JPH05320441A - Propylene polymer composition - Google Patents

Abstract

PURPOSE:To obtain a propylene polymer compsn. excellent in coatability with a urethane coating material, etc., by compounding a propylene polymer, an olefinic elastomer, and a saponified ethylene-vinyl ester copolymer each in a specified amt. CONSTITUTION:100 pts.wt. in total of 99-10 pts.wt. propylene polymer (e.g. an ethylene-propylene copolymer) and 1-90 pts.wt. olefin elastomer (e.g. an ethylene-butene-1 copolymer rubber) is compounded with 0.01-20 pts.wt. saponified ethylene-vinyl ester copolymer (e.g. a saponified ethylene-vinyl acetate copolymer) to give the objective compsn. The compsn. is pref. further compounded with 0.01-5 pts.wt. organotin compd. and/or tertiary amine compd. and dynamically thermally treated in the presence of an org. peroxide to thereby be partially crosslinked.

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 polymer composition having high adhesion to paints such as urethane paints even when the surface treatment with a primer or a solvent is not performed.

[0002]

TECHNICAL BACKGROUND OF THE INVENTION Propylene-based polymers are widely industrially manufactured because they have various properties such as mechanical properties, heat resistance, solvent resistance, oil resistance and chemical resistance. Such a propylene-based polymer is widely used as a raw material for manufacturing industrial parts such as automobiles and electric appliances and daily necessities. However, the propylene-based polymer does not have a polar group in the molecule and is chemically inert and excellent in stability, but on the other hand, since it does not have a polar group, it has an adhesive property with other resins. Is not good, for example, to paint with urethane paint, etc., use an electrical treatment method such as corona discharge, a mechanical surface roughening method, a flame treatment method, an oxygen treatment method or a surface treatment method such as an ozone treatment method. It is necessary to apply a treatment to the surface of the molded article so as to improve the affinity for other resins. When carrying out these surface treatments, a method of previously cleaning the surface of the molded product with a solvent such as alcohol or aromatic hydrocarbon, or a method of cleaning with a solvent vapor such as trichlene, perchlorethylene, pentachloroethylene or toluene is generally used. Has been taken.

In order to carry out these methods, an apparatus for processing all of them is required, which is disadvantageous in terms of equipment and requires a considerable amount of time for the processing. In addition to the method of coating after performing the pretreatment as described above, a primer capable of adhering to a propylene-based polymer is undercoated on the molded product, and a paint such as a urethane-based paint is applied on the undercoat layer. Although a method is also used, in this method as well, an undercoating step and an overcoating step are required, so that the coating step requires a long time, and the coating film has a two-layer structure, so that the cost of the molded product is low. There is a problem with getting higher.

As described above, with respect to the coating of the molded product made of the propylene-based polymer, it is general to subject the molded product itself to some treatment. As described above, in the conventionally known propylene-based polymer, a pretreatment was required when coating a molded article, but a propylene-based polymer excellent in coatability that does not require such a pretreatment was used. Development is coveted.

As a method for improving the coatability of a propylene-based polymer, for example, JP-A-51-145553 discloses a polyolefin containing an ethylene / unsaturated carboxylic acid copolymer and an ethylene / vinyl ester copolymer. Although a blended propylene-based polymer composition molded article is disclosed, its coatability is insufficient.

[0006]

SUMMARY OF THE INVENTION The present invention has been made to solve the above problems in a propylene resin composition, and has excellent coatability for urethane paints and other paints. The purpose is to provide a polymer composition.

[0007]

SUMMARY OF THE INVENTION In the present invention, (a) a propylene polymer (99 to 10 parts by weight), (b) an olefin elastomer (1 to 90 parts by weight), where (a) component and (b) are used.
The total amount with the components is 100 parts by weight] With respect to the total amount 100 parts by weight with the components (a) and (b),
(C) Saponified ethylene / vinyl ester copolymer
There is provided a propylene-based polymer composition comprising 0.01 to 20 parts by weight.

In the present invention, the above-mentioned propylene polymer composition further comprises (d) an organotin compound and / or a third component based on 100 parts by weight of the total amount of the components (a) and (b). The primary amino compound may contain 0.01 to 5 parts by weight.

Further, according to the present invention, there is provided a partially cross-linked propylene polymer composition obtained by dynamically heat treating the above propylene polymer composition in the presence of an organic peroxide. To be done.

[0010]

DETAILED DESCRIPTION OF THE INVENTION The propylene polymer composition according to the present invention will be described in detail below. The propylene-based polymer composition according to the present invention includes (a) a propylene-based polymer, (b) an olefin-based elastomer, (c) a saponified product of an ethylene / vinyl ester copolymer, and (d) an organic compound as necessary. It consists of a tin compound and / or a tertiary amino compound.

Each component of the propylene polymer composition according to the present invention will be specifically described below. [Propylene-based polymer (a)] The propylene-based polymer (a) used in the present invention is a homopolymer of propylene or a copolymer of propylene and another α-olefin. Examples of the α-olefin copolymerized with propylene include ethylene, butene-1, pentene-1, 2-methylbutene-1, 3-methylbutene-1, hexene-1,3.
-Methylpentene-1,4-methylpentene-1,3,
3-dimethylbutene-1, heptene-1, methylhexene-1, dimethylpentene-1, trimethylbutene-
1, ethylpentene-1, octene-1, methylpentene-1, dimethylhexene-1, trimethylpentene-
1, ethylhexene-1, methylethylpentene-1,
Diethyl butene-1, propyl pentene-1, decene-
1, methylnonene-1, dimethyloctene, trimethylheptene-1, ethyloctene-1, methylethylheptene-1, diethylhexene-1, dodecene-1, hexadodecene and the like can be mentioned. These α-
The olefin may form a random copolymer with propylene, or may form a block copolymer. The α-olefin content in the propylene-based polymer is
It is preferably 45 mol% or less. Of these,
In the present invention, as the propylene-based polymer (a), a propylene homopolymer, a crystalline propylene / ethylene block copolymer having an ethylene content of 2 to 40 mol%, and a crystal having an ethylene content of 0.5 to 10 mol% are used. Propylene / ethylene random copolymer is preferred.

Such a propylene-based polymer (a) is
The melt flow rate (MFR) measured at 230 ° C. and a load of 2.16 kg is 0.05 to 100 g / 10 minutes,
Further, the MFR is preferably within the range of 0.5 to 60 g / 10 minutes. By using a propylene-based polymer having such an MFR, good moldability can be ensured. The density of the propylene-based polymer (a) is
Usually, it is preferably in the range of 0.89 to 0.92 g / cm ³ .

[Olefin Elastomer (b)] The olefin elastomer (b) used in the present invention is ethylene, propylene, butene-1, pentene-1.
And the like, or a copolymer of these with a non-conjugated diene.

Examples of non-conjugated dienes include dicyclopentadiene, 1,4-hexadiene, dicyclooctadiene, methylene norbornene and 5-ethylidene-2-norbornene.

Specific examples of the olefin elastomer include ethylene / propylene copolymer rubber and ethylene / propylene copolymer rubber.
Butene-1 copolymer rubber, ethylene / propylene / butene-1 copolymer rubber, ethylene / propylene / non-conjugated diene copolymer rubber, ethylene / butene-1 / non-conjugated diene copolymer rubber, ethylene / propylene / butene-1 / An amorphous elastic copolymer containing an olefin as a main component such as a non-conjugated diene copolymer rubber can be mentioned.

Further, the Mooney viscosity ML _{1 + 4} (100 ° C.) of the above-mentioned olefinic elastomer is 10 to 150, preferably 40 to 120. The iodine value (degree of unsaturation) of the olefin elastomer is preferably 20 or less.

[Saponified Product of Ethylene / Vinyl Ester Copolymer (c)] The saponified product of ethylene / vinyl ester copolymer (c) used in the present invention may be a high molecular weight product to a low molecular weight product. In terms of compatibility and dispersibility with the above-mentioned propylene-based polymer and olefin-based elastomer, the number average molecular weight is preferably within the range of 800 to 100,000, and within the range of 1,500 to 20,000. Is particularly preferable.

Ethylene as a raw material for the saponified product (c) of the ethylene / vinyl ester copolymer used in the present invention.
The vinyl ester copolymer is produced by a known radical polymerization method such as high pressure polymerization, solution polymerization, suspension polymerization and emulsion polymerization. The low molecular weight ethylene / vinyl ester copolymer can also be produced by thermally degrading the high molecular weight ethylene / vinyl ester copolymer produced by the above radical polymerization method.

Specific examples of the vinyl ester monomer include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl pivalate, and vinyl benzoate, and acetic acid that is industrially easily and inexpensively available. Vinyl is preferred.

The ethylene / vinyl ester copolymer has a vinyl ester content of 5 to 50% by weight, preferably 10 to 4
It is in the range of 5% by weight. In addition to ethylene and vinyl ester as a constituent of the ethylene / vinyl ester copolymer, a third comonomer that can be copolymerized with these,
For example, unsaturated hydrocarbons such as propylene, butene and styrene, unsaturated carboxylic acids such as (meth) acrylic acid and its esters and derivatives thereof may be used in a proportion of 10% by weight or less.

The saponified product (c) of the ethylene / vinyl ester copolymer used in the present invention is produced by reacting the ethylene / vinyl ester copolymer with an aliphatic alcohol and an alkali catalyst.

Specific examples of the aliphatic alcohol used for saponification of the ethylene / vinyl ester copolymer include methanol, ethanol, propanol, butanol, and hexanol. Among them, the reaction rate is high, and after the reaction, Methanol, which is well separated from the saponified product, is preferable.

The above-mentioned aliphatic alcohol is 0.01 to 100 parts by weight of ethylene-vinyl ester copolymer.
10 parts by weight, preferably 0.1 to 5 parts by weight is used.
Further, as the alkali catalyst used for saponification of the ethylene / vinyl ester copolymer, specifically, sodium hydroxide, potassium hydroxide, lithium hydroxide and an alcoholate compound synthesized from them and an aliphatic alcohol can be used. Among these, sodium hydroxide and sodium methylate, which have a high reaction rate and are easily industrially available, are preferable.

The alkali catalyst is 0.0001-10 based on 100 parts by weight of the ethylene / vinyl ester copolymer.
Parts by weight, preferably 0.002 to 5 parts by weight are used. Saponification of the ethylene / vinyl ester copolymer can be performed by a conventionally known method.

For example, an ethylene / vinyl ester copolymer is saponified in a solvent such as the following (1) to (3) using an alkali metal compound such as sodium or potassium hydroxide or an alkoxide as a saponification reaction catalyst. .. (1) A good solvent for hydrocarbons such as toluene and xylene (2) A homogeneous mixed solvent obtained by adding alcohols such as methanol and ethanol to the good solvent for (1) above (3) Methanol for the good solvent above (1) , A heterogeneous mixed solvent in which a poor solvent is added by adding alcohols such as ethanol and water as required, and the saponification product (c) of the ethylene / vinyl ester copolymer used in the present invention has a saponification rate of 50 to 100%. It is preferably within the range.

[Organotin Compound and Tertiary Amino Compound (d)] The organotin compound (d) used in the present invention.
Is a formula R ₁ —SnX ₁ Y ₁ Y ₂ (wherein, R ₁ is an alkyl group having 4 to 10 carbon atoms, X ₁ is an alkyl group having 4 to 10 carbon atoms, a chlorine atom or a hydroxyl group; , Y ₁ and Y ₂ are chlorine atoms, −
OCOR ₂ or hydroxyl group, which may be the same or different. However, R ₂ is an alkyl group,
An aryl group and an allylalkyl group. ) Is an organotin compound.

Specific examples of such an organic tin compound include:
Specifically, n-C_FourH₉Sn (OH)₂Cl, n-C_FourH₉S
n (OH) Cl₂, N-C_FourH₉SnCl₃, C₈H₁₇Sn
(OH)₂Cl, C₈H₁₇Sn (OH) Cl₂, C₈H₁₇S
nCl₃, N-C_FourH₉Sn (OH)₂OCOC₇H₁₅, N
-C_FourH₉Sn (OH)₂OCOC₁₁H_{twenty three}, N-C₈H₁₇S
n (OH)₂OCOC₇H₁₅, N-C₈H₁₇Sn (OH) ₂
OCOC₁₁H_{twenty three}, N-C_FourH₉Sn (OCOC₇H₁₅)₃,
(N-C_FourH₉)₂Sn (OCOC₁₁H_{twenty three})₂, (N-C₈
H₁₇)₂Sn (OCOC₁₁H_{twenty three})₂, (N-C_FourH₉)₂S
n (OCOCH = CHCOOCH₃)₂, (N-C_FourH₉)
₂Sn (OCOCH = CHCOOCH₂Ph)₂Used by etc.
Be done.

Of these, n-C ₄ H ₉ SnCl ₃ , (n-
_{C 4 H 9) 2 Sn (} OCOC 11 H 23) 2, (n-C 8 H 17) 2
Sn (OCOC ₁₁ H ₂₃ ) ₂ is preferred. The blending amount of such an organic tin compound is 0.01 to 5 parts by weight, preferably 0.05 to 3 parts by weight.

Examples of the tertiary amino compound (d) used in the present invention include dimethylpropylamine, diethylpropylamine, tris (dimethylaminomethyl) phenol, tetraguanidine, N, N-dibutylethanolamine and N-methyl-. N, N-diethanolamine,
1,4-diazabicyclo [2.2.2] octane, 1,
8-diazabicyclo [5.4.0] -7-undecene,
Tetramethylbutanediamine may be mentioned.

The blending amount of such a tertiary amino compound is 0.01 to 5 parts by weight, preferably 0.05 to 3 parts by weight. [Production of Propylene-Based Polymer Composition] Suitable examples of the propylene-based polymer composition in the present invention are described above in (a).
Propylene polymer 99 to 10 parts by weight, preferably 85
˜15 parts by weight, and (b) olefin elastomer 1˜
90 parts by weight, preferably 15 to 85 parts by weight, and (c) an ethylene / vinyl ester copolymer saponified product of 0.1 part by weight per 100 parts by weight of the above-mentioned components (a) and (b). It is produced by melt-kneading 01 to 20 parts by weight, preferably 0.1 to 10 parts by weight.

Another preferred example of the propylene-based polymer composition of the present invention is the above-mentioned component (a), component (b) and component (c) plus the sum of component (a) and component (b). Quantity 1
0.01 to 5 parts by weight of (d) an organotin compound and / or a tertiary amino compound, relative to 00 parts by weight,
It is preferably produced by blending 0.05 to 3 parts by weight and melt-kneading.

Another preferred example of the propylene-based polymer composition in the present invention is that the above-mentioned component (a), component (b) and component (c) are dynamically heat-treated in the presence of an organic peroxide. And partially cross-linked.

Another preferred example of the propylene-based polymer composition of the present invention is the above-mentioned component (a), component (b), component (c) and component (d) in the presence of an organic peroxide. It is produced by dynamically heat treating and partially crosslinking.

In order to produce the propylene polymer composition of the present invention, a mixing method which is practiced in the field of ordinary propylene polymers is applied so that the above components are in the range of the above composition ratio. And mix so as to be uniform. At this time, all the composition components may be mixed at the same time, or a part of the composition components may be mixed in advance to produce a so-called masterbatch, and this masterbatch and the remaining composition components may be mixed. At this time, the physical properties of the composition, as long as the coating property is not impaired, other thermoplastic resins, softening agents, fillers, pigments, stabilizers, plasticizers, flame retardants, lubricants,
An antistatic agent and an electrical property improving agent can be added as needed.

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

Mineral oil-based softening agents can be mentioned as softening agents that can be used in the present invention. The mineral oil-based softening agent weakens the intermolecular action force of the olefin-based elastomer, facilitates the processing, and helps disperse carbon black, white carbon, etc. to be blended as a filler,
Alternatively, it is a high boiling point petroleum fraction used for the purpose of lowering the hardness and increasing the flexibility and elasticity of the vulcanized rubber, and is classified into paraffin type, naphthene type, aromatic type and the like.

Specific examples of the filler that can be used in the present invention include light calcium carbonate, heavy calcium carbonate, basic calcium carbonate, aluminum hydroxide, magnesium hydroxide, magnesium oxide, kaolin, clay and pyro. Ferrite, sericite, talc,
Calcium silicate (wollastonite, zonotolite, petal-shaped calcium silicate), diatomaceous earth, aluminum silicate, anhydrous silicic acid, hydrous silicic acid, mica, magnesium silicate (asbestos, PFM (Processed)
Mineral Fiber), sepiolite), potassium titanate, elestadite, gypsum sauce, glass balun, silica balun, fly ash balun, silas balun, carbon balun, phenolic resin, urea resin,
Styrene resin, organic balun such as Saran resin, silica, alumina, barium sulfate, aluminum sulfate, calcium sulfate, molybdenum disulfide, graphite, glass fiber (chopped strand, roping, milled glass fiber, glass flake, etc.), cut fiber , Rock fiber, microfiber, carbon fiber, aromatic polyamide fiber, potassium titanate fiber, coumarone indene resin, petroleum resin and the like.

Specific examples of the coloring agent that can be used in the present invention include carbon black, titanium oxide, zinc white, red iron oxide, ultramarine blue, dark blue, azo pigment, nitroso pigment,
Lake pigments, phthalocyanine pigments and the like can be mentioned.

In the present invention, known heat stabilizers such as phenol-based, sulfite-based, phenylalkane-based, phosphite-based or amine-based stabilizers, antiaging agents,
A weather resistance stabilizer, an antistatic agent, a metal soap, and a lubricant such as wax can be added to the extent of being used in an olefin plastic or an olefin copolymer rubber.

The propylene-based polymer composition of the present invention is produced by melt-kneading the above-mentioned components or by dynamically heat-treating them in the presence of an organic peroxide to partially cross-link them.

In the present invention, dynamically heat-treating in the presence of an organic peroxide to partially crosslink means kneading in a molten state in the presence of an organic peroxide. Examples of the organic peroxide used in the present invention include dicumyl peroxide, di-tert-butyl peroxide,
2,5-Dimethyl-2,5-di- (tert-butylperoxy) hexane, 2,5-dimethyl-2,5-di-
(Tert-Butylperoxy) hexyne-3,1,3
-Bis (tert-butylperoxyisopropyl) benzene, 1,1-bis (tert-butylperoxy)
-3,3,5-Trimethylcyclohexane, n-butyl-4,4'-bis (tert-butylperoxy) valerate, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tert -Butyl peroxybenzoate, tert-butyl peroxy isopropyl carbonate, diacetyl peroxide, lauroyl peroxide, tert-butyl cumyl peroxide, etc. can be mentioned.

Among these, in terms of odor, etc., 2,5
-Dimethyl-2,5-di- (tert-butylperoxy) hexane, 2,5-dimethyl-2,5-di- (te
rt-Butylperoxy) hexyne-3,1,3-bis (tert-butylperoxyisopropyl) benzene, 1,1-bis (tert-butylperoxy)-
3,3,5-trimethylcyclohexane, n-butyl-
4,4'-bis (tert-butylperoxy) valerate is preferred.

The amount of such an organic peroxide compounded is 0.05 to 3% by weight, preferably 0.1, based on the total amount of the components.
It is desirable to be in the range of 1 wt%. As a kneading device, an open type mixing roll, a non-open type Banbury mixer, an extruder, a kneader, a continuous mixer, etc.
It is preferable to use a conventionally known apparatus, and it is preferable to carry out kneading in an atmosphere of an inert gas such as nitrogen or carbon dioxide.
The kneading is performed at a temperature at which the half-life of the organic peroxide used is less than 1 minute, usually 150 to 280 ° C., preferably 170 to 2
It may be carried out at 40 ° C. for 1 to 20 minutes, preferably 3 to 10 minutes.

In the present invention, sulfur, p-quinonedioxime, and
p, p'-dibenzoylquinone dioxime, N-methyl-N, 4-dinitrosoaniline, nitrobenzene, diphenylguanidine, trimethylolpropane-N, N-
A crosslinking aid such as m-phenylene dimaleimide or a polyfunctional methacrylate monomer such as divinylbenzene, triallyl cyanurate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate or allyl methacrylate, Polyfunctional vinyl monomers such as vinyl butyrate or vinyl stearate can be incorporated. With such a compound, a uniform and mild crosslinking reaction can be expected. In particular, in the present invention, when divinylbenzene is used, it is easy to handle and has good compatibility with the olefin-based plastic which is the main component of the material to be treated, and also has an organic peroxide-soluble action, so that an organic peroxide is obtained. Since it functions as an oxide dispersion aid, a crosslinking effect by heat treatment is uniform, and a composition having a well-balanced fluidity and physical properties can be obtained, which is most preferable. In the present invention, the compounding amount of such a crosslinking aid or polyfunctional vinyl monomer is in the range of 0.1 to 2% by weight, particularly 0.3 to 1% by weight, based on the whole object to be treated. preferable.

In order to accelerate the decomposition of organic peroxide, triethylamine, tributylamine, 2,4,6
-Tertiary amines such as tris (dimethylamino) phenol, or aluminum, cobalt, vanadium,
Decomposition accelerators such as naphthenates such as copper, calcium, zirconium, manganese, magnesium, lead and mercury can also be used.

The kneading is preferably carried out in a non-open type apparatus, and is preferably carried out in an atmosphere of an inert gas such as nitrogen or carbon dioxide. The kneading temperature is a temperature at which the half-life of the organic peroxide used is 1 minute, usually 150 to 280 ° C, preferably 170 to 240 ° C, and the kneading time is usually 1 to
20 minutes, preferably 1-10 minutes.

As the kneading device, a mixing roll, an intensive mixer (for example, Banbury mixer, kneader), a single-screw or twin-screw extruder can be used, but a non-open type device is preferable.

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

The molded article formed from the propylene polymer composition of the present invention has excellent coatability with respect to urethane paint. Urethane-based paints are paints that generally form a coating film by reacting a polyisocyanate and a polyol compound, and there are one-pack type and two-pack type, and there are also powder paints using a block-type isocyanate. The molded product made of the polymer composition of the present invention has a good affinity with any of these urethane-based paints.

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

[0051]

The propylene-based polymer composition of the present invention is
Excellent coatability for paints such as urethane paints.

The propylene-based polymer composition of the present invention has excellent moldability and can be molded by an apparatus used for usual thermoplastics, and is suitable for extrusion molding, calender molding, injection molding and the like. There is.

Utilizing the above characteristics, the propylene polymer composition of the present invention can be used for automobile parts, motorcycle parts, electric equipment parts, daily necessities, civil engineering building materials, general industrial materials, office information equipment, packaging materials. It can be widely used for applications to which paint is applied such as sports equipment and medical equipment.

The present invention will be described below with reference to examples.
The invention is not limited to these examples.
Various properties of the propylene-based polymer composition used in the present invention were measured as follows. (1) According to MFR ASTM D-1238, a load of 2.16 kg,
It was measured at a temperature of 230 ° C. (2) Flexural Modulus (FM) Using a test piece having a thickness of 1/8 inch, ASTM D-7
90. (3) Coating test ○ Preparation of test piece The following paint was applied to a square plate molded by a 50-ton injection molding machine. The surface of the square plate was wiped with a cloth impregnated with isopropanol before applying the following paint. 1-component urethane-based paint: Flexen # 105 [Nippon Bee Chemical Co., Ltd., trade name) Dry film thickness: 60 μm Baking temperature and time: 120 ° C., 30 minutes 2-component urethane-based paint: R-271 [Nippon Bee Chemical ( Co., Ltd.] Dry film thickness: 60 μm Baking temperature and time: 100 ° C., 30 minutes ○ Cross-cut test According to the method of the cross-cut test described in JIS K5400, a test piece with a cross-cut is attached. A cellophane tape (trade name, manufactured by Nichiban Co., Ltd.) was prepared and attached to a test piece, which was then rapidly pulled in a direction of 90 ° for peeling, and the number of cross-cuts was counted and used as an index of adhesion. 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.

[0055]

Examples 1 to 14 [Production of propylene-based polymer composition] Each component shown in Table 1 was melt-kneaded with a twin-screw extruder to produce a propylene-based polymer composition. This composition was injection molded by an injection molding machine to mold various test pieces, and various properties were measured according to the above-mentioned methods.

The components in Table 1 are as follows. Propylene polymer ○ Propylene homopolymer (PP-1) MFR: 20 g / 10 minutes, density: 0.91 g / cm ³ ○ Propylene-ethylene random copolymer (PP-2) MFR: 30 g / 10 minutes, ethylene Content: 3 mol% Density: 0.91 g / cm ³ O Propylene-ethylene block copolymer (PP-3) MFR: 14 g / 10 min, ethylene content: 12 mol%,
Density: 0.91 g / cm ³ Olefin-based elastomer ○ Ethylene-propylene copolymer rubber (EPR) MFR (230 ° C.): 0.7 g / 10 min, ethylene content: 81 mol%, Mooney viscosity ML _{1 + 4} (100 ℃):
60, ○ ethylene-propylene-non-conjugated diene copolymer rubber (EPDM-1) Mooney viscosity [ML _{1 + 4} (100 ° C.)]: 90, ethylene content: 79 mol%, non-conjugated diene: 5-ethylidene-
2-norbornene, iodine value: 7 ○ ethylene / propylene / non-conjugated diene copolymer rubber (E
PDM-2) Mooney viscosity [ML _{1 + 4} (100 ° C.): 70, ethylene content: 78 mol%, non-conjugated diene: 5-ethylidene-2
-Norbornene, iodine value 13, oil extension amount: 40 parts by weight (based on 100 parts by weight of rubber component) -Ethylene / butene-1 copolymer rubber (EBR) Mooney viscosity ML _{1 + 4} (100 ° C): 45, ethylene Content: 90 mol% Thermoplastic resin other than the above ○ Linear low-density polyethylene (LLDPE) Comonomer: butene-1, butene-1 Content: 2 mol%
MFR: 25 g / 10 minutes, density: 0.925 g / cm ³ ○ High-density polyethylene (HDPE) MFR: 20 g / 10 minutes, density: 0.965 g / cm ³ ○ Styrene-butadiene-styrene block copolymer hydrogenated product (SEBS) MFR (230 ° C., 2.16 kg): 4 g / 10 minutes, styrene content: 30% by weight Saponification product of ethylene / vinyl ester copolymer ○ Saponification product of ethylene / vinyl acetate copolymer (EVOH
-1) Vinyl acetate content of ethylene / vinyl acetate copolymer: 35
% By weight, saponification rate: 97%, number average molecular weight: 15,00
0 ○ Saponified ethylene / vinyl acetate copolymer (EVOH
-2) Vinyl acetate content of ethylene / vinyl acetate copolymer: 20
% By weight, saponification rate: 95%, number average molecular weight: 80,000
0 Organotin compound ○ Dibutyltin dilaurate (DBTDL) ○ Dibutyltin malate (DBTM) Tertiary amino compound ○ 1,4-diazabicyclo [2.2.2] octane (D
ABCO) Organic peroxide O 2,5-Dimethyl-2,5-di- (tert-butylperoxy) hexyne-3 (PO) polyfunctional vinyl monomer O Divinylbenzene (DVB) The results are shown in Table 1.

[0057]

Comparative Examples 1 to 6 Each component shown in Table 2 was melt-kneaded by a twin-screw extruder to produce a propylene polymer composition.

This propylene-based polymer composition was injection molded by an injection molding machine to mold various test pieces, and various properties were measured according to the above-mentioned methods. The results are shown in Table 2.

The composition of Comparative Example 6 was too soft to measure the flexural modulus. In addition, during coating, the test piece was deformed during baking and drying after application of the coating material, and evaluation could not be performed.

[0060]

[Table 1]

[0061]

[Table 2]

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Claims (4)

[Claims] 1. (a) Propylene-based polymer 99 to 10 parts by weight, (b) Olefin-based elastomer 1 to 90 parts by weight, provided that the total amount of the components (a) and (b) is 100.
Parts by weight] Based on 100 parts by weight of the total amount of the above-mentioned components (a) and (b), (c) a saponified product of an ethylene / vinyl ester copolymer
A propylene-based polymer composition comprising 0.01 to 20 parts by weight. 2. A propylene polymer (a) 99 to 10 parts by weight, (b) an olefin elastomer 1 to 90 parts by weight, provided that the total amount of the components (a) and (b) is 100.
Parts by weight] Based on 100 parts by weight of the total amount of the above-mentioned components (a) and (b), (c) a saponified product of an ethylene / vinyl ester copolymer
0.01 to 20 parts by weight, and (d) 0.01 to 5 parts by weight of an organotin compound and / or a tertiary amino compound. A propylene-based polymer composition. 3. A propylene-based polymer composition characterized in that the propylene-based polymer composition according to claim 1 is dynamically heat-treated in the presence of an organic peroxide to be partially crosslinked. Composition. 4. A propylene-based polymer composition characterized in that the propylene-based polymer composition according to claim 2 is dynamically heat-treated in the presence of an organic peroxide to be partially crosslinked. Composition.