JPH05320442A - Propylene polymer composition - Google Patents

Abstract

PURPOSE:To obtain a propylene polymer compsn. having an improved coatability by compounding a propylene polymer, an olefinic elastomer, a hydroxyl- terminated conjugated diene polymer, and an organotin compd. and/or a tertiary amine compd. CONSTITUTION:100 pts.wt. mixture of 99-10 pts.wt. propylene polymer (e.g. an ethylene-propylene random copolymer) with 1-90 pts.wt. olefinic elastomer (e.g. an ethylene-butene-1 copolymer rubber). 0.01-20 pts.wt. conjugated diene polymer having at least one molecular terminal hydroxylated (e.g. a hydroxyl- terminated polybutadiene) or hydrogenation product thereof, and 0.05-10 pts.wt. organotin compd. (e.g. dibutyltin dilaurate) and/or a tertiary amine compd. (e.g. dimethylpropylamine) are compounded to give the objective compsn.

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-3-157168 discloses a composition in which a diene polymer having a hydroxyl group at the molecular end is added to a propylene-based polymer. Although a method for coating a molded body 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 of the components is 100 parts by weight] With respect to 100 parts by weight of the total amount of the components (a) and (b), (c)
0.01 to 10 parts by weight of a conjugated diene polymer having a hydroxyl group at at least one of the molecular ends or a hydrogenated product thereof,
(D) A propylene polymer composition comprising 0.05 to 10 parts by weight of an organotin compound and / or a tertiary amino compound is provided.

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.

[0009]

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 comprises (a) a propylene-based polymer, (b) an olefin-based elastomer, (c) a conjugated diene polymer having a hydroxyl group at at least one of the molecular terminals, or a hydrogenated product thereof, and (D) Consists of an organotin 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 .

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.

[Conjugated diene polymer having a hydroxyl group at at least one of its molecular ends or its hydrogenated product (c)] The conjugated diene polymer having a hydroxyl group at at least one of its molecular ends or its hydrogenated product ( Examples of c) include terminal hydroxyl group polybutadiene, terminal hydroxyl group polyisoprene, terminal hydroxyl group polybutadiene hydrogenated product, and terminal hydroxyl group polyisoprene hydrogenated product.

These polymers have a number average molecular weight (Mn)
Is 300 to 200,000, preferably 500 to 10
30,000, particularly preferably 1,000 to 10,000
Is in the range. Further, these polymers have an average number of hydroxyl groups per molecule of 0.5 to 10, preferably 1 to 5, and a hydroxyl value of 10 to 200, preferably 20 to 100.
KOH mg / g.

The conjugated diene polymer having a hydroxyl group at at least one of the molecular terminals is produced from the conjugated diene as a raw material by a conventionally known method such as a radical polymerization method or an anionic polymerization method. In the case of the radical polymerization method, the conjugated diene polymer can be easily obtained by polymerizing a diene-based monomer with hydrogen peroxide as a polymerization initiator. Further, in order to obtain a conjugated diene polymer having a hydroxyl group at the molecular end by an anionic polymerization method, the living polymer may be reacted with, for example, a monoepoxy compound, formaldehyde, acetaldehyde or acetone, or halogenoalkylene oxide or polyepoxide.

The living polymer referred to here is
According to a well-known method, a conjugated diene is an anionic polymerization catalyst,
For example, it refers to a polymer produced by polymerizing with an alkali metal or organic alkali metal compound and having a structure in which an alkali metal is bonded to at least one of both ends thereof.

Specific examples of the conjugated diene as a raw material for the above-mentioned conjugated diene polymer include 1,3-butadiene, isoprene, chloroprene, 1,3-pentadiene, 2,3-dimethyl-1, Examples thereof include 3-butadiene and 1-phenyl-1,3-butadiene. These conjugated dienes may be used alone or in combination.

Hydrogenation to the above conjugated diene polymer is
Generally used catalytic hydrotreating means can be adopted. As the hydrogenation catalyst, it is possible to use a nickel catalyst (for example, Raney nickel), cobalt, platinum palladium, ruthenium, rhodium, etc., a single, mixed or alloy type catalyst. These catalysts can be used alone, as a solid or soluble homogeneous complex, or supported on carbon, silica, alumina, diatomaceous earth or the like. Furthermore, the conjugated diene polymer may be hydrogenated using a metal complex obtained by reducing a compound containing nickel, titanium, and cobalt with an organometallic compound (eg, trialkylaluminum, alkyllithium, etc.).

Molecular hydrogen is usually used as the hydrogen used in the above hydrogenation, but a hydrogen-containing gas may be used as long as it does not contain a substance which becomes a catalyst poison. The hydrogen pressure may be either a normal pressure flow or a pressurized system. The temperature of hydrogen is room temperature to 200 ° C., preferably 1
It is 80 ° C or lower.

The conjugated diene polymer can be used alone or as a solvent solution. Examples of the solvent include aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, alcohols, and aliphatic carboxylic acids. These solvents can be used alone or in combination.

As another method for producing the conjugated diene polymer (c) used in the present invention, there is a method in which the conjugated diene polymer is oxidized, decomposed and then reduced.
For example, a polyhydroxy conjugated diene polymer can be obtained by subjecting a polymer obtained by cationically polymerizing a conjugated diene to ozone decomposition and then subjecting it to a reduction treatment with lithium aluminum hydride.

[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 compounding amount of such a tertiary amino compound is 0.05 to 10 parts by weight, preferably 0.05 to 5 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 95
10 to 10 parts by weight, particularly preferably 95 to 40 parts by weight,
(B) 1 to 90 parts by weight, preferably 5 to 90 parts by weight, and particularly preferably 5 to 60 parts by weight of the olefin elastomer, based on 100 parts by weight of the total amount of the above components (a) and (b) , (C) Conjugated diene polymer having a hydroxyl group at at least one molecular end or hydrogenated product thereof 0.0
1 to 10 parts by weight, preferably 0.1 to 5 parts by weight,
(D) The organotin compound and / or the tertiary amino compound is produced by melt-kneading 0.05 to 10 parts by weight, preferably 0.05 to 5 parts by weight.

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 usually used in the field of propylene polymers is applied so that the above components are in the above composition ratio range. 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 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 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, 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 performed in a non-open type apparatus, and is preferably performed 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. 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 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.

[0053]

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., trade name) Dry film thickness: 60 μm Baking temperature and time: 100 ° C., 30 minutes ○ Cross-cut test According to the cross-cut test method described in JIS K5400, a cross-cut test piece is prepared. 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.

[0057]

Examples 1 to 14 [Production of Conjugated Diene Polymer Having Hydroxyl Group on At least One of Molecular Ends] In an autoclave having a capacity of 500 ml, 1,3-butadiene 100 g, isopropyl alcohol 70 g, and 60% hydrogen peroxide solution 10
g, and heated at 90 ° C. for 5 hours under a nitrogen atmosphere. Next, after cooling the autoclave, unreacted 1,3-butadiene was removed, and the produced polymer was taken out and dried.

The resulting butadiene polymer (hereinafter referred to as PB
Abbreviated as D. ) Had a number average molecular weight of 3,360 as measured by Vapor Osmometer and a hydroxyl value of 48 mgKOH / g.

[Production of Hydrogenated Product of Conjugated Diene Polymer Having Hydroxyl Group on At least One of Molecular Ends] 50 g of the above conjugated diene polymer (PBD) and 5 g of carbon-supported ruthenium catalyst (5%) were autoclaved in a volume of 200 ml. After charging the inside and replacing the air in the system with nitrogen, hydrogen gas was fed until the gas pressure reached 50 kg / cm ² . Next, this autoclave was heated to 100 ° C., hydrogen gas was supplied so that the total pressure was maintained at 50 kg / cm ² , and the hydrogenation reaction was carried out for 8 hours. After completion of the reaction, hydrogen was removed and the catalyst was filtered off. Then, the hydrogenated product of the produced conjugated diene polymer was precipitated in methanol and dried.

The hydrogenated product of the obtained conjugated diene polymer (hereinafter abbreviated as HPBD) had an iodine value of 1.2 and a hydroxyl value of 45 mgKOH / g. [Production of Propylene-Based Polymer Composition] Each component shown in Table 1 was melt-kneaded at 230 ° C. by a twin-screw extruder to produce a propylene-based polymer composition.

Various test pieces were molded from this composition by an injection molding machine, and various properties were measured according to the above-mentioned methods. In addition,
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 ○ Propylene / ethylene block copolymer (PP-3) MFR: 14 g / 10 min, ethylene content 12 mol%, density: 0.91 g / cm ³ Olefin system Elastomer ○ Ethylene / propylene copolymer rubber (EPR) Mooney viscosity ML _{1 + 4} (100 ° C): 60, MFR (2
30 ° C.): 0.7 g / 10 minutes, ethylene content: 81 mol% ○ Ethylene / propylene / non-conjugated diene copolymer rubber (E
PDM-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: 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 resins 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 wt% 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.

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Comparative Examples 1 to 7 Each component shown in Table 2 was melt-kneaded at 230 ° C. by a twin-screw extruder to produce a propylene polymer composition.

Various test pieces were molded from this composition by an injection molding machine, and various properties were measured according to the above-mentioned methods. The results are shown in Table 2.

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[Table 1]

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[Table 2]

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Claims (2)

[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] With respect to 100 parts by weight of the total amount of the above-mentioned components (a) and (b), (c) a conjugated diene polymer having a hydroxyl group at at least one molecular end or a hydrogenated product thereof 0.01 10 to 10 parts by weight, (d) an organotin compound and / or a tertiary amino compound 0.05 to 10 parts by weight, which is a propylene polymer composition. 2. 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.