JPH09118794A - Propylene polymer composition - Google Patents

Abstract

(57) 【Abstract】 PROBLEM TO BE SOLVED: Excellent adhesion to paints such as melamine resin-based paints and urethane resin-based paints even without pretreatment such as surface treatment, solvent cleaning or primer undercoating. A propylene-based polymer composition is provided. SOLUTION: (a) Propylene-based polymer 1 to 99 parts by weight, (b) Olefin-based elastomer 99 to 1 parts by weight [however, the total amount of the components (a) and (b) is 100 parts by weight], And a propylene-based polymer composition comprising 1 to 30 parts by weight of (c) an oxidized polyolefin wax based on 100 parts by weight of the total amount of the components (a) and (b). (C) The oxidized polyolefin wax contains (i) an α-olefin unit having 2 to 10 carbon atoms as a main component,
(ii) Intrinsic viscosity 0.06-1.0 dl / g, (iii) Density 0.8
It is preferable that 6-0.99 g / cm ³ and (vi) acid value be 0.1-50.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD OF THE INVENTION The present invention relates to a propylene-based polymer composition having excellent coatability, more specifically, a surface treatment,
The present invention relates to a propylene-based polymer composition that exhibits excellent adhesion to paints such as melamine resin-based paints and urethane resin-based paints even when it is not pretreated by solvent cleaning or primer undercoating.

[0002]

TECHNICAL BACKGROUND OF THE INVENTION Propylene-based polymers such as crystalline polypropylene are excellent in various properties such as mechanical properties, heat resistance, solvent resistance, oil resistance and chemical resistance, and are suitable for use in automobiles, electric equipment, etc. It is widely used industrially as a raw material for manufacturing industrial parts and daily necessities.

Since this propylene-based polymer has no polar group in its molecular structure, it is chemically inert and highly safe, but on the other hand, it has poor affinity and adhesion with other resins. However, there is a problem in that the coatability is poor.

Therefore, when a propylene-based polymer molded article is coated with a urethane resin-based coating or the like, it is necessary to improve the affinity for the coating resin prior to coating. For example, an electrical treatment method such as corona discharge, Mechanical roughening method,
The surface treatment was performed on the molded product by a flame treatment method, an oxygen treatment method, an ozone treatment method, or the like. As a pretreatment for such surface treatment, the surface of the molded article is washed with a solvent such as alcohol or aromatic hydrocarbon, or is washed with a solvent vapor such as trichlene, perchlorethylene, pentachloroethylene or toluene. There is.

However, in order to surface-treat a molded article in this manner, an apparatus for surface treatment and cleaning treatment is required by any of the methods, which is disadvantageous in terms of equipment, and is not suitable for these treatments before coating. It takes a considerable amount of time.

In addition, the molded article which has been subjected to the surface treatment as described above may be primed with a primer before directly coating the urethane resin type paint or the like, but a coating film having a two-layer structure including an undercoat layer is formed. Therefore, the painting work becomes complicated and the painting process takes a long time. Therefore, there is a problem that the cost of the molded product is increased.

As described above, when a molded article made of a conventionally known propylene-based polymer is applied, it is generally necessary to perform some pretreatment on the molded article before coating. This is a cause of complicating the coating process of the propylene-based polymer molded product and increasing the coating cost. Therefore, it has been earnestly desired to develop a propylene-based polymer exhibiting excellent coatability without performing a pretreatment before coating.

[0008]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned prior art, and is a propylene-based resin which exhibits excellent coatability with respect to paints such as melamine resin paints and urethane resin paints. The purpose is to provide a combined composition.

[0009]

SUMMARY OF THE INVENTION The propylene polymer composition of the present invention comprises
(A) Propylene-based polymer 1 to 99 parts by weight, (b) Olefin-based elastomer 99 to 1 parts by weight [however, the total amount of components (a) and (b) is 100 parts by weight], and (c). Oxidized polyolefin wax 1 to 3 relative to 100 parts by weight of the total amount of the above components (a) and (b).
It is characterized by comprising 0 parts by weight. In the present invention, the (c) oxidized polyolefin wax contains (i) at least one unit derived from an α-olefin having 2 to 10 carbon atoms as a main component, and (ii) measured in decalin at 135 ° C. Has an intrinsic viscosity of 0.06 to 1.0 dl / g, (iii) a density of 0.80 to 0.99 g / cm ³ , and (vi) an acid value of 0.1 to 50 mgKOH / g. , Is preferred. The (c) oxidized polyolefin wax has an intrinsic viscosity of 0.1 measured in decalin at 135 ° C.
06-2.0 dl / g and a density of 0.80-0.9
It is preferable 9 g / cm ³ and a carbon number 2-10 α- olefin (co) is an oxide of the polymer wax.

[0010]

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the propylene polymer composition according to the present invention will be described in detail. The propylene-based polymer composition according to the present invention comprises (a) a propylene-based polymer, (b) an olefin-based elastomer, and (c) an oxidized polyolefin wax, and contains each of these components in a specific ratio. Each component forming the propylene-based polymer composition will be described.

(A) Propylene Polymer The propylene polymer used in the present invention may be a propylene homopolymer or a copolymer of propylene and another α-olefin.

Α forming a copolymer with propylene
As the olefin, specifically, ethylene, 1-butene, 1-pentene, 2-methyl-1-butene, 3-methyl-1-butene, 1-hexene, 3-methyl-1-pentene, 4-methyl -1-pentene, 3,3-dimethyl-1-butene, 1-heptene, methyl-
1-hexene, dimethyl-1-pentene, trimethyl-1-butene, ethyl-1-pentene, 1-octene, methyl-1-pentene, dimethyl-1-hexene, trimethyl-1-pentene, ethyl-1-hexene, Methyl ethyl-1-pentene, diethyl
-1-butene, propyl-1-pentene, 1-decene, methyl-1
-Nonene, dimethyloctene, trimethyl-1-heptene,
Mention may be made of ethyl-1-octene, methylethyl-1-heptene, diethyl-1-hexene, 1-dodecene and hexadodecene. These α-olefins may form a random copolymer with propylene,
Also, a block copolymer may be formed.

In the present invention, as the propylene-based polymer (a), those showing crystallinity are preferable, and specifically, a propylene homopolymer or a unit derived from ethylene in an amount of 2 to 40 mol%. A crystalline propylene / ethylene block copolymer containing, a crystalline propylene / ethylene block copolymer containing 0.5 to 10 mol% of a unit derived from ethylene.
An ethylene random copolymer is preferably used.

The propylene polymer used in the present invention has a melt flow rate (MFR, measured at 230 ° C. and a load of 2.16 kg) of usually 0.05 to 200 g / 10 minutes, preferably 0.05 to It is 100 g / 10 minutes, more preferably 0.5 to 60 g / 10 minutes. Such MFR
By using a propylene-based polymer having a value,
The propylene-based polymer composition can ensure good moldability. The density of the propylene-based polymer used in the present invention is usually desirably 0.89 to 0.92 g / cm ³ .

The propylene polymer (a) having the above characteristics can be produced by various methods. For example, a catalyst formed from a solid titanium catalyst component and an organometallic compound, or both components. And a catalyst formed from an electron donor.

As the solid titanium catalyst component, titanium trichloride, titanium tetrachloride or a composition produced by various methods, magnesium, halogen, an electron donor, preferably an aromatic carboxylic acid ester or an alkyl group-containing ether and titanium are used. And preferably a titanium catalyst component supported on a carrier having a specific surface area of 100 m ² / g or more. Particularly, the titanium catalyst component produced by using the latter catalyst component with a carrier is suitable.

The organometallic compound component is preferably an organoaluminum compound, and specific examples of the organoaluminum compound include trialkylaluminum,
Examples thereof include dialkylaluminum halide, alkylaluminum sesquihalide, and alkylaluminum dihalide. The organoaluminum compound can be appropriately selected according to the type of the titanium catalyst component used.

Examples of the electron donor include organic compounds having oxygen atom, nitrogen atom, phosphorus atom, sulfur atom, silicon atom or boron atom, and ester compounds and ether compounds having these atoms are suitable. As an example:

A method for producing a propylene-based polymer using the catalyst component with a carrier as described above is disclosed in, for example, Japanese Patent Laid-Open Publication No.
0-108385, 50-126590, 51
-20297, 51-18989, 52-15
It is disclosed in detail in publications such as 1691, and in the present invention, the propylene-based polymer can be produced by utilizing the techniques described therein. In the present invention,
It is also possible to use a combination of two or more of the above propylene-based polymers.

(B) Olefin Elastomer As the olefin elastomer used in the present invention,
Examples thereof include a random copolymer of two or more α-olefins, or a random copolymer of α-olefins and non-conjugated dienes. As this α-olefin, ethylene,
Propylene, 1-butene, 1-pentene and the like can be mentioned.
Examples of non-conjugated dienes include dicyclopentadiene, 1,4-hexadiene, dicyclooctadiene, methylene norbornene, and 5-ethylidene-2-norbornene.

Specific examples of such olefin elastomers include ethylene / propylene random copolymers, ethylene / 1-butene random copolymers, ethylene / propylene / 1-butene random copolymers and ethylene / ethylene / propylene random copolymers.
Main component is α-olefin such as propylene / non-conjugated diene random copolymer, ethylene / 1-butene / non-conjugated diene random copolymer, ethylene / propylene / 1-butene / non-conjugated diene random copolymer An amorphous elastic copolymer can be mentioned. Among these, those containing ethylene as a main component are preferable.

The melt flow rate (MFR) of the olefinic elastomer measured at 230 ° C. is from 0.01 to
It is preferably 50 g / 10 minutes, and more preferably 0.01
It is preferably from 10 to 10 g / 10 minutes, particularly from 0.01 to 5 g / 10 minutes. The Mooney viscosity of the olefinic elastomer used in the present invention [ML _{1 + 4} (100 ° C .; JIS K
6300)] is preferably 10 to 150,
It is more preferably 40 to 120.

The iodine value (unsaturation) of the olefin elastomer is preferably 16 or less. Further, in the present invention, two or more kinds of the above olefinic elastomers may be used in combination.

(C) Oxidized Polyolefin Wax (i) The oxidized polyolefin wax (c) used in the present invention contains at least one unit derived from an α-olefin having 2 to 10 carbon atoms as a main component. .
Specific examples of the α-olefin having 2 to 10 carbon atoms include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1
-For example, decene. Among the above, the oxidized polyolefin wax contains a unit derived from ethylene, propylene, 1-butene or 4-methyl-1-pentene as a main component and is compatible with the propylene polymer (a). It is preferable because it is excellent.

(Ii) Intrinsic viscosity of the oxidized polyolefin wax used in the present invention (measured in decalin at 135 ° C.)
Is from 0.06 to 1.0 dl from the viewpoint of the dispersibility in the propylene polymer (a) and the effect of improving the coatability of the resulting composition.
/ G, preferably 0.08 to 0.8 dl /
It is more preferably g, particularly 0.1 to 0.6 dl / g.

(Iii) The density of the oxidized polyolefin wax used in the present invention is usually 0.80 to 0.99 g / cm ^3.
And preferably 0.83 to 0.98 g / cm ³ , and more preferably 0.85 to 0.98 g / cm ³ .

(Vi) The acid value of the oxidized polyolefin wax used in the present invention is usually 0.1 to 50 mgKOH /
g, preferably 0.5 to 40 mgKOH / g, more preferably 1.0 to 35 mgKOH / g.

The crystallinity of the above-mentioned oxidized polyolefin wax (c) is preferably 50 to 90%, more preferably 53 to 85%, and particularly preferably 55 to 80%. When the crystallinity of the oxidized polyolefin wax is such a value, the composition can be formed without impairing the characteristics of the propylene polymer (a). GPC of oxidized polyolefin wax (c)
The molecular weight distribution (Mw / Mn) measured by (gel permeation chromatography) is usually preferably 10 or less, more preferably 5 or less, and particularly preferably 4 or less.

The oxidized polyolefin wax (c) used in the present invention is an α-olefin (co) polymer having as a main component a unit derived from at least one of the above-mentioned α-olefins having 2 to 10 carbon atoms. Obtained by oxidizing the combined wax. Specific examples of the raw material wax to be oxidized include ethylene homopolymer wax, ethylene / propylene random copolymer wax, ethylene / 1-butene copolymer wax, ethylene-4-methyl-1-pentene copolymer wax. , Propylene homopolymer wax, propylene / ethylene block copolymer wax, propylene / ethylene random copolymer wax, ethylene / 1-butene random copolymer wax, ethylene / propylene / 1-butene terpolymer wax Can be mentioned. Among these, ethylene homopolymer wax, propylene homopolymer wax, and propylene content of 10 mol% or less, preferably 1 to 5
Mol% ethylene / propylene random copolymer wax, ethylene content of 10 mol% or less, preferably 1 to 5 mol% or less, propylene / ethylene random copolymer wax, ethylene / 1-butene copolymer wax, ethylene / 4 -Methyl-1-pentene copolymer wax and the like are preferably used.

The intrinsic viscosity of this raw material polyolefin wax (measured in decalin at 135 ° C.) was 0.06 to 2.0 dl.
/ G is preferable, and further 0.08 to 1.6 dl
/ G, more preferably 0.1 to 1.4 dl / g.

The density of the raw material polyolefin wax is usually preferably 0.80 to 0.99 g / cm ³ . The raw material polyolefin wax has a crystallinity of 50.
It is preferably about 90%.

The raw material polyolefin wax as described above can be produced by various known methods. For example, in the presence of a catalyst formed from (1) a highly active titanium catalyst component containing a magnesium compound and an organoaluminum compound having a halogen / Al (atomic ratio) of 1 to 2 and preferably 1.05 to 1.4, A method of polymerizing an α-olefin having 2 to 10 carbon atoms in the presence of hydrogen at a temperature of 100 ° C. or higher, and (2) thermally degrading a high molecular weight polymer composed of an α-olefin having 2 to 10 carbon atoms. How to get,
(3) A method of performing polymerization in the presence of a chain transfer agent when radically polymerizing ethylene at high temperature and high pressure can be mentioned.

As the high activity titanium catalyst component used in the above method (1), a solid high activity catalyst component with a carrier is suitable. Such highly active titanium catalyst components are widely known, for example, Japanese Patent Publication No. 46-34092, Japanese Patent Publication No. 46-34094, Japanese Patent Publication No. 46-34098, Japanese Patent Publication No. 47-41676, Japanese Patent Publication No. 47-46269, and Japanese Patent Publication No. 5269.
No. 0-32270, Japanese Patent Publication No. 53-1796, and the like, and in the present invention, the polyolefin wax can be produced by utilizing the techniques described therein. The soluble high-activity titanium catalyst component is disclosed in, for example, JP-A-55-78004.

In the above method (2), the thermal degradation (thermal decomposition) of the high molecular weight polymer can be carried out in the presence or absence of a peroxide. As this high molecular weight polymer, a high molecular weight polymer formed from an olefin similar to the olefin forming the above-mentioned polyolefin wax is used.

When the thermal decomposition of the high molecular weight polymer is carried out in the absence of peroxide, the thermal decomposition reaction is carried out at 300-4
It is preferable to carry out at a temperature of 60 ° C., preferably 350 to 440 ° C. When the thermal decomposition of the high molecular weight polymer is carried out in the presence of peroxide, the thermal decomposition reaction is carried out at 150 to 3
It is preferable to carry out at a temperature of 80 ° C., preferably 170 to 300 ° C. Examples of peroxides include 2,5-dimethyl
-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, dibutyl peroxide, dicumyl peroxide, t-butyl. Cumyl peroxide, dialkyl peroxides such as α, α'-bis (t-butylperoxy-metaisopropyl) benzene, t-butyl hydroperoxide, cumene hydroperoxide, 2,5-dimethylhexane-2,5- Hydroperoxides such as dihydroperoxide and 1,1,3,3-tetramethylbutyl hydroperoxide can be used. It is also possible to use two or more of these in combination. Among these, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane and 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3 are preferably used. .
The peroxide can be used in an amount of usually about 0.01 to 5 parts by weight, preferably about 0.05 to 3 parts by weight, based on 100 parts by weight of the high molecular weight polymer.

As the thermal decomposition reactor, for example, a tubular reactor, a tank reactor, a single-screw or twin-screw extruder, etc. can be used without particular limitation. Among these, when the thermal decomposition reaction is carried out in the absence of peroxide, a tubular reactor which can easily be heated at a high temperature is suitable. When the thermal decomposition reaction is carried out in the presence of peroxide, an extruder capable of sufficiently kneading is suitable.

The oxidized polyolefin wax (c) according to the present invention is obtained by oxidizing the above-mentioned polyolefin wax, and specifically, it is obtained by bringing the polyolefin wax into contact with an oxygen-containing gas. The oxygen-containing gas may be pure oxygen (obtained by liquid air fractionation or electrolysis of water, and may contain other components to the extent that oxygen is contained as an impurity), and pure oxygen and other gases Mixed gas such as air, and ozone may be included.

When the polyolefin wax and the oxygen-containing gas are brought into contact with each other, for example, the molten polyolefin wax is heated to about 120 to 200 ° C., preferably
Contact with an oxygen-containing gas at about 140-170 ° C. At this time, the polyolefin wax may be dispersed in water and supplied to the oxidation reaction. More specifically, for example, it is preferable to continuously supply the oxygen-containing gas into the reactor from the lower part of the reactor to bring it into contact with the polyolefin wax. At this time, the oxygen-containing gas is polyolefin wax 1k.
It is preferable to supply oxygen in an amount of 1.0 to 10.0 Nl per minute with respect to g. As described above, it is preferable to obtain the oxidized polyolefin wax having the above-mentioned acid value. In the present invention, two or more kinds of the above oxidized polyolefin wax (c) may be used in combination.

Propylene-Based Polymer Composition The propylene-based polymer composition according to the present invention comprises the above-mentioned (a) propylene-based polymer, (b) olefin-based elastomer, and (c) oxidized polyolefin wax. When the total amount of the propylene polymer (a) and the olefin elastomer (b) is 100 parts by weight,
99 parts by weight of (a) propylene-based polymer, 1-99 parts by weight, preferably 20-95 parts by weight, and more preferably 30-80 parts by weight of (b) olefin-based elastomer.
To 1 part by weight, preferably 80 to 5 parts by weight, and more preferably 70 to 20 parts by weight, and (c) the oxidized polyolefin wax is 100 parts by weight in total of the components (a) and (b). To 1 to 30 parts by weight, preferably 1 to 1
It is contained in an amount of 0 parts by weight, more preferably 2 to 7 parts by weight.

Propylene-based polymer composition according to the present invention
Is the above components within the range not impairing the object of the present invention.
Both may optionally contain other components. like this
Examples of such optional components include organic compounds represented by the following formula.
Compound and a tertiary amino compound. R¹-SnX¹Y¹Y^Two (Where R¹Is an alkyl group having 4 to 10 carbon atoms, and X is
¹Is an alkyl group having 4 to 10 carbon atoms, a chlorine atom or hydroxy
Group, mercaptan, mercapto acid, Y¹And Y
^TwoIs a chlorine atom, OCOR^Two, Or a hydroxyl group,
They may be the same or different. R^TwoIs al
A kill group, an aryl group, and an allylalkyl group. ) As the organotin compound represented by the above formula,
Is n-C_FourH₉Sn (OH)_TwoCl, n-C_FourH₉Sn (O
H) Cl_Two, N-C_FourH₉SnCl _Three, C₈H₁₇Sn (OH)_Two
Cl, C₈H₁₇Sn (OH) Cl_Two, C₈H₁₇SnCl_Three,
n-C_FourH₉Sn (OH)_TwoOCOC₇H_Fifteen, N-C_FourH₉Sn
(OH)_TwoOCOC₁₁H_{Two Three}, N-C₈H₁₇Sn (OH)_TwoO
COC₇H_Fifteen, N-C₈H₁₇Sn (OH)_TwoOCOC
₁₁H_{twenty three}, N-C_FourH₉Sn (OCOC₇H_Fifteen)_Three, (N-C
_FourH₉)_TwoSn (OCOC₁₁H_{twenty three})_Two, (N-C₈H₁₇)_TwoSn
(OCOC₁₁H_{twenty three})_Two, (N-C_FourH₉)_TwoSn (OCOCH
= CHCOOCH_Three)_Two, (N-C_FourH₉)_TwoSn (OCOC
H = CHCOOCH_TwoPh)_TwoCan be mentioned
You. Among these, n-C_FourH₉SnCl_Three, (N-C
_FourH₉)_TwoSn (OCOC₁₁H_{twenty three}) _Two, (N-C₈H₁₇)_TwoSn
(OCOC₁₁H_{twenty three})_TwoAre preferred. According to the present invention
The ropylene polymer composition has an organotin compound as described above.
The propylene polymer (a) and the olefin elastomer.
0.01 to 5 with respect to 100 parts by weight in total with the mer (b).
Parts by weight, preferably in an amount of 0.05-5 parts by weight
May be.

Specific examples of the tertiary amino compound include dimethylpropylamine, diethylpropylamine, tris (dimethylaminomethyl) phenol, tetraguanidine, N, N-dibutylethanolamine, N-methyl-N, N-diethanolamine, 1,4-diazabicyclo [2.2.2.] Octane, 1,8-diazabicyclo [5.4.
0] -7-undecene and tetramethylbutanediamine.

The propylene-based polymer composition according to the present invention contains the above-described tertiary amino compound in a total amount of 1% of the propylene-based polymer (a) and the olefin-based elastomer (b).
It may be contained in an amount of 0.01 to 5 parts by weight, preferably 0.05 to 3 parts by weight, based on 00 parts by weight.

When the propylene polymer composition according to the present invention contains the above-mentioned organic tin compound and / or tertiary amine compound, the adhesiveness with the urethane coating is further improved. . That is, since these compounds act as a curing reaction catalyst for the isocyanate group and the polyol in the urethane-based paint, it is possible to form a coating film having excellent adhesion, particularly from the urethane-based paint.

Further, the propylene polymer composition according to the present invention comprises a thermoplastic resin other than the above, a softening agent, a filler, a pigment, a stabilizer, a plasticizer, a flame retardant, a lubricant, an antistatic agent, and an electrical agent. You may contain property improving agents etc. as needed.

Specific examples of such a thermoplastic resin include high-density polyethylene, medium-density polyethylene, high-pressure low-density polyethylene, linear low-density polyethylene, and poly-ethylene.
1-butene, propylene / 1-butene copolymer, styrene /
Examples thereof include a butadiene (.styrene) block copolymer and a hydrogenated product thereof, and a styrene-isoprene (.styrene) block copolymer and a hydrogenated product thereof.

Examples of the softening agent include mineral oil-based softening agents, for example, known high-boiling petroleum fractions classified into paraffin-based, naphthene-based, aromatic-based and the like. This softening agent weakens the intermolecular force of the olefin-based elastomer to facilitate processing, and also serves as a dispersion aid for carbon black, white carbon, etc. to be blended as a filler, or to lower the hardness of the vulcanized elastomer. It is used to increase flexibility and elasticity.

Specific examples of the filler include light calcium carbonate, heavy calcium carbonate, basic calcium carbonate,
Aluminum hydroxide, magnesium hydroxide, magnesium oxide, kaolin, clay, pyroferrite, sericite, talc, calcium silicate (wollastonite,
Zonotolite, petal-like calcium silicate), diatomaceous earth,
Aluminum silicate, anhydrous silicic acid, hydrous silicic acid, mica, magnesium silicate (asbestos, PMF (Proces
sed Mineral Fiber), sepiolite), potassium titanate, elestadite, gypsum, glass balun, silica balun, fly ash balun, silas balun, carbon balun, phenol 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 flakes), cut fibers, rock fibers, microfibers, carbon fibers, aromatic polyamide fibers, potassium titanate fibers, coumarone indene resins, petroleum resins and the like.

Specific examples of the colorant include carbon black, titanium oxide, zinc white, red iron oxide, ultramarine blue, dark blue, azo pigments, nitroso pigments, lake pigments and phthalocyanine pigments.

As the other component, a phenol type,
Known heat stabilizers such as sulfide-based, phenylalkane-based, phosphite-based or amine-based stabilizers,
Anti-aging agent, weather resistance stabilizer, antistatic agent, metal soap,
Lubricants such as wax can be mentioned. The propylene-based polymer composition according to the present invention can contain the above-mentioned various additives in an amount such that they are generally added to an olefin-based plastic or an olefin-based copolymer elastomer.

The propylene-based polymer composition according to the present invention is prepared by uniformly mixing the above-mentioned components. In order to uniformly mix the components, a mixing method generally used when preparing a composition containing an olefin polymer can be widely applied, but it is preferable to melt-knead the components. . As the kneading device, a mixing roll, an intensive mixer (for example, Banbury mixer, kneader, etc.), a single-screw or twin-screw extruder can be used,
A non-open device is desirable.

The kneading is usually carried out at a temperature of 150 to 280 ° C., preferably 170 to 240 ° C., usually for 1 to 20 minutes, preferably for 1 to 10 minutes. When mixing the respective components, the above-mentioned amounts of all the components may be mixed at the same time, or some of the components may be mixed in advance to prepare a mixture containing some of the components in a high concentration, that is, a so-called masterbatch. The masterbatch may then be mixed with the remaining ingredients to form a final composition containing the amounts of each ingredient.

After being kneaded in this way, the composition is usually obtained in the form of pellets. The propylene-based polymer molded product according to the present invention can be molded into a desired shape by a commonly used molding method such as an injection molding method, an extrusion molding method, a calender molding method, a blow molding method, or a vacuum molding method.

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

The amino resin-based paint includes melamine resin-based paint, benzoguanamine resin-based paint, and urea resin-based paint. These paints react a starting material having an amino group with formaldehyde to form a monomer having high reactivity, and form a coating film by a reaction between a methylol group formed by addition condensation and a hydroxyl group of an alcohol. It is a paint to be formed, and may be used in combination with a plasticized oil-modified alkyd resin, oil-free alkyd resin, oil varnish, acrylic resin, epoxy resin, or epoxy ester resin.

Of the above-mentioned paints, for example, a coating method using a urethane resin-based paint will be described as an example. A molded product formed from the propylene-based polymer composition according to the present invention is washed with water and generally. Washing with a typical industrial detergent is performed at least once, followed by washing with water and heating and drying. That is, when applying to a molded article formed from the propylene-based polymer composition according to the present invention, it is not always necessary to perform cleaning (surface treatment) using a chlorine-based solvent vapor, which has been conventionally performed. do not do. A urethane resin-based paint is applied to the dried body in this manner, and if necessary, heated, whereby a urethane resin coating film can be formed. The coating film thus formed has very good adhesion to the molded product, even though the cleaning using the chlorine-based solvent vapor has not been performed.

[0056]

The propylene polymer composition according to the present invention comprises a propylene polymer, an olefin elastomer,
Also, since it contains a specific oxidized polyolefin wax in a specific ratio, it has excellent coatability with respect to urethane resin-based paints, amino resin-based paints, and the like. Further, the propylene-based polymer composition as described above according to the present invention is excellent in 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. Are suitable. Utilizing the above characteristics, the propylene-based polymer composition according to the present invention is an automobile part, a motorcycle part, an electric device part, daily necessities, a civil engineering building material, a general industrial material, an office information device, a packaging material,
It can be widely used for applications to which painting is applied such as sports equipment and medical equipment.

[0057]

EXAMPLES The present invention will now be specifically described with reference to examples, but the present invention is not limited to these examples.
The various properties of the oxidized polyolefin wax and the propylene polymer composition used in Examples and Comparative Examples were measured as follows.

(1) Molecular Weight Distribution The molecular weight distribution (Mw / Mn) was measured by gel permeation chromatography as follows. Using GPC150C manufactured by Waters Co., temperature 140 ° C., solvent o-dichlorobenzene, measured flow rate 1.0 ml / min
Was measured at a concentration of 0.1 wt%. As columns, Tohso Corp. GMH-HT (60 cm) and GMH-HTL
(60 cm) connected was used. (2) Flexural Modulus (FM) Using a test piece having a thickness of 1/8 inch, ASTM D 79
0 was measured.

(3) Coating test [Preparation of test piece] The following paint was applied to a square plate molded by a 50-ton injection molding machine. Before applying the following paint, the surface of the square plate was wiped with a cloth impregnated with isopropanol. [Coating] A melamine resin-based coating [trade name R-320, manufactured by Nippon Bee Chemical Co., Ltd.] was coated with an air gun so that the dry film thickness was 60 μm. Baking at 120 ° C, 30
Performed in minutes. [Cross-cut test] A cross-cut test piece was produced according to the method of the cross-cut test described in JIS K 5400, and cellophane tape [Nichiban Co., Ltd., trade name] was attached to the test piece. Thereafter, this was quickly pulled in the direction of 90 ° to be peeled off, and the number of crosses where the coating film remained was counted and used as an index of adhesion. [Peeling strength test] A coating film was prepared on a base material, a cut was made in a width of 1 cm with a cutter blade until the blade reached the base material, and the end portion of the coating film was peeled off. 50 at the end
The peel strength was measured by pulling at a speed of mm / min in the direction of 180 ° until the coating film peeled.

In the following production examples, the intrinsic viscosity was 135.
It is a value measured in decalin at ° C. MFR is AST
According to MD 1238, it was measured at 230 ° C. under a load of 2.16 kg.

[0061]

[Production Example 1] Production of oxidized polyethylene wax Ethylene / propylene copolymer wax (intrinsic viscosity:
800 g of 0.23 dl / g, density: 0.931 g / cm ³ , propylene content: 4 mol%) was placed in a 2 liter capacity glass separable flask equipped with a stirrer, heated to 165 ° C. and melted. Then, while stirring, pure oxygen was continuously supplied from the bottom of the reactor at a rate of 6 Nl per minute and contacted for 10 hours to obtain 790 g of oxidized polyethylene wax having an acid value of 17 mgKOH / g. The obtained oxidized polyethylene wax (hereinafter abbreviated as MPO-1) has an intrinsic viscosity of 0.16 dl / g and a density of 0.947 g / cm.
^The crystallinity was ³ and the crystallinity was 62%.

[0062]

[Production Example 2] Production of oxidized polypropylene wax Propylene / ethylene random copolymer (MFR: 40
g / 10 minutes, ethylene content: 2 mol%) 1000 g 5
The mixture was placed in a liter reactor, heated to 380 ° C., and kept for 1 hour while stirring to carry out thermal degradation. The heat-degraded product was allowed to cool and then ground so as to pass through a 20-mesh sieve. The intrinsic viscosity [η] of the obtained propylene / ethylene random copolymer was 0.37 dl / g. 800 g of the obtained propylene / ethylene random copolymer was put in a glass separable flask with a stirrer and having a capacity of 2 liters.
It was heated to 70 ° C. and melted. Next, while stirring, an oxygen-containing gas having a composition of oxygen: nitrogen = 2: 1 (volume ratio) was continuously supplied from the bottom of the reactor at a rate of 3 Nl per minute and contacted for 5 hours to obtain an acid value of 2 mgKOH. 790 g of propylene oxide / ethylene copolymer wax / g was obtained. The intrinsic viscosity of the obtained propylene oxide / ethylene copolymer wax (hereinafter abbreviated as MPO-2) was 0.11 dl.
/ G, the density was 0.900 g / cm ³ , and the crystallinity was 60%.

[0063]

[Production Example 3] In Production Example 1, the intrinsic viscosity was changed to 1.16 dl / in place of the ethylene / propylene copolymer wax.
g, density: 0.931 g / cm ³ , propylene content: 4 mol% ethylene-propylene copolymer wax was used in the same manner as in Production Example 1 except that an acid value of 18 mgKOH /
Thus, g of ethylene oxide / propylene copolymer wax was obtained. The intrinsic viscosity of the obtained ethylene oxide / propylene copolymer wax (hereinafter abbreviated as MPO-3) is 0.81 dl /
g, the density was 0.900 g / cm ³ , and the crystallinity was 60%.

[0064]

Production Example 4 In place of the ethylene / propylene copolymer wax in Production Example 1, the intrinsic viscosity was 0.03 dl /
g, density: 0.931 g / cm ³ , and propylene content: 4 mol% in the same manner as in Production Example 1, except that an ethylene / propylene copolymer wax was used, with an acid value of 15 mgKOH /
Thus, g of ethylene oxide / propylene copolymer wax was obtained. The intrinsic viscosity of the obtained ethylene oxide / propylene copolymer wax (hereinafter abbreviated as MPO-4) is 0.81 dl /
g, the density was 0.900 g / cm ³ , and the crystallinity was 60%.

[0065]

MANUFACTURING EXAMPLE 5 In place of the ethylene / propylene copolymer wax in Manufacturing Example 1, the intrinsic viscosity was 1.73 dl /
g, density: 0.931 g / cm ³ , propylene content: 4 mol% ethylene-propylene copolymer wax was used in the same manner as in Production Example 1 except that an acid value of 18 mgKOH /
Thus, g of ethylene oxide / propylene copolymer wax was obtained. The intrinsic viscosity of the obtained ethylene oxide / propylene copolymer wax (hereinafter abbreviated as MPO-5) is 1.2 dl / g.
The density was 0.900 g / cm ³ and the crystallinity was 59%.

[0066]

Examples 1 to 6 Each component shown in Table 1 was melt-kneaded at a cylinder set temperature of 200 ° C. with a vented twin-screw extruder (screw diameter of 30 mm, L / D = 42) to obtain a propylene-based polymer composition. Was manufactured. This composition was molded by an injection molding machine to prepare a rectangular plate, and each test piece of the above bending test and coating test was obtained and tested. Table 1 shows the results. The components in Table 1 are as follows. (A) Propylene-based polymer PP-1 ... Propylene / ethylene block copolymer MFR (ASTM D 1238, 230 ° C, load 2.16 kg): 32 g /
10 minutes, ethylene content: 7 mol% (b) olefin elastomer EL-1 ... Ethylene / 1-butene random copolymer (rubber) MFR (ASTM D 1238, 230 ° C, load 2.16 kg): 3.6 g
/ 10 minutes, ethylene content: 90 mol%, density: 0.88 g / cm ³ EL-2 ... Ethylene / 1-butene random copolymer (rubber) MFR (ASTM D 1238, 230 ° C., load 2.16 kg): 0 .5g
/ 10 minutes, ethylene content: 80 mol%, density: 0.86 g / cm ³

[0067]

Comparative Example 1 A composition containing no component (c) as shown in Table 1 was molded by an injection molding machine in the same manner as in Example 1 to prepare a square plate, and each of the above bending test and coating test was performed. A test piece was obtained and tested. Table 1 shows the results.

[0068]

[Table 1]

Claims (3)

[Claims] 1. A propylene-based polymer (a) in an amount of 1 to 99 parts by weight, and (b) an olefin-based elastomer in an amount of 99 to 1 parts by weight [however, the total amount of components (a) and (b) is 100 parts by weight]. And (c) oxidized polyolefin wax
A propylene-based polymer composition comprising 1 to 30 parts by weight based on 100 parts by weight of the total of the components (a) and (b). 2. The (c) oxidized polyolefin wax contains (i) at least one unit derived from an α-olefin having 2 to 10 carbon atoms as a main component, and (ii) 13
Intrinsic viscosity measured in decalin at 5 ° C is 0.06-1.0.
dl / g, and (iii) density is 0.80 to 0.99 g / cm ^3.
And (vi) the acid value is 0.1 to 50 mgKOH / g, The propylene polymer composition according to claim 1, wherein 3. The (c) oxidized polyolefin wax has an intrinsic viscosity of 0.06 to 135 measured in decalin at 135 ° C.
2.0 dl / g and a density of 0.80-0.99 g / c
The propylene-based polymer composition according to claim 1 or 2, which is an oxide of an α-olefin (co) polymer wax having m ³ of 2 to 10 carbon atoms.