JPH069835A - Polypropylene-based resin composition - Google Patents

Abstract

PURPOSE:To provide a polypropylene resin composition containing polypropylene, an ethylene-alpha-olefin copolymer elastomer, a modified polyolefin, stearic acid monoglyceride, etc., capable of application immediately after defatting and excellent in coating properties. CONSTITUTION:With (A) 50 to 90wt.% polypropylene, (B) 50 to 10wt.% ethylene-alpha-olefin copolymer elastomer exhibiting 10 to 100 Mooney viscosity [ML 1+4 (100 deg.C)] is blended. To 100 pts.wt. total amount of the components (A) and (B), (C) 0.1 to 15 pts.wt. modified polyolefin synthesized by introducing a functional. group represented by formula I (R<1> is a 1 to 4C alkylene), etc., into both or one of the terminals of a straight chain polyolefin in an amount of 1 to 20wt.% based on the modified polyolefin and (D) 0.1 to 1 pts.wt. compound expressed by formula II (R is a 10 to 22C alkyl; X is, e.g. a group of formula III) or formula R-X are added, thus producing the objective polypropylene resin composition excellent in coating properties and capable of application immediately after defatting without pretreatment with a halogen- containing organic solvent.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polypropylene resin composition, and more particularly to a polypropylene resin composition having excellent coatability, peel strength and elasticity.

[0002]

2. Description of the Related Art Conventionally, polypropylene (PP) / ethylene-polypropylene rubber (EP
The composition of R) is used. Since polypropylene has no polar group in the molecule and is chemically inactive and extremely inferior in coatability, etching with trichloroethane or the like is indispensable when coating a bumper made of such a composition. Further, not only this automobile bumper, but also the coating of polypropylene-based composite material, it is common to perform etching treatment with trichloroethane as a pretreatment in order to develop its practical coating strength (Akira Yamamoto, Mikio Uchida, Practical Surface Technology, 31 (10), 44
0 (1984)). However, trichloroethane is a cause of environmental destruction such as ozone layer destruction, and it is necessary to avoid the method using trichloroethane. Therefore, as an alternative to trichloroethane, an alkaline aqueous solution type surfactant can be mentioned, but since it has a remarkably low dissolving power for washing with PP, it can be used for coating polypropylene composite materials such as bumpers made of the above composition. could not. On the other hand, a method of blending a polar substance with PP to improve paintability has been reported. For example, a composition obtained by adding polyvinylphenol to a PP resin (Japanese Patent Application Laid-Open No. Hei 3
No. 9941) or a composition obtained by adding an ethylene / carboxylic acid compound copolymer to a PP resin (JP-A-3-27).
8862). However, these compositions were not always sufficient in adhesion of the coating film as a bumper material for coating after washing with water.

[0003]

Therefore, the inventors of the present invention have solved the above-mentioned problems and can perform coating immediately after degreasing without pretreatment with a halogen-containing organic solvent such as trichloroethane, and further recoating is possible. We have earnestly conducted research to develop a PP resin composition.

[0004]

As a result, a composition obtained by using a specific compound conventionally used as a charging agent in combination with a functionalized modified polyolefin has an excellent coating property. It was found that the above object can be achieved by using this. The present invention has been completed based on such findings.

That is, in the present invention, (a) polypropylene is 50 to 90% by weight, (b) Mooney viscosity (ML1 + 4).
(100 ° C.)) 50 to 10% by weight of the ethylene-α-olefin copolymer elastomer of 10 to 100, and 100 parts by weight of the total of the components (a) and (b),
(C) 0.1 to 15 parts by weight of a modified polyolefin obtained by introducing a functional group into both ends or one end of a linear polyolefin, and (d) the general formula (I)

[0006]

[Chemical 4]

(In the formula, R represents a linear alkyl group having 10 to 22 carbon atoms, and X represents

[0008]

[Chemical 5]

Is shown. The present invention provides a polypropylene resin composition comprising 0.1 to 1 part by weight of a compound represented by the formula (1).

The polypropylene resin composition of the present invention comprises the above-mentioned components (a) to (d). The PP which is the component (a) of the present invention is not particularly limited, but preferred examples include crystalline isotactic propylene homopolymers and ethylene-propylene random copolymers having a low ethylene unit content. Polymer, a propylene block copolymer composed of a homo part consisting of a propylene homopolymer and a copolymer part consisting of an ethylene-propylene random copolymer having a relatively large content of ethylene units, said propylene block copolymer A crystalline propylene-ethylene-α-olefin copolymer or the like in which each of the homo- or copolymerized parts in is further copolymerized with an α-olefin such as butene-1. The melt index (MI) of these PP is not particularly limited, but is preferably 0.5 to 100 g / 10 minutes, particularly 1 to
The one with 50 g / 10 minutes is most suitable. The blending amount of the component (a) is 5 based on the total amount of the components (a) and (b).
It is 0 to 90% by weight, preferably 60 to 80% by weight. Here, if the amount is less than 50% by weight, the physical properties such as rigidity of the obtained composition deteriorate, and if it exceeds 90% by weight, high coating adhesion cannot be obtained.

Component (b), ethylene-α-olefin
The copolymerized elastomer is, for example, ethylene and propylene.
Ethylene, 1-butene, ethylene and 1-hexene
Any α-olefin copolymer or non-copolymer with these
Examples thereof include a copolymer with a role diene. This copolymer
Is the initial elastic modulus measured according to JIS-K6301.
Is 400 kg / cm²The following is preferable and more preferable:
More preferably 200 kg / cm ²Or less, particularly preferably 10
0 kg / cm²The following amorphous or low crystalline copolymers
Is. Here, the content of ethylene is 40-80% by weight.
It is preferably 50 to 75% by weight. In addition, above
Specific examples of the non-conjugated diene include dicyclopentadiene.
1,4-hexadiene; cyclooctadiene; disi
Crooctadiene; Methylene norbornene; 5-Ethyl
Den-2-norbornene; 5-vinyl-2-norbornene
5-methylene-2-norbornene; 5-methyl-
1,4-hexadiene; 7-methyl-1,6-octadiene
En can be mentioned. These ethylene-α-
The olefin copolymer elastomer has a Mooney viscosity ML1.
+4 (100 ° C) is usually 10 to 100, preferably 2
It is in the range of 0-70. The above ethylene-α-ole
Specific examples of the fin-copolymerized elastomer include ethylene
-Propylene copolymer rubber (EPM), ethylene-1-bu
Copolymer rubber, ethylene-propylene-1-butene
Polymerized rubber, ethylene-propylene-non-conjugated diene copolymer
Rubber (EPDM), ethylene-1-butene-non-conjugated die
Copolymer rubber, ethylene-propylene-1-butene-non
There are conjugated diene copolymer rubbers and the like. Especially preferred
Ethylene-propylene copolymer rubber, ethylene-propylene
Pyrene-non-conjugated diene terpolymer rubber, ethylene-pro
Pyrene-butene-1 copolymer rubber is mentioned. Said et
The propylene-propylene copolymer rubber has a propylene content of
20-60% by weight, Mooney viscosity ML1 + 4 (100
C.) of 10 to 100, especially 20 to 70 is preferable.
Yes. The ethylene-propylene non-conjugated diene rubber (EP
DM) preferably has an iodine value of 20 or less. the above
If it is out of the range, the coating performance and the balance of physical properties are poor and it is not suitable.
is there. The ethylene-propylene-butene-1 copolymer
The content of propylene and butene-1 in the
20-60% by weight and its MI (230 ° C, 2.16
It is preferable that the (kg load) is 0.5 to 25 g / 10 minutes,
Particularly, one having 1 to 20 g / 10 minutes is preferable. Each success here
The content of the component is determined by infrared spectroscopy and nuclear magnetic resonance.
It is a value measured by a method or the like. Also, the rubber is substantially
It is preferably amorphous, but has some crystallinity
Anything is fine. In this case, the crystallinity is preferably 5% or less.
More preferably 4% or less, especially 3% or less
It is fruitful. When using these rubbers in pellet form
However, even if it is in the form of crumbs or bales, it will hinder the kneading operation.
There is no problem unless you come. The blending amount of the above-mentioned component (b) is
50 to 10 times based on the total amount of the components (a) and (b)
%, Preferably 20 to 35% by weight. here
If it is less than 10% by weight, the composition obtained is sufficient.
Paintability cannot be imparted. Conversely, if it exceeds 50% by weight, rigidity etc.
Physical properties of.

Sufficient coatability can be obtained by using the component (b) as described above. As the component (b),
(A) The α-olefin content is 50 to 80% by weight, and the Mooney viscosity (ML1 + 4 (100 ° C.)) is 20 to.
80, and a copolymer rubber having 10 to 30 mol% of triads of α-olefin units determined by ¹³ C-NMR, and (a) an α-olefin content of 15 to 5
0% by weight, and the Mooney viscosity (ML1 + 4 (100
It has been found that the recoatability (overcoatability) is improved by using two copolymers having a copolymer rubber of 10 to 90). The preferable blending ratio of these is 20 to 80% by weight of the component (A) and 80 to 20% by weight of the component (A). Here, the repaintability means the performance that when a painted product is scratched, the performance that can be repaired by further painting on the scratch and the designability can be improved so that the product can be repeatedly painted. For those with poor repaintability,
During repainting, the paint thinner peels off the surface of the substrate due to paint thinner. The reason why the recoatability is improved by using the copolymer rubbers of the above-mentioned components (a) and (a) as the component (b) is not clear. For example, the α-olefin unit is a propylene unit (P). It is speculated that in the case of (3), the [PPP] triad is present at the interface between the polypropylene and the copolymer to increase the interfacial strength so that it is not attacked by the paint thinner during repainting.

The modified polyolefin which is the component (c) is
A functional group is introduced into both ends or one end of a linear polyolefin, and various types thereof can be mentioned. For example, the linear polyolefin part is a monomer such as ethylene, propylene, butene-1, butadiene. Examples thereof include homopolymers or copolymers of a plurality of components, specifically, polypropylene, polyethylene, hydrogenated polybutadiene, hydrogenated polyisoprene and the like. Furthermore, ethylene-
A propylene copolymer etc. can also be mentioned. The number average molecular weight of the linear polyolefin part in the modified polyolefin as the component (c) is 1,000 to 10,000.
Is preferable, and 2000-6000 is especially preferable. There are various functional groups to be introduced at the ends (one end or both ends) of the linear polyolefin part, and usually, polar groups such as a hydroxyl group and a maleic anhydride group (correctly a group derived from maleic anhydride). ) Or an unsaturated carboxylic acid group such as an acrylic acid group,

[0014]

[Chemical 6]

(In the formula, R ¹ represents an alkylene group having 1 to 4 carbon atoms) and the like. Of these, a hydroxyl group, a maleic anhydride group or a group represented by the above formula is preferable. The addition amount (introduction ratio) of this functional group is not particularly limited, but is usually 1 to 20% by weight, particularly preferably 5 to 10% by weight based on the modified polyolefin. The blending amount of the component (c) is 0.1 to 15 parts by weight, preferably 1 to 10 parts by weight, based on 100 parts by weight of the total of the components (a) and (b). Here, if it is less than 0.1 part by weight, it is not possible to impart high coating adhesion to the obtained composition, and if it exceeds 15 parts by weight, physical properties such as tensile strength and low temperature impact resistance are deteriorated. . Further, since the hygroscopicity of the composition is increased, silver is generated during molding.

Next, the compound represented by the general formula (I) which is the component (d) may be any compound containing a linear alkyl group having 10 to 22 carbon atoms and a substituent represented by X. . Preferable examples include stearic acid monoglyceride, stearyldiethanolamine, N-diethanolstearic acid amide, N-diethanoldodecanamide and the like. The blending amount of the component (d) is (a) and (b).
The amount is 0.1 to 1 part by weight, preferably 0.2 to 0.5 part by weight, based on 100 parts by weight of the total of the components. Where 0.1
If it is less than 1 part by weight, it is not possible to impart high coating adhesion to the composition obtained, and if it exceeds 1 part by weight, defective phenomena such as bleed-out occur during molding.

The polypropylene resin composition of the present invention comprises
Although it basically consists of components (a) to (d),
If necessary, heat-resistant stabilizers, weather-resistant stabilizers, antistatic agents, lubricants, slip agents, nucleating agents, flame retardants, pigments, dyes,
Various additives such as glass fiber, talc, calcium carbonate and carbon fiber can be added in appropriate amounts. In addition, ethylene-
It is also possible to add an impact improver such as an α-olefin copolymer elastomer.

The polypropylene resin composition of the present invention can be produced in the same manner as the conventional method for producing a polypropylene resin composition. In addition, (a)-
The mixing order of the component (d) and various additives can be freely selected as appropriate. Also in the kneading of the above components, a conventionally known kneader, roll, Banbury mixer or other mixer, a single-screw or twin-screw extruder or the like can be used.

[0019]

The present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. Examples 1 to 6 and Comparative Examples 1 to 5 First in a kneading extruder (NVC-50φ, manufactured by Nakatani Koki).
A predetermined amount described in the table was added all at once and kneaded to produce a resin composition. The coating is carried out by injection molding the obtained composition (14
(0 mm x 140 mm x 3 mm) is washed with a neutral detergent,
After thoroughly washing with ion-exchanged water and drying at 80 ° C for 30 minutes, a primer (RB123, manufactured by Nippon Bee Chemical Co., Ltd.) is applied, and then urethane coating is spray-painted, which is applied at 80 ° C for 30 minutes. It was done by baking. The adhesion of the urethane coating film of the coated molded product was determined by making a notch of 10 mm width in the coating film and measuring the 180 ° peel strength (Autograph D
SC2000, manufactured by Shimadzu Corporation. The results obtained are shown in Table 2.

[0020]

[Table 1]

[0021]

[Table 2]

* 1: Ethylene-propylene block copolymer (J-950H, manufactured by Idemitsu Petrochemical Co., Ltd., MI = 20 g
/ 10 minutes (230 ° C., ethylene content 6.3% by weight) * 2: Ethylene-propylene rubber (EP02P, manufactured by Nippon Synthetic Rubber Co., Ltd., ML1 + 4 (1
(00 ° C.) = 24, ethylene content 74% by weight) * 3: ethylene-propylene rubber (EP921, manufactured by Nippon Synthetic Rubber Co., Ltd., ML1 + 4 (1
(00 ° C) = 27, ethylene content 50% by weight) * 4: Maleic anhydride modified polypropylene (number average molecular weight = 4000, maleic anhydride content 10% by weight) * 5: Maleic anhydride modified polyethylene (number average molecular weight = 3000, Maleic anhydride content 5% by weight) * 6: Hydrogenated polybutadiene containing terminal hydroxyl groups (manufactured by Idemitsu Petrochemical Co., Ltd., number average molecular weight = 4000) * 7: Monoglyceride stearate (Denon 2068, Marubishi Yuka Kogyo Co., Ltd.) * 8: Stearyldiethanolamine (Denone 2862, manufactured by Marubishi Yuka Kogyo Co., Ltd.) * 9: N-diethanol dodecane amide (Denone 2863, manufactured by Marubishi Yuka Kogyo Co., Ltd.) * 10: Talc (Tasada Asada) CT76, manufactured by Asada Milling Co., Ltd.

[0023]

[Table 3]

Examples 7 to 11 and Comparative Examples 6 to 10 No. 3 in a kneading extruder (NVC-50φ, manufactured by Nakatani Koki).
A predetermined amount described in the table was added all at once and kneaded to produce a resin composition. The coating is carried out by injection molding the obtained composition (14
After washing 0 mm × 140 mm × 3 mm with isopropyl alcohol (IPA), the primer (RB12
3, manufactured by Nippon Bee Chemical Co., Ltd., and further, urethane coating was spray-coated, and this was baked at 80 ° C. for 30 minutes. The adhesion of the urethane coating film of the coated molded product was evaluated by the following method, and the result was evaluated as 4th.
Shown in the table.

Initial adhesion 1m to reach the substrate on the coated surface using a cutter knife
Make 100 square corners (10 x 10) and attach cellophane tape sufficiently onto the squares. Hold one end of the tape at right angles to the effective surface and remove it instantly. At this time, the adhesiveness to the substrate is evaluated based on the state of the first peeling. The remaining number n out of 100 is displayed as n / 100. Hot water resistance (secondary adhesion) The coated sample piece is immersed in warm water (distilled water) at 40 ° C for 240 hours. The sample piece is taken out from the warm water, the moisture is removed by wiping with a cloth or air blowing, and the sample piece is left at room temperature for 1 hour, and then the secondary adhesion is evaluated by the eye peeling method using cellophane tape. Repaintability A scratch reaching the base material is made on the coated surface of the coated test piece with a cutter knife over a length of 10 mm. Then
Apply the primer and urethane paint by the method described above. In the case of a test piece with poor repaintability, the coating film floats from the base material in a crack shape around the wound. This degree was evaluated as shown in FIG. In FIG. 1, sample piece A has no cracks around the scratch 1, but sample piece B has some cracks 2, sample piece C has some cracks 2 and sample piece D has cracks 2 on the entire surface. Is recognized. In the evaluation, sample piece A is indicated by ◯, sample piece B by Δ, sample piece C by x, and sample piece D by xx. Regarding the repaintability, in the evaluations shown in FIG. 1, those of ◯ and Δ (sample pieces A and B) are acceptable levels, and those of xx (sample piece D) are in a level that is difficult to use as a coating member. .

[0026]

[Table 4]

[0027]

[Table 5]

* 1: ethylene-propylene block copolymer (J-3050H, manufactured by Idemitsu Petrochemical Co., Ltd., MI = 30)
g / 10 minutes (230 ° C), ethylene content 6.5% by weight) * 2: ethylene-propylene rubber (EP02P, manufactured by Nippon Synthetic Rubber Co., Ltd., ML1 + 4 (1
00 ° C.) = 24, ethylene content 74% by weight, ¹³ C-NM
The triad component of [PPP] is 0 mol% as the evaluation result of R) * 3: Ethylene-propylene rubber (EP921P, manufactured by Nippon Synthetic Rubber Co., Ltd., ML1 + 4)
(100 ° C.) = 27, ethylene content 50% by weight, ¹³ C-
Triad component of [PPP] as a result of NMR evaluation 3.
5 mol%) * 4: Ethylene-propylene rubber (ML1 + 4 (100 ° C.) = 30, ethylene content 45% by weight, triad component of [PPP] 20 mol% as ¹³ C-NMR evaluation result) * 5: Ethylene-butene Copolymer (MI = 3.5 g / 10 min (230 ° C.), butene amount 20% by weight) * 6: Modified polyolefin (number average molecular weight = 4000, main chain: polypropylene, addition amount of the following functional group 5% by weight)

[0029]

[Chemical 7]

* 7: stearic acid monoglyceride (Denone 2068, manufactured by Marubishi Yuka Kogyo Co., Ltd.) * 8: N-diethanol dodecane amide (Denone 2863, manufactured by Marubishi Yuka Kogyo Co., Ltd.) * 9: talc ( Asada Talc CT76, manufactured by Asada Milling Co., Ltd.

[0031]

[Table 6]

[0032]

As described above, the polypropylene resin composition of the present invention can be applied immediately after degreasing without pretreatment with a halogen-containing organic solvent such as trichloroethane, and has elasticity, peel strength and re-use property. It is a polypropylene resin composition having excellent paintability. Therefore, the polypropylene resin composition of the present invention can be effectively used as a polypropylene bumper material for coating, a polypropylene resin for coating applications, and the like.

[Brief description of drawings]

FIG. 1 is a schematic diagram showing evaluation criteria of repaintability in Examples and Comparative Examples.

[Explanation of symbols]

 A test piece B test piece C test piece D test piece 1 Scratch 2 Crack

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[Procedure amendment]

[Submission date] April 15, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] Claim 3

[Correction method] Change

[Correction content]

[Chemical 3] (In the formula, R ¹ represents an alkylene group having 1 to 4 carbon atoms.)
The polypropylene resin composition according to claim 1, wherein the polypropylene resin composition is a polar group represented by, and the introduction ratio of the functional group is 1 to 20% by weight based on the modified polyolefin.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0014

[Correction method] Change

[Correction content]

[0014]

[Chemical 6]

[Procedure 3]

[Document name to be amended] Statement

[Name of item to be corrected] 0029

[Correction method] Change

[Correction content]

[0029]

[Chemical 7]

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display area // (C08L 23/10 23:08 23:26)

Claims (5)

[Claims] 1. (a) 50 to 90% by weight of polypropylene, (b) Mooney viscosity (ML1 + 4 (100 ° C.)) 1
50 to 10% by weight of an ethylene-α-olefin copolymerized elastomer of 0 to 100, and (a) and (b)
Based on 100 parts by weight of the total of the components, (c) 0.1 to 15 parts by weight of a modified polyolefin having functional groups introduced at both ends or one end of a linear polyolefin, and (d) a general formula: (In the formula, R represents a linear alkyl group having 10 to 22 carbon atoms, and X represents Indicates. ) A polypropylene resin composition comprising 0.1 to 1 part by weight of a compound represented by 2. The functional group introduced at both ends or one end of the linear polyolefin is a hydroxyl group or a maleic anhydride group, and the introduction ratio of the functional group is 5 to 10% by weight of the modified polyolefin. The polypropylene resin composition described. 3. A functional group introduced at both ends or one end of a linear polyolefin has the formula: (In the formula, R ¹ represents an alkylene group having 1 to 4 carbon atoms.)
The polypropylene resin composition according to claim 1, wherein the polypropylene resin composition is a polar group represented by, and the introduction ratio of the functional group is 1 to 20% by weight based on the modified polyolefin. 4. The linear polyolefin is polyethylene, polypropylene, polybutene or hydrogenated polybutadiene, and its number average molecular weight is 1000 to 1000.
The polypropylene resin composition according to claim 1, which is 0. 5. The ethylene-α-olefin copolymer elastomer of component (b) has (a) α-olefin content of 5.
0 to 80% by weight, Mooney viscosity (ML1 + 4
(100 ° C.)) is 20 to 80, and a triad of α-olefin units determined from ¹³ C-NMR (triad).
Of 20 to 80% by weight of (10) to 30% by mole of a copolymer rubber and (a) 15 to 50% by weight of α-olefin, and a Mooney viscosity (ML1 + 4 (100 ° C.)) of 10
The polypropylene resin composition according to claim 1, which comprises 80 to 20% by weight of a copolymer rubber of 90 to 90%.