CN105778388A - Polypropylene resin composition - Google Patents
Polypropylene resin composition Download PDFInfo
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- CN105778388A CN105778388A CN201610009345.2A CN201610009345A CN105778388A CN 105778388 A CN105778388 A CN 105778388A CN 201610009345 A CN201610009345 A CN 201610009345A CN 105778388 A CN105778388 A CN 105778388A
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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
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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
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
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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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L21/00—Compositions of unspecified rubbers
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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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
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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
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
The invention provides a polypropylene resin composition which comprises 30-69.8 weight percentage of polypropylene, 20-35 weight percentage of inorganic fillers, 10-25 weight percentage of rubber, 0.1-5 weight percentage of bulking agents and 0.1-5 weight percentage of scratch resistant agents, wherein the composition possesses a delta L(dL) value of no greater than 0.2, a flexural modulus of 1000-2100 MPa and acantilever type impact intensity strength of 16-40KJ/m2.
Description
The cross reference of related application
This application requires to enjoy in priority and the interests of the korean patent application the 10-2015-0006804th that on January 14th, 2015 submits in Korean Intellectual Property Office, and all interests produced by 35U.S.C.119, its full content is expressly incorporated herein by way of reference.
Background technology
1, field
The present invention relates to a kind of polypropylene resin composite, which show the excellent bending modulus when manufacturing automotive interior and external component, scratch resistance and resistance to impact.
2, description of Related Art
Scratch resistance is for considerable factor the interiorly or exteriorly parts of automobile.In order to make automobile component keep the state of high-quality before expiring the service life of automobile, sufficiently high scratch resistance it is necessary the impact preventing automobile component from avoiding outside stimulus thing (such as driver and the key of passenger, fingernail or ring), so should be kept.
In order to improve scratch resistance, disclose No. 10-2008-0074973 in Korean Patent and propose conventional method, it discloses and use density for 0.905g/cm with the amount less than 20 weight %3～0.930g/cm3Ethene polymers.But, along with the increase adding polyvinyl amount, polyvinyl rigidity (bending modulus) can be gradually lowered.
In order to improve scratch resistance, Korean Patent No. 10-0981391 discloses a kind of scuffing spontaneous recovery compositions, its comprise the polypropylene of maleic anhydride graft, thermoplastic elastomer (TPE), based on containing the polyolefinic resin of epoxide group, 2,4,6-tri-(dimethylaminomethyl) phenol and Talcums.According to the method, it is characterised by not using damage resistant agent.
Accordingly, it would be desirable to have the polypropylene resin composite of the scratch resistance of excellence while keeping excellent rigidity (bending modulus) and impact resistance.
Summary of the invention
Embodiments of the present invention provide a kind of polypropylene resin composite, and it has the rigidity of excellence, scratch resistance and resistance to impact when being applied to automotive interior and external component.
By the above-mentioned and other side of the present invention described in the explanation at example below embodiment, or can be seen that the above-mentioned of the present invention and other side will be apparent from from the explanation of example below embodiment.
According to an aspect of the present invention, provide a kind of polypropylene resin composite, it comprises: the damage resistant agent of the polypropylene of 30～69.8 weight %, the inorganic filler of 20～35 weight %, the rubber of 10～25 weight %, the bulking agent of 0.1～5 weight % and 0.1～5 weight %, wherein, described compositions has △ L (dL) value of 0.2 measured by Erichsen test or less, the bending modulus of 1000～2100MPa and 16～40KJ/m2Izod impact test intensity.
As it has been described above, the polypropylene resin composite according to the present invention demonstrates the bending modulus of excellence, resistance to impact and scratch resistance when as automotive interior and external component.
Accompanying drawing explanation
The illustrative embodiments of the present invention is described in detail by referring to accompanying drawing, the above-mentioned and further feature of the present invention will be apparent from, wherein:
Fig. 1 is the photo showing the preparation according to an embodiment of the invention for the surface of the sample of measuring scratch resistance.
Detailed description of the invention
Hereinafter, will be described in detail with reference to the accompanying drawings the embodiment of embodiments of the present invention and the physical property of various component so that those skilled in the art can be easily manufactured and use them.But, the present invention can be presented as many different forms and should not be construed as limited to embodiment set forth herein.
Fig. 1 is the photo showing the preparation according to an embodiment of the invention for the surface of the sample of measuring scratch resistance.
The present invention relates to a kind of polypropylene resin composite, it comprises: the damage resistant agent of the polypropylene of 30～69.8 weight % (wt%), the inorganic filler of 20～35wt%, the rubber of 10～25wt%, the bulking agent of 0.1～5wt% and 0.1～5wt%, wherein, described compositions has △ L (dL) value of 0.2 measured by Erichsen test or less, the bending modulus of 1000～2100MPa and 16～40KJ/m2Izod impact test intensity.
In the present invention, described polypropylene can be block copolymer polypropylene, and may further include HOPP or random polypropylene.Described block copolymer polypropylene has the rigidity of excellence, and improves resistance to impact.Described block copolymer polypropylene can have bending modulus and the 16～40KJ/m of 1000 to 2100MPa2Room temperature lzod impact proof strength.
Described HOPP preferably has bending modulus and the 2～6KJ/m of 1270～2350MPa2Room temperature lzod impact proof strength, and there is the impact characteristics lower than described block copolymer polypropylene, but still there is the rigidity of excellence.Additionally, described random polypropylene preferably has bending modulus and the 2～40KJ/m of 680～980MPa2Room temperature lzod impact proof strength, and there is the rigidity lower than described block copolymer polypropylene, but still there is the impact characteristics of excellence.
In more detail, described polypropylene includes the propylene monomer as main component and the monomer (such as ethylene, 1-butylene, 1-hexene, 1-octene, 4-methyl-1-pentene, etc.) as supplementary element.In detail, described polypropylene block copolymer includes the ethylene being bonded to main propylene chain of the propylene as main component and 1～13wt%, and preferentially farther include alpha-olefin (such as 1-butylene, 1-hexene, 1-octene, 4-methyl-1-pentene, etc.).
In the present invention, based on the gross weight of polypropylene resin composite, the content of described inorganic filler is preferably in the scope of 20～35wt%.When the content of described inorganic filler is lower than 20wt%, the bending modulus of polypropylene resin composite may reduce.But, when the content of described inorganic filler is more than 35wt%, the resistance to impact of described polypropylene resin composite may reduce.
Described inorganic filler is preferably selected from least one of Talcum, glass fibre, Muscovitum, calcium carbonate, wollastonite, barium sulfate, clay, calcium sulfate crystal whiskers and magnesium sulfate crystal whisker.
In the present invention, the content of described rubber is preferably in the scope of 10～25wt%.When the content of rubber is less than 10wt%, the resistance to impact of described polypropylene resin composite may reduce.But, when the content of rubber is more than 25wt%, the bending modulus of described polypropylene resin composite may reduce.
In the present invention, described rubber is preferably selected from least one of ethylene octene rubber (EOR), ethylene butene rubbers (EBR), ethylene propylene rubber (EPR) and styrene ethylene butylene styrene (SEBS).
In the present invention, the content of described bulking agent is preferably in the scope of 0.1～5wt%.When the content of bulking agent is less than 0.1wt%, it does not have demonstrate enough scratch resistances.But, when the content of bulking agent is more than 5wt%, the bending modulus of described polypropylene resin composite and impact resistance may reduce.
Described bulking agent is a kind of compositions, the polypropylene of its maleic acid comprising 0.1～10wt% or maleic anhydride and/or 99.9～90wt% and/or polyethylene.
In the present invention, polydimethylsiloxane (PDMS) is used as damage resistant agent and its content in the scope of 0.1～5wt%.When the content of PDMS is less than 0.1wt%, scratch resistance is not high enough.But, when the content of PDMS is more than 5wt%, bending modulus may reduce.
In the present invention, described compositions have 0.2 measured by Erichsen test or less, preferably 0.1 or less △ L (dL) value.
Described dL value is measuring of aberration, and it is the numeric representation of brightness.L*100 represents white and L*0 represents black.L-value is more high, and color is more bright.
According to the present invention, owing to damage resistant agent uses together with bulking agent, scratch resistance can improve further.When only using damage resistant agent, it is impossible to obtain the product with the dL value of 0.2 or less, it means that this bulking agent must exist as neccessary composition to improve scratch resistance.For the problem solving the damage resistant agent based on silicon of routine, i.e. the low surface tension of silicon, have been carried out improving the trial of scratch resistance by reducing coefficient of friction.But, the invention provides bulking agent to improving the discovery that scratch resistance plays an important role.
It is to say, when external impact is applied to the polypropylene resin composite comprising inorganic filler, inorganic filler can separate from polypropylene resin composite, scratch resistance so can be reduced.But, when adding bulking agent, it is possible to increase the adhesion between inorganic filler and polypropylene resin composite, thus suppressing the inorganic filler caused due to external impact to separate from complex polypropylene resin compositions considerably.
Polypropylene resin composite according to the present invention can have 1000～2100MPa, it is preferable that 1200～2100MPa, and the bending modulus of more preferably 1500～2100MPa.
When bending modulus is less than 1000MPa, the rigidity of described polypropylene resin composite may reduce.But, when bending modulus is more than 2100MPa, the resistance to impact of described polypropylene resin composite may reduce.
In the present invention, described polypropylene resin composite can have 16～40KJ/m2Izod impact test intensity.When izod impact test intensity is less than 16KJ/m2Time, impact strength is too weak and may not apply to automotive interior and outside parts.When izod impact test intensity is more than 40KJ/m2Time, rigidity becomes unsatisfactory, thus undesirably manufactures the product being easily deformed in appearance.
In the present invention, described polypropylene resin composite can have 0.2～150g/10min (ASTMD1238,2.16kg, 230 DEG C), it is preferable that 20～130g/10min (ASTMD1238,2.16kg, 230 DEG C), and the melt index (MI) (MI) of more preferably 30～120g/10min (ASTMD1238,2.16kg, 230 DEG C).
When melt index (MI) less than 0.2g/10min (ASTMD1238,2.16kg, 230 DEG C) time, it is most likely that produce defect, for instance formed gel.When melt index (MI) is greater than 150g/10min (ASTMD1238,2.16kg, 230 DEG C), mobility is excellent, but resistance to impact may reduce.
In the present invention, polypropylene resin composite is composite resin composition, and preferably has 3～40g/10min (ASTMD1238,2.16kg, 230 DEG C) melt index (MI), and more preferably there is 7～35g/10min (ASTMD1238,2.16kg, 230 DEG C) melt index (MI).
When melt index (MI) less than 3g/10min (ASTMD1238,2.16kg, 230 DEG C) time, it is most likely that cause bad outward appearance when injection mo(u)lding.When melt index (MI) more than 40g/10min (ASTMD1238,2.16kg, 230 DEG C) time, injection moulding pressure possibly cannot be normally applied to mechanograph when injection mo(u)lding, thus undesirably produce defect (as sink or burr).
Except mentioned component, can farther including to be selected from least one additive of antioxidant, lubricant, ultra-violet stabilizer, long-term heat-resisting stabilizing agent, antistatic additive, fire retardant, antibacterial and coloring agent according to the polypropylene resin composite of the present invention, as long as this additive does not damage the effect of the present invention.
Prepare the method according to the polypropylene resin composite of the present invention to include: at the suitable various composition of weight ratio lower-weighing (including polypropylene, inorganic filler, rubber, bulking agent, damage resistant agent and other additive), use blender (such as, the gloomy blender of the Chinese) mix described composition, products therefrom is incorporated into the main hopper on top at extruder, then melting mixing in an extruder, the strand being appropriately sized is formed with strands die head, cool down in a water bath, the water on dry strand surface, and strand is cut into pellet.
Hereinafter, the polypropylene resin composite according to the present invention will be further described by following embodiment.
<embodiment 1-7 and comparative example 1-2>
Polypropylene resin composite is through the following steps that prepare: mix various compositions with the various content ratio shown in table 1, mixture based on total content 100%, it is added thereto to 1.3% black masterbatch, and while the barrel zone temperature of extruder is adjusted to 150 to 220 DEG C, gained mixture is fed to double screw extruder (SM Alexandre Desplat gram company limited of Korea S, screw diameter: 30 Φ) main funnel, and use the screw speed mixing of the feed rate of 20kg/hr and 350rpm.
Table 1
Note: E: embodiment
CE: comparative example
BCPP-1: block copolymer polypropylene (Korea S Korea Spro Hua Daodaer Chemical trade company limited；MI=60 ± 3g/10min)
BCPP-2: block copolymer polypropylene (Korea S Korea Spro Hua Daodaer Chemical trade company limited；MI=25 ± 3g/10min)
Rubber-1: ethylene butene rubbers (EBR) (MI=0.48 ± 0.05g/10min)
Rubber-2: ethylene octene rubber (EOR) (MI=27 ± 3g/10min)
HDPE: high density polyethylene (HDPE) (MI=2.2 ± 1g/10min)
Talcum-1: Talcum (mean diameter=5.8 ± 1 μm)
Wollastonite: wollastonite (mean diameter=25 ± 5 μm；L/D=15:1)
Bulking agent: comprise the HOPP masterbatch of the maleic anhydride of 0.9 ± 0.1%
Table 2 below is shown in physical properties and the measuring method thereof of measurement/assessment in following test example.
Each sample measuring condition is as follows:
(1) bending modulus: according to the ASTMD790 method specified, at room temperature measuring, each sample is of a size of 127 × 12.7 × 6.4mm, and test speed is 10mm/min, and bending modulus represents with megapascal (MPa) (MPa).
(2) resistance to impact (izod impact test intensity): the ASTM mould manufactured by Hyundai EP company limited is carried out otch to produce the sample for measuring izod impact test intensity, and at room temperature measure by the method specified according to ASTMD256.Izod impact test intensity uses the otch sample being of a size of 63.5 × 12.7 × 6.4mm to measure, and represents with kg cm/cm.
(3) melt index (MI): use the load of 2.16kg to measure according to the ASTMD1238 method specified at the temperature of 230 DEG C (polypropylene) and 190 DEG C (polyethylene).
(4) scratch resistance: the sample with embossing pattern as shown in Figure 1 uses the HT26D Making mold that modern Kia Motors Corporation manufactures, and the injection moulding sample of embodiment as shown in Table 1 and comparative example is for measuring scratch resistance by Sven-Gan Eriksson tester.Each sample with HT26D embossing pattern is placed on Sven-Gan Eriksson table of equipment so that the relief surface of this sample is arranged to towards upper, and makes scuffing tip contact with relief surface.Make scuffing most advanced and sophisticated load be 10N, to scratch most advanced and sophisticated radius and be 0.5R and scratch speed be the relief surface scratching sample under 1000mm/min.Here, by scratching 20 lines with 2mm spaced horizontal and scratching 20 lines with 2mm interval vertical, the relief surface of sample is formed tessellated cut (see Fig. 1), brightness (L) value used color spectrophotometer (UltraScanPRO) to measure before and after forming cut, and scratch resistance is to be represented by the difference (that is, △ L (dL) value) formed between the L-value measured before and after cut.Here, dL value is more high, and scratch resistance is more poor.DL value is more low, and scratch resistance is more good.Additionally, color spectrophotometer has diffusion/8 ° structure, and measure dL value when D65/10 °.
Table 2
Note:
E: embodiment
CE: comparative example
It is ensured that bending modulus is more high from table 2, rigidity is more good, and therefore disposal ability is more good.Bending modulus is more low, and polypropylene resin composite is more pliable and tough, and therefore polypropylene resin composite is more easily deformed.
Additionally, compared with using HDPE with comparative example 2, use bulking agent to demonstrate better scratch resistance.
Therefore, the polypropylene resin composite according to the present invention, when being applied to automobile interior exterior portion decorative element, it is shown that the bending modulus of excellence, scratch resistance and resistance to impact.
Although the polypropylene resin composite of the present invention has been shown and described with reference to the illustrative embodiments of the present invention, it should be understood by those skilled in the art that various changes in form and details can be made when without departing from the spirit and scope of the present invention as defined by the following claims.
Claims (9)
1. a polypropylene resin composite, it comprises:
The polypropylene of 30～69.8 weight %；
The inorganic filler of 20～35 weight %；
The rubber of 10～25 weight %；
The bulking agent of 0.1～5 weight %；With
The damage resistant agent of 0.1～5 weight %,
Wherein, described compositions has △ L (dL) value of 0.2 measured by Erichsen test or less, the bending modulus of 1000～2100MPa and 16～40KJ/m2Izod impact test intensity.
2. polypropylene resin composite according to claim 1, wherein, described polypropylene has the melt index (MI) of 0.2～150g/10min, and it is to use the load of 2.16kg to determine according to ASTMD1238 at the temperature of 230 DEG C.
3. polypropylene resin composite according to claim 1, wherein, described polypropylene resin composite has the melt index (MI) of 3～40g/10min, and it is to use the load of 2.16kg to determine according to ASTMD1238 at the temperature of 230 DEG C.
4. polypropylene resin composite according to claim 1, wherein, described polypropylene is block copolymer polypropylene.
5. polypropylene resin composite according to claim 1, wherein, described inorganic filler is at least one selected from Talcum, glass fibre, Muscovitum, calcium carbonate, wollastonite, barium sulfate, clay, calcium sulfate crystal whiskers and magnesium sulfate crystal whisker.
6. polypropylene resin composite according to claim 1, wherein, described rubber is at least one selected from ethylene octene rubber (EOR), ethylene butene rubbers (EBR), ethylene propylene rubber (EPR) and styrene ethylene butylene styrene (SEBS).
7. polypropylene resin composite according to claim 1, wherein, described bulking agent is the compositions of the polypropylene of maleic acid or maleic anhydride and 99.9～90 weight % comprising 0.1～10 weight % or polyethylene.
8. polypropylene resin composite according to claim 1, wherein, described damage resistant agent is polydimethylsiloxane (PDMS).
9. polypropylene resin composite according to claim 1, it comprises at least one additive selected from antioxidant, lubricant, ultra-violet stabilizer, long-term heat-resisting stabilizing agent, antistatic additive, fire retardant, antibacterial and coloring agent further.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2015-0006804 | 2015-01-14 | ||
| KR1020150006804A KR20160087618A (en) | 2015-01-14 | 2015-01-14 | Polypropylene resin composition |
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| CN105778388A true CN105778388A (en) | 2016-07-20 |
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| CN201610009345.2A Pending CN105778388A (en) | 2015-01-14 | 2016-01-07 | Polypropylene resin composition |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106700254A (en) * | 2016-12-15 | 2017-05-24 | 广东圆融新材料有限公司 | Polypropylene composition with low gloss, scratch resistance and high impact resistance and preparation method of polypropylene composition |
| CN108070152A (en) * | 2016-11-17 | 2018-05-25 | 现代自动车株式会社 | Polyolefine resin composition, polyolefin masterbatches, the method for preparing polyolefin masterbatches and the product formed by polyolefin masterbatches |
| CN112175299A (en) * | 2019-07-01 | 2021-01-05 | 现代自动车株式会社 | Pipe composition for vehicle using ratproof agent and preparation method thereof |
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| CN106633837A (en) * | 2016-12-14 | 2017-05-10 | 广东圆融新材料有限公司 | High-glossiness scratch-resisting filled nylon 6 composition and preparation method thereof |
| KR102448610B1 (en) * | 2017-12-21 | 2022-09-28 | 현대자동차주식회사 | Polypropylene resin composition and article prepared therefrom |
| CN109485994B (en) * | 2018-09-18 | 2022-02-01 | 青岛国恩科技股份有限公司 | Antibacterial and mildewproof polypropylene for outer barrel of drum washing machine and preparation method thereof |
| KR102445189B1 (en) * | 2020-03-30 | 2022-09-20 | 신동수 | Polypropylene master batch having material of antibacterial and antimold effect |
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| CN112175299A (en) * | 2019-07-01 | 2021-01-05 | 现代自动车株式会社 | Pipe composition for vehicle using ratproof agent and preparation method thereof |
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| KR20160087618A (en) | 2016-07-22 |
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