JPH05320465A - Propylene polymer composition - Google Patents

Abstract

PURPOSE:To provide a propylene polymer compsn. which is excellent in impact strength and heat resistance and exhibits an improved coatability when coated with a urethane coating material, etc. CONSTITUTION:This compsn. comprises 100 pts.wt. compsn. comprising 90-10wt.% propylene polymer and 10-90wt.% olefin elastomer. 0.01-10 pts.wt. hydroxylated ethylenically unsatd. compd., 0.05-10 pts.wt. organotin compd. and/or tertiary amine compd., 0-100 pts.wt. rubberry substance which is not peroxide-crosslinkable, and 0-200 pts.wt. mineral oil-based softener, and is partially crosslinked by dynamic thermal treatment in the presence of an org. peroxide.

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-59-184245 and JP-A-59-184246 disclose an olefin obtained by modifying a polyolefin with a hydroxyl group-containing unsaturated compound. Although a polymer-based polymer composition molding 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) propylene-based polymer 90 to 10 parts by weight, (b) olefin-based elastomer 10 to 90 parts by weight, [however, the total amount of components (a) and (b) is Is 100 parts by weight] With respect to 100 parts by weight of the total amount of the components (a) and (b), (c) a hydroxyl group-containing ethylenically unsaturated compound 0.0
A composition containing 1 to 10 parts by weight, (d) 0.05 to 10 parts by weight of an organotin compound and / or a tertiary amino compound, and dynamically heat-treated in the presence of an organic peroxide. To provide a partially crosslinked propylene-based polymer composition.

In the present invention, the above-mentioned propylene-based polymer composition further comprises (e) a peroxide non-crosslinked rubber-like substance based on 100 parts by weight of the total of the components (a) and (b). 0 to 100 parts by weight, (f) mineral oil softener 0 to 20
It may contain 0 parts by weight.

[0009]

DETAILED DESCRIPTION OF THE INVENTION The propylene polymer composition according to the present invention will be described in detail below. The propylene polymer composition according to the present invention comprises (a) a propylene polymer, (b) an olefin elastomer, (c) a hydroxyl group-containing ethylenically unsaturated compound, (d) an organotin compound and / or a tertiary. It is composed of an amino compound and, if necessary, (e) a peroxide non-crosslinked rubber-like substance and (f) a mineral softener.

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 .

The propylene polymer (a) having such characteristics can be produced by various methods. As a typical production method, a solid titanium catalyst component and an organometallic compound catalyst component are used. It can be produced using the catalyst formed or a catalyst formed from both of these components and an electron donor.

The solid titanium catalyst component used in this method is titanium trichloride or a titanium trichloride composition produced by various methods and has a specific surface area of preferably 100 m ^2.
/ G or more of a titanium catalyst component supported on a carrier, or magnesium, a halogen, an electron donor, preferably an aromatic carboxylic acid ester or an alkyl group-containing ether and titanium are essential components, and a specific surface area is preferably 100.
It is a titanium catalyst component supported on a carrier of m ² / g or more. A propylene-based polymer produced by using the latter catalyst component with a carrier is particularly preferable.

Further, as the organometallic compound catalyst component,
Organoaluminum compounds are suitable, and specific examples of the organoaluminum compounds include trialkylaluminum, dialkylaluminum halides, alkylaluminum sesquihalides, alkylaluminum dihalides and the like. 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. Can be given 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-50-108385 and JP-A-50-12659.
No. 0, JP-A-51-20297, JP-A-51-281
No. 89, JP-A No. 52-151691, etc., and the techniques described therein can be used in the present invention.

[Olefin-based elastomer (b)] The olefin-based elastomer (b) used in the present invention means ethylene, propylene, butene-1, and penten-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.

The Mooney viscosity ML _{1 + 4} (100 ° C.) of the above-mentioned olefinic elastomer is preferably 10 to 150, and more preferably 40 to 120. The iodine value (unsaturation degree) of the olefin elastomer is preferably 16 or less.

[Hydroxyl group-containing ethylenically unsaturated compound (c)] The hydroxyl group-containing ethylenically unsaturated compound (c) used in the present invention is a monomer having at least one ethylenically unsaturated bond and at least one hydroxyl group. , For example, hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxy-3-phenoxy-
Propyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, glycerin mono (meth) acrylate, pentaerythritol mono (meth) acrylate, trimethylolpropane mono (meth) acrylate, tetramethylolethane mono (meth) Examples thereof include (meth) acrylic acid esters such as acrylate, butanediol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, and 2- (6-hydroxyhexanoyloxy) ethyl acrylate.

As the hydroxyl group-containing ethylenically unsaturated compound, in addition to the above (meth) acrylic acid ester, 1
0-undecen-1-ol, 1-octen-3-ol, 2-methanol norbornene, hydroxystyrene, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, N-methylol acrylamide, 2
-(Meth) acroyloxyethyl acid phosphate, glycerin monoallyl ether, allyl alcohol, allyloxyethanol, 2-butene-1,4-diol, glycerin monoalcohol and the like can also be used.

These hydroxyl group-containing ethylenically unsaturated compounds can be used alone or in combination. Among the above compounds, particularly in the present invention, 2-
It is preferable to use hydroxyethyl (meth) acrylate or 2-hydroxypropyl (meth) acrylate.

[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 compounding amount of such an organic tin compound is 0.05 to 10 parts by weight, preferably 0.05 to 5 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 0.05 to 10 parts by weight, preferably 0.05 to 5 parts by weight. [Peroxide non-crosslinking rubber-like substance (e)] The peroxide non-crosslinking rubber-like substance (e) used in the present invention does not crosslink even when mixed with a peroxide and kneaded under heating and flows. It is a hydrocarbon rubber-like substance that does not deteriorate in properties.

Examples of such non-peroxide type rubber-like substance (e) include polyisobutylene and butyl rubber (II
R), propylene having a propylene content of 55 mol% or more.
Examples thereof include ethylene copolymers and atactic polypropylene. Among these, polyisobutylene and butyl rubber (IIR) are preferable in terms of performance and handling.

Such a peroxide non-crosslinking rubber-like substance has a function of improving the fluidity of the propylene polymer composition, and in particular, it has a Mooney viscosity ML _{1 + 4} (100 ° C.) of 60 or more. Oxide non-crosslinked rubbery materials are preferred.

[Mineral oil-based softening agent (f)] The mineral oil-based softening agent (f) used in the present invention weakens the intermolecular action force of the olefin elastomer to facilitate the processing, and
A high boiling point petroleum fraction used to help disperse carbon black, white carbon, etc. blended as a filler or to reduce the hardness and flexibility and elasticity of vulcanized rubber. It is classified into a system and an aromatic system.

[Production of Propylene-Based Polymer Composition] Suitable examples of the propylene-based polymer composition in the present invention include the above-mentioned (a) propylene-based polymer 90 to 10 parts by weight, preferably 85 to 15 parts by weight. And (b) 10 to 90 parts by weight, preferably 15 to 85 parts by weight of the olefin elastomer, and (c) hydroxyl group-containing ethylene with respect to 100 parts by weight of the total amount of the components (a) and (b). 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight, and (d) an organotin compound and / or a tertiary amino compound 0.05 to 10 parts by weight, preferably 0.05 ~ 5
It is prepared by blending parts by weight and dynamically heat treating and partially crosslinking in the presence of an organic peroxide.

Another preferred example of the propylene polymer composition in the present invention is the above-mentioned component (a), component (b), component (c) and component (d), component (a) and component (b). (E) Peroxide non-crosslinking type rubbery substance 0 to 100 parts by weight, preferably 5 to 100 parts by weight, and (f) mineral oil softener 0-200
It is produced by blending parts by weight, preferably 1 to 100 parts by weight, particularly preferably 3 to 100 parts by weight, and dynamically heat treating in the presence of an organic peroxide to partially crosslink.

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.

Specific examples of the filler which 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 colorant usable 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-resistant 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 polymer composition of the present invention is produced by dynamically heat-treating each of the above-mentioned components in the presence of an organic peroxide to partially crosslink them. In the present invention, “dynamically heat-treating” means kneading in a molten state.

Examples of the organic peroxide used in the present invention include dicumyl peroxide and 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 (te
rt-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 peroxyisopropyl carbonate, diacetyl peroxide, lauroyl peroxide, tert-butyl cumyl peroxide, etc. can be mentioned.

Among these, 2,5 from the viewpoint of odor and the like.
-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 the 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, preferably in an inert gas atmosphere 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. The shearing force applied is usually 10 to 10 ⁴ se at a shearing rate.
c ⁻¹ , preferably 10 ² to 10 ³ sec ⁻¹ .

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 is molded 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.

Incidentally, after the propylene polymer composition of the present invention is obtained as described above or when it is used, an olefinic plastic can be blended within a range not impairing the object of the present invention.

Specific examples of such olefinic plastics include high-density polyethylene, medium-density polyethylene, low-density polyethylene, isotactic polypropylene, and copolymers of propylene and a small amount of other α-olefins, for example, Examples thereof include a propylene / ethylene copolymer, a propylene / hexene-1 copolymer and a propylene / 4-methyl-1-pentene copolymer. The blended olefinic plastic has a melt index (ASTM 1238-65T, 230 ° C.) of 0.
It is preferably in the range of 1 to 100, particularly 5 to 50. In the present invention, such an olefin-based plastic serves to improve the fluidity and heat resistance of the propylene-based polymer composition.

In the present invention, such an olefin-based plastic is usually 300 parts by weight or less, preferably 20 parts by weight, based on 100 parts by weight of the propylene-based polymer composition.
It is used in a proportion of 0 parts by weight or less.

The molded product formed from the propylene polymer composition of the present invention is excellent in impact resistance and heat resistance, and is also excellent in coatability with paints such as urethane paints.

For example, a mere blend (uncrosslinked product) of the above-mentioned components (a), (b) and (c), or a propylene-based polymer and an olefin-based elastomer graft-modified with an unsaturated carboxylic acid [(b Component)], the propylene-based polymer composition of the present invention is particularly excellent in heat resistance and coatability.

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.

[0055]

The propylene-based polymer composition of the present invention is
It has excellent impact resistance and heat resistance, as well as excellent paintability for paints such as urethane paints.

Further, the propylene 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) Physical properties A test piece was punched out from a 3 mm square plate and measured by the following methods.

Tensile properties: The stress at 100% elongation (M ₁₀₀ ), tensile strength (T _s ) and tensile elongation at break (E _s ) were measured according to the method of JIS K-6301.

[0060] Spring hardness (H _S): JIS K-
6301 JIS A type method or Shore D type method.

Initial flexural modulus (FM): ASTM D
It was measured according to the method of 790.・ Permanent elongation (P
S): 100 measured according to JIS K-6301
It was indicated by the residual elongation at the time of% elongation.

Softening temperature (SP): Measured with a DuPont TMA measuring device. It was expressed as the temperature at which a needle having a diameter of 0.8 mm penetrates into the test piece by 0.1 mm under the conditions of a temperature rising rate of 20 ° C./min and a load of 49 g. (2) Coating test ○ Preparation of test piece The following paint was applied to a rectangular plate molded by a 50-ton injection molding machine. 1-component urethane-based paint: Flexen # 105 (trade name, manufactured by Nippon Bee Chemical Co., Ltd.) Dry film thickness: 60 μm Baking temperature and time: 120 ° C., 30 minutes In addition, the above-mentioned coating is applied unless otherwise specified in the examples. The square plate surface was wiped with a cloth impregnated with isopropanol before. ○ Cross-cut test A cross-cut test piece was prepared according to the method of the cross-cut test described in JIS K5400, and a cellophane tape (manufactured by Nichiban Co., Ltd., trade name) was attached to the test piece. Was quickly pulled in the direction of 90 ° for peeling, and the number of crosses 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.

[0063]

Example 1 MFR (ASTM D-1238-85
T, 230 ° C.) 13 g / 10 min polypropylene (hereinafter abbreviated as PP) 30 parts by weight, ethylene content 70 mol%, iodine value 12, Mooney viscosity ML _{1 + 4} (100 ° C.)
120 ethylene propylene 5-ethylidene-2-
Norbornene diene copolymer rubber (hereinafter EPDM-1
70 parts by weight was kneaded with a Banbury mixer in a nitrogen atmosphere at 180 ° C. for 5 minutes, and then passed through a roll to produce square pellets with a sheet cutter.

Next, 100 parts by weight of the obtained square pellets were mixed with 2-hydroxyethyl acrylate (hereinafter referred to as HEA).
0.5 parts by weight, dibutyltin dilaurate (hereinafter abbreviated as DBTDL) 0.2 parts by weight, divinylbenzene (hereinafter abbreviated as DVB) 0.5 parts by weight,
0.3 parts by weight of 5-dimethyl-2,5-di- (tert-butylperoxy) hexyne-3 (hereinafter abbreviated as peroxide) was added and mixed with stirring with a Henschel mixer, and the pellets were A propylene-based polymer composition was produced by extruding a twin-screw extruder (L / D = 42, screw diameter 30 mm) at a temperature of 250 ° C. under a nitrogen atmosphere.

Table 1 shows various physical properties measured on the obtained propylene polymer composition and coating test results.

[0066]

Examples 2 to 3 A propylene polymer composition was produced in the same manner as in Example 1 except that the blending amount of HEA was changed as shown in Table 1.

Table 1 shows various physical properties of the obtained propylene polymer composition and coating test results.

[0068]

Comparative Example 1 A propylene-based polymer composition was produced in the same manner as in Example 1 except that HEA and DBTDL were not added.

Table 1 shows various physical properties measured on the obtained propylene polymer composition and coating test results.

[0070]

Comparative Example 2 A propylene-based polymer composition was produced in the same manner as in Example 1 except that DBTDL was not added.

Table 1 shows various physical properties of the obtained propylene-based polymer composition and coating test results.

[0072]

Comparative Example 3 A propylene polymer composition was produced in the same manner as in Example 1 except that HEA was not added.

Table 1 shows various physical properties measured on the obtained propylene polymer composition and coating test results.

[0074]

Examples 4 to 6 Propylene-based polymer compositions were produced in the same manner as in Example 1 except that the compounding amounts of the respective components were changed as shown in Table 1.

Table 1 shows various physical properties of the obtained propylene-based polymer composition and coating test results.

[0076]

Example 7 Example 1 was repeated except that 1,4-diazabicyclo [2.2.2] octane (hereinafter abbreviated as DABCO) was used in place of DBTDL in Example 1.
A propylene-based polymer composition was produced in the same manner as in.

Table 1 shows various physical properties and coating test results of the obtained propylene polymer composition.

[0078]

Example 8 Example 1 was repeated except that 0.2 parts by weight of DACBO was added in addition to the components of Example 1.
A propylene-based polymer composition was produced in the same manner as in.

Table 1 shows various physical properties and coating test results of the obtained propylene polymer composition.

[0080]

Example 9 In Example 1, the amount of PP is 50 parts by weight, and instead of EPDM-1, ethylene content is 70 mol%, iodine value is 10, Mooney viscosity ML _{1 + 4} (1
(00 ° C.) 70, oil extension amount of 20 parts by weight (that is, rubber component is 50 parts by weight) pelletized ethylene propylene 5-
Ethylidene-2-norbornene copolymer rubber (hereinafter referred to as E
(Abbreviated as PDM-2) and the extrusion temperature is 230
A propylene-based polymer composition was produced in the same manner as in Example 1 except that the temperature was changed to ° C.

Table 1 shows various physical properties and coating test results of the obtained propylene polymer composition.

[0082]

Examples 10 to 11 Propylene polymer compositions were produced in the same manner as in Example 9 except that the compounding amounts of the respective components were changed as shown in Table 1.

Table 1 shows various physical properties and coating test results of the obtained propylene polymer composition.

[0084]

[Table 1]

Claims (2)

[Claims] (A) 90 to 10 parts by weight of a propylene-based polymer, (b) 10 to 90 parts by weight of an olefinic elastomer, wherein the total amount of the (a) component and the (b) component is 100.
(C) Hydroxyl group-containing ethylenically unsaturated compound 0.01 to
A composition comprising 10 parts by weight, (d) 0.05 to 10 parts by weight of an organotin compound and / or a tertiary amino compound, which is dynamically heat treated in the presence of an organic peroxide. A propylene-based polymer composition, which is partially crosslinked. 2. (a) 90 to 10 parts by weight of a propylene-based polymer, (b) 10 to 90 parts by weight of an olefin elastomer, wherein the total amount of the (a) component and the (b) component is 100.
Parts by weight] With respect to 100 parts by weight of the total amount of the components (a) and (b), (c) a hydroxyl group-containing ethylenically unsaturated compound 0.01 to
10 parts by weight, (d) Organotin compound and / or tertiary amino compound 0.05 to 10 parts by weight, (e) Peroxide non-crosslinking rubbery substance 0 to 100 parts by weight, (f) Mineral oil-based Softening agent A composition comprising 0 to 200 parts by weight of a softening agent, which is dynamically heat-treated in the presence of an organic peroxide to be partially crosslinked, which is a propylene polymer composition. .