cyclohexane solution of TCD-3 was added from the top of the polymerization vessel at a rate of 0.4 liters per hour so that the TCD-3 concentration in the polymerization vessel was 60 g/liter, and VO (OC) was added as a catalyst.
2H5) A cyclohexane solution of Cl2 was added at 0.5 liters per hour so that the vanadium concentration in the polymerization vessel was 0.5 mmol/liter (the vanadium concentration supplied at this time was 2.86 times the concentration in the polymerization vessel). ), ethylaluminum sesquichloride [Al(C2H5)1.5
Cl1.5] in cyclohexane at a rate of 0.4 liters per hour so that the aluminum concentration in the polymerization vessel was 4.0 mmol/liter, and cyclohexane at a rate of 0.7 liters per hour in the polymerization vessel. On the other hand, the polymerization liquid in the polymerization vessel from the bottom of the polymerization vessel is always 1 liter (that is, the residence time is 0.
The polymerization reaction solution was continuously drawn out (for 5 hours).

[0115] Also, using a bubbling tube in the polymerization system, 30 liters of ethylene per hour, 10 liters of nitrogen per hour,
Hydrogen was then supplied at a rate of 0.3 liters per hour. The copolymerization reaction was carried out at 10° C. by circulating a refrigerant through a jacket attached to the outside of the polymerization vessel.

A copolymerization reaction was carried out under the above polymerization conditions to prepare an ethylene/TCD-3 random copolymer. That is, the polymerization liquid is extracted from the lower part of the polymerization vessel, and cyclohexane/isopropyl alcohol (volume ratio =
1/1) mixture was added to stop the polymerization reaction. Thereafter, an aqueous solution prepared by adding 5 ml of concentrated hydrochloric acid to 1 liter of water was brought into contact with the above polymerization solution at a ratio of 1:1 while stirring vigorously using a homomixer to transfer the catalyst residue to the aqueous phase. Ta.

[0117] After allowing the above mixture to stand and removing the aqueous phase,
Furthermore, the polymerization solution was purified by washing twice with distilled water, and then separated. The obtained polymerization liquid was brought into contact with three times the amount of acetone under strong stirring, and the precipitated solid portion was collected by filtration and thoroughly washed with acetone. Thereafter, the solids collected by filtration were dried at 130° C. and 350 mmHg for 24 hours under nitrogen flow.

[0118] By continuously carrying out the above operations, the ethylene/TCD-3 random copolymer can be produced at a rate of 76% per hour.
g (38 g/liter). 1
The ethylene composition in this copolymer determined from the measurement results of 3C-NMR analysis was 70 mol%. Furthermore, regarding this copolymer, the intrinsic viscosity [η] measured in decalin at 135°C is 0.6 dl/g, and the iodine value is 1.
．． 0, and TMA was 115°C.

Hereinafter, this cyclic olefin random copolymer (a) will be referred to as "PO-1".

[0120]

[Production Example 2] (Cyclic olefin random copolymer (a)
Polymerization Example) An ethylene/TCD-3 random copolymer was prepared in the same manner as in Preparation Example 1, except that ethylene was supplied at a rate of 20 liters per hour and hydrogen was supplied at a rate of 0.5 liters per hour.

The ethylene composition in this copolymer determined from the results of 13C-NMR analysis was 63 mol%. Further, regarding this copolymer, the intrinsic viscosity [η] measured in decalin at 135°C was 0.5 dl/g, the iodine number was 1.0, and the TMA was 150°C.

[0122] Hereinafter, this cyclic olefin random copolymer (a) will be referred to as "PO-2".

[0123]

[Production Example 3] (Cyclic olefin random copolymer (a)
Preparation example) Ethylene at 20 liters per hour, hydrogen at 0 liters per hour
．． An ethylene/TCD-3 random copolymer was prepared in the same manner as in Preparation Example 1 except that 3 liters of the copolymer was supplied.

The ethylene composition in this copolymer determined from the results of 13C-NMR analysis was 63 mol%. Further, regarding this copolymer, the intrinsic viscosity [η] measured in decalin at 135°C was 0.6 dl/g, the iodine value was 1.0, and the TMA was 150°C.

Hereinafter, this cyclic olefin random copolymer (a) will be referred to as "PO-3".

[0126]

[Production Example 4] (Cyclic olefin random copolymer (a)
Preparation example) Ethylene at 10 liters per hour, hydrogen at 0 liters per hour
．． An ethylene/TCD-3 random copolymer was prepared in the same manner as in Preparation Example 1 except that 3 liters of the copolymer was supplied.

The ethylene composition in this copolymer determined from the results of 13C-NMR analysis was 56 mol%. Further, regarding this copolymer, the intrinsic viscosity [η] measured in decalin at 135°C was 0.8 dl/g, the iodine value was 1.0, and the TMA was 170°C.

Hereinafter, this cyclic olefin random copolymer (a) will be referred to as "PO-4".

[0129]

[Production Example 5] (Preparation example of graft-modified elastomer (b)) Ethylene-propylene copolymer with an ethylene content of 80 mol% and an intrinsic viscosity [η] of 2.2 dl/g measured in decalin at 130°C (hereinafter referred to as this copolymer) 1 part by weight of maleic anhydride, 0.2 parts by weight of 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3 per 100 parts by weight of the copolymer (referred to as "MP-0") Mix parts and make a diameter of 3
By melt-kneading at 260°C using a twin-screw extruder with a 0 mm vent device, the graft-modified elastomer (b)
I got it.

The amount of maleic anhydride added to the graft-modified elastomer thus obtained was 0.90% by weight, and the tensile modulus was 80 kg/cm2. Hereinafter, this graft-modified elastomer (b) will be referred to as "MP-1".

[0131]

[Production Example 6] (Preparation of graft-modified elastomer (b)) In Preparation Example 5, “M
1 part by weight of glycidyl methacrylate was used for 100 parts by weight of "P-0", and this glycidyl methacrylate was
．． A graft-modified elastomer (b) was obtained in the same manner except that 2 parts by weight of 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3 was mixed.

[0132] The amount of glycidyl methacrylate added in the obtained graft-modified elastomer was 0.90% by weight, and the tensile modulus was 80 kg/cm2. Hereinafter, this graft-modified elastomer (b) will be referred to as "MP-
2”.

[0133]

[Production Example 7] (Preparation example of graft-modified elastomer (b)) 100 parts by weight of an ethylene-propylene copolymer with an ethylene content of 80 mol% and an intrinsic viscosity [η] of 1.4 dl/g measured in decalin at 130°C 1 part by weight of maleic anhydride and 0.2 parts by weight of 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3 were mixed,
260℃ using a twin screw extruder with a diameter of 30mm and a vent device.
By melt-kneading the mixture, a graft-modified elastomer (b) was obtained.

The amount of maleic anhydride added to the obtained graft-modified elastomer was 0.98% by weight, and the tensile modulus was 80 kg/cm2. Hereinafter, this graft-modified elastomer (b) will be referred to as "MP-3".

[0135]

[Production Example 8] (Preparation example of compound (C) having an amino group) Vacuum-dried ε-aminocaproic acid (hereinafter referred to as PA
-0) was left at 170°C under reduced pressure for 14 hours to obtain a polymer of PA-0.

The intrinsic viscosity [η] of this polymer measured in sulfuric acid at 25° C. was 0.4 dl/g. Hereinafter, the compound having this amino group will be referred to as "PA-1".

[0137]

[Example 1] 10 parts by weight of the graft-modified elastomer (MP-1) obtained in Production Example 5 and 5 parts by weight of nylon-6 (manufactured by Toray Industries, Inc., trade name: Amilan CM1007) as a compound having an amino group. and were melt-kneaded at 250° C. using a twin-screw extruder with a diameter of 30 mm and equipped with a vent device to prepare a precursor mixture. This precursor mixture and 85 parts by weight of the cyclic olefin random copolymer (PO-1) obtained in Production Example 1 were kneaded at 230°C using the extruder described above to obtain a polyolefin resin composition.

[0138] After drying this resin composition at 100°C for 8 hours, an injection molding machine (manufactured by Toshiba IS, 30EP) was used as a molding machine.
Test pieces and square pieces for measuring physical properties were prepared using the following method: N) at 250°C and the mold temperature at 70°C.

Table 1 shows the physical properties of the obtained test piece. Table 1
As is clear from the results shown in , a composition excellent in impact strength, rigidity, heat resistance, gloss, and fluidity was obtained.

[0140]

[Comparative Example 1] Graft-modified elastomer (MP-1) 15 obtained in Production Example 5 without using Amilan CM1007
The same procedure as in Example 1 was carried out, except that parts by weight and 85 parts by weight of the cyclic olefin random copolymer (PO-1) obtained in Production Example 1 were melt-kneaded at 230°C using a twin-screw extruder with a diameter of 30 mm and a vent device. A polyolefin resin composition was obtained, and using this resin composition, test pieces and square pieces were prepared in the same manner as in Example 1, and their physical properties were evaluated.

Table 1 shows the physical properties of the obtained test piece. Table 1
As is clear from the results shown in , this composition had good fluidity, and the test pieces formed from this composition had good rigidity and heat resistance, but the impact strength was low.

[0142]

[Example 2] In Example 1, the cyclic olefin copolymer (PO
-1) 85 parts by weight, graft modified elastomer (MP-
1) A polyolefin resin composition was prepared by melt-kneading 10 parts by weight and 5 parts by weight of a compound having an amino group (Amilan: CM1007) using the above extruder, and using this resin composition, the same procedure as in Example 1 was carried out. Test pieces and square timbers were prepared and their physical properties were evaluated.

Table 1 shows the physical properties of the obtained test piece. Table 1
As is clear from the results shown in , the test piece formed from this composition was excellent in impact strength, rigidity, heat resistance, and gloss, and the composition also had good fluidity.

[0144]

[Example 3] A polyolefin resin composition was prepared in the same manner as in Example 1 except that the graft-modified elastomer was changed to MP-2. Using this resin composition, test pieces and A square piece of wood was prepared and its physical properties were evaluated.

Table 1 shows the physical properties of the obtained test piece. Table 1
As is clear from the results shown in , the test piece formed from this composition was excellent in impact strength, rigidity, heat resistance, and gloss, and the composition also had good fluidity.

[0146]

[Comparative Example 2] In Example 1, amilan: CM100
Graft modified elastomer (MP-2
), 15 parts by weight of cyclic olefin random copolymer (P
85 parts by weight of O-1) were melt-kneaded at 230°C using a twin-screw extruder with a diameter of 30 mm and equipped with a vent device to obtain a polyolefin resin composition. Test pieces and square timbers were prepared in the same manner and their physical properties were evaluated.

Table 1 shows the physical properties of the obtained test piece. Table 1
As is clear from the results shown in , this composition had good fluidity, and the test pieces formed from this composition had good rigidity and heat resistance, but the impact strength was low.

[0148]

[Example 4] A polyolefin resin composition was prepared in the same manner as in Example 1 except that the graft-modified elastomer was changed to MP-3. Using this resin composition, test pieces and A square piece of wood was prepared and its physical properties were evaluated.

Table 1 shows the physical properties of the obtained test piece. Table 1
As is clear from the results shown in , the test piece formed from this composition was excellent in impact strength, rigidity, heat resistance, and gloss, and the composition also had good fluidity.

[0150]

[Comparative Example 3] In Example 1, amilan: CM100
Graft-modified elastomer (MP-3
), 15 parts by weight of cyclic olefin random copolymer (P
85 parts by weight of O-1) were melt-kneaded at 230°C using a twin-screw extruder with a diameter of 30 mm and equipped with a vent device to obtain a polyolefin resin composition. Test pieces and square timbers were prepared in the same manner and their physical properties were evaluated.

Table 1 shows the physical properties of the obtained test piece. Table 1
As is clear from the results shown in , this composition had good fluidity, and the test pieces formed from this composition had good rigidity and heat resistance, but the impact strength was low.

[0152]

[Example 5] 14 parts by weight of the graft-modified elastomer (MP-1) obtained in Production Example 5 and 1 part by weight of "PA-1" as a compound having an amino group were put into a twin screw extruder with a diameter of 30 mm and equipped with a vent device. A precursor mixture was prepared by melt-kneading at 250°C. This precursor mixture and 85 parts by weight of the cyclic olefin random copolymer (PO-1) obtained in Production Example 1 were kneaded at 230°C using the extruder described above to obtain a polyolefin resin composition.

[0153] Test pieces and square pieces similar to those in Example 1 were prepared using this resin composition, and their physical properties were evaluated. Table 1 shows the physical properties of the obtained test piece.

[0154] As is clear from the results shown in Table 1, the test pieces formed from this composition were excellent in impact strength, rigidity, heat resistance, and gloss, and the composition also had good fluidity. .

[0155]

[Example 6] 12 parts by weight of the graft-modified elastomer (MP-1) obtained in Preparation Example 5 and 3 parts by weight of the amino group-containing compound "PA-1" obtained in Production Example 8 were
A precursor mixture was prepared by melt-kneading at 250° C. using a twin-screw extruder equipped with a 0 mm vent device. This precursor mixture and the cyclic olefin random copolymer (PO
-1) 85 parts by weight were kneaded at 230°C using the extruder described above to obtain a polyolefin resin composition.

[0156] Test pieces and square pieces similar to those in Example 1 were prepared using this resin composition, and their physical properties were evaluated. Table 1 shows the physical properties of the obtained test piece.

[0157] As is clear from the results shown in Table 1, the test pieces formed from this composition were excellent in impact strength, rigidity, heat resistance, and gloss, and the composition also had good fluidity. .

[0158]

[Example 7] 10 parts by weight of the graft-modified elastomer (MP-1) obtained in Production Example 5 and 5 parts by weight of a compound having an amino group (amilan: CM1007) were mixed with a diameter of 30 m in diameter.
A precursor mixture was prepared by melt-kneading at 250° C. using a twin-screw extruder equipped with an m-vent device. This precursor mixture and production example 2
Cyclic olefin random copolymer (PO-2
) 85 parts by weight were kneaded at 230° C. using the extruder described above to obtain a polyolefin resin composition.

Using this resin composition, test pieces and square pieces similar to those in Example 1 were prepared and their physical properties were evaluated. Table 1 shows the physical properties of the obtained test piece.

[0160] As is clear from the results shown in Table 1, the test pieces formed from this composition were excellent in impact strength, rigidity, heat resistance, and gloss, and the composition also had good fluidity. .

[0161]

[Comparative Example 4] In Example 7, amilan: CM100
Graft modified elastomer (MP-1
), 15 parts by weight of cyclic olefin random copolymer (P
85 parts by weight of O-2) were melt-kneaded at 230°C using a twin-screw extruder with a diameter of 30 mm and equipped with a vent device to obtain a polyolefin resin composition. Using this resin composition, Example 1 and Test pieces and square timbers were prepared in the same manner and their physical properties were evaluated.

Table 1 shows the physical properties of the obtained test piece. Table 1
As is clear from the results shown in , the fluidity of this composition was good, and the rigidity and heat resistance of the test piece formed from this composition were good, but the impact strength was low.

[0163]

[Example 8] 10 parts by weight of the graft-modified elastomer (MP-1) obtained in Production Example 5 and 10 parts by weight of the amino group-containing compound amylan (CM1007) were mixed with a diameter of 30 m.
A precursor mixture was prepared by melt-kneading at 250° C. using a twin-screw extruder equipped with an m-vent device. This precursor mixture and production example 2
Cyclic olefin random copolymer (PO-2
) and 80 parts by weight were kneaded at 230° C. using the extruder described above to obtain a polyolefin resin composition.

[0164] Using this resin composition, test pieces and square pieces similar to those in Example 1 were prepared and their physical properties were evaluated. Table 1 shows the physical properties of the obtained test piece.

[0165] As is clear from the results shown in Table 1, the test pieces formed from this composition were excellent in impact strength, rigidity, heat resistance, and gloss, and the composition also had good fluidity. .

[0166]

[Example 9] 12 parts by weight of the graft-modified elastomer (MP-1) obtained in Production Example 5 and 3 parts by weight of the amino group-containing compound (PA-1) obtained in Production Example 8 were
A precursor mixture was prepared by melt-kneading at 250° C. using a twin-screw extruder equipped with a 0 mm vent device. This precursor mixture and the cyclic olefin random copolymer (PO
-3) 85 parts by weight were kneaded at 230°C using the extruder described above to obtain a polyolefin resin composition.

[0167] Using this resin composition, test pieces and square pieces similar to those in Example 1 were prepared and their physical properties were evaluated. Table 1 shows the physical properties of the obtained test piece.

[0168] As is clear from the results shown in Table 1, the test pieces formed from this composition were excellent in impact strength, rigidity, heat resistance, and gloss, and the composition also had good fluidity. .

[0169]

[Example 10] 10 parts by weight of the graft-modified elastomer (MP-1) obtained in Production Example 5 and 5 parts by weight of a compound having an amino group (amilan: CM1007) were mixed into
A precursor mixture was prepared by melt-kneading at 250° C. using a twin-screw extruder equipped with a mm vent device. This precursor mixture and the cyclic olefin random copolymer obtained in Production Example 3 (PO-
3) 85 parts by weight were kneaded at 230°C using the extruder described above to obtain a polyolefin resin composition.

[0170] Test pieces and square pieces similar to those in Example 1 were prepared using this resin composition, and their physical properties were evaluated. Table 1 shows the physical properties of the obtained test piece.

[0171] As is clear from the results shown in Table 1, the test pieces formed from this composition were excellent in impact strength, rigidity, heat resistance, and gloss, and the composition also had good fluidity. .

[0172]

[Comparative Example 5] In Example 10, amilan: CM10
Graft modified elastomer (MP-
1), 15 parts by weight of cyclic olefin random copolymer (
85 parts by weight of PO-3) were used, and these were 30 mm in diameter.
A polyolefin resin composition was obtained by melt-kneading at 230°C using a twin-screw extruder equipped with a vent device, and using this resin composition, test pieces and square pieces were prepared in the same manner as in Example 1, and their physical properties were evaluated. did.

Table 1 shows the physical properties of the obtained test piece. Table 1
As is clear from the results shown in , the fluidity of this composition was good, and the rigidity and heat resistance of the test piece formed from this composition were good, but the impact strength was low.

[0174]

[Example 11] 10 parts by weight of the graft-modified elastomer (MP-1) obtained in Production Example 5 and 5 parts by weight of a compound having an amino group (amilan: CM1007) were mixed into
A precursor mixture was prepared by melt-kneading at 250° C. using a twin-screw extruder equipped with a mm vent device. This precursor mixture and the cyclic olefin random copolymer (PO-
4) 85 parts by weight were kneaded at 230°C using the extruder described above to obtain a polyolefin resin composition.

Using this resin composition, test pieces and square pieces similar to those in Example 1 were prepared and their physical properties were evaluated. Table 1 shows the physical properties of the obtained test piece.

[0176] As is clear from the results shown in Table 1, the test pieces formed from this composition were excellent in impact strength, rigidity, heat resistance, and gloss, and the fluidity of the composition was also good. .

[0177]

[Comparative Example 6] In Example 11, graft modified elastomer (MP-1) was used at 15% without using CM1007.
Part by weight, cyclic olefin random copolymer (PO-4)
were melt-kneaded at 230°C using a twin-screw extruder with a diameter of 30 mm and equipped with a vent device to obtain a polyolefin resin composition. Using this resin composition, tests were conducted in the same manner as in Example 1. Pieces and squares were prepared and their physical properties were evaluated.

Table 1 shows the physical properties of the obtained test piece. Table 1
As is clear from the results shown in , this composition had good fluidity, and the test pieces formed from this composition had good rigidity and heat resistance, but the impact strength was low.

[0179]

[Table 1]

Claims (4)

[Claims] Claim 1: (a) A cyclic olefin random copolymer consisting of an ethylene component unit and a component unit derived from a cyclic olefin represented by the following formula [I], and/or a cyclic olefin random copolymer comprising an ethylene component unit and a component unit derived from a cyclic olefin represented by the following formula [I]. Ring-opened polymers or copolymers of cyclic olefins or hydrogenated products thereof, (b) 23
Tensile modulus at °C is 0.1-2000kg
/cm2, an elastomer graft-modified with an unsaturated carboxylic acid or its derivative;
The amount of component (a) in 100 parts by weight of the total of components (a), (b) and (c) is 50 to 95 parts by weight, and component (b) The amount of component (c) is 1 to 50 parts by weight and the amount of component (c) is 0.01
-45 parts by weight of a polyolefin resin composition; [I] (where n is 0 or 1, m is 0 or a positive integer, and q is 0 or 1, R1 to R18 and Ra and Rb each independently represent an atom or group selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group, and R15 to R18 are bonded to each other and It may form a monocyclic or polycyclic group, and the monocyclic or polycyclic group may have a double bond, and R
15 and R16 or R17 and R18 may form an alkylidene group). Claim 2: Component (a) has a softening temperature of 70 to 200.
The polyolefin resin composition according to claim 1, wherein the polyolefin resin composition has an intrinsic viscosity [η] of 0.3 to 2.0 dl/g as measured in decalin at 130°C. thing. [Claim 3] The graft-modified elastomer (b) comprises:
2. The polyolefin resin composition according to claim 1, which is a graft modified product of an amorphous or low crystalline α-olefin elastic copolymer formed from at least two types of α-olefins. 4. The polyolefin resin composition according to claim 1, wherein the compound (c) having one amino group in the molecule is ε-aminocaproic acid, a condensate thereof, or nylon-6. thing.