CN1723238A - Scratch and mar resistant soft ethylene elastomer compositions - Google Patents

Scratch and mar resistant soft ethylene elastomer compositions Download PDF

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Publication number
CN1723238A
CN1723238A CN200380105637.7A CN200380105637A CN1723238A CN 1723238 A CN1723238 A CN 1723238A CN 200380105637 A CN200380105637 A CN 200380105637A CN 1723238 A CN1723238 A CN 1723238A
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composition
filler
polysiloxane
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ethylene elastomer
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CN100582149C (en
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A·N·达里亚
N·A·法卡斯
C·图多尔
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Performance Materials NA Inc
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EI Du Pont de Nemours and Co
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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
    • C08K3/34—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
    • C08H1/00—Macromolecular products derived from proteins
    • C08H1/06—Macromolecular products derived from proteins derived from horn, hoofs, hair, skin or leather
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • 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
    • C08L23/04—Homopolymers or copolymers of ethene
    • 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
    • C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes

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Abstract

The invention provides a kind of soft ethylene elastomer compositions with better scratch resistance, wherein, said composition comprises preferably micaceous filler, polysiloxane and the compatilizer of a soft ethylene elastomer component and significant quantity, the softness of not obvious reduction composition or improve the glossiness of composition so that composition has the scratch resistance of improvement.

Description

Scratch and mar resistant soft ethylene elastomer compositions
Technical field
The present invention relates to soft ethylene elastomer compositions, particularly have the soft ethylene elastomer compositions of the scratch resistance of improvement.
Background technology
Traditionally, the manufacturing of automobile external part all relates to hard ethylene elastomer compound, and they make automobile external have good shock-resistant and scratch resistance.This class ethylene elastomer comprises a polypropylene main ingredient, more a spot of rubber toughening agent (EPDM or EPR rubber) and filler such as talcum powder.
In the last few years, developed the compound that softness increases.This class what is called " soft ethylene elastomer compound " is the main ingredient of composition with the polyethylene plastomers, is accessory constituent with the polypropylene.Add a small amount of organo-peroxide,, can change the melt rheological characteristics of compound, thereby improve the thermotolerance and the processing characteristics of compound and make compound have softness characteristics randomly with coagent.
An example of soft ethylene elastomer compound is disclosed in the U.S. patent 6,506,842 of authorizing Heck etc. and on July 30th, the 1998 disclosed International Patent Application WO 98/32795, and these patents are included in that this is for reference.U.S. patent 6,506,842 and International Patent Application WO 98/32795 a kind of ethylene elastomer compositions of rheology modified, basic gel-free is disclosed, it comprises a kind of ethylene-alpha-olefin (EAO) polymkeric substance or EAO blend polymer and at least a high-melting-point polymer that is selected from homopolymer polypropylene and propylene/ethylene (P/E) multipolymer.Said composition has at least three in following four characteristics: the thinning index of shear force (STI) is at least 20, melt strength (MS) is 1.5 times of not rheology modified composition at least, and temperature of solidification (ST) is higher at least 10 ℃ than not rheology modified composition than not rheology modified composition high at least 10 ℃ and the use temperature upper limit (UST).
The amount of EAO polymkeric substance or EAO multipolymer is 50～90 weight % of this component in the ethylene elastomer, preferred 65～85 weight %, and the amount of high-melting-point polymer is preferably 50-10 weight %, just preferred 35～15 weight %.
U.S. patent 6,506,842 and International Patent Application WO 98/32795 a kind of method for preparing the composition for thermoplastic elastomer of rheology modified, basic gel-free is also disclosed, comprise with organo-peroxide and handling, and the manufacture method of using the goods of this based composition.
Use for part in the automobile car that requires scrape resistant and other, there is weak point in soft ethylene elastomer compositions because of their flexible polymer character.
Therefore, still need to provide a kind of production to have the soft ethylene elastomer compositions of better scratch resistance compound.
Summary of the invention
According to an inventive point of the present invention, a kind of composition is provided, it comprises the filler of a soft ethylene elastomer component and significant quantity, so that composition has the scratch resistance of improvement and the softness of not obvious reduction composition.
According to an inventive point of the present invention, a kind of composition is provided, it comprises the filler and the compatilizer of a soft ethylene elastomer component and significant quantity, so that composition has the scratch resistance of improvement and the softness of not obvious reduction composition.
According to another inventive point of the present invention, a kind of composition is provided, it comprises the filler and the polysiloxane of a soft ethylene elastomer component and significant quantity, so that composition has the scratch resistance of improvement and the softness of not obvious reduction composition.
According to another inventive point of the present invention, a kind of composition is provided, it comprises filler, polysiloxane and the compatilizer of a soft ethylene elastomer component and significant quantity, so that composition has the scratch resistance of improvement and the softness of not obvious reduction composition.
According to another inventive point of the present invention, a kind of composition is provided, it comprises the mica and the compatilizer of a soft ethylene elastomer component and significant quantity, so that composition has the scratch resistance of improvement and the softness of not obvious reduction composition.
According to another inventive point of the present invention, a kind of composition is provided, it comprises the mica and the polysiloxane of a soft ethylene elastomer component and significant quantity, so that composition has the scratch resistance of improvement and the softness of not obvious reduction composition.
According to another inventive point again of the present invention, a kind of composition is provided, it comprises mica, compatilizer and the polysiloxane of a soft ethylene elastomer component and significant quantity, so that composition has the scratch resistance of improvement and the softness of not obvious reduction composition.
The preferred embodiments of the invention also comprise and a kind ofly prepare method for compositions and contain at least one is made parts by said composition goods.
Composition of the present invention has many advantages.Their both scrape resistants particularly, the softness of not obvious again reduction composition.Said composition also causes producing the goods with low-luster.
Embodiment
In a preferred embodiment, used soft ethylene elastomer component is a kind of rheology modified ethylene elastomer compositions among the present invention, and it comprises and accounts for about 50～about 95% the elastomeric ethylene polymer of ethylene elastomer gross weight or EAO blend polymer and about 5～50% high-melting-point polymers.
The elastomeric ethylene polymer that is applicable to ethylene elastomer compositions comprises interpolymer and diene modified interpolymer.Illustrative polymers is drawn together ethylene/propene (EP) multipolymer, ethylene/butylene (EB) multipolymer, ethylene/octene (EO) multipolymer, ethylene/alpha-olefin/diene modification (EAODM) interpolymer and ethylene/propylene/diene modification (EPDM) interpolymer.Example comprises linear ultra-low density polyethylene (ULD-PE) more specifically, as the Attane of Dow Chemical company manufacturing TMThe even linear EAO multipolymer of branching is as the Tafmer of Mitsui PetroChemicals company limited manufacturing TMExact with the manufacturing of Exxon Chemical company TMAnd the even linear substantially EAO polymkeric substance of branching, as the Affinity of Dow Chemical company manufacturing TMThe Engage that polymkeric substance and DuPont Dow Elastomers L.L.C produce Polymkeric substance.
Preferred EAO blend polymer comprises the linear and linear substantially ethylene copolymer of even branching, and the density of measuring by ASTM D-792 is 0.85～0.92g/cm 3, 0.85～0.90g/cm especially 3, and melt index or I 2(measuring (190 ℃/2.16kg counterweight) by ASTM D-1238) is 0.01～30g/10min, preferred 0.05～10g/10min.Especially preferred those linear substantially ethylene copolymers or interpolymer (being also referred to as " SLEP ").
In addition, various functional ethylene copolymers are also suitable derived from the unitary ethylene vinyl acetate (EVA) of vinyl acetate as containing 0.5～50 weight %.When with the EVA polymkeric substance, preferred I 2Be 0.01～500g/10min, more preferably those of 0.05～50g/10min.
Preferred SLEP comprises the Engage that Dow Chemical company and DuPont Dow EalstomersL.L.C. produce Polyolefin elastomer and other polymkeric substance.
The high-melting-point polymer that is applicable to soft ethylene elastomer component is homopolymer, propylene and the alpha-olefin of propylene such as the multipolymer of ethene, 1-butylene, 1-hexene or 4-methyl-1-pentene preferably.Polymkeric substance also can be homopolymer and multipolymer blend, nuclear homopolymer or the nuclear multipolymer is arranged is arranged.Can also be homopolymer and multipolymer the nuclear blend arranged.
Alpha-olefin is ethene preferably.Multipolymer can be the blend of random copolymers or segmented copolymer or random copolymers and segmented copolymer.It is 0.3～60g/10min that high-melting-point polymer is preferably selected from melt flow rate (MFR, 230 ℃ and 2.16kg counterweight), preferred 0.8～40g/10min, the more preferably homopolymer polypropylene of 1～35g/10min and polyethylene and ethylene copolymers.
About preferred elastomeric ethylene polymer or EAO blend polymer and high-melting-point polymer, U.S. patent 6,506,843 and WO98/32795 have provided more detailed description, and these reference are included in that this is for reference.
Soft ethylene elastomer component preferably a kind of rheology modified, gel content is low thereby can make composition remain real thermoplastic behavior's composition.
Soft ethylene elastomer component preferentially presses U.S. patent 6,506,842 with suitable organo-peroxide and the described method of WO98/32795 is handled.The organo-peroxide suitable for this used class of purpose of the present invention was at least 1 hour 120 ℃ half-life.Illustrative peroxides comprises a series of α of containing, α '-two (tert-butyl peroxide)-diisopropyl benzene and can be available from the commodity of Geo Specialty Chemicals Vuleup by name TMSulfuration and polymerizing agent, a series of dicumyl peroxides and can be of containing available from Geo Specialty Chemicals commodity Di-cup by name TMReagent, the Luperox that Atofina, North America make TMSuperoxide, or the Trigonox of Moury Chemical company manufacturing TMOrgano-peroxide.
Other superoxide that is suitable for comprises dicumyl peroxide, 2,5-dimethyl-2,5-two (tert-butyl peroxide) hexane, di-t-butyl peroxide, 2,5-two (peroxidation tert-pentyl)-2,5-dimethylhexane, 2,5-two-(tert-butyl peroxide)-2,5-phenylbenzene hexane, peroxidation two (α-Jia Jibianji), benzoyl peroxides, peroxidized t-butyl perbenzoate and two (tert-butyl peroxide)-diisopropylbenzene(DIPB).
Superoxide also can with a kind of suitable coagent, the I type polarity coagent lower as molecular weight uses together.The example of this class coagent is the trimethylammonium vinylformic acid trishydroxymethyl propyl ester (TMPTMA) that Sartomer sells with trade(brand)name SR-350.Also can be with the low polarity coagent of II type, as Sartomer with trade(brand)name Ricon 1 of sale, the 2-polyhutadiene.Add coagent and can improve the performance of rheology modified ethylene elastomer compound, or be reduced to and reach the required amount of peroxide of identical rheology modified effect.
The preferred proportion of used superoxide and coagent is a superoxide among the present invention: coagent=about 1: 1～about 1: 4, but can become with concrete application.
About the preferred properties of rheology modified ethylene elastomer compositions, U.S. patent 6,506,842 and WO98/32795 have provided more detailed description, and these documents are included in that this is for reference.Composition very preferably of the present invention comprises a soft ethylene elastomer component, and (calculate with Kayeness kapillary melt rheometer, wherein shear rate is 1s to its STI 20～110 -1With 1006s -1Under the ratio of melt viscosity) between, MS 〉=1.5, ST (calculates with dsc between 75～145 ℃, to measure the Tc at first peak in the cooling) and UST between 50～160 ℃, (calculate the temperature when determining during the perverse sample introduction product 600 μ m of probe with thermo-mechanical analysis) with 3 ℃/min constant heatingrate.
Soft ethylene elastomer component will with the filler combination of significant quantity to improve the scratch resistance of soft ethylene elastomer component.Filler can be flats filler such as mica, talcum or clay.Perhaps, soft ethylene elastomer component also can make up with a kind of spherical or elongate hard packing such as activated alumina.
The very preferably filler mica of soft ethylene elastomer component and significant quantity combination.Preferably a kind of 325 order wet-ground mica of mica.Preferably with white mica or phlogopite.
The amount of filler be composition total weight about 1～about 20%, preferred about 2～about 15%, more preferably from about 3～about 12%, very preferably about 4～about 10%.
Filler also can with compatilizer combination scratch resistance to be improved.
The method that adds filler and compatilizer in the present composition can be directly to add in the soft ethylene elastomer component during the compound manufacturing or preferably pass through prefabricated master batch to add.If use master batch, then preferred it form by filler, compatilizer and base resin, wherein compatilizer accounts for 1 of masterbatch composition total amount～about 20%, and filler accounts for about 10～about 90% of masterbatch composition total amount.Masterbatch comprises about 5～about 15% compatilizer and about 30～about 60% filler.
Preferably a kind of functionalised polyolefin of compatilizer comprises maleic anhydride graft Engage Or the metallocene PE plastomer of equivalent, maleic anhydride grafted ethene propylene copolymer, maleic anhydride grafted ethene propylene diene monomer, maleic anhydride graft linear low density of polyethylene, maleic anhydride graft very new LDPE (film grade) or maleic anhydride inoculated polypropylene.Compatilizer plays action of coupling agents, thereby helps to improve the cohesiveness of filler and soft ethylene elastomer component.Compatilizer have one with filler agglutinating polarity part and a nonpolar part compatible with soft ethylene elastomer component, with the effective adhesive that has between assurance filler and the soft ethylene elastomer component.In a kind of preferred composition of the present invention, compatilizer accounts for about 0.1%～about 10%, preferred about 0.25～about 7% of composition weight.
Preferably a kind of vector resin of base resin in the master batch is as Engage Polyolefin plastomers, linear low density of polyethylene, very new LDPE (film grade) or ethylene propylene copolymer.When the base resin in master batch was a kind of functionalized resins such as ethylene vinyl acetate or a kind of ethene and methacrylic acid or acrylic acid multipolymer, the behavior of functionalized resins partly resembled compatilizer.General and the composition of base resin in the master batch sex ethylene polymer-compatible of being hit by a bullet.
In the masterbatch melt viscosity of used compatilizer and base resin should be similar to or a little less than the melt viscosity of soft ethylene elastomer component to guarantee good dispersiveness.
The example that is applicable to the mica masterbatch of the present composition will comprise the 12% maleic anhydride functionalized resins as coupling agent (compatilizer), 30% mica and suitable polyethylene support resin.
Composition of the present invention and master batch also can comprise other additive and can not depart from the present invention, as claimed in claim.This class additive can comprise not rheology modified EAO class, treated oil, softening agent, specialist additive and pigment.Specialist additive comprises fire retardant; Oxidation inhibitor; Surface tension modifier; Release agent; Lubricant; Disinfectant is as organic metallic compound, isothiazolones, organosulfur and mercaptan; Oxidation inhibitor is as phenols, secondary amine, phosphite and thioesters; Static inhibitor is as quaternary ammonium compound, amine and ethoxylation, propoxylation or glycerol compounds; Hydrolysis stabilizer; Lubricant is as lipid acid, Fatty Alcohol(C12-C14 and C12-C18), ester class, fatty amide, Metallic stearates, paraffin and Microcrystalline Wax, polysiloxane and ortho-phosphoric acid ester; Releasing agent, as particulate or powdery solid, soap class, wax class, polysiloxane-based, polyoxyethylene glycol and complex ester as three stearic acid trihydroxymethylpropanyl ester or pentaerythritol tetrastearates; Pigment, dyes and dyestuffs; Softening agent is as the ester of diprotic acid (or their acid anhydrides) with single hydroxyl alcohol, as phthalic ester, adipic acid ester and benzoic ether; Thermo-stabilizer is as monooctyl ester and the carboxylic acid barium or the calcium of organo-tin mercaptide, ethyl thioglycollic acid; UV light stabilizing agent is as hindered amine, adjacent hydroxyl-phenyl-benzotriazole, 2-hydroxyl-4-alkoxyl group benzophenone, salicylate, cyanoacrylate, nickel chelate and benzylidene malonate and oxalic dianilide; And zeolite, molecular sieve and other known deodorant.Preferred hindered phenol antioxygen is the Irganox that Ciba-Geigy company produces TM1076 oxidation inhibitor.
Other filler also should with composition coupling of the present invention.This class filler can comprise carbon black, glass, carbonic acid metal salt such as lime carbonate, sulfuric acid metal-salt such as calcium sulfate, talcum, clay or graphite fibre.This class filler can further make composition have the scratch resistance of improvement.
Other additive, if used, then its amount is generally less than about 45% of composition total weight.Consumption is preferably about 0.001～and about 20%, preferred about 0.01～about 15%, more preferably from about 0.1～about 10%.
Very preferably in composition, add a kind of polysiloxane additives so that the scratch resistance of improvement to be provided.The add-on of polysiloxane is 0.10～2.50%, and is preferred 0.20～1.00%, very preferably 0.25～0.6%.The add-on of polysiloxane should be less than the amount of filler in the composition in the composition.
The add-on of polysiloxane general partly becomes with the fluid viscosity of the polysiloxane that will add in the composition.Fluid viscosity is the normal viscosity of measuring down at 25 ℃.Can add preferably that molecular weight is higher, fluid viscosity is at least 1,000Cst, preferably at least 10, the polysiloxane of 000CSt is as polydimethylsiloxane.Polysiloxane can be used as the master batch adding or injects into as neat liquid.If add with the form of master batch, then the consumption of polysiloxane generally account for master batch about 10%～about 50%, depend on the fluid viscosity of polysiloxane.
Polysiloxane can be added in the feed throat of forcing machine.But the polysiloxane of lubricate is preferably added in the molten soft ethylene elastomer component in the forcing machine downstream in composition.
When filler adds fashionablely as master batch, masterbatch and soft ethylene elastomer component can be added in the forcing machine feed throat simultaneously.Soft ethylene elastomer component also can be used as independent component and adds with master batch.Perhaps, master batch also can directly be added in the molten soft ethylene elastomer component after fusing.
When filler added soft ethylene elastomer component with its pure form, preferred filler will add after compatilizer adds soft ethylene elastomer component or at least simultaneously, though also may be with other in proper order.
Adding feed throat requires feed throat to remain under the enough cold temperature in case component is built bridge in feed throat.The following process of composition is at about 180 ℃～220 ℃, mixes under the preferred about 190 ℃～about 210 ℃ temperature.
In the expressing technique terminal, the molten polymer extrudate must be cooled to just can solidify and be cut granulating behind the low temperature.If molten polymer will cut under water, then water temperature should remain on or be lower than about 30 ℃, preferably or be lower than 15 ℃.
It will be apparent to one skilled in the art that, obviously can also prepare composition of the present invention, comprise Farrel continuous mixing device, single screw rod or twin screw extruder and buss kneader with multiple mixing equipment.
Composition of the present invention can be configured as goods such as part, sheet material or other form with the arbitrary method in many traditional methods of processing elastic composition.Said composition also can be drawn into film, multilayer layer pressing plate or extrusion sheet, with mixing of one or more organic or inorganic materials, be injection molded into goods,, be used for special-shaped extruded product or be used for coated textiles or other film and sheet applications as knob, the handle of the utensil or the consumer's goods.This based composition can be used for making part in the automobile car, the outer part of automobile car, with the consumer's goods of soft contact handgrip with the consumer appliances of soft surface in contact.Other application also is possible, and in those skilled in the art's ken.
Composition of the present invention has astonishing raising than other soft ethylene elastomer compositions aspect scratch resistance.This based composition also is applicable to makes the goods with low-luster.
Following embodiment illustrates but unrestricted the present invention.
Embodiment 1:
All used compositions are all at twin screw extruder (38: 1L/D or 50: 1L/D) upward prepare under 190～210 ℃ processing temperature.Under the 350RPM screw speed, productive rate is about 150 Pounds Per Hours.With tablets press is with fused mass granulating under water, cutting water keeps being chilled to about 11-14 ℃.Mica masterbatch is added feed throat.Feed melt polymers with silicone masterbatch from the side at the nearly downstream part of forcing machine.
With traditional processing means composition is configured as the embossment sheet material.The embossment sheet material has the hairline texture and dyes black.To the following performance shown in the relief surface test card 2 of every sheet material:
(a) according to the Shore A hardness of ASTM D 2240-00 in the following test sheet of permanent load (1 second);
(b) according to the % glossiness at 60 ° of angles of ASTM D 523 usefulness Grossmeters tests;
(c) refer to scraping experiment method test scraping degree with Ford FLTM BN 108-13 described 5, measuring 5 expressions has the most serious scratch, measures on the 1 expression sheet material and detects less than macroscopic scratch.Scraping experiment is with 1,2,3,6 and 7N power carry out.
In institute's test piece material, " contrast " sample is unmodified composition---be called Advantech8800A TM, can be available from DuPont.Said composition comprises following component:
(a) 74.53 weight % low density Engage The mixture of resin comprises main ingredient Engage 8100 and accessory constituent Engage 8842.
(b) 22.97 weight % polypropylene homo resins record at 230 ℃ with the 2.1kg counterweight Melt flow rate is 12g/10min;
(c) 2.5 weight %Vul-Cup 20P (Geo Specialty Chemicals) comprises 20% organo-peroxide/5% silicon-dioxide/75% polypropylene.
Sample A comprises mica masterbatch.The composition of master batch is: the 12% maleic anhydride functionalized resins as coupling agent (compatilizer), 30% mica and Engabe 8100.Mica accounts for 7% of final composition weight.
Sample B, C and D comprise mica masterbatch and silicone masterbatch additive.Sample A, B, C and D's is composed as follows.
The composition of table 1 sample
Sample Basic components Additive The weight % of additive in final composition
Contrast Advantech 8800A TM Do not have --
A Advantech 8800A TM Mica masterbatch 7% mica
B Advantech 8800A TM Mica masterbatch and silicone masterbatch 7% mica, 0.25% polysiloxane
C Advantech 8800A TM Mica masterbatch and silicone masterbatch 7% mica, 0.50% polysiloxane
D Advantech 8800A TM Mica masterbatch and silicone masterbatch 7% mica, 0.875% polysiloxane
The comparison of table 2 extrusion sheet relief surface performance
Sample Scraping experiment 7N Scraping experiment 6N Scraping experiment 3N Scraping experiment 2N Scraping experiment 1N 60 ° of angle glossiness Shao Shi A value
Contrast 3 3 2 1 1 1.2 90.5
A 1 1 1 1 1 0.8 92.5
B 2 1 1 1 1 0.9-1.2 92.6-93.2
C 1 1 1 1 1 0.9-1.1 93.0-93.7
D 1 1 1 1 1 1.0 93.5
Sample A has the best of breed of scratch resistance and glossiness.Add the softness that mica masterbatch does not obviously reduce composition in the composition.The adding of polysiloxane also makes composition have the scratch resistance of improvement, keeps the softness of composition simultaneously.All compositions of test all produce the low-luster sheet material.
Embodiment 2
To comprise Advantech 8800A TMThe sheet material of base resin, 7% mica and 0.50% polysiloxane (sample C) is shaped by preheating and sheet material, is thermoformed into goods.Test the relief surface and the articles thermoformed therefrom test scratch resistance of this sheet material with the described 5 finger scraping experiment methods of Ford FLTMBN 108-13.Press the glossiness % of 60 ° of ASTM D 523 test sheet relief surface and articles thermoformed therefroms simultaneously with Grossmeters.
Thermoforming is carried out with the Sencorp hot former, and method is that sheet material is placed between top board and the base plate.The top board temperature is 507 °F, and baseplate temp is 580 °F.With sheet material preheating 80～120 seconds, thermoforming was 18 seconds then.
The performance of table 3 thermoforming and non-thermoforming sheet material relatively
Sample Scraping experiment 10N Scraping experiment 7N Scraping experiment 5N 60 ° of angle glossiness
Contrast 4 3 2 1.2
Sample C 2-3 1 1 0.7-0.8
The contrast thermoforming 4 3 2 1.6
Sample C thermoforming 1-2 1 1 1.3-1.4
When testing under 5 and 7 newton, the thermoforming sheet material has identical scratch resistance with non-thermoforming sheet material, but much better than the scratch resistance of comparison sheet.Under 10 newton, the thermoforming sheet material is more much better than the sheet material than scratch resistance and result's comparison that non-thermoforming sheet material shows improvement.The glossiness of thermoforming sheet material increases to some extent than the summary of non-thermoforming sheet material, but lower than the gloss of the thermoforming comparison sheet that does not comprise mica and polysiloxane.
Embodiment 3
At twin screw extruder (50: 1L/D) go up preparation low viscosity injection moulding composition under a temperature between 190 ℃～210 ℃.Under the 350rpm screw speed, productive rate is about 150 Pounds Per Hours.With fused mass granulating, mica masterbatch is added composition by adding feed throat with the about 10-14 of water temperature ℃ underwater pelletizer.Silicone masterbatch also feeds melt composition from the side by the reinforced road in the forcing machine downstream.
With 198～216 ℃ of melt temperatures,, be air-bag door with the composition injection molded with screw speed and the about 27 ℃ of die temperatures of 50rpm.Refer to the scratch resistance that scraping experiment method experimental safe airbag deployment covers with Ford FLTM BN 108-13 described 5,5 grades of expressions have the most serious scratch, and macroscopic scratch is not observed in 1 grade of expression.Scraping experiment carries out with 7 Newton force.
" contrast " composition is made up of following component:
(a) 74.25 weight %Engage Resin 8130.
(b) 24 weight % homopolymer polypropylenes (nuclear is arranged and comprise static resistance) are 12g/10min with the 2.1kg counterweight at 230 ℃ of melt flow rates that record;
(c) 1.75 weight %Vul-Cup 20P (Geo Speciality Chemicals) master batch comprises 20% organo-peroxide/5% silicon-dioxide/75% polypropylene.
Sample A comprises " contrast " composition and 6.8 weight % micas and 0.5 weight % polysiloxane in final composition.The composition of used mica masterbatch comprises the maleic anhydride functionalized resins of 12 weight % as coupling agent (compatilizer) among the sample A, 30 weight % mica and Engage 8100.
The comparison of table 4 air-bag door scraping performance
Scraping experiment 7N (contrast) Scraping experiment 7N (sample A)
Shiny surface 4 2
Relief surface 3 2
The adding of mica and polysiloxane makes scratch resistance be significantly improved than " contrast " sample.
Like this, just in detail a plurality of embodiment of the present invention has been described in detail by way of example, has it will be apparent to one skilled in the art that, change and modification are conspicuous.The present invention includes all these class change and modifications of dropping in the appended claims scope of the present invention.

Claims (66)

1. composition comprises the filler of a soft ethylene elastomer component and significant quantity, so that composition has the scratch resistance of improvement and the softness of not obvious reduction composition.
2. composition comprises the filler and the compatilizer of a soft ethylene elastomer component and significant quantity, so that composition has the scratch resistance of improvement and the softness of not obvious reduction composition.
3. claim 1 or 2 composition, wherein filler account for composition total weight about 1%～about 20%, preferred about 2%～about 15%, more preferably from about 3%～about 12% and very preferably 4%～about 10%.
4. the composition of claim 3, wherein filler is a kind of flats filler.
5. the composition of claim 4, wherein filler is selected from following one group: mica, talcum or clay.
6. the composition of claim 3, wherein filler is a kind of spherical or elongate hard packing.
7. the composition of claim 6, wherein filler is an activated alumina.
8. composition comprises the mica and the compatilizer of a soft ethylene elastomer component and significant quantity, so that composition has the scratch resistance of improvement and the softness of not obvious reduction composition.
9. the composition of claim 8, wherein mica account for composition total weight about 1%～about 20%, preferred about 2%～about 1 5%, more preferably from about 3%～about 12% and very preferably 4%～about 10%.
10. the composition of any one in the claim 2,8 or 9, wherein compatilizer accounts for about 0.1%～about 10%, preferred about 0.25%～about 7% of composition weight.
11. the composition of any one in the claim 1～10, wherein soft ethylene elastomer component is a kind of rheology modified low gel thermoplastic elastomer composition, and it comprises at least a elastomerics EAO polymkeric substance or EAO blend polymer and at least a high-melting-point polymer that is selected from homopolymer polypropylene and propylene/ethylene copolymer.
12. the composition of claim 11, wherein elastomerics EAO polymkeric substance or EAO blend polymer account for about 50 weight %～about 95 weight % of soft ethylene elastomer component and about 5 weight %～about 50 weight % that high-melting-point polymer accounts for soft ethylene elastomer component.
13. the composition of claim 11 or 12, wherein rheology modified is with the peroxide-induced that presents in an amount at least sufficient to provide overall characteristic, described superoxide is a kind of following one group organo-peroxide: α that is selected from, α '-two (tert-butyl peroxide)-diisopropyl benzene, dicumyl peroxide, 2,5-dimethyl-2,5-two (tert-butyl peroxide)-hexane, di-t-butyl peroxide, 2,5-two (peroxide tert-pentyl)-2, the 5-dimethylhexane, 2,5-two (tert-butyl peroxide)-2,5-phenylbenzene hexane, peroxidation two (α-Jia Jibianji), benzoyl peroxide, peroxidized t-butyl perbenzoate and two (tert-butyl peroxide)-diisopropyl benzene.
14. the composition of claim 13 also comprises at least a suitable coagent with superoxide.
15. the composition of any one in the claim 1～14 also comprises at least a following one group additive that is selected from: rheology modified EAO, treated oil, softening agent, specialist additive and pigment.
16. the composition of claim 15, wherein specialist additive comprises one or more and is selected from following one group additive: fire retardant; Oxidation inhibitor; Surface tension modifier; Release agent; Lubricant; Disinfectant such as organic metallic compound, isothiazolones, organosulfur and mercaptan; Oxidation inhibitor is as phenols, secondary amine, phosphite and thioesters; Static inhibitor is as quaternary ammonium compound, amine and ethoxylation, propoxylation or glycerol compounds; Hydrolysis stabilizer; Lubricant is as lipid acid, Fatty Alcohol(C12-C14 and C12-C18), ester class, fatty amide, Metallic stearates, paraffin and Microcrystalline Wax, polysiloxane and ortho-phosphoric acid ester; Releasing agent, as particulate or powdery solid, soap, wax, polysiloxane, polyoxyethylene glycol and complex ester as three stearic acid trihydroxymethylpropanyl ester or pentaerythritol tetrastearates; Pigment, dyes and dyestuffs; Softening agent is as the ester of diprotic acid (or their acid anhydrides) with single hydroxyl alcohol, as phthalic ester, adipic acid ester and benzoic ether; Thermo-stabilizer is as monooctyl ester and the carboxylic acid barium or the calcium of organo-tin mercaptide, ethyl thioglycollic acid; The outer photostabilizer of bavin is as hindered amine, adjacent hydroxyl-phenyl-benzotriazole, 2-hydroxyl-4-alkoxyl group benzophenone, salicylate, cyanoacrylate, nickel chelate and benzylidene malonate and oxalic dianilide; And zeolite, molecular sieve and other known deodorant.
17. the composition of claim 16, wherein specialist additive is a polysiloxane.
18. the composition of claim 17, wherein polysiloxane is a polydimethylsiloxane.
19. the composition of claim 18, wherein polysiloxane accounts for about 0.1%～about 2.5%, preferred about 0.2%～about 1.0%, very preferably about 0.25%～about 0.6% of composition.
20. a composition comprises the filler and the polysiloxane of a soft ethylene elastomer component and significant quantity, so that composition has the scratch resistance of improvement and the softness of not obvious reduction composition.
21. the composition of claim 20, wherein filler account for composition total weight about 1%～about 20%, preferred about 2%～about 15%, more preferably from about 3%～about 12%, very preferably about 4%～about 10%.
22. the composition of claim 21, wherein filler is a kind of flats filler.
23. the composition of claim 22, wherein filler is selected from following one group: mica, talcum and clay.
24. the composition of claim 21, wherein filler is a kind of spherical or elongate hard packing.
25. the composition of claim 24, wherein filler is an activated alumina.
26. a composition comprises the mica and the polysiloxane of a soft ethylene elastomer component and significant quantity, so that composition has the scratch resistance of improvement and the softness of not obvious reduction composition.
27. the composition of claim 26, wherein mica account for composition total weight about 1%～about 20%, preferred about 2%～about 15%, more preferably from about 3%～about 12%, very preferably about 4%～about 10%.
28. the composition of any one in the claim 20～27, wherein polysiloxane accounts for about 0.1%～about 2.5%, preferred about 0.2%～about 1.0%, very preferably about 0.25%～about 0.6% of composition.
29. the composition of claim 28, wherein polysiloxane is a polydimethylsiloxane.
30. a composition comprises filler, polysiloxane and the compatilizer of a soft ethylene elastomer component and significant quantity, so that composition has the scratch resistance of improvement and the softness of not obvious reduction composition.
31. the composition of claim 30, wherein filler account for composition total weight about 1%～about 20%, preferred about 2%～about 15%, more preferably from about 3%～about 12%, very preferably about 4%～about 10%.
32. the composition of claim 31, wherein filler is a kind of flats filler.
33. the composition of claim 32, wherein filler is selected from following one group: mica, talcum and clay.
34. the composition of claim 31, wherein filler is a kind of spherical or elongate hard packing.
35. the composition of claim 34, wherein filler is an activated alumina.
36. a composition comprises mica, compatilizer and the polysiloxane of a soft ethylene elastomer component and significant quantity, so that composition has the scratch resistance of improvement and the softness of not obvious reduction composition.
37. the composition of claim 36, wherein mica account for composition total weight about 1%～about 20%, preferred about 2%～about 15%, more preferably from about 3%～about 12%, very preferably about 4%～about 10%.
38. the composition of any one in the claim 30～37, wherein compatilizer accounts for about 0.1%～about 10%, preferred about 0.25%～about 7% of composition weight.
39. the composition of any one in the claim 30～38, wherein polysiloxane accounts for about 0.1%～about 2.5%, preferred about 0.2%～about 1.0%, very preferably about 0.25～about 0.6% of composition.
40. the composition of claim 39, wherein polysiloxane is a polydimethylsiloxane.
41. the composition of any one in the claim 20～39, wherein soft ethylene elastomer component is a kind of composition for thermoplastic elastomer of rheology modified, basic gel-free, comprises at least a elasticity EAO polymkeric substance or EAO blend polymer and at least a high-melting-point polymer that is selected from homopolymer polypropylene and propylene/ethylene copolymer.
42. the composition of claim 41, wherein elasticity EAO polymkeric substance or EAO blend polymer account for about 50～about 95 weight % of soft ethylene elastomer component and about 5～about 50 weight % that high-melting-point polymer accounts for soft ethylene elastomer component.
43. the composition of claim 42, wherein rheology modified usefulness presents in an amount at least sufficient to provide the peroxide-induced of overall characteristic, described superoxide is a kind of following one group organo-peroxide: α that is selected from, α '-two (tert-butyl peroxide)-diisopropyl benzene, dicumyl peroxide, 2,5-dimethyl-2,5-two (tert-butyl peroxide) hexane, di-t-butyl peroxide, 2,5-two (peroxide tert-pentyl)-2, the 5-dimethylhexane, 2,5-two (tert-butyl peroxide)-2,5-phenylbenzene hexane, peroxidation two (α-Jia Jibianji), benzoyl peroxide, peroxidized t-butyl perbenzoate and two (tert-butyl peroxide)-diisopropyl benzene.
44. the composition of claim 43 also comprises at least a suitable coagent with superoxide.
45. preparation claim 2, any one method for compositions in 8,30 and 36 comprises the following step:
A. preparation comprises the master batch of filler, compatilizer and base resin;
B. with master batch and soft ethylene elastomer compositions at about 180 ℃～about 220 ℃, mix under the preferred about 190 ℃～about 210 ℃ temperature; And
C. the composition in the step (b) is being lower than granulation under second temperature of mixing temperature.
46. the method for claim 45, wherein said compatilizer are a kind of functionalised polyolefins.
47. the method for claim 45 or 46, wherein base resin is a kind of ethylene elastomer.
48. the method for any one in the claim 45～47, wherein compatilizer accounts for about 1～about 20%, preferred about 5～about 15% of master batch weight.
49. the method for any one in the claim 45～48, wherein filler accounts for about 10～about 90%, preferred about 30～about 60% of master batch weight.
50. the method for claim 49, wherein filler is a kind of flats filler.
51. the composition of claim 50, wherein filler is selected from following one group: mica, talcum or clay.
52. the composition of claim 51, wherein filler is a mica.
53. the composition of claim 49, wherein filler is a kind of spherical or elongate hard packing.
54. the composition of claim 53, wherein filler is an activated alumina.
55. the method for any one in the claim 45～54 also is included in the step that adds polysiloxane in the composition.
56. the method for claim 55, wherein polysiloxane is about 0.1～about 2.5%, preferred about 0.2～about 1.0%, very preferably about 0.25～about 0.6% of a composition.
57. the method for claim 56, wherein polysiloxane is a polydimethylsiloxane.
58. any one method for compositions in the preparation claim 1～44 comprises the following step:
A. at about 180 ℃～about 220 ℃, under the preferred about 190 ℃～about 210 ℃ temperature, with about 1～about 20%, preferred about 2～about 15%, more preferably from about 3～about 12% and very preferably about filler of 4～about 10% join in the soft ethylene elastomer.
B. the composition in the step (a) is being lower than granulation under second temperature of mixing temperature.
59. the composition of claim 58, wherein soft ethylene elastomer compositions comprises compatilizer.
60. the method for claim 59, wherein compatilizer will add in step (a) before the filler or with filler and add soft ethylene elastomer compositions simultaneously.
61. the method for claim 58 also is included in the step that adds polysiloxane in the composition.
62. the method for claim 61, wherein polysiloxane accounts for about 0.1～about 2.5%, preferred about 0.2～about 1.0%, very preferably about 0.25～about 0.6% of composition.
63. the method for claim 62, wherein polysiloxane is a polydimethylsiloxane.
64. one kind contain at least one by any one composition in the claim 1～44 make parts goods, described goods are selected from following one group: part in the automobile car, the outer part of automobile car, with the consumer's goods of soft contact handgrip with the consumer appliances of soft surface in contact.
65. one kind contains at least one and makes the injection-molded item of parts by any one composition in the claim 1～44, wherein said goods are used for using in air-bag door or other automobile car.
66. one kind contain at least one by any one composition in the claim 1～44 make parts goods, wherein said goods are used for using in the automobile car.
CN200380105637A 2002-10-22 2003-10-21 Scratch resistant soft ethylene elastomer compositions Expired - Fee Related CN100582149C (en)

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CN103275400A (en) * 2013-05-17 2013-09-04 浦江亿通塑胶电子有限公司 TPV and TPV thermoplastic elastomer composite sheet and preparation method thereof
CN104403200A (en) * 2014-12-15 2015-03-11 苏州宽温电子科技有限公司 Anti-aging composite material and preparation method thereof
CN110406212A (en) * 2018-04-28 2019-11-05 上海伟星新型建材有限公司 A kind of anti-scratch PE-PPR multiple tube and its manufacturing method

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CN103275400A (en) * 2013-05-17 2013-09-04 浦江亿通塑胶电子有限公司 TPV and TPV thermoplastic elastomer composite sheet and preparation method thereof
CN103275400B (en) * 2013-05-17 2016-03-09 浦江亿通塑胶电子有限公司 The making method of TPV, TPV thermoplastic elastomer composite sheet, TPV thermoplastic elastomer composite sheet
CN104403200A (en) * 2014-12-15 2015-03-11 苏州宽温电子科技有限公司 Anti-aging composite material and preparation method thereof
CN110406212A (en) * 2018-04-28 2019-11-05 上海伟星新型建材有限公司 A kind of anti-scratch PE-PPR multiple tube and its manufacturing method
CN110406212B (en) * 2018-04-28 2023-11-24 上海伟星新型建材有限公司 Scratch-resistant PE-PPR composite pipe and manufacturing method thereof

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