JP3311378B2 - Propylene polymer composition and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a propylene polymer composition having excellent coatability. More specifically, the present invention relates to a propylene-based polymer composition having excellent adhesion to a coating material such as polyurethane even when a surface treatment using a primer or a solvent is not performed.

[0002]

BACKGROUND OF THE INVENTION Propylene polymers (propylene homopolymers or propylene copolymers) have good properties such as mechanical properties, heat resistance, solvent resistance, oil resistance and chemical resistance. This propylene-based polymer is widely and industrially manufactured, and is widely used as a raw material for manufacturing industrial parts such as automobiles and electric appliances and daily necessities.

[0003] This propylene-based polymer is a highly stable or safe resin because it is a chemically inert polymer material having no polar group in the molecule. Therefore, the adhesion to other resins is not good. For example, in order to apply a molded product made of a propylene-based polymer with a paint such as a polyurethane-based paint, an electric treatment method such as corona discharge, a mechanical surface roughening method, a flame treatment method, an oxygen treatment method or an ozone treatment method is used. By using such a surface treatment method, it is necessary to perform a treatment for improving the affinity of the surface of the molded product with another resin. When performing these surface treatments, the surface of the molded product is washed in advance with a solvent such as alcohol or aromatic hydrocarbon, or with a solvent vapor such as trichlene, perchlorethylene, pentachloroethylene or toluene. Is generally adopted.

However, in order to carry out any of these surface treatment methods, an apparatus for performing the treatment is required, which is disadvantageous in terms of equipment and requires a considerable time for these treatments. In addition, after performing the above-mentioned pre-treatment on the surface of the propylene-based polymer molded product, in addition to the method of coating, the primer of the propylene-based polymer molded product can be adhered to the surface of the propylene-based polymer molded product with a primer. However, a method of applying a paint such as a polyurethane-based paint as an overcoat on the undercoat layer is used, but also in this method, the undercoating step and the overcoating step are required as a painting step, so that a long time is required for the painting step. , And there is also a problem that the cost of the molded article is increased due to the two-layer structure.

As described above, when coating a molded article made of a propylene-based polymer, it is general to apply some treatment to the molded article itself. Therefore, the conventional process of coating a molded article made of a propylene polymer complicates the process, and there is a strong demand for the development of a propylene polymer having excellent coating properties. As a method for improving the coating property of a propylene-based polymer, for example, JP-A-62-280267 discloses a polypropylene resin composition obtained by modifying polypropylene and an ethylene / α-olefin copolymer with an unsaturated carboxylic acid. And that the composition has good coatability. In addition, there are various proposals for a polypropylene resin composition containing such a carboxylic acid-modified product.

In order to improve the properties of such a polypropylene-based resin composition, the required properties must be imparted on top of the excellent properties inherent in the base polypropylene. However, when the characteristics of such a resin composition are examined in detail, depending on the order of modification and the dispersion state of the resin to be mixed, the characteristics of the obtained composition, for example, characteristics such as coatability and impact resistance, etc. The compositions known hitherto have room for further improvement in properties such as coatability and impact resistance.

[0007]

An object of the present invention is to provide a polypropylene-based polymer without impairing its excellent properties.
In particular, it is an object of the present invention to provide a propylene-based polymer composition having excellent coatability and improved impact resistance, and a method for producing the composition.

[0008]

SUMMARY OF THE INVENTION The first propylene polymer composition according to the present invention has a melt flow rate of 0.1 to 30 g / 10.
Is the partial unmodified propylene-based polymer (A-1) 20~9
9% by weight and an ethylene content of 6% modified with an ethylenically unsaturated group-containing carboxylic acid hydroxyalkyl ester.
0 to 95 mol%, and the melt flow rate is 0.1 to
A modified amorphous ethylene-propylene copolymer (B-1) having a content of 10 g / 10 minutes and 1 to 80% by weight is represented by the following formula [I].
The expressed specific energy (e) is 0.26-0.36k
Obtained by melt-kneading under kneading conditions of W · hr / kg
The modified amorphous ethylene-propylene copolymer (B-1) is contained in the propylene-based polymer (A-1) in an amount of 0.0
It is characterized in that it is dispersed with an average dispersed particle size of the 3～3Myuemu. e = Motor Power / resin extrusion amount · · · [I]

The first method for producing a propylene polymer composition according to the present invention is characterized in that the melt flow rate is 0.1 to 30.
g / 10 minutes unmodified propylene-based polymer (A-1)
20 to 99% by weight, modified with an ethylenically unsaturated group-containing carboxylic acid hydroxyalkyl ester, having an ethylene content of 60 to 95 mol% and a melt flow rate of 0.1 to 10 g / 10 min. When the specific energy (e) represented by the following formula [I] is from 0.26 to 80% by weight of the shaped ethylene-propylene copolymer (B-1),
By melting and kneading under a kneading condition of 0.36 kW · hr / kg, the propylene-based polymer (A-1) contains
Water-soluble amorphous ethylene-propylene copolymer (B-1)
Disperse with an average dispersed particle diameter of 0.03 to 3 μm
It is characterized by obtaining a len-based polymer composition. e = motor power consumption / resin extrusion amount [I] The second propylene polymer composition according to the present invention is a melt flow modified with a carboxylic acid hydroxyalkyl ester containing an ethylenically unsaturated group. Rate is 0.
Modified propylene polymer (A-
2) 20 to 99% by weight, modified with an ethylenically unsaturated group-containing carboxylic acid hydroxyalkyl ester, having an ethylene content of 60 to 95 mol% and a melt flow rate of 0.1 to 10 g / 10 min. Modified amorphous ethylene
-The propylene copolymer (B-1) in an amount of 1 to 80% by weight, and in the modified propylene-based polymer (A-2), the modified amorphous ethylene-propylene copolymer (B-
1) is characterized by being dispersed with an average dispersed particle diameter of 5 μm or less.

[0010] The second propylene polymer composition according to the present invention comprises a hydroxycarboxylic acid having an ethylenically unsaturated group.
A modified propylene polymer (A) having a melt flow rate of 0.1 to 60 g / 10 min, which has been modified with an alkyl ester.
-2) 20 to 99% by weight of ethylenically unsaturated group-containing
Modified amorphous ethylene-propylene copolymer (B-1) 1 modified with hydroxyalkyl rubonic acid, having an ethylene content of 60 to 95 mol% and a melt flow rate of 0.1 to 10 g / 10 min. ~ 80% by weight is characterized in that the specific energy (e) represented by the above formula [I] is melt-kneaded under kneading conditions of 0.25 kWhr / kg or more.

Further, the third propylene polymer composition according to the present invention comprises a carboxylic acid hydride containing an ethylenically unsaturated group.
A modified propylene polymer (A-3) modified with a droxyalkyl ester having a melt flow rate of 0.1 to 65 g / 10 min (A-3);
0 to 95 mol%, and the melt flow rate is 0.1 to
1 to 80% by weight of an amorphous ethylene-propylene copolymer (B-2) having a weight of 10 g / 10 minutes, and the modified ethylene-propylene copolymer (A-3) is contained in the modified ethylene-propylene copolymer (A-3). It is characterized in that the copolymer (B-2) is dispersed with an average dispersed particle diameter of 5 μm or less.

The third propylene polymer composition according to the present invention comprises a hydroxycarboxylic acid having an ethylenically unsaturated group.
Modified propylene polymer (A) having a melt flow rate of 0.1 to 65 g / 10 min.
-3) 20-99% by weight and ethylene content of 60-95.
Mol%, and the melt flow rate is 0.1 to 10 g /
Amorphous ethylene-propylene copolymer (B
-2) from 1 to 80% by weight by melt-kneading under a kneading condition in which the specific energy (e) represented by the above formula [I] is 0.25 kW · hr / kg or more.

As described above, by introducing a polar group into the propylene polymer and / or the rubber component in the propylene polymer composition and controlling the dispersed particle diameter of the rubber component in the composition. In particular, the coatability and adhesiveness of the resin composition are particularly improved.

[0014]

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the first, second and third propylene polymer compositions according to the present invention and methods for producing these compositions will be described in detail. First, the first propylene-based polymer composition according to the present invention will be described. The first propylene-based polymer composition according to the present invention comprises an unmodified propylene-based polymer (A-1) and a modified amorphous ethylene-propylene copolymer (B-1). Unmodified propylene-based polymer (A-1) The unmodified propylene-based polymer (A-
1) (hereinafter simply referred to as “propylene-based polymer (A-1)”)
Referred) is a propylene homopolymer, or a copolymer of propylene and other α- olefins. Examples of the α-olefin copolymerized with propylene include ethylene and 1-butene. These monomers may form a random copolymer with propylene, or may form a block copolymer.

In the present invention, 230 ° C., load 2.16 kg
Melt flow rate (MFR) measured under the condition of 0.1.
A propylene-based polymer in the range of 1 to 30 g / 10 minutes is used. In particular, a propylene polymer having an MFR in the range of 0.5 to 20 g / 10 minutes is preferably used. By using a propylene-based polymer having such an MFR, a composition having good moldability can be obtained.

Further, the propylene unit content of the propylene polymer (A-1) used in the present invention is usually 90 mol% or more. The boiling n-heptane-insoluble content of the propylene polymer (A-1) is usually 90%.
%, Preferably 93% or more. That is, the propylene-based polymer (A-1) is a (co) polymer having relatively few amorphous parts.

Such a propylene polymer (A-1)
Is usually in the range of 0.90 to 0.92 g / cm ³ . The propylene-based polymer (A-1) having such properties can be produced by various methods. As a typical production method, a propylene-based polymer (A-1) is formed from a solid titanium catalyst component and an organometallic compound component. A method using a catalyst or a catalyst formed from both of these components and an electron donor is exemplified.

The solid titanium catalyst component used in this method includes titanium trichloride or a titanium trichloride composition produced by various methods, or magnesium, halogen, an electron donor, preferably an aromatic carboxylic acid ester or There is a titanium catalyst component which contains an alkyl group-containing ether and titanium as essential components and is supported on a carrier having a specific surface area of preferably 100 m ² / g or more. In particular, a propylene-based polymer produced using the latter catalyst component with a carrier is preferred.

As the organometallic compound component, an organoaluminum compound is preferable. Specific examples of the organoaluminum compound include trialkylaluminum, dialkylaluminum halide, alkylaluminum sesquihalide, and alkylaluminum dihalide. Can be mentioned. The organoaluminum compound can be appropriately selected according to the type of the titanium catalyst component used.

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. Ester compounds and ether compounds having the above-mentioned atoms are preferred. Examples can be given. The method for producing a propylene-based polymer using the above-described catalyst component with a carrier is described in, for example, JP-A-50-108385 and JP-A-50-108385.
Nos. 0-126590, 51-20297, 51-
Nos. 28189 and 52-151691 are disclosed in detail, and the technology described in these publications can also be used in the present invention. Modified amorphous ethylene-propylene copolymer (B-1) Modified amorphous ethylene-propylene copolymer (B-1) constituting the first propylene-based polymer composition according to the present invention.
Is a modified product of a copolymer rubber in which ethylene and propylene are randomly copolymerized [amorphous ethylene-propylene copolymer (B-2)].

The content of the repeating unit derived from ethylene in the amorphous ethylene-propylene copolymer (B-2) is usually 60 to 95 mol%, preferably 7 to 95 mol%.
It is in the range of 0-90 mol%. Therefore, the content of the repeating unit derived from propylene in the copolymer (B-2) is usually in the range of 5 to 40 mol%, preferably 10 to 30 mol%. The repeating unit derived from ethylene and the repeating unit derived from propylene are randomly bonded in the copolymer (B-2).

The copolymer (B-2) contains 230
The melt flow rate (MFR) measured at a temperature of 2.degree. C. and a load of 2.16 kg is usually in the range of 0.1 to 10 g / 10 min, preferably 0.1 to 4 g / 10 min. By using such a copolymer (B-2), the composition has good moldability. This copolymer (B
-2) is an amorphous copolymer having a degree of crystallinity measured by an X-ray diffraction method of usually 40% or less, preferably 20% or less, and having relatively low crystallinity. That is, this amorphous ethylene-propylene copolymer (B-2)
It has rubber elasticity. Such an amorphous ethylene-propylene copolymer can be produced, for example, by copolymerizing ethylene and propylene in the presence of a catalyst comprising a soluble vanadium compound and an alkylaluminum halide compound.

The polymerization catalyst which can be used in this method includes, for example, vanadium tetrachloride, vanadium oxytrichloride, vanadium triacetyl acetate and oxyvanadium triacetyl acetate. Examples of the alkyl aluminum halide compound constituting the polymerization catalyst in combination with the soluble vanadium compound include, for example, ethyl aluminum dichloride, diethyl aluminum monochloride, ethyl aluminum sesquichloride, diethyl aluminum monobromide, diisobutyl aluminum monochloride, isobutyl aluminum dichloride and Isobutylaluminum sesquichloride and the like can be mentioned.

The copolymerization reaction using the above-mentioned catalyst can be carried out in a solution or suspension or in an intermediate region between them. In any case, an inert solvent is preferably used as a reaction medium (solvent). You. As such a copolymerization reaction medium, usually, an aliphatic hydrocarbon or a halogenated hydrocarbon having about 3 to 12 carbon atoms is used. Specific examples of the aliphatic hydrocarbon used as the reaction medium include propane, butane, pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, and kerosene (aliphatic having a boiling point of about 150 to 250 ° C). A mixture of hydrocarbons).

Specific examples of the halogenated hydrocarbon used as a reaction medium include methyl chloride, ethyl chloride and ethylene dichloride. These reaction media can be used alone or as a mixture. The polymerization temperature when the above-mentioned catalyst is used is usually 0 to 100 ° C.

The modified amorphous ethylene-propylene copolymer (B-1) constituting the first propylene-based polymer composition according to the present invention is the same as the above-mentioned amorphous ethylene-propylene copolymer (B-2). a modified product, the modified amorphous ethylene - propylene copolymer (B-1) is, for example, in the presence of a radical initiator, the amorphous ethylene - propylene copolymer, et ethylenic unsaturated group-containing It is produced by heating a carboxylic acid hydroxyalkyl ester.

[0027] Specific examples of d ethylenic unsaturated group-containing carboxylic acid hydroxyalkyl esters, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2
-Hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 3-chloro-2-hydroxypropyl acrylate, 3-chloro-2-hydroxypropyl methacrylate, 3-hydroxy-2-phenoxypropyl acrylate, 3-hydroxy And 2-phenoxypropyl methacrylate.

Among them , 2 -hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate and the like are preferable. These modifiers can be used alone or in combination. In the modification of the amorphous ethylene-propylene copolymer, in addition to the above-mentioned modifier, polymerization of styrene, α-methylstyrene, or the like may be performed within a range that does not impair the properties of the composition of the present invention. Aromatic aromatic compounds can be used in combination.

As the radical initiator used for preparing the modified amorphous ethylene-propylene copolymer (B-1), usually, an organic peroxide or an azo compound is used. Specific examples of the above organic peroxide include 1,1-bis (t-butylperoxy) -3,
5,5-trimethylcyclohexane, 1,1-bis (t-
Butylperoxy) cyclohexane, 2,2-bis (t-butylperoxy) octane, n-butyl-4
Peroxyketals such as 4-bis (t-butylperoxy) paralate and 2,2-bis (t-butylperoxy) butane; di-t-butyl peroxide, dicumyl peroxide, t-butylcumylper Oxide, α, α'-bis (t-butylperoxy-m-isopropyl) benzene, 2,5-dimethyl-2,5-bis (t
-Butylperoxy) hexane and 2,5-dimethyl
Dialkyl peroxides such as -2,5-bis (t-butylperoxy) hexyne-3; acetyl peroxide, isobutyryl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, 3,5 Diacyl peroxides such as 5-trimethylhexanoyl peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide and m-trioyl peroxide; t-butylperoxyacetate, t-butylperoxyisobutyrate, t-butylperoxy-2-ethylhexanoate, t-butylperoxylaurate, t-butylperoxybenzoate, di-t-butylperoxyisophthalate, 2,5-dimethyl-2,5-di ( Benzoylperoxy) hexane, t- Peroxyesters such as tiloperoxymalic acid, t-butylperoxyisopropyl carbonate and cumylperoxyoctate; and t-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, 2,5 -Dimethylhexane-2,5-dihydroperoxide and 1,
Hydroperoxides such as 1,3,3-tetramethylbutyl hydroperoxide can be exemplified.

Among these compounds, 1,1-bis (t-butylperoxy) -3,5,5-trimethylcyclohexane, di-t-butyl peroxide, dicumyl peroxide, 2,5-dimethyl -2,5-bis (t-
Butylperoxy) hexane and 2,5-dimethyl-
2,5-Bis (t-butylperoxy) hexyne-3 is preferred.

Further, specific examples of the azo compound used as the radical initiator include azoisobutyronitrile. Such radical initiators can be used alone or in combination. In preparing the modified amorphous ethylene-propylene copolymer (B-1), a carboxylic acid containing an ethylenically unsaturated group is used.
The modifier for the acid hydroxyalkyl ester is usually 0.01 to 50 parts by weight, preferably 0.1 to 100 parts by weight, based on 100 parts by weight of the amorphous ethylene-propylene copolymer (B-2).
Used in an amount of ４０40 parts by weight.

The radical initiator is an amorphous ethylene
-0.01 to 10 parts by weight, preferably 0.05 to 100 parts by weight of propylene copolymer (B-2)
Used in an amount of up to 8 parts by weight. Further, the polymerizable aromatic compound is an amorphous ethylene-propylene copolymer (B-
2) It is usually used in an amount of 0.01 to 50 parts by weight, preferably 0.1 to 40 parts by weight based on 100 parts by weight.

The modified amorphous ethylene-propylene copolymer (B-1) constituting the first propylene polymer composition according to the present invention can be produced by using a known method. For example, a method of melt-kneading an amorphous ethylene-propylene copolymer (B-2) and a modifier in the presence of a radical initiator, a method in which the amorphous ethylene-propylene copolymer (B-2) is previously A solution (or dispersion) is prepared by dissolving or dispersing the compound in a solvent, and a modifier and a radical initiator are added thereto, followed by heating.

For example, the grafting amount (in terms of monomer) of the modifying agent in the modified amorphous ethylene-propylene copolymer (B-1) prepared as described above is determined by the modified amorphous ethylene-propylene copolymer. Usually, 0.01 to 20% by weight, preferably 0.05%, based on the weight of (B-1).
８8% by weight. The modified amorphous ethylene-propylene copolymer (B-1) is blended with the modifier and the amorphous ethylene-propylene copolymer (B-2) so that the amount of grafting falls within the above range. Or a modified amorphous ethylene-propylene copolymer having a high grafting amount, for example, by increasing the amount of a modifying agent, and then the grafting amount falls within the above range. It can also be prepared by diluting with an unmodified amorphous ethylene-propylene copolymer.

The modified amorphous ethylene-propylene copolymer (B-1) forming the first propylene-based polymer composition according to the present invention has a load of 21.6 kg and a temperature of 230.
A copolymer having a melt flow rate (MFR) measured at a temperature of 0 ° C. within a range of 0.1 to 10 g / 10 minutes is used. In particular, the modified amorphous ethylene-propylene copolymer (B) whose MFR is in the range of 0.2 to 4 g / 10 min.
-1) is preferably used. The modified amorphous ethylene-propylene copolymer having such MFR (B-
By using 1), the composition of the present invention has good processability, and the modified amorphous ethylene-propylene copolymer (B-1) is converted into a propylene-based polymer (A). The dispersibility is improved, the coatability is further improved, and the impact resistance is also improved. First propylene-based polymer composition The first propylene-based polymer composition according to the present invention comprises 20 to 99% by weight of the above-mentioned propylene-based polymer (A-1) and a modified amorphous ethylene-propylene. The copolymer (B-
1) A composition comprising 1 to 80% by weight. further,
The content of the propylene-based polymer (A-1) is 55 to 85% by weight, and the modified amorphous ethylene-propylene copolymer (B-
The propylene polymer composition having a content of 1) in the range of 15 to 45 parts by weight is a propylene polymer (A-1).
In it, a modified amorphous ethylene-propylene copolymer (B-
1) is very well dispersed and shows excellent properties.
Note that the total amount of the components (A-1) and (B-1) is 100% by weight.

Furthermore, a propylene polymer (A-A) constituting the first propylene polymer composition according to the present invention.
The ratio of the MFR of 1) to the MFR of the modified amorphous ethylene-propylene copolymer (B-1) [MFR (A-1) / MF
[R (B-1)] is used in combination with the propylene-based polymer (A-1) and the modified amorphous ethylene-propylene copolymer (B-1) so that the ratio falls within the range of 0.1 to 50. It is preferable to combine both so as to be in the range of 0.5 to 30. By combining both such that the MFR ratio becomes as described above, the dispersion state of the modified amorphous ethylene-propylene copolymer (B-1) becomes very good.

In the first propylene polymer composition according to the present invention, the modified amorphous ethylene-propylene copolymer (B-1) is contained in the propylene polymer (A-1) in an amount of 5 μm.
It is finely dispersed so as to have the following average dispersed particle diameter to form a so-called polymer alloy. Further, the average dispersed particle diameter is preferably in the range of 0.03 to 3 μm, and particularly preferably in the range of 0.05 to 2 μm. By finely dispersing the modified amorphous ethylene-propylene copolymer (B-1) in the propylene-based polymer (A-1), the impact resistance is improved and the coating property is improved. . This modified amorphous ethylene
The average dispersed particle size of the propylene copolymer (B-1) is determined by observing the fracture surface of the core of the test piece with an electron microscope and dispersing the modified amorphous ethylene-propylene copolymer (B-1).
Is the average value calculated from the measured values. When an inorganic filler is added to the first propylene-based polymer composition according to the present invention, the dispersion particle diameter of the modified amorphous ethylene-propylene copolymer (B-1) measured by an electron microscope is considered. However, in this case, the dispersed particles of the modified amorphous ethylene-propylene copolymer (B-1) in the composition prepared under the same conditions without adding the inorganic filler were used. The diameter may be within the above range.

With respect to such a first propylene polymer composition according to the present invention, a load of 2.16 kg and 230 ° C.
The melt flow rate (MFR) measured under the conditions described above is usually 20 to 0.1 g / 10 min, and often 15 to 1 g / min.
1/8 inch thick test specimen (notched) within 10 minutes and measured according to ASTM D-256
The Izod impact strength at -30 ° C is usually
20 kg / cm.cm, often 5-15 kg / cm
・ It is within the range of cm. In addition, the flexural modulus (FM) of a 1/8 inch thick specimen measured according to ASTM D-790 is typically 5,000 to 16,000 kg / m.
² , often in the range of 6,500 to 14,000 kg / m ² . Method for Producing the First Propylene Polymer Composition The first propylene polymer composition according to the present invention as described above is modified with the propylene polymer (A-1) so as to correspond to the above composition ratio. It can be produced by mixing with an amorphous ethylene-propylene copolymer (B-1) and melt-kneading. Then, at the time of this melt-kneading, 0.1.
26 kW · hr / kg or more, preferably 0.26-0.
4 kW · hr / kg, more preferably 0.26-0.
Melt and knead with a specific energy (e) within the range of 36 kW · hr / kg. By melt-kneading under such conditions, the modified amorphous ethylene-propylene copolymer (B-1) can be finely dispersed in the propylene-based polymer (A-1).

Here, the specific energy (e) is the amount of energy per unit volume used for pulverizing the aggregate, and can be expressed by the following formula [I]. e = Motor Power / resin extrusion amount · · · [I] with respect to the specific energy (e), the Kimimasa Ito, plastic, 3
6 , No. 737 (1988).

In order to produce the first propylene polymer composition according to the present invention, the specific energy (e) as described above is used.
Any known kneading apparatus used in the field of ordinary olefin-based polymers can be used as long as the apparatus can melt and knead while applying. Examples of the kneading apparatus that can be used to produce the first propylene-based polymer composition according to the present invention include an extruder, a mixing roll, a Banbury mixer, and a kneader.

For example, the heating temperature at the time of melt-kneading using the above-described kneading apparatus can be appropriately set within a range from the melting point of the raw material used to the decomposition temperature or less. 170-350 ° C, preferably 1
The temperature is set within the range of 80 to 250 ° C. In producing the first propylene polymer composition according to the present invention, the propylene polymer (A-1) and the modified amorphous ethylene-propylene copolymer (B-1) are mixed with the propylene polymer (A-1). A method of mixing and melting and kneading the mixture so as to be within the range of the composition ratio is adopted.In addition, a part of the composition components is previously mixed to produce a so-called master batch, and the master batch is manufactured. And the remaining components may be mixed.

The first propylene polymer composition according to the present invention is basically composed of the propylene polymer (A-1)
And modified amorphous ethylene-propylene copolymer (B-1)
However, other resins or additives can be further compounded within a range that does not impair the properties of the propylene polymer composition of the present invention. Examples of other resins that can be blended in the present invention include high-density polyethylene, medium-density polyethylene, low-density polyethylene, poly-1-butene, ethylene-1-butene copolymer, and propylene-1-butene copolymer. Coalescence, propylene-1-butene-
Ethylene copolymer, styrene-butadiene (-styrene) block copolymer and its hydrogenated product, styrene
-Isoprene (-styrene) block copolymers and hydrogenated products thereof.

Examples of other additives that can be added in the present invention include antioxidants, ultraviolet absorbers, lubricants, nucleating agents, antistatic agents, flame retardants, pigments, dyes, plasticizers, Characteristic improvers, inorganic fillers and organic fillers. For example, specific examples of the inorganic filler used in the present invention include aluminum, copper,
Metals such as nickel, iron and lead, metals such as magnesium, calcium, barium, zinc, zirconium, molybdenum, silicon, antimony and titanium, and their oxides, hydroxides, sulfates, carbonates and silicates And furthermore talc, mica, silica, glass fibers and graphite. These other resins or additives can be blended when preparing the propylene-based polymer composition according to the present invention, or added after preparing the propylene-based polymer composition according to the present invention. You can also.

Next, the second propylene polymer composition according to the present invention will be described. The second propylene-based polymer composition according to the present invention comprises a modified propylene-based polymer (A
-2) and the above-mentioned modified amorphous ethylene-propylene copolymer (B-1). Modified propylene polymer (A-2) Modified propylene polymer (A-2) used in the present invention
Can be prepared by modifying the propylene polymer (A-1) with a specific modifier.

This modified propylene polymer (A-2)
For example, in the presence of a radical initiator, the above-mentioned propylene-based polymer (A-1) and a monomer containing an ethylenically unsaturated group are
It is produced by heating rubonic acid hydroxyalkyl ester . The modifying agent is the same as the modifying agent used in the preparation of the modified amorphous ethylene-propylene copolymer (B-1) described above.

Further, the propylene-based polymer (A-1)
When modifying styrene and α, in addition to the above-mentioned modifiers, styrene and α may be used as long as the properties of the composition of the present invention are not impaired.
-A polymerizable aromatic compound such as methylstyrene can be used in combination. As the radical initiator used for preparing the modified propylene-based polymer (A-2), an organic peroxide or an azo compound is usually used.

Specific examples of the organic peroxide and the azo compound are as described above, and the radical initiator can be used alone or in combination. In preparing the modified propylene copolymer (A-2), the hydroxyalkyl carboxylic acid containing an ethylenically unsaturated group is used.
The modifier of the stele is an unmodified propylene polymer (A-
1) It is usually used in an amount of 0.01 to 50 parts by weight, preferably 0.1 to 40 parts by weight, based on 100 parts by weight.

The radical initiator is used in an amount of usually 0.01 to 10 parts by weight, preferably 0.05 to 8 parts by weight, based on 100 parts by weight of the unmodified propylene polymer (A-1). Used. Further, the polymerizable aromatic compound is usually 0.01 to 50 parts by weight, preferably 0.1 to 50 parts by weight, based on 100 parts by weight of the unmodified propylene-based polymer (A-1).
It is used in an amount of 40 parts by weight.

This modified propylene polymer (A-2)
Can be manufactured using a known method. For example, a method of melt-kneading a propylene-based copolymer (A-1) and a modifier in the presence of a radical initiator, a solution in which the propylene-based polymer (A-1) is previously dissolved or dispersed in an organic solvent ( Alternatively, a method of preparing a dispersion, adding a modifier and a radical initiator thereto, and heating the mixture may be used.

For example, the grafting amount (in terms of monomer) of the modifying agent in the modified propylene polymer (A-2) prepared as described above is determined by the weight of the modified propylene polymer (A-2). On a basis, it is usually 0.01 to 20% by weight, preferably 0.05 to 8% by weight. The modified propylene polymer (A-2) may be produced by adjusting the blending amount of the modifier and the propylene polymer (A-1) so that the graft amount is within the above range. Alternatively, for example, a modified propylene-based polymer having a high grafting amount is prepared by increasing the amount of the modifying agent, and then diluted with an unmodified propylene-based polymer so that the grafting amount is within the above range. Can also be prepared.

In the present invention, a load of 21.6 kg and a temperature of 23
A modified propylene polymer (A-2) having a melt flow rate (MFR) measured at 0 ° C. within the range of 0.1 to 60 g / 10 minutes is used. Particularly, a modified propylene polymer (A-2) having an MFR in the range of 0.5 to 58 g / 10 minutes is preferably used. By using the modified propylene polymer (A-2) having such an MFR, the composition of the present invention has good processability and the modified propylene polymer (A
-2) The dispersibility of the modified amorphous ethylene-propylene copolymer (B-1) therein is improved, so that the coating property is further improved and the impact resistance is also improved.

The modified propylene polymer (A-
The boiling n-heptane insoluble content of 2) is usually 90% or more,
It is preferably at least 93%. The density of such a modified propylene polymer (A-2) is usually 0.90.
０．９0.92 g / cm ³ . Modified amorphous ethylene-propylene copolymer (B-1) The modified amorphous ethylene-propylene copolymer (B-1) is as described above in the first propylene-based polymer composition according to the present invention. . Second propylene-based polymer composition The second propylene-based polymer composition according to the present invention is a modified propylene-based polymer (A-2) 20 to 99 as described above.
And a modified amorphous ethylene-propylene copolymer (B-1) in an amount of 1 to 80% by weight. Further, the content of the modified propylene polymer (A-2) is 5%.
A copolymer composition having a content of 5 to 85% by weight and a modified amorphous ethylene-propylene copolymer (B-1) in a range of 15 to 45% by weight is a modified propylene-based polymer (A-
In 2), the modified amorphous ethylene-propylene copolymer (B-1) is very well dispersed and shows excellent properties. In addition, the total amount of the components (A-2) and (B-1) is 100% by weight.

Further, the MFR of the modified propylene polymer (A-2) constituting the propylene polymer composition of the present invention and the modified amorphous ethylene-propylene copolymer (B
-1) to the MFR [MFR (A-2) / MFR (B
-1)] may be used in combination with the modified propylene-based polymer (A-2) and the modified amorphous ethylene-propylene copolymer (B-1) so that the ratio falls within the range of 0.1 to 200. It is preferable to combine both so as to be particularly in the range of 0.5 to 20. By combining both such that the MFR ratio becomes as described above, the dispersion state of the modified amorphous ethylene-propylene copolymer (B-1) becomes very good.

In the second propylene polymer composition according to the present invention, the modified propylene polymer (A-2) contains 5 modified amorphous ethylene-propylene copolymers (B-1).
Finely dispersed so as to have an average dispersed particle diameter of μm or less,
A so-called polymer alloy is formed. Further, the average dispersed particle diameter is preferably in the range of 0.03 to 3 μm, and particularly preferably in the range of 0.05 to 2 μm. As described above, the modified amorphous ethylene-propylene copolymer (B-1) is converted into a modified propylene-based polymer (A-
2) By finely dispersing it in, the impact resistance is improved and the coatability is improved. The method for obtaining the average dispersed particle diameter of the modified amorphous ethylene-propylene copolymer (B-1) is as described above in the description of the first propylene-based polymer composition according to the present invention.

With respect to the second propylene polymer composition according to the present invention, a load of 2.16 kg and 230 ° C.
The melt flow rate (MFR) measured under the conditions described above is usually 20 to 0.1 g / 10 min, and often 17 to 1 g / min.
1/8 inch thick test specimen (notched) within 10 minutes and measured according to ASTM D-256
The Izod impact strength at -30 ° C is usually
70 kg / cm · cm, often 3-30 kg / cm
・ It is within the range of cm. In addition, the flexural modulus (FM) of a 1/8 inch thick specimen measured according to ASTM D-790 is typically 5,000 to 16,000 kg / m.
² , often in the range of 6,500 to 14,000 kg / m ² . Method for producing second propylene-based polymer composition The second propylene-based polymer composition according to the present invention as described above comprises a modified propylene-based polymer (A-2) corresponding to the above composition ratio. It can be produced by mixing with the modified amorphous ethylene-propylene copolymer (B-1) and melt-kneading. And at the time of this melt kneading, 0.25 kW · hr / kg or more, preferably 0.25 kW · hr / kg or more.
0.4 kW · hr / kg, more preferably 0.25 to
Melt and knead with a specific energy (e) within the range of 0.36 kW · hr / kg. By melt-kneading under such conditions, the modified amorphous ethylene-propylene copolymer (B-1) can be finely dispersed in the propylene-based polymer (A-2).

The specific energy (e), the kneading apparatus, the heating temperature at the time of melting and kneading, and the like according to the first embodiment of the present invention are described below.
As described above in the method for producing a propylene-based polymer composition. Further, in the second propylene-based polymer composition according to the present invention, another resin or additive as described above in the method for producing the first propylene-based polymer composition according to the present invention may be used. Can be blended within a range that does not impair the properties of the composition.

The above-mentioned other resins or additives can be blended when preparing the second propylene-based polymer composition according to the present invention, or can be mixed with the second propylene-based polymer composition according to the present invention. It can also be added after preparing the product.
Next, the third propylene polymer composition according to the present invention will be described. A third propylene polymer composition according to the present invention comprises a modified propylene polymer (A-3) and an amorphous ethylene-propylene copolymer (B-2). Modified propylene polymer (A-3) Modified propylene polymer (A-3) used in the present invention
Can be prepared in the same manner as in the preparation of the modified propylene-based polymer (A-2).

The grafting amount (in terms of monomer) of the modifying agent in the modified propylene polymer (A-3) is usually 0.01% based on the weight of the modified propylene polymer (A-3).
-20% by weight, preferably 0.05-8% by weight.
In the present invention, the melt flow rate (MFR) measured under the conditions of a load of 21.6 kg and a temperature of 230 ° C. is 0.1 to 65.
g / 10 minutes of the modified propylene-based polymer (A
-3) is used. In particular, this MFR is 0.5 to 45
g / 10 minutes of the modified propylene-based polymer (A
-3) is preferably used. By using the modified propylene polymer (A-3) having such an MFR, the composition of the present invention has good processability, and the modified propylene polymer (A-3) The dispersibility of the amorphous ethylene-propylene copolymer (B-2) in the rubber composition is improved, and the coating property is further improved, and the impact resistance is also improved.

The modified propylene polymer (A-
The boiling n-heptane insoluble content of 3) is usually 90% or more,
It is preferably at least 93%. The density of such a modified propylene polymer (A-3) is usually 0.90.
０．９0.92 g / cm ³ . Amorphous ethylene-propylene copolymer (B-2) Amorphous ethylene-propylene copolymer (B-) used in the third propylene-based polymer composition according to the present invention.
2) is an unmodified amorphous ethylene-propylene copolymer used in the preparation of the modified amorphous ethylene-propylene copolymer (B-1) used in the first propylene polymer composition according to the present invention. It is the same as the polymer (B-2). Third propylene-based polymer composition The third propylene-based polymer composition according to the present invention is a modified propylene-based polymer (A-3) 20 to 99 as described above.
% By weight of an amorphous ethylene-propylene copolymer (B-
2) 1 to 80% by weight. further,
When the content of the modified propylene-based polymer (A-3) is 55 to 8
5% by weight of an amorphous ethylene-propylene copolymer (B-
The copolymer composition having a content of 2) in the range of 15 to 45% by weight contains, in the modified propylene-based polymer (A-3),
The amorphous ethylene-propylene copolymer (B-2) is very well dispersed and shows excellent properties. The total amount of the components (A-3) and (B-2) was 10
0% by weight.

Further, the MF of the modified propylene polymer (A-3) constituting the propylene polymer composition of the present invention
Ratio of R to MFR of amorphous ethylene-propylene copolymer (B-2) [MFR (A-3) / MFR (B-2)]
Is preferably used in combination with the modified propylene-based polymer (A-3) and the amorphous ethylene-propylene copolymer (B-2) so that the content of the modified propylene polymer (A-3) falls within the range of 0.1 to 200. It is preferable to combine both so as to be within the range of 5 to 120. By combining both such that the MFR ratio becomes as described above, the dispersion state of the amorphous ethylene-propylene copolymer (B-2) becomes very good.

In the third propylene polymer composition according to the present invention, the modified propylene polymer (A-3) contains 5 μm of the amorphous ethylene-propylene copolymer (B-2).
It is finely dispersed so as to have the following average dispersed particle diameter to form a so-called polymer alloy. Further, the average dispersed particle diameter is preferably in the range of 0.03 to 3 μm, and particularly preferably in the range of 0.05 to 2 μm. By finely dispersing the amorphous ethylene-propylene copolymer (B-2) in the modified propylene-based polymer (A-3), the impact resistance is improved and the coatability is improved. . The method for obtaining the average dispersed particle size of the amorphous ethylene-propylene copolymer (B-2) is as described above in the description of the first propylene-based polymer composition according to the present invention.

For the third propylene polymer composition according to the present invention, a load of 2.16 kg and a temperature of 23
The melt flow rate (MFR) measured at 0 ° C. is typically 20-0.1 g / 10 min, often 17-1 g / 1.
The Izod impact strength at −30 ° C. of a 1/8 inch thick test piece (notched) within 0 min and measured according to ASTM D-256 is typically 2-7.
0 kg / cm · cm, often 3-30 kg / cm ·
cm. In addition, the flexural modulus (FM) of a 1/8 inch thick specimen measured according to ASTM D-790 is typically 5,000 to 16,000 kg / m.
² , often in the range of 6,500 to 14,000 kg / m ² . Method for Producing Third Propylene-Based Polymer Composition The third propylene-based polymer composition according to the present invention as described above comprises a modified propylene-based polymer (A-3) corresponding to the above composition ratio. It can be produced by mixing with an amorphous ethylene-propylene copolymer (B-2) and melt-kneading. Then, at the time of this melt-kneading, 0.1.
25 kW · hr / kg or more, preferably 0.25-0.
4 kW · hr / kg, more preferably 0.25-0.
Melt and knead with a specific energy (e) within the range of 36 kW · hr / kg. By melt-kneading under such conditions, the amorphous ethylene-propylene copolymer (B-1) can be finely dispersed in the modified propylene-based polymer (A-3).

The specific energy (e), the kneading apparatus, the heating temperature at the time of melting and kneading, etc.
As described above in the method for producing a propylene-based polymer composition. Further, in the third propylene polymer composition according to the present invention, another resin or additive as described above in the method for producing the first propylene polymer composition according to the present invention is added to the third propylene polymer composition according to the present invention. Can be blended within a range that does not impair the properties of the composition.

The above-mentioned other resin or additive can be blended when preparing the third propylene polymer composition according to the present invention, or can be mixed with the third propylene polymer composition according to the present invention. It can also be added after preparing the product. Molded article comprising propylene-based polymer composition of the present invention The first, second and third propylene-based polymer compositions according to the present invention obtained as described above (hereinafter referred to as “the propylene-based polymer of the present invention” Composition).
Usually, it is molded into a pellet, and a molding having a desired shape can be manufactured by employing a molding method generally used in the field of thermoplastic resin, for example, an injection molding method or an extrusion molding method. The temperature at the time of this molding is a temperature higher than the melting point of the propylene-based polymer composition to be used, and is set to a temperature within the range of not more than the thermal decomposition temperature, and is generally 170 to 300 ° C, preferably 180 ° C. ~ 2
It is set within the range of 50 ° C.

The molded article formed from the propylene polymer composition of the present invention has excellent affinity with other resins.
Therefore, a molded article formed from the propylene-based polymer composition of the present invention is a step which is considered to be an essential step when a molded article formed from a propylene-based resin is conventionally applied. -Very good adhesion of the coating even if the steam cleaning step with a chlorine-based solvent such as trichloroethane is omitted. Further, the molded article formed from the propylene polymer composition of the present invention has very good adhesion of the coating film without performing the primer treatment.

For coating of a molded article formed from the propylene polymer composition of the present invention, a solvent-based coating, a water-based coating, and a solvent-free coating can be used. Examples of solvent-based paints include alkyd resin paints, amino alkyd resin paints, vinyl resin paints, room temperature dry acrylic resin paints, baking dry acrylic resin paints, tar epoxy epoxy resin paints, varnish enamels Epoxy resin-based paints, one-pack urethane resin-based paints, multi-package urethane resin-based paints, unsaturated polyester resin-based paints, and chlorinated rubber-based paints.

Examples of the water-based paint include an emulsion paint and a water-soluble resin-based paint. Furthermore, examples of the solventless paint include a powder paint and a traffic paint. The molded article formed from the propylene-based polymer composition of the present invention is particularly suitable for coating with a solvent-based paint, and has particularly good affinity for a urethane resin-based paint. Urethane-based resin paints are generally paints that form a coating film by the reaction of a polyisocyanate and a polyol compound, and there are one-pack type and two-pack type. There is an oil-modified urethane coating, and there is also a powder coating using a block type isocyanate. The molded article made of the propylene-based polymer composition of the present invention has good affinity with any of these urethane resin-based paints.

Among the urethane resin paints as described above,
For example, a coating method using a one-pack type urethane resin-based paint will be described by way of an example.A molded article formed from the propylene-based polymer composition of the present invention is washed with water and using a general industrial cleaning agent. Washing is performed at least once, and further, after washing with water, drying by heating. That is, when coating a molded article formed from the propylene-based polymer composition of the present invention, it is not always necessary to perform steam cleaning using a chlorine-based solvent, which has been conventionally performed. On the molded body dried as described above,
A urethane resin coating film can be formed by applying a one-pack type urethane resin-based coating material and heating as necessary.

The coating film thus formed has very good adhesion to the molded article, even though cleaning (surface treatment) using chlorine-based solvent vapor has not been performed. I have. Further, the molded article formed from the propylene-based polymer composition of the present invention has good adhesiveness,
It shows good affinity for various adhesives without performing primer treatment or the above-mentioned solvent washing.

Examples of the adhesive which can be used for bonding the molded article include urea resin adhesive, melamine resin adhesive, phenol resin adhesive, epoxy resin adhesive, and vinyl acetate solvent adhesive. Agent, polyurethane resin adhesive, α-olefin / maleic anhydride resin adhesive, aqueous polymer / isocyanate adhesive, reactive acrylic resin adhesive, ultraviolet curable modified acrylic resin adhesive and anaerobic modified Synthetic resin adhesives such as acrylic resin adhesives; vinyl acetate emulsion adhesives, vinyl acetate copolymer resin emulsion adhesives,
Emulsion adhesives such as ethylene-vinyl acetate copolymer resin emulsion adhesives and acrylic emulsion adhesives; vinyl acetate hot melt adhesives, elastomer hot melt adhesives, and polyamide hot melt adhesives Hot-melt adhesives such as adhesives; synthetic rubber-based adhesives such as chloroprene-type synthetic rubber-based adhesives and synthetic rubber-based latex-type adhesives.

As a bonding method using such an adhesive, a conventionally used method can be adopted. In such an adhesive method, a desired adhesive strength can be obtained even when the primer treatment or the organic solvent vapor cleaning is not particularly performed. Utilizing the above properties, the propylene-based polymer composition of the present invention is used for automobile parts, motorcycle parts, electric equipment parts,
Can be widely used for painted or bonded applications such as daily necessities, vending machine parts, civil engineering building materials, general industrial materials, office information equipment, packaging materials, sports equipment, medical equipment, nuclear power parts, etc. it can.

[0072]

The propylene polymer composition of the present invention comprises:
As described above, propylene-based polymer and amorphous ethylene
-By introducing a polar group into at least one of the propylene copolymer (rubber component) and controlling the dispersed particle size of the rubber component in the composition, the coatability and adhesion of the resin composition are improved. Especially improved. Further, such improved properties do not impair the excellent properties such as flexural modulus inherent of the propylene-based polymer. In particular, the propylene-based polymer composition of the present invention has excellent adhesion to polyurethane, so that a urethane paint can be applied directly to the surface of a molded article.

Further, according to the process for producing a propylene polymer composition of the present invention, by setting the melt-kneading conditions in the kneading step within a specific range, the rubber component in the obtained propylene polymer composition is obtained. In particular, since the dispersed particle diameter of the modified rubber component can be controlled, a propylene-based polymer composition capable of providing a molded article having excellent coatability and adhesion can be produced.

[0074]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples. Various properties of the propylene polymer composition used in the present invention were measured as follows. (1) According to MFR ASTM D-1238, the load is 2.16 kg,
It was measured at a temperature of 230 ° C. (2) Graft Amount The polymer after the reaction was dissolved in p-xylene at 130 ° C. and allowed to cool. Then, the polymer was precipitated with acetone, and the unreacted material was removed and purified. The graft amount of the purified polymer was calculated from the result of oxygen analysis. (3) Izod impact strength (with notch) (Iz) ASTM D-256 using a 1/8 inch thick test piece
Was measured at -30 ° C according to the above. (4) Flexural modulus (FM) ASTM D-790 using a 1/8 inch thick test piece
It was measured according to. (5) Coating test The coating property in the present invention was evaluated by a cross-cut test and a peel strength test of a coating film formed by applying a one-component urethane coating to a test piece prepared as follows.

Preparation of Test Piece The following paint was applied to a square plate molded by a 50-ton injection molding machine. -One-part urethane paint Flexen # 105 [trade name, manufactured by Nippon Bee Chemical Co., Ltd.]-Film thickness after drying 60 µm-Baking conditions: 120 ° C, 30 minutes. Prior to coating, steam cleaning with 1,1,1-trichloroethane was performed.

Cross-cut test According to the cross-cut test described in JIS K-5400, a cross-cut test piece was prepared, and a cellotape (trade name, manufactured by Nichiban Co., Ltd.) was used. After the cellophane tape was adhered, the cellophane tape was quickly pulled in a direction of 90 ° to be peeled off, and the number of remaining cross-cut coatings was counted, and this number was used as an index of adhesion.

○ Peel strength test A coating film was prepared on a substrate, a cut was made with a cutter blade to a width of 1 cm until the blade reached the substrate, and the end of the coating film was peeled off. The edge of the film was pulled at a speed of 50 mm / min in a direction of 180 degrees until the coating film was peeled, and the peel strength was measured. (6) Adhesion test The adhesion in the present invention was evaluated by bonding a test piece and a cloth to the test piece prepared as follows using the adhesive shown below, and performing a cross-cut test and peeling of the adhesive layer. This was performed in a strength test.

Preparation of Test Piece A water dispersion of styrene / acrylonitrile / ethylhexyl acrylate / ethyl acrylate / n-butyl acrylate copolymer (molar ratio: 35/35/13/15/7) [trade name] , Iodosol, manufactured by Kanebo NSC Co., Ltd.] to a coating amount of 200 g / m ² , lightly put a cloth on the top and hold it by hand.
Drying was performed for minutes. -Peeling strength test One hour after the above drying, the peeling strength was measured using a tensile tester by pulling the fabric in a direction of 180 degrees at a pulling speed of 50 mm / min in a direction of 180 degrees.

Cross-cut test According to the cross-cut test described in JIS K-5400, cross-cut test pieces were prepared, and cellotape (trade name, manufactured by Nichiban Co., Ltd.) was used. After the cellophane tape was adhered, the cellophane tape was quickly pulled in a direction of 90 ° to be peeled off, and the number of remaining cross-cut coatings was counted, and this number was used as an index of adhesion. (7) Dispersed phase particle size It was determined from an electron micrograph image of the fracture surface of the core portion of the test piece.

[Examples in First Propylene Polymer Composition According to the Present Invention]

[0081]

REFERENCE EXAMPLE 1 Amorphous ethylene-propylene copolymer: 100 parts by weight (ethylene content: 81 mol%, MFR: 0.7 g / 10 min, density: 0.87 g / cm ³ , hereinafter referred to as “EP -1 ")-Maleic anhydride (hereinafter abbreviated as" MAH ") ... 1.2 parts by weight-2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3- 0.2 parts by weight (hereinafter abbreviated as “PO-1”) After mixing the above components with a Henschel mixer, a twin-screw extruder with vent (L / D = 42, screw diameter 30 m)
m) using a modified amorphous ethylene-propylene copolymer (hereinafter referred to as “MEP-1”) under a nitrogen atmosphere at a temperature of 230 ° C.
Abbreviated). The graft amount of MAH of MEP-1 was 0.9% by weight.

Then, a propylene homopolymer: 65 parts by weight (MFR: 7.0 g / 10 min, density: 0.91 g / cm ³ , hereinafter abbreviated as “PP-1”) ..35 parts by weight were mixed with a Henschel mixer, and the mixture was vented 2
0.27 kW · h at a temperature of 200 ° C. under a nitrogen atmosphere using a screw extruder (L / D = 42, screw diameter 50 mm)
A pellet (composition) was produced while being melt-kneaded at a specific energy of r / kg.

A test piece was prepared from the composition thus prepared as described above, and the flexural modulus and
The Izod impact strength, coating test, adhesive strength, and the particle size of the dispersed phase of the modified amorphous ethylene-propylene copolymer were determined. Table 2 shows the results.

[0084]

Reference Examples 2 to 4 In Reference Example 1, MAH, PO-1
Reference Example 1 except that the compounding amount of was changed as shown in Table 1.
In the same manner as described above, a modified amorphous ethylene-propylene copolymer (MEP-2 to 4) was obtained. Next, in Reference Example 1, the modified amorphous ethylene-propylene copolymer (ME
Instead of P-1), the modified amorphous ethylene-propylene copolymer (MEP-2 to 4) obtained as described above
And a composition was produced in the same manner as in Reference Example 1, except that the specific energy value was set as shown in Table 2.

A test piece was prepared from the composition thus prepared as described above, and the flexural modulus and
The Izod impact strength, coating test, adhesive strength, and the particle size of the dispersed phase of the modified amorphous ethylene-propylene copolymer were determined. Table 2 shows the results.

[0086]

Reference Examples 5 to 7 In Reference Example 1, PP-1 and M
A composition was produced in the same manner as in Reference Example 1, except that the amount of EP-1 and the specific energy were changed as shown in Table 2. A test piece was prepared from the composition thus prepared as described above, and using this test piece, the flexural modulus,
The Izod impact strength, coating test, adhesive strength, and the particle size of the dispersed phase of the modified amorphous ethylene-propylene copolymer were determined.

The results are shown in Table 2.

[0088]

Example 1 Amorphous ethylene-propylene copolymer 100 parts by weight (ethylene content 81 mol%, MFR 1.8 g / 10 min, hereinafter abbreviated as "EP-2") 2-hydroxypropyl Acrylate: 0.8 parts by weight (hereinafter abbreviated as “HPA”) PO-1: 0.1 parts by weight After mixing the above components with a Henschel mixer, a twin-screw extruder with a vent (L / D = 42, screw diameter 30m
m) at 230 ° C. under a nitrogen atmosphere at a temperature of 230 ° C. using a modified amorphous ethylene-propylene copolymer (hereinafter referred to as “MEP-5”).
Abbreviated). The graft amount of HPA of MEP-5 was 0.8% by weight.

Next, a propylene homopolymer: 65 parts by weight (MFR: 11 g / 10 min, density: 0.91 g / cm ³ , hereinafter abbreviated as “PP-2”) MEP-5: 35 parts by weight were mixed with a Henschel mixer, and the mixture was vented 2
0.27 kW · h at a temperature of 200 ° C. under a nitrogen atmosphere using a screw extruder (L / D = 42, screw diameter 50 mm)
A pellet (composition) was produced while being melt-kneaded at a specific energy of r / kg.

A test piece was prepared from the composition thus prepared as described above, and the flexural modulus and
The Izod impact strength, coating test, adhesive strength, and the particle size of the dispersed phase of the modified amorphous ethylene-propylene copolymer were determined. Table 2 shows the results.

[0091]

Examples 2 to 4 In Example 1 , 2-hydroxypropyl acrylate (HPA) which is a modifier used for producing a modified amorphous ethylene-propylene copolymer (MEP-5) and a radical initiator were used. A modified amorphous ethylene-propylene copolymer (MEP-6 to MEP-6) was prepared in the same manner as in Example 1 except that the amount used was changed as shown in Table 1 .
8) was obtained.

Then, the modified amorphous ethylene-propylene copolymers (MEP-6 to 8) were used, and the values of the specific energies were changed as shown in Table 2.
In the same manner as in Example 1 , a composition was produced. A test piece was prepared from the composition thus prepared as described above, and using this test piece, flexural modulus, Izod impact strength, coating test, adhesive strength, and dispersed phase particles of a modified amorphous ethylene-propylene copolymer were used. The diameter was determined.

Table 2 shows the results.

[0094]

Examples 5-7 In Example 1 , PP-2 and M
A composition was obtained in the same manner as in Example 1 , except that the amount of EP-5 and the value of specific energy were changed as shown in Table 2. A test piece was prepared from the composition thus prepared as described above, and using this test piece, flexural modulus, Izod impact strength, coating test, adhesive strength, and dispersed phase particles of a modified amorphous ethylene-propylene copolymer were used. The diameter was determined.

Table 2 shows the results.

[0096]

Examples 8 to 11 EP-1 100 parts by weight 2-hydroxyethyl acrylate 0.7 parts by weight (hereinafter abbreviated as "HEA") PO-1 0.07 Parts by weight After mixing the above components with a Henschel mixer, a twin-screw extruder with vent (L / D = 42, screw diameter 30 m)
m) under a nitrogen atmosphere at a temperature of 230 ° C. under a nitrogen atmosphere using a modified amorphous ethylene-propylene copolymer (hereinafter referred to as “MEP-9”).
Abbreviated). The HEA graft amount of MEP-9 was 0.6% by weight.

Next, PP-2 and MEP-9 were mixed in the amounts shown in Table 2 using a Henschel mixer, and the mixture was used using a vented twin-screw extruder (L / D = 42, screw diameter 50 mm). At a temperature of 200 ° C under a nitrogen atmosphere,
Pellets (compositions) were produced while the specific energy values were set as shown in Table 2 and melt-kneaded. A test piece was prepared from the composition thus prepared as described above, and using this test piece, flexural modulus, Izod impact strength, coating test, adhesive strength, and dispersed phase particles of a modified amorphous ethylene-propylene copolymer were used. The diameter was determined.

Table 2 shows the results.

[0099]

[Reference Example 8] EP-1 100 parts by weight Acrylic acid (hereinafter abbreviated as "AA") 0.5 parts by weight PO-1 0.05 parts by weight Was mixed with a Henschel mixer, and a vented twin-screw extruder (L / D = 42, screw diameter 30 m)
m) at 230 ° C. under a nitrogen atmosphere at a temperature of 230 ° C.
0 "). The graft amount of AA of MEP-10 was 0.2% by weight.

Then, 65 parts by weight of PP-2 and 35 parts by weight
Mix parts by weight of MEP-10 with a Henschel mixer,
The mixture was melt-kneaded using a vented twin-screw extruder (L / D = 42, screw diameter 50 mm) at a temperature of 200 ° C. under a nitrogen atmosphere at a specific energy of 0.31 kW · hr / kg, and pellets (composition) Product). A test piece was prepared from the composition thus prepared as described above, and using this test piece, flexural modulus, Izod impact strength, coating test, adhesive strength, and dispersed phase particles of a modified amorphous ethylene-propylene copolymer were used. The diameter was determined.

Table 2 shows the results.

[0102]

[Reference Example 9] EP-1 100 parts by weight Methacrylic acid (hereinafter abbreviated as "MA") 0.6 parts by weight PO-1 0.05 parts by weight The above components Was mixed with a Henschel mixer, and then a twin-screw extruder with a vent (L / D = 42, screw diameter 30 m) was used.
m) at 230 ° C. under a nitrogen atmosphere at a temperature of 230 ° C.
1 "). The amount of MA grafted on MEP-11 was 0.1% by weight.

Then, 65 parts by weight of PP-2 and 35 parts by weight
Parts by weight of MEP-11 were mixed with a Henschel mixer,
The mixture was melt-kneaded using a vented twin-screw extruder (L / D = 42, screw diameter 50 mm) at a temperature of 200 ° C. in a nitrogen atmosphere at a specific energy of 0.30 kW · hr / kg, and the pellets (composition) Product). A test piece was prepared from the composition thus prepared as described above, and using this test piece, flexural modulus, Izod impact strength, coating test, adhesive strength, and dispersed phase particles of a modified amorphous ethylene-propylene copolymer were used. The diameter was determined.

Table 2 shows the results.

[0105]

Examples 12 and 13 EP-1 100 parts by weight 2-hydroxyethyl methacrylate 0.8 parts by weight (hereinafter abbreviated as "HEMA") PO-1 0.07 Parts by weight After mixing the above components with a Henschel mixer, a twin-screw extruder with vent (L / D = 42, screw diameter 30 m)
m) at 230 ° C. under a nitrogen atmosphere at a temperature of 230 ° C.
2 "). The amount of HEMA grafted on MEP-12 was 0.2% by weight.

Next, PP was added in the amount shown in Table 2.
-2 and MEP-12 were mixed using a Henschel mixer, and the mixture was vented into a twin-screw extruder (L / D = 4).
2, under a nitrogen atmosphere using a screw diameter of 50 mm).
At a temperature of 0 ° C., pellets (compositions) were produced while melting and kneading while setting specific energy values as shown in Table 2.

A test piece was prepared from the composition thus prepared as described above, and the flexural modulus and
The Izod impact strength, coating test, adhesive strength, and the particle size of the dispersed phase of the modified amorphous ethylene-propylene copolymer were determined. Table 2 shows the results.

[0108]

Example 14 EP-2: 100 parts by weight 2-Hydroxypropyl methacrylate: 0.8 parts by weight (hereinafter abbreviated as "HPMA") PO-1: 0.07 parts by weight After mixing the above components with a Henschel mixer, a twin-screw extruder with vent (L / D = 42, screw diameter 30 m)
m) at 230 ° C. under a nitrogen atmosphere at a temperature of 230 ° C.
3 "). The graft amount of HPMA of MEP-13 was 0.2% by weight.

Then, 75 parts by weight of PP-1 and 25 parts by weight
Parts by weight of MEP-13 mixed with a Henschel mixer,
The mixture was melt-kneaded using a vented twin-screw extruder (L / D = 42, screw diameter 50 mm) at a temperature of 200 ° C. under a nitrogen atmosphere at a specific energy of 0.27 kW · hr / kg while pellets (composition). Product). A test piece was prepared from the composition thus prepared as described above, and using this test piece, flexural modulus, Izod impact strength, coating test, adhesive strength, and dispersed phase particles of a modified amorphous ethylene-propylene copolymer were used. The diameter was determined.

The results are shown in Table 2.

[0111]

[Reference Example 10] EP-1 100 parts by weight MAH 1.2 parts by weight Styrene (hereinafter abbreviated as "St") 1.1 parts by weight The above components were mixed with a Henschel mixer. After mixing, a twin-screw extruder with a vent (L / D = 42, screw diameter 30 mm)
Was used to produce a modified amorphous ethylene-propylene copolymer (hereinafter abbreviated as “MEP-14”) at a temperature of 230 ° C. under a nitrogen atmosphere. The graft amount of MAH of MEP-14 was 0.7% by weight.

Then, PP-1 ... 62 parts by weight MEP-14 ... 38 parts by weight were mixed with a Henschel mixer, and the mixture was vented to 2 parts.
0.30 kW · h at a temperature of 200 ° C. under a nitrogen atmosphere using a screw extruder (L / D = 42, screw diameter 50 mm).
A pellet (composition) was produced while being melt-kneaded at a specific energy of r / kg.

From the composition thus prepared, a test piece was prepared as described above, and the flexural modulus and
The Izod impact strength, coating test, adhesive strength, and the particle size of the dispersed phase of the modified amorphous ethylene-propylene copolymer were determined. Table 2 shows the results.

[0114]

Example 15: EP-2: 100 parts by weight HPA: 1.4 parts by weight St: 1.1 parts by weight PO-1: 0.05 parts by weight Was mixed with a Henschel mixer, and a vented twin-screw extruder (L / D = 42, screw diameter 30 m)
m) at 230 ° C. under a nitrogen atmosphere at a temperature of 230 ° C.
5 "). The amount of HPA grafted on MEP-15 was 0.6% by weight.

Next, 65 parts by weight of PP-2 and 35 parts by weight of MEP-15 were mixed with a Henschel mixer, and the mixture was vented to 2 parts.
Using a screw extruder (L / D = 42, screw diameter 50 mm) at a temperature of 200 ° C. under a nitrogen atmosphere at 0.29 kW · h
A pellet (composition) was produced while being melt-kneaded at a specific energy of r / kg.

A test piece was prepared from the composition thus prepared as described above, and the flexural modulus,
The Izod impact strength, coating test, adhesive strength, and the particle size of the dispersed phase of the modified amorphous ethylene-propylene copolymer were determined. Table 2 shows the results.

[0117]

Example 16 Amorphous ethylene-propylene copolymer: 100 parts by weight (ethylene content: 81 mol%, MFR: 5.4 g / 10 min, density: 0.87 g / cm ³ , hereinafter referred to as “EP HEA 0.7 parts by weight PO-1 0.07 parts by weight After mixing the above components with a Henschel mixer, a twin-screw extruder with vent (L / D = 42, screw diameter 30 m)
m) at 230 ° C. under a nitrogen atmosphere at a temperature of 230 ° C.
6 "). The grafting amount of MAH of MEP-16 was 0.6% by weight.

Next, 55 parts by weight of PP-1 and 45 parts by weight of MEP-16 were mixed with a Henschel mixer, and the mixture was vented to 2 parts.
0.32 kW · h at a temperature of 200 ° C. under a nitrogen atmosphere using a screw extruder (L / D = 42, screw diameter 50 mm).
A pellet (composition) was produced while being melt-kneaded at a specific energy of r / kg.

From the composition thus prepared, a test piece was prepared as described above, and the flexural modulus,
The Izod impact strength, coating test, adhesive strength, and the particle size of the dispersed phase of the modified amorphous ethylene-propylene copolymer were determined. Table 2 shows the results.

[0120]

Example 17 Amorphous ethylene-propylene copolymer: 100 parts by weight (ethylene content: 81 mol%, MFR: 8.1 g / 10 min, density: 0.87 g / cm ³ , hereinafter referred to as “EP -HPMA ... 0.7 parts by weight-PO-1 ... 0.07 parts by weight After mixing the above components with a Henschel mixer, a vented twin-screw extruder (L / D = 42, screw diameter 30m
m) at 230 ° C. under a nitrogen atmosphere at a temperature of 230 ° C.
7 "). The graft amount of MAH of MEP-17 was 0.5% by weight.

Next, 65 parts by weight of PP-1 and 35 parts by weight of MEP-17 were mixed with a Henschel mixer, and the mixture was vented to 2 parts.
0.32 kW · h at a temperature of 200 ° C. under a nitrogen atmosphere using a screw extruder (L / D = 42, screw diameter 50 mm).
A pellet (composition) was produced while being melt-kneaded at a specific energy of r / kg.

From the composition thus prepared, a test piece was prepared as described above, and the flexural modulus,
The Izod impact strength, coating test, adhesive strength, and the particle size of the dispersed phase of the modified amorphous ethylene-propylene copolymer were determined. Table 2 shows the results.

[0123]

REFERENCE EXAMPLES 11 AND 12 65 parts by weight of PP-1 35 parts by weight of MEP-3 The above components were mixed with a Henschel mixer, and the mixture was vented into a twin-screw extruder (L / D = 42, screw diameter 50 m).
m) in a nitrogen atmosphere at 170 ° C. ( Reference Example 11 ),
At a temperature of 185 ° C. ( Reference Example 12 ), pellets (composition) were produced while melting and kneading while setting the value of the specific energy as shown in Table 2.

From the composition thus prepared, a test piece was prepared as described above, and the flexural modulus and
The Izod impact strength, coating test, adhesive strength, and the particle size of the dispersed phase of the modified amorphous ethylene-propylene copolymer were determined. Table 2 shows the results.

[0125]

REFERENCE EXAMPLE 13 A test piece prepared from the propylene polymer composition prepared in Reference Example 1 was coated with 1,1,1
-Trichloroethane steam washing, water washing, general industrial detergent ID-112 [Tosoh Corporation, trade name]
Washing with a 4% aqueous solution (60 ° C.) of 1.5 minutes, washing with water, general industrial detergent ID-113 [trade name, manufactured by Tosoh Corporation]
1% aqueous solution (55 ° C) for 1 minute
C. and dried for 10 minutes.

Reference Example 1
A urethane-based paint was applied and cured in the same manner as described above. Table 2 shows the physical properties of the composition obtained, the cross-cut test of the coating film, and the measurement results of the peel strength.

[0127]

REFERENCE EXAMPLE 14 A test piece prepared from the propylene polymer composition prepared in Reference Example 1 was coated with 1,1,1
-Without trichloroethane steam cleaning, wipe the specimen with a cloth impregnated with isopropanol,
A urethane-based paint was applied and cured in the same manner as in Reference Example 1.

Table 2 shows the physical properties of the composition obtained, the cross-cut test of the coating film, and the measurement results of the peel strength.

[0129]

Reference Example 15 52 parts by weight of PP-1, 28 parts by weight of M
EP-1 and 20 parts by weight of talc were stirred with a Henschel mixer to prepare a blend. After that, a twin screw extruder was used to obtain 0.30 kW ·
The composition was produced by melt-kneading at a specific energy of hr / kg.

From the composition thus prepared, a test piece was prepared as described above, and the flexural modulus and
The Izod impact strength, coating test, adhesive strength, and the particle size of the dispersed phase of the modified amorphous ethylene-propylene copolymer were determined. Table 2 shows the results.

[0131]

Reference Example 16 Propylene-ethylene random copolymer: 65 parts by weight (ethylene content: 6 mol%, MFR: 11 g / 10 min, density: 0.91 g / cm ³ , hereinafter, referred to as “PP-3”) MEP-1 35 parts by weight The above components were mixed with a Henschel mixer, and the mixture was vented into a twin-screw extruder (L / D = 42, screw diameter 50 m).
m) in a nitrogen atmosphere at a temperature of 200 ° C.
A pellet (composition) was produced while being melt-kneaded at a specific energy of kW · hr / kg.

From the composition thus prepared, a test piece was prepared as described above, and the flexural modulus and
The Izod impact strength, coating test, adhesive strength, and the particle size of the dispersed phase of the modified amorphous ethylene-propylene copolymer were determined. Table 2 shows the results.

[0133]

[Comparative Example 1] · PP-1 ··· 65 parts by weight · EP-1 ··· 35 parts by weight After mixing the above components with a Henschel mixer, a twin-screw extruder with vent (L / D = 42, screw diameter) 50mm)
0.27 kW at a temperature of 200 ° C. under a nitrogen atmosphere using
A composition was produced at a specific energy of hr / kg.

A test piece was prepared from the composition thus prepared as described above, and the flexural modulus,
Izod impact strength, painting test, adhesive strength and EP-
1 was obtained. Table 2 shows the results.

[0135]

Comparative Example 2 Amorphous ethylene-propylene copolymer: 100 parts by weight (ethylene content: 40 mol%, MFR: 0.4 g / 10 min, density: 0.86 g / cm ³ , hereinafter referred to as “EP MAH: 1.2 parts by weight PO-1: 0.08 parts by weight After mixing the above components with a Henschel mixer, a twin-screw extruder with vent (L / D = 42) , Screw diameter 30mm)
Was used to produce a modified amorphous ethylene-propylene copolymer (hereinafter abbreviated as “MEP-18”) at a temperature of 230 ° C. under a nitrogen atmosphere. The graft amount of MAH of MEP-18 was 0.4% by weight.

Next, PP-1 ... 65 parts by weight MEP-18 ... 35 parts by weight were mixed with a Henschel mixer, and the mixture was vented to 2 parts.
Using a screw extruder (L / D = 42, screw diameter 50 mm) at a temperature of 200 ° C. under a nitrogen atmosphere at 0.25 kW · h
A pellet (composition) was produced while being melt-kneaded at a specific energy of r / kg.

A test piece was prepared from the composition thus prepared as described above, and the flexural modulus,
The Izod impact strength, coating test, adhesive strength, and the particle size of the dispersed phase of the modified amorphous ethylene-propylene copolymer were determined. Table 2 shows the results.

[0138]

Comparative Example 3 Amorphous ethylene-propylene copolymer: 100 parts by weight (ethylene content: 81 mol%, MFR: 2.0 g / 10 min, density: 0.89 g / cm ³ , hereinafter referred to as “EP HPA: 0.8 parts by weight PO-1: 0.07 parts by weight After mixing the above components with a Henschel mixer, a twin-screw extruder with vent (L / D = 42) , Screw diameter 30mm)
Was used to produce a modified amorphous ethylene-propylene copolymer (hereinafter abbreviated as “MEP-19”) at a temperature of 230 ° C. under a nitrogen atmosphere. The amount of HPA grafted on MEP-19 was 0.4% by weight.

65 parts by weight PP-1 35 parts by weight MEP-19 The above components were mixed in a Henschel mixer, and the mixture was vented into a twin-screw extruder (L / D = 42, screw Diameter 50m
m) at a temperature of 200 ° C. in a nitrogen atmosphere at a temperature of 0.26
A pellet (composition) was produced while being melt-kneaded at a specific energy of kW · hr / kg.

A test piece was prepared from the composition thus prepared as described above, and the flexural modulus and
The Izod impact strength, coating test, adhesive strength, and the particle size of the dispersed phase of the modified amorphous ethylene-propylene copolymer were determined. Table 2 shows the results.

[0141]

Comparative Example 4 62 parts by weight of PP-2 and 38 parts by weight of MEP-2 were added at a temperature of 200 ° C. at a rate of 0.25 kW · hr /
A pellet (composition) was produced while being melt-kneaded at a specific energy of kg. A test piece was prepared from the composition thus prepared as described above, and using this test piece, flexural modulus, Izod impact strength, coating test, adhesive strength, and dispersed phase particles of a modified amorphous ethylene-propylene copolymer were used. The diameter was determined.

Table 2 shows the results.

[0143]

[Reference Example 17] EP-3 ... 100 parts by weight MAH ... 1.1 parts by weight PO-1 ... 0.06 parts by weight After mixing the above components with a Henschel mixer, vented Twin screw extruder (L / D = 42, screw diameter 30m
m) at 230 ° C. under a nitrogen atmosphere at a temperature of 230 ° C. using a modified amorphous ethylene-propylene copolymer (hereinafter referred to as “MEP-2”).
0 "). The graft amount of MAH of MEP-20 was 0.8% by weight, and the MFR was 0.3 g / 10
Minutes.

Next, a propylene homopolymer: 28 parts by weight (MFR: 26 g / 10 min, density: 0.91 g / cm ³ , hereinafter abbreviated as “PP-4”); MEP-20: 72 parts by weight were mixed with a Henschel mixer and the mixture was vented 2
0.35 kW · h at a temperature of 250 ° C. under a nitrogen atmosphere using a screw extruder (L / D = 42, screw diameter 50 mm)
A pellet (composition) was produced while being melt-kneaded at a specific energy of r / kg.

From the composition thus prepared, a test piece was prepared as described above, and the flexural modulus,
The Izod impact strength, coating test, adhesive strength, and the particle size of the dispersed phase of the modified amorphous ethylene-propylene copolymer were determined. Table 2 shows the results.

[0146]

Example 18 EP-3 100 parts by weight HEA 1.5 parts by weight PO-1 0.1 part by weight After mixing the above components with a Henschel mixer, vented Twin screw extruder (L / D = 42, screw diameter 30m
m) at 230 ° C. under a nitrogen atmosphere at a temperature of 230 ° C. using a modified amorphous ethylene-propylene copolymer (hereinafter referred to as “MEP-2”).
1 "). The HEA graft amount of MEP-21 was 1.2% by weight.

Next, a propylene-ethylene copolymer: 40 parts by weight (MFR: 20 g / 10 min, density: 0.90 g / cm ³ , ethylene content: 3 mol%, hereinafter referred to as “PP-5”) MEP-21: 60 parts by weight are mixed with a Henschel mixer, and the mixture is vented 2
0.30 kW · h at a temperature of 250 ° C. under a nitrogen atmosphere using a screw extruder (L / D = 42, screw diameter 50 mm).
A pellet (composition) was produced while being melt-kneaded at a specific energy of r / kg.

A test piece was prepared from the composition thus prepared as described above, and the flexural modulus and
The Izod impact strength, coating test, adhesive strength, and the particle size of the dispersed phase of the modified amorphous ethylene-propylene copolymer were determined. Table 2 shows the results.

[0149]

[Table 1]

[0150]

[Table 2]

[0151]

[Table 3]

[0152]

[Table 4]

[0153]

[Table 5]

[0154]

[Table 6]

[0155]

[Table 7]

[0156]

[Table 8]

[0157]

[Table 9]

[Examples of Second Propylene Polymer Composition According to the Present Invention]

[0159]

Reference Example 18 The following components were mixed using a Henschel mixer. · Propylene homopolymer ··· 100 parts by weight (MFR: 0.3 g / 10 min, density: 0.91 g / cm ³ ; hereinafter abbreviated as “PP-6”) · MAH ··· 1.1 parts by weight -PO-1 ... 0.1 part by weight The obtained mixture was fed into a vented twin-screw extruder (L / D = 4).
2, screw diameter 30 mm) under nitrogen atmosphere
Modified polypropylene (hereinafter referred to as “M”) is kneaded at a temperature of 0 ° C.
PP-1 "). The amount of MAH grafted on MPP-1 was 0.3% by weight.

Next, the above MPP-1 and MEP-1
Was mixed using a Henschel mixer at the ratios described below.・ MPP-1 65 parts by weight ・ MEP-1 35 parts by weight A twin screw extruder equipped with a vent (L / D = 4)
2, under a nitrogen atmosphere using a screw diameter of 50 mm).
A pellet (composition) was produced by melt-kneading at a temperature of 0 ° C. and a specific energy of 0.28 kW · hr / kg.

A test piece was prepared from the composition thus prepared as described above, and the flexural modulus and
The Izod impact strength, coating test, adhesive strength, and the particle size of the dispersed phase of the modified amorphous ethylene-propylene copolymer were determined. Table 4 shows the results.

[0162]

REFERENCE EXAMPLES 19-21 MPP-1 in Reference Example 18
In the preparation process, the amount of MAH and PO-1 was changed to the third amount.
A modified polypropylene (MPP-2 to 4) was obtained in the same manner as in Reference Example 18 except that it was changed as shown in the table.
In Reference Example 18 , as described in Table 4, MPP
-1 is used instead of MPP-2-4, and MEP-1
Instead of using MEP-2-4 above,
A composition was produced in the same manner as in Reference Example 18 .

A test piece was prepared from the composition thus prepared as described above, and the flexural modulus and
The Izod impact strength, coating test, adhesive strength, and the particle size of the dispersed phase of the modified amorphous ethylene-propylene copolymer were determined. Table 4 shows the results.

[0164]

Reference Examples 22 to 24 In Reference Example 18 , MPP-1
A composition was obtained in the same manner as in Reference Example 18 , except that the amounts of MEP-1 and MEP-1 were changed as shown in Table 4. A test piece was prepared from the composition thus prepared as described above, and using this test piece, flexural modulus, Izod impact strength, coating test, adhesive strength, and dispersed phase particles of a modified amorphous ethylene-propylene copolymer were used. The diameter was determined.

Table 4 shows the results.

[0166]

Example 19 The components described below were mixed using a Henschel mixer. · PP-6 ··· 100 parts by weight · HPA ··· 0.8 parts by weight · PO-1 ··· 0.07 parts by weight A vented twin screw extruder (L / D = 4)
2, screw diameter 30 mm) under nitrogen atmosphere
Modified polypropylene (hereinafter referred to as “M”) is kneaded at a temperature of 0 ° C.
PP-5 "). The amount of HPA grafted on MPP-5 was 0.2% by weight.

Next, the MPP-5 and MEP-5 described above were used.
Was mixed using a Henschel mixer at the ratios described below. MPP-5: 65 parts by weight MEP-5: 35 parts by weight A twin screw extruder equipped with a vent (L / D = 4)
2, under a nitrogen atmosphere using a screw diameter of 50 mm).
A pellet (composition) was produced by melt-kneading at a temperature of 0 ° C. and a specific energy of 0.28 kW · hr / kg.

A test piece was prepared from the composition thus prepared as described above, and the flexural modulus and
The Izod impact strength, coating test, adhesive strength, and the particle size of the dispersed phase of the modified amorphous ethylene-propylene copolymer were determined. Table 4 shows the results.

[0169]

Examples 20 to 22 Modified polypropylene (MPP-6 to 8) was prepared in the same manner as in Example 19 except that the amounts of HPA and PO-1 were changed in the production process of MPP-5 in Example 19 . I got Next, the modified polypropylene (MPP-6 to 8) and the modified amorphous ethylene-propylene copolymer (MEP-6 to 8) were melt-kneaded in the amounts and conditions shown in Table 4 and pelletized (composition). Product).

From the composition thus prepared, a test piece was prepared as described above, and the flexural modulus and
The Izod impact strength, coating test, adhesive strength, and the particle size of the dispersed phase of the modified amorphous ethylene-propylene copolymer were determined. Table 4 shows the results.

[0171]

Embodiments 23 to 25 In the embodiment 19 , the MPP-5
A composition was obtained in the same manner as in Example 19 , except that the blending amount of MEP-26 and MEP-26 and the specific energy were changed as described in Table 4. A test piece was prepared from the composition thus prepared as described above, and using this test piece, flexural modulus, Izod impact strength, coating test, adhesive strength, and dispersed phase particles of a modified amorphous ethylene-propylene copolymer were used. The diameter was determined.

Table 4 shows the results.

[0173]

Examples 26 to 29 The components described below were mixed using a Henschel mixer. · PP-6 ··· 100 parts by weight · HEA ··· 4.0 parts by weight · PO-1 ··· 0.2 parts by weight The obtained mixture is subjected to a vented twin-screw extruder (L / D = 4).
2, screw diameter 30 mm) under nitrogen atmosphere
The modified polypropylene copolymer (hereinafter, abbreviated as “MPP-9”) was produced by kneading at a temperature of 0 ° C. The HEA graft amount of MPP-9 was 2.5% by weight.

Next, the above-mentioned MPPs were added in the amounts shown in Table 4.
-9 and MEP-9 were mixed using a Henschel mixer, and the mixture was vented into a twin-screw extruder (L / D = 4).
2, under a nitrogen atmosphere using a screw diameter of 50 mm).
Pellets (compositions) were produced by melt-kneading at a temperature of 0 ° C. and the specific energies shown in Table 4. A test piece was prepared from the composition thus prepared as described above, and using this test piece, flexural modulus, Izod impact strength, coating test, adhesive strength, and dispersed phase particles of a modified amorphous ethylene-propylene copolymer were used. The diameter was determined.

The results are shown in Table 4.

[0176]

Reference Example 25 The components described below were mixed using a Henschel mixer. · PP-6 ··· 100 parts by weight · AA · ··· 1.5 parts by weight · PO− ··· 0.03 parts by weight A vented twin screw extruder (L / D = 4)
2, screw diameter 30 mm) under nitrogen atmosphere
Modified polypropylene (hereinafter referred to as “M”) is kneaded at a temperature of 0 ° C.
PP-10 "). AA of MPP-10
Was 0.6% by weight.

Next, the above MPP-10 and MEP-
No. 10 were mixed using a Henschel mixer in the amounts shown in Table 4 and the resulting mixture was vented into a twin-screw extruder (L
/ D = 42, screw diameter 50 mm), and melt-kneaded at a temperature of 200 ° C. in a nitrogen atmosphere at a specific energy shown in Table 4 to produce a pellet (composition).

A test piece was prepared from the composition thus prepared as described above, and the flexural modulus and
The Izod impact strength, coating test, adhesive strength, and the particle size of the dispersed phase of the modified amorphous ethylene-propylene copolymer were determined. Table 4 shows the results.

[0179]

Reference Example 26 The components described below were mixed using a Henschel mixer. · PP-6 ··· 100 parts by weight · MA ··· 1.5 parts by weight · PO-1 ··· 0.03 parts by weight A vented twin screw extruder (L / D = 4)
2, screw diameter 30 mm) under nitrogen atmosphere
Modified polypropylene (hereinafter referred to as “M”) is kneaded at a temperature of 0 ° C.
PP-11 "). MPP-11 MA
Was 0.4% by weight.

Next, the MPP-11 and MEP-
11 were mixed using a Henschel mixer in the proportions shown in Table 4 and the mixture was vented into a twin-screw extruder (L / D
= 42, screw diameter 50 mm) and melt-kneaded at a temperature of 200 ° C in a nitrogen atmosphere at a specific energy shown in Table 4 to produce pellets (composition). A test piece was prepared from the composition thus prepared as described above, and using this test piece, flexural modulus, Izod impact strength, coating test, adhesive strength, and modified amorphous ethylene-
The dispersed phase particle size of the propylene copolymer was determined.

Table 4 shows the results.

[0182]

Examples 30 and 31 The components described below were mixed using a Henschel mixer. · PP-6 ··· 100 parts by weight · HEMA ··· 2.5 parts by weight · PO-1 ··· 0.05 parts by weight A vented twin screw extruder (L / D = 4)
2, screw diameter 30 mm) under nitrogen atmosphere
The modified polypropylene copolymer (hereinafter, abbreviated as “MPP-12”) was produced by kneading at a temperature of 0 ° C. MPP-1
The graft amount of HEMA No. 2 was 0.6% by weight.

Next, the MPP-12 and MEP-
12 were mixed in the proportions shown in Table 4 using a Henschel mixer, and the mixture was mixed with a vented twin-screw extruder (L / L
D = 42, a screw diameter of 50 mm) was melt-kneaded at a temperature of 200 ° C. in a nitrogen atmosphere at a specific energy shown in Table 4 to produce a pellet (composition).

A test piece was prepared from the composition thus prepared as described above, and the flexural modulus and
The Izod impact strength, coating test, adhesive strength, and the particle size of the dispersed phase of the modified amorphous ethylene-propylene copolymer were determined. Table 4 shows the results.

[0185]

Example 32 The components described below were mixed using a Henschel mixer. · PP-6 ··· 100 parts by weight · HPMA ··· 2.5 parts by weight · PO-1 ··· 0.05 parts by weight A vented twin-screw extruder (L / D = 4)
2, screw diameter 30 mm) under nitrogen atmosphere
Modified polypropylene (hereinafter referred to as “M”) is kneaded at a temperature of 0 ° C.
PP-13 "). MPP-13 HP
The graft amount of MA was 0.5% by weight.

Next, the MPP-13 and MEP-
13 were mixed at the ratios shown in Table 4 using a Henschel mixer, and the mixture was vented into a twin-screw extruder (L / D = 4).
2, under a nitrogen atmosphere using a screw diameter of 50 mm).
Pellets (compositions) were produced by melt-kneading at a temperature of 0 ° C. and the specific energies shown in Table 4. A test piece was prepared from the composition thus prepared as described above, and using this test piece, flexural modulus, Izod impact strength, coating test, adhesive strength, and dispersed phase particles of a modified amorphous ethylene-propylene copolymer were used. The diameter was determined.

The results are shown in Table 4.

[0188]

Reference Example 27 The components described below were mixed using a Henschel mixer. · PP-6 ··· 100 parts by weight · MAH ··· 2.3 parts by weight · St ··· 2.4 parts by weight · PO-1 ··· 0.1 parts by weight The resulting mixture is vented 2 Screw extruder (L / D = 4
2, screw diameter 30 mm) under nitrogen atmosphere
Modified polypropylene (hereinafter referred to as “M”) is kneaded at a temperature of 0 ° C.
PP-14 "). MA of MPP-14
The graft amount of H was 0.9% by weight.

Next, the MPP-14 and MEP-
No. 14 were mixed at the ratios shown in Table 4 using a Henschel mixer, and the mixture was mixed with a vented twin-screw extruder (L / D).
= 42, screw diameter 50 mm) and melt-kneaded at a temperature of 200 ° C in a nitrogen atmosphere at a specific energy shown in Table 4 to produce pellets (composition). A test piece was prepared from the composition thus prepared as described above, and using this test piece, flexural modulus, Izod impact strength, coating test, adhesive strength, and dispersed phase particles of a modified amorphous ethylene-propylene copolymer were used. The diameter was determined.

Table 4 shows the results.

[0191]

Example 33 The components described below were mixed using a Henschel mixer. -PP-6 ... 100 parts by weight-HPA ... 2.0 parts by weight-St ... 1.6 parts by weight-PO-1 ... 0.1 parts by weight The obtained mixture is vented 2 Screw extruder (L / D = 4
2, screw diameter 30 mm) under nitrogen atmosphere
Modified polypropylene (hereinafter referred to as “M”) is kneaded at a temperature of 0 ° C.
PP-15 "). MPP-15 HP
The graft amount of A was 1.4% by weight.

Next, the MPP-15 and MEP-
No. 15 were mixed using a Henschel mixer in the amounts shown in Table 4 and the mixture was vented into a twin-screw extruder (L / D = 4).
2, under a nitrogen atmosphere using a screw diameter of 50 mm).
Pellets (compositions) were produced by melt-kneading at a temperature of 0 ° C. and the specific energies shown in Table 4. A test piece was prepared from the composition thus prepared as described above, and using this test piece, flexural modulus, Izod impact strength, coating test, adhesive strength, and dispersed phase particles of a modified amorphous ethylene-propylene copolymer were used. The diameter was determined.

The results are shown in Table 4.

[0194]

Examples 34 and 35 The components described below were mixed using a Henschel mixer. · PP-6 ··· 100 parts by weight · HEA · · · 1.0 parts by weight · Benzoyl peroxide (hereinafter abbreviated as “PO-2”) ··· 0.2 parts by weight · Toluene ··· 5. 0 parts by weight The resulting mixture was maintained at 100 ° C. for 2 hours under a nitrogen stream to obtain modified polypropylene (hereinafter referred to as “MPP-1”).
6 "). The HEA graft amount of MPP-16 was 1.4% by weight.

Next, the above MPP-16 and MEP
-5 was mixed with a Henschel mixer in the amounts shown in Table 4 and the mixture was vented into a twin-screw extruder (L / D = 4).
2, under a nitrogen atmosphere using a screw diameter of 50 mm).
Pellets (compositions) were produced by melt-kneading at a temperature of 0 ° C. and the specific energies shown in Table 4. A test piece was prepared from the composition thus prepared as described above, and using this test piece, flexural modulus, Izod impact strength, coating test, adhesive strength, and dispersed phase particles of a modified amorphous ethylene-propylene copolymer were used. The diameter was determined.

The results are shown in Table 4.

[0197]

EXAMPLE 36 The above-mentioned MPP-8 and MEP-16 were mixed in the amounts shown in Table 4 using a Henschel mixer, and the mixture was vented into a twin-screw extruder (L / D = 4).
2, under a nitrogen atmosphere using a screw diameter of 50 mm).
Pellets (compositions) were produced by melt-kneading at a temperature of 0 ° C. and the specific energies shown in Table 4.

A test piece was prepared from the composition thus prepared as described above, and the flexural modulus,
The Izod impact strength, coating test, adhesive strength, and the particle size of the dispersed phase of the modified amorphous ethylene-propylene copolymer were determined. Table 4 shows the results.

[0199]

Example 37 The above-mentioned MPP-13 and MEP-17
Were mixed using a Henschel mixer in the amounts shown in Table 4 and the mixture was fed to a vented twin-screw extruder (L / D = 4).
2, under a nitrogen atmosphere using a screw diameter of 50 mm).
Pellets (compositions) were produced by melt-kneading at a temperature of 0 ° C. and the specific energies shown in Table 4.

A test piece was prepared from the composition thus prepared as described above, and the flexural modulus,
The Izod impact strength, coating test, adhesive strength, and the particle size of the dispersed phase of the modified amorphous ethylene-propylene copolymer were determined. Table 4 shows the results.

[0201]

Reference Examples 28 and 29 The components described below were mixed using a Henschel mixer.・ MPP-2
... 60 parts by weight, MEP-3
... 40 parts by weight of the obtained mixture
° C, specific energy 0.38 kW · hr / kg (Example 6
5) and 180 ° C., specific energy 0.32 kW · hr
Pellets (composition) by melt-kneading under nitrogen atmosphere using a vented twin-screw extruder (L / D = 42, screw diameter 50 mm) under the condition of / kg (Example 66).
Was manufactured.

From the composition thus prepared, a test piece was prepared as described above, and the flexural modulus and
The Izod impact strength, coating test, adhesive strength, and the particle size of the dispersed phase of the modified amorphous ethylene-propylene copolymer were determined. Table 4 shows the results.

[0203]

REFERENCE EXAMPLE 30 A water washing, general industrial cleaning agent ID-112 [manufactured by Tosoh Corporation] without performing 1,1,1-trichloroethane vapor cleaning before coating the paint on the test piece performed in reference example 18 1% aqueous solution (60 ° C.)
Washing for 5 minutes, washing with water, washing for 1 minute with a 1% aqueous solution (55 ° C) of a general industrial detergent ID-113 [trade name, manufactured by Tosoh Corporation], washing with water, and drying for 10 minutes at 80 ° C.

[0204] Reference Example 1
A urethane paint was applied and cured in the same manner as in No. 8 . Table 4 shows the physical properties of the obtained composition, the cross-cut test of the coating film, and the measurement results of the peel strength.

[0205]

[Reference Example 31] A test piece prepared from the polymer composition prepared in Reference Example 18 was not washed with 1,1,1-trichloroethane vapor before coating with a paint, but was washed with a cloth impregnated with isopropanol. After wiping, the test piece was treated with Reference Example 18
A urethane-based paint was applied and cured in the same manner as described above.

Table 4 shows the physical properties of the composition obtained, the results of a grid test of the coating film, and the measurement of the peel strength.

[0207]

Reference Example 32 The components described below were mixed using a Henschel mixer. MPP-1: 59 parts by weight MEP-1: 31 parts by weight The obtained mixture was mixed under a nitrogen atmosphere using a twin screw extruder.
The composition was manufactured by kneading at a temperature of 00 ° C.

Next, 90 parts by weight of the above composition pellets and 10 parts by weight of talc were mixed using a Henschel mixer, and the resulting mixture was mixed at a temperature of 200 ° C. under a nitrogen atmosphere using a twin-screw extruder. 0.31 kWh energy
A pellet (composition) was produced by melt kneading at a setting of r / kg. A test piece was prepared from the composition thus prepared as described above, and the flexural modulus, Izod impact strength, coating test, and adhesive strength were determined using the test piece.

Table 4 shows the results.

[0210]

Reference Example 33 The components described below were mixed using a Henschel mixer. · MPP-1 ··· 52 parts by weight · MEP-1 ··· 28 parts by weight The obtained mixture was mixed under nitrogen atmosphere using a twin screw extruder.
The composition was manufactured by kneading at a temperature of 00 ° C.

Next, 80 parts by weight of the above composition pellets and 20 parts by weight of talc were mixed using a Henschel mixer, and the resulting mixture was mixed at a temperature of 200 ° C. under a nitrogen atmosphere using a twin-screw extruder. 0.31 kWh energy
A pellet (composition) was produced by melt kneading at a setting of r / kg. A test piece was prepared from the composition thus prepared as described above, and the flexural modulus, Izod impact strength, coating test, and adhesive strength were determined using the test piece.

Table 4 shows the results.

[0213]

Example 38 The components described below were mixed using a Henschel mixer. Propylene - ethylene random copolymer.. 100 parts by weight (ethylene content: 6 mol%, MFR: 0.5 g / 10 min, density: 0.91 g / cm ^3, hereinafter, abbreviated as "PP-7") · HPMA ··· 1.4 parts by weight · PO-1 ··· 0.03 parts by weight The obtained mixture is subjected to a vented twin-screw extruder (L / D = 4).
2, screw diameter 30 mm) under nitrogen atmosphere
Modified polypropylene (hereinafter referred to as “M”) is kneaded at a temperature of 0 ° C.
PP-17 "). MPP-17 HP
The graft amount of A was 0.6% by weight.

Next, the components described below were mixed using a Henschel mixer. · MPP-17 ··· 65 parts by weight · MEP-1 ··· 35 parts by weight The obtained mixture is subjected to a vented twin-screw extruder (L / D = 4).
2, under a nitrogen atmosphere using a screw diameter of 50 mm).
At a temperature of 0 ° C., specific energy 0.38 kW · hr / kg
The pellets (composition) were produced by melt-kneading in the above.

From the composition thus prepared, a test piece was prepared as described above, and the flexural modulus,
The Izod impact strength, coating test, adhesive strength, and the particle size of the dispersed phase of the modified amorphous ethylene-propylene copolymer were determined. Table 4 shows the results.

[0216]

Comparative Example 5 The components described below were mixed using a Henschel mixer. · PP-6 ··· 60 parts by weight · EP-1 ··· 40 parts by weight A vented twin-screw extruder (L / D = 4)
2, under a nitrogen atmosphere using a screw diameter of 50 mm).
The composition was produced at a temperature of 0 ° C.

A test piece was prepared from the composition thus prepared as described above, and the flexural modulus and
The Izod impact strength, coating test, adhesive strength, and the particle size of the dispersed phase of the modified amorphous ethylene-propylene copolymer were determined. Table 4 shows the results.

[0218]

Comparative Example 6 The components described below were mixed using a Henschel mixer. · PP-6 ··· 100 parts by weight · MAH ··· 2.3 parts by weight · PO-1 ··· 0.2 parts by weight The obtained mixture is subjected to a vented twin-screw extruder (L / D = 4).
2, screw diameter 30 mm) under nitrogen atmosphere
Modified polypropylene (hereinafter referred to as “M”) is kneaded at a temperature of 0 ° C.
PP-18 "). MPP-18 MA
The graft amount of H was 0.4% by weight.

Next, the components described below were mixed using a Henschel mixer. · MPP-18 ··· 65 parts by weight · MEP-1 ··· 35 parts by weight The resulting mixture is vented into a twin-screw extruder (L / D = 4).
2, under a nitrogen atmosphere using a screw diameter of 50 mm).
At a temperature of 0 ° C., specific energy 0.22 kW · hr / kg
The pellets (composition) were produced by melt-kneading under the following conditions.

From the composition thus prepared, a test piece was prepared as described above, and the flexural modulus and
The Izod impact strength, coating test, adhesive strength, and the particle size of the dispersed phase of the modified amorphous ethylene-propylene copolymer were determined. Table 4 shows the results.

[0221]

Comparative Example 7 The components described below were mixed using a Henschel mixer. · PP-6 ··· 100 parts by weight · MAH ··· 1.5 parts by weight · PO-1 ··· 0.2 parts by weight The obtained mixture is subjected to a vented twin-screw extruder (L / D = 4).
2, screw diameter 30 mm) under nitrogen atmosphere
Modified polypropylene (hereinafter referred to as “M”) is kneaded at a temperature of 0 ° C.
PP-19 "). MA of MPP-19
The graft amount of H was 0.9% by weight.

Next, the components described below were mixed using a Henschel mixer. · MPP-19 ··· 65 parts by weight · MEP-1 ··· 35 parts by weight The obtained mixture is vented into a twin-screw extruder (L / D = 4).
2, under a nitrogen atmosphere using a screw diameter of 50 mm).
At a temperature of 0 ° C., specific energy 0.23 kW · hr / kg
The pellets (composition) were produced by melt-kneading under the following conditions.

From the composition thus prepared, a test piece was prepared as described above, and the flexural modulus and
The Izod impact strength, coating test, adhesive strength, and the particle size of the dispersed phase of the modified amorphous ethylene-propylene copolymer were determined. Table 4 shows the results.

[0224]

Reference Example 34 The following components were mixed using a Henschel mixer. · PP-6 ··· 100 parts by weight · MAH ··· 1.1 parts by weight · PO-1 ··· 0.1 parts by weight The obtained mixture is fed into a vented twin-screw extruder (L / D = 4).
2, screw diameter 30 mm) under nitrogen atmosphere
Modified polypropylene (hereinafter referred to as “M”) is kneaded at a temperature of 0 ° C.
PP-20 "). MA of MPP-20
The amount of H grafted was 0.3% by weight, and the MFR was 40 g.
/ 10 minutes.

Next, the components described below were mixed using a Henschel mixer. · EP-3 ··· 100 parts by weight · MAH ··· 1.2 parts by weight · PO-1 ··· 0.2 parts by weight A vented twin screw extruder (L / D = 4)
2, screw diameter 30mm) under nitrogen atmosphere using 23
Kneaded at a temperature of 0 ° C. to produce a modified amorphous ethylene-propylene copolymer (hereinafter abbreviated as “MEP-20”). The graft amount of MAH of MEP-20 is 0.8% by weight.
And the MFR was 0.3 g / 10 min.

Next, the MPP obtained as described above
-20 and MEP-20 were mixed using a Henschel mixer in the proportions described below. MPP-20: 30 parts by weight MEP-20: 70 parts by weight A twin screw extruder equipped with a vent (L / D = 4)
2, screw diameter 50mm) under nitrogen atmosphere using 23
A pellet (composition) was produced by melt-kneading at a temperature of 0 ° C. and a specific energy of 0.35 kW · hr / kg.

A test piece was prepared from the composition thus prepared as described above, and the flexural modulus and
The Izod impact strength, coating test, adhesive strength, and the particle size of the dispersed phase of the modified amorphous ethylene-propylene copolymer were determined. Table 4 shows the results.

[0228]

In Reference Example 35 Reference Example 34, the amount of MPP-20 and MEP-20 except for changing as described in Table 4, in the same manner as in Reference Example 34, the pellets (composition) Manufactured. A test piece was prepared from the composition thus prepared as described above, and using this test piece, flexural modulus, Izod impact strength, coating test, adhesive strength, and dispersed phase particles of a modified amorphous ethylene-propylene copolymer were used. The diameter was determined.

Table 4 shows the results.

[0230]

Example 39 The following components were mixed using a Henschel mixer. Propylene-ethylene copolymer: 100 parts by weight (ethylene content: 2 mol%, MFR: 0.3 g / 10 min, density: 0.91 g / cm ³ , hereinafter abbreviated as “PP-8”) HEA: 1.2 parts by weight PO-1: 0.06 parts by weight The obtained mixture is fed into a vented twin-screw extruder (L / D = 4).
2, screw diameter 30 mm) under nitrogen atmosphere
Modified polypropylene (hereinafter referred to as “M”) is kneaded at a temperature of 0 ° C.
PP-21 "). MPP-21 HE
The graft amount of A was 0.7% by weight.

Next, the components described below were mixed using a Henschel mixer. · EP-3 ··· 100 parts by weight · HEA ··· 1.5 parts by weight · PO-1 ··· 0.1 parts by weight A vented twin screw extruder (L / D = 4)
2, screw diameter 30mm) under nitrogen atmosphere using 23
Kneaded at a temperature of 0 ° C. to produce a modified amorphous ethylene-propylene copolymer (hereinafter abbreviated as “MEP-21”). HEA graft amount of MEP-21 is 1.2% by weight
Met.

Next, the above MPP-21 and MEP
-21 was mixed using a Henschel mixer in the proportions described below. · MPP-21 ··· 25 parts by weight · MEP-21 · · · 75 parts by weight The obtained mixture is subjected to a vented twin-screw extruder (L / D = 4).
2, screw diameter 50mm) under nitrogen atmosphere using 23
A pellet (composition) was produced by melt-kneading at a temperature of 0 ° C. and a specific energy of 0.31 kW · hr / kg.

A test piece was prepared from the composition thus prepared as described above, and the flexural modulus and
The Izod impact strength, coating test, adhesive strength, and the particle size of the dispersed phase of the modified amorphous ethylene-propylene copolymer were determined. Table 4 shows the results.

[0234]

In Example 40 Example 39, the amount of MPP-21 and MEP-21 except for changing as described in Table 4, in the same manner as in Example 39, the pellets (composition) Manufactured. A test piece was prepared from the composition thus prepared as described above, and using this test piece, flexural modulus, Izod impact strength, coating test, adhesive strength, and dispersed phase particles of a modified amorphous ethylene-propylene copolymer were used. The diameter was determined.

The results are shown in Table 4.

[0236]

[Table 10]

[0237]

[Table 11]

[0238]

[Table 12]

[0239]

[Table 13]

[0240]

[Table 14]

[0241]

[Table 15]

[0242]

[Table 16]

[0243]

[Table 17]

[0244]

[Table 18]

[Examples of Third Propylene Polymer Composition According to the Present Invention]

[0246]

Reference Example 36 The components described below were mixed with a Henschel mixer. · MPP-1 ··· 65 parts by weight · EP-1 ··· 35 parts by weight The obtained mixture was vented into a twin-screw extruder (L / D = 4).
2, under a nitrogen atmosphere using a screw diameter of 50 mm).
A pellet (composition) was produced by melt-kneading at a temperature of 0 ° C. and a specific energy of 0.27 kW · hr / kg.

A test piece was prepared from the composition thus prepared as described above, and the flexural modulus,
The Izod impact strength, coating test, adhesive strength, and particle size of the dispersed phase of the amorphous ethylene-propylene copolymer were determined.
Table 5 shows the results.

[0248]

Reference Examples 37 to 39 In Reference Example 36 , the above modified propylene polymers (MPP-2 to 4) were used in place of the modified propylene polymers (MPP-1). except that you set as described in the reference
A composition was prepared as in Example 36 . A test piece was prepared from the composition thus prepared as described above, and using this test piece, flexural modulus, Izod impact strength, coating test, adhesive strength, and the dispersed phase particle size of the amorphous ethylene-propylene copolymer I asked.

The results are shown in Table 5.

[0250]

Reference Examples 40 to 42 In Reference Example 36 , MPP-1
And the amount of EP-1 was changed as shown in Table 5, and the specific energy was set as shown in Table 5.
A composition was produced in the same manner as in Reference Example 36 . A test piece was prepared from the composition thus prepared as described above, and using this test piece, flexural modulus, Izod impact strength, coating test, adhesive strength, and the dispersed phase particle size of the amorphous ethylene-propylene copolymer I asked.

The results are shown in Table 5.

[0252]

Example 41 The following components were mixed with a Henschel mixer. MPP-5: 62 parts by weight EP-5: 38 parts by weight A temperature of 200 ° C. under nitrogen atmosphere using a vented twin-screw extruder (L / D = 42, screw diameter 50 mm). Then, pellets (composition) were produced by melt-kneading while setting the specific energy as shown in Table 5.

A test piece was prepared from the composition thus prepared as described above, and the flexural modulus and
The Izod impact strength, coating test, adhesive strength, and particle size of the dispersed phase of the amorphous ethylene-propylene copolymer were determined.
Table 5 shows the results.

[0254]

Embodiments 42 to 44 In the embodiment 41 , the MPP-5
In place of the above, using MPP-6 to 8, the specific energy was set as shown in Table 5 and melt-kneaded to obtain a composition (pellet). A test piece was prepared from the composition thus prepared as described above, and using this test piece, flexural modulus, Izod impact strength, coating test, adhesive strength, and the dispersed phase particle size of the amorphous ethylene-propylene copolymer I asked.

The results are shown in Table 5.

[0256]

Embodiments 45 to 47 In the embodiment 41 , the MPP-5
A composition was obtained in the same manner as in Example 41 , except that the blending amounts of EP-5 and EP-5 were changed as described in Table 5. A test piece was prepared from the composition thus prepared as described above, and using this test piece, flexural modulus, Izod impact strength, coating test, adhesive strength, and the dispersed phase particle size of the amorphous ethylene-propylene copolymer I asked.

The results are shown in Table 5.

[0258]

Examples 48 to 51 The above-mentioned MPP-9 and EP-5
Was mixed using a Henschel mixer in an amount shown in Table 5, and the mixture was mixed at a temperature of 200 ° C under a nitrogen atmosphere using a vented twin-screw extruder (L / D = 42, screw diameter 50 mm). Were set as described in Table 5 and melt-kneaded to produce pellets (composition).

A test piece was prepared from the composition thus prepared as described above, and the flexural modulus and
The Izod impact strength, coating test, adhesive strength, and particle size of the dispersed phase of the amorphous ethylene-propylene copolymer were determined.
Table 5 shows the results.

[0260]

REFERENCE EXAMPLE 43 The above MPP-10 and EP-1 were mixed in the amounts shown in Table 5 using a Henschel mixer, and the mixture was passed through a vented twin-screw extruder (L / D = 42, screw diameter 50 mm). Pellets (compositions) were produced by melting and kneading under a nitrogen atmosphere at a temperature of 200 ° C. and a specific energy set as shown in Table 5.

A test specimen was prepared from the composition thus prepared as described above, and the flexural modulus and
The Izod impact strength, coating test, adhesive strength, and particle size of the dispersed phase of the amorphous ethylene-propylene copolymer were determined.
Table 5 shows the results.

[0262]

REFERENCE EXAMPLE 44 The above-mentioned MPP-11 and EP-1 were mixed in the amounts shown in Table 5 using a Henschel mixer, and the mixture was passed through a vented twin-screw extruder (L / D = 42, screw diameter 50 mm). Pellets (compositions) were produced by melting and kneading under a nitrogen atmosphere at a temperature of 200 ° C. and a specific energy set as shown in Table 5.

A test piece was prepared from the composition thus prepared as described above, and the flexural modulus and
The Izod impact strength, coating test, adhesive strength, and particle size of the dispersed phase of the amorphous ethylene-propylene copolymer were determined.
Table 5 shows the results.

[0264]

Examples 52 and 53 The above MPP-12 and E
P-1 was mixed using a Henschel mixer as shown in Table 5 and the mixture was vented into a twin screw extruder (L / D = 4).
2, under a nitrogen atmosphere using a screw diameter of 50 mm).
At a temperature of 0 ° C., pellets (composition) were produced by melt-kneading while setting the specific energy as shown in Table 5.

A test specimen was prepared from the composition thus prepared as described above, and the flexural modulus and
The Izod impact strength, coating test, adhesive strength, and particle size of the dispersed phase of the amorphous ethylene-propylene copolymer were determined.
Table 5 shows the results.

[0266]

Example 54 The above MPP-13 and EP-1 were mixed in the amounts shown in Table 5 using a Henschel mixer, and the mixture was vented into a twin-screw extruder (L / D = 42, screw diameter 5).
0 mm) and melt-kneaded at a temperature of 200 ° C. in a nitrogen atmosphere at a specific energy as shown in Table 5 to produce pellets (composition).

A test piece was prepared from the composition thus prepared as described above, and the flexural modulus and
The Izod impact strength, coating test, adhesive strength, and particle size of the dispersed phase of the amorphous ethylene-propylene copolymer were determined.
Table 5 shows the results.

[0268]

REFERENCE EXAMPLE 45 The above MPP-14 and EP-1 were mixed in the amounts shown in Table 5 using a Henschel mixer, and the mixture was vented to a twin-screw extruder (L / D = 42, screw diameter 50 mm). The pellets (composition) were produced by melting and kneading at a temperature of 200 ° C. in a nitrogen atmosphere at a specific energy as shown in Table 5 by using the above method.

A test piece was prepared from the composition thus prepared as described above, and the flexural modulus and
The Izod impact strength, coating test, adhesive strength, and particle size of the dispersed phase of the amorphous ethylene-propylene copolymer were determined.
Table 5 shows the results.

[0270]

Example 55 The above MPP-15 and EP-5 were mixed in the amounts shown in Table 5 using a Henschel mixer, and the mixture was vented to a twin-screw extruder (L / D = 42, screw diameter 50 mm). The mixture was melt-kneaded at a temperature of 200 ° C. in a nitrogen atmosphere at a temperature of 200 ° C. as shown in Table 5 to produce pellets (composition).

A test piece was prepared from the composition thus prepared as described above, and the flexural modulus and
The Izod impact strength, coating test, adhesive strength, and particle size of the dispersed phase of the amorphous ethylene-propylene copolymer were determined.
Table 5 shows the results.

[0272]

Examples 56 and 57 The above MPP-16 and E
P-5 was mixed in the amount shown in Table 5 using a Henschel mixer, and the mixture was vented into a twin-screw extruder (L / D = 4).
2, under a nitrogen atmosphere using a screw diameter of 50 mm).
At a temperature of 0 ° C., pellets (composition) were produced by melt-kneading while setting the specific energy as shown in Table 5.

A test piece was prepared from the composition thus prepared as described above, and the flexural modulus and
The Izod impact strength, coating test, adhesive strength, and particle size of the dispersed phase of the amorphous ethylene-propylene copolymer were determined.
Table 5 shows the results.

[0274]

Reference Example 46 The components described below were mixed using a Henschel mixer. · MPP-1 ··· 65 parts by weight · EP-2 ··· 35 parts by weight The resulting mixture is vented into a twin screw extruder (L / D = 4
2, under a nitrogen atmosphere using a screw diameter of 50 mm).
At a temperature of 0 ° C., pellets (composition) were produced by melt-kneading while setting the specific energy as shown in Table 5.

A test piece was prepared from the composition thus prepared as described above, and the flexural modulus,
The Izod impact strength, coating test, adhesive strength, and particle size of the dispersed phase of the amorphous ethylene-propylene copolymer were determined.
Table 5 shows the results.

[0276]

Reference Example 47 The components described below were mixed using a Henschel mixer. · MPP-1 ··· 65 parts by weight · EP-3 ··· 35 parts by weight The resulting mixture is vented into a twin screw extruder (L / D = 4
2, under a nitrogen atmosphere using a screw diameter of 50 mm).
At a temperature of 0 ° C., pellets (composition) were produced by melt-kneading while setting the specific energy as shown in Table 5.

A test piece was prepared from the composition thus prepared as described above, and the flexural modulus and
The Izod impact strength, coating test, adhesive strength, and particle size of the dispersed phase of the amorphous ethylene-propylene copolymer were determined.
Table 5 shows the results.

[0278]

Reference Examples 48 and 49 The components described below were mixed using a Henschel mixer. MPP-2: 60 parts by weight EP-2: 40 parts by weight 170 ° C. under nitrogen atmosphere using a vented twin-screw extruder (L / D = 42, screw diameter 50 mm).
At a temperature of (Example 105) or 185 ° C. (Example 106), pellets (composition) were produced by melt-kneading while setting the specific energy as shown in Table 5.

A test piece was prepared from the composition thus prepared as described above, and the flexural modulus and
The Izod impact strength, coating test, adhesive strength, and particle size of the dispersed phase of the amorphous ethylene-propylene copolymer were determined.
Table 5 shows the results.

[0280]

REFERENCE EXAMPLE 50 A water washing, general industrial cleaning agent ID-112 [manufactured by Tosoh Corporation] without performing 1,1,1-trichloroethane vapor cleaning on a test piece before coating with a paint performed in reference example 36. 1% aqueous solution (60 ° C.)
Washing for 5 minutes, washing with water, washing for 1 minute with a 1% aqueous solution (55 ° C) of a general industrial detergent ID-113 [trade name, manufactured by Tosoh Corporation], washing with water, and drying for 10 minutes at 80 ° C.

The test piece subjected to the above treatment was subjected to Example 7
A urethane-based paint was applied and cured in the same manner as in No. 6. Table 5 shows the physical properties of the obtained composition, the cross-cut test of the coating film, and the measurement results of the peel strength.

[0282]

REFERENCE EXAMPLE 51 A test piece prepared from the polymer composition produced in Reference Example 36 was not washed with 1,1,1-trichloroethane vapor before coating with a paint, but was washed with a cloth impregnated with isopropanol. After wiping, the test piece was treated with Reference Example 36.
A urethane-based paint was applied and cured in the same manner as described above.

Table 5 shows the physical properties of the composition obtained, the results of a grid test of the coating film and the measurement of the peel strength.

[0284]

Reference Example 52 The components described below were mixed using a Henschel mixer. · MPP-1 ··· 59 parts by weight · EP-1 ··· 31 parts by weight The obtained mixture was mixed under a nitrogen atmosphere using a twin-screw extruder.
The composition was produced by melt-kneading at a temperature of 00 ° C.

Next, 90 parts by weight of the composition pellets and 10 parts by weight of talc were stirred with a Henschel mixer to prepare a blend. Using a twin-screw extruder, the blend was heated at a temperature of 200 ° C. under a nitrogen atmosphere at 0.30 kW · h.
The composition was produced by melt-kneading at a specific energy of r / kg. A test piece was prepared from the composition thus prepared as described above, and the flexural modulus, Izod impact strength, coating test, and adhesive strength were determined using the test piece.

The results are shown in Table 5.

[0287]

Reference Example 53 The components described below were mixed using a Henschel mixer. · MPP-1 ··· 52 parts by weight · EP-1 ··· 28 parts by weight The obtained mixture was mixed under a nitrogen atmosphere using a twin-screw extruder.
The composition was produced by melt-kneading at a temperature of 00 ° C.

Next, 80 parts by weight of the above composition pellets and 20 parts by weight of talc were stirred with a Henschel mixer to prepare a blend. Using a twin-screw extruder, the blend was heated at a temperature of 200 ° C. under a nitrogen atmosphere at 0.30 kW · h.
The composition was produced by melt-kneading at a specific energy of r / kg. A test piece was prepared from the composition thus prepared as described above, and the flexural modulus, Izod impact strength, coating test, and adhesive strength were determined using the test piece.

The results are shown in Table 5.

[0290]

Example 58 The above MPP-17 and EP-1 were mixed in the amounts shown in Table 5 using a Henschel mixer.
The mixture was melt-kneaded using a vented twin-screw extruder (L / D = 42, screw diameter 50 mm) at a temperature of 200 ° C. under a nitrogen atmosphere at a specific energy set as described in Table 5. A pellet (composition) was produced.

A test piece was prepared from the composition thus prepared as described above, and the flexural modulus,
The Izod impact strength, coating test, adhesive strength, and particle size of the dispersed phase of the amorphous ethylene-propylene copolymer were determined.
Table 5 shows the results.

[0292]

Comparative Example 8 The components described below were mixed using a Henschel mixer. · PP-6 ··· 65 parts by weight · EP-1 ··· 35 parts by weight The obtained mixture is subjected to a twin-screw extruder equipped with a vent (L / D = 4).
2, under a nitrogen atmosphere using a screw diameter of 50 mm).
At a temperature of 0 ° C., a specific energy of 0.27 kW · hr / k
The composition was manufactured by melt kneading while setting to g.

A test piece was prepared from the composition thus prepared as described above, and the flexural modulus,
The Izod impact strength, coating test, adhesive strength, and particle size of the dispersed phase of the amorphous ethylene-propylene copolymer were determined.
Table 5 shows the results.

[0294]

Comparative Example 9 The components described below were mixed with a Henschel mixer. · MPP-18 ··· 65 parts by weight · EP-1 ··· 35 parts by weight The resulting mixture is vented into a twin-screw extruder (L / D = 4).
2, under a nitrogen atmosphere using a screw diameter of 50 mm).
At a temperature of 0 ° C., a specific energy of 0.21 kW · hr / k
Then, pellets (composition) were produced by melt-kneading the resulting mixture into a mixture.

A test piece was prepared from the composition thus prepared as described above, and the flexural modulus and
The Izod impact strength, coating test, adhesive strength, and particle size of the dispersed phase of the amorphous ethylene-propylene copolymer were determined.
Table 5 shows the results.

[0296]

Comparative Example 10 The above MPP-19 and EP-1 were mixed in the amounts shown in Table 5 using a Henschel mixer, and the mixture was vented into a twin-screw extruder (L / D = 42, screw diameter 50 mm). The pellets were produced by melting and kneading under a nitrogen atmosphere at a temperature of 200 ° C. and a specific energy of 0.22 kW · hr / kg using the above method.

A test piece was prepared from the composition thus prepared as described above, and the flexural modulus and
The Izod impact strength, coating test, adhesive strength, and particle size of the dispersed phase of the amorphous ethylene-propylene copolymer were determined.
Table 5 shows the results.

[0298]

Comparative Example 11 In Example 105, the kneading temperature was changed to 25.
Change to 0 ° C and change specific energy to 0.22kW · hr / kg
A composition was prepared in the same manner as in Example 105 except that the composition was changed to A test piece was prepared from the composition thus prepared as described above, and using this test piece, flexural modulus, Izod impact strength, coating test, adhesive strength, and the dispersed phase particle size of the amorphous ethylene-propylene copolymer I asked.

Table 5 shows the results.

[0300]

Reference Example 54 The components described below were mixed using a Henschel mixer. · MPP-20 ··· 30 parts by weight · EP-1 · · · 70 parts by weight The obtained mixture is supplied to a vented twin-screw extruder (L / D = 4).
2, screw diameter 50mm) under nitrogen atmosphere using 23
0.30kW · hr / kg specific energy at 0 ° C
Pellets (composition) by melting and kneading with setting to
Was manufactured.

A test piece was prepared from the composition thus prepared as described above, and the flexural modulus and
Izod impact strength, coating test and adhesive strength were determined. Table 5 shows the results.

[0302]

Example 59 The components described below were mixed using a Henschel mixer. · MPP-21 ··· 35 parts by weight · EP-1 ··· 65 parts by weight The obtained mixture is fed into a twin-screw extruder with vent (L / D = 4).
2, screw diameter 50mm) under nitrogen atmosphere using 23
0.28 kW · hr / kg specific energy at 0 ° C
Pellets (composition) by melting and kneading with setting to
Was manufactured.

A test piece was prepared from the composition thus prepared as described above, and the flexural modulus and
Izod impact strength, coating test and adhesive strength were determined. Table 5 shows the results.

[0304]

[Table 19]

[0305]

[Table 20]

[0306]

[Table 21]

[0307]

[Table 22]

[0308]

[Table 23]

[0309]

[Table 24]

[0310]

[Table 25]

Continuation of front page (56) References JP-A-61-89235 (JP, A) JP-A-62-280267 (JP, A) JP-A-63-241036 (JP, A) JP-A-58-84838 (JP) , A) JP-B-54-40112 (JP, B1) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08L 23/00-23/36

Claims (4)

(57) [Claims] 1. A melt flow rate of 0.1 to 30 g / 1.
0 minute unmodified propylene polymer (A-1) 20-
99% by weight, modified with an ethylenically unsaturated group-containing carboxylic acid hydroxyalkyl ester, having an ethylene content of 60 to 95 mol% and a melt flow rate of 0.1 to 10 g / 10
Is a modified amorphous ethylene-propylene copolymer (B
-1) 1 to 80% by weight , the specific energy (e) represented by the following formula [I] is 0.26
Melt kneading under the conditions of ~ 0.36 kWhr / kg
The modified amorphous ethylene-propylene copolymer (B-1) is contained in the propylene-based polymer (A-1) in an amount of 0.03 to 3
propylene-based polymer composition, characterized in that dispersed with an average dispersed particle size of the [mu] m; e = Motor Power / resin extrusion amount · · · [I] 2. The ratio of the melt flow rate of the unmodified propylene-based polymer (A-1) to the melt flow rate of the modified amorphous ethylene-propylene copolymer (B-1) [M
FR (A-1) / MFR (B-1)] is 0.1 to 50. The propylene-based polymer composition according to claim 1, wherein 3. The melt flow rate is 0.1 to 30 g / 1.
0 minute unmodified propylene polymer (A-1) 20-
99% by weight, modified with an ethylenically unsaturated group-containing carboxylic acid hydroxyalkyl ester, having an ethylene content of 60 to 95 mol% and a melt flow rate of 0.1 to 10 g / 10
Is a modified amorphous ethylene-propylene copolymer (B
-1) 1 to 80% by weight, the specific energy (e) represented by the following formula [I] is 0.26
Melt kneading under the conditions of ~ 0.36 kWhr / kg
Thereby, in the propylene-based polymer (A-1),
Modified amorphous ethylene-propylene copolymer (B-1)
Disperse with an average dispersed particle diameter of 0.03 to 3 μm
A method for producing a propylene-based polymer composition characterized by obtaining a len-based polymer composition ; e = motor power consumption / resin extrusion amount [I] 4. The ratio of the melt flow rate of the unmodified propylene-based polymer (A-1) to the melt flow rate of the modified amorphous ethylene-propylene copolymer (B-1) [M
FR (A-1) / MFR (B-1)] is 0.1 to 50, the method for producing a propylene-based polymer composition according to claim 3, wherein