JPH072876B2 - Propylene polymer composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a propylene-based polymer composition which not only has excellent adhesion to polyurethane without using a primer but also has good weather resistance, and has a high rigidity. It has excellent mechanical properties such as impact resistance and good weather resistance,
Moreover, it is an object of the present invention to provide a propylene-based polymer composition having excellent adhesion to polyurethane without using a primer.

BACKGROUND ART As is well known, propylene-based polymers (propylene homopolymers and propylene copolymers) have not only excellent moldability but also mechanical properties, heat resistance, solvent resistance, oil resistance and chemical resistance. Since it has good properties such as properties, it is industrially manufactured in large quantities and widely used in various fields as industrial parts such as automobiles, electric appliances, electronic devices, and daily necessities. However, since the propylene-based polymer does not have a polar group in the molecule (so-called non-polar), the adhesion to polyurethane is not good, which causes various problems. A widely used automobile bumper will be described as an example.

Conventionally, bumpers made of metal or polyurethane have been widely used, but in recent years, propylene-based polymers containing propylene as a main component (propylene homopolymer, ethylene Bumpers made from compositions based on propylene random or block copolymers) or propylene-based polymers are widely used. When this bumper is mounted on a vehicle, it is often the case that the surface of the molded product is pre-textured and is used as it is without being painted. However, in order to make the bumper fresher and more luxurious, it is often the case that the bumper is coated with a polyurethane-based paint and mounted on the vehicle, and this tendency is further increasing under the intention of upsizing the automobile.

However, as mentioned above, the propylene-based polymer is a chemically very inactive polymer substance because it does not have a polar group in the molecule. The molded product is treated electrically (for example, by
Corona discharge treatment method, plasma treatment method), mechanical surface roughening method, flame treatment method and surface treatment method such as oxygen or ozone treatment method are generally used. Furthermore, prior to these surface treatments, it is recommended that the surface be previously cleaned with a solvent such as alcohol or aromatic hydrocarbon. Also known is a method in which an article is immersed in an organic solvent such as trichlene, perchlorethylene, pentachloroethylene, or toluene at a temperature close to the boiling point or exposed to a solvent vapor (for example, Kenyuki Takagi, Taira Sasaki). Edited by San, "Plastic Materials Course, Polypropylene Resin," pages 216-219, 1969, published by Nikkan Kogyo Shimbun). However, each of these methods has a problem that not only a device for processing is required, but also a considerable time is required for the processing. Therefore, in reality, a molded article (bumper) is undercoated with a primer capable of adhering to a propylene-based polymer, and a polyurethane coating is applied as an overcoat. That is, in this method, primer primer coating → baking → polyurethane coating → baking (2 coat 2 bake or 3 coat 2
This requires a long time (usually about 1 hour and 30 minutes) for this coating process. For this reason, in order to manufacture a propylene-based polymer bumper coated with polyurethane, the coating cycle is long, making mass production difficult and increasing the cost.

In addition, when manufacturing propylene-based polymers for automobile parts, motorcycle parts, electric appliance parts, electronic appliance parts, etc., the coating method also differs when applying polyurethane, but the same problems as described above There is.

A propylene-based polymer or a composition thereof generally used for bumpers and the like is an ultraviolet absorber for enhancing weather resistance,
A combination of UV stabilizers, antioxidants, etc., added in an arbitrary formulation, is used. However, after a few years of actual running, the surface of the molded product will become discolored, and chalking or cracking will occur, which is not sufficient under the current conditions, and furthermore, a bumper with good weather resistance. This tendency is intensifying as the demand for grades increases as automobiles become more upscale and the ratio of use in regions with bad climate increases.

Therefore, as a countermeasure, it is conceivable to increase the conventional weather resistance formulation or add a new additive, but if these are simply increased or added, appearance problems at the time of molding (for example, uneven gloss on the surface or whitening) And various additives such as increased amount or added additive bleed on the surface of the molded product after molding, which deteriorates the appearance, and whitening of the surface of the molded product due to long-term use during actual running. is there.

Problems to be Solved by the Invention The object of the present invention is to solve the problems or drawbacks of the above-mentioned conventional propylene-based polymer compositions, and to provide various mechanical properties (for example, impact strength, rigidity) having the propylene-based polymer. And the like), and also has good moldability and excellent weather resistance, and at the same time, obtains a propylene-based polymer composition exhibiting good adhesion to polyurethane without the use of a primer. is there.

Means and Actions for Solving Problems According to the first aspect of the present invention, the problems are (A) propylene polymer, (B) (1) propylene homopolymer and Mooney viscosity [ML _{1 +4} (100 ° C)] is 10 to 50 and 100 parts by weight of a mixture with 1 to 40% by weight of an ethylene-propylene copolymer rubber (2) having at least one unsaturated bond in a molecule and having a hydroxyl group A modified propylene-based polymer obtained by treating with 0.1 to 50 parts by weight of an organic compound containing (3) and 0.01 to 20 parts by weight of an organic peroxide, and (C) Mooney viscosity [ML _{1 + 4} (100 ° C. )] Is from 20 to 100 and the content of propylene is from 20 to 50% by weight, the composition comprising an amorphous ethylene-propylene copolymer, and the components (B) and (C) in the composition. ) Composition ratio of 5.0 to 50% by weight and A 35 wt%, the components (A) and the total amount of (B) (B)
The composition ratio of 5 to 90% by weight, and the components (A) and (B)
This can be solved by a propylene-based polymer composition in which the composition ratio of the component (B) (2) to the total amount of (C) and (C) is 0.1 to 10% by weight, and further according to the second embodiment of the present invention. The above-mentioned problems are (A) a propylene polymer, (B) (1) a propylene homopolymer and an ethylene-propylene copolymer rubber having a Mooney viscosity [ML _{1 + 4} (100 ° C.)] of 10 to 50. 100 parts by weight of a mixture with 1 to 40% by weight (2) 0.1 to 50 parts by weight of an organic compound having at least one unsaturated bond in the molecule and containing a hydroxyl group, and (3) an organic peroxide of 0.01 to A modified propylene polymer obtained by treating with 20 parts by weight, and (C) a Mooney viscosity [ML _{1 + 4} (100 ° C)] of 20 to 100 and a propylene content of 20 to 35% by weight. An amorphous ethylene-propylene copolymer, (D ) A composition comprising a high-density ethylene polymer having a density of 0.935 g / cm ³ or more and (E) an inorganic filler, wherein the components (B), (C), (D) and The composition ratio of (E) is 5 to 50% by weight, 3 to 35% by weight, 3 to 20% by weight and 3 to 35% by weight, respectively, and the components relative to the total amount of the components (A) and (B). Propylene system in which the ratio of (B) is 5 to 90% by weight, and the composition ratio of component (B) (2) to the total amount of components (A), (B) and (C) is 0.1 to 10% by weight. Solved by a polymer composition.

Description of Specific Embodiments of the Invention Hereinafter, the present invention will be specifically described.

(A) Propylene-based polymer The propylene-based polymer to be blended in the composition of the present invention is a propylene homopolymer, a block copolymer mainly composed of propylene with ethylene and / or α-olefin, and propylene as a main component. It is selected from random copolymers with ethylene and / or α-olefin as a component. In both of these block copolymers and random copolymers, the copolymerization ratio of ethylene and α-olefin is 20% by weight or less, preferably 15% by weight or less, as their total amount. The carbon number of the α-olefin is 4 to
It is preferably 12, and typical examples of such α-olefins include butene-1, methylhexene-1 and octene-1.

These propylene-based polymers are industrially produced and widely used. The physical properties and production method of these propylene-based polymers are well known. Among the propylene-based polymers, it is preferable to use the block copolymer and the random copolymer.

Melt flow rate (MFR) of this propylene polymer
(Measured under condition 14 according to JIS K7210) is usually 1.0 to 100g / 1
It is 0 minutes, 1.0 to 80 g / 10 minutes is desirable, and 2.0 to 60 g / 10 minutes is particularly preferable. When a propylene-based polymer having an MFR of less than 1.0 g / 10 minutes is used, not only the kneadability with the modified propylene-based polymer tends to be poor, but also the moldability of the resulting composition may be poor, Conversely, MFR is 100g / 10
The use of a propylene-based polymer in excess of the amount is not preferable because the mechanical strength of the resulting composition tends to decrease.

(B) Modified Propylene Polymer The modified propylene polymer of the present invention can be obtained by treating a mixture of a propylene homopolymer and an ethylene-propylene copolymer rubber with a hydroxyl compound and an organic peroxide compound. The manufacturing method and the like can be as described in detail in, for example, JP-A-58-154732.

(1) Mixture of Propylene Homopolymer and Ethylene-Propylene Copolymer Rubber In producing the modified propylene polymer of the present invention, the propylene homopolymer is an ethylene-propylene copolymer rubber as described below. Are mixed and used. The ethylene-propylene copolymer rubber used in this manner has ethylene and propylene as main components. As this ethylene-propylene copolymer rubber,
A copolymer rubber obtained by copolymerizing ethylene and propylene, and ethylene and propylene as the main components, such as 1,4-pentadiene, 1,5-hexadiene and 3,3-dimethyl-1,5-hexadiene. Linear or branched diolefins containing two double bonds at the ends, linear or branched diolefins containing 1,4-hexadiene and 6-methyl-1,5-heptadiene at the ends or bicyclo ( 2,2,1) -Heptene-2-
(Norbornene) and its derivatives (eg ethylidene norbornene) in small amounts (typically 10% by weight) of monomers with double bonds such as cyclic diene hydrocarbons.
The following is roughly classified into multi-component copolymer rubbers obtained by copolymerization. In any of the above-mentioned copolymer rubber and multi-component copolymer rubber, the preferable propylene content is
20 to 50% by weight. The Mooney viscosity [ML _{1 + 4} (100 ° C.)] of the ethylene-propylene copolymer rubber is 10 to 50, preferably 10 to 40, and particularly preferably 15 to 40. When an ethylene-propylene copolymer rubber having a Mooney viscosity of less than 10 is used, the moldability is good, but the improvement of the adhesion strength with the urethane coating described below is not sufficient, and on the contrary, the Mooney viscosity is 50. If the amount exceeds the limit, flow marks or the like are generated on the surface of the molded product, which is not preferable in appearance.

In producing the modified propylene-based polymer of the present invention using the ethylene-propylene-based copolymer rubber, the ethylene-propylene-based copolymer rubber occupies in the total amount of the propylene homopolymer and the ethylene-propylene-based copolymer rubber. The ratio is 1 to 40% by weight, and particularly preferably 2 to 35% by weight. When the proportion of the ethylene-propylene copolymer rubber in the total amount of the propylene homopolymer and the ethylene-propylene copolymer rubber exceeds 40% by weight, the adhesion strength with the coating film is good, but the molded product is Not only flow marks are generated on the surface, but also the gloss tends to decrease, which is not preferable.

Melt flow rate (MFR) of this propylene polymer
From the viewpoint of moldability, mechanical properties of the resulting composition,
It is usually 0.01 to 100 g / 10 minutes, preferably 0.01 to 80 g / 10 minutes, and particularly preferably 0.02 to 60 g / 10 minutes.

(2) Hydroxyl compound The hydroxyl compound used for producing the modified propylene polymer has at least one unsaturated bond (double bond, triple bond) and contains a hydroxyl group. It is a compound. Typical examples of such a hydroxyl compound include an alcohol having a double bond, an alcohol having a triple bond, an ester of a monovalent or divalent unsaturated carboxylic acid and an unsubstituted dihydric alcohol, and an unsaturated carboxylic acid and an unsubstituted carboxylic acid. Examples thereof include esters with trihydric alcohols, esters with unsubstituted tetrahydric alcohols and esters with unsubstituted pentavalent or higher alcohols. Typical examples of such a hydroxy compound include 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, and 2-hydroxybutyl methacrylate.

In producing the modified propylene polymer according to the present invention, the hydroxyl compound is 0.1 to 50 parts by weight, preferably 0.2 to 50 parts by weight, relative to 100 parts by weight of the propylene homopolymer and the specific ethylene-propylene copolymer rubber. 30 parts by weight,
Particularly preferably, 0.3 to 20 parts by weight is used. The propylene homopolymer and a specific ethylene-propylene copolymer rubber
The proportion of hydroxyl-based compound used is 100 parts by weight
If it is less than 0.1 part by weight, the effect of improving the adhesiveness is insufficient. On the other hand, even if it is used in an amount of more than 50 parts by weight, the effect of improving the adhesiveness depending on the amount used is not recognized, and rather the original properties of the propylene homopolymer are impaired, which is not preferable.

(3) Organic peroxide The organic peroxide used for producing the modified propylene-based polymer described above is generally used as an initiator in radical polymerization and a crosslinking agent for the polymer,
The one having a half-life of 1 minute is 100 ° C. or more, and the one having a half-life of 1 minute is 130 ° C. or more is particularly preferable. When an organic peroxide having a temperature of less than 100 ° C. is used, it is not preferable because it is difficult to handle and the effect of use is not recognized so much.

The proportion of the organic peroxide used is 0.01 to 20 parts by weight, preferably 0.05 to 10 parts by weight, particularly preferably 0.1 to 7 parts by weight, based on 100 parts by weight of the propylene homopolymer and the specific ethylene-propylene copolymer rubber. . The propylene homopolymer and a specific ethylene-propylene copolymer rubber 100
If the mixing ratio of the organic peroxide with respect to parts by weight is less than 0.01 parts by weight, not only the effect of improving the adhesiveness with polyurethane is low, but also the durability of the adhesive strength of the mixture is reduced, which is not preferable, and conversely 20 parts by weight. When it exceeds, the original excellent mechanical properties of the propylene polymer are deteriorated, which is not desirable.

(4) Method for producing modified propylene-based polymer In order to produce the modified propylene-based polymer used in the present invention, the above-mentioned propylene homopolymer, a specific ethylene-propylene copolymer rubber, a hydroxyl-based compound and an organic peroxide are used. It can be produced by treating (heating) the oxide in the above proportion. At this time, the propylene homopolymer and the specific ethylene-propylene copolymer rubber, the hydroxyl-based compound and the organic peroxide may be treated while being mixed, but in advance, these may be mixed by dry blending, or It can also be obtained by kneading at a relatively low temperature (a temperature at which a hydroxyl-based compound does not react) and heating the resulting mixture as described below.

When the treatment of the propylene homopolymer and the specific ethylene-propylene copolymer rubber is carried out at a high temperature, the propylene homopolymer and the specific ethylene-propylene copolymer rubber may deteriorate, but the propylene homopolymer And a specific ethylene-propylene copolymer rubber and a hydroxyl-based compound should be carried out at a temperature at which the organic peroxide used for graft polymerization is decomposed.
From the above, this treatment is generally carried out at 160 to 300 ° C., preferably 170 to 280 ° C., depending on the type of organic peroxide used.

The general formulas and typical examples of the hydroxyl compounds and organic peroxides, the mixing method and the treating method are as described in detail in JP-A-58-154732, for example.

(C) Amorphous ethylene-propylene copolymer The Mooney viscosity of the amorphous ethylene-propylene copolymer used as the component (C) in the present invention [ML _{1 + 4} (100
C)) is 20-100, preferably 20-80, especially 3
0 to 75 is preferable. If an amorphous ethylene-propylene copolymer with a Mooney viscosity of less than 20 is used, the moldability will be improved, but layer separation may occur during gate cutting of the molded product, causing troubles. There is. On the other hand, when a Mooney viscosity of more than 100 is used, not only it becomes difficult to uniformly disperse other composition components during kneading, but even if a uniform composition is obtained,
Flow marks, weld lines, etc. are noticeable on the surface of the molded product, and a molded product with a good appearance cannot be obtained. Furthermore, the propylene content of this copolymer is generally 20
% To 50% by weight, preferably 25 to 45% by weight, and particularly preferably 25 to 40% by weight. This amorphous ethylene-propylene copolymer has rubber-like properties, is industrially produced and is used in various fields, and its manufacturing method is also widely known.

The amorphous ethylene-propylene copolymer is a copolymer rubber obtained by copolymerizing ethylene and propylene, and ethylene and propylene as main components, 1,4-pentadiene, 1,5-hexadiene and 3,3.
Included at the ends such as 1,4-hexadiene and 6-methyl-1,5-heptadiene, linear or branched diolefins containing two double bonds at the ends such as -diethyl-1,5-hexadiene Monomers having double bonds such as linear or branched diolefins or cyclic diene hydrocarbons such as bicyclo [2,2,1] -heptene-2 (norbornene) and its derivatives (eg ethylidene norbornene) It can be roughly classified into a multi-component copolymer rubber obtained by copolymerizing a small amount (generally 10% by weight or less).

(D) High Density Ethylene Polymer The high density ethylene polymer used as the component (D) in the present invention is an ethylene polymer having a density of 0.935 g / cm ³ or more, and is 0.935 g / cm ^{3 to} 0.980. g / cm ³ is preferable,
In particular, 0.935 to 0.975 g / cm ³ is preferable. Such ethylene polymers are generally ethylene homopolymers and ethylene and α-olefins (carbon number is generally 3 to
12 pieces, preferably 3 to 8 pieces). Suitable α-olefins include propylene, butene-1, hexene-1, 4-methylpentene-1 and octene-
1 is given.

Melt flow index of this high-density ethylene-based polymer [measured under condition 4 according to JIS K-7210;
(I) ”is generally 0.5 to 100 g / 10 minutes, and
It is preferably 5 to 80 g / 10 minutes, and particularly preferably 1.0 to 60 g / 10 minutes. When a high-density ethylene polymer having an MFR (I) of less than 0.5 g / 10 minutes is used, not only it becomes difficult to uniformly disperse it at the time of kneading, but also a cause of generation of flow marks on the surface of the obtained molded product. May be.
On the other hand, when an ethylene polymer having an MFR (I) of more than 100 g / 10 minutes is used, it is still difficult to uniformly disperse it during kneading, and the impact resistance of the resulting composition tends to be lowered. .

(E) Inorganic Filler The inorganic filler used as the component (E) in the present invention is generally widely used in the fields of synthetic resins and rubbers. As such an inorganic filler, an inorganic compound that does not react with oxygen and water and does not decompose during kneading and molding is preferably used. As the inorganic filler, metals such as aluminum, copper, iron, lead and nickel, oxides of these metals and metals such as magnesium, calcium, barium, zinc, zirconium, molybdenum, silicon, antimony and titanium,
Compounds such as hydrates (hydroxides), sulfates, carbonates, and silicates, double salts thereof, and mixtures thereof can be roughly classified. Representative examples of such inorganic fillers are described in Japanese Patent Application No. 59-8535 (JP-A-60-153202). Of these inorganic fillers, the powdered ones have a diameter of 30 microns or less (preferably 10 microns or less).
Are preferred. For fibrous materials, the diameter is 1 to 50.
0 micron (preferably 1 to 30 micron) with a length of
It is preferably 0.1 to 6 mm (preferably 0.1 to 5 mm). Further, it is preferable that the flat plate has a diameter of 30 microns or less (preferably 10 microns or less). Of these inorganic fillers, flat plate-shaped (flake-shaped) and powdered ones are particularly preferable. Suitable inorganic fillers include talc, mica, silica, glass fibers, graphite and the like.

The composition ratio of the component (B) in the composition of the present invention, that is, the modified propylene-based polymer is 5.0 to 50% by weight and 5.0 to 40%.
Weight% is preferable, and 7.0-40 weight% is especially preferable. The composition ratio of the modified propylene-based polymer in the composition is 5.
If it is less than 0% by weight, the resulting composition does not have good adhesion to polyurethane, and conversely, even if it is compounded at more than 50% by weight, it exhibits an effect of improving adhesion and weather resistance depending on the amount used. Not only is it impossible, but rather the mechanical strength of the resulting composition tends to decrease.

The composition ratio of the component (C), ie, the amorphous ethylene-propylene copolymer, to be incorporated in the composition of the present invention is 3 to 35% by weight, preferably 3 to 30% by weight, particularly preferably 5 to 30% by weight. Is. If the composition ratio of the component (C) is less than 3% by weight, the impact resistance is not sufficiently improved, while if it exceeds 35% by weight, the rigidity of the composition is lowered and it tends to cause flow marks during molding. .

The composition ratio of the component (B) to the total amount of the components (A) and (B) in the composition of the present invention is 5 to 90% by weight, preferably 5 to 60% by weight. If this ratio is less than 5% by weight, the adhesion to the urethane coating will not be sufficiently improved, and if it exceeds 90% by weight, the rigidity and heat resistance of the composition will decrease and the characteristics of the propylene composition will tend to be impaired. .

The composition ratio of the component (B) (2) to the total amount of the components (A), (B) and (C) in the composition of the present invention is
It is 0.1 to 10% by weight. If this proportion is less than 0.1% by weight, the adhesion of the composition to the urethane coating will not be sufficiently improved, and conversely
Even if it exceeds 10% by weight, the adhesiveness and the weather resistance are not improved together therewith, and on the contrary, the rigidity, the heat resistance and the like tend to be deteriorated, which is not preferable.

In the second aspect of the present invention, the above-mentioned component (A),
In addition to (B) and (C), component (D) (that is, high-density ethylene polymer) and component (E) (that is, inorganic filler)
Is compounded.

The composition ratio of the component (D) blended in the composition of the present invention is 3 to 20% by weight, preferably 3 to 15% by weight. If this proportion is less than 3% by weight, improvement in glossiness and impact resistance will be insufficient, and conversely, if it exceeds 20% by weight, the heat resistance will deteriorate and the characteristics of the propylene composition will tend to be impaired.

Further, the composition ratio of the component (E) blended in the composition of the present invention is 3 to 35% by weight, preferably 3 to 30% by weight.
If this proportion is 3% by weight, the improvement in rigidity is insufficient, and conversely, if it exceeds 35% by weight, the impact resistance is lowered, and flow marks and silver streaks tend to occur.

Further, the total amount of component (B) and components (A), (B) and (C) relative to the total amount of components (A) and (B) in the composition of the present invention containing components (D) and (E). The composition ratio of component (B) (2) to
It is 0.1 to 10% by weight. Components (A), (B) and (C)
If the proportion of each of the components (B) and (B) (2) with respect to the above is too small, the adhesion of the composition to the urethane coating will not be sufficiently improved, and conversely if there is too much, the rigidity and heat resistance will tend to decrease. .

In order to produce the composition of the present invention, the above-mentioned component (A),
(B) and (C) and the above (A) to (E) are homogenized by applying a mixing method carried out in the field of ordinary olefin-based polymers so that the composition ratio falls within the above range. So that they can be mixed. At this time, all the composition components may be mixed at the same time, or a part of the composition components may be mixed in advance to produce a so-called masterbatch, and this masterbatch and the remaining composition components may be mixed. At this time, the heat generally added (added) to the olefin polymer,
Additives such as stabilizers against oxygen or ultraviolet rays, metal deterioration inhibitors, plasticizers, flame retardants, lubricants, fillers, colorants, antistatic agents and electrical property improvers are essential for the physical properties of the composition. You may mix | blend according to the use purpose of a composition in the range which does not impair.

The composition thus obtained is usually molded into pellets, and is manufactured into a desired molded product by a molding method such as an injection molding method or an extrusion molding method that is generally performed in the field of each thermoplastic resin.

The melting point of the polymer to be used is higher even when it is melt-kneaded or when it is molded when the composition is produced, but it is a temperature at which it is not thermally decomposed. For these reasons, it is generally carried out at 180 to 300 ° C (preferably 190 to 250 ° C).

In general, olefin polymers have extremely poor adhesion to polyurethane, so when applying a polyurethane paint to a molded product of an olefin polymer or a composition thereof, a primer must be applied and dried in advance and the polyurethane paint must be applied. I won't. However, since the propylene-based polymer composition of the present invention has excellent adhesion to polyurethane, it is possible to directly apply polyurethane to the surface of a molded article without applying a primer to the surface of the molded article (primer). Is used, the adhesion is further improved).

Examples and Comparative Examples Hereinafter, the present invention will be described in more detail with reference to Examples.
It goes without saying that the technical scope of the present invention is not limited to these examples.

The physical properties of the examples and comparative examples were measured as follows.

(I) The flexural modulus was measured according to ASTM D790.

(Ii) Izod impact strength was measured according to ASTM D256.

(Iii) The adhesion strength of the coating film is a flat plate test piece (thickness 2 mm, 130 × 1
30 mm) in steam of 1,1,1-trichloroethane for 30 seconds and thoroughly dried, and then a high urethane paint (Nippon Pee Chemical Co., Ltd., trade name R257, Solid) has a dry thickness of 20 ~ It was applied so as to have a thickness of 30 microns. After leaving for about 15 minutes, urethane paint (trade name, manufactured by Nippon Pea Chemicals Co., Ltd.)
R266, Wacker Top) was applied so that the dry thickness would be 30 to 40 microns, and dried at 90 ° C for 30 minutes. Then, it was allowed to stand for 48 hours in a constant room temperature (temperature 23 ° C, humidity 65%). The obtained coated product (test piece) is cut into a width of 10 mm, a part (about 10 mm) of the coating film is forcibly peeled from the resin portion of the test piece, and the remaining adhesion portion is used by a tensile tester. 50
Pull in the opposite direction (180 degrees) to the coating film at a speed of mm / min,
It was determined by measuring the peel strength.

(Iv) The same as the above except that a polyurethane paint (Nippon Pea Chemicals Co., Ltd., trade name R255, metallic red) was used in place of the high urethane paint used to measure the coating film adhesion strength. Similarly, treatments such as coating and drying were performed. On the coating surface of the obtained test piece, 100 eyes were cut at 1 mm intervals, and cellophane tape was completely adhered to the eyes by finger pressure. 45 this cellophane tape
It was rapidly peeled off at an angle of degrees. This operation was repeated twice to determine the percentage of the leftover coating film.

(V) For the weather resistance test, the flat plate test piece was cut into 50 mm x 50 mm, and a sunshine weatherometer (manufactured by Suga Test Instruments Co., Ltd.)
With a black panel temperature of 83 ° C and rainfall conditions of 12
The sample was irradiated under the condition of min / 60 min and taken out at each irradiation time, and the change in the appearance of the sample was observed. The results are shown below.

⊚: No change ∘: Slight choking occurs Δ: Cracks occur ×: Violent cracks occur (vi) In the gloss test, the flat plate test piece was measured according to JIS K 7150.

The modified propylene-based polymer and ethylene-propylene copolymer used in Examples and Comparative Examples, heat,
Stabilizers against oxygen or ultraviolet rays, other compositions, and physical properties and manufacturing methods thereof are shown below.

1) Ethylene-propylene block copolymer with propylene polymer PP (A) MFR of 15 g / 10 minutes (ethylene content 8.8% by weight) PP (B) ethylene-propylene block copolymer with MFR of 30 g / 10 minutes Polymer (ethylene content 7.5%) PP (C) MFR is 1.5g / 10 minutes ethylene-propylene block copolymer (ethylene content 10.0% by weight) PP (D) MFR is 100g / 10 minutes ethylene -Propylene block copolymer (ethylene content 8.5% by weight) PP (E) Propylene homopolymer with MFR of 10 g / 10 minutes PP (F) Ethylene-propylene random copolymer with ethylene content 3.1% by weight 2) Modified propylene homopolymer As modified propylene homopolymer, 85 parts by weight of propylene homopolymer having MFR of 0.5 g / 10 minutes and Mooney viscosity (ML
_{1 + 4} , 100 ° C) 20 Amorphous ethylene-propylene copolymer 15 parts by weight to 30 parts by weight of 2-hydroxyethyl methacrylate and 0.7 parts by weight of 2,2'-bis (tertiary-butylperoxide) Oxyisopropyl) benzene was previously dry blended for 5 minutes using a Henschel mixer. A mixture (hereinafter referred to as "modified PP") obtained by kneading the obtained mixture with an extruder with a vent (diameter 65 mm, cylinder temperature 160 to 200 ° C) was used.

3) Amorphous ethylene-propylene copolymer Amorphous ethylene-propylene copolymer has a Mooney viscosity [ML ₁₄ (100 ° C)] of 35.
Propylene copolymer (propylene content 27% by weight, hereinafter referred to as EPR).

4) High Density Ethylene Polymer As the high density ethylene polymer, an ethylene-butene-1 copolymer having a density of 0.945 g / cm ³ (MFR (I) 0.7 g /
10 minutes, hereinafter referred to as HDPE (A)) and density 0.960 g / c
An ethylene homopolymer of m ³ (MFR (I) 20 g / 10 minutes, hereinafter referred to as HDPE (B)) was used.

5) Inorganic filler As the inorganic filler, talc having an average particle size of 2.0 μm and calcium carbonate (C having an average particle size of 2.0 μm)
aCO ₃ ) and wollastonite with an average particle size of 7.0 microns were used.

6) Stabilizer As various stabilizers, bis (2,2,6,6-tetramethyl-4
-Piperidine sebacate (hereinafter referred to as stabilizer (1)), 2 (3-tertiary-butyl-5-methyl-2-hydroxyphenyl-5-chlorobenzotriazole (hereinafter referred to as stabilizer (2)) ) And tetra [methylene-3
-(3,5-Ditertiary-butyl-4-hydroxyphenyl) propionate] methane (hereinafter referred to as stabilizer (3)) was used.

Examples 1 to 11 and Comparative Examples 1 to 3 The propylene-based polymers, modified propylene polymers and amorphous ethylene-of which the respective compounding amounts are shown in Table 1
The propylene random copolymer and stabilizer were mixed for 5 minutes with a super mixer. Pellets (composition) were produced while kneading the obtained mixtures with a vented two-wheel extruder (cylinder temperature 180 to 200 ° C, diameter 30 mm). Each pellet was flat plate (thickness) using a 5 ounce injection molding machine.
2 mm, 130 × 130 mm), bending elastic modulus measuring specimens and Izod impact strength measuring specimens were manufactured. Bending elastic modulus and Izod impact strength (temperature 23
℃), weather resistance test, coating film adhesion strength, and the eyes test. The results are shown in Table 2.

From the results of the above Examples and Comparative Examples, the propylene polymer composition obtained according to the present invention has not only excellent mechanical strength (flexural modulus, impact resistance) but also good processability. It is also clear that the adhesiveness with polyurethane is also excellent. Furthermore, it is clear that the most characteristic effect is that when a stabilizer against heat, oxygen and ultraviolet rays is added, a synergistic effect is exerted.

Examples 12 to 19 and Comparative Examples 4 to 6 Propylene-based polymers (PP-based resins) and modified propylene-based polymers (modified P
P), amorphous ethylene-propylene random copolymer (E
PR), high density ethylene polymer (HDPE), inorganic filler and stabilizer were mixed for 5 minutes using a super mixer. Each of the resulting mixtures was vented on a twin-screw extruder (cylinder temperature
Pellets (composition) were produced while kneading using 180 to 20 ° C. and a diameter of 30 mm. A flat plate (thickness: 2 mm, 130 × 130 mm), a test piece for flexural modulus measurement, and a test piece for Izod impact strength measurement were manufactured from each pellet by using a 5 ounce injection molding machine. The bending elastic modulus, Izod impact strength (temperature: 23 ° C.), weather resistance test, and coating adhesion strength of each of the obtained test pieces were measured. The results are shown in Table 4.

From the results of the above Examples and Comparative Examples, the propylene-based polymer composition obtained by the present invention is not only excellent in mechanical strength (flexural modulus, impact resistance),
It is clear that the processability is good and the adhesion to polyurethane is also excellent. Furthermore, it is clear that the most characteristic effect is that when a stabilizer against heat, oxygen and ultraviolet rays is added, a synergistic effect is exerted.

Effects of the Invention The propylene-based polymer composition obtained by the present invention is
Compared with the conventional propylene polymer composition, the following effects are exhibited.

(1) Workability and formability are equal or higher.

(2) The weather resistance is good because it exerts the synergistic effect as described above.

(3) Excellent adhesion to polyurethane paint,
By applying a polyurethane coating on the surface, the primer undercoating step can be omitted.

(4) Generally used activation treatment methods (for example, corona discharge treatment, plasma treatment method, ultraviolet treatment method)
By applying to the surface of the molded article, it is possible to achieve a sufficient degree of adhesion with the polyurethane paint.

(5) The propylene-based polymer composition of the present invention can be used in various fields in order to exert the above effects. Typical applications include automobile bumpers,
Examples include exterior parts such as bumper corners, interior parts such as door liners, and motorcycle parts such as fenders.

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Claims (2)

[Claims] 1. A propylene-based polymer (A), (B) (1) propylene homopolymer and Mooney viscosity [ML
_{1 + 4} (100 ° C.)] is 10 to 50 and 100 parts by weight of a mixture with 1 to 40% by weight of an ethylene-propylene copolymer rubber (2) having at least one unsaturated bond in a molecule and a hydroxyl group. A modified propylene polymer obtained by treating with 0.1 to 50 parts by weight of a group-containing organic compound and (3) 0.01 to 20 parts by weight of an organic peroxide, and (C) Mooney viscosity [ML _{1 + 4} (100 C)) is from 20 to 100 and the content of propylene is from 20 to 50% by weight, which is a composition comprising an amorphous ethylene-propylene copolymer, wherein the components (B) and ( The composition ratio of C) is 5.0 to 50% by weight and 3 to 35% by weight, respectively, and the component (B) relative to the total amount of the components (A) and (B).
The composition ratio of 5 to 90% by weight, and the components (A) and (B)
And the composition ratio of the component (B) (2) to the total amount of (C) is 0.1 to 10% by weight. 2. A (A) propylene polymer, (B) (1) propylene homopolymer and Mooney viscosity [ML
_{1 + 4} (100 ° C.)] is 10 to 50 and 100 parts by weight of a mixture with 1 to 40% by weight of an ethylene-propylene copolymer rubber (2) having at least one unsaturated bond in a molecule and a hydroxyl group. A modified propylene polymer obtained by treating with 0.1 to 50 parts by weight of a group-containing organic compound and (3) 0.01 to 20 parts by weight of an organic peroxide, and (C) Mooney viscosity [ML _{1 + 4} (100 C)] is 20 to 100 and the content of propylene is 20 to 50% by weight, and an amorphous ethylene-propylene copolymer (D) a high density ethylene-based polymer having a density of 0.935 g / cm ³ or more. A composition comprising a coalesced product and (E) an inorganic filler, wherein the composition ratios of the components (B), (C), (D) and (E) in the composition are 5 to 50% by weight, respectively. 3 to 35% by weight, 3 to 20% by weight and 3 to 35% by weight, and the content of component (A) and The ratio of the component (B) to the total amount of (B) is 5 to 90% by weight, and the composition ratio of the component (B) (2) to the total amount of the components (A), (B) and (C) is 0.1. ~ 10 wt% propylene polymer composition.