KR101847258B1 - Polypropylene composition with good paintability - Google Patents
Polypropylene composition with good paintability Download PDFInfo
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- KR101847258B1 KR101847258B1 KR1020160010940A KR20160010940A KR101847258B1 KR 101847258 B1 KR101847258 B1 KR 101847258B1 KR 1020160010940 A KR1020160010940 A KR 1020160010940A KR 20160010940 A KR20160010940 A KR 20160010940A KR 101847258 B1 KR101847258 B1 KR 101847258B1
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- South Korea
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- resin composition
- polypropylene resin
- polypropylene
- crystalline
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/14—Copolymers of propene
- C08L23/142—Copolymers of propene at least partially crystalline copolymers of propene with other olefins
Abstract
The present invention relates to a polypropylene resin composition, which comprises 55 to 85% by weight of a crystalline polypropylene, 5 to 20% by weight of a rubber component having an intrinsic viscosity of 2 to 4 dl / g and an ultrafine inorganic filler 10 to 25% by weight. The polypropylene resin composition can provide an automotive exterior plastic part having excellent paintability.
Description
The present invention relates to a highly crystalline polypropylene resin composition comprising a high crystalline polypropylene resin, a rubber component and ultrafine talc, and excellent in paint adhesion and impact resistance, and a molded article using the same.
The polypropylene resin composition is excellent in workability and mechanical properties, and is a material having a wide range of industrial applications such as automobile interior / exterior parts, home appliance parts, and industrial materials. Especially, parts such as automobile bumpers, door trims, panels and the like are mainly painted with colors for high-end appearance. Painting plants are very complex, and paint types, painting techniques, material composition, and molding conditions affect paint adhesion.
In this connection, since parts for automobile exterior materials use high-temperature and high-pressure washing equipment for washing, a resin composition having improved paint adhesion on the surface of an injection molded article is further required.
Particularly, a resin composition improved in paint adhesion is required in parts for automobile exterior materials. This is because the conventional resin composition is not only an injection molded surface itself, but also a silver streak or gas (gas) marks appear on the surface of the molded body, it is difficult to obtain a good appearance because unevenness is generated on the surface when the parts are painted. In addition, when the surface is polished, adhesion of the coating film is poor, and when the surface defective portion of the injection-molded article appears, it is difficult to use the product as a good product, and productivity is lowered.
Korean Patent Laid-Open Publication No. 10-2005-0093186 discloses that talc or glass fiber, which is an inorganic filler, is used for securing rigidity. However, in the case of talc, a decrease in impact strength is a problem. In the case of glass fiber, There is a problem, and appearance becomes coarse, so that it is limited to use as an automobile interior / exterior material.
An object of the present invention is to provide a highly crystalline polypropylene resin composition excellent in paint adhesion and impact resistance.
Another object of the present invention is to provide a molded article made of the polypropylene resin composition.
According to an aspect of the present invention,
55 to 85% by weight of crystalline polypropylene; 5 to 20% by weight of a rubber component having an intrinsic viscosity of 2 to 4 dl / g; And
10 to 25% by weight of an ultrafine inorganic filler having an average particle size of 0.1 to 5 占 퐉; Based on the total weight of the polypropylene resin composition.
INDUSTRIAL APPLICABILITY The polypropylene resin composition of the present invention is excellent in paint adhesion and impact resistance, and can be effectively applied to a bumper, a side seal molding, a door trim, and the like as a painted plastic part for automobile interior / exterior use.
Hereinafter, the present invention will be described in more detail.
The present invention relates to a composition comprising 55 to 85% by weight of crystalline polypropylene; 5 to 20% by weight of a rubber component having an intrinsic viscosity of 2 to 4 dl / g; And 10 to 25% by weight of an ultrafine inorganic filler having an average particle diameter of 0.1 to 5 占 퐉; Based on the total weight of the polypropylene resin composition.
In the present invention, the content of the crystalline polypropylene may be 55 to 85% by weight based on the total weight of the polypropylene resin composition.
If the content of the polypropylene is less than 55% by weight, the paint adhesion may be deteriorated. If the content is more than 85% by weight, the flexural modulus may decrease.
The crystalline polypropylene may comprise at least one selected from a crystalline polypropylene homopolymer and a propylene-alpha olefin crystalline copolymer comprising C2-C20 (excluding C3) alpha-olefin monomers.
Specific examples of the alpha-olefin monomers include ethylene, 1-butene, 1-pentene, 1-hexene, 4-methylpentene, 1-heptene, 1-octene and 1-decene, have.
The propylene-alpha olefin crystalline copolymer may be, but is not limited to, a block copolymer or a random copolymer.
The content of the polymerization unit of propylene in the propylene-alpha-olefin crystalline copolymer is not particularly limited, but is preferably 50 wt% or more in the copolymer.
The crystalline polypropylene is not particularly limited as far as its stereoregularity is concerned, but any crystalline polypropylene that can achieve the object of the present invention can be used without limitation, and isotactic as measured by C-NMR (nuclear magnetic resonance spectrum) The peptad fraction may be from 0.80 to 0.99.
The melt index of the crystalline polypropylene is 10 to 50 g / 10 min at 230 占 폚 and 2.16 kg of ASTM D1238.
If the melt index is less than 10 g / 10 min, injection moldability is deteriorated and productivity is lowered. If the melt index is more than 50 g / 10 min, impact strength and mechanical properties are deteriorated.
In the present invention, the polypropylene resin composition may contain a rubber component in order to further improve the paintability or to reinforce the low-temperature impact resistance.
The content of the rubber component is preferably 5 to 20% by weight based on the total weight of the polypropylene resin composition.
When the content of the rubber component is less than 5% by weight, the effect of alleviating the impact due to the rubber component is insignificant. When the content of the rubber component exceeds 20% by weight, the ductility is strengthened.
The rubber contained in the composite resin composition of the present invention is an ethylene-? -Olefin random copolymer rubber having ethylene and an? -Olefin having 4 to 12 carbon atoms and having an? -Olefin content of 20 to 50% by weight . The? -Olefin of the random copolymer may be, for example, 1-butene, 1-pentene, 1-hexene, 1-heptene, Decene, 1-undecene, 1-dodecene, and the like.
Examples of the styrenic thermoplastic elastomer include styrene-ethylene-butylene-styrene block copolymer (SEBS), styrene-ethylene-propylene-styrene block copolymer (SEPS), styrene- Ethylene-propylene-styrene (SEEPS), styrene-butadiene-styrene (SBS) and styrene-isoprene-styrene (SIS).
Preferred are 1-butene and 1-octene, and styrene-based thermoplastic elastomers may be used in combination.
The viscosity of the rubber component used in the present invention should be equal to or higher than the viscosity of the propylene-alpha olefin copolymer contained in the crystalline polypropylene so that it is prevented from being stretched in shape on the surface of the molded article and the coating adhesion is excellent. Accordingly, an intrinsic viscosity of the outer rubber may be 2 to 4 dl / g.
If the rubber component is less than 2 dl / g, the external rubber is smeared on the surface of the molded product, and the coating adhesion force is poor. If the rubber component is more than 4 dl / g, the gel surface may cause a failure phenomenon on the coating surface.
In the present invention, the polypropylene resin composition may contain an ultrafine inorganic filler to reinforce rigidity.
The content of the ultrafine inorganic filler may be 10 to 25 wt%, preferably 10 to 20 wt%, based on the total weight of the polypropylene resin composition.
If the content of the ultrafine inorganic filler is less than 10% by weight, the flexural modulus may be insufficient or the coating adhesion may be deteriorated. If the content is more than 25% by weight, the impact resistance may be deteriorated.
The ultrafine inorganic filler may be at least one selected from the group consisting of talc, mica, barium sulfate, calcium carbonate and glass fiber, and is preferably talc.
The talc may be prepared by grafting various organic titanate coupling agents, organosilane coupling agents, unsaturated carboxylic acids or anhydrides thereof in order to improve the adhesiveness or dispersibility with the polymer The surface of the talc can be treated with a modified polyolefin, a fatty acid, a fatty acid metal salt, and a fatty acid ester.
The particle diameter of the talc can be determined from the grain size distribution of cumulative 50% by weight read from the particle cumulative distribution curve measured according to the laser diffraction method. Ultrafine talc having a particle size of 0.1 to 5 탆 desirable.
If the particle diameter of the ultrafine talc is out of the above range, the paint adhesion on the surface of the molded product may be drastically deteriorated by the fillers of large particles, which is not preferable.
The polypropylene composite material of the present invention can be used additionally or separately as an additive, depending on its application range, in addition to the above components, such as an antioxidant, a processing lubricant, an ultraviolet stabilizer, a long-term heat stabilizer, an antistatic agent, a flame retardant, an antibacterial agent and a colorant have.
The present invention can be further illustrated by the following examples, and the following examples are intended to illustrate the present invention and are not intended to limit the scope of protection of the present invention.
The measurement / evaluation items of the physical properties and their measurement methods in the respective Examples and Comparative Examples are as follows.
(1) Flexural modulus
It is evaluated by ISO R178 specimen, and preferably not less than 1500 MPa.
(2) Izod (IZOD) impact strength
The thickness of the injection molded article was 4 mm and was based on performing the ISO 180A test specification.
(3) Melt index
Measured according to ASTM D1238 at 230 DEG C and 2.16 kg.
(4) Coating adhesion
Using a Karcher high-pressure equipment, the distance from the specimen to the specimen is 10 cm, and water at 70 ° C and 65 bar high temperature and high pressure is fired on the surface of the test specimen through a pipe nozzle to evaluate the damage on the surface of the coating. At this time, the surface of the coated film has a cross-cut mark and is left to stand for about 24 hours after coating, and then the test is carried out.
The adhesion evaluation criteria are classified into 0 (when there is no abnormality in the surface coat after high-temperature / high-pressure water discharge), 4 (large area desorption on the surface of the coat) and 0 to 1 level.
Hereinafter, the present invention will be described in more detail with reference to the following examples, but the scope of the present invention is not limited to these examples.
Preparation of polypropylene resin composition
The crystalline polypropylene and the ethylene-octene copolymer rubber used in Examples 1 to 4 and Comparative Examples 1 to 8, talc, various additives and coloring agents were mixed in the respective contents as shown in the following Table 1 to obtain a blend . The blend was fed into a main hopper in a twin-screw extruder (SM PLATEK, screw diameter 30), the barrel temperature was adjusted to 150 to 210 DEG C, kneaded at an extrusion rate of 30 kg / hour and a screw rotation speed of 250 rpm, To prepare a resin composition.
Preparation and physical property measurement of injection specimen
The polypropylene resin compositions obtained in Examples 1 to 4 and Comparative Examples 1 to 8 were subjected to an injection molding machine of TOYO (180 Torr of mold clamping force) to prepare the necessary specimens for the measurement of physical properties, and the flexural modulus, Izod impact strength , And the coating adhesion was measured. The results are shown in Table 2 below.
(A): crystalline polypropylene: a crystalline ethylene-propylene block copolymer having a melt index (2.16 kg according to ASTM D1238, molten resin flow rate at 230 占 폚 for 10 minutes) of 30 g / 10 min
(B) -1: ethylene-octene random copolymer rubber, an intrinsic viscosity of 2.5 dl / g
(B) -2: ethylene-octene random copolymer rubber, an intrinsic viscosity of 1.5 dl / g
(B) -3: ethylene-butene random copolymer rubber, an intrinsic viscosity of 1.7 dl / g
(C) -1: Organosilane coupling agent Ultrafine talc having an average particle diameter of 1.0 μm
(C) -2: Organosilane-based coupling agent Ultrafine talc having an average particle diameter of 2.0 μm
(C) -3: Talc having an average particle diameter of 8.0 탆
Modulus of elasticity
(MPa)
Shock
burglar
(Room temperature, KJ / cm 2 )
* NB means non-break.
As a result of comparing Examples 1 to 4 and Comparative Examples 1 to 8, it was found that the polypropylene resin compositions of Comparative Examples 1 and 2 corresponding to the present invention were applied as exterior materials when the content of the rubber component was out of the content range according to the present invention Impact strength or flexural modulus was poor in the following. In Comparative Examples 3, 4 and 8, the intrinsic viscosity of the rubber component was out of the range of the present invention, which was favorable in terms of mechanical properties, but showed an undesirable result in the coating adhesion. In Comparative Examples 5 and 6, the talc content was out of the content range according to the present invention, and the flexural modulus or impact strength was poor. In Comparative Example 7, the use of talc having a good mechanical property but a large particle size showed a problem in paint adhesion.
On the other hand, the polypropylene resin compositions of Examples 1 to 4 exhibited excellent results in not only the flexural modulus and the impact strength but also the paint adhesion by using the rubber component and the ultrafine talc having a high intrinsic viscosity.
Claims (9)
5 to 20% by weight of a rubber component having an intrinsic viscosity of 2 to 4 dl / g; And
10 to 25% by weight of an ultrafine inorganic filler having an average particle size of 0.1 to 5 占 퐉; Wherein the polypropylene resin composition comprises:
Wherein the rubber component is an ethylene-? -Olefin random copolymer rubber comprising ethylene and an? -Olefin having 4 to 12 carbon atoms.
Wherein the crystalline polypropylene has a melt index of 10 to 50 g / 10 min at 230 占 폚 and 2.16 kg according to ASTM D1238.
Wherein the crystalline polypropylene has an isotactic peptad fraction of 0.80 to 0.99 as determined by C-NMR.
Characterized in that the crystalline polypropylene comprises at least one selected from a crystalline polypropylene homopolymer and a propylene-alpha olefin crystalline copolymer comprising C2 to C20 (exclusive of C3) alpha olefins. Composition.
Wherein the ultrafine inorganic filler is at least one selected from talc, mica, barium sulfate, calcium carbonate, and glass fiber.
Wherein the ultrafine inorganic filler is an organic titanate-based coupling agent, an organosilane-based coupling agent, a polypropylene resin characterized by being surface-treated with a modified polyolefin grafted with an unsaturated carboxylic acid or an anhydride thereof, a fatty acid, a fatty acid metal salt or a fatty acid ester Composition.
Wherein the polypropylene resin composition further comprises at least one additive selected from the group consisting of antioxidants, processing activators, ultraviolet stabilizers, long-term heat stabilizers, antistatic agents, flame retardants, antibacterial agents and coloring agents.
Wherein the molded body is a part for automobile exterior materials.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020160010940A KR101847258B1 (en) | 2016-01-28 | 2016-01-28 | Polypropylene composition with good paintability |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020160010940A KR101847258B1 (en) | 2016-01-28 | 2016-01-28 | Polypropylene composition with good paintability |
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| KR20170090285A KR20170090285A (en) | 2017-08-07 |
| KR101847258B1 true KR101847258B1 (en) | 2018-04-09 |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109135054B (en) * | 2018-07-23 | 2021-03-09 | 杭州联通管业有限公司 | Antibacterial flame-retardant polypropylene pipe and preparation method thereof |
| CN110128745A (en) * | 2019-04-24 | 2019-08-16 | 杭州余杭振华日化玻璃有限公司 | A kind of formula of perfume bottle cap and preparation method thereof |
| KR102209155B1 (en) * | 2019-12-31 | 2021-01-28 | 한화토탈 주식회사 | Polypropylene Resin Composition with Excellent Platability |
| CN114316415B (en) * | 2021-11-23 | 2023-09-12 | 金发科技股份有限公司 | Masterbatch for improving coating adhesion, polypropylene material and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004217896A (en) | 2002-12-26 | 2004-08-05 | Sunallomer Ltd | Polypropylene-based resin composition |
| JP2011127058A (en) | 2009-12-21 | 2011-06-30 | Nissan Motor Co Ltd | Injection molded part for automobile |
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- 2016-01-28 KR KR1020160010940A patent/KR101847258B1/en active IP Right Grant
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004217896A (en) | 2002-12-26 | 2004-08-05 | Sunallomer Ltd | Polypropylene-based resin composition |
| JP2011127058A (en) | 2009-12-21 | 2011-06-30 | Nissan Motor Co Ltd | Injection molded part for automobile |
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