CN1326916C - Conductive masterbatch and conductive resin composition - Google Patents

Conductive masterbatch and conductive resin composition Download PDF

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CN1326916C
CN1326916C CNB038243180A CN03824318A CN1326916C CN 1326916 C CN1326916 C CN 1326916C CN B038243180 A CNB038243180 A CN B038243180A CN 03824318 A CN03824318 A CN 03824318A CN 1326916 C CN1326916 C CN 1326916C
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conductive
carbon black
pill
graphitized carbon
polymeric amide
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CN1688639A (en
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寺田和范
野田和弥
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Asahi Kasei Corp
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Asahi Kasei Chemicals Corp
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Abstract

A conductive master batch containing polyamide and conductive carbon black, characterized in that 1-100 pieces of agglomerate each having a longer diameter of 20-100 mum are present in at least part of the conductive carbon black when continuous 3-mm<2>-surfaces are observed under an optical microscope.

Description

Conductive agglomerate and conductive resin composition
Background of invention
Invention field
The present invention relates to conductive agglomerate.More specifically, the present invention relates to comprise the conductive agglomerate of polymeric amide and graphitized carbon black, wherein graphitized carbon black is that the form of at least a agglomerated particle of 20-100 μ m exists with the major axis, wherein under opticmicroscope to 3mm 2The quantity of the observed agglomerated particle in successive zone is 1-100.The conductive agglomerate of the application of the invention, can obtain not only have excellent thermotolerance, and show simultaneously excellent electroconductibility and shock resistance conductive resin composition (wherein said " excellent electroconductibility " refer to the electroconductibility of the conventional material of the processing that is used for relating to electrostatic coating quite or than its superior electroconductibility, that is, make the electroconductibility of the enough electrostatic coatings of material).This conductive resin composition can be widely used in various fields, as the Electrical and Electronic parts, and the parts of office automated machine, trolley part and other mechanical part.Especially, conductive resin composition is very favorable as the material of producing automobile exterior panel (for example automobile baffle), because when above-mentioned resin combination is molded as massive article (as automobile exterior panel, door-plate etc.) and then the gained moulded product is carried out electrostatic coating, can obtain excellent moulded product, wherein thermal distortion not only can not take place in this moulded product, nor can reduce shock resistance, and wherein on described moulded product, form excellent coating owing to the superior electrical conductivity of this resin combination.The invention still further relates to the method for preparing above-mentioned resin combination effectively.
Prior art
Polyphenylene oxide not only has excellent machinery and electric property and excellent thermotolerance, but also has excellent size stability.Therefore, polyphenylene oxide has been widely used in the various fields.Yet the mouldability of polyphenylene oxide is relatively poor.In order to improve the mouldability of polyphenylene oxide, the open Sho45-997 of the Japanese Patent of authorization discloses wherein polymeric amide has been joined in the polyphenylene oxide, obtains the technology of polyamide-polyphenylene ether alloy thus.Now, polymeric amide-polyethers alloy is widely used in the various fields.
Recently, but use the polyamide-polyphenylene ether alloy give electroconductibility as the material of electrostatic coating in automobile exterior panel (as baffle plate and door-plate) field rapidly expansion come.For example, attempted using the automobile baffle of making by the polyamide-polyphenylene ether alloy, with the security (for example protecting the pedestrian) that not only improves automobile, but also the restorability after the distortion of improvement automobile baffle.
The material requirements that is used for automobile exterior panel has various superperformances, as is enough to electroconductibility, shock resistance, thermotolerance and the fluidity of molten of electrostatic coating.
About giving the method for polyamide-polyphenylene ether alloy with electroconductibility, for example unexamined Japanese Patent Application Publication Hei 2-201811 disclose by wherein make polymeric amide that carbon black mainly is included in the polyamide-polyphenylene ether alloy in mutually method or by wherein making carbon black be dispersed in the polymeric amide and then itself and polyphenylene oxide blended method being reduced the technology of the surface resistivity of polyamide-polyphenylene ether alloy.Usually known have a kind of product that fine particle (as carbon black pellet) is evenly dispersed in the method in the high-viscosity material and is obtained by this method (referring to for example " Kagakugijutsushi (chemical technology magazine) MOL ", the 41-46 page or leaf, publish Japan, in November, 1987 by Ohmsha Ltd..
Unexamined Japanese Patent Application Publication Hei 8-48869 is (corresponding to United States Patent (USP) 5,977,240) disclose and wherein made polymeric amide and polyphenylene oxide mutual compatibilized in advance, add carbon black then, obtain to have good shock strength thus, the technology of the resin combination of good fluidity of molten and low volume resistivity.
In addition, unexamined Japanese Patent Application Publication Hei 4-300956 (corresponding to EP 506386) has described preparing in the process of the composition that contains described component by regulating polymeric amide, polyphenylene oxide, carbon black and the amount of compatilizer and polyphenylene oxide and the polymeric amide that use has specific relative viscosity, can improve the electroconductibility and the processibility of said composition.
The open WO 01/81473 of international patent application discloses polyphenylene oxide that the carbonaceous feedstock (Ketjen Black (KB)) that wherein makes conduction is present in polymeric amide/polyphenyl ether resin composition with the particle form technology in mutually.In this patent documentation, the structure of having observed this resin combination under up to 20,000 times transmission electron microscope in magnification, but this observations only proves and has the KB particle (size: about 50nm) that is far smaller than 20 μ m.In addition, the shock resistance of this resin combination and unsatisfactory.In this patent documentation, resin combination uses master batch to prepare; Yet, do not have the description of the concrete feature of relevant master batch.
Thermal distortion might take place in the resin combination and the moulded product that obtain by above-mentioned routine techniques.In addition, can not prepare all improved resin combination of electroconductibility, shock resistance and resistance to heat distorsion usually.Especially, conventional resin combination is used to relate to the processing of electrostatic coating and requirement as production large size and requirement and has high resistance to heat distorsion, high impact properties and be enough to the material of goods (as automobile exterior panel) of the electroconductibility of electrostatic coating and unsatisfactory.Therefore, wish to develop the new technology that preparation is suitable for producing the material of said products in the art.
Summary of the invention
The inventor is through extensively and fully studying, in the hope of addressing the above problem.The result, be surprised to find: specific conductive agglomerate can prepare the thermotolerance that not only has excellence, and show simultaneously excellent electroconductibility and shock resistance conductive resin composition (wherein " excellent electroconductibility " refer to the electroconductibility of the conventional material of the processing that is used for relating to electrostatic coating quite or than its superior electroconductibility, that is, make the electroconductibility of the enough electrostatic coatings of material).Above-mentioned particular conductivity master batch comprises polymeric amide and graphitized carbon black, and wherein graphitized carbon black is that the form of at least a agglomerated particle of 20-100 μ m exists with the major axis, wherein under opticmicroscope to 3mm 2The quantity of the observed agglomerated particle in successive zone is 1-100.When the moulded product by above-mentioned conductive resin composition production carried out electrostatic coating, not only thermal distortion can not take place and reduce shock resistance in moulded product, and forms excellent coating owing to the superior electrical conductivity of this resin combination on described moulded product.The present invention is based on these new discoveries just is accomplished.
Therefore, the purpose of this invention is to provide and to be advantageously used in the thermotolerance that preparation not only has excellence, and show the conductive agglomerate of the conductive resin composition of excellent electroconductibility and shock resistance simultaneously, make when by the moulded product of this resin combination acquisition when carrying out electrostatic coating, not only thermal distortion can not take place and reduce shock resistance in moulded product, and forms excellent coating owing to the superior electrical conductivity of this resin combination on described moulded product.
Another object of the present invention provides above-mentioned conductive resin composition.
Another purpose of the present invention provides the method for the above-mentioned conductive resin composition of effective preparation.
By following detailed and in conjunction with the accompanying drawings with the appended claim book, aforementioned and other purpose, feature and advantage of the present invention will become apparent.
The accompanying drawing summary
In the accompanying drawings:
Fig. 1 is the synoptic diagram of the cylindrical pellets of conductive agglomerate, and it has shown the skeleton view of the cross section of this pill, observes the quantity of this cross section with the agglomerated particle of mensuration graphitized carbon black;
Fig. 2 is the synoptic diagram of the spherical pill of conductive agglomerate, and it has shown the skeleton view of the cross section of this pill, observes the quantity of this cross section with the agglomerated particle of mensuration graphitized carbon black;
Fig. 3 (a) is the synoptic diagram of the pill of the conductive agglomerate (PA/KB-MB1) of acquisition in the Comparative Examples 1, and it has shown the skeleton view of the cross section of this pill, observes the quantity of this cross section with the agglomerated particle of mensuration graphitized carbon black;
Fig. 3 (b) is the light micrograph (* 50) of the cross section of the pill of demonstration among Fig. 3 (a);
Fig. 4 (a) is the synoptic diagram of the conductive agglomerate (PA/KB-MB2) of acquisition among the embodiment 1, and it has shown the skeleton view of the cross section of this pill, observes the quantity of this cross section with the agglomerated particle of mensuration graphitized carbon black;
Fig. 4 (b) is the light micrograph (* 50) of the cross section of the pill of demonstration among Fig. 4 (a);
Fig. 4 (c) is the explanatory view that shows the surface profile of pill shown in Fig. 4 (a), and this is used for explaining hereinafter the method for the roughness (Ra) on the surface of measuring pill;
Fig. 5 (a) is the synoptic diagram of the car body part around the front-wheel, and this part comprises baffle plate;
Fig. 5 (b) is the scanning probe microscopic images of the baffle part of demonstration among Fig. 5 (a); And
Fig. 5 (c) is the synoptic diagram that shows the surface profile of the baffle part that shows among Fig. 5 (a).
The reference number explanation
1: the cross section of pill
1a: the part at the surfaceness of pill (Ra) (according to the center line average roughness of JIS B0601 (1982) mensuration or the arithmetic average roughness of measuring according to JIS B0601 (1994)) mensuration place
2: graphitized carbon black
3: polymeric amide
The medullary ray of definition among the 4:JIS B0601 (1982) (it is corresponding to " average line " described among the JIS B0601 (1994)))
5: the surfaceness of pill (Ra)
6: the baffle plate of automobile
7: the automobile baffle part that comprises the part at surface roughness measurement place
8: the part of the scanning probe microscopic images of the part 7 of display automobile baffle plate, wherein surfaceness is measured in this part
9: the surfaceness of automobile baffle (maximum height of the surface portion of automobile baffle and minimum constructive height poor)
Detailed Description Of The Invention
In one aspect of the invention, provide a kind of conductive agglomerate that comprises polyamide and conductive black, wherein conductive black exists take the form of major axis as at least a agglomerated particle of 20-100 μ m, wherein under light microscope to 3mm2The quantity of the agglomerated particle that the continuum is observed is 1-100.
In order to understand easily the present invention, the below's numbering is described essential characteristic of the present invention and various embodiment.
1. conductive agglomerate that comprises polyamide and conductive black, wherein said conductive black exists take the form of major axis as at least a agglomerated particle of 20-100 μ m, wherein under light microscope to 3 mm2The quantity of the described at least a agglomerated particle that the continuum is observed is 1-100.
2. according to above-mentioned the 1st conductive agglomerate, the quantity of wherein said at least a agglomerated particle is 1-50.
3. according to above-mentioned the 1st conductive agglomerate, the quantity of wherein said at least a agglomerated particle is 2-40.
4. according to above-mentioned the 1st conductive agglomerate, the quantity of wherein said at least a agglomerated particle is 2-30.
5. according to each conductive agglomerate in the above-mentioned 1-4 item, the dibutyl phthalate of wherein said graphitized carbon black (DBP) oil number is 250ml/100g carbon black at least.
6. according to each conductive agglomerate in the above-mentioned 1-4 item, it is the form of pill.
7. according to above-mentioned the 6th conductive agglomerate, wherein the surfaceness of each pill is counted 0.3-2.0 μ m by the mean value of surfaceness (Ra) value, and described surface roughness value is measured at 10 different surfaces positions of each pill by the surfaceness meter.
8. according to above-mentioned the 6th conductive agglomerate, wherein the surfaceness of each pill is 0.4-1.5 μ m.
9. according to above-mentioned the 7th conductive agglomerate, wherein each described pill has cylindrical shape, and diameter is that 1.5-3.5mm and length are 2.0-3.5mm.
10. according to each conductive agglomerate in the above-mentioned 1-4 item, the amount of wherein said graphitized carbon black is 5-40 weight % based on the weight of master batch.
11. according to above-mentioned the 10th conductive agglomerate, the amount of wherein said graphitized carbon black is 6-10 weight % based on the weight of master batch.
12. a conductive resin composition that comprises polymeric amide, polyphenylene oxide and graphitized carbon black, it is by preparing each the conductive agglomerate and the molten polyamide kneading of polyphenylene oxide and the additional quantity of choosing wantonly in the above-mentioned 1-11 item.
13. according to above-mentioned the 12nd conductive resin composition, wherein the amount of graphitized carbon black is the 0.2-5 weight part with respect to the total amount of each component except that this graphitized carbon black in this conductive resin composition of 100 weight parts.
14. according to above-mentioned the 12nd or 13 conductive resin composition, it is used to produce automobile exterior panel.
15. injection-molded item that comprises each conductive resin composition in the above-mentioned 12-14 item.
16. an automobile exterior panel, it comprises in the above-mentioned 12-14 item each conductive resin composition.
17. according to above-mentioned the 16th automobile exterior panel, it is an automobile baffle.
18. according to above-mentioned the 17th automobile exterior panel, it is an injection-molded item.
19. according to above-mentioned the 18th automobile exterior panel, its surfaceness is counted 0.05-1 μ m by the difference of altitude between the lowermost portion on the highest part on automobile exterior panel surface and automobile exterior panel surface, wherein said height is observed under Scanning Probe Microscopy.
20. one kind prepares and comprises polymeric amide, the method for the conductive resin composition of polyphenylene oxide and graphitized carbon black, and it comprises the following steps:
(1) provide the conductive agglomerate that comprises polymeric amide and graphitized carbon black, wherein said graphitized carbon black with the major axis be the form of at least a agglomerated particle of 20-100 μ m exist and
(2) described conductive agglomerate is added in the fused polyphenylene oxide.
21. according to above-mentioned the 20th method, wherein in step (2), the polymeric amide of additional quantity is added in the fused polyphenylene oxide, adds conductive agglomerate simultaneously.
22. according to above-mentioned the 20th or 21 method, wherein the described conductive agglomerate that provides in step (1) is each a master batch in the above-mentioned 1-11 item.
Hereinafter, each component of conductive agglomerate of the present invention and conductive resin composition will be described in detail.
About the type that can be used for polymeric amide of the present invention without limits, as long as it is the polymkeric substance that has amido linkage { NH-C (=O)-} in its main chain.
Usually, polymeric amide is by the ring-opening polymerization of lactan, the polycondensation of the polycondensation of diamines and di-carboxylic acid and omega-amino-carboxylic acid and obtaining.Yet in the present invention, the method that obtains polymeric amide is not limited to these examples.
The example of above-mentioned diamines comprises aliphatic diamine, alicyclic diamine and aromatic diamine.Particularly, can mention tetramethylene-diamine, hexamethylene-diamine, 11 methylene diamine, ten dimethylene diamines, ten trimethylene diamines, 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 5-methyl ball methylene diamine, 1, the two amino methyl hexanaphthenes, 1 of 3-, the two amino methyl hexanaphthenes of 4-, mphenylenediamine, Ursol D, m-xylene diamine and p-Xylol diamines.
The example of di-carboxylic acid comprises aliphatic dicarboxylic acid, alicyclic di-carboxylic acid and aromatic dicarboxylate.Particularly, can mention hexanodioic acid, suberic acid, calculation in the ninth of the ten Heavenly Stems two, sebacic acid, 12 intact diacid, 1,1,3-undecane dicarboxylic acid, 1,3-cyclohexane cyclohexanedimethanodibasic, terephthalic acid, m-phthalic acid, naphthalic acid and dimer acids.
Interior acyl by specific examples comprise ε-Ji Neixianan, oenantholactam and ω-bay hexanolactam.
In addition, the specific examples of omega-amino-carboxylic acid comprises epsilon-amino caproic acid, 7-aminoheptylic acid, 8-aminocaprylic acid, 9 aminononanoic acid, the amino undecanoic acid of 11-, 12 amino dodecanoic acid and the amino tridecanoic acid of 13-.
In the present invention, polymeric amide can be the homopolymer that obtains by with arbitrary above-claimed cpd (being lactan, diamines, di-carboxylic acid and omega-amino-carboxylic acid) homopolymerization, perhaps carries out the multipolymer that polycondensation obtains by the mixture with at least two kinds of above-claimed cpds.
In the present invention, also preferred the use by wherein with at least a above-claimed cpd (being lactan, diamines, di-carboxylic acid and omega-amino-carboxylic acid) polymerization in polymerization reactor, obtain low-molecular-weight oligomer thus, and, obtain the polymeric amide of the method acquisition of high-molecular weight polymer thus with the oligopolymer further polymerization in forcing machine or similar devices that is obtained.
The example that can be advantageously used in polymeric amide of the present invention comprises polyamide 6, polyamide 6,6, polymeric amide 4,6, polymeric amide 11, polymeric amide 12, polyamide 6,10, polyamide 6,12, polyamide 6/6,6, polyamide 6/6,12, polymeric amide MXD (m-xylene diamine), 6, polyamide 6, T, polyamide 6, I, polyamide 6/6, T, polyamide 6/6, I, polyamide 6,6/6, T, polyamide 6,6/6, I, polyamide 6/6, T/6, I, polyamide 6,6/6, T/6, I, polyamide 6/12/6, T, polyamide 6,6/12/6, T, polyamide 6/12/6, I and polyamide 6,6/12/6, I.Can use polymeric amide in addition by using the multiple different polyamide of forcing machine or similar devices copolymerization to obtain.
The preferred embodiment of polymeric amide comprises polyamide 6, polyamide 6,6, polyamide 6/6,6 and composition thereof.
The number-average molecular weight preferably 5 that is used for the present invention's polymeric amide, 000-100,000, more preferably 10,000-30,000.
The polymeric amide that is used for the present invention is not limited to above-mentioned those that enumerate, and it can also be the mixture with multiple polymeric amide of different molecular weight.For example polymeric amide can be that to be lower than 15,000 low molecular polyamides and number-average molecular weight be 15,000 or the mixture of higher superpolyamide to number-average molecular weight.
The terminal group of polymeric amide participates in the reaction with polyphenylene oxide.Polymeric amide have amino usually and carboxyl as its terminal group.Usually, when the carboxyl concentration of polyamide resin increases, the shock resistance step-down of this polymeric amide, and the fluidity of molten of polymeric amide improves.On the other hand, when the amino group concentration of polyamide resin increased, the shock resistance of this polymeric amide was improved, and the fluidity of molten of polymeric amide reduces.
In the present invention, amino concentration ratio (amino/carboxyl ratio) with carboxyl is preferably 9/1-1/9, more preferably 8/2-1/9, most preferably 6/4-1/9.
The concentration of the terminal amino group of polymeric amide is preferably every kg polymeric amide at least 10 milliequivalents, more preferably at least 30 milliequivalents.
Any ordinary method all can be used for controlling the amount of the terminal group of polymeric amide.For example, can mention wherein diamines, di-carboxylic acid or monocarboxylic acid are added the polymerization reaction system that is used for producing polymeric amide, so that obtain to have the method for the polymeric amide of required terminal amino group concentration, the method that mixes with the polymeric amide that wherein two or more is had different terminal group ratios.
In addition, in order to improve the thermostability of polymeric amide, can use the metallic compound stablizer of describing as among the unexamined Japanese Patent Application Publication Hei 1-163262.
In the common metal compound stabiliser, especially preferred is CuI, CuCl 2, venus crystals and cerium stearate.Further preferably alkali-metal halogen is as potassiumiodide and Potassium Bromide.These metallic compound stablizers can use separately or coupling.
Preferably, with the metallic compound stablizer being that the amount of 0.001-1 weight part is added in the polymeric amide with respect to 100 weight parts of polyamide.
In addition, also any other conventional additives of polymeric amide can be added in the polymeric amide.This additive can be less than 10 weight parts with respect to the consumption of 100 weight parts of polyamide.
The example that can be used for the polyphenylene oxide among the present invention comprises homopolymer and multipolymer, and they contain the structural unit of following formula (1) expression independently of one another:
Wherein O represents Sauerstoffatom, and each R represents hydrogen atom, halogen atom, uncle or secondary C independently 1-C 7Alkyl, phenyl, C 1-C 7Haloalkyl, C 1-C 7Aminoalkyl group, C 1-C 7-oxyl or halo-oxyl (wherein at least two carbon atoms are present between halogen atom and the Sauerstoffatom).
The specific examples that is used for the present invention's polyphenylene oxide comprises poly-(2,6-dimethyl-1,4-phenylene ether), poly-(2-methyl-6-ethyl-1,4-phenylene ether), poly-(2-methyl-6-phenyl-1,4-phenylene ether) and poly-(2,6-two chloro-1,4-phenylene ether).Other example of polyphenylene oxide comprises 2, the multipolymer of 6-xylenol and other phenol (for example 2,6-xylenol and 2,3, the multipolymer of 6-pseudocuminol and 2, the multipolymer of 6-xylenol and 2-methyl-6-butylphenol, they are described among the Japanese Patent Application Publication Sho 52-17880 of authorization).
In the middle of above-mentioned polyphenylene oxide, preferably poly-(2,6-dimethyl-1,4-phenylene ether), 2,6-xylenol and 2,3, multipolymer of 6-pseudocuminol and composition thereof.
The method that is used for the present invention's polyphenylene oxide about preparation is not particularly limited, and can use any ordinary method.For example, can mention as being described in United States Patent (USP) 3,306,874,3,306,875,3,257,357 and 3,257,358 and unexamined Japanese Patent Application Publication Sho 50-51197 and Sho63-152628 in method.
About can be used for the polyphenylene oxide among the present invention, its reduced viscosity (η Sp/ c) be preferably 0.15-0.70dl/g, more preferably 0.20-0.60dl/g, 0.40-0.55dl/g most preferably, wherein this viscosity is measured at the 0.5g/dl of 30 ℃ of following polyphenylene ether chloroformic solution.
In the present invention, can use the mixture of two or more dissimilar polyphenylene oxide and not cause any problem with different reduced viscositys.Example as this class mixture, can mention that its reduced viscosity surpasses the mixture that 0.40dl/g to 0.45dl/g or lower polyphenylene oxide and its reduced viscosity are 0.50dl/g or higher polyphenylene oxide, with and reduced viscosity be that 0.40dl/g or lower low-molecular polyphenylene ether and its reduced viscosity are the mixture of 0.50dl/g or higher polyphenylene oxide, but polyser mixture be not limited to above-named those.
The polyphenylene oxide that is used for the present invention can contain with respect to the organic solvent of 100 weight part polyphenylene oxide less than 5 weight %, and wherein this organic solvent is the residual polymer solvent that is used to prepare polyphenylene oxide.Be difficult to remove the residual polymerization solvent by the drying operation of carrying out after polyreaction, this solvent often remains in the polyphenylene oxide to the concentration of several weight % with hundreds of ppm.Wherein said organic solvent is the residual polymerization solvent, and it can be at least a solvent of each isomer, ethylbenzene, the alcohol with 1-5 carbon atom, chloroform, methylene dichloride, chlorobenzene and the dichlorobenzene that are selected from toluene, dimethylbenzene.
In addition, the polyphenylene oxide that is used for the present invention can be modified form, the form (hereinafter, the mixture of Noryl and unmodified polyphenylene oxide and Noryl is referred to as " Noryl ") that perhaps is the mixture of unmodified polyphenylene oxide and Noryl.
In the present invention, " Noryl " refers to have the polyphenylene oxide that at least one is selected from the unsaturated link(age) of carbon-to-carbon double bond and carbon-to-carbon three key and has the modifier compound modification of at least one group that is selected from carboxylic acid group, anhydride group, amino, hydroxyl and glycidyl with at least a.
As the example of the method for preparing Noryl, can mention following method (1)-(3):
(1) wherein makes polyphenylene oxide and modifier compound having or not having in the presence of the radical initiator in 100 ℃ or higher temperature but be lower than under the temperature of reaction of second-order transition temperature of this polyphenylene oxide and react, make the carrying out of reaction not cause polyphenylene oxide fused method;
(2) wherein make polyphenylene oxide and modifier compound have or not have in the presence of the radical initiator in the second-order transition temperature that is equal to or higher than this polyphenylene oxide but be not higher than melt kneading under 360 ℃ the temperature, the method for reacting thus; And
(3) wherein make polyphenylene oxide and modifier compound in their solvent, have or not have the method for under the temperature of the second-order transition temperature that is lower than this polyphenylene oxide, reacting in the presence of the radical initiator.
In the present invention, can adopt any in aforesaid method (1)-(3), but preferred method (1) and (2).
To specifically set forth below and above-mentionedly have at least one and be selected from the unsaturated link(age) of carbon-to-carbon double bond and carbon-to-carbon three key and have the modifier compound that at least one is selected from the group of carboxylic acid group, anhydride group, amino, hydroxyl and glycidyl.
As the example of modifier compound with carbon-to-carbon double bond and carboxylic acid group and/or anhydride group, can mention unsaturated dicarboxylic acid, for example toxilic acid, fumaric acid, chloromaleic acid, cis-4-hexamethylene finish-1,2-dioctyl phthalate and acid anhydrides thereof.In the middle of above-claimed cpd, preferred fumaric acid, toxilic acid and maleic anhydride, more preferably fumaric acid and maleic anhydride.
In addition, the compound that also can use one or two carboxyl by any above-mentioned unsaturated dicarboxylic acid of esterification to obtain.
As the example of modifier compound, can mention allyl glycidyl ether, vinylformic acid glycidyl esters, methyl propenoic acid glycidyl base ester and the natural oil ﹠ fat of epoxidation with carbon-to-carbon double bond and glycidyl.
In the middle of above-claimed cpd, especially preferred vinylformic acid glycidyl esters and methyl propenoic acid glycidyl base ester.
As the example of modifier compound, can mention formula C with carbon-to-carbon double bond and hydroxyl nH 2n-3The unsaturated alcohol of OH (wherein n is a positive integer) expression, for example vinyl carbinol, 4-amylene-1-ol and 1,4-pentadiene-3-alcohol; And formula C nH 2n-5OH and C nH 2n-7The unsaturated alcohol of OH (wherein n is a positive integer) expression.
Above-mentioned modifier compound can use separately or coupling.
The consumption that is used to prepare the modifier compound of Noryl is preferably the 0.1-10 weight part with respect to 100 weight part polyphenylene oxide, more preferably the 0.3-5 weight part.
As above-mentioned radical initiator, can use conventional organo-peroxide and contain any in the compound of azo-group.The specific examples of radical initiator comprises benzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, tert-butyl peroxide cumyl, t-butyl hydroperoxide, cumene hydroperoxide and Diisopropyl azodicarboxylate.
When preparing Noryl by the use radical initiator, the consumption of radical initiator is preferably the 0.001-1 weight part with respect to 100 weight part polyphenylene oxide.
Preferably, the amount that is incorporated into the modifier compound in the Noryl is 0.01-5 weight %, more preferably 0.1-3% weight % based on the weight of Noryl.
Noryl also can contain the polymkeric substance of unreacted modifier compound and/or modifier compound.
Amount for the polymkeric substance that reduces the unreacted modifier compound that contains in the Noryl and/or modifier compound needs, and can add have amido linkage and/or amino compound in the process of preparation Noryl.
In the present invention, " compound " with amido linkage refer to have formula-NH-C (=O)-compound and " have amino compound " of the structure of expression refer to have at least one end-NH 2The compound of group.Specific examples with compound of amido linkage and/or amino comprises aliphatic amine, as octyl amine, nonyl amine, tetramethylene-diamine and hexamethylene-diamine; Aromatic amines is as aniline, mphenylenediamine, Ursol D, m-xylene diamine and p-Xylol diamines; By the product that the reaction of any above-mentioned amine and carboxylic acid or di-carboxylic acid is obtained; Lactams is as ε-Ji Neixianan; And polyamide resin, but have amido linkage and/or amino compound be not limited to above-named those.
When use has amido linkage and/or amino change when containing thing, preferably, the consumption of this compound is 0.001 weight part or more but be less than 5 weight parts with respect to 100 weight part polyphenylene oxide, more preferably 0.01 weight part or more but be less than 1 weight part, even more preferably 0.01 weight part or more but be less than 0.1 weight part.
Set forth the graphitized carbon black that is used for the present invention below.In the present invention, preferably, the every 100g carbon black of the dibutyl phthalate of graphitized carbon black (DBP) oil number is 250ml at least, more advantageously is 300ml at least, the most advantageously is 350ml at least.In the present invention, the DBP oil number is the value that obtains according to ASTM D2414.
In addition, preferably, to be every gram sooty BET surface-area be 200cm at least to the graphitized carbon black that is used for the present invention 2, 400cm at least more advantageously 2Carbon black.The example of this commercially available class graphitized carbon black comprises Ketjen black EC and Ketjen black EC-600JD, and the two is by KetjenBlack International Co., and Japan produces.
Conductive agglomerate of the present invention can obtain by melt kneading polymeric amide and graphitized carbon black.
Conductive agglomerate of the present invention can be pill, powder or particulate form, and preferably, master batch is the form of pill, and more advantageously being diameter is that 1.5mm-3.5mm and length are the form of the cylindric pill of 2.0mm-3.5mm.Hereinafter, the pill of conductive agglomerate is called " master batch pill ".
The content of graphitized carbon black in conductive agglomerate is preferably 5-40 weight % based on the weight (more precisely, based on the gross weight of polymeric amide and graphitized carbon black) of master batch, more preferably 5-25 weight %, especially preferably 6-15 weight %, most preferably 6-10 weight %.Especially when the amount of the graphitized carbon black in the conductive agglomerate is 6-10 weight %, can prevents that not only the molecular weight of the polymeric amide that contains in the master batch from reducing, but also can improve the productivity of master batch.
In the present invention, importantly, the graphitized carbon black in the master batch is that the form of at least a agglomerated particle of 20-100 μ m exists (when master batch existed with the form of multiple agglomerated particle, the particulate major axis can be identical or different) with the major axis.When the graphitized carbon black in the master batch existed with the form of agglomerated particle, the electroconductibility of the master batch that the electroconductibility of master batch and graphitized carbon black wherein do not exist with the form of agglomerated particle was compared and is improved.In addition, the quantitative requirement of above-mentioned agglomerated particle is 1-100, is preferably 1-50, and more preferably 2-40 most preferably is 2-30, and this quantity is to 3mm under opticmicroscope 2The successive zone is observed.When the master batch that uses the agglomerated particle that does not contain above-mentioned size prepared resin combination, the electroconductibility of this resin combination reduced.On the other hand, when the master batch that contains the agglomerated particle that surpasses 100 above-mentioned sizes when use prepared resin combination, the shock resistance of this resin combination reduced.In addition, master batch of the present invention also can contain major axis surpasses 100 μ m less than at least a agglomerated particle of 20 μ m and major axis at least a agglomerated particle.
In the present invention, be not particularly limited about the quantity of major axis less than the agglomerated particle of 20 μ m.Surpass the quantity of the agglomerated particle of 100 μ m about major axis, also be not particularly limited, but preferably, the quantity of the big agglomerated particle of this class is that the quantity of the agglomerated particle of 20-100 μ m is 1/5 or still less based on major axis, more preferably 1/10 or still less.
In the present invention, the size of the agglomerated particle of graphitized carbon black and quantity are measured by the method set forth below and with reference to Fig. 1 and 2.The pill (being the master batch pill) of master batch is cut by the slicing machine that the glass blade is housed, obtain to have the cross section 1 of minute surface thus.Under opticmicroscope (for example " PME3 ", by Olympus Optical Co.Ltd., Japan makes and sells), observe from the light of cross section 1 reflection, and cross section 1 is taken Photomicrograph with * 50 magnifications.3mm at this Photomicrograph 2Count the quantity of the agglomerated particle 2 (major axis that has 20-100 μ m independently of one another) that exists in the polyamide matrix 3 in the successive zone by visual observations.When the master batch pill has cylinder or rectangular parallelepiped shape, pill along the direction longitudinally cutting that is basically perpendicular to this pill, is obtained cross section thus, and the cross section (see figure 1) that gets of observation post.
When the master batch pill has particle or when spherical, with the plane cutting of pill along the center that comprises this pill, and the cross section (see figure 2) of the pill that gets of observation post.To the quantity of at least three cross section counting agglomerated particles (major axis that has 20-100 μ m independently of one another), described at least three cross sections are obtained by different pills respectively, and calculate the mean value of measured value.The mean value that obtains is defined as the quantity of the agglomerated particle (major axis that has 20-100 μ m independently of one another) that exists in the conductive agglomerate.When the difference of the quantity of the agglomerated particle between each cross section is big, 3 above cross sections of preferred view.Particularly, for example observe 5-10 cross section, obtain the mean value of 5-10 measured value.When not obtaining 3mm 2Or during the cross section of bigger successive zone, observe a plurality of cross sections, be 3mm with the counting total area 2Cross section in the quantity of the agglomerated particle that exists.
In the present invention, preferably, the surfaceness of each pill (master batch pill) is by by surfaceness the mean value of surfaceness (Ra) value of a plurality of surface element position-findings of each pill being counted 0.3-2.0 μ m, more preferably 0.4-1.5 μ m.Because this particular surface roughness of master batch pill, when the moulded product of the resin combination that will use this master batch pill preparation carried out electrostatic coating, thermal distortion can not take place in this moulded product, showed excellent electroconductibility and excellent shock resistance simultaneously.When the surfaceness of master batch pill was lower than 0.3 μ m, the electroconductibility of gained resin combination and thermotolerance can not reduce; When the surfaceness of master batch pill surpassed 2.0 μ m, the shock resistance of gained resin combination can not reduce.
Above-mentioned surfaceness meter is a device of measuring the unevenness on surface, and the surfaceness meter also comprises Scanning Probe Microscopy.
Even when down the use forcing machine prepared the pill (being the master batch pill) of conductive agglomerate in identical kneading condition (being resin temperature, screw speed, discharge rates etc.), the quantity of the sooty agglomerated particle in the master batch pill also can be different because of factors such as the type of forcing machine and sizes.The quantity of sooty agglomerated particle and above-mentioned surfaceness have close relation, and (quantity of agglomerated particle is big more, surfaceness is just big more), the quantity of agglomerated particle can be controlled in the institute of the present invention restricted portion by the kneading condition that employing falls in the above-mentioned scope mean value of surfaceness (Ra) value of prepared master batch pill.
In the present invention, the surfaceness of master batch pill (Ra) is according to the center line average roughness of JIS B0601 (1982) mensuration or the arithmetic average roughness of measuring according to JIS B0601 (1994).Above-mentioned center line average roughness is basic identical with arithmetic average roughness.That is to say center line average roughness (Ra) and arithmetic average roughness (Ra) value that the roughness curve that uses the surfaceness meter to obtain is measured of all serving as reasons.Particularly, about roughness curve part (for example part shown in Fig. 4 (c))--this part shows the surface profile of the target surface part of pill, the arithmetical mean of the absolute deviation of the roughness curve that calculating is obtained by medullary ray (for example medullary ray 4 among Fig. 4 (c)) (should " medullary ray " be described among the JIS B0601 (1982) and corresponding to " average line " that be described among the JIS B0601 (1994)) obtains mean roughness (Ra).Above-mentioned medullary ray is measured automatically by following apparatus, and calculates mean roughness (Ra) based on the medullary ray of determining thus.Yet JIS B0601 (1994) is the revised edition of JISB0601 (1982), and the condition (for example intercepting value of roughness curve) that obtains center line average roughness (Ra) is different from those that obtain arithmetic average roughness (Ra).Because this difference of described condition, the center line average roughness of single sample and arithmetic average roughness each other can be slightly different, but this Light Difference is in same level, and this can cause any problem in the present invention.For this reason, in the present invention, surfaceness of master batch pill (Ra) or center line average roughness (Ra) or arithmetic average roughness (Ra).
Surfaceness (Ra) can for example be measured by following method.When the master batch pill had flat position, the surfaceness at this flat position (Ra) used surfaceness meter Surfcom 579A (by Tokyo Seimitsu Co., Ltd., also sale of Japan's manufacturing) to measure, and wherein measuring length is 2.5mm.When the master batch pill does not have the flat position that can obtain 2.5mm measurement length, a plurality of flat positions are measured, to obtain the overall measurement length of 2.5mm.Under the situation that does not have the master batch pill at flat position (as granular master batch pill), by using Scanning Probe Microscopy (SPA300HV, by Seiko Instruments Inc., Japan makes also and sells) observe the image (80 μ m * 80 μ m) on pill surface, subsequently this image is carried out three-dimensional and proofread and correct, obtain the image of the surface profile of this pill of demonstration.Use the image that is obtained of the surface profile that shows pill, obtain center line average roughness (Ra).In the present invention, the surfaceness of pill is the mean value of 10 (Ra) values.
In the present invention, the glossiness of the mean value of surfaceness (Ra) value and pill and the dispersion state of graphitized carbon black in pill are inversely proportional to.That is to say, when not having agglomerated particle to be present in the pill basically, the glossiness height of pill, and surfaceness is little.On the other hand, when agglomerated particle was present in the pill, the glossiness of pill was low, and surfaceness is big.
As the preferred method of preparation conductive agglomerate, can mention the method for wherein raw material of conductive agglomerate being come melt kneading by use twin screw extruder or kneader.Especially preferred is wherein with molten polyamide, adds the method for graphitized carbon black then.The specific examples of these class methods comprises that following use has at least one first inlet and the twin screw extruder of at least one second inlet or method of kneader, and described inlet is separately positioned on the upstream portion and the downstream part of forcing machine or kneader:
Wherein first inlet of polymeric amide from forcing machine or kneader infeeded,, and second inlet of graphitized carbon black from this forcing machine or kneader be added in wherein the molten polyamide, subsequently with the method for gained mixture melt kneading thus with molten polyamide; With
Wherein first inlet of polymeric amide from forcing machine or kneader infeeded, thus with molten polyamide, and with the polymeric amide of graphitized carbon black and additional quantity from second inlet of this forcing machine or kneader is added in wherein molten polyamide simultaneously, subsequently with the method for gained mixture melt kneading.
Melt kneading temperature for the preparation master batch is not particularly limited, but this melt kneading temperature can suitably be selected from and is not higher than 350 ℃ temperature.
Can mediate with the molten polyamide of polyphenylene oxide and the additional quantity of choosing wantonly by the conductive agglomerate that any aforesaid method obtains, obtain conductive resin composition of the present invention thus.
The content of graphitized carbon black in conductive resin composition is preferably the 0.2-5 weight part with respect to the total amount of the component except that graphitized carbon black in the 100 weight part conductive resin compositions.In addition, when the amount of graphitized carbon black was the 0.2-3 weight part, resin combination demonstrated the excellent balance of shock resistance, fluidity of molten and electroconductibility.
Polymeric amide about the additional quantity that is used to prepare resin combination can use above-mentioned any polymeric amide of enumerating.The polymeric amide that adds in the master batch can be identical or different with the polymeric amide that contains in the master batch.
Conductive resin composition of the present invention can contain cinnamic thermoplastic resin, and its content is less than 50 weight parts with respect to the total amount of 100 weight parts of polyamide and polyphenylene oxide.As the example that contains cinnamic thermoplastic resin that is used for the present invention, can mention polystyrene (HIPS), styrene-acrylonitrile copolymer (AS resin) and the vinylbenzene-rubber polymer-acrylonitrile copolymer (ABS resin) of polystyrene (homopolymer), modified rubber.
Any conventional additives that can be used for polyphenylene oxide can add in the conductive resin composition with the amount that is less than 10 weight parts with respect to 100 weight part polyphenylene oxide.The example of conventional additives comprises the metallic compound stablizer, as zinc oxide and zinc sulphide; And organic stabilizer, as steric hindrance phenolic stabilizer, phosphorous type stablizer and bulky amine type stablizer.
In addition, conductive resin composition of the present invention can contain impact modifying agent.
As the impact modifying agent that adds in the conductive resin composition of the present invention, for example can use at least a being selected to comprise mainly the polymer blocks (abbreviating " aromatic vinyl polymer block " hereinafter as) that constitutes by the aromatic vinyl monomer unit and the aromatic vinyl compound/conjugated diene block copolymer of the main polymer blocks (abbreviating " conjugated diolefin polymer block " hereinafter as) that constitutes by conjugated diene monomeric unit and the polymkeric substance of hydrogenated products and ethylene/alpha-olefin copolymer thereof.
The specific examples that is used for preparing the aromatic vinyl compound of the aromatic vinyl compound/conjugated diene block copolymer that is used for the present invention comprises vinylbenzene, alpha-methyl styrene and Vinyl toluene.These compounds can use separately or coupling.In the middle of the compound of enumerating in the above, optimization styrene especially.
Be used for preparing the specific examples that the aromatic vinylization that is used for the present invention contains the conjugated diolefine of thing/conjugated diene block copolymer and comprise divinyl, isoprene, piperylene and 1,3-pentadiene.These compounds can use separately or coupling.In the middle of the compound of enumerating in the above, preferred divinyl, isoprene and composition thereof.
The specific examples of impact modifying agent comprises segmented copolymer, as SBS and SEBS.
About the microstructure of soft section (constituting) of above-mentioned segmented copolymer by conjugated diene monomeric unit, preferably, 1,2-ethylenic linkage content or 1,2-ethylenic linkage and 3, the total content of 4-ethylenic linkage are 5-80%, more preferably 10-50%, most preferably 10-40%.
Preferably, above-mentioned segmented copolymer has the A-B of being selected from, the block arrangement of A-B-A and A-B-A-B, and wherein A represents the aromatic vinyl polymer block, B represents the conjugated diolefin polymer block.The segmented copolymer that is used for the present invention can be the mixture with segmented copolymer of different block arrangement.
In the middle of above-mentioned block arrangement, preferred A-B-A and A-B-A-B.Segmented copolymer can be the mixture with different segmented copolymers of above-mentioned block arrangement.
In addition, further preferably, the aromatic vinyl compound/conjugated diene block copolymer that is used for the present invention is a hydrogenated block copolymer." hydrogenated block copolymer " refers to the multipolymer that obtains by any above-mentioned aromatic vinyl compound of hydrogenation/conjugated diene block copolymer herein, and wherein the degree of hydrogenation of the aliphatic double bond in the conjugated diolefin polymer block is greater than 0% and be no more than 100%.The degree of hydrogenation of hydrogenated block copolymer is preferably 50% or higher, and more preferably 80% or higher, most preferably 98% or higher.
In the present invention, can use the mixture of unhydrided segmented copolymer and hydrogenant segmented copolymer, and not cause any problem.
About being used for the segmented copolymer of conductive resin composition of the present invention, preferably, this segmented copolymer is the mixture of lower molecular weight segmented copolymer and high molecular weight block copolymer.Particularly, preferably using number-average molecular weight to be lower than 120,000 lower molecular weight segmented copolymer and number-average molecular weight is 120,000 or the mixture of higher high molecular weight block copolymer.It is preferred that to be to use number-average molecular weight to be lower than 100,000 lower molecular weight segmented copolymer and number-average molecular weight be 200,000 or the mixture of higher high molecular weight block copolymer.
In the present invention, (for example GPCSYSTEM 21 by gel infiltration look popularize law (GPC) device for number-average molecular weight, by Showa Denko Co., Japan makes also and sells) use UV spectrum detector (UV-41 for example, by Showa Denko Co., Japan makes also and sells) and the calibrating curve determining that obtains by the polystyrene standard sample.It is as follows to measure the condition that number-average molecular weight adopted:
(condition)
Solvent: chloroform,
Temperature: 40 ℃,
Pillar: sample column (K-G, K-800RL and K-800R) and contrast post (K-805L, 2 pillars),
Flow velocity: 10ml/min,
Detect use wavelength: 254nm and
Pressure: 15-17kg/cm 2
In measuring the process of number-average molecular weight, can detect the low molecular weight compositions that the passivation because of polymerizing catalyst produces as by product, but this low molecular weight compositions can be ignored when calculating molecular weight.Usually, the correct molecular weight distribution of calculating (weight-average molecular weight/number-average molecular weight ratio) is 1.0-1.2.
In the mixture of lower molecular weight segmented copolymer and high molecular weight block copolymer, the weight ratio of lower molecular weight segmented copolymer and high molecular weight block copolymer (lower molecular weight segmented copolymer/high molecular weight block copolymer weight ratio) is generally 95/5-5/95, preferred 90/10-10/90.
In addition, in the present invention, be 20,000 or during higher aromatic vinyl polymer block when the lower molecular weight segmented copolymer that is used for said mixture comprises number-average molecular weight, except shock resistance, can improve the thermotolerance of conductive resin composition.
The number-average molecular weight of the aromatic vinyl polymer block of segmented copolymer can be calculated by the number-average molecular weight of above-mentioned segmented copolymer according to following formula:
Mn(a)＝{Mn×a/(a+b)}/N
Wherein Mn (a) represents the number-average molecular weight of aromatic vinyl polymer block; Mn represents the number-average molecular weight of segmented copolymer; " a " expression is based on the weight % of all aromatic vinyl polymer blocks of the weight of segmented copolymer; " b " expression is based on the weight % of all conjugated diolefin polymer blocks of the weight of segmented copolymer; And N represents the quantity of aromatic vinyl polymer block in the segmented copolymer.
In the present invention, preferably, the aromatic vinyl polymer block content of lower molecular weight segmented copolymer is 55 weight % or higher but be lower than 90 weight %.When the aromatic vinyl polymer block content of lower molecular weight segmented copolymer was positioned at above-mentioned scope, the thermotolerance of conductive resin composition can be improved.
In addition, in the present invention, when the lower molecular weight segmented copolymer is that aromatic vinyl polymer block content is 55 weight % or higher but to be lower than the segmented copolymer of 90 weight % and aromatic vinyl polymer block content be 20 weight % or higher but when being lower than the mixture of segmented copolymer of 55 weight %, can improve the fluidity of molten of conductive resin composition.
With segmented copolymer with before conductive resin composition of the present invention mixes, this segmented copolymer can be mixed with the oil of mainly being made up of paraffinic hydrocarbons.Add the oil of mainly forming to can cause improving resin combination in the block polymer processibility by paraffinic hydrocarbons.The content of oil in segmented copolymer is preferably the 1-70 weight part with respect to 100 parts of block copolymer.When segmented copolymer contains above 70 weight parts oil, the handling property variation of segmented copolymer.
In the present invention, mainly the oil of being made up of paraffinic hydrocarbons refers to and has 500-10 independently of one another, the mixture of the hydrocarbon compound of 000 weight-average molecular weight, this mixture comprises the compound that contains aromatic ring, naphthalene-ring containing compound and paraffin compound, and wherein the content of paraffin compound is 50 weight % or higher.Preferably, based on the weight of oil, oil contains paraffin compound, the naphthalene-ring containing compound of 10-40 weight % of 50-90 weight % and is no more than the compound that contains aromatic ring of 5 weight %.
This class mainly by paraffinic hydrocarbons form oily commercially available.For example, can mention KosanCo., Ltd, the PW 380 that Japan produces and sells by Idemitsu.
Above-mentioned aromatic vinyl compound/conjugated diene block copolymer can be the mixture of different segmented copolymers, as long as each segmented copolymer can influence the performance of resin combination of the present invention sharply.For example, segmented copolymer can be the mixture with segmented copolymer of different block arrangement, the mixture that contains the unitary segmented copolymer of different aromatic vinyl monomers, the mixture that contains the segmented copolymer of different conjugated diene monomeric units, have different 1,2-contents of ethylene or different 1,2-vinyl bonds and 3, the mixture of the segmented copolymer of the total content of 4-vinyl bonds has the mixture of segmented copolymer of different aromatic vinyl monomers unit content and the mixture of the segmented copolymer with different degree of hydrogenation.
As the specific examples that can be used for the ethene-alpha-olefin copolymer among the present invention, can mention one that is described among the unexamined Japanese Patent Application Publication 2001-302911.
In addition, the impact modifying agent that is used for conductive resin composition of the present invention can be the mixture of impact-modified properties-correcting agent or impact-modified properties-correcting agent and unmodified impact modifying agent.
The impact-modified properties-correcting agent of herein mentioning refers to at least a has an impact modifying agent that at least one is selected from the unsaturated link(age) of carbon-to-carbon double bond and carbon-to-carbon three key and has the modifier compound modification of at least one group that is selected from carboxylic acid group, anhydride group, amino, hydroxyl and glycidyl.
As the example of the method for preparing impact-modified properties-correcting agent, can mention following method (1)-(3):
(1) wherein impact modifying agent and modifier compound are being had or do not having in the presence of the radical initiator in the softening temperature that is not less than this impact modifying agent and be not higher than melt kneading under 250 ℃ the temperature of reaction, the method for reacting thus;
(2) wherein make impact modifying agent and modifier compound in their solvent, have or not have the method for under the temperature of the softening temperature that is not higher than this impact modifying agent, reacting in the presence of the radical initiator; And
(3) impact modifying agent and modifier compound are being had in the presence of solvent-free or do not have in the presence of the radical initiator reaction under the temperature of reaction of the softening temperature that is not higher than this impact modifying agent and do not cause this impact modifying agent fused method.
Can adopt any in aforesaid method (1)-(3), but preferred method (1), the more preferably method of in the presence of radical initiator, carrying out (1).
As having the above-mentioned modifier compound that at least one is selected from the unsaturated link(age) of carbon-to-carbon double bond and carbon-to-carbon three key and has at least one group that is selected from carboxylic acid group, anhydride group, amino, hydroxyl and glycidyl, above can using as being used for any in the middle of cited those of the modifier compound of Noryl.
Preferably, conductive resin composition of the present invention contains 30-70 weight parts of polyamide, 20-50 weight part polyphenylene oxide and 5-30 weight part impact modifying agent with respect to the total amount of 100 weight parts of polyamide, polyphenylene oxide and impact modifying agent.More preferably, conductive resin composition of the present invention contains 40-60 weight parts of polyamide, 30-40 weight part polyphenylene oxide and 5-15 weight part impact modifying agent with respect to the total amount of 100 weight parts of polyamide, polyphenylene oxide and impact modifying agent.
In addition, in the present invention, also compatilizer can be added in this conductive resin composition in the process of preparation conductive resin composition.Usually, compatilizer is mainly used in the physicals (as shock resistance and fluidity of molten) of improving the polyamide-polyphenylene ether alloy.Can be used for compatilizer among the present invention and be with polyphenylene oxide and polymeric amide in one or both all interactional polyfunctional compounds.
In conductive resin composition of the present invention, preferably, the words of consistency necessity of polymeric amide and polyphenylene oxide are improved by using compatilizer.
The example that can be used for the compatilizer in the conductive resin composition of the present invention comprises and is described among open Hei 8-48869 of unexamined Japanese Patent and the Hei 9-124926 those.All conventional compatilizers that are described in these patent documentations all can be used among the present invention, and these compatilizers can use separately or coupling.
In the middle of various conventional compatilizers, especially preferred toxilic acid, maleic anhydride and citric acid.
The polymeric amide that the consumption of compatilizer in conductive resin composition of the present invention contains in resin combination of the present invention with respect to 100 weight parts and the total amount of polyphenylene oxide are preferably the 0.1-20 weight part, more preferably the 0.1-10 weight part.
This extra component in the present invention, except the said components of conductive resin composition, needs, extra component can be joined in the conductive resin composition, as long as can influence the excellent properties of resin combination of the present invention sharply.
The additional component that below elaboration is used for the present invention.
The example of additional component comprises thermoplastic resin, as polyester and polyolefine; Mineral filler (as talcum, kaolin, xonotlite, wollastonite, titanium oxide, potassium titanate and glass fibre); Strengthen the conventional adhesion modifier of the affinity between mineral filler and the resin; Fire retardant (as halogenated resin, polysiloxane fire retardant, magnesium hydroxide, aluminium hydroxide, organophosphorus compounds, ammonium polyphosphate and red phosphorus); Have and reduce the fluorine resin that fire-retardant particle descends; Softening agent (as oil, low-molecular-weight polyolefin, polyoxyethylene glycol and fatty acid ester); Auxiliary flame retardant is as ANTIMONY TRIOXIDE SB 203 99.8 PCT; Carbon black as pigment; Give the reagent of electroconductibility, as carbon fiber, carbon nanotube and carbon nanofiber; Static inhibitor; Various superoxide; Zinc oxide; Zinc sulphide; Antioxidant; UV light absorber; And photostabilizer.
In the present invention, the amount of adding the additional component in the resin combination to is no more than 100 weight parts with respect to the gross weight of 100 weight parts of polyamide and polyphenylene oxide.
As the specific examples of the processing unit (plant) that can be used for preparing conductive resin composition of the present invention, can mention single screw extrusion machine, twin screw extruder, roller, kneader, Brabender Plastograph and Banbury mixing machine.In these devices, twin screw extruder preferably, especially preferred is the twin screw extruder that is provided with first inlet and at least one second inlet, described inlet lays respectively at the upstream portion and the downstream part of this forcing machine.
Be not particularly limited about the melt kneading temperature that is used to prepare resin combination.Usually, the optimal temperature that obtains required resin combination is 240-360 ℃.
Preferred embodiment as the method for preparing conductive resin composition of the present invention, can mention the method for using twin screw extruder with first inlet and second inlet, described inlet is separately positioned on the upstream portion and the downstream part of this forcing machine, wherein impact modifying agent and polyphenylene oxide are infeeded the forcing machine from first inlet, impact modifying agent and polyphenylene oxide are in the same place in the upstream portion melt kneading of this forcing machine, simultaneously conductive agglomerate is infeeded the forcing machine from second inlet, make impact modifying agent thus, polyphenylene oxide is in the same place in the downstream part of this forcing machine melt kneading with conductive agglomerate.
In another aspect of this invention, the method that provides a kind of preparation to comprise the conductive resin composition of polymeric amide, polyphenylene oxide and graphitized carbon black, this method comprises the following steps:
(1) provide the conductive agglomerate that comprises polymeric amide and graphitized carbon black, wherein said graphitized carbon black with the major axis be the form of at least a agglomerated particle of 20-100 μ m exist and
(2) described conductive agglomerate is added in the fused polyphenylene oxide.
In aforesaid method, preferably, when adding in the fused polyphenylene oxide, adds the polymeric amide with additional quantity conductive agglomerate.
So the conductive resin composition that obtains can be molded as various moulded products as injection moulding by various ordinary methods.
The example of various moulded products comprises electric or electron device part, IC plate for example, the shelf of various magnetic disc players and chest; The parts of office automated machine are as various computers and peripherals thereof; Mechanical part; Motorcycle part is as nose cone; The external component of automobile, as baffle plate, door skin, preceding coaming plate, back plate, jam plate and the anti-plate of back insurance, back door decoration, emblem mark decoration, fuel feed mouth plate, interior lining panel, outer door handle, door mirror housing, the engine shield air suction inlet, collision bumper, bumper guard, roof-rack, the roof-rack leg, post, post cover, axle cap, various aerodynamic features (as director), various automobiles are with moulding drilling and sign; And the automobile internal part, as dashboard, cabinet control deck and ornament.
In the middle of the above-mentioned moulded product of enumerating, conductive resin composition of the present invention is suitable for producing automobile exterior panel, automobile baffle especially, and the latter will carry out electrostatic coating.
When conductive resin composition of the present invention is used to produce automobile exterior panel, during as automobile baffle, the angle of the outward appearance of the outside plate after electrostatic coating, preferably, the mean value that uses the surfaceness that Scanning Probe Microscopy measures is 0.05-1 μ m (wherein surfaceness is defined as the poor of the maximum height of automobile exterior panel surface and minimum constructive height).
Particularly, in the present invention, the surfaceness of automobile exterior panel can be by following mensuration.From automobile exterior panel, choose eight different surperficial positions.About in eight positions choosing each, observe the area of 20 μ m * 20 μ m down at Scanning Probe Microscopy (for example SPA300HV, by Seiko Instruments Inc., Japan makes also and sells).The image at eight positions being obtained is carried out three-dimensional proofread and correct, obtain to show the surface profile at eight positions.Use gained through the gauged image of three-dimensional, measure eight surperficial positions each maximum height and minimum low poor (wherein each maximum height and minimum constructive height are definite (for example in Fig. 5 (c) by predetermined baseline, described baseline is corresponding to horizontal line)), calculate the mean value of eight differences of gained then.
Implement best mode of the present invention
Hereinafter, describe the present invention in detail with reference to the following examples and Comparative Examples, described embodiment and Comparative Examples should not thought limitation of the scope of the invention.
(raw material)
Among below the embodiment and Comparative Examples, use following raw materials according.
(1) polymeric amide (being abbreviated as " PA " hereinafter)
(1-1) polyamide 6 (being abbreviated as " PA6 " hereinafter)
Trade(brand)name: UBE Nylon 6 SF1013A (by UBE INDUSTRIES, LTD., Japan makes and sells)
(1-2) polyamide 66 (being abbreviated as " PA66 " hereinafter)
Number-average molecular weight=14,000
The concentration of terminal amino group=30 milliequivalent/kilograms
The concentration of terminal carboxyl(group)=100 milliequivalent/kilograms
(2) graphitized carbon black
Trade(brand)name: Ketjenblack EC-600JD (by Ketjenblack InternationalCorporation, Japan makes and sells) (being abbreviated as " KB " hereinafter)
(3) polyphenylene oxide (being abbreviated as " PPE " hereinafter)
Poly-(2,6-dimethyl-1,4-phenylene ether) (by Asahi Kasei Kabushiki Kaisha, Japan makes and sells)
(3-1) polyphenylene oxide (being abbreviated as " PPE-1 " hereinafter)
Reduced viscosity: 0.52dl/g (using the 0.5g/dl chloroformic solution of PPE-1 to measure down) at 30 ℃
(3-2) polyphenylene oxide (being abbreviated as " PPE-2 " hereinafter)
Reduced viscosity: 0.42dl/g (using the 0.5g/dl chloroformic solution of PPE-2 to measure down) at 30 ℃
(3-3) with maleic anhydride modified polyphenylene oxide (being abbreviated as " M-PPE " hereinafter)
M-PPE is by joining 0.1 weight part radical initiator and 1.5 weight part maleic anhydrides among the 100 weight part PPE-2, and (ZSK-5 is by KruppWerner ﹠amp at twin screw extruder then; Pfleiderer GmbH, Germany makes also and sells) melt kneading and preparing under 320 ℃ cylinder temperature.
The amount that is incorporated into the maleic anhydride in the Noryl is 0.5 weight % based on the weight of Noryl
(4) polystyrene (being abbreviated as " PS " hereinafter)
Trade(brand)name: A﹠amp; M polystyrene 685 is (by A﹠amp; M vinylbenzene Co., Ltd., Japan makes and sells)
(5) segmented copolymer
(5-1) polystyrene/hydrogenated butadiene polymer/polystyrene block copolymer (being abbreviated as " SEBS-1 " hereinafter)
Number-average molecular weight=246,000
Total styrene content=33%
(5-2) polystyrene/hydrogenated butadiene polymer/polystyrene block copolymer (being abbreviated as " SEBS-2 " hereinafter)
Number-average molecular weight=77,000
Total styrene content=67%
(6) compatilizer
(6-1) citric acid (by Wako Pure Chemical Industries, Ltd., also sale of Japan's manufacturing)
(6-2) maleic anhydride (by Mitsubishi Chemical Corporation, Japan makes and sells)
(measuring method)
To set forth the method for quantity (being called " quantity of agglomerated particle " hereinafter), surfaceness, shock resistance, thermotolerance, electroconductibility (surface resistivity and volume resistivity), conduction coating property and the heat distortion amount of the agglomerated particle of measuring graphitized carbon black below.
(1) quantity of agglomerated particle
The pill (being the master batch pill) of master batch is cut by the slicing machine that the glass blade is housed, obtain to have the cross section of minute surface thus.Under opticmicroscope (for example " PME3 ", by Olympus Optical Co.Ltd., Japan makes and sells), observe from the light of cross section reflection, and cross section is taken Photomicrograph with * 50 magnifications.3mm at this Photomicrograph 2Count the quantity of the agglomerated particle of the major axis that has 20-100 μ m independently of one another in the successive zone by visual observations.Also count the quantity of the agglomerated particle that major axis is 30-100 μ m (if having words) and major axis in the same manner and be the quantity of 100 μ m or bigger agglomerated particle (if the words that have).Because the master batch pill has cylindrical shape, pill along the cutting of direction longitudinally that is basically perpendicular to this pill, is obtained cross section thus, and the cross section that gets of observation post.Observe three cross sections that obtain by different pills respectively, and determine the quantity of agglomerated particle with the mean value of three count values obtaining from these three cross sections.What also confirm is, the quantity of the agglomerated particle between three cross sections does not almost have difference.
(2) mean value of the surfaceness of master batch pill (Ra)
The center line average roughness of master batch pill (Ra) passes through to use surfaceness meter (Surfcom 579 A according to JIS B0601 (1994), by Tokyo Seimitsu Co., Ltd., Japan makes also and sells) measure, wherein to the plat part position-finding Ra value of pill.Center line average roughness uses the canonical measure head (to be made tip radius (R) by diamond: 5 μ m) measure as the contact finger.Measuring therein that the rate travel of contact finger is 0.3mm/sec, measuring length is that 2.5mm and intercepting value are to carry out under the condition of 0.8mm.Measurement is carried out at 10 flat positions of pill, and calculates the mean value of these ten observed values.
(3) Izod shock strength and load deflection temperature
The pill of resin combination is by using mould machine (IS-80EPN mould machine, by TOSHIBACORPORATION, Japan makes also and sells) therein cylinder temperature be that 280 ℃ and die temperature are molding under 80 ℃ the condition, obtain the test bar that thickness is respectively 3.2mm and 6.4mm thus.Measure the breach Izod shock strength of thick 3.2mm test bar according to ASTM D256.In addition, under the 1.82Mpa load, measure the load deflection temperature (i.e. heat deflection temperature (HDT) under high loading (HDT)) of the test bar of thick 6.4mm according to ASTM D648.
(4) surface resistivity and volume resistivity-1
The pill of resin combination is passed through to use mould machine (IS-80EPN mould machine, by TOSHIBACORPORATION, Japan makes also and sells) therein cylinder temperature be that 280 ℃ and die temperature are to be molded as test board (size: 100 * 50 * 2.5mm) under 80 ℃ the condition.The surface resistivity of the test board of gained and volume resistivity-1 measured down in 500V by using high resistivity meter (MCP-HT450, by MITSUBISHI CHEMICAL CORPORATION, Japan makes and sells).Five different tests plates (preparing in the above described manner separately) are measured, obtained each surface resistivity value and volume resistivity-1 value represented by the mean value of five observed values.
(5) volume resistivity-2
The method of describing among the embodiment of pill according to unexamined Japanese Patent Application Publication Hei 8-48869 with resin combination is used mould machine (IS-80EPN mould machine, by TOSHIBACORPORATION, Japan makes also and sells) therein cylinder temperature be that 280 ℃ and die temperature are to be molded as described dumb-bell shape bar under ISO294 under 80 ℃ the condition.The dumb-bell shape bar that so obtains is used as sample.The fracture two ends of sample are that 10nm * 4mm and length are about 70mm and the part that section is all arranged at two ends to obtain even cross section.About the concrete grammar of the end of the sample that fractures, the embodiment of unexamined Japanese Patent Application Publication Hei 8-48869 does not describe.Therefore, the end of sample is disconnected by following method, in the method, the sample that utilizes slicing machine to cut from both sides is immersed temperature for reaching 1 hour-75-70 ℃ the dry ice/methanol mixture, and the gained sample is fractureed two cracked parts.With argentiferous coating composition (Silbest, by NISSHIN EM CO., LTD., also sale of Japan's manufacturing) is applied over gained fracture end partly, and by using the digital insulation test device wherein apply 250V voltage (DG 525, SANWA ELECTRICINSTRUMENT CO., LTD., Japan) measure the volume resistivity between the two ends that are coated with silver.Five various sample (preparing in the same manner described above separately) are measured, obtained volume resistivity-2 value of representing by the mean value of five observed values.
(6) surfaceness of automobile baffle
Required mould by using automobile baffle cylinder temperature therein is that 310 ℃ and die temperature are to produce automobile baffle under 110 the condition.Measure the surfaceness of the automobile baffle of being produced by using Scanning Probe Microscopy (SPA300HV, by Seiko Instruments Inc., Japan makes and sells).Particularly, eight different surperficial positions of picked at random from automobile baffle (area separately is 20 μ m * 20 μ m), and under Scanning Probe Microscopy, observe.The gained image at eight surperficial positions is carried out three-dimensional proofread and correct, obtain to show the image (shown in Fig. 5 (c)) of the surface profile at these eight surperficial positions, and in these eight surperficial positions each is measured the poor of maximum height and minimum constructive height.The mean value that gained is got eight differences is defined as the surfaceness of automobile baffle.Use SI-DF20 (by Seiko Instruments Inc., Japan makes also and sells) as microscopical cantilever, and atmosphere is that air, temperature are that 25 ℃, sweep rate are that 0.5Hz, detecting pattern are that dynamic force pattern (DFM) and amplitude are to observe under the condition of 0.8V therein.
(7) electrostatic coating performance
To carry out the electrostatic coating of automobile by the automobile baffle that the method for describing in (6) is produced.Estimate the appearance (glossiness, the transparency and color) of the property used and the formed coating of electrostatic coating by visual inspection.
(8) heat distortion amount
To be connected with the vehicle body of automobile by the automobile baffle that the method for describing in (6) is produced.Measure gap between automobile baffle and the door and the difference gap between the different sites of automobile baffle by visual inspection, estimate the heat distortion amount that during electrostatic coating, causes thus by the thermal history that baffle plate experienced
Comparative Examples 1
By use have one at its upstream part inlet and at the twin screw extruder of another inlet of its downstream part (ZSK-25 is by Krupp Werner ﹠amp; Pfleiderer GmbH, Germany makes and sells), with 92 weight parts of polyamide 6 and 8 weight part graphitized carbon blacks under 270 ℃ the cylinder temperature according to the method for describing among the embodiment at unexamined Japanese Patent Application Publication Hei 2-201811 melt kneading equably, make the conductive agglomerate that is the pill form (master batch pill) thus with surface luster.In used forcing machine, the design of screw rod should make and make the surfaceness (mean value of center line average roughness (Ra) value) of gained pill be lower than 0.3 μ m by the generation high shear force.About gained master batch pill (being abbreviated as " PA/KB-MB1 " hereinafter), measure the quantity of the agglomerated particle that wherein contains and the center line average roughness (Ra) (seeing Fig. 3 (a) and 3 (b)) at flat position thereof.
In addition, by using the master batch that is obtained, prepare resin combination according to the method for in the embodiment of unexamined Japanese Patent Application Publication Hei2-201811, describing.Particularly, the pill that under 300 cylinder temperature, prepares the resin combination that comprises polyamide 6, polyphenylene oxide and graphitized carbon black.The pill of the resin combination that obtained is molded as sample, uses this sample to measure the surface resistivity and the volume resistivity-1 of resin combination.The performance of resin combination and the prescription of resin combination are illustrated in the table 1 together.
Embodiment 1
To prepare the conductive agglomerate that comprises polyamide 6 and graphitized carbon black (polyamide 6/graphitized carbon black master batch) (master batch pill) of the form that is pill with low surface gloss with Comparative Examples 1 essentially identical mode, but (ZSK-25 is by Krupp Werner ﹠amp to change twin screw extruder; Pfleiderer GmbH, Germany makes also and sells) design of the screw rod of (being used for melt kneading 92 weight parts of polyamide 6 and 8 weight part graphitized carbon blacks under 270 ℃ cylinder temperature).Particularly, in the preparation master batch, control melt kneading condition (being screw speed, rate of extrusion etc.) is 0.3 μ m or bigger master batch pill (it is gentle that those conditions that adopted in the melt kneading condition that is adopted among the embodiment 1 and the Comparative Examples 1 are compared) to obtain surfaceness (mean value of center line average roughness (Ra) value).About the master batch pill (being abbreviated as " PA/KB-MB2 " hereinafter) that is obtained, measure the quantity of the agglomerated particle that wherein contains and the center line average roughness (Ra) (seeing Fig. 4 (a), 4 (b) and 4 (c)) at flat position thereof.
In addition, by using the conductive agglomerate obtained, to prepare the pill of the resin combination that comprises polyamide 6, polyphenylene oxide and graphitized carbon black with Comparative Examples 1 essentially identical mode.The pill of the resin combination that obtained is molded as sample, uses this sample to measure the surface resistivity and the volume resistivity-1 of resin combination.The performance of resin combination and the prescription of resin combination are illustrated in the table 1 together.
Table 1
The feed entrance of forcing machine Component Unit Comparative Examples 1 Embodiment 1
The prescription of resin combination
The inlet of forcing machine upstream portion PPE-1 Weight part 38 38
Citric acid 1 1
PS 12 12
PA6 6.5 6.5
PA/KB-MB1 37.5
PA/KB-MB2 37.5
Measurement result (about among master batch PA/KB-MB1 and the PA/KB-MB2 each)
The quantity of agglomerated particle (major axis: 20-100 μ m) - 0 16
The quantity of agglomerated particle (major axis: 30-100 μ m) - 0 9
The quantity of agglomerated particle (major axis:＞100 μ m) - 0 0
Surfaceness (mean value of center line average roughness (Ra) value) μm 0.22 1.04
Measurement result (about among resin combination PA6/PPE/KB-MB1 and the PA6/PPE/KB-MB2 each)
Surface resistivity Ω 4.5×10 9 3.6×10 7
Volume resistivity-1 Ω·cm 3.7×10 10 3.0×10 7
In Comparative Examples 1, in the mode identical but use the raw material described in the patent document to prepare master batch with a embodiment among the unexamined Japanese Patent Application Publication Hei 2-201811.Particularly, in Comparative Examples 1,, extrude the master batch (master batch pill) that preparation is the pill form subsequently by even melt kneading graphitized carbon black and polymeric amide.About prepared master batch, do not observe major axis and be the agglomerated particle of 20 μ m or bigger graphitized carbon black.In addition, by using prepared master batch pill, under the condition of describing among the embodiment at unexamined Japanese Patent Application Publication Hei 2-201811, prepare resin combination.Particularly, polyphenylene oxide, citric acid, polystyrene and polyamide 6 are extruded with master batch, obtained to be the resin combination of pill form thus by using twin screw extruder.
On the other hand, the master batch pill of preparation contains 16 sooty agglomerated particles (having 20 μ m or bigger major axis independently of one another) in the Comparative Examples 1, and the existence of these agglomerated particles is one of characteristic features of the present invention.In addition, prepared master batch pill and polyphenylene oxide, citric acid, polystyrene and polyamide 6 are extruded together in the mode identical with Comparative Examples 1 by using twin screw extruder, acquisition is the resin combination of pill form thus.
The resin combination that obtains among Comparative Examples 1 and the embodiment 1 is carried out injection moulding respectively, obtain sample thus, and use the sample that obtains to estimate the surface resistivity and the volume resistivity-1 of every kind of resin combination.As shown in table 1, the surface resistivity of the resin combination among the embodiment 1 and volume resistivity-1 is respectively than low two orders of magnitude of the resin combination in the Comparative Examples 1 (it is corresponding to an embodiment among the unexamined Japanese Patent Application Publication Hei 2-201811) and three orders of magnitude.By these results as seen, the resin combination of embodiment 1 demonstrates excellent electroconductibility.
Therefore, it is evident that the electroconductibility that comprises the resin combination of polymeric amide, polyphenylene oxide and graphitized carbon black can be significantly improved as the master batch of the present invention that the form of at least a agglomerated particle of 20-100 μ m exists with major axis by using graphitized carbon black wherein.
Comparative Examples 2
The method of describing among the embodiment according to unexamined Japanese Patent Application Publication Hei 2-201811, even melt kneading 90 weight parts of polyamide 66 and 10 weight part graphitized carbon blacks under 270 ℃ cylinder temperature make the conductive agglomerate that is the pill form (master batch pill) with surface luster thus.In used forcing machine, the design of screw rod should make and make the surfaceness (mean value of center line average roughness (Ra) value) of gained pill be lower than 0.3 μ m by the generation high shear force.About gained master batch pill (being abbreviated as " PA/KB-MB3 " hereinafter), measure the quantity of the agglomerated particle that wherein contains and the center line average roughness (Ra) at flat position thereof.
In addition, use gained master batch pill, (ZSK-25 is by Krupp Werner ﹠amp by using the twin screw extruder that partly has another inlet that enters the mouth and have in its downstream part at its upstream; Pfleiderer GmbH, Germany makes also and sells) preparation is the resin combination of pill form.Particularly, in forcing machine under 300 ℃ cylinder temperature with conductive agglomerate (PA/KB-MB3) with polyphenylene oxide, segmented copolymer and polyamide 66 melt kneading, wherein polyphenylene oxide and the segmented copolymer inlet from the upstream portion that is arranged on forcing machine is infeeded the forcing machine, and polyamide 66 and conductive agglomerate (PA/KB-MB3) inlet from the downstream part that is arranged on forcing machine is infeeded the forcing machine, obtain to comprise polyamide 66, the resin combination of polyphenylene oxide and graphitized carbon black thus.The gained resin combination is molded as sample, and uses volume resistivity-2, load deflection temperature and the Izod shock strength of this sample evaluating resin composition.The prescription of result and resin combination is shown in Table 2 together.
Comparative Examples 3
(ZSK-25 is by Krupp Werner ﹠amp to use the twin screw extruder that partly has two inlets that enter the mouth and have in its downstream part at its upstream; Pfleiderer GmbH, Germany makes also and sells) (about two inlets of the downstream part that is arranged on forcing machine, first and second inlets as observe along the upstream direction downstream of forcing machine is called " first downstream side inlet " and " second downstream side inlet " respectively) prepare resin combination.According to the method for describing among the unexamined Japanese Patent Application Publication Hei 8-48869, under 300 ℃ cylinder temperature with polyphenylene oxide, segmented copolymer, polyamide 66 and graphitized carbon black be melt kneading together, wherein polyphenylene oxide and the segmented copolymer inlet from the forcing machine upstream portion is infeeded the forcing machine, and polyamide 66 is infeeded the forcing machine from first downstream side inlet, make polyphenylene oxide and polymeric amide compatibilized thus, infeed graphitized carbon black from second downstream side inlet simultaneously, make the resin combination that is the pill form thus, said composition comprises polyamide 66, polyphenylene oxide and graphitized carbon black.The resin combination that gained is the pill form is molded as sample, and uses this sample to measure the volume resistivity of resin combination-2, load deflection temperature and Izod shock strength in the above described manner.The prescription of result and resin combination is shown in Table 2 together.
Comparative Examples 4
Prepare resin combination by the method for describing in the claim 9 of unexamined Japanese Patent Application Publication Hei 8-48869.Particularly, to prepare resin combination, still use master batch PA/KB-MB3 to replace graphitized carbon black, and master batch is infeeded the forcing machine from second downstream side inlet with the amount shown in the table 2 with Comparative Examples 3 essentially identical modes.The performance of resin combination and prescription are shown in Table 2 together.
Embodiment 2-4
In embodiment 2-4 in each, to prepare the conductive agglomerate that is the pill form (master batch pill), still change the design (being used for melt kneading 90 weight parts of polyamide 6 and 10 weight part graphitized carbon blacks under 270 ℃ cylinder temperature) of the screw rod of twin screw extruder with low surface gloss with Comparative Examples 2 essentially identical modes.Particularly, in the preparation master batch, control melt kneading condition (screw speed, rate of extrusion etc.) is 0.3 μ m or bigger master batch pill (it is gentle that the condition that is adopted in the melt kneading condition of each employing among the embodiment 2-4 and the Comparative Examples 2 is compared) to obtain surfaceness (mean value of center line average roughness (Ra) value).(master batch of preparation is called " PA/KB-MB4 ", " PA/KB-MB5 " and " PA/KB-MB6 " respectively among the embodiment 2,3 and 4).About gained master batch pill, measure the quantity of the agglomerated particle that wherein contains and the center line average roughness (Ra) at flat position thereof.
In embodiment 2-4,, still use the conductive agglomerate that obtains above according to the prescription shown in the following table 2 to prepare each resin combination with Comparative Examples 2 essentially identical modes.The performance of resin combination and prescription are shown in Table 2 together.
Embodiment 5
To prepare resin combination, infeed the forcing machine but replace graphitized carbon black to enter the mouth from second downstream side master batch PA/KB-MB5 with the amount shown in the table 2 with Comparative Examples 3 essentially identical modes.The performance of resin combination and prescription are shown in Table 2 together.
Table 2
The feed entrance of forcing machine The component of resin combination Unit Comparative Examples 2 Comparative Examples 3 Comparative Examples 4 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5
The prescription of resin combination
Be arranged on the inlet of forcing machine upstream portion PPE-1 Weight part 20 20 20 20 20 20 20
M-PPE 14 14 14 14 14 14 14
SEBS-1 8.5 8.5 8.5 8.5 8.5 8.5 8.5
SEBS-2 2.5 2.5 2.5 2.5 2.5 2.5 2.5
First downstream side inlet PA66 36 53 36 36 36 36 36
PA/KB-MB3 19
PA/KB-MB4 19
PA/KB-MB5 19
PA/KB-MB6 19
Second downstream side inlet PA/KB-MB3 19
PA/KB-MB5 19
KB 1.9
Measuring result (about among master batch PA/KB-MB3, PA/KB-MB4, PA/KB-MB5 and the PA/KB-MB6 each)
The quantity of agglomerated particle (major axis: 20-100 μ m) - 0 - 0 19 4 44 4
Surfaceness (center line average roughness (Ra) value mean value) μm 0.25 - 0.25 1.18 0.49 1.6 0.49
Measuring result is (about the resin combination that makes (PA66/PPE/KB ' among the s each)
Volume resistivity-2 Ω·cm 4×10 6 5×10 4 7×10 6 8×10 4 7×10 4 8×10 4 7×10 4
High loading HDT (1.82MPa) ℃ 125 124 125 129 128 130 129
The Izod shock strength J/m 210 180 210 210 220 185 205
The method that adopts in the Comparative Examples 3 identical with disclosed method among the unexamined Japanese Patent Application Publication Hei 8-48869 (see claim 7 and 8 and paragraph [0008], [0010] and [0011]).Particularly, step by being included in the polyphenylether/polyamide base resin mixture that forms compatibilized in have the side opening for feed forcing machine of (that is, being arranged on the inlet of downstream part) and with graphitized carbon black be melt form and temperature method and prepare resin combination for the polyphenylether/polyamide base resin mixture blended step of at least 300 ℃ compatibilized.
On the other hand, in in embodiment 2-4 each, by comprising that preparation comprises polymeric amide and being that the step of conductive agglomerate of the graphitized carbon black that exists of the form of the agglomerated particle (existence of these agglomerated particles is one of characteristic features of the present invention) of 20-100 μ m and the method for simultaneously gained conductive agglomerate and polymeric amide being added to the step in the fusion polyphenylene oxide prepare resin combination with the major axis.
Each resin combination that obtains among Comparative Examples 3 and the embodiment 2-4 is carried out injection moulding respectively, obtain sample thus, and use the gained sample to measure the volume resistivity-2 of each resin combination, load deflection temperature (high loading HDT) and Izod shock strength.Found that, the volume resistivity-2 that each resin combination among the embodiment 2-4 demonstrates is different from the resin combination (it is by the method preparation corresponding to the method for describing among the unexamined Japanese Patent Application Publication Hei 8-48869) of Comparative Examples 3, but the resin combination that load deflection temperature that demonstrates and Izod shock strength are higher than Comparative Examples 3.Therefore, it is evident that the resin combination for preparing among the embodiment of the invention 2-4 has excellent resistance to heat distorsion and shock resistance.
Therefore, by the master batch of the present invention that uses graphitized carbon black wherein to exist with the form of agglomerated particle, the load deflection temperature (or high loading HDT) that comprises the resin combination of polymeric amide, polyphenylene oxide and graphitized carbon black can be improved, and can obtain high conductivity when keeping shock resistance.
In addition, there be not a kind of containing to be the graphitized carbon black that major axis is the form of 100 μ m or bigger agglomerated particle in the master batch that makes among the embodiment 2-5.In addition, measure the melt flow (MFR: measure according to ASTM D 1238, promptly under the 5kg load, descend per 10 minutes melt flow) of each resin combination that makes among the embodiment 3 and 5 in 280 ℃.Found that the MFR of embodiment 3 and 5 resin combination is respectively 24g/10min and 19g/10min.It is evident that by top, the conductive resin composition that demonstrates excellent electroconductibility, shock resistance, resistance to heat distorsion and fluidity of molten can obtain by the method that comprises the following steps: (1) provides the conductive agglomerate that comprises polymeric amide and graphitized carbon black, wherein said graphitized carbon black is that the form of at least a agglomerated particle of 20-100 μ m exists and add described conductive agglomerate in the fused polyphenylene oxide to (2) with the major axis.
Comparative Examples 5
By the conductive resin composition that makes in the molding Comparative Examples 2 car bumper plate that steams next life, and the gained baffle plate carried out the automobile coating processes, thus with the baffle plate electrostatic coating.Found that the electrostatic coating performance of gained baffle plate is also unsatisfactory.In addition, the heat distortion amount of baffle plate is bigger, therefore can not drop into practical application.Particularly, the gap between automobile baffle and the door is bigger, and the difference gap between the different sites of baffle plate is also bigger.
Comparative Examples 6
By the conductive resin composition that makes in the molding Comparative Examples 3 car bumper plate that steams next life, and the gained baffle plate carried out the automobile coating processes, thus with the baffle plate electrostatic coating.Found that, bigger through the heat distortion amount of the baffle plate of electrostatic coating, therefore can not drop into practical application.Particularly, the gap between automobile baffle and the door is bigger, and the difference gap between the different sites of baffle plate is also bigger.
Embodiment 6
By the conductive resin composition that makes among the molding embodiment 2 car bumper plate that steams next life, and the gained baffle plate carried out the automobile coating processes, thus with the baffle plate electrostatic coating.Use the baffle plate through electrostatic coating of the resin combination production of embodiment 2 only to demonstrate considerably less heat distortion amount (that is, the gap between automobile baffle and the door is less, and the gap is even), and the electrostatic coating performance is satisfactory.In addition, the baffle plate through electrostatic coating has gratifying shock resistance.Therefore, the baffle plate through electrostatic coating can advantageously drop into practical application.The surfaceness of baffle plate is 0.65 μ m, and baffle plate even also have excellent outward appearance (seeing Fig. 5 (a), 5 (b) and 5 (c)) after electrostatic coating.
Industrial applicability
The conductive agglomerate of the application of the invention, can obtain not only have excellent heat resistance, and (wherein said " excellent electric conductivity " refers to the electric conductivity of the conventional material that carries out electrostatic coating quite or than its superior conduction life to demonstrate simultaneously the conductive resin composition of excellent electric conductivity and impact resistance, that is, make the electric conductivity of the enough electrostatic coatings of material). This conductive resin composition can be widely used in various fields, such as the Electrical and Electronic parts, and the parts of office automated machine, automobile component and other mechanical part. Especially, conductive resin composition of the present invention is very favorable as the material of producing automobile exterior panel (for example automobile baffle), because when above-mentioned resin combination is molded as massive article (such as automobile exterior panel, door-plate etc.) and then the gained mechanograph is carried out electrostatic coating, can obtain excellent mechanograph, wherein thermal deformation not only can not occur in this mechanograph, nor may reduce impact resistance, and form excellent coating owing to the superior electrical conductivity of this resin combination at described mechanograph.

Claims (22)

1. conductive agglomerate that comprises polymeric amide and graphitized carbon black, wherein said graphitized carbon black is that the form of at least a agglomerated particle of 20-100 μ m exists with the major axis, wherein under opticmicroscope to 3mm 2The quantity of the observed described at least a agglomerated particle in successive zone is 1-100.
2. according to the conductive agglomerate of claim 1, the quantity of wherein said at least a agglomerated particle is 1-50.
3. according to the conductive agglomerate of claim 1, the quantity of wherein said at least a agglomerated particle is 2-40.
4. according to the conductive agglomerate of claim 1, the quantity of wherein said at least a agglomerated particle is 2-30.
5. according to each conductive agglomerate among the claim 1-4, the dibutyl phthalate of wherein said graphitized carbon black (DBP) oil number is 250ml/100g carbon black at least.
6. according to each conductive agglomerate among the claim 1-4, it is the form of pill.
7. according to the conductive agglomerate of claim 6, wherein the surfaceness of each pill is counted 0.3-2.0 μ m by the mean value of surfaceness (Ra) value, and described surface roughness value is measured at 10 different surfaces positions of each pill by the surfaceness meter.
8. according to the conductive agglomerate of claim 6, wherein the surfaceness of each pill is 0.4-1.5 μ m.
9. according to the conductive agglomerate of claim 7, wherein each described pill has cylindrical shape, and diameter is that 1.5-3.5mm and length are 2.0-3.5mm.
10. according to each conductive agglomerate among the claim 1-4, the amount of wherein said graphitized carbon black is 5-40 weight % based on the weight of master batch.
11. according to the conductive agglomerate of claim 10, the amount of wherein said graphitized carbon black is 6-10 weight % based on the weight of master batch.
12. according to each conductive agglomerate among the claim 1-11, the method production of this conductive agglomerate by comprising the steps:
(1) polymeric amide is infeeded in twin screw extruder or the kneader, makes described molten polyamide then, obtain the fused polymeric amide,
Wherein said twin screw extruder or kneader have at least one first inlet and at least one second inlet, and described at least one first inlet is observed the upstream that is arranged on described at least one second inlet by the direction of extruding of described forcing machine or kneader,
Wherein described polymeric amide is infeeded described forcing machine or kneader from described at least one first inlet; And
(2) with the polymeric amide of graphitized carbon black and additional quantity from described at least one second inlet of described forcing machine or kneader is added in molten polyamide described forcing machine or the kneader simultaneously, subsequently with gained mixture melt kneading, obtain conductive agglomerate.
13. a conductive resin composition that comprises polymeric amide, polyphenylene oxide and graphitized carbon black, it is by preparing each the conductive agglomerate and the molten polyamide kneading of polyphenylene oxide and the additional quantity of choosing wantonly among the claim 1-12.
14. according to the conductive resin composition of claim 13, wherein the amount of graphitized carbon black is the 0.2-5 weight part with respect to the total amount of each component except that this graphitized carbon black in this conductive resin composition of 100 weight parts.
15. one kind prepares and comprises polymeric amide, the method for the conductive resin composition of polyphenylene oxide and graphitized carbon black, and it comprises the following steps:
(1) provide among the claim 1-12 each conductive agglomerate and
(2) described conductive agglomerate is added in the fused polyphenylene oxide.
16. according to the method for claim 15, wherein in step (2), the polymeric amide of additional quantity is added in the fused polyphenylene oxide, adds conductive agglomerate simultaneously.
17. the purposes of conductive resin composition in producing automobile exterior panel according to claim 13 or 14.
18. injection-molded item that comprises the conductive resin composition of claim 13 or 14.
19. an automobile exterior panel, it comprises the conductive resin composition of claim 13 or 14.
20. according to the automobile exterior panel of claim 19, it is an automobile baffle.
21. according to the automobile exterior panel of claim 20, it is an injection-molded item.
22. according to the automobile exterior panel of claim 21, its surfaceness is counted 0.05-1 μ m by the difference of altitude between the lowermost portion on the highest part on automobile exterior panel surface and automobile exterior panel surface, wherein said height is observed under Scanning Probe Microscopy.
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