CN1329416C - Modified propylene polymer and polyolefin resin composition - Google Patents

Abstract

A polyolefin resin composition containing the following (A), (B) and (C) or containing the following (A), (B), (C) and (D): (A) α- Polymers of olefins; (B) modified propylene-based polymers satisfying the following (1)-(4): (1) polarity derived from compounds containing ethylenic double bonds and polar groups in the same molecule The content of the group part is 0.10-0.30mmol/g, (2) the intrinsic viscosity ([η] _A ) measured in tetralin at 135°C is 0.8-3.0dl/g, (3) the molecular weight distribution (Mw/Mn ) exceeds 2.5, (4) the molecular weight (Mw) of 10,000 or less is 5% by weight or less; (C) an organic layered inorganic compound; (D) a rubbery polymer.

Description

Modified propylene polymer and polyolefin resin composition

technical field

The present invention relates to a modified propylene-based polymer, a polyolefin resin composition, and a method for producing them, which are used in automotive materials requiring low specific gravity and high physical properties (mechanical properties, thermal properties, etc.), and industrial materials using engineering plastics.

Background technique

Acrylic resins having physical properties comparable to engineering plastics (high heat resistance, high strength, etc.) have conventionally been produced by compounding inorganic fillers such as glass fibers and talc with propylene polymers. In addition, in order to improve the above-mentioned comprehensive physical properties to the level of engineering plastics such as nylon, increasing the content of inorganic fillers and using special inorganic fillers have been carried out. As a result, the comprehensive physical properties have been greatly improved, but on the other hand, the advantages of low specific gravity and low price of polypropylene itself have been completely lost.

Therefore, the development of nano-dispersion technology of inorganic fillers is constantly being developed to achieve a dramatic improvement in comprehensive physical properties without significantly compromising the excellent advantages of polyolefins. For example, it is disclosed that layered clay minerals are dispersed in an acrylic resin at a nanoscale level to achieve a dramatic improvement in physical properties (for example, refer to JP-A-6-41346). In addition, improvements to this technology are also disclosed (for example, refer to JP-A-2001-240709, JP-A-2002-37940, and JP-A-2002-167484). These are all techniques for improving physical properties by uniformly and highly dispersing (nanodispersing) clay in an acrylic resin that has no compatibilizing performance originally.

However, these techniques have not yet achieved the desired high overall physical properties, and are considered to have a disadvantage of lack of flexibility from the viewpoint of resin design.

On the other hand, attempts to improve the propylene-based polymer itself have also been made. For example, an acid-modified product in which an unsaturated carboxylic acid or an anhydride thereof is added to a propylene-based polymer and a method for producing the same are known. Most of the acid-modified products are low-molecular-weight high-acid addition products for the purpose of resin modification. Therefore, it has not been able to be used as a molded body so far.

On the other hand, although there are few attempts to produce a chemically reactive polymer while maintaining the physical properties of the propylene-based polymer.

When modifying polypropylene with unsaturated carboxylic acid or its anhydride, it is disclosed that about 10% of by-product low-molecular-weight substances that adversely affect the physical properties are disclosed. After dissolving the modified polypropylene in a solvent, A method of precipitating it in a poor solvent, or (2) a technique of removing it by extracting it while refluxing it with a specific solvent (for example, refer to JP-A-63-90511). This technology often produces low molecular weight bodies.

In addition, a technique of removing unreacted unsaturated carboxylic acid or anhydride thereof at a high temperature of 120° C. using a large amount of diketone compound 30 times the amount of modified polypropylene is disclosed (for example, refer to JP-A-2-185505 Bulletin). In addition, a technique for removing unreacted unsaturated carboxylic acid or its anhydride at a high temperature of 90-110° C. using a mixed solvent of a large amount of diketone and aromatic hydrocarbon 7 times the amount for modified polypropylene (e.g. , refer to Japanese Patent Laid-Open Publication No. 4-202202), in addition to the disadvantages of using a large amount of solvent, the two technologies are processed at high temperatures, so the modified polypropylene may melt and stick.

As described above, for the production method of an acid-modified propylene-based polymer that hardly by-produces a low-molecular-weight body that adversely affects physical properties, the unreacted unsaturated carboxylic acid or its anhydride is removed under mild conditions using a small amount of solvent Methods and researches on actively controlling the balance between the amount of acid addition and resin properties (molecular weight, regularity, etc.) have hardly been conducted.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a polyolefin resin composition having high comprehensive properties without impairing properties of polyolefin, and a method for producing the same.

Another object of the present invention is to provide a low-molecular-weight modified propylene-based polymer having excellent resin properties and hardly having by-products adversely affecting physical properties, and a method for producing the same.

Contents of the invention

The present invention provides the following modified propylene-based polymers, polyolefin resin compositions, and methods for producing them.

[1], modified propylene polymer, which satisfies the following (1)-(4):

(1) The content of the polar group moiety derived from a compound containing an ethylenic double bond and a polar group in the same molecule is 0.10-0.30 mmol/g,

(2) The intrinsic viscosity ([η] _A ) measured in tetralin at 135°C is 0.8-3.0dl/g,

(3) The molecular weight distribution (Mw/Mn) exceeds 2.5,

(4) The amount of components having a molecular weight (Mw) of 10,000 or less is 5% by weight or less.

[2] The modified propylene-based polymer described in [1], wherein the intrinsic viscosity ([η] _A ) of the modified propylene-based polymer and the propylene-based polymer used as its raw material are equal to each other at 135°C and 4°C. The ratio ([η] _A /[η] _s ) of the intrinsic viscosity ([η] _S ) measured in hydrogenated naphthalene is 0.2 or more.

[3], [1], or [2], wherein the compound containing an ethylenic double bond and a polar group in the same molecule is an unsaturated carboxylic acid and/or its derivatives.

[4], The method for producing a modified propylene-based polymer according to any one of [1]-[3], comprising: combining a propylene-based polymer, a radical initiator, and an ethylenic bond-containing compound in the same molecule Compounds having a double bond and a polar group are mixed and melt-kneaded at a temperature not lower than the melting point of the propylene-based polymer but lower than 180°C.

[5] A polyolefin resin composition comprising the following (A), (B) and (C) or the following (A), (B), (C) and (D):

(A) Polymers of α-olefins having 3 or more carbon atoms,

(B) The modified propylene polymer according to any one of [1] to [3],

(C) Organic layered inorganic compound,

(D) Rubbery polymer.

[6], The polyolefin resin composition described in [5], wherein the melt flow rate of the α-olefin polymer (A) is 0.1-200 g/10 minutes,

The α-olefin polymer (A) is an average of a first α-olefin having a carbon number of 3 or more and 0-20% by weight of a second α-olefin having a carbon number of 2-20 different from the first α-olefin. polymer or copolymer.

[7], [5] or [6], the production method of the polyolefin resin composition, which comprises the above (A), (B) and (C), or (A), (B), ( C) and (D) are mixed and melt-kneaded.

Description of drawings

Figure 1 is a schematic diagram of a twin-screw extruder.

Detailed ways

The polyolefin resin composition of the present invention will be described below.

The resin composition of this invention contains following (A), (B) and (C), or following (A), (B), (C) and (D).

(A) Polymers of α-olefins having 3 or more carbon atoms;

(B) A modified propylene-based polymer satisfying the following (1)-(4):

(1) The content of the polar group moiety derived from a compound containing an ethylenic double bond and a polar group in the same molecule is 0.10-0.30 mmol/g,

(2) The intrinsic viscosity ([η] _A ) measured in tetralin at 135°C is 0.8-3.0dl/g,

(3) The molecular weight distribution (Mw/Mn) exceeds 2.5,

(4) The amount of components with molecular weight (Mw) less than 10,000 is less than 5% by weight;

(C) organic layered inorganic compounds;

(D) Rubbery polymer.

First, each component of the composition of the present invention will be described.

Examples of the α-olefin polymer (A) include homopolymers of α-olefins having 3 or more carbon atoms, preferably 3 to 20 carbon atoms, and α-olefins having 3 or more carbon atoms and other α-olefins having 2 to 20 carbon atoms. , preferably random copolymers, block copolymers, and graft copolymers of α-olefins having 2 to 10 carbon atoms. Here, the amount of the copolymerized portion of the α-olefin having a carbon number of 2 to 20 is preferably 0 to 20% by weight, more preferably 0 to 10% by weight.

Specific examples of the α-olefin polymer (A) include homopolymers such as propylene, 1-butene, and 4-methyl-1-pentene, propylene and ethylene, propylene and 1-butene, 4-methylpentene, etc. Various copolymers of -1-pentene. Among them, a homopolymer of propylene and a block copolymer of propylene and ethylene are preferable. These may be used alone or in combination of two or more.

The melt flow rate of the α-olefin polymer (A) is preferably 0.1 to 200 g/10 minutes, more preferably 1 to 100 g/10 minutes. If it is less than 0.1 g/10 minutes, the moldability of a composition may fall. On the other hand, when it exceeds 200 g/10 minutes, the impact resistance of a composition may fall.

The α-olefin polymer (A) can be produced by a known method.

The modified propylene polymer (B) satisfies the following (1)-(4).

(1) The content of the polar group moiety derived from a compound (modifier) containing an ethylenic double bond and a polar group in the same molecule is 0.10-0.30 mmol/g,

(2) The intrinsic viscosity ([η] _A ) measured in tetralin at 135°C is 0.8-3.0dl/g,

(3) The molecular weight distribution exceeds 2.5,

(4) The amount of components having a molecular weight of 10,000 or less is 5% by weight or less.

In the above (1), if the content of the polar group part is less than 0.10mmol/g, when it is used in combination with other resins and fillers, in order to fully demonstrate the effect of the polar group, the mixing amount must be increased. cause economic loss. On the other hand, if it exceeds 0.30 mmol/g, the hue will decrease, and production stability and molecular weight adjustment during production will become difficult. In particular, when used in the composition of the present invention, if it is less than 0.10 mmol/g, the exfoliation and dispersion of the organic layered inorganic compound (C) will not sufficiently occur. On the other hand, if it exceeds 0.30 mmol/g, the compatibility with the α-olefin polymer (A) decreases. The content of the polar group moiety is preferably 0.15-0.3 mmol/g, more preferably 0.2-0.3 mmol/g.

The modifying agent constituting the polar group part will be described below.

In the above (2), if the intrinsic viscosity ([η] _A ) is less than 0.8 dl/g, it is likely to cause a decrease in mechanical properties when used alone or in combination with other resins and fillers. On the other hand, if it exceeds 3.0 dl/g, when used alone or in combination with other resins and fillers, it will cause a reduction in moldability and cause gelation in molded articles. The intrinsic viscosity ([η] _A ) is preferably 0.9-2.5 dl/g, more preferably 1.0-2.0 dl/g.

The ratio ([η] _A /[η] _S ) of the above intrinsic viscosity ([η] A ) to the intrinsic viscosity ([η] _{S )} of the propylene-based polymer used as a raw material for the modified polymer is preferably 0.2 or more, more preferably Preferably it is 0.25 or more. If the ratio is less than 0.2, the molecular weight distribution of the modified polymer tends to be 2.5 or less.

In addition, this ratio indicates the degree of cutting of the molecular chain of the modified polymer, and the larger the ratio, the less the molecular chain of the modified polymer is cut.

The raw material propylene-based polymer will be described below.

In the above (3), if the molecular weight distribution (Mw/Mn) is 2.5 or less, mixing in the composition becomes considerably difficult and the rigidity decreases. The molecular weight distribution preferably exceeds 2.8, more preferably exceeds 3.0. Here, Mw represents a weight average molecular weight, and Mn represents a number average molecular weight.

The molecular weight distribution (Mw/Mn) can be measured by, for example, gel permeation chromatography (GPC).

In the above (4), if the amount of the component having a molecular weight (Mw) of 10,000 or less exceeds 5% by weight, the impact resistance of the composition will decrease. In addition, it may cause adhesion of the entire surface of the molded article and deterioration of the surface properties. The amount of this component is preferably 3% by weight or less, more preferably 2% by weight or less.

In addition, the amount of components having a molecular weight (Mw) of 10,000 or less means the amount of components having a molecular weight (Mw) of 10,000 or less in the GPC curve.

The modified propylene-based polymer (B) preferably satisfies the following (5)-(6).

(5) The content of unreacted modifier is below the analysis limit value

(6) The melting point is 145-170°C

In the above (5), the content of the unreacted modifier can be obtained by the following operation.

After dissolving the modified polymer in p-xylene, it was precipitated in acetone to completely remove the unreacted modifier. This operation was repeated five times in total, and the content of the polar group moiety in the modified polymer was quantified by the above-mentioned method. This quantitative value was defined as the content of the modifier in the modified polymer containing no unreacted modifier (solvent refining method).

The content of the unreacted modifier being below the analytical limit value means that the content of the modifier in the modified polymer is within the analytical error range of the above quantitative value.

In the above (6), if the melting point is less than 145° C., when used alone or in combination with other resins and fillers, the heat resistance may be lowered together. The melting point is more preferably 155-170°C.

The modified polymer (B) can be added to the raw material propylene polymer by mixing the raw material propylene polymer, a radical initiator, and a compound (modifier) containing an ethylenic double bond and a polar group in the same molecule. It is produced by melt-kneading at a temperature of not less than the melting point of the polymer and less than 180°C.

Examples of raw material propylene-based polymers include propylene homopolymers, random copolymers and block copolymers of propylene and α-olefins (such as ethylene, 1-butene, 4-methyl-1-pentene, etc.). , graft copolymers and mixtures thereof. Among them, a propylene homopolymer is preferable.

The intrinsic viscosity [η] _s of the raw material propylene-based polymer measured in tetralin at 135°C is preferably 3 dl/g or more, more preferably 4 to 10 dl/g. If it is less than 3 dl/g, the polar group content may decrease (0.10 or less) or the molecular weight may decrease (η<0.8).

The raw material propylene-based polymer preferably satisfies the following (1)-(3).

(1) The amount of soluble components in boiling heptane is below the analytical limit value

(2) Molecular weight distribution (Mw/Mn) is 5 or less

(3) The amount of components having a molecular weight (Mw) of 1 million or more is 25% by weight or more

In the above (1), the so-called boiling heptane soluble content below the analytical limit means that the amount of extracted residual polymer obtained by extracting 10.000 g of the raw material polymer Soxhlet 5 times is within the range of 10 ± 0.002 g ( substantially below the analytical limit).

In (2) above, if the molecular weight distribution (Mw/Mn) exceeds 5, there is a high possibility of by-production of components having a molecular weight (Mw) of 10,000 or less in the modified polymer exceeding 5% by weight. The molecular weight distribution is not particularly limited as long as it is 5 or less, but is more preferably 3-5.

In addition, this molecular weight distribution can be calculated similarly to the molecular weight distribution of a modified polymer.

In the above (3), if the amount of components having a molecular weight (Mw) of 1,000,000 or more is less than 25% by weight, the content of the polar group portion may decrease. The amount of the component is not particularly limited as long as it is 25% by weight or more, but is more preferably 25 to 50% by weight.

In addition, the amount of components having a molecular weight (Mw) of 1 million or more means the amount of components having a molecular weight (Mw) of 1 million or more in the GPC curve.

Examples of radical initiators include butyl peroxide, α, α-di(t-butylperoxy) dicumyl, benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, tert-butyl peracetate, tert-butyl peroxydiethyl acetate, tert-butyl perisobutyrate, tert-butyl per-sec-octoate, tert-butyl perpivalate, cumyl perpivalate, benzene tert-butyl formate, tert-butyl peroxyphenyl acetate, tert-butyl cumyl peroxide, di-tert-butyl peroxide, 1,1-di-tert-butyl peroxy-3,3,5- Trimethylcyclohexane, 1,1-di-tert-butylperoxycyclohexane, 2,2-di-(tert-butylperoxy)butane, lauroyl peroxide, 2,5-dimethyl- 2,5-bis(peroxybenzoate)hexyne-3, 1,3-bis(tert-butylperoxyisopropyl)benzene, 1,4-bis(tert-butylperoxyisopropyl) Benzene, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexyne-3, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane, 2,4,4-trimethylbenzyl-2-hydroperoxide, dicumene hydroperoxide, cumene hydroperoxide, 4,4-di-tert-butylperoxyvalerate n-butyl, Di-tert-butyl peroxyhexahydrophthalate, di-tert-butyl peroxy azelate, tert-butyl peroxy-3,3,5-trimethylhexanoate, tert-butyl peroxy - Isopropyl carbonate, succinic acid peroxide and vinyltris-(tert-butylperoxy)silane, etc. Among them, 1,3-di(tert-butylperoxyisopropyl)benzene, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexyne-3, dicumyl peroxide α,α-di(tert-butylperoxy)dicumene, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane. These may be used alone or in combination of two or more.

Examples of the polar group contained in the modifier include carboxylic acid group, carboxylic acid anhydride group, carboxylate group, carboxyl halide group, carboxamide group, carboximide group, carboxylate group, sulfonic acid group, etc. group, sulfonate group, sulfonyl chloride group, sulfonamide group, sulfonate group, epoxy group, amino group, oxazoline group, etc. Among them, carboxylic acid groups and carboxylic anhydride groups are preferable.

The modifying agent used in the present invention is not particularly limited, and is preferably an unsaturated carboxylic acid containing the aforementioned polar group and/or its derivatives.

Examples of unsaturated carboxylic acids or derivatives thereof include unsaturated monocarboxylic or dicarboxylic acids or derivatives thereof. Specific examples of these derivatives include acid anhydrides, esters, halides, amides, imides, and salts of carboxylic acids. Among these, unsaturated dicarboxylic acids or anhydrides thereof are preferred.

Specific examples of unsaturated monobasic or dibasic carboxylic acids include acrylic acid, methacrylic acid, maleic acid, endobicyclo[2.2.1]-5-heptene-2,3-dicarboxylic acid (Endic acid), Malic acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, najic acid, and the like.

Specific examples of derivatives of unsaturated carboxylic acids include maleic acid chloride, maleimide, maleic anhydride, Endik anhydride, methyl acrylate, acrylamide, methyl methacrylate, and glycidyl methacrylate. , Methacrylamide, Citraconic Anhydride, Itaconic Anhydride, Nagic Anhydride, Monomethyl Maleate, Dimethyl Maleate, Monomethyl Fumarate, Dimethyl Fumarate, etc.

Among these unsaturated carboxylic acids or derivatives thereof, acrylic acid, methacrylic acid and maleic anhydride are preferred, and maleic anhydride is more preferred. These may be used alone or in combination of two or more.

When producing a modified polymer, the radical initiator is preferably mixed in an amount of 0.1 to 5 parts by weight, more preferably 0.5 to 2 parts by weight, based on 100 parts by weight of the base polymer. When the compounding quantity is less than 0.1 weight part, a polar group content may fall. On the other hand, if it exceeds 5 parts by weight, the molecular weight may decrease and the molecular weight distribution (Mw/Mn) may be 2.5 or less.

In addition, the modifier is preferably mixed in an amount of 1.5 to 10 parts by weight, more preferably 2 to 6 parts by weight, based on 100 parts by weight of the base polymer. When the compounding quantity is less than 1.5 weight part, a polar group content may fall. On the other hand, if it exceeds 10 parts by weight, the residual amount of unreacted modifier may increase and production stability may decrease. Furthermore, the hue of a product may also deteriorate significantly.

The mixing method of the components is not particularly limited, and examples thereof include a dry mixing method. After mixing, for example, a twin-screw extruder shown in FIG. 1 can be used to melt and knead at a temperature not lower than the melting point of the base polymer but lower than 180°C. When melting and kneading, it is preferable to make the temperature of the resin from the lower part 1 of the hopper of the barrel of the twin-screw extruder to the front part 2 of the plasticizing zone be below 150°C, and make the resin temperature from the plasticizing zones 3 and 4 of the barrel to the die head The resin temperature of 5 is not less than the melting point of the base polymer and less than 180°C. At this time, in order to prevent scattering of the modifier, the temperature of the resin in the lower part of the hopper 1 is preferably 130°C or lower, more preferably 100°C or lower, and particularly preferably room temperature - 60°C.

When the melt-kneading temperature is 180° C. or higher and the base polymer is modified so that the content of the polar group portion of the modified polymer falls within the above-mentioned range, the molecular weight distribution tends to narrow to 2.5 or less. In addition, the so-called melt kneading temperature means the temperature of the highest temperature part in the barrel of the twin-screw extruder. In FIG. 1, it means the temperature between the plasticizing zones 3 and 4 from the die head 5 to the barrel. .

The melt-kneading (residence) time is preferably 10 to 120 seconds.

It is preferable to perform melt kneading under an inert atmosphere. At this point, steam can be added, or the volatile components can be removed under reduced pressure.

As the molding machine, a single-screw extruder, a twin-screw extruder, or the like is used.

Examples of the twin-screw extruder include 20 mm Raboplastic Mill, 35 mm TEM (twin-screw extruder manufactured by Toshiba Machinery), and the like.

If the modified propylene-based polymer (B) is produced by this method, it is not necessary to use an ultrahigh molecular weight polymer as a production raw material. In addition, since the decomposition ratio of manufacturing raw materials and the like is small, production stability and cost reduction at the time of manufacturing can be achieved. In addition, since the usage-amount of a radical initiator (peroxide) can be reduced, improvement of the hue of a modified polymer can also be expected.

The modified propylene-based polymer of the present invention maintains the characteristics of the raw material polymer due to its high molecular weight, so it can be used as a film or a molded article. In addition, since almost no unreacted modifier is contained, and the content of low molecular weight body is also small, there is little precipitation of low molecular weight body. Therefore, it can also be used in applications where precipitation, such as a thin film, becomes a problem.

In addition to these characteristics, the modified propylene polymer of the present invention has the characteristics of a large content of polar group moieties and a wide molecular weight distribution, so it is suitable as a material for producing polyolefin nanocomposites. If it is the modified polymer of the present invention, even if it is mixed in a large amount during the production of the nanocomposite, it is possible to remarkably suppress a decrease in physical properties.

That is, the modified propylene-based polymer (B) has characteristics of high polar group content, high molecular weight, wide molecular weight distribution, and low content of low molecular weight components. The use of a modified polymer having such properties is effective in improving the overall physical properties of the composition of the present invention.

Examples of the organic layered inorganic compound (C) include layered silicates in which interlayer cations are substituted with alkylammonium. Examples of layered silicates include layered clay minerals, specifically, layered minerals of smectites such as montmorillonite, bentonite, saponite, hectorite, beidellite, steibunsite, and nontronite. Clay minerals; vermiculite; halloysite; mica; fluorides of these, etc. These can be natural or synthetic.

The phyllosilicate is preferably a swelling substance in which interlayer cations are easily substituted with alkylammonium. The cation exchange capacity of the layered silicate is preferably 70 meq/100 g or more, more preferably 85 to 250 meq/100 g.

Specific examples of preferably used layered silicates include montmorillonite, bentonite, swelling mica, swelling fluoromica, etc., and montmorillonite and swelling fluoromica are particularly preferable.

The interlayer cations are cations held by the layered silicate between layers, and examples thereof include potassium ions, sodium ions, calcium ions, and barium ions.

Examples of alkyl ammonium include hexyl ammonium ion, octyl ammonium ion, 2-ethylhexyl ammonium ion, dodecyl ammonium ion, octadecyl ammonium ion, dioctyl dimethyl ammonium ion, trioctyl ammonium ion, trioctyl ammonium ion, and trioctyl ammonium ion. Ammonium ion, stearyl ammonium ion, distearyl ammonium ion, etc. Among them, stearyl ammonium ion, dioctyldimethyl ammonium ion, trioctyl ammonium ion, stearyl ammonium ion, and distearyl ammonium ion are preferable.

Some or all of the interlayer cations may be substituted. The replacement amount is preferably more than 50% of the interlayer cations, more preferably 80-100%.

The organic layered inorganic compound (C) can be produced by a known method. For example, the suspension obtained by dispersing the above-mentioned phyllosilicate in water and the aqueous solution of the above-mentioned alkylammonium salt are mixed, and after stirring at room temperature for 30 minutes to 5 hours, the solid content is extracted from the reaction solution. It is obtained by solid-liquid separation, washing and drying. When mixing the phyllosilicate and the alkylammonium salt, the cation exchange capacity of the phyllosilicate is preferably mixed in an amount of 0.5 to 1.5 times, more preferably 0.8 to 1.2 times the equivalent of the alkylammonium salt.

Since the interlayer cations of the organic layered inorganic compound (C) are substituted by the alkylammonium, the interlayer distance is increased compared with the phyllosilicate before replacement. When the organic layered inorganic compound (C) in this state is mixed with the modified propylene polymer (B), a part of the chain of the modified propylene polymer (B) is bonded to the organic layered inorganic compound (C) , or invade its interlayer. As a result, in the composition, the interlayer distance of the organic layered inorganic compound (C) is further increased. In the present invention, the organic layered inorganic compound (C) is uniformly and finely dispersed in the composition by the shear stress received during melt-kneading.

The organic layered inorganic compound (C) may be used alone or in combination of two or more.

Examples of the rubbery polymer (D) include olefin-based elastomers such as ethylene/propylene rubber, olefin-based elastomers such as ethylene/1-octene copolymers, and hydrogenated styrene/butadiene block copolymers (SEBS). and other styrene elastomers. Among these, styrene-based elastomers are preferred, and hydrogenated styrene/butadiene block copolymers are more preferred. These may be used alone or in combination of two or more.

Other additives such as nucleating agents, antioxidants, ultraviolet absorbers, external lubricants, plasticizers, antistatic agents, colorants, flame retardants, and flame retardant aids can be appropriately mixed in the composition of the present invention as needed . Examples of the nucleating agent include metal salts of carboxylic acids such as aluminum di(p-tert-butylbenzoate), phosphoric acids such as methylene bis(2,4-di-tert-butylphenol) acid sodium phosphate, etc. Metal salts, talc, phthalocyanine derivatives, etc. Examples of plasticizers include polyethylene glycol, polyamide oligomers, ethylene bisstearamide, phthalates, polystyrene oligomers, polyethylene wax, mineral oil, silicone oil, etc. . Examples of the flame retardant include brominated polystyrene, brominated syndiotactic polystyrene, and brominated polyphenylene ether. As a flame retardant auxiliary agent, antimony compounds, such as antimony trioxide, etc. are mentioned, for example. Examples of antioxidants include phosphorus-based antioxidants such as (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphate (manufactured by Adeka Aigas, PEP-36), four [Methylene-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)] propionate (manufactured by Adeka Aigas, MARK A060) and other hindered phenolic antioxidants, etc. . These additives may be used alone or in combination of two or more.

The production method of the composition of this invention is demonstrated below.

The composition of the present invention can be produced by mixing and melt-kneading the above components. In addition, there are no particular limitations on the production conditions such as the mixing method of each component, the temperature and time during melt-kneading, and can be appropriately adjusted.

The mixing amount of each component, in the composition containing α-olefin polymer (A), modified propylene polymer (B) and organic layered inorganic compound (C), (A) component is preferably 50 -95 parts by weight, more preferably 50-85 parts by weight, (B) component is preferably 4-50 parts by weight, more preferably 10-50 parts by weight, (C) component is preferably 1-30 parts by weight, more preferably Preferably it is 5-20 parts by weight.

Furthermore, in a composition containing an α-olefin polymer (A), a modified propylene-based polymer (B), an organic layered inorganic compound (C) and a rubbery polymer (D), the (A) component Preferably 30-95 parts by weight, more preferably 40-75 parts by weight, (B) component is preferably 4-50 parts by weight, more preferably 10-50 parts by weight, (C) component is preferably 1-30 parts by weight Parts, more preferably 5-20 parts by weight, (D) component is preferably 5-40 parts by weight, more preferably 10-30 parts by weight.

If the compounding quantity of (A) component is less than 50 weight part or 30 weight part, cost may rise, and the balance of rigidity and impact resistance may fall. On the other hand, if it exceeds 95 parts by weight, the effect of the (C) component may be difficult to exhibit and the balance of rigidity and impact resistance may decrease.

If the compounding quantity of (B) component is less than 4 weight part, peeling dispersion|distribution of (C) component may become difficult. On the other hand, if it exceeds 50 parts by weight, physical properties such as impact resistance may decrease while cost increases.

If the compounding quantity of (C) component is less than 1 weight part, the rigidity improvement effect of a composition may become small. On the other hand, when it exceeds 30 weight part, peeling dispersion|distribution of (C)component will become difficult, and the lightweight effect of a composition may reduce.

If the compounding quantity of (D) component is less than 5 weight part, the impact resistance of a product may fall. On the other hand, when it exceeds 40 weight part, rigidity may fall.

In the composition of the present invention, by mixing the modified propylene-based polymer (B), the amount of the organic layered inorganic compound (C) can be mixed in a small amount, so that the low-temperature properties of the α-olefin polymer (A) can not be impaired. specific gravity properties. In addition, since the organic layered inorganic compound (C) can be highly dispersed, physical properties such as rigidity, impact resistance, and heat resistance can be maintained at a high level and well-balanced. The composition of the present invention not only has a low specific gravity, but also exhibits properties equivalent to or better than conventional high specific gravity polypropylene-based composite materials (such as talc-filled polypropylene, etc.).

The composition of the present invention is suitable for automobile materials such as bumpers and instrument panels, and industrial materials using engineering plastics.

Example

Examples of the present invention will be described below, but the present invention is not limited to these Examples.

In addition, the content of the polar group moiety of the modified propylene polymer, the intrinsic viscosity [η] _A , the molecular weight distribution (Mw/Mn), the amount of components with a molecular weight (Mw) of 10,000 or less (LP amount) and the amount of the modified propylene polymer The intrinsic viscosity [η] _S and melting point of the raw material propylene polymer of the product were measured by the following method.

(1) Content of polar groups

The modified polymer film was molded, and the Fourier transform infrared absorption spectrum was measured using it to calculate.

(2) Intrinsic viscosity [η] _A , [η] _S

Measured at 135°C in tetralin.

(3) Mw/Mn, LP amount

Calculated from Mw and Mn in terms of polypropylene measured on the following apparatus and conditions. The amount of LP was determined as the amount of components having a molecular weight (Mw) of 10,000 or less in the GPC curve.

(GPC measurement device)

Column: TOSOGMHHR-H(S)HT

Detector: RI detector WATERS 150C for liquid chromatography

(measurement conditions)

Solvent: 1,2,4-Trichlorobenzene

Temperature: 145°C

Flow rate: 1.0mL

Sample concentration: 2.2mg/mL

Injection volume: 160μL

Detection line: Universal Calibration

Analysis program: HT-GPC (version 1.0)

(4) Melting point

Using a differential scanning calorimeter (DSC), the sample was melted at 220°C for 3 minutes under nitrogen flow, then cooled to 25°C at 10°C/min, kept at 25°C for 3 minutes, and then heated at 10°C/min to obtain It was obtained by melting the peak top of the endothermic curve.

In addition, the melt flow rate (M.I.) of the propylene-based polymers (A-1 and A-2) was measured at a resin temperature: 230° C. and a load: 2.16 kg in accordance with JIS-K7210.

Manufacturing example 1

[Synthesis of raw material propylene polymer]

(1) Preparation of prepolymerized catalyst components

After replacing the three-necked flask with a stirrer with an inner volume of 0.5L with nitrogen, add dehydration-treated heptane 400ml, diethylaluminum chloride 18g, commercially available Solvay type titanium trichloride catalyst (Toray Fine Chemicals) product company) 2g. While maintaining the internal temperature at 20°C, propylene was introduced while stirring. After 80 minutes, stirring was stopped to obtain a prepolymerized catalyst component in which 0.8 g of propylene was polymerized per 1 g of the solid catalyst.

(2) Synthesis of raw material propylene polymer

A stainless steel autoclave with an internal volume of 10 L was fully dried and replaced with nitrogen, and then 6 L of dehydrated heptane was added to replace the nitrogen in the system with propylene. Then, 0.06 MPaG of hydrogen was added, and propylene was introduced with stirring. After stabilizing the system at an internal temperature of 65°C and a propylene pressure of 0.75 MPaG, in terms of a solid catalyst, 50 ml of heptane slurry containing 0.5 g of the prepolymerized catalyst component prepared in (1) above was added, and propylene was continuously supplied at 65 Polymerization was carried out at °C for 1.5 hours.

Then, the internal temperature was adjusted to 50° C., the stirring was weakened, and the pressure was released. Then, 0.04 MPaG of hydrogen was added, and propylene was introduced while stirring. Polymerization was carried out at 50°C for 6 hours while continuously feeding propylene at an internal temperature of 50°C and a propylene pressure of 0.75 MPaG. After completion of the polymerization, 50 ml of methanol was added, and the temperature was lowered and the pressure was released. All the contents were transferred to a filter tank with a filter, and the temperature was raised to 85° C. for solid-liquid separation. Then, the solid portion was washed twice with 6 L of heptane at 85° C., and vacuum-dried to obtain 2.1 kg of a propylene polymer. The polymer had an intrinsic viscosity [?] _S of 4.02 dl/g and a melting point of 162. In addition, the catalytic activity per 1 g of the solid catalyst was 4.2 kg/g-cat.·7.5 hr at 7.5 hours of polymerization. Propylene polymerization was repeated under the same conditions as above, and the obtained polymer was used as a raw material propylene polymer.

Manufacturing example 2

[Synthesis of raw material propylene polymer]

In Production Example 1 (2), a raw material propylene-based polymer was synthesized in the same manner as in Production Example 1 except that the hydrogen pressures in the first and second stages were changed to 0.03 MPaG and 0.025 MPaG, respectively. The polymer had an intrinsic viscosity [?] _S of 6.05 dl/g and a melting point of 161C.

Manufacturing example 3

[Synthesis of raw material propylene polymer]

(1) Preparation of solid catalyst components

After replacing the three-neck flask with an internal volume of 0.5 L with a stirrer with nitrogen, 60 ml of dehydrated octane and 16 g of diethoxymagnesium were added. After heating to 40°C, 2.4 ml of silicon tetrachloride was added, and after stirring for 20 minutes, 1.6 ml of dibutyl phthalate was added. The temperature of the solution was raised to 80°C, and then 77 ml of titanium tetrachloride was added dropwise, and stirred at an internal temperature of 125°C for 2 hours to carry out a contact operation. Then, stirring was stopped to allow solids to settle, and the upper clear fraction was removed. Add 100ml of dehydrated octane, heat up to 125°C while stirring, and keep it for 1 minute, then stop stirring to precipitate the solid, and take out the upper clear part. This washing operation was repeated 7 times. Then, 122 ml of titanium tetrachloride was added, stirred at an internal temperature of 125° C. for 2 hours, and the second contact operation was performed. Then, the above-mentioned washing with dehydrated octane at 125° C. was repeated six times to obtain a solid catalyst component.

(2) Preparation of prepolymerized catalyst components

After replacing the three-necked flask with an internal volume of 0.5L with a stirrer with nitrogen, add 400ml of dehydrated heptane, 25mmol of triisobutylaluminum, 2.5mmol of dicyclopentyldimethoxysilane, and prepare in (1) above The solid catalyst component 4g. Propylene was introduced with stirring at room temperature. One hour later, the stirring was stopped, and as a result, a prepolymerized catalyst component in which 4 g of propylene was polymerized per 1 g of the solid catalyst was obtained.

(3) Synthesis of raw material propylene polymer

A stainless steel autoclave with an internal volume of 10 L was sufficiently dried and replaced with nitrogen, and then 6 L of dehydrated heptane, 12.5 mmol of triethylaluminum, and 0.3 mmol of dicyclopentyldimethoxysilane were added. After the nitrogen in the system was replaced with propylene, propylene was introduced thereinto with stirring. After stabilizing the system at an internal temperature of 80°C and a total pressure of 0.8 MPa, 50 ml of heptane slurry containing 0.08 mmol of the prepolymerized catalyst component prepared in (2) above was added in terms of Ti atoms, and propylene was continuously supplied at 80 Polymerization was carried out at °C for 3 hours.

After completion of the polymerization, 50 ml of methanol was added, and the temperature was lowered and the pressure was released. All the contents were transferred to a filter tank with a filter, and the temperature was raised to 85° C. for solid-liquid separation. Then, the solid portion was washed twice with 6 L of heptane at 85° C., and vacuum-dried to obtain 2.5 kg of a propylene polymer. The polymer had an intrinsic viscosity [?] _S of 7.65 dl/g and a melting point of 164C. In addition, the catalytic activity per 1 g of the solid catalyst was 9.8 kg/g-cat.·3hr at 3 hours of polymerization. Propylene polymerization was repeated under the same conditions as above, and the obtained polymer was used as a raw material propylene polymer.

Example 1

[Synthesis of maleic anhydride-modified propylene polymer]

5 parts by weight of maleic anhydride and Parkadox 14-40C (trade name, 1,3-di-(tert-butylperoxyisopropyl)benzene) were added to 100 parts by weight of the raw material propylene polymer synthesized in Production Example 1. / Calcium carbonate: 40/60 (weight ratio), 2.5 parts by weight of Kayaku Akuzo Co., Ltd., dry-blended, and melt-kneaded using a 35 mm twin-screw extruder. The temperature of the twin-screw extruder during melt mixing is: the lower part of the hopper is 40°C, the front of the plasticizing zone is 120°C, the plasticizing zone is 170°C, and the die head is 180°C. In addition, these respective parts correspond to the parts with reference numerals in FIG. 1 .

50 parts by weight of acetone and 50 parts by weight of heptane were added to 100 parts by weight of the prepared granular sample, and heated and stirred at 85° C. for 2 hours (implemented in a pressure-resistant container). After completion of this operation, the particles were recovered with a metal mesh and immersed in 100 parts by weight of acetone for 15 hours. Then, the pellets were recovered with a wire mesh, air-dried, and then vacuum-dried at 80° C. for 6 hours and 130° C. for 6 hours to obtain a maleic anhydride-modified propylene polymer. The physical property values are shown in Table 1.

Example 2

[Synthesis of maleic anhydride-modified propylene polymer]

In Example 1, a maleic anhydride-modified propylene polymer was synthesized in the same manner as in Example 1 except that the blending amount of Parkadux 14-40C was changed to 1.5 parts by weight. The physical property values are shown in Table 1.

Example 3

[Synthesis of maleic anhydride-modified propylene polymer]

In Example 1, a maleic anhydride-modified propylene polymer was synthesized in the same manner as in Example 1, except that the raw material propylene polymer synthesized in Production Example 2 was used instead of the raw material propylene polymer synthesized in Production Example 1. The physical property values are shown in Table 1.

Comparative example 1

[Synthesis of maleic anhydride-modified propylene polymer]

To 100 parts by weight of the raw material propylene polymer synthesized in Production Example 3, 1 part by weight of maleic anhydride and 1 part by weight of Kayabuchol B (trade name, tert-butyl peroxybenzoate, manufactured by Kayaku Akuzo Co., Ltd.) were added to carry out Dry mixing, using a 35mm twin-screw extruder for melt mixing. The temperature of the twin-screw extruder during melt mixing is: the lower part of the hopper, the front part of the plasticizing zone, the plasticizing zone, and the die head are all 210°C.

50 parts by weight of acetone and 50 parts by weight of heptane were added to 100 parts by weight of the prepared granular sample, and heated and stirred at 85° C. for 2 hours (implemented in a pressure-resistant container). After completion of this operation, the particles were recovered with a metal mesh and immersed in 100 parts by weight of acetone for 15 hours. Then, the pellets were recovered with a wire mesh, air-dried, and then vacuum-dried at 80° C. for 6 hours and 130° C. for 6 hours to obtain a maleic anhydride-modified propylene polymer. The physical property values are shown in Table 1.

Comparative example 2

Add 5 parts by weight of maleic anhydride and 5 parts by weight of Parkadox 14-40C to 100 parts by weight of the raw material propylene polymer synthesized in Production Example 3, dry blend, use a 35 mm twin-screw extruder, and compare 1 Melt and knead under the same temperature conditions. 50 parts by weight of acetone and 50 parts by weight of heptane were added to 100 parts by weight of the prepared granular sample, and heated and stirred at 85° C. for 2 hours (implemented in a pressure-resistant container). After completion of this operation, the particles were recovered with a metal mesh and immersed in 100 parts by weight of acetone for 15 hours. Then, the pellets were recovered with a wire mesh, air-dried, and then vacuum-dried at 80° C. for 6 hours and 130° C. for 6 hours to obtain a maleic anhydride-modified propylene polymer. The physical property values are shown in Table 1.

Table 1

project unit Example 1 Example 2 Example 3 Comparative example 1 Comparative example 2 modified polymer   Content of polar group moiety mmol/g 0.15 0.13 0.20 0.08 0.10 [η] _A dl/g 0.86 1.18 1.21 0.70 0.72 Mw/Mn - 3.2 3.4 3.5 1.9 1.9 LP amount weight% 2.6 1.4 2.7 2.3 2.0 [η] _A /[η] _S - 0.21 0.29 0.30 0.09 0.09

Embodiment 4-18 and comparative example 3-9

[Preparation of polypropylene resin composition]

The propylene-based polymer (A), modified propylene polymer (B), organic layered inorganic compound (C), and rubber-like polymer (D) shown below were mixed according to the mixing ratio shown in Table 2 and Table 3. After kneading, melt-kneading was carried out at 230° C. using a twin-screw extruder to prepare a polypropylene resin composition.

As the propylene-based polymer (A), the following A-1 and A-2 were used.

A-1: High-impact polypropylene (propylene-ethylene block copolymer) (J784H (trade name), manufactured by Idemitsu Petrochemical Co., Ltd., copolymer content: 12% by weight, M.I.: 10 g/10 minutes)

A-2: Propylene homopolymer (J3000GP (trade name), manufactured by Idemitsu Petrochemical Co., Ltd., M.I.: 30 g/10 minutes)

As the modified propylene polymer (B), the following B-1 to B-7 were used.

B-1: The maleic anhydride-modified propylene polymer synthesized in Example 1

B-2: the maleic anhydride-modified propylene polymer synthesized in Example 2

B-3: the maleic anhydride-modified propylene polymer synthesized in Example 3

B-4: Commercially available maleic anhydride-modified propylene polymer (Polybond 3200 (trade name), manufactured by Clompton Co., Ltd., content of polar group moiety: 0.048 mmol/g, [η] _A : 0.76 dl/g, Mw/Mn: 2.4, LP amount: 4.0% by weight)

B-5: Commercially available maleic anhydride-modified propylene polymer (Umex 1010 (trade name), manufactured by Sanyo Chemical Industry Co., Ltd., content of polar group moiety: 0.43 mmol/g, [η] _A : 0.19 dl /g, Mw/Mn: 4.1, LP amount: 43.5% by weight)

B-6: Maleic anhydride-modified propylene polymer synthesized in Comparative Example 1

B-7: Maleic anhydride-modified propylene polymer synthesized in Comparative Example 2

As the organic layered inorganic compound (C), the following C-1 and C-2 were used.

C-1: Montmorillonite (Kunipia F (trade name), manufactured by Kunimine Industry Co., Ltd., organic ammonium salt: 40% by weight)

C-2: Swellable synthetic mica (Somasif (trade name), manufactured by Copp Chemical Co., Ltd., swellable fluoromica, organic ammonium salt: 30% by weight)

As the rubbery polymer (D), the following D-1 and D-2 were used.

D-1: Ethylene-propylene copolymer rubber (EP02P (trade name), manufactured by Nippon Synthetic Rubber Co., Ltd.)

D-2: SEBS (Creinton G1652 (trade name), manufactured by Shell Chemical Corporation)

[Physical evaluation]

For the prepared polypropylene resin composition, the physical properties of the following (1)-(3) were evaluated (for the compositions of Examples 11-18 and Comparative Examples 7-9, the physical properties of the following (1)-(2) were evaluated ). The evaluation results are shown in Table 2 and Table 3.

(1) Flexural modulus of elasticity: According to JIS K7203

(2) Izod impact strength: in accordance with JIS K7110 (23°C, notched)

(3) Heat distortion temperature: According to JIS K7207

Table 2

project unit Example 4 Example Example 6 Example 7 Example 8 Example 9 Example 10 Comparative example 3 Comparative example 4 Comparative Example 5 Comparative example 6 combination Component A type - A-1 A-1 A-1 A-1 A-1 A-2 A-1 A-1 A-1 A-1 A-1 Mixing amount parts by weight 65 65 65 50 50 65 65 65 65 65 50 Component B type - B-1 B-2 B-3 B-1 B-1 B-1 B-1 B-4 B-5 B-6 B-7 Mixing amount parts by weight 30 30 30 50 50 30 30 30 30 30 50 Component C type - C-1 C-1 C-1 C-1 C-1 C-1 C-2 C-1 C-1 C-1 C-1 Mixing amount parts by weight 8 8 8 8 20 8 7 8 8 8 8 Physical value Flexural modulus of elasticity MPa 2710 2680 2620 2960 4340 3290 3450 1880 2410 2240 2330 Izod impact strength KJ/ ^m2 5.4 6.5 7.1 4.6 3.1 2.2 4.9 5.0 1.9 4.2 2.8 Heat distortion temperature ℃ 138 135 132 134 140 142 140 124 109 128 129

table 3

project unit Example 11 Example 12 Example 13 Example 14 Example 15 Example 16 Example 17 Example 18 Comparative Example 7 Comparative example 8 Comparative example 9 combination Component A type - A-1 A-1 A-1 A-1 A-1 A-2 A-1 A-1 A-1 A-1 A-1 Mixing amount parts by weight 55 55 55 50 40 55 55 55 55 55 50 Component B type - B-1 B-2 B-3 B-1 B-1 B-1 B-1 B-1 B-4 B-5 B-7 Mixing amount parts by weight 25 25 25 50 40 25 25 25 25 25 50 Component C type - C-1 C-1 C-1 C-1 C-1 C-1 C-2 C-1 C-1 C-1 C-1 Mixing amount parts by weight 8 8 8 8 20 8 8 8 8 8 8 Component D type - D-1 D-1 D-1 D-1 D-1 D-1 D-1 D-2 D-1 D-1 D-1 Mixing amount parts by weight 15 15 15 15 15 15 15 15 15 15 15 Physical value Flexural modulus of elasticity MPa 1820 1730 1690 1910 3800 2660 2010 1790 1010 1610 1490 Izod impact strength KJ/ ^m2 54 62 74 40 18 8.9 48 68 50.0 5.6 34

Since the compositions of Comparative Examples 3-9 did not use a modified polymer satisfying the requirements of the present invention, the balance of physical property values was inferior to that of the compositions of Examples 4-18.

According to the present invention, it is possible to provide a low-molecular-weight modified propylene-based polymer having excellent resin properties and hardly causing adverse effects on physical properties due to by-products, and a method for producing the same.

According to the present invention, a polyolefin resin composition having a high balance of physical properties and a method for producing the same can be provided without impairing the properties of polyolefin.

Claims (9)

1. A modified propylene polymer, which satisfies the following (1)-(4): (1) The content of the polar group part from unsaturated carboxylic acid and/or its derivative is 0.10-0.30mmol/g, (2) The intrinsic viscosity [η] _A measured in tetralin at 135°C is 0.8-3.0dl/g, (3) The molecular weight distribution Mw/Mn exceeds 2.5, (4) The amount of components having a molecular weight Mw of 10,000 or less is 5% by weight or less. 2. The modified propylene-based polymer according to claim 1, wherein the intrinsic viscosity [η] _A of the modified propylene-based polymer and the propylene-based polymer as its raw material are measured at 135° C. in tetralin The intrinsic viscosity [η] _S ratio [η] _A / [η] _S is 0.2 or more. 3. The manufacturing method of the modified propylene-based polymer according to claim 1, comprising: mixing 100 parts by weight of a propylene-based polymer, 0.1-5 parts by weight of a free radical initiator, and unsaturated carboxylic acid and/or its derivative 1.5-10 parts by weight of the propylene-based polymer are mixed, and melt-kneaded at a temperature above the melting point of the propylene-based polymer and below 180°C. 4. A polyolefin resin composition comprising the following (A), (B) and (C): (A) 50-95 parts by weight of polymers of α-olefins with 3 or more carbon atoms, (B) 4-50 parts by weight of the modified propylene polymer according to claim 1, (C) 1-30 parts by weight of an organic layered inorganic compound. 5. A polyolefin resin composition comprising the following (A), (B), (C) and (D): (A) 30-95 parts by weight of a polymer of α-olefin having 3 or more carbon atoms, (B) 4-50 parts by weight of the modified propylene polymer according to claim 1, (C) 1-30 parts by weight of organic layered inorganic compound, (D) 5-40 parts by weight of rubbery polymer. 6. The polyolefin resin composition according to claim 4 or 5, wherein the intrinsic viscosity [η] _A of the modified propylene-based polymer (B) is different from that of the propylene-based polymer as its raw material at 135° C., tetrahydrogenated The ratio [η] _A / [η] _S of the intrinsic viscosity [η] _S measured in naphthalene is 0.2 or more. 7. The polyolefin resin composition according to claim 4 or 5, wherein the melt flow rate of the polymer (A) of the α-olefin is 0.1-200 g/10 minutes, The α-olefin polymer (A) is a first α-olefin having 3 or more carbon atoms and 0-20% by weight of a second α-olefin having 2-20 carbon atoms different from the first α-olefin. Homopolymer or Copolymer. 8. The method for producing a polyolefin resin composition according to claim 4, comprising mixing (A), (B) and (C) and performing melt-kneading. 9. The method for producing a polyolefin resin composition according to claim 5, comprising mixing (A), (B), (C) and (D) and performing melt-kneading.