KR20100033256A - Polypropylene resin composition and plastic article prepared by the same - Google Patents

Polypropylene resin composition and plastic article prepared by the same Download PDF

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Publication number
KR20100033256A
KR20100033256A KR1020080092340A KR20080092340A KR20100033256A KR 20100033256 A KR20100033256 A KR 20100033256A KR 1020080092340 A KR1020080092340 A KR 1020080092340A KR 20080092340 A KR20080092340 A KR 20080092340A KR 20100033256 A KR20100033256 A KR 20100033256A
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South Korea
Prior art keywords
polypropylene resin
resin composition
ethylene
weight
polypropylene
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KR1020080092340A
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Korean (ko)
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문태식
이주호
최현민
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호남석유화학 주식회사
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Priority to KR1020080092340A priority Critical patent/KR20100033256A/en
Publication of KR20100033256A publication Critical patent/KR20100033256A/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60R—VEHICLES, VEHICLE FITTINGS, OR VEHICLE PARTS, NOT OTHERWISE PROVIDED FOR
    • B60R13/00—Elements for body-finishing, identifying, or decorating; Arrangements or adaptations for advertising purposes
    • B60R13/04—External Ornamental or guard strips; Ornamental inscriptive devices thereon
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/54—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
    • C08L23/12—Polypropene
    • 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
    • C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/005—Additives being defined by their particle size in general

Abstract

PURPOSE: A polypropylene resin composition is provided to ensure excellent weather resistance, dimensional stability, and mechanical properties, especially, scratch and mar resistance by comprising highly crystalline polypropylene resin with isotactic index of 98.5% or more. CONSTITUTION: A polypropylene resin composition comprises 47~79 weight% highly crystalline polypropylene resin with isotactic index of 98.5% or more; 10~30 weight% thermoplastic elastomer rubber; 10~25 weight% inorganic filler; and 1~10 weight% silicon-based lubricant. The highly crystalline polypropylene comprises a propylene homopolymer or a copolymer of propylene and C2~10 monomer of 10 mole % or less.

Description

POLYPROPYLENE RESIN COMPOSITION AND PLASTIC ARTICLE PREPARED BY THE SAME}

The present invention relates to a polypropylene resin composition excellent in impact resistance and scratch resistance and a plastic molded article thereby.

There is an increasing interest in the automotive industry for resin compositions having good paint adhesion, especially for items such as automobile bumper fascia. Such resin compositions for automotive exteriors must have suitable mechanical properties for their use, such as high flexible modulus, high Izod impact energy, low temperature impact energy and ductility and elongation at break. In addition, there should be a paintability that makes the appearance of the whole product to which they apply beautify.

Conventional automobile exterior bumper fascia manufacturing method is performed by the method of injection molding the material after injection molding, there is a problem that a scratch occurs in a portion of the human hand during transport or storage after injection molding. In particular, in the case where paint is applied where scratches are generated, a lot of defects in external appearance occur, which is the main cause of productivity decrease due to an increase in the defective rate.

 Meanwhile, the automobile exterior bumper fascia, which has been recently developed and attempted, has a mold-in-color (MIC) bumper that does not require a paint coating process, thereby lowering the cost. In the development of such materials, physical properties having impact resistance and weather resistance are basic, and scratch properties are one of the physical properties that are highly required. General physical properties with impact resistance mean impact strengths that meet the 5 mile bumper standard for automotive exterior materials. In addition, the scratch resistance is measured by a pencil hardness test conducted with a prescribed pencil, a five finger test or a sapphire ball test based on five different specimens, and recently, a sapphire ball test mainly uses a scratch resistance specification. Deciding.

Although the research on the development of bumper resins for automobile exterior materials having general physical properties such as excellent impact resistance as well as excellent scratch resistance is ongoing, it is possible to achieve scratch resistance suitable for MIC bumper fascia that does not require paint coating. There is no technical advance on the resin composition to a degree. The conditions necessary for the development of these MIC bumpers should be matched with the boy color, and have excellent weather resistance, dimensional stability, mechanical properties, and especially scratch and mar resistance.

Accordingly, the inventors of the present invention overcome the problems of the prior art as described above, and have completed the present invention while studying a resin composition having excellent impact resistance and scratch resistance suitable for MIC bumper fascia that do not require paint coating. .

The present invention is to provide a polypropylene resin composition excellent in impact resistance and scratch resistance.

In addition, the present invention is to provide a plastic molded article made of the polypropylene resin composition.

The polypropylene resin composition of the present invention is 47 to 79% by weight of high crystalline polypropylene resin having an isotactic index (II) of 98.5% or more, 10 to 30% by weight of thermoplastic elastomer rubber, 10 to 25% by weight of inorganic filler, and silicone lubricant It contains 1 to 10% by weight.

When the highly crystalline polypropylene resin having an isotactic index of 98.5% or more is used, the crystallinity of the polypropylene is increased to improve the mechanical properties and heat resistance of the polypropylene. In addition, the range of 47 to 79% by weight of the highly crystalline polypropylene resin is exhibited moldability, impact resistance, chemical resistance enough to be used in automobile bumper fascia.

Thermoplastic elastomer rubber is added to improve impact resistance, and is added in an amount of 10 to 30% by weight. When the thermoplastic elastomer rubber is less than 10% by weight, the degree of impact resistance is insufficient. There is a problem that the heat resistance is lowered.

The inorganic filler is contained in 10 to 25% by weight, when the inorganic filler is less than 10% by weight stiffness and dimensional stability is lowered, when it exceeds 25% by weight, there is a problem that the impact strength is lowered and the density is increased.

Silicon-based lubricant is contained in 1 to 10% by weight, when the silicone-based lubricant is less than 1% by weight has a slight improvement in scratch resistance, when the amount exceeds 10% by weight there is a problem that the cost rises.

Hereinafter, each component contained in the polypropylene resin composition and the polypropylene resin composition according to the specific embodiment of the present invention will be described.

(One) High crystallinity  Polypropylene

Unlike conventional polypropylene, high crystallinity polypropylene (High Crystallinity PolyPropylene) is also called High Isotacticity PolyPropylene (HIPP), High Stiffness PolyPropylene (HSPP), and is designed to improve impact resistance, high hardness and scratch resistance. It is a compound that replaces polypropylene of polypropylene and has 20 ~ 40% higher stiffness, excellent heat resistance and scratch resistance due to its high hardness and high crystallinity compared to conventional commercial isotactic polymers. Impact has similar advantages.

The isotactic index for stereoregularity of polypropylene, which is currently widely used, is 94-97%. However, for high stereoregular polypropylene, the isotactic index is required at least 98.5%. As the isotactic index increases, the degree of crystallinity of polypropylene increases, resulting in excellent mechanical properties and heat resistance of polypropylene.

Highly crystalline polypropylene can be used for the overall parts of the interior and exterior of automobiles. Among them, the stiffness and heat resistance are superior to those of existing polypropylene. Can be.

In the case of the highly crystalline polypropylene resin according to the present invention, an isotactic index of 98.5% or more may be used. As the high crystalline polypropylene resin according to the present invention, any copolymer may be used without particular limitation as long as the isotactic index is 98.5% or more.

Highly crystalline polyester of the present invention, the propylene resins may be used are copolymers with C 2 ~ 10 monomers (excluding propylene) of not more than 10 mol% and a propylene homopolymer or propylene. A high crystalline polypropylene resin comprises a copolymer of propylene and a C 2 ~ 10 monomers, at which time, a C 2 ~ 10 monomers in the copolymer may include less than 10 mol%. That is, preferably there is a high crystalline polypropylene containing a C 2 ~ 10, and propylene monomer may be used in 0 to 10 mol%. Most preferably a copolymer of propylene and 0-10 mole% ethylene can be used.

In addition, the high crystalline polypropylene resin according to the present invention is used that has a melt index of 8 ~ 150g / 10 minutes (230 ℃). If the melt index of the polypropylene resin to be used is less than 8g / 10 minutes (230 ℃), there is a problem that the moldability is lowered, the impact strength is lowered if it exceeds 150g / 10 minutes (230 ℃) .

(2) thermoplastic elastomer rubber

As a component used for impact resistance reinforcement, the thermoplastic elastomer rubber of the present invention is a polymer of ethylene and an α-olefin of C 2 to C 10 , preferably in propylene, butene, pentene, hexene, propene, octene Copolymers of ethylene with any one selected may be used. More preferably, any one selected from ethylene-propylene rubber (EPR), ethylene-propylene-diene rubber (EPDM), ethylene-butene copolymer (EBR), and ethylene-octene (EOR) may be used. Most preferably ethylene-octene copolymer (EOR) or ethylene-butene copolymer (EBR) can be used.

Polymers of ethylene and α-olefins of C 2 to C 10 may have a melt index of 0.5 to 150 g / 10 min (190 ° C. and 2.6 kgf) and a density of 0.868 to 0.885 g / cc.

In the case of the ethylene-octene copolymer (EOR), the impact strength improvement effect is excellent by the octene group of the long side chain and can be preferably used because the stiffness which is relatively lowered can be reduced as much as possible.

When an ethylene-butene copolymer is used as the thermoplastic elastic rubber body, one containing preferably 50% or more of butene CO-monomer content may be applied. Butene CO-monomer content of 50% or more may be preferably applied.

In addition, an ethylene-butene copolymer (EBR) having a melt index of 0.5 to 150 g / 10 min (190 ° C. and 2.6 kgf) and a density of 0.868 to 0.885 g / cc may be preferably used.

(C) weapon Filling

As components used for heat resistance and rigidity reinforcement, talc, calcium carbonate, calcium sulfate, magnesium oxide, calcium stearate, wollastonite, mica, silica, calcium silicate, clay, and carbon black may be used. It does not specifically limit. In the use of the inorganic filler, it is preferable that the rigidity and hardness of the resin composition increase with increasing content, and examples thereof include wollastonite and talc. In the present invention, the inorganic filler may have an average particle diameter of 1 to 30 μm and preferably 5 to 10 μm.

(D) silicone Lubricant

Lubricants are additives that reduce friction and heat of friction during synthetic resin processing and increase the fluidity of the polymer to make the process smooth. It can be divided into two types according to the method of use. The first is mainly lubrication during molding process. For example, in order to prevent adhesion between mold surface and resin, kneading with resin lowers melt viscosity of resin to improve molding processability. Examples used herein include metal soaps, fatty acids and their derivatives, fatty acid amides, higher alcohols, paraffin wax and the like. If the lubricant is classified according to its function, it is classified into internal lubricant and external lubricant.

The internal lubricant lowers the friction between the contact surface of the polymer and the processing machine, the polymer ring, and each other, thereby improving the releasability and injection fluidity of the molded article. In addition, by adding the lubricant, the strength between the polymers is weakened to provide slippage between the molecular rings, and this principle is used to improve scratching.

Mainly used as internal lubricants include lower alcohol esters of higher alcohol fatty acids and aliphatic polyhydric alcohol ester liquid paraffin. External lubricant refers to the reduction of friction between polymer and surface of processing machine.

As a general chemical structure, both polar groups and non-polar groups are used to help maintain compatibility with the polymers.The polar groups are lubricated to the surface of non-polar functional processing machines, or higher fatty acids, fatty acid amide compounds, waxes, silicones, etc. have.

In the present invention, any silicone-based lubricant may be used without particular limitation.

In addition, the present invention provides a plastic molded article manufactured using a polypropylene resin composition comprising a high crystalline polypropylene resin according to another embodiment.

Hereinafter, a plastic molded article according to a specific embodiment of the present invention will be described. The plastic molded article of the present invention is in the form of an inorganic filler and a silicone lubricant dispersed in a resin substrate made of a highly crystalline polypropylene resin having an isotactic index (I.I) of 98.5% or more and a thermoplastic elastomer rubber.

Although the manufacturing method of a polypropylene molded article is not specifically limited, Blow molding (blow molding) used for automobile bumper fascia can be used among the plastic injection molding systems.

Injection blow molding heat-melts the molding material and injection-fills the cavity of the pre-closed mold, then inflates the parison or sheet of thermoplastic using pneumatic pressure, and solidifies or hardens at the same time by being in close contact with the mold. It is a method of obtaining a molded article.

The plastic molded article according to the present invention is not particularly limited, but is manufactured by injection blow molding, and the polypropylene resin composition pellets extruded and cooled and solidified at 190 to 250 ° C. are heated and melted at 190 to 250 ° C. to form a cavity of the mold. After injection-filling into a parison or sheet of thermoplastic, it may be prepared by inflating the sheet using air pressure or the like, and then solidifying or curing the sheet by closely contacting the mold.

The final form of the plastic molded article according to the present invention may be provided in a form containing an inorganic filler and a silicone lubricant dispersed in a resin substrate made of a highly crystalline polypropylene resin having a isotactic index (II) of 98.5% or more and a thermoplastic elastomer rubber. have.

The plastic molded article according to the present invention is not limited in the field of use, but can be used in MIC automobile bumper fascia.

As described above, the polypropylene resin composition according to the present invention includes a highly crystalline polypropylene resin having an isotactic index of 98.5% or more, and thus can be applied to automotive exterior materials having excellent impact resistance and scratch resistance, particularly bumper fascia. It provides a polypropylene composition. Polypropylene composition of the present invention is excellent in scratch resistance, it can be widely used in automotive exterior material MIC (mold-in-color) bumper fascia.

Hereinafter, the present invention will be described in more detail with reference to specific examples for better understanding. However, the following examples are only intended to more clearly understand the present invention, and the present invention is not limited thereto.

[ Example Preparation of Polypropylene Resin Composition

<Examples 1 to 4>

First, the components of the polypropylene, thermoplastic elastomer rubber, talc, and silicone, which are specified in Table 1, were mixed with a Henschel mixer for 3 minutes. The component content ratio of the polypropylene resin composition is shown in Table 1. The polypropylene resin composition was extruded with an extruder at a temperature in the range of 190 to 250 ° C., and then cooled and solidified to obtain a composition on a pellet. The obtained composition was injected in a temperature range of 180 ~ 250 ℃ according to the melt index, and then measured various physical properties. The results are shown in Table 2.

<Examples 5 to 10>

First, the component content of silicone in polypropylene, thermoplastic elastomer rubber, talc, and silicone, as shown in Table 1, was changed and mixed with a Henschel mixer for 3 minutes. The mixture was extruded in an extruder at a temperature in the range of 190 to 250 ° C., and then cooled and solidified to obtain a composition on pellets. The obtained composition was injected in a temperature range of 180 ~ 250 ℃ according to the melt index, and then measured various physical properties. The results are shown in Table 2.

Polypropylene (% by weight) Rubber (% by weight) Talc (% by weight) Silicone (% by weight) Example 1 79 10 10 One Example 2 68 15 15 2 Example 3 57 20 25 3 Example 4 46 25 25 4 Example 5 55 20 20 One Example 6 54 20 20 2 Example 7 53 20 20 4 Example 8 52 20 20 6 Example 9 51 20 20 8 Example 10 50 20 20 10

Polypropylene Co., Ltd.: Highly crystalline polypropylene resin with melt index of 35g / 10min (230 ℃, 2.16kgf), isotactic index of 99% and ethylene content of 6 mol%

Rubber: Ethylene-butene copolymer with a butene content of 25% and a melt index of 0.5 g / 10 min (190 ° C, 2.16 kgf)

Talc: Talc with an average particle diameter of 18.5㎛ and weight loss rate of less than 0.1% after combustion

Silicone: Germany WACKER Products

Flow Index (g / 10min) I ZOD strength (kgfcm / cm) Flexural modulus (㎏f / ㎠) Heat Deflection Temperature (℃) Scratch (△ L) 23 ℃ -30 ℃ Example 1 25.7 37.6 8.7 13,800 128 5.89 Example 2 20 47.2 13.3 14,100 130 5.39 Example 3 24.2 50.4 10.5 15,700 134 2.98 Example 4 24.9 53.8 12.2 15,200 131 2.81 Example 5 23.8 46.8 10.3 15,500 128 7.5 Example 6 25.7 45.8 10.4 15,500 130 6.12 Example 7 26.2 46.1 10.3 15,600 134 2.72 Example 8 26.7 46.5 10.5 15,720 132 2.1 Example 9 27.8 46.3 10.2 15,700 134 1.31 Example 10 29.8 32.9 9.4 15,470 128 1.11

Hereinafter, the evaluation method of the polypropylene composition described in the Example is based on the following Experimental example.

[ Experimental Example ] Example  Measurement of Physical Properties of Polypropylene Compositions

(1) Melt index measurement: measured by ASTM D-1238 method. Test conditions were measured at 230 ° C, 2.16kgf.

(2) Measurement of flexural modulus and flexural strength: measured by ASTM D-790 method, the specimen size is 12.7 × 127 × 6.4mm, the crosshead speed was 28mm / min under the test conditions.

(3) Izod impact strength measurement: Izod impact strength was measured by ASTM D-256 method and the specimen size was 63.5 × 12.7 × 3mm.

(4) Heat deflection temperature measurement: The heat deflection temperature was measured by ASTM D-648 method, the specimen size was 12.7 × 127 × 6.4mm, the load value (4.6kgf) used in the test conditions.

(5) Scratch Resistance Hardness Measurement: Scratch resistance hardness was measured by ISO7727 method, and the equipment used was Japanese HEIDON Hard Metal Pen r = 0.05 Load: 10N Speed: 1000 ± 50mm / min (2mmX2mm) A scratch screen net was made and the color ΔL value was measured.

Evaluation criteria: △ L means a higher degree of whitening and a higher degree of scratching

As a result of the above examples and experimental examples, the polypropylene composition according to the present invention uses a polypropylene resin having an isotactic index of 98.5% or more, so that impact resistance and strength are similar to those of the conventional polypropylene resin composition. In spite of being maintained at, it was found that scratch resistance is excellent. In particular, it can be seen that the scratch resistance is much improved as the amount of the silicone lubricant is increased.

Therefore, the polypropylene resin composition including the high crystalline polypropylene resin according to the present invention is excellent in both impact resistance and scratch resistance, and can be widely used in MIC (mold-in-color) bumper fascia.

1 is a view showing the results of scratch resistance according to the silicone additive content of the polypropylene resin composition of the present invention.

Claims (11)

47 to 79% by weight of a high crystalline polypropylene resin having an isotactic index (I.I) of 98.5% or more; 10-30% by weight of thermoplastic elastomer rubber; 10-25 wt% of inorganic filler; And Polypropylene resin composition comprising 1 to 10% by weight of the silicone lubricant. The method of claim 1 wherein the high crystalline polypropylene resin is a polypropylene resin composition comprising a copolymer of a propylene homopolymer or propylene with 10 mol% of C 2 ~10 monomer. The polypropylene resin composition according to claim 1, wherein the melt index of the highly crystalline polypropylene resin is 8 to 150 g / 10 minutes (230 ° C). The polypropylene resin composition according to claim 1, wherein the thermoplastic elastomer rubber comprises a copolymer of ethylene and C 2 -C 10 α-olefins. The polypropylene resin composition of claim 4, wherein the α-olefin comprises any one or more selected from the group consisting of propylene, butene, pentene, hexene, propene, and octene. The method of claim 1, wherein the thermoplastic elastomer rubber is any selected from the group consisting of ethylene-propylene rubber (EPR), ethylene-propylene-diene rubber (EPDM), ethylene-butene copolymer (EBR) and ethylene-octene (EOR). Polypropylene resin composition comprising one or more. The polypropylene of claim 1, wherein the inorganic filler comprises at least one selected from the group consisting of talc, calcium carbonate, wollastonite, calcium sulfate, magnesium oxide, calcium stearate, mica, calcium silicate, clay, and carbon black. Resin composition. The polypropylene resin composition according to claim 1, wherein the inorganic filler has an average particle diameter of 1 to 30 mu m. The plastic molded article manufactured from the polypropylene resin composition of any one of Claims 1-8. Highly crystalline polypropylene resins having an isotactic index (I.I) of at least 98.5%; And A resin substrate made of a thermoplastic elastomer rubber; Inorganic fillers dispersed in the resin substrate; And A plastic molded article comprising a silicone-based lubricant dispersed in the resin substrate. 11. The plastic molded article according to claim 9 or 10, wherein the plastic molded article is used as a vehicle exterior bumper fascia.
KR1020080092340A 2008-09-19 2008-09-19 Polypropylene resin composition and plastic article prepared by the same KR20100033256A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20170143265A (en) 2016-06-21 2017-12-29 (주)켐코정밀 Manufacturing method of talc master batch resin composition with scratch resistant for interior or exterior material of automobile

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20170143265A (en) 2016-06-21 2017-12-29 (주)켐코정밀 Manufacturing method of talc master batch resin composition with scratch resistant for interior or exterior material of automobile

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