JP3354233B2 - Olefin resin composition for automotive exterior parts - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an olefin resin composition for automotive exterior parts, and more particularly, to an acrylic melamine resin composition even when pretreatment (surface treatment) using a primer or a solvent is not performed. The present invention relates to an olefin-based resin composition having excellent moldability, which is excellent in coatability with respect to paints such as paints and can provide automobile exterior parts such as bumpers having excellent rigidity and impact resistance.

[0002]

2. Description of the Related Art In recent years, regarding exterior parts of automobiles represented by bumpers and the like, workability, mechanical strength characteristics,
Olefin resins are increasingly used from the viewpoints of chemical resistance and recyclability.

[0003] However, olefin resins usually have no polar group in the molecule and are chemically inert, so that the adhesion of a coating film or the like in coating and bonding of the molded product is not good. In addition, there is a problem that secondary processing of the olefin resin molded article is difficult.

Therefore, conventionally, for example, when an olefin resin molded article is coated with an acrylic melamine resin paint or the like, the surface of the olefin resin molded article is subjected to a solvent treatment method, a flame treatment method, a plasma treatment method, or an ultraviolet treatment method. Or a pretreatment such as painting with a primer such as a primer to obtain good coating film adhesion.

[0005] However, such pretreatment is problematic in terms of environmental pollution, worker safety, and manufacturing cost of automobile exterior parts. In recent years, in order to simplify the steps of the pretreatment as described above, for example, as in an olefin-based resin composition to which a resin having a polar group in a molecule is added,
Many proposals have been made regarding improvements from resin compositions.

For example, Japanese Patent Application Laid-Open No. Hei 5-70637,
JP-A-4-335053, JP-A-4-33505
4, JP-A-4-272948 and JP-A-4-272948.
JP-A-272938 and JP-A-4-270744 disclose that an olefin-based resin composition having improved coating film adhesion (coatability) can be obtained by adding a resin having a hydroxyl group in the molecule. It is shown.

However, the olefin-based resin composition described in the above-mentioned publication cannot obtain a sufficient effect of improving both the coating film adhesion and the mechanical strength characteristics.

Therefore, conventionally, an automobile exterior part which is excellent in the coating property with respect to a paint such as an acrylic melamine resin paint and the like in rigidity, impact resistance, appearance and the like without performing the pretreatment as described above has been provided. An appearance of an olefin resin composition having excellent moldability, which can be provided, is desired.

[0009]

SUMMARY OF THE INVENTION An object of the present invention is to solve the problems associated with the prior art as described above, and it is possible to use an acrylic melamine resin paint or the like without performing a pretreatment using a primer or a solvent on the surface. It is an object of the present invention to provide an olefin-based resin composition for an automobile exterior part having excellent moldability and excellent moldability, which is excellent in coating property and can prepare an automobile exterior part excellent in rigidity, impact resistance, appearance and the like.

[0010]

The olefin resin composition for automotive exterior parts according to the present invention has an [A] melt flow rate of 50 to 50.
200 g / 10 min crystalline polypropylene portion 85-9
A melt flow rate of 20 to 100 g, containing 5% by weight and 5 to 15% by weight of a propylene / ethylene random copolymer portion having an ethylene content of 20 to 50% by weight;
/ 10 minute propylene / ethylene block copolymer 20
To 70% by weight, [B] Mooney viscosity [ML _{1 + 4} (100
° C)] is 10 to 60, and the ethylene content is 60 to 95.
15 to 40% by weight of an ethylene / α-olefin copolymer rubber which may contain a non-conjugated diene,
[C] The graft amount of maleic anhydride is 0.5 to 5% by weight.
1 to 15% by weight of a graft-modified propylene polymer having an intrinsic viscosity [η] of 0.2 to 0.5 dl / g;
[D] 1 to 15% by weight of a hydrogenated conjugated diene polymer having a hydroxyl group at at least one molecular terminal and having a number average molecular weight of 1,000 to 8,000, and [E] a specific surface area of 30,000 cm ² / g or more,
A resin composition comprising 8 to 30% by weight of an inorganic filler having an average particle size of 0.8 to 2.5 μm, a length of substantially 12 μm or less, and an average aspect ratio of 5 or more. And the molded body of the resin composition is 8,000 kg /
It has a flexural modulus of not less than cm ² .

[0011]

DETAILED DESCRIPTION OF THE INVENTION The olefin resin composition for automotive exterior parts according to the present invention will be specifically described below.

The olefin resin composition for automotive exterior parts according to the present invention comprises a specific propylene / ethylene block copolymer [A], a specific ethylene / α-olefin copolymer rubber [B], and a specific olefin / α-olefin copolymer rubber [B]. It contains a specific amount of a graft-modified propylene polymer [C], a specific conjugated diene polymer [D], and a specific inorganic filler [E], and the molded product has a specific flexural modulus. .

First, these components will be described. Propylene / ethylene block copolymer [A] The propylene / ethylene block copolymer [A] used in the present invention comprises a propylene / ethylene block copolymer or propylene / ethylene / other α-olefin. Is a block copolymer.

Specific examples of the α-olefin include butene-1, pentene-1, 2-methylbutene-1, 3-methylbutene-1, hexene-1, 3-methylpentene-1, and 4-methylpentene. -1,3,3-dimethylbutene-1, heptene-1, methylhexene-1, dimethylpentene-1, trimethylbutene-1, ethylpentene-1, octene-1, methylpentene
-1, dimethylhexene-1, trimethylpentene-1, ethylhexene-1, methylethylpentene-1, diethylbutene-1, propylpentene-1, decene-1, methylnonene-
1, dimethyloctene-1, trimethylheptene-1, ethyloctene-1, methylethylheptene-1, diethylhexene-1, dodecene-1, hexadodecene and the like.

The propylene / ethylene block copolymer [A] used in the present invention has a melt flow rate (MFR: 230) measured in accordance with ASTM D-1238.
C., load 2.16 kg) is 50 to 200 g / 10 min, preferably 80 to 160 g / 10 min, and more preferably 1 to 160 g / 10 min.
A crystalline polypropylene portion in the range of 100 to 140 g / 10 minutes and a propylene / ethylene random having an ethylene content in the range of 20 to 50% by weight, preferably 30 to 50% by weight, and more preferably 35 to 45% by weight. And a polymer part.

In the propylene / ethylene block copolymer [A], the amount of the crystalline polypropylene is 8% based on 100% by weight of the total amount of the crystalline polypropylene and the propylene / ethylene random copolymer.
The content is 5 to 95% by weight, preferably 90 to 95% by weight, more preferably 91 to 94% by weight. That is, in the propylene / ethylene block copolymer [A], the propylene / ethylene random copolymer portion is 5% by weight based on the total amount of the crystalline polypropylene portion and the propylene / ethylene random copolymer portion of 100% by weight.
-15% by weight, preferably 5-10% by weight, more preferably 6-9% by weight.

The content of the crystalline polypropylene portion and the propylene / ethylene random copolymer portion is as follows:
cooling the polymer solution dissolved in n-decane at 145 ° C.,
By filtering and separating, it can be obtained by separating into a crystalline polypropylene portion and a propylene / ethylene random copolymer portion.

The measurement of the melt flow rate of the crystalline polypropylene portion is performed on the crystalline polypropylene portion separated as described above. The ethylene content of the propylene / ethylene random copolymer portion can be determined by measuring the infrared absorption spectrum of the propylene / ethylene random copolymer portion separated as described above.

The propylene / ethylene block copolymer [A] has a melt flow rate (MFR; 230 ° C., load 2.16 kg) measured according to ASTM D-1238 of 20 to 100 g / 10 min. Preferably 30 to 80 g / 10 min, more preferably 40 to 60 g
/ 10 minutes.

When the propylene / ethylene block copolymer [A] having the above melt flow rate is used, an olefin resin composition excellent in moldability can be obtained. In the present invention, the density of the propylene / ethylene block copolymer [A] is usually 0.89 to 0.91 g.
/ Cm ³ is preferably in the range.

The propylene / ethylene block copolymer [A] having the above properties can be produced by various methods. A typical method for producing the propylene / ethylene block copolymer [A] includes a catalyst formed from a solid titanium catalyst component and an organometallic compound catalyst component, or both of these catalyst components and an electron donor catalyst component. A method for producing a propylene / ethylene block copolymer [A] using a catalyst formed from

The solid titanium catalyst component used in this production method is titanium trichloride or a titanium trichloride composition produced by various methods, and preferably has a specific surface area of 1%.
A titanium catalyst component supported on a support of at least 00 m ² / g,
Alternatively, a titanium catalyst component comprising titanium, magnesium, halogen and an electron donor, preferably an aromatic carboxylic acid ester or an alkyl group-containing ether as essential components, and supported on a carrier having a specific surface area of preferably 100 m ² / g or more. Can be Particularly, a propylene / ethylene block copolymer produced using the latter titanium catalyst component with a carrier is preferred.

Further, as the organometallic compound catalyst component,
Organic aluminum compounds are preferred, and specific examples of the organic aluminum compounds include trialkylaluminum, dialkylaluminum halide, alkylaluminum sesquihalide, and alkylaluminum dihalide. The organoaluminum compound can be appropriately selected according to the type of the solid titanium catalyst component.

As the electron donor, an organic compound having a nitrogen atom, a phosphorus atom, a sulfur atom, a silicon atom, a boron atom or the like can be used, and an ester compound and an ether compound having the above-mentioned atoms are preferable. A simple example.

A method for producing a propylene / ethylene block copolymer using a solid titanium catalyst component with a carrier as described above is described in, for example, Japanese Patent Application Laid-Open No.
JP-A-50-126590, JP-A-51-202
No. 97, JP-A-51-28189, JP-A-52-15
No. 1691 and other publications, and the technology described therein can be used in the present invention.

In the present invention, the propylene / ethylene block copolymer [A] includes a propylene / ethylene block copolymer [A], an ethylene / α-olefin copolymer rubber [B], and a graft-modified propylene polymer. 20 to 70% by weight, preferably 25 to 65% by weight, more preferably 3 to 100% by weight of the total amount of [C], conjugated diene polymer [D] and inorganic filler [E].
It is used at a ratio of 0 to 60% by weight.

By using the propylene / ethylene block copolymer [A] in the above ratio, it is possible to provide a molded article which is excellent in impact resistance, rigidity and the like, and is excellent in heat resistance and processing dimensional stability. An olefin resin composition having excellent moldability can be obtained.

[0028]Ethylene / α-olefin copolymer rubber
[B] Ethylene / α-olefin copolymer used in the present invention
Rubber [B] is composed of ethylene, propylene, butene-1,
Non-conjugated diene
May or may not be contained
No.

Examples of such non-conjugated dienes include 1,4-hexadiene, dicyclopentadiene, dicyclooctadiene, methylenenorbornene, and 5-ethylidene-2.
-Norbornene and the like.

Specific examples of the ethylene / α-olefin copolymer rubber [B] include ethylene / propylene copolymer rubber, ethylene / butene-1 copolymer rubber, and ethylene / propylene / butene-1 copolymer rubber. Combined rubber, ethylene / propylene / non-conjugated diene copolymer rubber, ethylene / butene-1 / non-conjugated diene copolymer rubber, olefins such as ethylene / propylene / butene-1 / non-conjugated diene copolymer rubber as main components And an amorphous elastic copolymer.

The Mooney viscosity of the ethylene / α-olefin copolymer rubber [B] used in the present invention [ML _{1 + 4} (1
00 ° C; JIS K-6300) is in the range of 10 to 60, preferably 10 to 50, more preferably 10 to 30.

The ethylene content of the ethylene / α-olefin copolymer rubber [B] is 60 to 95 mol%, preferably 70 to 90 mol%, more preferably 75 to 85 mol%.
Mol% range.

In the present invention, the ethylene / α-olefin copolymer rubber [B] includes a propylene / ethylene block copolymer [A], an ethylene / α-olefin copolymer rubber [B], and a graft-modified propylene-based rubber. 15 to 40% by weight, preferably 15 to 30% by weight, more preferably 1 to 30% by weight, based on 100% by weight of the total of the polymer [C], the conjugated diene polymer [D] and the inorganic filler [E].
It is used at a ratio of 7 to 25% by weight.

By using the ethylene / α-olefin copolymer rubber [B] at the above ratio, an olefin resin composition excellent in moldability, which can provide a molded article excellent in impact resistance, can be obtained. can get.

Graft-modified propylene-based polymer [C] The graft-modified propylene-based polymer [C] used in the present invention is a homopolymer or a copolymer of propylene, and is graft-modified with maleic anhydride. .

Examples of the propylene polymer as a raw material of the graft-modified propylene polymer include propylene homopolymer, propylene / ethylene random copolymer, propylene / ethylene block copolymer, and propylene / butene-polymer. 1 random copolymer and the like.

The graft modification in the present invention means that the propylene polymer as described above and maleic anhydride which is a polar group-containing ethylenically unsaturated compound are heated in the presence of a radical initiator to obtain maleic anhydride. Is grafted to a propylene-based polymer.

As the radical initiator, organic peroxides, azo compounds and the like are used. The radical initiator is
With respect to 100 parts by weight of the propylene-based polymer, 0.0
It is used in a proportion of 1 to 10 parts by weight, preferably 0.05 to 8 parts by weight.

The graft modification in the present invention can be performed by a conventionally known method. For example, a method in which a propylene polymer and maleic anhydride are melt-kneaded in the presence of a radical initiator, a method in which maleic anhydride and a radical initiator are added to an organic solvent solution of a propylene polymer and heating is performed, and the like. No.

The graft amount of maleic anhydride in the graft-modified propylene polymer produced by the above method is preferably 0.5 to 5% by weight, based on 100% by weight of the propylene polymer before the graft modification. Is 1 to 5% by weight, more preferably 2 to 4% by weight.

The amount of the graft can be determined by infrared absorption analysis. The intrinsic viscosity [η] of the graft-modified propylene polymer measured in decalin at 135 ° C. is 0.2 to 0.5 dl / g, and preferably 0.1 to 0.5 dl / g.
It is in the range of 3 to 0.5 dl / g.

In the present invention, the graft-modified propylene polymer [C] includes a propylene / ethylene block copolymer [A], an ethylene / α-olefin copolymer rubber [B], and a graft-modified propylene polymer [C]. C], the total amount of the conjugated diene polymer [D] and the inorganic filler [E] is 1
1 to 15% by weight, preferably 5 to
It is used in a proportion of 15% by weight, more preferably 8 to 15% by weight.

By using the graft-modified propylene-based polymer [C] in the above ratio, an olefin-based resin composition capable of providing a molded article having excellent coating properties can be obtained.

Conjugated diene polymer [D] The conjugated diene polymer [D] used in the present invention is a homopolymer or copolymer of a conjugated diene which may be hydrogenated, and has at least one molecular terminal. Has a hydroxyl group.

Examples of the conjugated diene which is a raw material of the conjugated diene polymer [D] include 1,3-butadiene, isoprene, chloroprene, 1,3-pentadiene, 2,3-dimethyl-1,3 -Butadiene, 1-phenyl-1,3-butadiene and the like.

These conjugated dienes are used alone or in combination. Such a conjugated diene polymer [D]
As, polybutadiene having a hydroxyl group at the molecular terminal,
Examples thereof include polyisoprene having a hydroxyl group at a molecular end, hydrogenated polybutadiene having a hydroxyl group at a molecular end, and hydrogenated polyisoprene having a hydroxyl group at a molecular end. In the present invention, a hydrogenated conjugated diene polymer is preferred.

The conjugated diene polymer [D] used in the present invention has a number average molecular weight (Mn) of 1,000 to 8,000, preferably 2,000 to 8,000 as measured by a vapor osmometer (Vapor Osmome-ter). In the range of 5,000.

Further, this conjugated diene polymer [D] has 1
The average number of hydroxyl groups per molecule is 0.5 to 10, preferably 1 to 5, and the hydroxyl value is 10 to 200 KOHmg /
g, preferably 20 to 100 KOH mg / g.

The conjugated diene polymer [D] having a hydroxyl group at at least one molecular terminal can be prepared by using a conjugated diene as a raw material in a known manner, for example, a radical polymerization method.
It is produced by an anionic polymerization method or the like.

The above hydrogenated conjugated diene polymer can be prepared by hydrogenating the conjugated diene polymer obtained by the above method. This hydrogenation can be carried out by employing a generally used means of catalytic hydrogenation.

In the present invention, the conjugated diene polymer [D] includes a propylene / ethylene block copolymer [A], an ethylene / α-olefin copolymer rubber [B], and a graft-modified propylene polymer [C]. Amount of conjugated diene polymer [D] and inorganic filler [E] 1
1 to 15% by weight, preferably 2 to 15% by weight
It is used in a proportion of 10% by weight, more preferably 3 to 8% by weight.

By using the conjugated diene polymer [D] in the above ratio, an olefin resin composition capable of providing a molded article having excellent coatability can be obtained. Inorganic Filler [E] As the inorganic filler [E] used in the present invention, a conventionally known inorganic filler used for modifying polyolefin or the like is used.

Specific examples of the inorganic filler [E] include:
Light calcium carbonate, heavy calcium carbonate, basic calcium carbonate, aluminum hydroxide, magnesium hydroxide, magnesium oxide, kaolin, clay, talc, calcium silicate (wollastonite, zonotrite,
Petal calcium silicate), diatomaceous earth, aluminum silicate, anhydrous silicic acid, hydrous silicic acid, mica, magnesium silicate (asbestos, PFM (Processed Mineral Fibe)
r) etc.), potassium titanate, gypsum fiber, silica, alumina, barium sulfate, aluminum sulfate, calcium sulfate, molybdenum disulfide, graphite, glass fiber (chopped strand, roping, milled glass fiber,
Glass flakes), cut fibers, rock fibers, microfibers, carbon fibers, potassium titanate fibers, magnesium sulfate fibers, and the like.

The inorganic filler [E] used in the present invention includes:
The specific surface area is 30,000 cm ² / g or more, preferably 3
000-50,000 cm ² / g, average particle size 0.8-2.5 μm, preferably 1.5-2.5 μm
And the length is substantially 12 μm or less, preferably 5 μm.
m and an average aspect ratio (indicating the ratio of length to thickness in either the vertical or horizontal direction) of 5 or more, preferably 5 to 20. Here, “substantially the length” means that most of the inorganic filler particles are in the above range. In the present invention, talc in the form of fine powder having the above characteristics is particularly preferred.

When an inorganic filler [E] having a specific surface area, an average particle diameter, a particle length and an average aspect ratio within the above ranges is used, a molded article excellent in balance of mechanical strength characteristics and appearance is obtained. Is obtained.

The specific surface area of the inorganic filler can be measured by an air permeation method, and the average particle diameter can be measured by a liquid phase sedimentation method. Further, the length and the aspect ratio of the inorganic filler can be measured by microscopic observation.

In the present invention, the inorganic filler [E] is
Total of propylene / ethylene block copolymer [A], ethylene / α-olefin copolymer rubber [B], graft-modified propylene polymer [C], conjugated diene polymer [D], and inorganic filler [E] For an amount of 100% by weight,
It is used at a ratio of 8 to 30% by weight, preferably 10 to 30% by weight, more preferably 12 to 30% by weight.

By using the inorganic filler [E] in the above ratio, the elastic modulus of the molded article can be improved. The olefin resin composition for automobile exterior parts according to the present invention comprises the propylene / ethylene block copolymer [A], the ethylene / α-olefin copolymer rubber [B], and the graft-modified propylene polymer [C]. , A conjugated diene polymer [D] and an inorganic filler [E].
In the present invention, an olefin-based resin composition capable of providing a molded article having a flexural modulus of 8,000 kg / cm ² or more is preferable from the viewpoint of being used for automotive exterior parts.
In particular, an olefin resin composition capable of providing a molded article having a flexural modulus of 8,000 to 20,000 kg / cm ² is preferable.

Production of Olefin-Based Resin Composition The olefin-based resin composition for automotive exterior parts according to the present invention comprises the above-mentioned propylene / ethylene block copolymer [A] and ethylene which may contain a non-conjugated diene. The ratio of the α-olefin copolymer rubber [B], the graft-modified propylene polymer [C], the conjugated diene polymer [D] which may be hydrogenated, and the inorganic filler [E] as described above. And can be produced by melt-kneading.

The above kneading can be carried out using a kneading device such as a single screw extruder, a twin screw extruder, a twin screw kneader, a Banbury mixer, a roll and the like. In order to produce this olefin resin composition, the above components are made uniform by applying a mixing method practiced in the field of ordinary olefin resin compositions so as to have the specific composition ratio described above. What is necessary is just to mix.

At this time, all the components may be mixed at the same time, or a part of the components may be mixed in advance to produce a so-called master batch, and the master batch and the remaining components may be mixed. Good.

Various additives may be added to the olefin resin composition according to the present invention as long as the physical properties of the molded article and the coating property are not impaired. As such additives, specifically, phenol-based, sulfur-based, phosphorus-based antioxidants, lubricants, antistatic agents, dispersants, copper harm inhibitors, neutralizers, plasticizers, flame retardants , A crosslinking agent, a flow improver such as a peroxide, an electric property improver, an ultraviolet absorber, a light stabilizer, a weld strength improver, and a nucleating agent.

Further, other thermoplastic resins and pigments can be added to the olefin resin composition according to the present invention, if necessary, as long as the physical properties of the molded article and the coatability are not impaired.

Specific examples of the other thermoplastic resins that can be used in the present invention include high-density polyethylene,
Medium-density polyethylene, high-pressure low-density polyethylene, linear low-density polyethylene, polybutene-1, propylene / butene-1 copolymer, styrene / butadiene (styrene)
Block copolymers and hydrogenated products thereof, styrene / isoprene (· styrene) block copolymers and hydrogenated products thereof can be mentioned.

Specific examples of the pigment that can be used in the present invention include carbon black, titanium oxide, zinc white,
Bengala, ultramarine, navy blue, azo pigments, nitroso pigments, lake pigments, phthalocyanine pigments and the like can be mentioned.

The olefin resin composition for automotive exterior parts according to the present invention is usually kneaded with a kneading apparatus such as an extruder, and then the kneaded product is formed into pellets. Is manufactured into a desired molded article by a molding method such as injection molding method, extrusion molding method, calender molding method and the like generally performed in the above.

The molded article formed from the olefin resin composition for automotive exterior parts according to the present invention has excellent coatability with acrylic melamine resin paint, urethane resin paint and the like.

For example, a coating method using an acrylic melamine resin paint will be described by way of example. A molded article formed from the olefin resin composition according to the present invention is washed with water and a general industrial detergent. The used washing is performed at least once each, and after further washing with water, the molded body is dried by heating. That is, when this paint is applied to a molded article formed from the olefin-based resin composition according to the present invention, it is not always necessary to perform the conventional cleaning using a chlorine-based solvent vapor. An acrylic melamine resin-based coating material is applied to the dried molded article in this manner and, if necessary, heated to form an acrylic melamine resin coating film on the surface of the molded article. The coating film formed in this way has very good adhesion to the molded article, even though the molded article has not been subjected to pretreatment such as chlorine-based solvent vapor cleaning and application of a primer. I have.

[0069]

The olefin resin composition for automotive exterior parts according to the present invention comprises a specific propylene / ethylene block copolymer [A], a specific ethylene / α-olefin copolymer rubber [B], A specific graft-modified propylene polymer [C], a specific conjugated diene polymer [D],
Since it is possible to provide a molded article having a specific flexural modulus by containing a specific amount of the specific inorganic filler [E], a primer or a solvent is formed on the surface of the molded article formed from this resin composition. Even when a paint such as an acrylic melamine resin paint is applied directly without performing such pre-treatments, sufficient coatability is obtained so that the coatability is excellent and the rigidity, impact resistance, appearance, etc. are excellent. Automotive exterior parts can be provided.

The olefin resin composition for automotive exterior parts according to the present invention has excellent moldability. Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples.

Various properties of the molded articles of the olefin resin compositions in the examples and comparative examples were measured as follows. (1) Coating property (adhesion of coating film)-Preparation of test piece The following paint was applied to a square plate molded by a 45-ton injection molding machine. In Examples 1 and 2 and Comparative Examples 1 to 4, the surface of the square plate was wiped with a cloth impregnated with isopropanol before applying the following paint.

Coating One-component acrylic melamine resin paint (trade name: Lugabake, manufactured by Kansai Paint Co., Ltd.) has a coating thickness of 35 μm after drying.
m was applied to the surface of the test piece with an air gun. The baking was performed at 140 ° C. for 30 minutes.

Cross-cut test According to the cross-cut test method described in JIS K-5400, cross-cut test pieces are prepared, and
After attaching ^TD (trade name, manufactured by Nichiban Co., Ltd.) to the test piece, immediately pull the cellophane tape in the direction of 90 ° to peel it off, count the number of remaining cross-cut coatings, and apply this number to the coating. It was an index of sex. (2) Flexural modulus (FM) The flexural modulus was measured according to JIS for a 4 mm thick test piece.
It was determined by performing a bending test according to K-7203.

[0074]

Reference Example 1 [Production of a hydrogenated product of a conjugated diene polymer having a hydroxyl group at at least one molecular terminal] In a 500 ml capacity autoclave, 100 g of 1,3-butadiene, 70 g of isopropyl alcohol, and 10 g of 60% hydrogen peroxide were added. After charging, these compounds were added at 90 ° C. for 5 hours under a nitrogen atmosphere.
Heated for hours.

Next, after cooling the autoclave, unreacted 1,3-butadiene was removed, and the produced polymer was taken out and dried. The butadiene polymer thus obtained (hereinafter sometimes referred to as PBD) is
The number average molecular weight measured by a vapor osmometer (Vapor Osmometer) was 3,360, and the hydroxyl value was 48.

Next, 50 g of the above-mentioned PBD and a ruthenium catalyst supported on carbon (ruthenium metal concentration: 5% by weight)
g in an autoclave having a capacity of 200 ml, and replacing air in the system with nitrogen.
kg / cm ² .

Then, the temperature of the autoclave was raised to 100 ° C., hydrogen gas was supplied into the autoclave so that the total pressure in the system was maintained at 50 kg / cm ² , and a hydrogenation reaction was carried out for 8 hours.

After completion of the reaction, hydrogen was removed and the catalyst was separated by filtration. The resulting hydrogenated product was precipitated in methanol, and the deposited hydrogenated product was dried. The hydrogenated product obtained as described above (hereinafter sometimes referred to as HPBD) has a number average molecular weight of 4,0 measured by a vapor osmometer.
00, an iodine value of 1.2 and a hydroxyl value of 45
Met. It was confirmed by nuclear magnetic resonance analysis and infrared absorption analysis that this HPBD had a hydroxyl group at the molecular terminal.

[0079]

[Reference Example 2] [Production of maleic anhydride-modified propylene homopolymer] Propylene homopolymer (MFR: 10 g / 10 min, AST
MD-1238, 230 ° C, load 2.16kg) 50g
Then, 500 ml of p-xylene was placed in a 1-liter glass separable flask and heated to 130 ° C. to dissolve the propylene homopolymer in p-xylene.

Next, 5 g of maleic anhydride and 0.5 g of dicumyl peroxide were added dropwise to the obtained solution over 4 hours, and the mixture was further heated at 130 ° C. for 2 hours. Then
The solution was allowed to cool and then poured into acetone to obtain a propylene homopolymer graft-modified with maleic anhydride.

The amount of maleic anhydride grafted in the obtained propylene homopolymer graft-modified with maleic anhydride (hereinafter sometimes referred to as MPP) is 100% by weight of the propylene homopolymer before graft modification. The intrinsic viscosity [η] measured in decalin at 135 ° C. was 0.4 dl / g.

The above graft amount was measured by infrared absorption spectroscopy.

[0083]

Example 1 Propylene / ethylene block copolymer [melt flow rate: 40 g / 10 min, density: 0.9]
1 g / cm ³ , content of crystalline polypropylene portion: 92
% By weight, propylene / ethylene random copolymer part:
8% by weight, melt flow rate of crystalline polypropylene part: 120 g / 10 min, ethylene content in propylene / ethylene random copolymer part: 30% by weight, hereinafter sometimes referred to as PP] 32 parts by weight, Propylene / 5-ethylidene-2-norbornene copolymer rubber [Mooney viscosity [ML _{1 + 4} (100 ° C)]: 15,
Ethylene content: 81 mol%, hereinafter sometimes referred to as EPT] 25 parts by weight, 10 parts by weight of MPP of Reference Example 2, 5 parts by weight of HPBD of Reference Example 1, and talc [specific surface area: 40,000 cm ^2] / G, average particle size: 2.2 μm,
Average aspect ratio: 10] 28 parts by weight was melt-kneaded at a predetermined temperature by a twin-screw extruder, and pelletized with an olefin resin composition using a pelletizer.

This composition was molded by an injection molding machine under the following conditions to prepare a square plate, and the above-mentioned cross-cut test and bending test specimens were obtained. These tests were performed. (Square plate forming conditions)-Resin temperature: 200 ° C,-Mold temperature: 40 ° C,-Pressure: 600 kg / cm ^{2 The} results are shown in Table 1.

[0085]

Example 2 In Example 1, the amounts of PP, EPT and talc were changed to 51 parts by weight, 20 parts by weight,
The procedure was performed in the same manner as in Example 1 except that the parts by weight were used.

The results are shown in Table 1.

[0087]

Comparative Example 1 In Example 1, EPT, MPP, HP
The same operation as in Example 1 was performed except that only PP was used without using BD and talc.

The results are shown in Table 1.

[0089]

Comparative Example 2 In Example 1, PP, MPP, HPB
The same operation as in Example 1 was performed except that only EPT was used without using D and talc.

The results are shown in Table 1.

[0091]

Comparative Example 3 Example 1 was repeated except that the amounts of PP and HPBD were changed to 37 parts by weight and 0 part by weight, respectively.
Performed in the same manner as in Example 1.

The results are shown in Table 1.

[0093]

Comparative Example 4 Example 1 was repeated, except that the amounts of PP and MPP were changed to 42 parts by weight and 0 part by weight, respectively.

The results are shown in Table 1.

[0095]

[Table 1]

[0096]

Example 3 The procedure of Example 1 was repeated, except that the surface of the test piece was not wiped with a cloth impregnated with isopropanol, but was painted and subjected to a grid test.

The results are shown in Table 2.

[0098]

Example 4 The procedure of Example 1 was repeated, except that instead of wiping the surface of the test piece with a cloth impregnated with isopropanol, a test piece subjected to the following surface treatment was applied and a grid test was performed. Performed in a similar manner to 1. [Surface treatment] After washing the test piece with water, General Industrial Cleaning Agent I
Washed with a 4% aqueous solution (60 ° C.) of D-112 [trade name, manufactured by Tosoh Corporation] for 1.5 minutes and washed with water.

Further, this test piece was washed with General Industrial Cleaning Agent I.
It was washed with a 1% aqueous solution of D-113 (trade name, manufactured by Tosoh Corporation) (55 ° C) for 1 minute, washed with water, and dried at 80 ° C for 10 minutes.

The results are shown in Table 2.

[0101]

[Table 2]

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Shoji Hiraoka 6-1-2, Waki, Waki-machi, Kuga-gun, Yamaguchi Prefecture Inside Mitsui Petrochemical Industry Co., Ltd. (72) Inventor Tetsu Nagami Chikusa, Ichihara-shi, Chiba Coast No. 3 Inside Mitsui Petrochemical Industry Co., Ltd. (56) References JP-A-5-15844 (JP, A) JP-A-58-15544 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , (DB name) C08L 23/00-23/36 C08L 53/00-53/02

Claims (5)

(57) [Claims] [1] A melt flow rate is from 50 to 200.
g / 10 minutes of a crystalline polypropylene portion of 85 to 95% by weight, and an ethylene content of 20 to 50% by weight of propylene.
Having a melt flow rate of 20 to 100 g / 10 containing 5 to 15% by weight of an ethylene random copolymer part
Propylene / ethylene block copolymer 20-70
% By weight, [B] Mooney viscosity [ML _{1 + 4} (100 ° C)] is 1
0 to 60 and an ethylene content of 60 to 95 mol%, which may contain a non-conjugated diene.
Graft modification in which the olefin copolymer rubber is 15 to 40% by weight, the graft amount of [C] maleic anhydride is 0.5 to 5% by weight, and the intrinsic viscosity [η] is 0.2 to 0.5 dl / g. 1 to 15% by weight of a propylene polymer, [D] a hydrogenated conjugated diene polymer having a hydroxyl group at at least one molecular end and having a number average molecular weight of 1,000 to 8,000, which may be hydrogenated. % By weight, and [E] specific surface area of 30,000 cm ² / g or more, average particle size of 0.8 to 2.5 μm, length of substantially 12 μm or less, and average aspect ratio A resin composition comprising 8 to 30% by weight of an inorganic filler having a modulus of 5 or more, and a molded article of the resin composition having a flexural modulus of 8,000 kg / cm ² or more. Olefin resin set for exterior parts Thing. 2. An ethylene / α-olefin copolymer rubber [B] containing 25 to 65% by weight of a propylene / ethylene block copolymer [A] and optionally containing a non-conjugated diene.
15 to 30% by weight, 5 to 15% by weight of a graft-modified propylene polymer [C], 2 to 10% by weight of a conjugated diene polymer [D] which may be hydrogenated, and an inorganic filler [E] The olefin resin composition for automotive exterior parts according to claim 1, comprising 10 to 30% by weight. 3. The olefin resin composition for automotive exterior parts according to claim 1, wherein the inorganic filler [E] is talc. 4. The propylene / ethylene block copolymer [A] has a melt flow rate of 80 to 160 g / 1.
90-95% by weight of a 0 minute crystalline polypropylene portion;
The propylene / ethylene random copolymer portion having an ethylene content of 30 to 50% by weight and a melt flow rate of 30 to 80 g / 10 minutes. 4. The olefin-based resin composition for automotive exterior parts according to any one of 1 to 3. 5. The ethylene / α-olefin copolymer rubber [B] having a Mooney viscosity [ML 1 _{+ 4} (100 ° C.)] of 10
The olefin-based resin composition for automotive exterior parts according to any one of claims 1 to 4, wherein the ethylene content is 70 to 90 mol%.