JP2011052147A - Polyolefin resin composition and molding thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a molding having good elongation, impact resistance and scratch resistance. <P>SOLUTION: The polyolefin resin composition includes 99-60 mass% of (A) a polyolefin resin, 40-1 mass% of (B) an inorganic filler, 0-30 mass% of (E) an olefinic elastomer and/or a vinyl aromatic compound-based elastomer (provided that the aggregate of (A), (B) and (E) is 100 mass%), (C) an olefin copolymer-modified product substance in an amount 0.01-1 pt.mass to 100 pts.mass of (A), (B) and (E), and 0.01-1 pt.mass of (D) a lubricant. Olefin copolymer-modified product (C) is obtained by reacting 100 pts.mass of (a) a copolymer of at least one kind of olefin compound selected from the group consisting of ethylene, and a ≥3C α-olefin compound, and an alicyclic vinyl compound, 0.01-20 pts.wt. of (b) a compound having at least one kind of unsaturated group (i) and at least one kind of polar group (ii), and 0.001-20 pts.wt. of (c) an organic peroxide. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a polyolefin resin composition and a molded body produced using this resin composition.

Polyolefin resin compositions are used in various molded articles in the field of industrial parts, for example, parts for automobiles, such as bumpers, instrument panels and pillars, and parts for household appliances such as vacuum cleaners and televisions.
In recent years, in these applications, the scratch resistance of polyolefin resin compositions has been highlighted as a problem with the penetration of non-coating due to solvent regulations and the like.

  In order to improve the scratch resistance, a technique using a modified polyolefin is disclosed. For example, Patent Document 1 discloses (a) a specific crystalline propylene-based block copolymer, (b) a specific polyethylene, (c) an elastomer, (d) an inorganic filler, and (e) a fatty acid amide or its A polypropylene resin composition comprising a derivative, (f) a silicone compound, and (g) a polyolefin modified with an unsaturated carboxylic acid or derivative thereof is disclosed.

JP 2002-3692 A

However, in the resin composition described in Patent Document 1, since a modifier based on polypropylene is used, although the scratch resistance of the obtained molded body is improved, the elongation and impact strength of the molded body are reduced. There was something to do.
In view of the above problems, an object of the present invention is to provide a polyolefin resin composition capable of obtaining a molded article having good elongation and impact resistance and good scratch resistance.

The present invention
99% by mass to 60% by mass of polyolefin resin (A),
40% by mass to 1% by mass of inorganic filler (B),
Olefin-based elastomer and / or vinyl aromatic compound-based elastomer (E) 0% by mass to 30% by mass (provided that the total of (A), (B), and (E) is 100% by mass),
The following modified olefin copolymer (C), 0.01 parts by mass to 5 parts by mass with respect to 100 parts by mass of the above (A), (B), and (E),
0.01 parts by mass to 1 part by mass of a lubricant (D),
The polyolefin resin composition containing this is provided.
Olefin copolymer modified product (C): copolymer of at least one olefin compound selected from the group consisting of ethylene and an α-olefin compound having 3 or more carbon atoms, and an alicyclic vinyl compound ( a) 100 parts by mass;
0.01 to 20 parts by weight of a compound (b) having at least one unsaturated group (i) and at least one polar group (ii);
0.001 to 20 parts by weight of organic peroxide (c),
It is obtained by reacting.

  According to the present invention, it is possible to obtain a molded article having good elongation and impact resistance and good scratch resistance.

The polyolefin resin composition according to the present invention contains a polyolefin resin (A), an inorganic filler (B), a predetermined modified olefin copolymer (C), and a lubricant (D). Details will be described below.
[Polyolefin resin (A)]
Examples of the polyolefin resin (A) (hereinafter also referred to as component (A)) used in the present invention include a polyethylene resin, a polypropylene resin, and a polybutene resin. These may be homopolymers or copolymers with other monomers. The copolymer may be a block copolymer or a random copolymer.
Examples of the polyethylene resin include high density polyethylene, medium density polyethylene, low density polyethylene, linear low density polyethylene, a copolymer of ethylene and an α-olefin having 4 or more carbon atoms, and ethylene and cyclic having 4 or more carbon atoms. Examples thereof include copolymers with olefins and mixtures thereof.

  Examples of the polypropylene resin include a propylene homopolymer, a block copolymer with ethylene, a random copolymer with ethylene, a copolymer of propylene and an α-olefin having 4 or more carbon atoms, propylene and 4 or more carbon atoms. And a copolymer of these with a cyclic olefin, and a mixture thereof.

  Among these, as the polyolefin resin (A), propylene-1-butene copolymer, ethylene-1-butene copolymer, ethylene-1-hexene copolymer, ethylene-1-octene copolymer, ethylene-propylene It is particularly preferable to use a -1-butene copolymer, an ethylene-propylene-1-hexene copolymer, an ethylene-propylene-1-octene copolymer, a propylene homopolymer, and an ethylene-propylene block copolymer.

  Examples of the α-olefin having 4 or more carbon atoms include 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, Linear α-olefins such as tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene and 1-eicosene; and 3-methyl-1-butene Branched α-olefins such as 3-methyl-1-pentene, 4-methyl-1-pentene, 2-ethyl-1-hexene, and 2,2,4-trimethyl-1-pentene. These can be used alone or in combination of two or more.

  The cyclic olefin in the present invention refers to an alicyclic hydrocarbon compound having a double bond in the alicyclic ring. Specifically, cyclobutene, cyclopentene, cyclopentadiene, 4-methylcyclopentene, 4,4-dimethylcyclopentene, cyclohexene, 4-methylcyclohexene, 4,4-dimethylcyclohexene, 1,3-dimethylcyclohexene, 1,3-cyclo Examples include hexadiene, 1,4-cyclohexadiene, cycloheptene, 1,3-cycloheptadiene, 1,3,5-cycloheptatriene, cyclooctene, 1,5-cyclooctadiene, and cyclododecene. These can be used alone or in combination of two or more.

  The molecular weight distribution (Mw / Mn) of the polyolefin resin (A) is preferably 1 to 4. The molecular weight distribution in the present invention is a value obtained by dissolving the polyolefin resin (A) in o-dichlorobenzene and converting it to the molecular weight of polystyrene measured by gel permeation chromatography (GPC) method. The value calculated from the weight average molecular weight (Mw) and the number average molecular weight (Mn) is used.

  The melt flow rate of the polyolefin resin (A) is preferably 0.5 g / 10 min to 300 g / 10 min, more preferably 1 g / 10 min to 150 g / 10 min (JIS-K-6758 230). Measured in degrees Celsius).

  The content of the polyolefin resin (A) in the polyolefin resin composition according to the present invention is 99 to 60 masses when the component (B) and the component (E) to be described later are combined to be 100 mass%. %, Preferably 90 to 65% by mass. When the content is more than 99% by mass, since the component (B) and the component (E) are small, the impact resistance and rigidity of the molded body may be lowered. Moreover, if content is less than 60 mass%, scratch resistance may fall.

As a manufacturing method of polyolefin resin (A), the method of superposing | polymerizing using a polymerization catalyst is mentioned. Examples of the polymerization catalyst include Ziegler catalysts and metallocene catalysts. Ziegler catalysts include (a) a solid catalyst component containing magnesium, titanium, halogen and an electron donor as essential components, (b) an organoaluminum compound, and (c) a catalyst system formed from the electron donor component. Can be mentioned. Methods for producing these catalysts are disclosed in JP-A-1-319508, JP-A-7-216017, JP-A-10-212319, JP-A-2004-182876, and the like.
Examples of the polymerization method include, for example, a slurry polymerization method using an inert hydrocarbon solvent, a solvent polymerization method, a liquid phase polymerization method without a solvent, a gas phase polymerization method, or a gas phase-gas phase polymerization method in which they are continuously performed. And liquid phase-gas phase polymerization method. These polymerization methods may be a batch method (batch method) or a continuous method. Moreover, the method of manufacturing a polyolefin-type polymer in one step may be sufficient, and the method of manufacturing in multiple steps of two steps or more may be sufficient.
In particular, as a method for producing a polypropylene copolymer comprising the propylene homopolymer component and the ethylene-propylene block copolymer, preferably, the step of producing the ethylene-propylene block copolymer, and the ethylene-propylene A multi-stage production method having at least two steps of producing a block copolymer and the like.

[Inorganic filler (B)]
As an inorganic filler (B) (henceforth a component (B)) used by this invention, a non-fibrous inorganic filler and a fibrous inorganic filler are mentioned.
Non-fibrous inorganic fillers include talc, mica, calcium carbonate, barium sulfate, magnesium carbonate, clay, alumina, silica, calcium sulfate, silica sand, carbon black, titanium oxide, magnesium hydroxide, zeolite, molybdenum, diatom Examples include soil, sericite, shirasu, calcium hydroxide, calcium sulfite, sodium sulfate, bentonite, and graphite. From the viewpoint of obtaining a molded article having a good impact strength and a good appearance, talc is preferably used.

The average particle diameter of the non-fibrous inorganic filler is preferably 10 μm or less, and more preferably 5 μm or less. The “average particle size” in the present invention is a 50% equivalent particle obtained from an integral distribution curve of a sieving method measured by suspending in a dispersion medium such as water or alcohol using a centrifugal sedimentation type particle size distribution measuring device. It means the diameter D50.
The non-fibrous inorganic filler may be used as it is, but in order to improve the interfacial adhesion with the component (A), a silane coupling agent, a titanium coupling agent, or a surfactant is used. You may use it, after surface-treating. Examples of the surfactant include higher fatty acids, higher fatty acid esters, higher fatty acid amides, and higher fatty acid salts.

  Examples of the fibrous inorganic filler include fibrous magnesium oxysulfate, potassium titanate fiber, magnesium hydroxide fiber, aluminum borate fiber, calcium silicate fiber, calcium carbonate fiber, carbon fiber, glass fiber, and metal fiber. . From the viewpoint of obtaining a molded article having sufficient impact strength and good appearance, it is preferable to use fibrous magnesium oxysulfate and calcium silicate fiber, and more preferably to use fibrous magnesium oxysulfate. preferable.

The average fiber length of the fibrous inorganic filler is preferably 3 μm or more, more preferably 3 μm to 20 μm, and still more preferably 8 μm to 15 μm. The average fiber diameter is preferably 0.2 μm to 1.5 μm, and more preferably 0.3 μm to 1.0 μm. In the present invention, “average fiber length” and “average fiber diameter” mean the average value of the fiber length and fiber diameter of a predetermined number of fibers measured by electron microscope observation.
The aspect ratio is preferably 10 or more, more preferably 10 to 30, and still more preferably 12 to 25.

The fibrous inorganic filler may be used as it is, but in order to improve the interfacial adhesion with the component (A), after performing a surface treatment using a silane coupling agent or a higher fatty acid metal salt. May be used. Examples of the higher fatty acid metal salt include calcium stearate, magnesium stearate, and zinc stearate.
Examples of the form of the fibrous inorganic filler include powder form, flake form, and granular form, and any form may be used. Among these, it is preferable to use a granular material from the viewpoint of easy handling.

  The content of the inorganic filler (B) in the polyolefin resin composition according to the present invention is 40% by mass to 1% by mass when the component (A) and the component (E) are combined to be 100% by mass. %, And preferably 30 to 2% by mass. If the content is more than 40% by mass, the scratch resistance of the molded product may be reduced, and if the content is less than 1% by mass, the rigidity may be reduced.

[Modified olefin copolymer (C)]
The modified olefin copolymer (C) used in the present invention (hereinafter also referred to as component (C)) is the modified olefin copolymer (C) is the predetermined copolymer (a) and the predetermined compound. It is obtained by reacting (b) with an organic peroxide (c).

<Copolymer (a)>
The copolymer (a) is a copolymer of at least one olefin compound selected from the group consisting of ethylene and an α-olefin compound having 3 or more carbon atoms, and an alicyclic vinyl compound.

Specific examples of the α-olefin compound having 3 or more carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1 -Dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nanodecene, 1-eicocene and the like.
Of these, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, and 1-octene are preferably used as the first olefin compound, and ethylene and propylene are more preferably used. These can be used alone or in combination of two or more.

An alicyclic vinyl compound refers to an alicyclic hydrocarbon compound having a vinyl group. The alicyclic structure of the alicyclic hydrocarbon compound is preferably a 3- to 16-membered ring. Specifically, monocyclic alicyclic structures such as cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring and cyclooctane ring, polycyclic alicyclic such as adamantane ring, norbornene ring, etc. Structure is mentioned.
Specific examples of the compound having an alicyclic structure as described above include vinylcyclopropane, vinylcyclobutane, vinylcyclopentane, vinylcyclohexane, vinylcycloheptane, vinylcyclooctane, and the like. Of these, vinylcyclopentane, vinylcyclohexane, vinylcycloheptane, and vinylcyclooctane are more preferably used, and vinylcyclohexane is more preferably used.

  The copolymer composition of the olefin compound and the alicyclic vinyl compound in the copolymer (a) is preferably 0.1 mol% to 99 mol% of the olefin compound, and 1 mol% to 80 mol%. It is more preferable. It is preferable that an alicyclic vinyl compound is 99.9 mol%-1 mol%, and it is more preferable that it is 99 mol%-20 mol%.

The molecular weight distribution (Mw / Mn) of the copolymer (a) is preferably from 1.2 to 5, and more preferably from 1.5 to 3. In addition, the value computed by the method similar to the molecular weight distribution of the said polyolefin resin (A) is used for the molecular weight distribution of a copolymer (a).
The melt flow rate of the copolymer (a) is preferably 50 g / 10 min to 500 g / 10 min, more preferably 100 g / 10 min to 300 g / 10 min (JIS-K-6758 190 ° C.). Measured in).

  As a manufacturing method of a copolymer (a), the method of manufacturing using a polymerization catalyst is mentioned. Examples of the polymerization catalyst include Ziegler catalysts and metallocene catalysts. Ziegler catalysts include (a) a solid catalyst component containing magnesium, titanium, halogen and an electron donor as essential components, (b) an organoaluminum compound, and (c) a catalyst system formed from the electron donor component. Can be mentioned. Methods for producing these catalysts are disclosed in JP-A-1-319508, JP-A-7-216017, JP-A-10-212319, JP-A-2004-182876, and the like.

<Compound (b)>
The compound (b) is a compound having at least one unsaturated group (i) and at least one polar group (ii).
The unsaturated group (i) in the present invention refers to a carbon-carbon double bond or a carbon-carbon triple bond. The polar group (ii) is a carboxyl group, an ester group, an amino group, a group having an ammonium salt structure derived from an amino group, an amide group, an imide group, a nitrile group, an epoxy group, a hydroxyl group, or an isocyanate group. 2-oxa-1,3-dioxo-1,3-propanediyl group, dihydrooxazolyl group and the like.

Such compounds (b) include unsaturated carboxylic acids, unsaturated carboxylic esters, unsaturated carboxylic amides, unsaturated carboxylic anhydrides, unsaturated epoxy compounds, unsaturated alcohols, unsaturated amines, and unsaturated An isocyanate etc. are mentioned.
Specific examples of the compound (b) include the following groups (1) to (14). In addition, you may use a compound (b) individually or in combination of 2 or more types.

[Group (1)]
Maleic acid, maleic anhydride, fumaric acid, maleimide, maleic hydrazide, methyl nadic anhydride, dichloromaleic anhydride, maleic amide, itaconic acid, itaconic anhydride, glycidyl (meth) acrylate, 2-hydroxyethyl methacrylate, and Allyl glycidyl ether.

[Group (2)]
A compound represented by the following structural formula, such as a reaction product of maleic anhydride and diamine (wherein R represents an aliphatic group or an aromatic group).

[Group (3)]
Natural fats such as soybean oil, tung oil, castor oil, flaxseed oil, hemp seed oil, cottonseed oil, sesame oil, rapeseed oil, peanut oil, coconut oil, olive oil, coconut oil, and sardine oil.
[Group (4)]
A compound obtained by epoxidizing natural fats and oils of group (3).

[Group (5)]
Acrylic acid, butenoic acid, crotonic acid, vinyl acetic acid, methacrylic acid, pentenoic acid, angelic acid, tiglic acid, 2-pentenoic acid, 3-pentenoic acid, α-ethylacrylic acid, β-methylcrotonic acid, 4-pentenoic acid 2-hexene, 2-methyl-2-pentenoic acid, 3-methyl-2-pentenoic acid, α-ethylcrotonic acid, 2,2-dimethyl-3-butenoic acid, 2-heptenoic acid, 2-octenoic acid, 4-decenoic acid, 9-undecenoic acid, 10-undecenoic acid, 4-dodecenoic acid, 5-dodecenoic acid, 4-tetradecenoic acid, 9-tetradecenoic acid, 9-hexadecenoic acid, 2-octadecenoic acid, 9-octadecenoic acid, Eicosenoic acid, docosenoic acid, erucic acid, tetracosenoic acid, mycolic acid, 2,4-hexadienoic acid, diallylacetic acid, geranium acid, 2,4-decadienoic acid 2,4-dodecadienoic acid, 9,12-hexadecadienoic acid, 9,12-octadecadienoic acid, hexadecatrienoic acid, eicosadienoic acid, eicosatrienoic acid, icosatetraenoic acid, ricinoleic acid, eleostearin Unsaturated carboxylic acids such as acids, oleic acid, eicosapentaenoic acid, erucic acid, docosadienoic acid, docosatrienoic acid, docosatetraenoic acid, docosapentaenoic acid, tetracosenoic acid, hexacosenoic acid, hexacodienoic acid, octacosenoic acid, and traacontenoic acid .
[Group (6)]
An ester, amide or anhydride of the unsaturated carboxylic acid.

[Group (7)]
Allyl alcohol, crotyl alcohol, methyl vinyl carbinol, allyl carbinol, methyl propenyl carbinol, 4-penten-1-ol, 10-undecen-1-ol, propargyl alcohol, 1,4-pentadiene-3- Unsaturated alcohols such as all, 1,4-hexadien-3-ol, 3,5-hexadien-2-ol, and 2,4-hexadien-1-ol.
[Group (8)]
3-butene-1,2-diol, 2,5-dimethyl-3-hexene-2,5-diol, 1,5-hexadiene-3,4-diol, and 2,6-octadiene-4,5-diol Unsaturated alcohol like.
[Group (9)]
Unsaturated amine in which the hydroxyl group of the unsaturated alcohol of the above groups (7) and (8) is substituted with an amino group.

[Group (10)]
A compound obtained by adding maleic anhydride or phenols to a low molecular weight polymer having a number average molecular weight of about 500 to about 10,000 of a diene compound such as butadiene and isoprene.
[Group (11)]
A compound obtained by adding maleic anhydride or phenols to a high molecular weight polymer having a number average molecular weight of about 10,000 or more of diene compounds such as butadiene and isoprene.
[Group (12)]
A compound in which a group such as an amino group, a carboxyl group, a hydroxyl group, or an epoxy group is introduced into a low molecular weight polymer having a number average molecular weight of about 500 to about 10,000 of a diene compound such as butadiene and isoprene.
[Group (13)]
A compound in which a group such as an amino group, a carboxyl group, a hydroxyl group, or an epoxy group is introduced into a high molecular weight polymer having a number average molecular weight of about 10,000 or more of a diene compound such as butadiene and isoprene.
[Group (14)]
Allyl isocyanate.

  Among these, it is preferable to use maleic anhydride, maleic acid, fumaric acid, itaconic anhydride, itaconic acid, glycidyl (meth) acrylate, or 2-hydroxyethyl methacrylate as the compound (b).

<Organic peroxide (c)>
The organic peroxide (c) used in the present invention is an organic peroxide having an action of extracting protons from the copolymer (a) after generating radicals by decomposing at a predetermined temperature. From the viewpoint of improving the graft ratio of the compound (b) to the copolymer (a) and preventing the decomposition of the copolymer (a), the decomposition temperature at which the half-life is 1 minute is 50 ° C to 210 ° C. It is preferable that it is an organic peroxide of ° C.
Among these, the decomposition temperature at which the half-life is 1 minute is more preferably 70 ° C to 200 ° C, and further preferably 90 ° C to 190 ° C.

Examples of the organic peroxide having a decomposition temperature of 50 ° C. to 210 ° C. with a half-life of 1 minute include diacyl peroxide, dialkyl peroxide, peroxy ketal, alkyl peroxy ester, and peroxy carbonate. Among these, diacyl peroxide, dialkyl peroxide, alkyl peroxy ester, or peroxy carbonate is preferably used.
Specific examples of the organic peroxide (c) include dicetylperoxydicarbonate, di-3-methoxybutylperoxydicarbonate, di-2-ethylhexylperoxydicarbonate, bis (4-t-butylcyclohexylperoxide). Oxy) dicarbonate, diisopropylperoxydicarbonate, t-butylperoxyisopropylcarbonate, dimyristylperoxycarbonate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, α-cumylperoxyneo Decanoate, t-butylperoxyneodecanoate, 1,1-bis (t-butylperoxy) cyclohexane, 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane, , 1-bis (t-butylperoxy) cyclododecane, t Hexylperoxyisopropyl carbonate, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, t-butyl peroxyacetate, 2,2-bis (t-butylperoxy) butene, t-butylperoxybenzoate, n-butyl-4,4-bis (t-butylperoxy) valerate, di-t- Butyl peroxyisophthalate, dicumyl peroxide, α-α′-bis (t-butylperoxy-m-isopropyl) benzene, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 1,3-bis (t-butylperoxyisopropyl) benzene, t-butylcumyl peroxide, di-t-butylper Kisaido, and p- menthane hydroperoxide, and 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, and the like. These can be used alone or in combination of two or more.

  The graft ratio of the compound (b) to the copolymer (a) in the present invention is preferably 0.005% by mass to 10% by mass, and more preferably 0.05% by mass to 1% by mass. By setting the graft ratio to 0.005% by mass or more, it becomes possible to improve the scratch resistance of the obtained molded body. Moreover, by setting the graft ratio to 10% by mass or less, it is possible to suppress the decomposition of the copolymer (a) and the crosslinking of the compound (b) and obtain a molded body having sufficient scratch resistance.

The modified olefin copolymer (C) is obtained by reacting the copolymer (a) with the compound (b) using the organic peroxide (c). The compounding ratio of each component is 0.01 part by weight to 20 parts by weight, preferably 0.1 part by weight to 10 parts by weight, and the organic peroxide with respect to 100 parts by weight of the copolymer (a). (C) is 0.001 to 20 parts by mass, preferably 0.1 to 3 parts by mass.
When the compounding ratio of the compound (b) is less than 0.01 parts by mass, the graft ratio of the compound (b) to the copolymer (a) is lowered, so that the resulting molded article may have low scratch resistance. . Moreover, since the quantity of a copolymer (a) and an unreacted compound (b) will increase when a mixture ratio exceeds 20 mass parts, the mechanical physical property of a molded object may fall.
Moreover, since the graft ratio of the compound (b) with respect to a copolymer (a) falls when the mixture ratio of an organic peroxide (c) is less than 0.001 mass part, the damage resistance of the obtained molded object is May be lower. Moreover, when a mixture ratio exceeds 20 mass parts, decomposition | disassembly of a copolymer (a) and bridge | crosslinking of a compound (b) will advance, and the molded object which has sufficient damage resistance may not be obtained.
In addition, in this invention, when 2 or more types of compounds (b) and / or organic peroxides (c) are used, let the total amount be the said usage-amount.

The following method is mentioned as a manufacturing method of an olefin copolymer modified material (C).
[1]: Method of melt-kneading copolymer (a), compound (b) and organic peroxide (c) [2]: Copolymer (a), compound (b) and organic peroxide (c) ) Is dissolved in an organic solvent and the resulting solution is heated [3]: The copolymer (a), the compound (b) and the organic peroxide (c) are suspended in water, and the resulting suspension is obtained. Method of heating the turbid liquid Among these, it is preferable to use the method [1] above. Examples of the kneader used in the melt kneading include known devices such as a Banbury mixer, a plast mill, a Brabender plastograph, a single screw extruder, and a twin screw extruder. Among these, from the viewpoint of continuous production and high productivity, a single screw extruder or a twin screw extruder is preferable.

Specific examples of the method [1] include the following.
(1): Method of melt-kneading all the amounts of copolymer (a), compound (b) and organic peroxide (c) all together (2): melt-kneading copolymer (a), Method (3) of melt-kneading by adding compound (b) and organic peroxide (c) simultaneously or in any order to the obtained kneaded product: a part of copolymer (a) is melt-kneaded A method of adding the remaining total amount of component (a), compound (b) and organic peroxide (c) to the obtained kneaded material at the same time or in any order and melt-kneading;
The temperature of melt kneading (in the case of an extruder, the temperature of the cylinder) is to improve the graft ratio of the compound (b) to the copolymer (a), and to decompose the copolymer (a) during melt kneading. From the viewpoint of suppressing, it is preferably 50 ° C to 300 ° C, more preferably 80 ° C to 270 ° C. The melt kneading time is preferably from 0.1 to 30 minutes, and preferably from 0.5 to 5 minutes from the viewpoint of improving the graft ratio of the compound (b) to the copolymer (a). Is more preferable.

  The content of the modified olefin copolymer (C) in the polyolefin resin composition according to the present invention is 0.01 to 5 parts by mass with respect to 100 parts by mass of the entire polyolefin resin composition. It is preferable that it is 1 mass part-3 mass parts. When the content is less than 0.01 parts by mass, a molded product having sufficient scratch resistance may not be obtained. When the content exceeds 5 parts by mass, the molded product has rigidity and impact resistance. May decrease.

[Lubricant (D)]
Examples of the lubricant (D) (hereinafter also referred to as component (D)) used in the present invention include silane compounds, polyolefin waxes, fatty acid amides and the like. Of these, fatty acid amides are preferably used, and fatty acid amides having 6 to 22 carbon atoms are more preferably used. Specific examples of the fatty acid amide include lauric acid amide, stearic acid amide, oleic acid amide, behenic acid amide, and erucic acid amide.

  The content of the lubricant (D) in the polyolefin resin composition according to the present invention is 0.01 parts by mass to 1 part by mass with respect to 100 parts by mass of the whole polyolefin resin composition, and 0.1 parts by mass to 0 parts by mass. It is preferably 0.5 parts by mass. When the content is less than 0.01 parts by mass, a molded article having sufficient scratch resistance may not be obtained. When the content exceeds 1 part by mass, too much lubricant appears on the surface. The fogging property may be deteriorated.

[Olefin elastomer and / or vinyl aromatic compound elastomer (E)]
The polyolefin resin composition according to the present invention may further contain an olefin elastomer and / or a vinyl aromatic compound elastomer (E) (hereinafter also referred to as component (E)).
Examples of the olefin elastomer include a copolymer of ethylene and an α-olefin having 4 to 20 carbon atoms. Examples of the α-olefin having 4 to 20 carbon atoms include 1-butene, isobutene, 1-pentene, 2-methyl-1-butene, 3-methyl-1-butene, 1-hexene, 2-methyl-1- Examples include pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, and the like. These may be used alone or in combination of two or more. May be. 1-butene, 1-hexene and 1-octene are preferred.

The density of the olefin elastomers, from the viewpoint of increasing the impact strength of the viewpoints and moldings of enhancing the dispersibility of the polyolefin resin ^(A), the a ^{0.85g / cm 3 ~0.885g / cm 3} , preferably is ^{0.85g / cm 3 ~0.88g / cm 3} , more preferably ^{0.855g / cm 3 ~0.875g / cm 3} . Moreover, the melt flow rate measured by JIS-K-6758 190 degreeC of an olefin type elastomer is 0.1 g / 10min-30g / 10min from a viewpoint of raising the impact strength of a molded object, Preferably it is 0.8. It is 5 g / 10 minutes to 20 g / 10 minutes.

  As a manufacturing method of an olefin type elastomer, the method of manufacturing using a polymerization catalyst is mentioned. Known polymerization catalysts include, for example, a Ziegler-Natta catalyst system comprising a vanadium compound, an organoaluminum compound, and a halogenated ester compound, and at least one cyclopentadienyl anion skeleton on a titanium atom, a zirconium atom or a hafnium atom. Examples include a catalyst system in which a metallocene compound in which a group is coordinated and an alumoxane or boron compound are combined, or a so-called metallocene catalyst system. Known polymerization methods include, for example, a method of copolymerizing ethylene and α-olefin in an inert organic solvent such as a hydrocarbon compound, and a method of copolymerizing in ethylene and α-olefin without using a solvent. Can be mentioned.

The vinyl aromatic compound-based elastomer in the present invention is a block copolymer composed of a vinyl aromatic compound polymer block and a conjugated diene polymer block, and a double bond of a conjugated diene portion of the block copolymer is hydrogenated. Block polymer. Among these, it is preferable to use a block polymer in which the double bond of the conjugated diene portion of the block copolymer is hydrogenated by 80% or more, and a block polymer in which the double bond is hydrogenated by 85% or more is used. It is more preferable.
Specifically, styrene-ethylene-butene-styrene copolymer (SEBS), styrene-ethylene-propylene-styrene copolymer (SEPS), styrene-butadiene copolymer (SBR), styrene-butadiene- Examples thereof include block copolymers such as styrene copolymer (SBS) and styrene-isoprene-styrene copolymer (SIS), and block copolymers obtained by hydrogenating these block copolymers. These can be used alone or in combination of two or more.
Further, an elastomer obtained by reacting an olefin copolymer elastomer such as ethylene-propylene-nonconjugated diene elastomer (EPDM) with a vinyl aromatic compound such as styrene can also be suitably used. Further, at least two kinds of vinyl aromatic compound elastomers may be used in combination.

The molecular weight distribution (Mw / Mn) of the vinyl aromatic compound elastomer determined from the mass average molecular weight (Mw) and the number average molecular weight (Mn) measured by gel permeation chromatography (GPC) is preferably 2. 5 or less, more preferably 2.3 or less.
The vinyl aromatic compound content in the vinyl aromatic compound-based elastomer is preferably 10% by mass to 20% by mass, more preferably 12% by mass to 19% by mass (provided that (B-2 ) The total amount of vinyl aromatic compound elastomer is 100% by mass).

  The melt flow rate (JIS-K-6758) at 230 ° C. of the vinyl aromatic compound-based elastomer is 1 g / 10 min to 15 g / 10 min, preferably 2 g, from the viewpoint of increasing the impact strength of the molded product. / 10 minutes to 13 g / 10 minutes.

  Examples of the method for producing a vinyl aromatic compound elastomer include a method in which a vinyl aromatic compound is bonded to an olefin copolymer rubber or a conjugated diene rubber by polymerization, reaction, or the like.

  The content of the olefin-based elastomer and / or the vinyl aromatic compound-based elastomer (E) in the polyolefin resin composition according to the present invention is selected from the viewpoints of improving the impact resistance of the molded product. ) And 100% by mass, it is 0% by mass to 30% by mass, and preferably 5% by mass to 20% by mass.

  The polyolefin resin composition according to the present invention includes an antioxidant, an ultraviolet absorber, a pigment, an antistatic agent, a copper damage inhibitor, a flame retardant, a neutralizing agent, a foaming agent, a plasticizer, and a nucleating agent as necessary. In addition, additives such as an anti-bubble agent and a crosslinking agent may be blended.

  The polyolefin resin composition according to the present invention can be obtained by melting and kneading all components at once or by dividing them into several parts and mixing them uniformly with a mixer. The apparatus used for melt kneading is not particularly limited, but it is preferable to use a Banbury mixer, a plast mill, a Brabender plastograph, a single screw extruder, a twin screw extruder, etc., which can be continuously produced and has high productivity. From the viewpoint, it is preferable to use a single screw extruder or a twin screw extruder.

The melt kneading temperature (cylinder temperature in the case of an extruder) is preferably 50 ° C. to 300 ° C., and preferably 80 ° C. to 270 ° C. from the viewpoint of suppressing decomposition and crosslinking of the component (A). More preferred. The time for melt kneading is preferably from 0.1 minutes to 30 minutes, and more preferably from 0.5 minutes to 5 minutes, from the viewpoint of sufficiently dispersing the component (A).
The polyolefin resin composition thus obtained can be used for automobile parts such as bumpers, instrument panels and pillars, parts for household appliances such as vacuum cleaners and televisions, parts for electronic products, and building material parts.

  The present invention will be described with reference to the following examples and comparative examples, but the present invention is not limited to these examples.

(1) Intrinsic viscosity ([η], unit: dl / g)
Using a Ubbelohde viscometer, reduced viscosities were measured at three concentrations of 0.1, 0.2 and 0.5 g / dl. The intrinsic viscosity is calculated by the calculation method described in “Polymer Solution, Polymer Experiments 11” (published by Kyoritsu Shuppan Co., Ltd.), page 491. That is, the reduced viscosity is plotted against the concentration, and the concentration is extrapolated to zero. Obtained by extrapolation. Note that tetralin was used as a solvent, and measurement was performed at a temperature of 135 ° C.

(2) Graft ratio (mass%)
The graft ratio of the compound (b) in the modified olefin copolymer (C) was determined by the following method (procedures [1] to [7]).
[1] A solution was prepared by dissolving 1.0 g of the modified olefin copolymer (C) in 10 ml of xylene.
[2] The prepared solution was added dropwise to 300 ml of methanol with stirring to reprecipitate the modified olefin copolymer (C).
[3] The reprecipitated olefin copolymer modified product (C) was recovered.
[4] The recovered modified olefin copolymer (C) was vacuum dried at 80 ° C. for 8 hours.
[5] The dried modified olefin copolymer (C) was hot-pressed to produce a film having a thickness of 100 μm.
[6] The infrared absorption spectrum of this film was measured, and the graft ratio was determined from the absorption near 1730 cm ⁻¹ of the spectrum.

(3) Izod impact strength (IZOD, unit: KJ / m ² )
The impact strength of the molded body produced from the polyolefin resin composition was measured according to the method defined in JIS-K-7110. The test piece used was a 3.2 mm thick test piece formed by injection molding. The measurement was performed at 23 ° C., 10 ° C., and −30 ° C.

(4) Elongation at break (UE) (unit%)
The elongation at break of the molded product produced from the polyolefin resin composition was measured at 23 ° C. and a tensile speed of 50 mm / min using the same test piece as described above in accordance with ASTM D638.

(5) Scratch resistance test The scratch resistance of the molded body produced from the polyolefin resin composition was determined using a scratch tester (special large UF manufactured by Ueshima Seisakusho Co., Ltd.) for a scratch test with a tip having a radius of 300 μm. A load of 350 g was placed on the needle and evaluated at a speed of 600 mm / min. The test piece used was a 100 mm × 400 mm × 3 mm flat plate.
In the case where scratches could not be confirmed by visual observation, the evaluation was made as ◯, and when the scratches could be confirmed, evaluation was made as x.

<Production of modified olefin copolymer (C)>
[Production of Copolymer (a)]
In an approximately 1,500 liter stirring tank replaced with dry nitrogen gas, 39 kg of vinylcyclohexane and 357 kg of dehydrated toluene were charged.
The temperature of the stirring tank was raised to 47 ° C., charged with 0.015 MPa of hydrogen and 0.6 MPa of ethylene, and then a toluene solution of triisobutylaluminum [manufactured by Tosoh Finechem Co., Ltd., Al atom equivalent concentration 20.3 mass %] 1.2 kg, dehydrated toluene 7 kg, diethylsilylene (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride 66 mg dissolved in dehydrated toluene 1.7 kg Then, 7 kg of dehydrated toluene, 3 g of N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate accompanied by 7 kg of dehydrated toluene, and 7 kg of dehydrated toluene were sequentially added to initiate polymerization.
During the reaction, ethylene was continuously replenished so as to maintain 0.6 MPa, and the temperature was kept at about 54 ° C. After stirring for 2 hours, 1 kg of ethanol was charged and the polymerization was stopped. The reaction solution and 195 kg of 2% by mass hydrochloric acid were brought into contact with stirring once. After removing the aqueous layer, 194 kg of water was stirred into contact with the organic layer, and the aqueous layer was removed. The same operation was repeated twice more, and then the pressure was reduced under heating to evaporate the non-initial components. As a result, 30 kg of an ethylene-vinylcyclohexane copolymer containing 10% by mass of volatile matter was obtained.
As a result of analyzing the polymer partially taken from this, the content of the vinylcyclohexane monomer unit of the polymer was 12 mol%, and [η] was 0.54 dl / g.

<Production of modified olefin copolymer (C)>
With respect to 100 parts by mass of the copolymer (a) obtained by the above method, 0.4 parts by mass of maleic anhydride as the compound (b) and (1,3-bis (t- Butyl peroxyisopropyl) benzene was used in an amount of 0.04 parts by mass (trade name Perkadox 14-40C manufactured by Kayaku Akzo Co., Ltd.) The kneading part of the extruder was divided into the first half and the second half, and the granulation temperature of the first half The kneading was carried out at 250 ° C., the kneading temperature in the latter half part at 60 ° C., and the screw rotation speed at 260 rpm, and the graft ratio of maleic anhydride was 0.2% by mass.

In Examples 1 and 2 and Comparative Examples 1 and 2, each component as shown in Table 1 was used.
(1) Component (A) (BC-1)
The intrinsic viscosity ([η] P) of the propylene homopolymer portion is 1.0 dl / g, and the intrinsic viscosity ([η] EP) of the propylene-ethylene random copolymer portion is 5.0 dl / g. -The content of the propylene-ethylene random copolymer part relative to the ethylene block copolymer is 16% by mass, the ethylene content of the propylene-ethylene random copolymer part is 35% by mass, and the MFR (230 ° C) is 32 g / It was 10 minutes.
(2) Component (A) (H-1)
A propylene homopolymer (trade name: U501E1) manufactured by Sumitomo Chemical Co., Ltd. was used. The propylene homopolymer had a melt flow rate (MFR) at 230 ° C. of 120 g / 10 minutes.
(3) Component (B) (T-1)
Talc (trade name: MWHST) manufactured by Hayashi Kasei Co., Ltd. was used.
(4) Component (C) (M-1)
The modified olefin copolymer (C) produced by the method described above was used.
(5) Component (C) (M-2)
Maleic anhydride-modified polypropylene (trade name: MPA101) manufactured by Sumitomo Chemical Co., Ltd. was used. The graft ratio of maleic anhydride was 0.4% by mass.
(6) Component (D) (E-1)
Erucic acid amide (trade name: Neutron-S) manufactured by Nippon Seika Co., Ltd. was used.

(7) Component (E) (ER-1)
Ethylene-1-octene copolymer rubber (trade name: ENGAGE 8200) manufactured by Dow Chemical Company was used. The melt flow rate at 190 ° C. of this ethylene-1-octene copolymer rubber was 5 g / 10 minutes.
(8) Component (E) (ER-2)
Ethylene-1-octene copolymer rubber (trade name: ENGAGE 8150) manufactured by Dow Chemical Company was used. The ethylene-1-octene copolymer rubber had a 190 ° C. melt flow rate of 0.5 g / 10 min.

Ingredient (A), ingredient (B), ingredient (C), ingredient (D), and ingredient (E) were blended at the composition ratio shown in Table 1. At that time, 0.05 parts by weight of an organic peroxide (manufactured by Kayaku Akzo Co., Ltd.) was added to the heat stabilizer (Sumitomo Chemical Co., Ltd., trade name: Sumilizer GA-80) with respect to 100 parts by weight of the total amount of the above components. , Trade name: Parka Dox 14-40C) was added in an amount of 0.032 parts by mass with respect to 100 parts by mass of the total amount of the above components.
These were uniformly premixed with a Henschel mixer and a tumbler, and then using a twin-screw kneading extruder (TEX44αII manufactured by Nippon Steel), the cylinder temperature was 200 ° C., the extrusion amount was 50 kg / hr, the screw rotation speed was 200 rpm, and under vent suction. Thus, a polyolefin resin composition was produced.

  Test pieces for evaluating physical properties were produced under the following injection molding conditions. The polyolefin resin composition obtained above was dried at 120 ° C. for 2 hours with a hot air drier, 3 parts of the pigment master batch was dry blended, and then the molding temperature was 180 ° C. using an IS150E-V type injection molding machine manufactured by Toshiba Machine. Injection molding was performed at a mold cooling temperature of 50 ° C., an injection time of 15 sec, and a cooling time of 30 sec.

  The evaluation results are shown in Table 2. Comparative Example 1 containing no component (C) was poor in scratching properties, and Comparative Example 2 to which maleic anhydride-modified polypropylene was added improved scratching properties, but reduced elongation and IZOD impact strength. Comparative Example 3 to which the unmodified copolymer (a) was added showed good elongation and IZOD, but poor scratching properties.

Claims (3)

99% by mass to 60% by mass of polyolefin resin (A),
40% by mass to 1% by mass of inorganic filler (B),
Olefin-based elastomer and / or vinyl aromatic compound-based elastomer (E) 0% by mass to 30% by mass (provided that the total of (A), (B), and (E) is 100% by mass),
The following modified olefin copolymer (C), 0.01 parts by mass to 5 parts by mass with respect to 100 parts by mass of the above (A), (B), and (E),
0.01 parts by mass to 1 part by mass of a lubricant (D),
A polyolefin resin composition containing
Olefin copolymer modified product (C): copolymer of at least one olefin compound selected from the group consisting of ethylene and an α-olefin compound having 3 or more carbon atoms, and an alicyclic vinyl compound ( a) 100 parts by mass;
0.01 to 20 parts by weight of a compound (b) having at least one unsaturated group (i) and at least one polar group (ii);
0.001 to 20 parts by weight of organic peroxide (c),
It is obtained by reacting.   The compound (b) is composed of an unsaturated carboxylic acid, an unsaturated carboxylic acid ester, an unsaturated carboxylic acid amide, an unsaturated carboxylic acid anhydride, an unsaturated epoxy compound, an unsaturated alcohol, an unsaturated amine, and an unsaturated isocyanate. The polyolefin resin composition according to claim 1, which is at least one selected from the group consisting of:   The molded object manufactured using the polyolefin resin composition of Claim 1 or 2.