CN109423150A - The excellent polypropylene resin composite of coating - Google Patents
The excellent polypropylene resin composite of coating Download PDFInfo
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- CN109423150A CN109423150A CN201810931535.9A CN201810931535A CN109423150A CN 109423150 A CN109423150 A CN 109423150A CN 201810931535 A CN201810931535 A CN 201810931535A CN 109423150 A CN109423150 A CN 109423150A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D153/00—Coating compositions based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
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Abstract
The present invention relates to the polypropylene resin composites that coating is excellent.Specifically, the present invention provides a kind of polypropylene resin composite, excellent rigidity, impact resistance and water paint adhesion, water resistance can be assigned simultaneously when being applied to automobile interior exterior portion decorated molded article, while keeping low specific gravity.
Description
Technical field
The present invention relates to the polypropylene resin composites for being suitable for automobile interior exterior portion decorative element water paint.
Background technique
Acrylic resin it is cheap, and mouldability, chemical-resistant, mechanical properties etc. are excellent, are most commonly used to vapour
Interior external decorative material.But the crystallinity of acrylic resin is high, be it is nonpolar, when coating, it is common that with have
Polar resin mixing, or there is the chlorinated resin of chlorine to be used for acrylic resin chemical bonding.Therefore, to for automobile interior exterior
The painting operation of the polypropylene member of portion's ornament materials mainly using it is low with drying temperature, using it is convenient, uniform painting can be formed
The oil paint of the advantages that film.But the generations such as organic solvent due to containing in the oil paint containing chlorinated resin are volatilized
Property organic compound, causes environmental pollution, stink is serious, the problem of health of operator etc. is damaged, in Europe, the U.S., China
Equal countries, the sanction by environmental correclation regulation.
For this purpose, studying the various plastic material water paint groups for replacing oil-based solvent using aqueous solvent
Object is closed, but in order to which they are applied to plastic automotive parts, other than the physical property required by with general oil paint, tool
The resin combination for having more excellent performance is also required.In particular, the polypropylene resin composite used as automobile component
Water paint poor water resistance, it is necessary to make improvements.Therefore, seeking a kind of good to environment, smelly in use
It can ensure that and existing oil paint appearance having the same when the few water paint of the generation of taste and volatile organic compounds
With the polypropylene resin composite of reliability as water resistance.
Japan Kokai the 2007-523220th discloses the following contents: in order to improve coating, polypropylene copolymer
Portion EP rubbers (EPR) that composition passes through blending dimethylbenzene insoluble homopolypropylene portion and xylene soluble in the reactor
Divide and manufacture, the intrinsic viscosity of Xylene-Soluble Fraction is about 1.0~3.0dl/g, and Xylene-Soluble Fraction has about 15~25
The ethylene unit of mole %.
Summary of the invention
Subject to be solved by the invention
Embodiments of the present invention provide a kind of polypropylene resin composite, and being applied to, automobile interior exterior portion is decorated molded
Excellent rigidity, impact resistance and water paint adhesion, water resistance can be assigned when product simultaneously, while keeping low specific gravity.
The method to solve the problem
Embodiments of the present invention provide a kind of polypropylene resin composite, containing matrix resin, thermoplastic elastomer (TPE),
With fine inorganic filler.
Invention effect
Above-mentioned polypropylene resin composite can assign excellent simultaneously when being applied to automobile interior exterior portion decorated molded article
Rigidity, impact resistance and water paint adhesion, water resistance, while keeping low specific gravity.
Specific embodiment
It is clear that advantages and features of the invention and their implementation method can refer to aftermentioned embodiment.However, it should
Understand, the present invention is not limited to embodiments disclosed below, but can by it is mutually different it is diversified in the form of come
Specific implementation, however, embodiment is to make the disclosure become complete and make the technical field of the invention
People with general knowledge understands scope of the invention completely and provides, and the present invention is limited by the scope of the claims.
In one embodiment of the present invention, provide containing matrix resin, thermoplastic elastomer (TPE), fine inorganic filler it is poly-
Propylene resin composition.Above-mentioned polypropylene resin composite is keeping low specific gravity by containing inorganic filler with low content
Meanwhile, it is capable to when being shaped to big component while assign excellent rigidity, impact resistance and coating characteristic.
Above-mentioned polypropylene resin composite contains matrix resin, and above-mentioned matrix resin can contain: (i) Noblen and
(ii) resin in combination selected from propylene and the copolymer of the 'alpha '-olefin monomers of carbon number 2 and 4 to 20.
The 'alpha '-olefin monomers of above-mentioned carbon number 2 and 4 to 20 can for example enumerate ethylene, 1- butylene, 1- amylene, 1- hexene, 4- first
Base amylene, 1- heptene, 1- octene and 1- decene etc..Specifically, above-mentioned propylene and the 'alpha '-olefin monomers of carbon number 2 and 4 to 20 are total to
Polymers can be ethylene-propylene copolymer.In addition, the copolymer of the 'alpha '-olefin monomers of above-mentioned propylene and carbon number 2 and 4 to 20 can be with
For block copolymer or random copolymer.In addition, the copolymer of the 'alpha '-olefin monomers of above-mentioned propylene and carbon number 2 and 4 to 20 can be with
Propylene recurring units containing about 50 weight % or more.Specifically, can containing about 50 weight % with up to about 90 weight % with
Under propylene recurring units.Above-mentioned copolymer contains the propylene of high relative contents, so as to improve the crystallinity of resin, and mentions
The rigidity of polypropylene resin composite of the height containing above-mentioned resin.
Above-mentioned matrix resin passes through13The ratio of the five unit group of isotaxy of the measurements such as C-NMR method can be about 0.80
To about 0.99." five unit group ratios " indicates to use13The isotactic chain of five unit group units in the strand of C-NMR measurement
There are ratio, refer to the propylene monomer list that 5 propylene monomer units are carried out continuously at the center of chain made of middle key bonding
The ratio of member.Above-mentioned polypropylene resin composite passes through the above-mentioned matrix tree containing the five unit group ratios with above range
Rouge can assign excellent mechanical strength and impact resistance.
The melt index that above-mentioned matrix resin measures at 230 DEG C of temperature and the loading of 2.16kg according to ASTM D1238
It can be about 20g/10 minutes to about 100g/10 minutes.Above-mentioned polypropylene resin composite, which passes through, to be contained with above range
The matrix resin of melt index, can assign the mouldability and appearance characteristics of raising, while can assign excellent mechanical properties.Specifically
Ground, in the case where the melt index of above-mentioned matrix resin is lower than above range, when injection moulding, the mobility of resin is reduced,
Processability can also reduce, in the case where the melt index of above-mentioned matrix resin is higher than above range, the rigidity of injected material and resistance to
The balance of impact can reduce.
The intrinsic viscosity of the xylene solubles of ethylene-propylene copolymer can be 1.0~3.0 (dl/g).It is less than
When 1.0dl/g, impact resistance is substantially deteriorated, and when being greater than 3.0dl/g, can be occurred on the coating surface in gel (gel) form
Bad phenomenon.
Above-mentioned polypropylene resin composite contains thermoplastic elastomer (TPE), can assign excellent impact strength, heat resistance and
Coating adhesive force can show excellent injection moldability.
Above-mentioned thermoplastic elastomer (TPE) can contain the olefin copolymer selected from ethylene and the alpha-olefin of carbon number 3 to 12, benzene second
Substance in alkene based copolymer and their combination.In above-mentioned thermoplastic elastomer (TPE), the content of above-mentioned alpha-olefin can be about 20
Weight % to about 50 weight %.
The alpha-olefin of above-mentioned carbon number 3 to 12 can be for selected from 1- propylene, 1- butylene, 1- amylene, 4-methyl-1-pentene, 1-
Alpha-olefin compound in hexene, 1- heptene, 1- octene, 1- decene, 1- hendecene, 1- laurylene and their combination.For example,
Above-mentioned olefin copolymer can be random copolymer.
Above-mentioned styrene based copolymer can be for selected from styrene-ethylene copolymers, styrene-butylene copolymer, benzene second
Alkene-ethylene-propylene copolymer, styrene-isoprene-styrene copolymer, styrene-butylene-styrene copolymer, benzene second
Alkene-ethylene-butylene, Styrene copolymer, styrene ethylene-propylene-styrol copolymer, styrene-ethylene-ethylene-the third
Copolymer in alkene-styrol copolymer and their combination.For example, above-mentioned styrene based copolymer can be block copolymerization
Object.
Above-mentioned polypropylene resin composite contains similar with the viscosity of above-mentioned matrix resin or has higher than above-mentioned matrix
The thermoplastic elastomer (TPE) of the viscosity of resin, be able to suppress injected material injected material as above-mentioned polypropylene resin composite at
The form of drip on type product surface, assigns excellent coating characteristic.
Above-mentioned thermoplastic elastomer (TPE) can have the intrinsic viscosity of about 0.8dl/g to about 2.0dl/g.In above-mentioned thermoplastic elastomehc
Property body intrinsic viscosity lower than in the case where above range, impact resistance characteristic can reduce, and in the case where being higher than above range, add
Work mouldability can reduce.
Above-mentioned thermoplastic elastomer (TPE) can be contained with the content of 13 weight % to 25 weight %.Specifically, in above-mentioned thermoplastic
Property elastomer content lower than in the case where above range, impact strength can reduce, soft in the case where being higher than above range
Property enhancing, the mechanical properties of bending elastic modulus etc. can reduce, as a result, be difficult to be used as automotive part sometimes.
Above-mentioned polypropylene resin composite contains average diameter and is about 0.1 μm to about 5 μm of fine inorganic filler, and has
There is excellent dispersibility, it has big surface area, assigns improved mechanical rigid, such as excellent rigidity and impact resistance
Deng.Specifically, in the case where the average diameter of above-mentioned inorganic filler is less than above range, surface area becomes excessive, so that with
The compatibility of matrix resin becomes problem, it is more likely that the problem of being difficult to fine dispersion, and agglomerating.In addition, above-mentioned
In the case that the average diameter of inorganic filler is greater than above range, rigidity and impact strength are reduced, when applied to thin molded article
When, it can be crushed and physical property reduction, or make appearance deformation.In addition, the partial size of inorganic filler beyond above range when, molded product
Bulky grain filler on surface can greatly reduce painting adhesion, this is undesirable.
Above-mentioned fine inorganic filler can selected from talcum (talc), whisker (whisker), nanoclay (nanoclay) and
Their combination.
The content of above-mentioned fine inorganic filler can be 7 weight % to 10 weight %.Specifically, it is filled out in above-mentioned fine inorganic
In the case that the content of material is lower than above range, bending elastic modulus can be significantly reduced, and in the case where being higher than above range, be gathered
The light weight of propylene resin composition can be reduced.
Above-mentioned polypropylene resin composite properly mixes above-mentioned matrix resin and above-mentioned fine inorganic filler, is remaining low
Specific gravity while, be applied to thin wall type molded product when can assign simultaneously excellent processability, high bending elastic modulus,
Impact strength and coating characteristic.
Above-mentioned polypropylene resin composite can also containing selected from antioxidant, processing activating agent, colorant and they
Additive in combination.
Antioxidant can be for selected from phenolic antioxidant, phosphorous acid system antioxidant, thiodipropionate
(Thiodipropionate) substance and in their combination.
The halogen object for removing and containing in resin combination can be had containing in polypropylene resin composite by processing activating agent
Matter, the characteristic for increasing processability, above-mentioned processing activating agent can be in calcium stearate, magnesium stearate and their combinations
Substance.
Hereinafter, showing specific embodiment of the invention.But the embodiment of following records is only used for this hair of particular instantiation
It is bright, or for illustrating, the present invention is not limited thereto.
<embodiment and comparative example>
Examples 1 to 2
Polypropylene resin composite is manufactured, the polypropylene resin composite contains: matrix resin；As thermoplastic elastic
The intrinsic viscosity of body is the ethylene-octene random copolymer of 1.5dl/g；It is 1.0 μm with the average diameter as inorganic filler
Talcum.Described matrix resin contains: being referred to according to the melting that ASTMD1238 is measured at 230 DEG C of temperature and the loading of 2.16kg
The dimethylbenzene for the Ethylene-Propylene Block Copolymer that the Noblen and intrinsic viscosity that number is 30g/10 minutes are 1.5dl/g is molten
Object is solved, the melt index of described matrix resin is 50g/10 minutes.
Above-mentioned polypropylene resin composite is put into the master of double screw extruder (SM PLATEK, 30 φ of screw diameter)
In hopper (hopper), whisker is broken because of threaded rod shear shear force in order to prevent, appropriate in lateral feeder (side feeder)
Put into whisker.At this point, barrel temperature is adjusted to 150 DEG C to 210 DEG C, in rate of extrusion 30kg/ hours, screw speed 250rpm
Lower kneading is shaped to test film using TOYO (180 tons of forming force) injection (mo(u)lding) machine.
Embodiment 3
It is xylene solubles of the mixing containing the Ethylene-Propylene Block Copolymer that above-mentioned intrinsic viscosity is 2.2dl/g, molten
Melt the matrix resin that index is 50g/10 minutes, in addition to this, using method similarly to Example 1, manufactures acrylic resin
Composition.
Comparative example 1
It is xylene solubles of the mixing containing the Ethylene-Propylene Block Copolymer that above-mentioned intrinsic viscosity is 4.5dl/g, molten
Melt the matrix resin that index is 50g/10 minutes, in addition to this, using method similarly to Example 1, manufactures acrylic resin
Composition.
Comparative example 2
It is xylene solubles of the mixing containing the Ethylene-Propylene Block Copolymer that above-mentioned intrinsic viscosity is 2.2dl/g, molten
Melt the matrix resin that index is 50g/10 minutes, and the ethylene-octene that the intrinsic viscosity as thermoplastic elastomer (TPE) is 2.5dl/g
Random copolymer using method same as comparative example 1, manufactures polypropylene resin composite in addition to this.
Comparative example 3
It is xylene solubles of the mixing containing the Ethylene-Propylene Block Copolymer that above-mentioned intrinsic viscosity is 2.2dl/g, molten
Melt the matrix resin that index is 50g/10 minutes and the talcum that average diameter is 8.0 μm, in addition to this, using same with comparative example 1
The method of sample manufactures polypropylene resin composite.
[table 1]
<evaluation>
Experimental example 1: melt index
Embodiment and the melt index of the sample of comparative example manufacture are measured according to ASTM D1238, and the results are shown in [tables 2].
Experimental example 2: specific gravity
The specific gravity of embodiment and the test film of comparative example manufacture is measured according to ASTM D792, and the results are shown in [tables 2].
Experimental example 3: bending elastic modulus
Embodiment and the bending elastic modulus of the test film of comparative example manufacture are according to the specification of ASTM D790 measurement test piece
For 12.7 × 127 × 6.4mm, it is measured under being 10mm/ minutes in the speed of crosshead (Crosshead), the results are shown in
[table 2].
Experimental example 4: Ai Zuode (IZOD) impact strength
Ai Zuode (IZOD) impact strength for the test film that embodiment and comparative example manufacture is according to ASTMD256 in room temperature (23
DEG C) under measure, the results are shown in [tables 2].
Experimental example 5: coating adhesive force
Using Karcher high-pressure installation, with test film vertical range 10cm at, by 70 DEG C, the high-temperature high pressure water of 65bar
It is ejected into test film surface by ozzle, is evaluated by the way that whether film coated surface is damaged.At this point, being set on film test film surface
It is equipped with crosscutting (cross-cut) trace, after the sample of each embodiment of coating and comparative example, after placing about 24 hours, is tested.
About adhesive force evaluation criteria, film coated surface is expressed as " 0 " without the case where removing, about 5% feelings removed occur for film coated surface
Condition is expressed as " 1 ", there is a situation where about 5~35% removings to be expressed as " 2 " for film coated surface, and about 35~65% strippings occur for film coated surface
From the case where be expressed as " 3 ", film coated surface all remove the case where be expressed as " 4 ".
Experimental example 6: coating water resistance
After being precipitated 240 hours in 40 ± 2 DEG C of temperature of tap water, take out, by blowing away surface aqueous vapor, in room temperature
After lower placement 1 hour, the surface state (bubble (bl is ter), gloss difference) of film is investigated, implements above-mentioned adhesion immediately
Test.Here, bubble is known to be such a phenomenon: mainly in priming paint (primer) treatment process, working as water-soluble substances
When (salt) is present in interface as polluter, bubble is generated by the saline solution condensed.In severe cases, outlet is shown
Form as bubble expansion or very tiny colour fading, disappears with the time most of the time.
It is as described below to this evaluation criteria.
Zero: without blister, △: a small amount of bubble is generated, ×: generate a large amount of bubbles
[table 2]
Confirmed by above-mentioned [table 2], embodiment 1 to 3 not only has high processability (melt index >=25g/10 minutes), protects
Low specific gravity is held, shows the bending elastic modulus of about 1550MPa or more, about 45kJ/cm2Above high impact strength, and
And show " 1 " excellent coating adhesive force and coating water resistance below.
Claims (12)
1. polypropylene resin composite contains matrix resin, thermoplastic elastomer (TPE) and inorganic filler.
2. polypropylene resin composite described in claim 1, wherein above-mentioned matrix resin contains: (i) Noblen and
(ii) resin in combination selected from propylene and the copolymer of the alpha-olefin of carbon number 2 and 4 to 20.
3. polypropylene resin composite described in claim 1, wherein above-mentioned matrix resin is according to ASTM D1238 at 230 DEG C
Temperature and 2.16kg loading under the melt index that measures be 20g/10 minutes to 100g/10 minutes.
4. polypropylene resin composite described in claim 1, wherein above-mentioned matrix resin passes through13C-NMR method measures complete same
The ratio of vertical five unit group of structure is 0.80 to 0.99.
5. polypropylene resin composite described in claim 1, wherein in above-mentioned matrix resin, ethylene-propylene copolymer
The intrinsic viscosity of xylene solubles is 1.0~3.0dl/g.
6. polypropylene resin composite described in claim 1, wherein above-mentioned thermoplastic elastomer (TPE) has 0.8dl/g extremely
The intrinsic viscosity of 2.0dl/g.
7. polypropylene resin composite described in claim 1, wherein above-mentioned thermoplastic elastomer (TPE) contains selected from ethylene and carbon number
Substance in the olefin copolymer of 3 to 12 alpha-olefin, styrene based copolymer and their combination.
8. polypropylene resin composite described in claim 1 contains the above-mentioned thermoplastic elastomehc of 13 weight % to 25 weight %
Property body.
9. polypropylene resin composite described in claim 1, wherein above-mentioned inorganic filler contains selected from talcum, whisker, nanometer
Substance in clay and their combination.
10. polypropylene resin composite described in claim 1, wherein above-mentioned inorganic filler is averaged with 0.1 μm to 5 μm
Diameter.
11. polypropylene resin composite described in claim 1 contains the above-mentioned inorganic filler of 7 weight % to 10 weight %.
12. polypropylene resin composite described in claim 1 also contains selected from antioxidant, processing activating agent, colorant
With the additive in their combination.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR20170107976 | 2017-08-25 | ||
| KR10-2017-0107976 | 2017-08-25 |
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| CN109423150A true CN109423150A (en) | 2019-03-05 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201810931535.9A Pending CN109423150A (en) | 2017-08-25 | 2018-08-16 | The excellent polypropylene resin composite of coating |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1324889A (en) * | 2000-05-19 | 2001-12-05 | 现代自动车株式会社 | Polypropylene resin composition |
| JP2002003692A (en) * | 2000-04-18 | 2002-01-09 | Japan Polychem Corp | Polypropylene resin composition that is superiorly resistant to injury |
| JP2002283518A (en) * | 2001-03-23 | 2002-10-03 | Shin Etsu Polymer Co Ltd | Composite material of olefin polymer composition and metal |
| CN101343393A (en) * | 2007-07-13 | 2009-01-14 | Sk能源株式会社 | Ethylene-propylene segmented copolymer polypropylene composite with good fluidity, rigidity and impact strength |
| CN103403041A (en) * | 2011-03-04 | 2013-11-20 | 博里利斯股份公司 | Exterior automotive article with reduced paintability failure |
-
2018
- 2018-08-16 CN CN201810931535.9A patent/CN109423150A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002003692A (en) * | 2000-04-18 | 2002-01-09 | Japan Polychem Corp | Polypropylene resin composition that is superiorly resistant to injury |
| CN1324889A (en) * | 2000-05-19 | 2001-12-05 | 现代自动车株式会社 | Polypropylene resin composition |
| JP2002283518A (en) * | 2001-03-23 | 2002-10-03 | Shin Etsu Polymer Co Ltd | Composite material of olefin polymer composition and metal |
| CN101343393A (en) * | 2007-07-13 | 2009-01-14 | Sk能源株式会社 | Ethylene-propylene segmented copolymer polypropylene composite with good fluidity, rigidity and impact strength |
| CN103403041A (en) * | 2011-03-04 | 2013-11-20 | 博里利斯股份公司 | Exterior automotive article with reduced paintability failure |
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Application publication date: 20190305 |