JPH09118762A - Surface treatment method for molded article of propylene-based polymer composition - Google Patents

Abstract

(57) [Abstract] [PROBLEMS] To obtain a propylene-based polymer composition molded article having excellent adhesion to paints such as melamine resin-based paints and urethane resin-based paints by performing extremely simplified surface treatment. A method for surface treatment of a molded article of a propylene-based polymer composition capable of SOLUTION: A specific amount of (a) a propylene-based polymer,
(B) Oxygen-containing gas obtained by heating a propylene-based polymer composition molded product comprising an olefin-based elastomer (c) oxidized polyolefin wax to a temperature not lower than the melting point of the propylene-based polymer (a) and not higher than 500 ° C. Contact with. At this time, the difference in the number of oxygen atoms on the surface of the molded product before and after the contact treatment between the molded product of the propylene-based polymer composition and the oxygen-containing gas is determined by X-ray photoelectron spectroscopy. / C) It is preferable to bring them into contact such that the atomic ratio is 5/100 or more.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a surface treatment method for coating a molded body of a propylene-based polymer composition, and more specifically, to improve adhesion to coating materials such as melamine resin-based coating materials and urethane resin-based coating materials. The present invention relates to a method for surface-treating a propylene-based polymer composition molded article, which can eliminate the need for pretreatment with a primer or a solvent.

[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 the propylene-based polymer molded article is coated with a urethane resin-based coating material 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 molded body was subjected to surface treatment by a flame treatment method, an oxygen treatment method, an ozone treatment method, or the like. Further, as a pretreatment for such a surface treatment, the surface of the molded product is also washed with a solvent such as alcohol or aromatic hydrocarbon, or washed with a solvent vapor such as trichlene, perchlorethylene, pentachloroethylene or toluene. There is.

However, in order to perform the surface treatment on the molded body in this way, an apparatus for the surface treatment and the 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.

[0006] Further, the molded article having the above-mentioned surface treatment may be primed with a primer before directly coating the urethane resin-based paint, etc., but a coating having a two-layered structure including an undercoat layer is formed. Therefore, the painting work becomes complicated and the painting process takes a long time. For this reason, there is a problem that the cost of the molded product increases.

Therefore, a propylene-based polymer composition that does not impair the excellent characteristics inherent to the propylene-based polymer and can easily improve the adhesion (paintability) with a coating material without involving complicated steps. The advent of a surface treatment method for molded articles has been earnestly desired.

[0008]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned prior art, in which a specific propylene-based polymer composition molded article is subjected to an extremely simplified surface treatment to obtain the propylene. With the object of providing a surface treatment method for a propylene-based polymer composition molded article, which can improve the adhesion of a melamine resin-based coating material of a polymer-based polymer composition molded article, a coating material such as a urethane resin-based coating material. There is.

[0009]

SUMMARY OF THE INVENTION A surface treatment method for a propylene-based polymer composition molded article according to the present invention is (a) a propylene-based polymer.
1 to 99 parts by weight, (b) olefin elastomer 9
9 to 1 part by weight [however, the total amount of the components (a) and (b) is 100 parts by weight], and (c) the oxidized polyolefin wax The total amount of the components (a) and (b) is 100.
1 to 30 parts by weight relative to 1 part by weight of a propylene-based polymer composition molded article, and an oxygen-containing gas heated to a temperature not lower than the melting point of the propylene-based polymer (a) and not higher than 500 ° C. It is characterized by making contact.

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 (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 an oxide of an α-olefin (co) polymer wax having 2 to 10 carbon atoms and having 9 g / cm ³ .

In the present invention, the number of oxygen atoms on the surface of the molded product after the contact treatment and the number of oxygen atoms on the surface of the molded product before the contact treatment are used for the propylene-based polymer composition molded product and the oxygen-containing gas. It is preferable that the difference is 5/100 or more in terms of the ratio of the number of oxygen atoms / the number of carbon atoms (O / C) measured by X-ray photoelectron spectroscopy.

[0013]

DETAILED DESCRIPTION OF THE INVENTION The surface treatment method of the propylene polymer composition according to the present invention will be specifically described below. In the surface treatment method for a propylene-based polymer composition molded body according to the present invention, a specific propylene-based polymer composition molded body is brought into contact with an oxygen-containing gas heated to a specific temperature range.

The specific propylene-based polymer composition molded article to be surface-treated in the present invention includes (a) a propylene-based polymer, (b) an olefin-based elastomer, and (c).
It is composed of an oxidized polyolefin wax and contains these components in specific proportions. First, each component forming the propylene-based polymer composition molded body will be specifically 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. Specific examples of the α-olefin that forms a copolymer with propylene include ethylene, 1-butene, 1-pentene, and 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, methylethyl-1-pentene, diethyl-1-butene, propyl-1-pentene, 1-decene, methyl Examples thereof include -1-nonene, dimethyloctene, trimethyl-1-heptene, ethyl-1-octene, methylethyl-1-heptene, diethyl-1-hexene, 1-dodecene and hexadodecene.

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

The propylene polymer used in the present invention has a melt flow rate (MFR, measured at 230 ° C. under 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 prepared 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.

As the organometallic compound component, an organoaluminum compound is suitable, 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 described in, for example, Japanese Patent Laid-Open 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 the 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 / 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 olefin elastomer used in the present invention has a melt flow rate (MF) measured at 230 ° C.
R) is preferably 0.01 to 50 g / 10 minutes, more preferably 0.01 to 10 g / 10 minutes, and especially 0.01 to 5 minutes.
It is preferably g / 10 minutes.

Further, Mooney viscosity of olefin elastomer [ML _{1 + 4} (100 ° C .; JIS K 6300)]
Is preferably 10 to 150, and 40 to 120
Is more preferable, and the iodine value (unsaturation degree) is
It is preferably 16 or less. In the present invention, two or more kinds of the above olefin 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-decene and the like.

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 becomes the above-mentioned propylene polymer (a). It is preferable because it has excellent compatibility.

(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).

The molecular weight distribution (Mw / Mn) of the oxidized polyolefin wax (c) measured by GPC (gel permeation chromatography) is usually preferably 10 or less, more preferably 5 or less, especially 4 or less. Is more preferable.

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 polyolefin 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 /
Examples thereof include propylene / 1-butene terpolymer wax.

Among these, ethylene homopolymer wax, propylene homopolymer wax, and propylene content of 10 mol% or less, preferably 1 to 5 mol% of ethylene.
Propylene random copolymer wax, propylene / ethylene random copolymer wax having an ethylene content of 10 mol% or less, preferably 1 to 5 mol% or less, ethylene / 1-
Butene copolymer wax and ethylene-4-methyl-1-pentene copolymer wax 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 the peroxide 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, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3 and the like are preferably used. The peroxide is usually about 0.01 to 5 parts by weight, preferably 0.05 to 5 parts by weight, based on 100 parts by weight of the high molecular weight polymer.
It can be used in a ratio of about 3 parts by weight.

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 can be obtained by oxidizing the above-mentioned polyolefin wax, and specifically, it can be 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 impurities). The gas may contain a mixed gas such as air and ozone.

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 preferably supplied so that the amount of oxygen is equivalent to 1.0 to 10.0 Nl per minute per 1 kg of the polyolefin wax.

It is preferable to obtain the oxidized polyolefin wax having the above-mentioned acid value as described above.
In the present invention, the above oxidized polyolefin wax (c) is used.
It is also possible to use two or more types 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.

The propylene polymer composition according to the present invention may optionally contain other components in addition to the above components as long as the object of the present invention is not impaired. Examples of such an optional component include an organotin compound represented by the following formula 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)_TwoOCOC₁H_{twenty three}, N-C₈H₁₇Sn (OH)_TwoOC
OC₇H_Fifteen, N-C₈H₁₇Sn (OH)_TwoOCOC₁₁H_{twenty three}, N
-C_FourH₉Sn (OCOC₇H_Fifteen)_Three, (N-C_FourH₉)_TwoSn
(OCOC₁₁H_{twenty three})_Two, (N-C₈H₁₇)_TwoSn (OCOC
₁₁H_{twenty three})_Two, (N-C_FourH₉)_TwoSn (OCOCH = CHCO
OCH_Three)_Two, (N-C_FourH₉)_TwoSn (OCOCH = CHC
OOCH_TwoPh)_TwoAnd the like. these
At home n-C_FourH₉SnCl_Three, (N-C_FourH₉)_TwoSn (OC
OC₁₁H_{twenty three}) _Two, (N-C₈H₁₇)_TwoSn (OCOC
₁₁H_{twenty three})_TwoAre preferred.

The propylene-based polymer composition according to the present invention contains the organotin compound as described above in a total amount of 100% of the propylene-based polymer (a) and the olefin-based elastomer (b).
0.01 to 5 parts by weight, preferably 0.0
It may be contained in an amount of 5 to 3 parts by weight, more preferably 0.05 to 1 part by weight.

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-mentioned 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, and more preferably 0.05 to 1 part by weight, based on 00 parts by weight.

When the propylene polymer composition according to the present invention contains the organotin compound and / or the tertiary amine compound as described above, 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-based 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 other components, phenol-based compounds,
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 polymer composition according to the present invention may contain the above-mentioned various additives in such an amount that they are generally added to an olefin plastic or an olefin 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.

It is desirable that the kneading is carried out at a temperature of usually 150 to 280 ° C., preferably 170 to 240 ° C., usually 1 to 20 minutes, preferably 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.

Molding of Propylene-Based Polymer Composition The propylene-based polymer composition as described above is molded by the commonly used injection molding method, extrusion molding method, calender molding method, blow molding method, vacuum molding method or the like. It can be formed into a desired shape depending on the method. This molding is carried out at a temperature higher than the melting point of the propylene-based polymer composition and at a temperature within the range of the thermal decomposition temperature or less, and usually 170 to
It is carried out at 300 ° C, preferably 170 to 250 ° C.

Surface Treatment Method In the present invention, prior to applying a coating to the molded product of the propylene-based polymer composition obtained as described above, the molded product has a temperature of not less than the melting point of the propylene-based polymer composition. And is contacted with an oxygen-containing gas heated to a temperature of 500 ° C. or lower.

The oxygen-containing gas only needs to contain oxygen, and examples thereof include oxygen gas, air, a mixed gas of oxygen and an inert gas such as nitrogen or argon, and a mixed gas of an inert gas and air. The oxygen-containing gas preferably contains oxygen at 5 mol% or more.

The oxygen-containing gas is heated to a temperature not lower than the melting point of the propylene-based polymer composition and not higher than 500 ° C. This temperature is specifically propylene homopolymer as the propylene-based polymer (a). 1 if coalescing is used
The temperature is 60 to 400 ° C, preferably 180 to 350 ° C, more preferably 200 to 330 ° C. When a propylene / ethylene random copolymer is used as the propylene polymer (a), it is 140 to 400 ° C., preferably 1
The temperature is 80 to 350 ° C, and more preferably 200 to 330 ° C.

Even if the propylene-based polymer composition molded article is treated with an oxygen-containing gas at a temperature not higher than the melting point of the propylene-based polymer composition, the moldability is not improved, and if the oxygen-containing gas at a temperature of 500 or higher is used. When the treatment is performed, the appearance of the surface of the molded product is deteriorated, and the molded product may be deformed.

The contact between the molded body and the heated oxygen-containing gas is preferably carried out by blowing the heated gas onto the surface of the molded body. At this time, it is not necessary to particularly heat the molded body, and the temperature of the molded body is preferably about 120 to 300 ° C. This spray is 0.1-1
0 kg / cm ^2, preferably wind pressure 0.5~5kg / cm ^2, 0.
It is preferable that the treatment is performed for 1 to 30 seconds, preferably 0.2 to 10 seconds. Such contact can be performed using a dryer, an oven, an electric furnace, a dryer, or the like.

By carrying out the surface treatment as described above, oxygen is taken into the surface of the propylene-based polymer composition molded body, and the number of oxygen atoms on the surface of the molded body after the contact treatment and the molding after the contact treatment. There is a difference between the number of oxygen atoms inside the body.

In the present invention, the difference between the number of oxygen atoms on the surface of the molded body after the surface treatment and the number of oxygen atoms on the surface of the molded body before the surface treatment is specifically determined by X-ray photoelectron spectroscopy (XP
The ratio of the number of oxygen atoms / the number of carbon atoms (O / C) measured in S) is 5/100 or more, preferably 5/100 to 2
0/100, more preferably 5/100 to 10/100
It is desirable that

The number of oxygen atoms on the surface of the molded product before the surface treatment is almost the same as the number of oxygen atoms inside the molded product at a depth of 0.1 μm or more from the surface of the molded product. This is because such surface treatment does not increase the number of oxygen atoms inside the molded body.

The propylene-based polymer molded product subjected to the surface treatment in the present invention has excellent coatability with respect to urethane resin-based paints and amino resin-based 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 coating materials, for example, a coating method using a urethane resin coating material will be described by way of example. A molded body formed from the propylene 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.

[0082]

EFFECTS OF THE INVENTION The surface treatment method for a propylene-based polymer composition molded article according to the present invention is an extremely simplified method as compared with the conventional surface treatment method. By subjecting the combined composition to the surface treatment, it is possible to obtain a propylene-based polymer composition having excellent coatability with respect to urethane resin-based paints, amino resin-based paints and the like.

The surface treatment method for the molded article of the propylene-based polymer composition according to the present invention utilizes the above characteristics,
Auto parts, motorcycle parts, electric equipment parts, daily necessities,
It can be widely used for applications such as civil engineering and construction materials, general industrial materials, office information equipment, packaging materials, sports equipment and medical equipment to which painting is applied.

[0084]

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) Ratio of (O / C) Atom Number Oxygen atom / Carbon atom (O /
C) The atomic ratio was determined by X-ray photoelectron spectroscopy (XPS). The O / C atomic number ratio was measured for each of the square plates before and after the surface treatment. X-ray photoelectron spectrometer ESCA-7
Using a 50 type (manufactured by Shimadzu Corporation), 7 × 10-8
Under vacuum of less than Torr, Al Kα ray (1486.6)
eV) was measured as an X-ray source. The emission angle of photoelectrons is 90
°. Among the carbon atom peaks, the C1s peak (285
The atomic number ratio was determined using eV). The photoionization cross-sections at this time were 1.00 for C1s and 2.93 for O1s.

(3) Flexural Modulus (FM) Using a test piece having a thickness of 1/8 inch, ASTM D 79
0 was measured.

(4) 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 [manufactured by Nichiban Co., Ltd., trade name] was attached to the test piece. Then, this was rapidly 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.

[0090]

[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 an acid value polyethylene wax having an acid value of 17 mgKOH / g. The obtained acid value 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%.

[0091]

[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%.

[0092]

[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 , 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 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%.

[0093]

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%.

[0094]

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%.

[0095]

Examples 1 to 9 The components shown in Table 1 were melt-kneaded at a cylinder set temperature of 200 ° C. by a vented twin-screw extruder (screw diameter 30 mm, L / D = 42) to prepare a propylene polymer composition. Manufactured. This composition was molded by an injection molding machine to prepare a square plate, and air or pure oxygen heated to 250 ° C. was blown onto the surface thereof at a wind pressure of ² Kg / cm ² for 1 second to perform a surface treatment.
The square plate surface after the surface treatment has an oxygen atom number / carbon atom number (O / C) atom number ratio of 8 as compared with the square plate before the surface treatment.
/ 100 was increased. The above bending test and coating test were performed using the square plate surface-treated in this way.
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% PP-2 ... Homopolypropylene MFR (ASTM D 1238, 230 ° C, load 2.16 kg): 20 g /
10 minutes,

(B) Olefin-based elastomer EBR-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 EBR-2 ... Ethylene / 1-butene random copolymer (rubber) MFR (ASTM D 1238, 230 ° C., load 2.16 kg): 0.5 g
/ 10 minutes, ethylene content: 80 mol%, density: 0.86
g / cm ³ EPR ... Ethylene / propylene copolymer rubber MFR (ASTM D 1238, 190 ° C, load 2.16 kg): 0.8 g
/ 10 minutes, ethylene content: 81 mol%

[0098]

Comparative Example 1 A propylene-based polymer composition molded body was obtained in the same manner as in Example 1 except that the components shown in Table 1 were used. The obtained propylene-based polymer composition molded body was subjected to surface treatment in the same manner as in Example 1 and subjected to the above-mentioned bending test and coating test. Table 1 shows the results.

[0099]

Comparative Examples 2 to 3 Molded articles of propylene-based polymer composition were obtained in the same manner as in Example 1 except that the components shown in Table 1 were used. The obtained propylene-based polymer composition molded body was subjected to the above-mentioned bending test and coating test without surface treatment. Table 1 shows the results.

[0100]

[Table 1]

Continuation of the front page (72) Inventor Yuko Harada 6-12 Waki, Waki-cho, Kuga-gun, Yamaguchi Mitsui Petrochemical Industry Co., Ltd.

Claims (4)

[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 molded body comprising 1 to 30 parts by weight based on 100 parts by weight of the total amount of the components (a) and (b), having a melting point of the propylene-based polymer (a) or higher. And 50
A surface treatment method for a propylene-based polymer composition molded article, which comprises contacting with an oxygen-containing gas heated to a temperature of 0 ° C. or lower. 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 method for surface treatment of a propylene-based polymer composition molded article 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 surface treatment method for a propylene-based polymer composition molded article according to claim 1, which is an oxide of an α-olefin (co) polymer wax having m ³ of 2 to 10 carbon atoms. 4. A molded product of the propylene-based polymer composition,
The difference between the number of oxygen atoms on the surface of the molded product after the contact treatment with the oxygen-containing gas and the number of oxygen atoms on the surface of the molded product before the contact treatment is the number of oxygen atoms / carbon atoms measured by X-ray photoelectron spectroscopy. The surface treatment method for a propylene-based polymer composition molded article according to claim 1, wherein the surface treatment is performed so that the number (O / C) atomic ratio is 5/100 or more.