JPH0559132A - Propylene polymer composition and its production - Google Patents

Abstract

PURPOSE:To subject composition having a modified amorphous ethylene/ propylene copolymer dispersed therein in a specific average particle size in a specific modified propylene polymer, and having excellent adhesively to coating material such as polyurethane coatings without pre-coatings. CONSTITUTION:The objective composition produced by modifying (A) an amorphous ethylene/propylene copolymer comprising (i) 20-99wt.% of propylene polymer having a melt flow rate of 0.1-30g/10min and (ii) 1-80wt.% of an amorphous ethylene/propylene copolymer having an ethylene content of 60-95mol.% and a melt flow rate of 0.1-10g/10min with (B) a modifying agent comprising an ethylenically unsaturated group-containing carboxylic acid (anhydride) and/or an ethylenically unsaturated group-containing carboxylic acid hydroxyalkyl ester, the modified amorphous ethylene/propylene copolymer being dispersed in the modified propylene polymer in an average dispersed particle size of <=5mum.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD OF THE INVENTION 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 it is not surface-treated with a primer or a solvent.

[0002]

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

This propylene-based polymer is a resin having no polar group in the molecule and being chemically inactive and highly safe, but on the other hand, since it has no polar group, it does not contain other resins. Adhesion with is not good. For example, to coat a molded product made of a propylene-based polymer with a polyurethane-based paint or the like, an electrical treatment method such as corona discharge, a mechanical roughening method,
It is necessary to use a surface treatment method such as a flame treatment method, an oxygen treatment method, or an ozone treatment method to perform a treatment for improving the affinity of the surface of the molded product with other resins.
When performing these surface treatments, the surface of the molded article is washed with a solvent such as alcohol or aromatic hydrocarbon in advance, or with a solvent vapor such as trichlene, perchlorethylene, pentachloroethylene or toluene. The method is generally adopted.

However, in order to carry out these surface treatment methods, an apparatus for performing the treatments is required, which is disadvantageous in terms of equipment and requires a considerable amount of time for these treatments. Further, in addition to the method of coating after the above-mentioned pretreatment on the surface of the propylene-based polymer molded product, the surface of the propylene-based polymer molded product is undercoated with a primer capable of adhering to the propylene-based polymer. However, a method of applying a paint such as a polyurethane-based paint on this undercoat layer is also used, but even in this method, since the undercoating step and the topcoating step are required, the coating step takes a long time, Further, since the coating film has a two-layer structure, there is a problem that the cost of the molded product becomes high.

As described above, when coating a molded article made of a propylene-based polymer, the molded article itself is generally subjected to some treatment. Therefore, the process of coating a molded article made of a propylene-based polymer, which has been conventionally performed, becomes complicated, so that development of a propylene-based polymer excellent in coatability has been earnestly desired. As a method for improving the coatability 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. Is disclosed, and this composition is shown to have good coatability. In addition to this, there are various proposals regarding a polypropylene resin composition containing such a carboxylic acid modified product.

[0006] In order to improve the properties of such polypropylene-based resin composition, in addition to the excellent properties inherent to the base polypropylene, a further required property, that is, good coatability is required. Must be granted. However, when the characteristics of such a resin composition are examined in detail, the characteristics of the composition obtained by the order of modification and the dispersion state of the resin to be mixed,
For example, properties such as coatability and impact resistance are remarkably different, and conventionally known compositions have room for further improvement in properties such as coatability and impact resistance.

[0007]

An object of the present invention is to provide a propylene-based polymer composition in which the excellent properties inherently possessed by a propylene-based polymer are not impaired, and in particular, the paintability is excellent and the impact resistance is also improved. It is intended to provide a product and a method of manufacturing the composition.

[0008]

SUMMARY OF THE INVENTION The propylene polymer composition of the present invention comprises
The propylene-based polymer (A-1) has a melt flow rate of 0.1 to 30 g / 10 min, the ethylene content is 60 to 95 mol%, and the melt flow rate is 0.1 to 10 g / min. An unmodified propylene-based polymer composed of 1 to 80% by weight of an amorphous ethylene-propylene copolymer (B-1) for 10 minutes was treated with an ethylenically unsaturated group-containing carboxylic acid, its anhydride and ethylenically unsaturated. A composition modified with at least one modifier selected from the group consisting of hydroxyalkyl esters containing a group of carboxylic acids, wherein the modified propylene polymer (A) contains a modified amorphous ethylene-propylene copolymer. The polymer (B) is characterized by being dispersed with an average dispersed particle diameter of 5 μm or less.

The propylene-based polymer composition of the present invention has a melt flow rate of 0.1 to 30 g / 10 min, a propylene-based polymer (A-1) of 20 to 99% by weight, and an ethylene content of 60 to 95 mol. %, And an unmodified propylene-based polymer composition consisting of 1 to 80% by weight of an amorphous ethylene-propylene copolymer (B-1) having a melt flow rate of 0.1 to 10 g / 10 min. When modified with at least one modifier selected from the group consisting of a carboxylic acid containing an unsaturated unsaturated group, an anhydride thereof and a hydroxyalkyl ester of an unsaturated carboxylic acid containing an ethylenic group, the propylene polymer (A-1) And amorphous ethylene
-When preparing an unmodified propylene-based polymer composition by melt-kneading with a propylene copolymer (B-1), the following formula [I]
The specific energy (e) represented by is 0.25 kW · hr
It can be manufactured by melt-kneading under a kneading condition of / kg or more.

E = motor power consumption / resin extrusion amount ... [I] Thus, in the propylene-based polymer composition of the present invention,
For example, an unmodified composition is prepared by kneading a propylene-based polymer and a rubber component while imparting a specific energy, and the composition is modified with a specific modifier. The particles of the modified rubber component can be finely dispersed. A molded article formed from such a composition is particularly excellent in coating properties and adhesion properties, and is also excellent in properties such as impact resistance.

[0011]

DETAILED DESCRIPTION OF THE INVENTION The propylene polymer composition and the method for producing the same according to the present invention will be specifically described below. The propylene-based polymer composition according to the present invention uses an unmodified composition comprising a propylene-based polymer (A-1) and an amorphous ethylene-propylene copolymer (B-1) with a specific modifier. It can be prepared by denaturing.

Propylene Polymer (A-1) The propylene polymer (A-1) used in the present invention is
Homopolymer of propylene, or propylene and other α-
It is a copolymer with an olefin. 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
The melt flow rate (MFR) measured under the conditions of 0.
A propylene-based polymer in the range of 1 to 30 g / 10 minutes is used. Particularly, a propylene-based polymer having an MFR in the range of 0.5 to 15 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 content of propylene units in the propylene polymer (A-1) used in the present invention is usually 90 mol% or more. The boiling n-heptane-insoluble matter of the propylene polymer (A-1) is usually 90
% Or more, 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)
The density is usually in the range of 0.90 to 0.92 g / cm ³ . The propylene-based polymer (A-1) having such characteristics can be produced by various methods, but as a typical production method, it is formed from a solid titanium catalyst component and an organometallic compound component. A method using a catalyst or a catalyst formed from both components and an electron donor can be mentioned.

As the solid titanium catalyst component used in this method, titanium trichloride or a titanium trichloride composition produced by various methods, magnesium, halogen, an electron donor, preferably an aromatic carboxylic acid ester or There is a titanium catalyst component which has 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. A propylene-based polymer produced by using the latter catalyst component with a carrier is particularly preferable.

The organometallic compound component is preferably an organoaluminum compound, and 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 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, and an ester compound and an ether compound having the above atoms are preferable. As an example: Regarding the method for producing a propylene-based polymer using the catalyst component with a carrier as described above, for example, JP-A Nos. 50-108385, 50-126590, 51-20297, and 51-20297.
No. 28189 and No. 52-151691, etc., and the techniques described in these publications can be used in the present invention.

Amorphous ethylene-propylene copolymer (B
-1) Amorphous ethylene-propylene copolymer (B-1) used for producing the propylene polymer composition according to the present invention
Is a copolymer rubber (B-1) in which ethylene and propylene are randomly copolymerized. This amorphous ethylene
-The content of the repeating unit derived from ethylene in the propylene copolymer (B-1) is in the range of 60 to 95 mol%, preferably 70 to 90 mol%. Therefore, the content of the repeating unit derived from propylene in this copolymer (B-1) is 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-1).

Further, 230 of this copolymer (B-1)
The melt flow rate (MFR) measured under the conditions of ° C and a load of 2.16 kg is in the range of 0.1 to 10 g / 10 minutes, preferably 0.1 to 4 g / 10 minutes. By using such a copolymer (B-1), the composition has good moldability. This copolymer (B-1)
Is amorphous and has a crystallinity measured by an X-ray diffraction method,
It is usually 40% or less, preferably 20% or less, and is a copolymer having relatively low crystallinity. That is, the amorphous ethylene-propylene copolymer (B-
1) 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 composed of a soluble vanadium compound and an alkylaluminum halide compound. .. Examples of the polymerization catalyst that can be used in this method include vanadium tetrachloride,
Examples thereof include vanadium oxytrichloride, vanadium triacetyl acetate, oxyvanadium triacetyl acetate and the like.

Examples of the alkylaluminum halide compound which constitutes the catalyst for polymerization in combination with the soluble vanadium compound include, for example, ethylaluminum dichloride, diethylaluminum monochloride, ethylaluminum sesquichloride, diethylaluminum monobromide, diisobutylaluminum monochloride, isobutyl. Aluminum dichloride and isobutylaluminum sesquichloride can be mentioned.

The copolymerization reaction using the above-mentioned catalyst can be carried out in the form of a solution or suspension or an intermediate region between them, and in any case, an inert solvent is preferably used as a reaction medium (solvent). It As such a copolymerization reaction medium, an aliphatic hydrocarbon or a halogenated hydrocarbon having about 3 to 12 carbon atoms is usually used. Specific examples of the aliphatic hydrocarbon used as a 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 the 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 using the above catalyst is usually 0 to 100 ° C.

Unmodified propylene-based polymer composition In the present invention, an unmodified propylene-based polymer is prepared from the above-mentioned propylene-based polymer (A-1) and amorphous ethylene-propylene copolymer (B-1). A coalescing composition is prepared. This unmodified propylene-based polymer composition comprises 20 to 99% by weight of the propylene-based polymer (A-1) as described above and an amorphous ethylene-propylene copolymer (B-1).
1 to 80% by weight. Further, the content of the propylene polymer (A-1) is 55 to 85% by weight, and the content of the amorphous ethylene-propylene copolymer (B-1) is 15 to 85% by weight.
It is preferable to mix both components so as to be in the range of 45% by weight. The total amount of both components is 100.
% By weight.

Further, the propylene polymer (A-
Ratio [MFR (A-1) / MFR] of MFR of 1) and MFR of amorphous ethylene-propylene copolymer (B-1)
(B-1)] is in the range of 0.1 to 200,
It is preferable to use the propylene polymer (A-1) and the amorphous ethylene-propylene copolymer (B-1) in combination, and particularly to combine both components so as to be in the range of 0.5 to 100. Preferably. By combining both components so that the MFR ratio is as described above, the dispersion state of each component in the composition becomes good.

Such a propylene polymer (A-1)
And amorphous ethylene-propylene copolymer (B-1) are mixed, if necessary, by melt-kneading,
An unmodified propylene-based polymer composition can be prepared. A known mixer such as a Henschel mixer can be used for this mixing.

The mixture of the propylene polymer (A-1) thus prepared and the amorphous ethylene-propylene copolymer (B-1) is melt-kneaded to obtain an unmodified propylene polymer composition. Upon preparation, melt kneading is performed while imparting a specific energy. In this melt-kneading, 0.25 kW · hr / kg or more, preferably 0.2
5 to 0.4 kW · hr / kg, more preferably 0.2
The specific energy (e) within the range of 5 to 0.36 kW · hr / kg is imparted. By melt-kneading under such conditions, the amorphous ethylene-propylene copolymer (B-1) forms fine particles and is dispersed in the propylene-based polymer (A-1).

Here, the specific energy (e) is the amount of energy per unit volume used for crushing the agglomerates, and can be expressed by the following formula [I]. e = motor power consumption / resin extrusion amount ... [I] This specific energy (e) is described in detail in Kohei Ito, Plastics, 36 , No. 7 37 (1988).

As a kneading device used in the production of the propylene polymer composition according to the present invention, an ordinary olefin-based compound can be used as long as it is a device capable of melt-kneading while imparting the specific energy (e) as described above. A known kneading device utilized in the field of polymers can be used.
Examples of the kneading device that can be used for producing the composition of the present invention include an extruder, a mixing roll, a Banbury mixer and a kneader.

The heating temperature at the time of melt-kneading using the kneading apparatus as described above can be appropriately set within the range of not lower than the melting point of the raw material used and not higher than the decomposition temperature, but usually 170 to 350 ° C, preferably 180-2
The temperature is set within the range of 50 ° C. The propylene-based polymer (A-1) and the amorphous ethylene-propylene copolymer (B-1) are mixed so as to be within the above composition ratio, and the mixture is melt-kneaded. In addition to this, a part of the composition components may be kneaded in advance to produce a so-called masterbatch, and the masterbatch and the remaining composition components may be mixed.

Propylene-Based Polymer Composition The propylene-based polymer composition according to the present invention is a composition obtained by modifying the unmodified propylene-based polymer composition prepared as described above with a specific modifier. is there. The modifier used for modifying the unmodified propylene-based polymer composition is at least one selected from an ethylenically unsaturated group-containing carboxylic acid, an anhydride thereof or an ethylenically unsaturated group-containing carboxylic acid hydroxyalkyl ester. It is a kind of modifier.

Examples of the ethylenically unsaturated group-containing carboxylic acid or acid anhydride thereof used in the present invention include:
For example, (meth) acrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, norbornene dicarboxylic acid and bicyclo [2,2,1] hept-2-ene-5,6-dicarboxylic acid. An unsaturated carboxylic acid such as an acid or an acid anhydride thereof may be mentioned.

Specific examples of the ethylenically unsaturated group-containing carboxylic acid hydroxyalkyl ester include 2
-Hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 3-chloro-2-hydroxyacrylate, 3-chloro-2- Hydroxy methacrylate, 2-hydroxy-3-phenoxypropyl acrylate and 2
-Hydroxy-3-phenoxypropyl methacrylate may be mentioned.

Of the above compounds, the most preferable are
Examples thereof include acrylic acid, methacrylic acid, maleic acid, fumaric acid, maleic anhydride, 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate. These modifiers can be used alone or in combination. When modifying the unmodified propylene-based polymer composition, in addition to the above-mentioned modifier, styrene and α-methylstyrene are used as long as the characteristics of the propylene-based polymer composition of the present invention are not impaired. And other polymerizable aromatic compounds can be used in combination.

The unmodified propylene polymer composition as described above is preferably modified in the presence of a radical initiator. As such a radical initiator, 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)
Peroxyketals such as octane, n-butyl-4,4-bis (t-butylperoxy) paralate and 2,2-bis (t-butylperoxy) butane; di-t-butylperoxide, dicumyl Peroxide, t-butylcumyl peroxide, α, α'-bis (t-butylperoxy-m-isopropyl) benzene, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane and 2 Dialkyl peroxides such as 5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3;
Acetyl peroxide, isobutyryl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide and m- Diacyl peroxides such as trioyl peroxide; t-butyl peroxyacetate, t-
Butyl peroxyisobutyrate, t-butyl peroxy-2-ethylhexanoate, t-butyl peroxylaurylate, t-butyl peroxybenzoate, di-
t-butylperoxyisophthalate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, t-
Butyl peroxy maleic acid, peroxy esters such as t-butyl peroxy isopropyl carbonate and cumyl peroxy octate; and
t-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide and 1,1,3,3-tetramethylbutyl hydroperoxide Hydroperoxides can be mentioned.

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

Specific examples of the azo compound used as the radical initiator include azoisobutyronitrile. Such radical initiators can be used alone or in combination. In the above modification, the modifier such as carboxylic acid containing an ethylenically unsaturated group is usually 0.01 to 50 parts by weight, preferably 0.1 to 50 parts by weight with respect to 100 parts by weight of the unmodified propylene polymer composition. Used in an amount of 1 to 40 parts by weight.

The radical initiator is usually 0.0 to 100 parts by weight of the unmodified propylene polymer composition.
It is used in an amount of 1 to 10 parts by weight, preferably 0.05 to 8 parts by weight. Furthermore, when a polymerizable aromatic compound is used, the polymerizable aromatic compound is usually added in an amount of 0.01 to 100 parts by weight of the unmodified propylene-based polymer composition.
It is used in an amount of -50 parts by weight, preferably 0.1-40 parts by weight.

As a method for modifying the unmodified propylene-based polymer composition with the modifier as described above, the unmodified propylene-based polymer composition is modified with a modifier, and optionally a radical initiator and a polymerizable aromatic compound. A method of adding and melt-kneading, an unmodified propylene-based polymer composition containing a modifier and optionally a radical initiator and a polymerizable aromatic compound, and the unmodified propylene-based polymer composition is in a solid state. It is possible to use a method of heating and denaturing at a temperature that can be maintained.

The method for producing the propylene-based polymer composition of the present invention by melt-kneading is as follows: the unmodified propylene-based polymer composition prepared as above and a modifier.
Further, it is a method of kneading a radical initiator and a polymerizable aromatic compound under specific conditions, if necessary. At the time of this melt-kneading, it is within the range of 0.25 kW · hr / kg or more, preferably 0.25 to 0.4 kW · hr / kg, and more preferably 0.25 to 0.36 kW · hr / kg. Specific energy (e) can be imparted and melt-kneaded. By melt-kneading under such conditions, the propylene polymer (A-1) and the amorphous ethylene-propylene copolymer (B-1) are modified, and the modified propylene polymer (A) and the modified propylene polymer (A) are respectively modified. Amorphous ethylene-propylene copolymer (B) is obtained, and the modified propylene-based polymer (A) in the composition is modified amorphous ethylene-
The propylene copolymer (B) can be dispersed more finely.

Here, the specific energy (e) is defined by the formula shown in the above [I]. As the kneading device used when the propylene polymer composition of the present invention is produced by melt kneading, a known kneading device used in the field of ordinary olefin polymers can be used. As a kneading device used for melt kneading while imparting the above specific energy (e), for example, an extruder, a mixing roll, a Banbury mixer, a kneader and the like can be mentioned.

For example, the heating temperature at the time of melt-kneading using the above-mentioned kneading device can be appropriately set within the range of not lower than the melting point of the raw material used and not higher than the decomposition temperature. 170-350 ° C, preferably 1
The temperature is set within the range of 80 to 250 ° C. In the present invention, at least when preparing an unmodified propylene-based polymer composition or when introducing a modifying group into the unmodified propylene-based polymer composition by blending a modifier and melt-kneading. The melt-kneading may be performed while imparting the above-mentioned specific energy in any stage, and the melt-kneading may be performed while imparting the above-mentioned specific energy in both stages.

As another modification method that can be adopted when producing the propylene-based polymer composition of the present invention from the unmodified propylene-based polymer composition, a modifying agent and optionally a radical initiator and a polymerizable aromatic compound can be used. There is a method of modifying an unmodified propylene-based polymer composition containing a compound by heating it to a temperature at which the unmodified propylene-based polymer composition can maintain a solid state.

In this method, an unmodified propylene polymer composition (usually formed into pellets) prepared as described above, a modifier, and if necessary, a radical initiator and a polymerizable aromatic are added. In this method, the compound is blended, and the unmodified propylene-based polymer composition pellets are heated to a temperature at which the shape of the pelletized unmodified propylene-based polymer composition is maintained. In this method, the heating temperature may be equal to or lower than the melting point of the unmodified propylene-based polymer composition, and is usually in the range of melting point to a temperature 100 ° C. lower than the melting point, preferably in the range of 70 to 140 ° C. Is set. The reaction time can be appropriately set in consideration of the heating temperature, but is usually 0.1 to 10 hours.

In such modification, it is preferable to add a small amount of an organic solvent to carry out the modification reaction. That is, since the pellet swells to some extent by using a small amount of the organic solvent, the modifying agent or the like can penetrate into the inside of the pellet to uniformly modify the unmodified propylene polymer composition. Therefore, the organic solvent used here does not excessively dissolve the unmodified propylene-based polymer composition, and has a solubility that allows the unmodified propylene-based polymer composition to swell to some extent. An organic solvent having is used.

Specific examples of such an organic solvent include aromatic hydrocarbon solvents such as benzene, toluene and xylene; aliphatic hydrocarbon solvents such as pentane, hexane, heptane, octane, nonane and decane. Solvents; cycloaliphatic hydrocarbon solvents such as cyclopentene, cyclohexane and decahydronaphthalene; chlorine solvents such as chlorobenzene, dichlorobenzene, methylene chloride, chloroform and carbon tetrachloride; acetone, methyl ethyl ketone and methyl isobutyl ketone Ketone-based solvents; and alcohols such as ethanol and methanol can be used, and it is also possible to use other solvents having an action equivalent to these.

Such an organic solvent is used in an amount of usually 50 parts by weight or less, preferably 20 parts by weight or less, based on 100 parts by weight of the unmodified propylene polymer composition to be modified. In the present invention, when the method of modifying the unmodified propylene-based polymer composition in the solid state as described above is adopted, the specific energy is imparted when the unmodified propylene-based polymer composition is produced. However, it is necessary to melt and knead.

In producing the propylene-based polymer composition of the present invention, all of the unmodified propylene-based polymer composition is used and modified so that the composition has the above-mentioned modification amount. In addition to this, a part of the unmodified propylene-based polymer composition is modified in advance at a high concentration to produce a so-called masterbatch, and this masterbatch and the remaining unmodified propylene-based polymer composition are used. The combined composition may be mixed to adjust the modification amount within the above range.

In the propylene polymer composition according to the present invention, the modified amorphous ethylene-propylene copolymer (B) has an average dispersed particle size of 5 μm or less in the modified propylene polymer (A). It is finely dispersed to form a so-called polymer alloy. Further, it is preferable that the average dispersed particle diameter is within the range of 0.03 to 3 μm,
It is particularly preferable that it is in the range of 0.05 to 2 μm.
Thus, by finely dispersing the modified amorphous ethylene-propylene copolymer (B) in the modified propylene-based polymer (A), impact resistance is improved and coatability is improved. The average dispersed particle size of the modified amorphous ethylene-propylene copolymer (B) is the modified amorphous ethylene-propylene copolymer (B) in which the fracture surface of the core of the test piece is observed by an electron microscope and dispersed. Is an average value calculated from the measured values. When an inorganic filler is added to the propylene-based polymer composition of the present invention, it may be difficult to confirm the dispersed particle size of the modified amorphous ethylene-propylene copolymer (B) by an electron microscope. In some cases, the dispersed particle size of the modified amorphous ethylene-propylene copolymer (B) in the composition prepared under the same conditions without adding the inorganic filler may be within the above range.

The melt flow rate (MFR) of the propylene polymer composition of the present invention as measured under a load of 2.16 kg and 230 ° C. is usually 0.5 to
The Izod impact strength at -30 ° C of a test piece (notched) having a thickness of 1/8 inch, measured according to ASTM D-256, was in the range of 30 g / 10 minutes, often 1 to 20 g / 10 minutes. , Usually 3-60kg / cm
-Cm, in most cases 5 to 30 kg / cm-cm. In addition, the flexural modulus (FM) of a 1/8 inch thick test piece, measured according to ASTM D-790, is usually 5,000 to 17,000 kg / m ² , often 6,000 to 12,000 kg. Within the range of / m ² .

The propylene polymer composition according to the present invention is basically a composition comprising the modified propylene polymer (A) and the modified amorphous ethylene-propylene copolymer (B), Further, other resins or additives can be added 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, propylene-1-butene copolymer. Copolymers, propylene-1-butene-ethylene copolymers, styrene-butadiene (-styrene) block copolymers and hydrogenated products thereof, styrene-isoprene (-styrene) block copolymers and hydrogenated products thereof, etc. You can

Further, examples of other additives which can be blended in the present invention include antioxidants, ultraviolet absorbers, lubricants, nucleating agents, antistatic agents, flame retardants, pigments, dyes, plasticizers, and electric agents. Mention may be made of physical property modifiers, 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 oxides, hydroxides, sulfates, carbonates and silicates thereof. Furthermore, talc, mica, silica, glass fibers and graphite can be mentioned. These other resins or additives can be blended when preparing the propylene-based polymer composition according to the present invention, or are added after the propylene-based polymer composition according to the present invention is prepared. You can also

Molded Product The propylene-based polymer composition of the present invention obtained as described above is usually molded into pellets and is generally used in the field of thermoplastic resins, for example, injection molding. Alternatively, an extrusion molding method or the like can be adopted to produce a molded product having a desired shape.

The temperature at the time of this molding is higher than the melting point of the propylene polymer composition used, and
Can be set to a temperature within the pyrolysis temperature,
Generally from 170 to 300 ° C, preferably from 180 to 250
It is set within the range of ° C. The molded product formed from the propylene-based polymer composition of the present invention has excellent affinity with other resins. Therefore, the molded body formed from the propylene-based polymer composition of the present invention has hitherto been considered to be an indispensable step when coating a molded body formed from a propylene-based resin. Even if the steam cleaning step with a chlorine-based solvent such as 1-trichloroethane is omitted, the adhesion of the coating film is very good. Further, this molded product also has very good adhesion of the coating film without the primer treatment.

Solvent-based paints, water-based paints and solvent-free paints can be used for coating the molded articles formed from the propylene polymer composition of the present invention. Examples of the above solvent-based paints include alkyd resin-based paints, aminoalkyd resin-based paints, vinyl resin-based paints, room temperature dry acrylic resin-based paints, baking dry acrylic resin-based paints, tar-epoxy epoxy resin paints, and varnishes. -Enamel type epoxy resin-based paint, one-component urethane resin-based paint, multi-component urethane resin-based paint, unsaturated polyester resin-based paint and chlorinated rubber-based paint can be mentioned.

Further, examples of the above water-based paint include emulsion paints and water-soluble resin paints. Further, examples of the above solventless paint include powder paint and traffic paint.
In particular, solvent-based paints are suitable for coating molded articles formed from the propylene-based polymer composition according to the present invention, and among them, the affinity with urethane resin-based paints is good. Urethane resin paints are generally paints that form a coating film by reacting a polyisocyanate and a polyol compound, and there are one-pack type and two-pack type. There are oil-modified urethane paints, and there are also powder paints using blocked isocyanates. The molded product made of the propylene-based polymer composition according to the present invention has good affinity with any of the urethane resin-based paints described above.

Among the urethane resin type paints as described above,
For example, a coating method using a one-component urethane resin-based paint will be described by way of an example. First, a molded body formed from the propylene-based polymer composition of the present invention,
Washing with water and washing with a general industrial detergent are carried out at least once, respectively, and further washed with water and then dried by heating. That is, when coating a molded product 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.

Next, a urethane resin coating film can be formed by applying a one-pack type urethane resin coating material to the molded product dried as described above and heating it as necessary. The coating film formed in this way has very good adhesion to the molded product, even though it is not washed (surface treated) with chlorine-based solvent vapor. As described above, the molded article formed from the propylene-based polymer composition of the present invention has a good adherence property, and various adhesives can be adhered without performing the primer treatment or the washing with the solvent as described above. It shows a good affinity for the agent.

Examples of the adhesive that can be used for adhering this molded product include urea resin adhesives, melamine resin adhesives, phenol resin adhesives, epoxy resin adhesives, and vinyl acetate solvent adhesives. Agent, polyurethane resin adhesive, α-olefin-maleic anhydride resin adhesive, water-based polymer-isocyanate adhesive, reactive acrylic resin adhesive, UV 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 type adhesives such as ethylene-vinyl acetate copolymer resin emulsion type adhesives and acrylic emulsion type adhesives; vinyl acetate type hot melt type adhesives, elastomer type hot melt type adhesives and polyamide type hot melt type adhesives. Hot melt type adhesives such as agents; and synthetic rubber type adhesives such as chloroprene type synthetic rubber type adhesives and synthetic rubber type latex type adhesives.

As a bonding method using such an adhesive, a conventionally used method can be adopted. In such an adhesive method, desired adhesive strength is exhibited even when the primer treatment or the organic solvent vapor cleaning is not particularly performed. Utilizing the above characteristics, the resin composition of the present invention is used for automobile parts, motorcycle parts, electric device parts, daily necessities, vending machine parts, civil engineering building materials, general industrial materials, office information equipment, packaging materials, It can be widely used for applications such as sports equipment, medical equipment, and parts related to nuclear power, to which painting is applied, or applications where they are adhered.

[0062]

The propylene polymer composition according to the present invention is obtained by modifying an unmodified propylene polymer composition in which particles of a rubber component are finely dispersed in a propylene polymer with a specific modifier. A polar group is introduced into both components. Then, by setting the melt-kneading conditions in any of the kneading steps carried out for producing the propylene-based polymer composition of the present invention within a specific range, the dispersed particle diameter of the modified rubber component in the composition Can be controlled. By controlling the particle size of the modified rubber component in this manner, the coatability and adherence of the resin composition are particularly improved. Furthermore, such improved properties do not impair the excellent properties such as the flexural modulus inherently possessed by the modified propylene polymer. In particular, since the propylene-based polymer composition of the present invention has excellent adhesion to polyurethane, it is possible to directly apply the urethane paint to the surface of the molded product.

[0063]

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-based polymer composition of the present invention were measured as follows. (1) MFR MFR has a load of 2.1 in accordance with ASTM D-1238.
The measurement was performed under the conditions of 6 kg and a temperature of 230 ° C.

(2) Grafting amount The polymer after the reaction was dissolved in p-xylene at 130 ° C., allowed to cool and then precipitated with acetone to remove unreacted substances for purification. The grafted amount of the purified polymer was calculated from the result of oxygen analysis. (3) Izod impact strength (with notch) (Iz) The Izod impact strength was measured at -30 ° C according to ASTM D-256 using a test piece having a thickness of 1/8 inch.

(4) Flexural Modulus (FM) The flexural modulus was measured using a test piece having a thickness of 1/8 inch
It was measured according to STM D-790. (5) Coating test In the present invention, the coating property was evaluated by a cross-cut test and a peel strength test of a coating film formed by applying a one-pack type urethane paint 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-component urethane-based paint Flexen No. 105 [trade name, manufactured by Nippon Bee Chemical Co., Ltd.] ・ Dry film thickness 60 μm ・ Baking 120 ° C., 30 minutes In addition, what is not mentioned in the examples is 1 Steam cleaning with 1,1,1-trichloroethane was performed.

Cross-cut test According to the method of the cross- cut test described in JIS K 5400, a cross- cut test piece was prepared, and a cellophane tape (manufactured by Nichiban Co., Ltd., trade name) was applied to the test piece. After sticking to the surface of the film, it was quickly pulled in the direction of 90 ° to be peeled off, and the number of crosses remaining on the test piece was counted and used as an index of the adhesiveness.

Peel Strength Test A coating film was prepared on a base material, a 1 cm width was cut with a cutter blade until the blade reached the base material, and the edges were peeled off.
180 at the speed of 50 mm / min.
The peel strength was measured by pulling in the direction of ° until the coating film peeled. (6) Adhesion test The evaluation of the adhesiveness in the present invention is performed by adhering a test piece and a cloth to the test piece prepared in the following manner using the adhesive shown below to form a cross-cut test and peeling of the adhesive layer. The strength test was performed.

Preparation of Test Pieces Aqueous dispersion of styrene / acrylonitrile / ethylhexyl acrylate / ethyl acrylate / n-butyl acrylate copolymer (molar ratio: 35/35/13/15/7) [trade name, Yodozole, manufactured by Kanebo NSC Ltd.] 2
It was applied so that the amount would be 00 g / m ^2, and the cloth was lightly placed on it and pressed by hand, followed by drying in an air oven at 100 ° C. for 30 minutes.

Peel strength test After 1 hour of drying, the peel strength was measured using a tensile tester at a pulling speed of 50 mm / min so as to peel the cloth in the direction of 180 °. Cross- cut test According to the method of the cross-cut test described in JIS K 5400, a cross-cut test piece was prepared, and after sticking cellotape [Nichiban Co., Ltd., trade name] on the test piece, This was rapidly pulled in the direction of 90 ° for peeling, and the number of remaining grids was counted and used as an index of adhesion.

(7) Particle size of dispersed phase The particle size of dispersed phase was determined from an electron micrograph image of the fracture surface of the core portion of the test piece.

[0072]

Example 1 The ingredients described below were mixed in a Henschel mixer. Polypropylene ... 65 parts by weight (propylene homopolymer, MFR: 0.3 g / 10 min, density: 0.91 g / cm ³⁾ (hereinafter, abbreviated as "PP-1"), an amorphous ethylene - propylene copolymer Polymer: 35 parts by weight (ethylene content: 81 mol%, MFR: 0.7 g / 10 minutes) (hereinafter, abbreviated as "EP-1") The obtained mixture was a twin-screw extruder with a vent (L / D = 4
2, screw diameter 50mm) under nitrogen atmosphere 200
The unmodified propylene-based polymer composition (hereinafter,
"Abbreviated as" PEP-1 ").

The MFR of this PEP-1 and the flexural modulus, Izod impact strength, coating test, adhesive strength and unmodified amorphous ethylene-propylene copolymer measured on the test piece prepared using this PEP-1. The particle size of the dispersed phase was measured. The results are shown in Table 1.

[0074]

[Table 1]

Next, the components described below were mixed in a Henschel mixer.・ PEP-1 ・ ・ ・ 100 parts by weight ・ Maleic anhydride (hereinafter abbreviated as "MAH") ・ ・ ・ 1.2 parts by weight ・ 2,5-Dimethyl-2,5-bis (t-butylperoxy) Hexin-3: 0.03 parts by weight (hereinafter, abbreviated as "PO-1") This mixture is mixed with a vented twin-screw extruder (L / D = 42,
Pellets (modified propylene polymer composition) were produced by melt-kneading at a temperature of 200 ° C. in a nitrogen atmosphere using a screw diameter of 30 mm). The graft amount of maleic anhydride in this composition was 1.0% by weight.

The MFR, flexural modulus, Izod impact strength, coating test result, adhesion test result, and dispersed particle size of the rubber component of the obtained maleic anhydride-modified propylene polymer composition were measured. The results are shown in Table 2.

[0077]

[Table 2]

The above results are also shown in Table 3.

[0079]

[Examples 2 to 4] In Example 1, the specific energy was 0.29 kW · hr / kg (Example 2), 0.30 kW.
-Hr / kg (Example 3), 0.27 kW-hr / kg
In the same manner as in Example 1 except that (Example 4) was used,
An unmodified propylene polymer composition was obtained.

Then, in Example 1, except that the compounding amounts of MAH and PO-1 were changed as shown in Table 3,
A modified propylene-based polymer composition was obtained in the same manner as in Example 1. A test piece was prepared from the thus-prepared modified propylene-based polymer composition as described above, and using this test piece, flexural modulus, Izod impact strength, coating test, adhesive strength and modified amorphous ethylene-propylene copolymer weight were used. The dispersed phase particle size of the coalescence was determined.

The results are shown in Table 3.

[0082]

Examples 5-7 In Example 1, PP-1 and E
The compounding amount of P-1 was changed as shown in Table 3, and the specific energy was 0.25 kW · hr / kg (Example 5),
0.28 kW · hr / kg (Example 6), 0.31 kW
-Unmodified propylene-based polymer composition (hereinafter, referred to as "Example 1") except that it was changed to hr / kg (Example 7).
"PEP-2 to 4"), and further a modified propylene-based polymer composition was obtained.

From the modified propylene polymer composition thus prepared, a test piece was prepared as described above, and the flexural modulus, Izod impact strength, coating test, adhesive strength and modified amorphous ethylene- were used. The dispersed phase particle size of the propylene copolymer was determined. The results are shown in Table 3.

[0084]

Example 8 The ingredients described below were mixed in a Henschel mixer. Polypropylene ... 62 parts by weight (propylene homopolymer, MFR: 3.0 g / 10 min, density: 0.91 g / cm ³⁾ (hereinafter, abbreviated as "PP-2"), an amorphous ethylene - propylene copolymer Polymer: 38 parts by weight (ethylene content: 81 mol%, MFR: 0.4 g / 10 minutes) (hereinafter, abbreviated as "EP-2") The obtained mixture was a twin-screw extruder with a vent (L / D = 4
2, screw diameter 50mm) under nitrogen atmosphere 200
Specific energy of 0.27kW · hr / kg at temperature of ℃
And melt-kneaded to produce an unmodified propylene-based polymer composition (hereinafter abbreviated as "PEP-5").

Next, the components described below were mixed using a Henschel mixer. -PEP-5 ... 100 parts by weight 2-hydroxypropyl acrylate (hereinafter abbreviated as "HPA") ... 1.5 parts by weight PO-1 ... 0.03 parts by weight Twin screw extruder with vent (L /
Pellets (modified propylene-based polymer composition) were produced while melt-kneading at a temperature of 200 ° C. under a nitrogen atmosphere using D = 42, screw diameter 30 mm). H of this composition
The grafted amount of PA was 1.2% by weight.

Test pieces were prepared from the modified propylene polymer composition thus prepared as described above, and flexural modulus, Izod impact strength, coating test, adhesive strength and modified amorphous ethylene- were used. The dispersed phase particle size of the propylene copolymer was determined. The results are shown in Table 3.

[0087]

[Examples 9 to 11] In Example 8, the specific energies were 0.29 kW · hr / kg (Example 9) and 0.30 kW.
-Hr / kg (Example 10), 0.029 kW-hr /
An unmodified propylene-based polymer composition was obtained in the same manner as in Example 8 except that the amount was changed to kg (Example 11).

Then, in Example 8, except that the compounding amounts of HPA and PO-1 were changed as shown in Table 3,
A modified propylene polymer composition was obtained in the same manner as in Example 8. A test piece was prepared from the thus-prepared modified propylene-based polymer composition as described above, and using this test piece, flexural modulus, Izod impact strength, coating test, adhesive strength and modified amorphous ethylene-propylene copolymer weight were used. The dispersed phase particle size of the coalescence was determined.

The results are shown in Table 3.

[0090]

Examples 12 to 14 Unmodified propylene-based polymer was prepared in the same manner as in Example 8 except that the compounding amounts of PP-2 and EP-2 and the specific energy were changed as shown in Table 3. A combined composition (hereinafter abbreviated as "PEP-6-8") was produced. A modified propylene-based polymer composition was obtained in the same manner as in Example 8 except that this unmodified propylene-based polymer composition (PEP-6 to 8) was used.

From the modified propylene-based polymer composition thus prepared, a test piece was prepared as described above, and this test piece was used to flexural modulus, Izod impact strength, coating test, adhesive strength and modified amorphous ethylene- The dispersed phase particle size of the propylene copolymer was determined. The results are shown in Table 3.

[0092]

Examples 15 to 18 PP-1 and EP-2 were mixed with a Henschel mixer in a mixing ratio shown in Table 3, and then a twin-screw extruder with a vent (L / D = 42, screw diameter 50) was used.
mm) in a nitrogen atmosphere at a temperature of 200 ° C. at a specific energy shown in Table 3 to melt-knead the unmodified propylene polymer composition (hereinafter, “PEP-9 to 1”).
2 ").

Next, the components described below were mixed in a Henschel mixer. PEP-9-12 (corresponding to Examples 15-18, respectively): 100 parts by weight HEA: 1.5 parts by weight PO-1: 0.03 parts by weight This mixture was vented 2 Pellets (modified propylene-based polymer composition) were produced by melt-kneading at a temperature of 200 ° C. in a nitrogen atmosphere using a shaft extruder (L / D = 42, screw diameter 30 mm). The amount of HEA grafted in this composition was 0.6% by weight (Example 15) and 0.
7 wt% (Example 16), 0.8 wt% (Example 1)
7) and 1.4% by weight (Example 18).

A test piece was prepared from the modified propylene-based polymer composition thus prepared as described above, and the flexural modulus, Izod impact strength, coating test, adhesive strength and modified amorphous ethylene- were used. The dispersed phase particle size of the propylene copolymer was determined. The results are shown in Table 3.

[0095]

Example 19 The ingredients described below were mixed in a Henschel mixer. -PP-1 ... 65 parts by weight-EP-2 ... 35 parts by weight The obtained mixture was mixed with a vented twin-screw extruder (L / D = 4).
2, screw diameter 50mm) under nitrogen atmosphere 200
The unmodified propylene-based polymer composition (hereinafter,
"Abbreviated as" PEP-13 ") was manufactured.

The ingredients described below were mixed in a Henschel mixer.・ PEP-13 ・ ・ ・ 100 parts by weight ・ Acrylic acid (hereinafter abbreviated as "AA") ・ ・ ・ 1.4 parts by weight ・ PO-1 ・ ・ ・ 0.03 parts by weight The obtained mixture was vented 2 Axial extruder (L / D = 4
2, under a nitrogen atmosphere using a screw diameter of 30 mm)
Pellets (modified propylene-based polymer composition) were produced by melt-kneading at a temperature of ° C. AA of this composition
The graft amount was 1.1% by weight.

A test piece was prepared from the modified propylene polymer composition thus prepared as described above, and the flexural modulus, Izod impact strength, coating test, adhesive strength and modified amorphous ethylene- were used. The dispersed phase particle size of the propylene copolymer was determined. The results are shown in Table 3.

[0098]

Example 20 The ingredients described below were mixed in a Henschel mixer.・ PEP-13 ・ ・ ・ 100 parts by weight ・ Methacrylic acid (hereinafter abbreviated as "MA") ・ ・ ・ 1.5 parts by weight ・ PO-1 ・ ・ ・ 0.03 parts by weight The obtained mixture was vented 2 Axial extruder (L / D = 4
2, under a nitrogen atmosphere using a screw diameter of 30 mm)
Pellets (modified propylene-based polymer composition) were produced by melt-kneading at a temperature of ° C. MA of this composition
The amount of grafts was 0.8% by weight.

Test pieces were prepared from the thus-prepared modified propylene-based polymer composition as described above, and the flexural modulus, Izod impact strength, coating test, adhesive strength and modified amorphous ethylene- were used. The dispersed phase particle size of the propylene copolymer was determined. The results are shown in Table 3.

[0100]

Example 21 The ingredients described below were mixed in a Henschel mixer. -PEP-4: 100 parts by weight 2-Hydroxyethyl methacrylate (hereinafter abbreviated as "HEMA"): 1.4 parts by weight-PO-1: 0.03 parts by weight Vented mixture obtained Twin screw extruder (L / D = 4
2, under a nitrogen atmosphere using a screw diameter of 30 mm)
Pellets (modified propylene-based polymer composition) were produced by melt-kneading at a temperature of ° C. HE of this composition
The graft amount of MA was 1.0% by weight.

A test piece was prepared from the modified propylene polymer composition thus prepared as described above, and the flexural modulus, Izod impact strength, coating test, adhesive strength and modified amorphous ethylene- were used. The dispersed phase particle size of the propylene copolymer was determined. The results are shown in Table 3.

[0102]

Example 22 The ingredients described below were mixed in a Henschel mixer. -PP-1 ... 70 parts by weight-EP-1 ... 30 parts by weight The obtained mixture was mixed with a vented twin-screw extruder (L / D = 4).
2, screw diameter 50mm) under nitrogen atmosphere 200
The unmodified propylene-based polymer composition (hereinafter,
"Abbreviated as" PEP-14 ") was manufactured.

The ingredients described below were mixed in a Henschel mixer.・ PEP-14 ・ ・ ・ 100 parts by weight ・ HEMA ・ ・ ・ 1.4 parts by weight ・ PO-1 ・ ・ ・ 0.03 parts by weight The obtained mixture was mixed with a vented twin-screw extruder (L / D = 4).
2, under a nitrogen atmosphere using a screw diameter of 30 mm)
Pellets (modified propylene-based polymer composition) were produced by melt-kneading at a temperature of ° C. AA of this composition
The amount of grafts was 0.8% by weight.

Test pieces were prepared from the modified propylene-based polymer composition thus prepared as described above, and the flexural modulus, Izod impact strength, coating test, adhesive strength and modified amorphous ethylene- were used. The dispersed phase particle size of the propylene copolymer was determined. The results are shown in Table 3.

[0105]

Example 23 The ingredients described below were mixed in a Henschel mixer. -PP-2 ... 75 parts by weight-EP-1 ... 25 parts by weight The obtained mixture was mixed with a vented twin-screw extruder (L / D = 4).
2, screw diameter 50mm) under nitrogen atmosphere 200
The unmodified propylene-based polymer composition (hereinafter,
"Abbreviated as" PEP-15 ") was manufactured.

The ingredients described below were mixed in a Henschel mixer. -PEP-15: 100 parts by weight 2-Hydroxypropyl methacrylate (hereinafter abbreviated as "HPMA"): 1.7 parts by weight-PO-1: 0.03 parts by weight Vented mixture obtained Twin screw extruder (L / D = 4
2, using a screw diameter of 30 mm) under a nitrogen atmosphere 230
Melt kneading was performed at a temperature of ° C to produce pellets (modified propylene-based polymer composition). The HPMA graft amount of this composition was 0.9% by weight.

Test pieces were prepared from the thus-prepared modified propylene polymer composition as described above, and the flexural modulus, Izod impact strength, coating test, adhesive strength and modified amorphous ethylene- were used. The dispersed phase particle size of the propylene copolymer was determined. The results are shown in Table 3.

[0108]

Example 24 The ingredients described below were mixed in a Henschel mixer. Polypropylene ... 62 parts by weight (propylene homopolymer, MFR: 11g / 10 min, density: 0.91 g / cm ³⁾ (hereinafter, abbreviated as "PP-3"), an amorphous ethylene - propylene copolymerization Combined: 38 parts by weight (ethylene content: 81 mol%, MFR: 1.8 g / 10 minutes) (hereinafter, abbreviated as "EP-3") The obtained mixture was a twin-screw extruder with a vent (L / D). = 4
2, screw diameter 50mm) under nitrogen atmosphere 200
The unmodified propylene-based polymer composition (hereinafter,
"Abbreviated as" PEP-16 ") was manufactured.

Next, the components described below were mixed in a Henschel mixer. -PEP-16: 100 parts by weight-MAH: 1.1 parts by weight-Styrene (hereinafter abbreviated as "St"): 1.1 parts by weight-PO-1: 0.02 parts by weight Part The obtained mixture was mixed with a vented twin-screw extruder (L / D = 4
2, under a nitrogen atmosphere using a screw diameter of 30 mm)
Pellets (modified propylene-based polymer composition) were produced by melt-kneading at a temperature of ° C. MA of this composition
The graft amount of H was 1.0% by weight.

Test pieces were prepared from the thus-prepared modified propylene-based polymer composition as described above, and the flexural modulus, Izod impact strength, coating test, adhesive strength and modified amorphous ethylene- were used. The dispersed phase particle size of the propylene copolymer was determined. The results are shown in Table 3.

[0111]

Example 25 The ingredients described below were mixed in a Henschel mixer. -PP-3: 65 parts by weight-EP-3: 35 parts by weight The obtained mixture was mixed with a vented twin-screw extruder (L / D = 4).
2, screw diameter 50mm) under nitrogen atmosphere 200
The unmodified propylene-based polymer composition (hereinafter,
"Abbreviated as" PEP-17 ") was manufactured.

The ingredients described below were mixed in a Henschel mixer.・ PEP-17 ・ ・ ・ 100 parts by weight ・ HPA ・ ・ ・ 1.3 parts by weight ・ St ・ ・ ・ 1.2 parts by weight ・ PO-1 ・ ・ ・ 0.02 parts by weight The obtained mixture was vented 2 Axial extruder (L / D = 4
2, under a nitrogen atmosphere using a screw diameter of 30 mm)
Melt kneading was performed at a temperature of ° C to produce pellets (modified propylene-based polymer composition). The HPA graft amount of this composition was 1.1% by weight.

A test piece was prepared from the modified propylene-based polymer composition thus prepared as described above, and the flexural modulus, Izod impact strength, coating test, adhesive strength and modified amorphous ethylene- were used. The dispersed phase particle size of the propylene copolymer was determined. The results are shown in Table 3.

[0114]

Examples 26 and 27 PP-3 and EP-3 were mixed in a mixing ratio shown in Table 3 using a Henschel mixer, and then a twin screw extruder with a vent (L / D = 42, screw diameter 50 mm). ) In a nitrogen atmosphere at a temperature of 200 ° C. and a specific energy of 0.32 kW · hr / g (Example 26),
The unmodified propylene-based polymer composition was produced by melt-kneading at 0.31 kW · hr / kg (Example 27).

Then, with respect to 100 parts by weight of this resin,
The ingredients described below were mixed in a Henschel mixer.・ HEA ・ ・ ・ 1.0 parts by weight ・ Benzoyl peroxide ・ ・ ・ 0.1 parts by weight ・ Toluene ・ ・ ・ 5.0 parts by weight Modified propylene by keeping this mixture at 100 ° C. for 2 hours under a nitrogen stream. A polymer composition was prepared. The HEA graft amount of this composition is 0.7% by weight, respectively.
(Example 26) and 0.6 weight% (Example 27).

Test pieces were prepared from the modified propylene-based polymer composition thus prepared as described above, and flexural modulus, Izod impact strength, coating test, adhesive strength and modified amorphous ethylene- were used. The dispersed phase particle size of the propylene copolymer was determined. The results are shown in Table 3.

[0117]

Example 28 The ingredients described below were mixed in a Henschel mixer.・ PP-1 ・ ・ ・ 65 parts by weight ・ EP-3 ・ ・ ・ 35 parts by weight Using a twin screw extruder with a vent (L / D = 42, screw diameter 50 mm), the above mixture was heated at a temperature of 200 ° C. under a nitrogen atmosphere. Then, an unmodified propylene polymer composition (pellets) was produced by melt-kneading at a specific energy of 0.29 kW · hr / kg (hereinafter, abbreviated as “PEP-18”).

Next, the components described below were mixed in a Henschel mixer. PEP-18 100 parts by weight MAH 1.0 parts by weight PO-1 0.03 parts by weight The obtained mixture was mixed with a vented twin-screw extruder (L / D = 4).
2, under a nitrogen atmosphere using a screw diameter of 30 mm)
Pellets (modified propylene-based polymer composition) were produced by melt-kneading at a temperature of ° C. HP of this composition
The graft amount of A was 0.8% by weight.

A test piece was prepared from the modified propylene-based polymer composition thus prepared as described above, and the flexural modulus, Izod impact strength, coating test, adhesive strength and modified amorphous ethylene- were used. The dispersed phase particle size of the propylene copolymer was determined. The results are shown in Table 3.

[0120]

Example 29 The ingredients described below were mixed in a Henschel mixer. -PP-1 ... 65 parts by weight-Amorphous ethylene-propylene copolymer (ethylene content: 81 mol%, MFR: 8.1 g / 10 minutes) ... 35 parts by weight (hereinafter, "EP-4") The obtained mixture is mixed with a vented twin-screw extruder (L / D = 4).
2, screw diameter 50mm) under nitrogen atmosphere 200
An unmodified propylene-based polymer composition (pellets) was prepared by melt-kneading at a temperature of ° C at a specific energy of 0.30 kW · hr / kg (hereinafter, abbreviated as "PEP-19").

Next, the components described below were mixed using a Henschel mixer.・ PEP-19 ・ ・ ・ 100 parts by weight ・ MAH ・ ・ ・ 1.0 parts by weight ・ PO-1 ・ ・ ・ 0.03 parts by weight The obtained mixture was mixed with a vented twin-screw extruder (L / D = 4).
2, under a nitrogen atmosphere using a screw diameter of 30 mm)
Melt kneading was performed at a temperature of ° C to produce pellets (modified propylene-based polymer composition). The MAH graft amount of this composition was 0.8% by weight.

From the modified propylene polymer composition thus prepared, a test piece was prepared as described above, and this test piece was used to flexural modulus, Izod impact strength, coating test, adhesive strength and modified amorphous ethylene- The dispersed phase particle size of the propylene copolymer was determined. The results are shown in Table 3.

[0123]

Example 30 The ingredients described below were mixed using a Henschel mixer. -PP-2 ... 60 parts by weight-EP-3 ... 40 parts by weight The obtained mixture was mixed with a vented twin-screw extruder (L / D = 4).
2, screw diameter 50mm) 170 in nitrogen atmosphere
An unmodified propylene-based polymer composition (pellets) was prepared by melt-kneading at a temperature of ° C at a specific energy of 0.36 kW · hr / kg (hereinafter, abbreviated as "PEP-20").

Next, the components described below were mixed using a Henschel mixer.・ PEP-20 ・ ・ ・ 100 parts by weight ・ HPA ・ ・ ・ 1.3 parts by weight ・ PO-1 ・ ・ ・ 0.03 parts by weight The obtained mixture was mixed with a vented twin-screw extruder (L / D = 4).
2. Use a screw diameter of 30 mm) under nitrogen atmosphere 170
Melt kneading was performed at a temperature of ° C to produce pellets (modified propylene-based polymer composition). The HPA graft amount of this composition was 1.0% by weight.

From the modified propylene polymer composition thus prepared, a test piece was prepared as described above, and this test piece was used to flexural modulus, Izod impact strength, coating test, adhesive strength and modified amorphous ethylene- The dispersed phase particle size of the propylene copolymer was determined. The results are shown in Table 3.

[0126]

Example 31 The ingredients described below were mixed using a Henschel mixer. -PP-1 ... 60 parts by weight-EP-1 ... 40 parts by weight The obtained mixture was mixed with a vented twin-screw extruder (L / D = 4).
2, screw diameter 50mm) under a nitrogen atmosphere 185
An unmodified propylene-based polymer composition (pellets) was prepared by melt-kneading at a temperature of ° C at a specific energy of 0.35 kW · hr / kg (hereinafter, abbreviated as "PEP-21").

Next, the components described below were mixed using a Henschel mixer.・ PEP-21 ・ ・ ・ 100 parts by weight ・ HPA ・ ・ ・ 1.3 parts by weight ・ PO-1 ・ ・ ・ 0.03 parts by weight The obtained mixture was mixed with a vented twin-screw extruder (L / D = 4).
2, screw diameter 30mm) under nitrogen atmosphere 185
Melt kneading was performed at a temperature of ° C to produce pellets (modified propylene-based polymer composition). The HPA graft amount of this composition was 1.1% by weight.

Test pieces were prepared from the thus-prepared modified propylene-based polymer composition as described above, and the flexural modulus, Izod impact strength, coating test, adhesive strength and modified amorphous ethylene- were used. The dispersed phase particle size of the propylene copolymer was determined. The results are shown in Table 3.

[0129]

Example 32 A test piece prepared from the propylene-based polymer composition prepared in Example 1 was coated with 1,1,1-
Instead of performing trichloroethane vapor washing, washing with water, washing with a 4% aqueous solution (60 ° C.) of a general industrial detergent ID-112 [manufactured by Tosoh Corp., trade name] for 1.5 minutes, washing with water,
General industrial cleaning agent ID-113 [trade name, manufactured by Tosoh Corporation] was washed with a 1% aqueous solution (55 ° C.) for 1 minute, and after washing with water, 8
A test piece was prepared by drying at 0 ° C. for 10 minutes.

Example 1 was applied to the test piece subjected to the above treatment.
Similarly to the above, a urethane-based paint was applied and cured. The physical properties of the obtained composition, the cross-cut test of the coating film, and the peel strength were measured. The results are shown in Table 3.

[0131]

Example 33 A test piece prepared from the polymer composition prepared in Example 1 was replaced with a cloth impregnated with isopropanol instead of performing 1,1,1-trichloroethane vapor cleaning before coating the coating. A test piece was prepared by wiping. A urethane-based paint was applied to this test piece in the same manner as in Example 1,
Cured.

The physical properties of the obtained composition, the cross-cut test of the coating film, and the peel strength were measured. The results are shown in Table 3.

[0133]

Example 34 The ingredients described below were mixed using a Henschel mixer. -PP-1 ... 59 parts by weight-EP-1 ... 31 parts by weight The obtained mixture was mixed with a vented twin-screw extruder (L / D = 4).
2, screw diameter 50mm) under nitrogen atmosphere 200
An unmodified propylene polymer composition (pellets) was prepared by melt-kneading at a temperature of ° C at a specific energy of 0.30 kW · hr / kg (hereinafter, abbreviated as "PEP-22").

Next, the components described below were mixed using a Henschel mixer.・ PEP-22 ・ ・ ・ 90 parts by weight ・ talc ・ ・ ・ 10 parts by weight ・ HEA ・ ・ ・ 1.5 parts by weight ・ PO-1 ・ ・ ・ 0.02 parts by weight The obtained mixture is biaxially extruded with a vent. Machine (L / D = 4
2, under a nitrogen atmosphere using a screw diameter of 30 mm)
Pellets (modified propylene-based polymer composition) were produced by melt-kneading at a temperature of ° C and a specific energy of 0.30 kW · hr / kg. The HEA graft amount of this composition was 1.1% by weight.

Test pieces were prepared from the thus-prepared modified propylene copolymer composition as described above, and the flexural modulus, Izod impact strength, coating test and adhesive strength of dispersed phase particle diameters were used. I asked. The results are shown in Table 3.

[0136]

Example 35 The ingredients described below were mixed using a Henschel mixer. -PP-1 ... 52 parts by weight-EP-1 ... 28 parts by weight The obtained mixture was mixed with a vented twin-screw extruder (L / D = 4).
2, screw diameter 50mm) under nitrogen atmosphere 200
An unmodified propylene-based polymer composition (pellets) was prepared by melt-kneading at a temperature of ° C at a specific energy of 0.30 kW · hr / kg (hereinafter, abbreviated as "PEP-23").

Next, the components described below were mixed using a Henschel mixer.・ PEP-23 ・ ・ ・ 80 parts by weight ・ Talc ・ ・ ・ 20 parts by weight ・ HEA ・ ・ ・ 1.5 parts by weight ・ PO-1 ・ ・ ・ 0.02 parts by weight The obtained mixture is biaxially extruded with a vent. Machine (L / D = 4
2, under a nitrogen atmosphere using a screw diameter of 30 mm)
Pellets (modified propylene-based polymer composition) were produced by melt-kneading at a temperature of ° C and a specific energy of 0.30 kW · hr / kg. The HEA graft amount of this composition was 1.1% by weight.

A test piece was prepared from the modified propylene polymer composition thus prepared as described above, and the flexural modulus, Izod impact strength, coating test and adhesive strength were measured for the dispersed phase particle size. I asked. The result is the third
Shown in the table.

[0139]

Example 36 The ingredients described below were mixed in a Henschel mixer. Propylene - ethylene random copolymer ... 65 parts by weight (ethylene content: 6 mol%, MFR: 0.5 g / 10 min, density: 0.91 g / cm ³⁾ (hereinafter, abbreviated as "PP-4" ) -EP-2 ... 35 parts by weight The obtained mixture was mixed with a vented twin-screw extruder (L / D = 4).
2, screw diameter 50mm) under nitrogen atmosphere 200
An unmodified propylene-based polymer composition was produced by melt-kneading at a temperature of ° C at a specific energy of 0.27 kW · hr / kg (hereinafter abbreviated as "PEP-24").

Next, the components described below were mixed using a Henschel mixer. PEP-24 ... 100 parts by weight HPMA ... 1.7 parts by weight PO-1 ... 0.05 parts by weight The obtained mixture was mixed with a vented twin-screw extruder (L / D = 4).
2, screw diameter 50mm) under nitrogen atmosphere 200
Pellets (modified propylene-based polymer composition) were produced while melt-kneading at a temperature of ° C. HPMA of this composition
The amount of grafts was 1.0% by weight.

A test piece was prepared from the modified propylene-based polymer composition thus prepared as described above, and the flexural modulus, Izod impact strength, coating test, adhesive strength and modified amorphous ethylene- were used. The dispersed phase particle size of the propylene copolymer was determined. The results are shown in Table 3.

[0142]

[Comparative Example 1] Resin having the same composition as PEP-1 was heated at 230 ° C.
Kneaded in. The specific energy at this time is 0.22 kW.
It was hr / kg. Next, 100 parts by weight of this resin and the following components were mixed using a Henschel mixer. -MAH: 1.2 parts by weight-PO-1: 0.02 parts by weight The obtained mixture was mixed with a vented twin-screw extruder (L / D = 4).
2, using a screw diameter of 30 mm) under a nitrogen atmosphere 230
Pellets at a temperature of ℃ (modified propylene polymer composition)
Was manufactured. The amount of MAH grafted on this resin was 1.0% by weight.

Test pieces were prepared from the thus-prepared modified propylene-based polymer composition as described above, and the flexural modulus, Izod impact strength, coating test, adhesive strength and modified amorphous ethylene- were used. The dispersed phase particle size of the propylene copolymer was determined. The results are shown in Table 3.

[0144]

Comparative Example 2 The components described below were mixed in a Henschel mixer.・ PP-1 ・ ・ ・ 62 parts by weight ・ EP-1 ・ ・ ・ 38 parts by weight The obtained mixture was mixed with a vented twin-screw extruder (L / D = 4).
2, screw diameter 50mm) under nitrogen atmosphere 250
Specific energy of 0.24 kW · hr / kg at temperature of ℃
And melt-kneaded to produce an unmodified polypropylene-based polymer composition (hereinafter abbreviated as "PEP-25").

Next, the components described below were mixed in a Henschel mixer.・ PEP-25 ・ ・ ・ 100 parts by weight ・ HPA ・ ・ ・ 1.3 parts by weight ・ PO-1 ・ ・ ・ 0.02 parts by weight This mixture is provided with a vented twin-screw extruder (L / D = 42, screw diameter). Pellets (modified polypropylene-based polymer composition) were produced by melt-kneading (30 mm) in a nitrogen atmosphere at a temperature of 250 ° C. The HPA graft amount of this composition was 1.2% by weight.

A test piece was prepared from the modified polypropylene-based polymer composition thus prepared as described above, and the flexural modulus, Izod impact strength, coating test, adhesive strength and modified amorphous ethylene- were used. The dispersed phase particle size of the propylene copolymer was determined. The results are shown in Table 3.

[0147]

Example 37 The ingredients described below were mixed using a Henschel mixer.・ PP-1 ・ ・ ・ 25 parts by weight ・ EP-1 ・ ・ ・ 75 parts by weight The obtained mixture was mixed with a vented twin-screw extruder (L / D = 4).
2, screw diameter 50mm) under nitrogen atmosphere 180
The unmodified propylene-based polymer composition (hereinafter,
"Abbreviated as" PEP-26 ") was manufactured.

Next, the components described below were mixed using a Henschel mixer.・ PEP-26 ・ ・ ・ 100 parts by weight ・ MAH ・ ・ ・ 1.1 parts by weight ・ PO-1 ・ ・ ・ 0.06 parts by weight The obtained mixture was mixed with a vented twin-screw extruder (L / D = 4).
2, under a nitrogen atmosphere using a screw diameter of 30 mm)
Pellets (modified propylene-based polymer composition) were produced by melt-kneading at a temperature of ° C. MA of this composition
The amount of H grafted was 0.9% by weight.

Test pieces were prepared from the modified propylene-based polymer composition thus prepared as described above, and flexural modulus, Izod impact strength, coating test, adhesive strength and modified amorphous ethylene- were used. The dispersed phase particle size of the propylene copolymer was determined. The results are shown in Table 3.

[0150]

Examples 38 and 39 In Examples 37 and 39, except that the compounding amounts of PP-1 and EP-1 were changed as shown in Table 3 and the specific energy was changed as shown in Table 3.
In the same manner as in Example 37, an unmodified propylene-based polymer composition and a modified propylene-based polymer composition were produced.

A test piece was prepared from the modified propylene-based polymer composition thus prepared as described above, and the flexural modulus, Izod impact strength, coating test, adhesive strength and modified amorphous ethylene- were used. The dispersed phase particle size of the propylene copolymer was determined. The results are shown in Table 3.

[0152]

Example 40 The ingredients described below were mixed using a Henschel mixer.・ PP-2 ・ ・ ・ 30 parts by weight ・ EP-2 ・ ・ ・ 70 parts by weight The obtained mixture was mixed with a vented twin-screw extruder (L / D = 4).
2, screw diameter 50mm) under nitrogen atmosphere 180
The unmodified propylene-based polymer composition (hereinafter,
(Abbreviated as "PEP-27") was manufactured.

Then, this composition (PEP-27) 10
1.5 parts by weight of HEA and 0.06 parts to 0 parts by weight
Part by weight of PO-1 was mixed with a Henschel mixer, and the mixture was melt-kneaded at a temperature of 200 ° C. under a nitrogen atmosphere using a vented twin-screw extruder (L / D = 42, screw diameter 30 mm) to form pellets. (Modified propylene-based polymer composition) was produced. The HEA graft amount of this composition was 1.0% by weight.

Test pieces were prepared from the modified propylene-based polymer composition thus prepared as described above, and the flexural modulus, Izod impact strength, coating test, adhesive strength and modified amorphous ethylene- were used. The dispersed phase particle size of the propylene copolymer was determined. The results are shown in Table 3.

[0155]

Example 41 In Example 40, PP-2 and E
Except that the compounding amount of P-2 was changed as shown in Table 3 and the specific energy was changed to 0.26 kW · hr / kg.
In the same manner as in Example 40, an unmodified propylene-based polymer composition and a modified propylene-based polymer composition were produced.

Test pieces were prepared from the modified propylene-based polymer composition thus prepared as described above, and the flexural modulus, Izod impact strength, coating test, adhesive strength and modified amorphous ethylene- were used. The dispersed phase particle size of the propylene copolymer was determined. The results are shown in Table 3.

[0157]

Example 42 The ingredients described below were mixed using a Henschel mixer. -PP-3 ... 40 parts by weight-EP-1 ... 60 parts by weight The obtained mixture was mixed with a vented twin-screw extruder (L / D = 4).
2, screw diameter 50mm) under nitrogen atmosphere 180
The unmodified propylene-based polymer composition (hereinafter,
"Abbreviated as" PEP-28 ") was manufactured.

Next, the components described below were mixed using a Henschel mixer.・ PEP-28 ・ ・ ・ 100 parts by weight ・ HEA ・ ・ ・ 1.5 parts by weight ・ PO-1 ・ ・ ・ 0.05 parts by weight The obtained mixture was mixed with a vented twin-screw extruder (L / D = 4).
2, under a nitrogen atmosphere using a screw diameter of 30 mm)
Pellets (modified propylene-based polymer composition) were produced by melt-kneading at a temperature of ° C. HE of this composition
The graft amount of A was 1.2% by weight.

From the modified propylene polymer composition thus prepared, a test piece was prepared as described above, and the flexural modulus, Izod impact strength, coating test, adhesive strength and modified amorphous ethylene- were used. The dispersed phase particle size of the propylene copolymer was determined. The results are shown in Table 3.

[0160]

[Table 3]

[0161]

[Table 4]

[0162]

[Table 5]

[0163]

[Table 6]

[0164]

[Table 7]

[0165]

[Table 8]

Claims (4)

[Claims] 1. A melt flow rate of 0.1 to 30 g / 1.
20 to 99% by weight of propylene-based polymer (A-1) for 0 minutes
And amorphous ethylene having an ethylene content of 60 to 95 mol% and a melt flow rate of 0.1 to 10 g / 10 min.
-An unmodified propylene-based polymer composition comprising 1 to 80% by weight of a propylene copolymer (B-1), an ethylenically unsaturated group-containing carboxylic acid, an anhydride thereof and an ethylenically unsaturated group-containing carboxylic acid hydroxy. A composition modified with at least one modifier selected from the group consisting of alkyl esters, in which the modified amorphous ethylene-propylene copolymer (B) is added to the modified propylene polymer (A). Is 5
A propylene-based polymer composition characterized in that it is dispersed with an average dispersed particle size of not more than μm. 2. An amorphous ethylene-propylene copolymer (B
The ratio of the melt flow rate of the propylene polymer (A-1) to the melt flow rate of (-1) [MFR (A-
1) / MFR (B-1)] is 0.1 to 200, The propylene-based polymer composition according to claim 1, wherein 3. A melt flow rate of 0.1 to 30 g / 1.
20 to 99% by weight of propylene-based polymer (A-1) for 0 minutes
And amorphous ethylene having an ethylene content of 60 to 95 mol% and a melt flow rate of 0.1 to 10 g / 10 min.
-An unmodified propylene-based polymer composition comprising 1 to 80% by weight of a propylene copolymer (B-1), an ethylenically unsaturated group-containing carboxylic acid, an anhydride thereof and an ethylenically unsaturated group-containing carboxylic acid hydroxy. When modifying with at least one modifier selected from the group consisting of alkyl esters, the propylene-based polymer (A-1) and the amorphous ethylene-propylene copolymer (B-1) are not melt-kneaded. When preparing the modified propylene-based polymer composition, the specific energy (e) represented by the following formula [I] is 0.25 k.
A method for producing a propylene-based polymer composition, which comprises melt-kneading under a kneading condition of W · hr / kg or more; e = motor power consumption / resin extrusion amount ... [I] 4. An amorphous ethylene-propylene copolymer (B
The ratio of the melt flow rate of the propylene polymer (A-1) to the melt flow rate of (-1) [MFR (A-
1) / MFR (B-1)] is 0.1 to 200, The method for producing a propylene-based polymer composition according to claim 3, wherein