CN101161724B - Conductive resin composition and moulded body produced thereby - Google Patents
Conductive resin composition and moulded body produced thereby Download PDFInfo
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- CN101161724B CN101161724B CN2007101628395A CN200710162839A CN101161724B CN 101161724 B CN101161724 B CN 101161724B CN 2007101628395 A CN2007101628395 A CN 2007101628395A CN 200710162839 A CN200710162839 A CN 200710162839A CN 101161724 B CN101161724 B CN 101161724B
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Abstract
The present invention is to provide a conductive resin composition, which can offer shaped body with excellent surface smoothness. According to the invention, a conductive resin composition is provided, which comprises (a) thermoplastic polyamide 12 elastomer, (b) thermoplastic aromatic polyester or its derivant with 1 to 30 mass ratio relative to 100 mass composition, and (c) conductive carbon black with 1 to 25 mass ratio relative to 100 mass composition.
Description
Technical field
The present invention relates to contain the conductive resin composition of conductive carbon black and the formed body that forms by the said composition manufacturing.At length say, relate to be suitable for making Electrofax with various rollers, belt member or trolley part with the conductive resin composition of various flexible pipes, duct member etc. and the formed body that forms by the said composition manufacturing.
Background technology
The conductive resin composition that in polyamide resin, has mixed conductive carbon black uses (patent documentation 1) in Electrofax requires the various fields of flexibility and toughness, resistance to bend(ing) with various parts etc.; But; When mixing mixed carbon black in polyamide resin, disperse bad problem (patent documentation 2, patent documentation 3) when existing the forming process that generates charcoal gel etc. and cause.To address this problem is purpose, has proposed the whole bag of tricks.For example, mixed carbon black and specific multipolymer in polyamide resin have been proposed and the electroconductive resin soft solid materials (patent documentation 2) that forms.In addition, mixed polyamide and carbon black, carboxylic acid or its acid anhydrides have been proposed and the electroconductive resin soft solid materials (patent documentation 3) that forms.But the surface smoothness of the formed body that is formed by these conductive resin composition manufacturings can't be said fully.
Patent documentation 1: TOHKEMY 2001-350347
Patent documentation 2: International Publication the 2006/049139th pph
Patent documentation 3: TOHKEMY 2002-322366
Summary of the invention
Invent problem to be solved
The object of the present invention is to provide a kind of conductive resin composition, it can keep flexibility and tensile properties, and can obtain the excellent formed body of surface smoothness.The present invention also aims to provide the formed body of surface smoothness excellence.
The method that is used to deal with problems
The inventor furthers investigate, and the result finds, through adopting specific elastomerics as polyamide resin, it is mixed with thermoplasticity aromatic polyester or derivatives thereof, can access the excellent conductive resin composition of surface smoothness.Promptly; The present invention provides conductive resin composition, and it comprises: (a) polyamide thermoplastic 12 elastomericss, (b) are the thermoplasticity aromatic polyester or derivatives thereof of 1～30 mass parts with respect to 100 mass parts compsns and (c) are the conductive carbon black of 1～25 mass parts with respect to 100 mass parts compsns.
The present invention also provides the formed body that is formed by above-mentioned conductive resin composition manufacturing.
The effect of invention
According to the present invention, can access the conductive resin composition that the excellent formed body of surface smoothness can be provided.The formed body that is formed by compsn manufacturing of the present invention also has H.T., high flexibility, high resistance to bend(ing).
Embodiment
Composition (a) polyamide thermoplastic 12 elastomericss
In this manual, polyamide thermoplastic 12 elastomericss (PAE12) are meant that with polymeric amide 12 be hard segment, and aliphatic polyether is the segmented copolymer of soft chain segment.Polyamide thermoplastic 12 elastomericss are that thermal property (fusing point, heat resisting temperature etc.), mechanical properties (various intensity, hardness etc.) change according to these two unitary bonding states (ratio, kind etc.) as unitary polymeric amide 12 of fatty polyamide (common name nylon 12) and aliphatic poly ether unit bonded thermoplastic resin.
As operable polyamide thermoplastic 12 elastomericss among the present invention; Can enumerate out the material that for example obtains: will form omega-lauric lactam and the dicarboxylicacid of hard segment, the polyether glycol that forms soft chain segment is put in the reactive tank simultaneously through following method; Make it carry out the lactan ring-opening reaction; Generate midbody, then, under reduced pressure make this midbody and polyether glycol carry out the method for condensation reaction; The reaction of omega-lauric lactam and dicarboxylicacid is formed after the hard segment, add polyether glycol, the method for under high temperature, decompression, carrying out condensation reaction.Other method below also having combines through amido linkage with polyether units in order to make polyamide units, uses the terminal amino group modified polyether as polyethers, perhaps makes the method for the terminal amino group polycondensation of terminal carboxyl(group) modified polyether and polymeric amide.
Aforementioned dicarboxylicacid plays the effect of the molecular weight regulator of hard segment.As dicarboxylicacid, can enumerate out the alicyclic dicarboxylic acid, like aliphatic dicarboxylic acids such as succsinic acid, pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid, sebacic acid, undecane diacid, dodecanedioic acids; 1,4-cyclohexane dicarboxylic acid, dicyclohexyl-4,4-dicarboxylicacid etc.; Aromatic dicarboxylic acid; Like terephthalic acid, m-phthalic acid, phthalic acid, 2; 6-naphthalene dicarboxylic acids, 2; 7-naphthalene dicarboxylic acids, biphenoxyl ethane dicarboxylicacid, phenylbenzene-4,3-sulfo-m-phthalic acid an alkali metal salts such as 4 '-dicarboxylicacid, 3-sulfo-m-phthalic acid sodium, 3-sulfo-m-phthalic acid potassium etc.The above-mentioned material of enumerating can use separately, perhaps also can suitably make up two or more uses.Among these, preferably aliphatic dicarboxylic acid, aromatic dicarboxylic acid and 3-sulfo-m-phthalic acid an alkali metal salt, preferred especially material can be enumerated out hexanodioic acid, sebacic acid, terephthalic acid, m-phthalic acid, 3-sulfo-m-phthalic acid sodium.
The aliphatic polyether composition of soft chain segment can be enumerated out polyoxyethylene glycol, polyoxy (1; 2-or 1; 3-) the copolymerization glycol of Ucar 35, polyoxy tetramethylene glycol, polyoxy hexamethylene glycol, polyoxy oxyethane and polyoxy propylene oxide, and these two or more mixture etc.
It as the preferred Shore D hardness of operable polyamide thermoplastic 12 elastomericss 30～70 material.Shore D hardness is under the situation more than 30, can obtain good forming process property, and Shore D hardness is under the situation below 70, and the mechanical characteristics of formed body (particularly flexibility) is better.Further, be under 40～65 the situation, not only to have above-mentioned good shaping processability and mechanical characteristics, and can access formed body, when Shore D hardness so preferred with higher surface smoothness.In order to obtain the high formed body of surface smoothness, particularly preferably be Shore D hardness and be 40～60 material.Polyamide thermoplastic 12 elastomericss of required Shore D hardness can be modulated through suitably mixing polyamide thermoplastic with different Shore D hardness 12 elastomericss of Shore D hardness in 30～70 scopes.In addition; In this manual; Under employed polyamide thermoplastic 12 elastomericss are a kind of situation; Shore D hardness is meant the value of these polyamide thermoplastic 12 elastomeric Shore D hardness, is that Shore D hardness is meant the MV that is calculated by each polyamide thermoplastic 12 elastomeric Shore D hardness and blending ratio under the situation of multiple mixture at employed polyamide thermoplastic 12 elastomericss.
Spendable in the present invention polyamide thermoplastic 12 elastomericss are preferably crystalline, fusing point is 130～180 ℃ material.Fusing point is under the situation more than 130 ℃, can access good forming process property, and fusing point is under the situation below 180 ℃, and the mechanical characteristics of formed body (particularly flexibility) is better.In order to obtain the high formed body of surface smoothness, more preferably fusing point is 145～170 ℃, is preferably 145～160 ℃ especially.In addition, in this manual, fusing point can be measured through DSC (DSC).
Polyamide thermoplastic 12 elastomeric relative viscosities (0.5 quality % m-cresol solution, 25 ℃) preferred 1.1～3.0, more preferably 1.2～2.5.Relative viscosity is 1.1 when following, and thermotolerance, shaping processability variation surpass at 3.0 o'clock, and plasticity reduces.
As polyamide thermoplastic 12 elastomericss, can also use the material of making through known method, also can use EMS-CHEMIE (Japan), the commercially available article such as UBESTA XPA9044X2 that the ELY60 that Ltd. (strain) produces, the emerging product of space portion (strain) are produced.These elastomericss can be given formed body of the present invention especially with H.T., flexibility, resistance to bend(ing).In addition, the high dispersive that also helps electroconductibility charcoal in the compsn of the present invention.
Composition (a) is with respect to 100 mass parts conductive resin composition of the present invention, preferably with 50～98 mass parts, more preferably with 60～90 mass parts, further preferably mix with the amount of 65～80 mass parts.Under the situation more than 50 mass parts, the mechanical characteristics of formed body of the present invention particularly flexibility is good, so preferred.Under the situation below 98 mass parts, so the good dispersibility of electroconductibility charcoal is preferred.
Composition (b) thermoplasticity aromatic polyester or derivatives thereof
In the present invention, the affinity of thermoplasticity aromatic polyester or derivatives thereof and conductive carbon black is excellent, can improve the dispersiveness of conductive carbon black in the compsn of the present invention.Its result can improve the surface smoothness of the formed body that is formed by compsn manufacturing of the present invention.Further, when using with polyamide thermoplastic 12 elastomericss, even the amount of conductive carbon black is few, the electroconductibility that also can obtain to expect.
In the present invention, operable thermoplasticity aromatic polyester is meant that with aromatic dicarboxylic acids such as phthalic acid, m-phthalic acid, terephthalic acid, naphthalene dicarboxylic acids and aklylene glycol be that staple is carried out the material that polycondensation generates.Ordered state does not have special restriction, random polycondensate, block polycondensate, wire, branch, crosslinked etc. arbitrary all passable.
As operable thermoplasticity aromatic polyester among the present invention; Can enumerate out polyalkylene terephthalates homopolymer, multipolymer etc., for example polybutylene terephthalate, polybutylene terephthalate m-phthalic acid ester copolymer, polybutylene terephthalate ethylene glycol copolymer, polyethylene terephthalate, polyethylene terephthalate m-phthalic acid ester copolymer, polyethylene terephthalate ethylene glycol copolymer etc.
Can enumerate out as the verivate of operable thermoplasticity aromatic polyester among the present invention aliphatic polyether or aliphatic polyester are imported the multipolymer (aromatic polyester elastomerics) that above-mentioned aromatic polyester obtains; For example, polyalkylene terephthalates such as polybutylene terephthalate ethylene glycol copolymer, polyethylene terephthalate ethylene glycol copolymer multipolymer etc.
Wherein, preferred fusing point is that 150～240 ℃, Shore D hardness are 20～80 and intrinsicviscosity be 0.5～1.5 material of (100ml/g, orthomonochlorphenol solution, 25 ℃).Through it is used as composition (b), better with the affinity of conductive carbon black, can bring higher dispersiveness.In addition, the aromatic polyester verivate that contains aliphatic polyether also helps the improvement of mechanical characteristics, so preferred.
Especially preferably gather terephthalic acid butanediol ester or derivatives thereof.This is because it helps to improve the dispersiveness of the conductive carbon black in the compsn of the present invention most.
Operable thermoplasticity aromatic polyester can use the material of making according to known method among the present invention, also can use commercially available article.Can enumerate for example Polyplastics Co. as commercially available article, the Duranex 600FP that Ltd. produces.
With respect to 100 mass parts conductive resin composition of the present invention, composition (b) is with 1～30 mass parts, preferably with 5～25 mass parts, more preferably mix with the amount of 10～20 mass parts.The amount of composition (b) is when above-mentioned scope, and the dispersiveness of electroconductibility charcoal and the surface smoothness of formed body and flexibility are better.
In the present invention, the blending ratio of composition (a) and composition (b) be preferably more than 2 by quality ratio, more preferably greater than 3.During mass ratio less than 2, the inadequate situation of flexibility is arranged.
Composition (c) conductive carbon black
In the present invention, conductive carbon black is meant: in the carbon black since structure to be chain or branched microtexture flourishing and can in dispersion medium such as resin, form the material of effective galvanic circle.
Operable in the present invention conductive carbon black does not have special restriction, can suitably select according to purpose, for example can enumerate out, utilizes the oil oven method to make the raw oil incomplete combustion and the oil oven method carbon black that obtains; The Ketjen black that utilizes special oven process to make; With the acetylene gas is the acetylene black that raw material is made; The thermal black of making through the thermolysis of Sweet natural gas; These are carried out oxidation or reduction handle the material obtain etc.
Wherein, the preferred positive dibutylester of phthalic acid (DBP) oil number is the material of 100～500ml/100g.Oil number is 100ml/100g when above, gives the respond well of electroconductibility, and oil number is 500ml/100g when following, and the dispersiveness in resin is more excellent.More preferably the positive dibutylester of phthalic acid (DBP) oil number is the material of 100～300ml/100g.Oil number can more easily be made the compsn of good dispersibility when such scope, so preferred.The DBP oil number can use the DBP absorption apparatus to measure according to ASTMD2414.
Preferred average primary particle diameter is the material of 20～50nm.When this scope, existence can not obtain the possibility of good electrical conductivity to average primary particle diameter.Preferred specific surface area is 50～1000m
2The material of/g.The not enough 50m of specific surface area
2During/g, necessary electroconductibility when guaranteeing to use it for Electrofax with various rollers etc. must be mixed a large amount of conductive carbon blacks, also has the possibility of surface smoothness reduction.Specific surface area surpasses 1000m
2During/g, exist to be difficult to make conductive carbon black to be dispersed in the possibility in the formed body.
Operable in the present invention conductive carbon black also can use commercially available article.Can enumerate out the for example Ensaco250G of TIMCAL company production.
With respect to 100 mass parts conductive resin composition of the present invention, composition (c) is with 1～25 mass parts, preferred 5～25 mass parts, the more preferably amount mixing of 5～20 mass parts.The amount of composition (c) when above, is given the respond well of electroconductibility in particular for 5 mass parts when above-mentioned scope, be 25 mass parts when following, the good dispersibility of conductive carbon black in compsn, and desired mechanical characteristics is also good, so preferred.
Other blendable composition (composition arbitrarily)
Conductive resin composition of the present invention in the scope of not damaging its characteristic, can have no particular limits ground, according to suitably selection of purpose, mixed thermoplastic resin, conductive compositions, additive etc.
As thermoplastic resin; For example can enumerate out in addition thermoplastic elastomer of in addition polyamide resin of the multipolymer of polyvinyl resin, acrylic resin, Injecatable EVA Copolymer, propenoate or methacrylic ester and other compound, phenylethylene resin series, composition (a), polycarbonate resin, aliphatic polyester resin, polychlorostyrene ethenoid resin, composition (a), polyacetal resin, modified polyphenylene ether resin, polysulfone resin, polyetherimide resin, polyarylate resin, polyphenylene sulfide, liquid crystalline polymers, polyethersulfone resin, polyether-ether-ketone resin, polyimide resin, polyamide-imide resin etc.
As conductive compositions, for example can enumerate out, fiber is that metals such as carbon, zinc oxide, titanium oxide are static eliminator, titanate whisker, ionic conductive agent be the such low molion static eliminator of inorganic salt/organic salt or macroion static eliminator etc. for example.The preferred ion static eliminator, especially preferably low molion static eliminator or macroion static eliminator.
As the example of low molion static eliminator, can enumerate out basic metal, alkaline-earth metal, zinc or the ammonium salt of inorganic or the organic protonic acid of lower molecular weight.Be preferably LiClO in the middle of these
4, LiCF
3SO
3, NaClO
4, LiBF
4, NaBF
4, KBF
4, NaCF
3SO
3, KClO
4, KPF
6, KCF
3SO
3, KC
4F
9SO
3, Ca (ClO
4)
2, Ca (PF
6)
2, Mg (ClO
4)
2, Mg (CF
3SO
3)
2, Zn (ClO
4)
2, Zn (PF
6)
2Or Ca (CF
3SO
3)
2
But the macroion static eliminator is meant the polymkeric substance or the multipolymer of ionic conduction.As an example, can enumerate out low polyethoxylated propenoate or low polyethoxylated methacrylic ester, aromatic ring by vinylbenzene, poly(ether-urethene), polyethers urea, polyetheramides, polyether ester amides or the polyether ester etc. of low polyethoxylated.Wherein, preferred, polyethers acid amides or polyether ester amides.
But low molion static eliminator and macroion static eliminator also former state are coupled in the resin; But be easy to the aspect and consider from handling, preferably with in (A) organic polymer material, cooperate in advance aforementioned (B) macroion static eliminator and/or (C) form of the masterbatch that forms of low molion static eliminator use.
As the example of (A) organic polymer material, can enumerate out polyacrylic ester, Rohm tech inc, polyacrylonitrile, Z 150PH, PVA, polymeric amide, urethane, polyester etc.
As the material that in (A), cooperates (B), can obtain PELESTAT NC6321 (Sanyo changes into (strain) and produces).
As ionic conductive agent, be preferably the compsn that in (A), cooperates (B) and (C) obtain, particularly with (B) composition: contain (CH as polyether components
2-CH
2-O) and contain as the polyetheramides of the nylon 12 of polymeric amide composition or nylon 6 or polyether ester amides and (C) composition: NaClO
4It is suitable especially that combination is used.Polyetheramides that contains sodium perchlorate like this or polyether ester amides elastomerics can be used as Irgastat (registered trademark) P18 and Irgastat (registered trademark) P22 (being Ciba Specialty Chemicals Inc. production) and obtain.
As the present invention, when using the static eliminator of the such electronic conductivity of conductive carbon black, known have such shortcoming, that is, in the semi-conductivity zone, resistance value is big to the dependency that applies voltage.Among the present invention,, thereby can suppress this resistance value to applying the dependency of voltage through except that conductive carbon black, also add ionic conductive agent.
Such character is particularly suitable for being applied to and applies voltage and the purposes of the transfer belt of the charged roller of the laser printer that uses, duplicating machine, color laser printer, color copy machine about several kV.
For example; Use through the time by the charged roller of the conductive resin composition manufacturing of the present invention of (a)～(c) forms; During to the applying voltage and in the scope of 100V～1000V, change of charged roller, surface resistivity (surface resistivity:SR) changes more than 1.5, with respect to this sometimes; Use simultaneously in the situation of conductive resin composition of the present invention of ionic conductive agent, can the aforementioned variation that applies the SR in the voltage range be suppressed in 1.Through suppressing SR in this wise to applying the dependency of voltage, thereby prevent the generation of the image deflects that the charged bad grade of part on charged roller causes, can obtain high-resolution image.
Preferably with respect to 100 mass parts conductive resin composition of the present invention, cooperate 0.05～1.25 mass parts, preferred 0.1～1.0 mass parts, the more preferably above-mentioned ionic conductive agent of the amount of 0.25～0.75 mass parts.When the amount of above-mentioned ionic conductive agent is bigger than above-mentioned lower value, can suppress well the volume specific resistance (Volume resistivity:VR) of conductive resin composition of the present invention is set in semi-conductivity zone (10
5～10
12About Ω cm) time resistance value to applying the dependency of voltage.Through littler, can suppress the dependency of aforementioned electric resistance to humidity than higher limit.
When making charged roller or intermediate transfer belt through the conductive resin composition that uses ionic conductive agent simultaneously of the present invention; Preferably through suitable adjustment (c) conductive carbon black and (d) use level of ionic conductive agent, thereby the resistance value of charged roller or intermediate transfer belt is arranged on these purposes institutes preferred semi-conductivitys zone, is that SR is 10
9～10
12Ω/ and VR are 10
5～10
9Ω cm further preferably is made as the denary logarithm value (LogSR) of SR poor (Δ (LogSR-LogVR)) with the denary logarithm value (LogVR) of VR more than 2.SR is in above-mentioned scope the time, and the resolving power of the image that mirrors through charged roller or intermediate transfer belt becomes good, can obtain images with high image quality.In addition, Δ (LogSR-LogVR) value is 2 when above, can repeat the charged of charged roller or intermediate transfer belt rapidly and removes electricity, is printing continuously, can obtain preferable image when duplicating.Δ (LogSR-LogVR) value does not have the special upper limit, and from the rerum natura of electroconductive resin, it is difficult that difference surpasses 7, in the time of in this scope, can obtain good aforementioned effect.
When formed body of the present invention is charged roller or intermediate transfer belt; The not special restriction of these method for making; For example can make:, use annular die the mixing thing extrusion molding of gained through the resinous principle and the conductive material of the mixing base material of twin-screw mixer machine through following.In addition, also can temporarily obtain saccharoid after, with extrusion shaper saccharoid is extruded processing.Extrusion shaper can all can for single-screw, double-screw type.Mold shape can be used any one of T type die, inflating die, pipe mold (cylindric mould).When using inflating die/pipe mold, consider from obtaining seamless tube/seamless band (jointless pipe/band) aspect, preferably pipe mold.Extrusion temperature can carry out under 160～260 ℃, is preferably 200～240 ℃.
For above-mentioned various uses; The particularly above-mentioned polyether ester amides elastomeric-type macroion static eliminator that contains sodium perchlorate; It is with good as the polyamide thermoplastic 12 elastomeric consistencies on basis; Can not damage high surface smoothness of the present invention, toughness, flexibility, resistance to bend(ing), can give above-mentioned target capabilities.
As additive, can enumerate out for example fire retardant, pigment, dyestuff, toughener (thomel etc.), weighting agent, heat-resistant agent, weather resisting agent, lubricant, releasing agent, nucleus agent, softening agent, fluidity amendment, static inhibitor, expanding material, stablizer etc.
Can make conductive resin composition of the present invention through the whole bag of tricks.Can modulate through known continous way or the mixing method of batch-type,, can mixingly under the fused state modulate more than 30 seconds through at thermoplastic resin (a) and (b) being heated for example at above-mentioned (a)～(c) composition all under the coexistence.Particularly, can enumerate out in advance with mixing machines such as cylinder with (a) and (b) composition mix, and after the forcing machine that supplies to single screw rod or twin screw carries out melting mixing, supply with (c) composition by the side feeding machine and carry out mixing method; In advance (a)～(c) composition is mixed and supply to single screw rod or twin screw extruder or Banbury and carry out method of melting mixing etc.Melting temperature is preferably high 5～50 ℃ than the melt temperature of thermoplastic resin.Melting temperature is crossed when hanging down, and it is bad to cause that owing to fusion is insufficient (c) composition disperses; When melting temperature is too high, exists and to bring out that resin decomposes and the possibility of the reaction that abnormal response etc. is not expected.Preferred 30 seconds～10 minutes of mixing time, more preferably 1～5 minute.Treatment time is when too short, owing to mixing insufficient causing (c) composition disperses bad; Treatment time is when long, and the possibility of bringing out the reaction that resin decomposition, abnormal response etc. do not expect is arranged.
Use conductive resin composition of the present invention,, can make various electroconductibility formed bodys such as film, sheet, pipe through known forming methods such as injection molding, extrusion moulding, blow moldings.In addition, term film among the present invention and sheet are according to JIS packing term specification, and the plastics membranoid substance of thickness less than 250 μ m is called film; Sheet plastic shape thing more than the thickness 250 μ m is called sheet.Mechanical characteristics, particularly flexibilities such as the toughness of the formed body that is formed by conductive resin composition manufacturing of the present invention, flexibility, resistance to bend(ing) are good, so preferred its Shore D hardness is the material below 80.More preferably the Shore D hardness of formed body is 55～75 material.Shore D hardness is 55 when above, can access good especially forming process property, and Shore D hardness is 75 when following, and the mechanical characteristics of formed body (particularly flexibility) is better.
The formed body that forms by conductive resin composition manufacturing of the present invention; Because have characteristics such as high surface smoothness (polymolecularity of carbon), toughness, flexibility, resistance to bend(ing), be suitable for Electrofax with in various rollers, belt member, the use of automobile with various flexible pipes, duct member etc.More preferably conduct for example; There is the Electrofax of chance long-time or that contact at a high speed to use parts with other position, for example the employed band of parts such as charged roller, developer roll, transfer belt, the tubulose formed body as managing or use as the film formed body of its precursor, sheet-like formed body.The formed body that is formed by conductive resin composition manufacturing of the present invention is because conductive carbon black dispersed high, thereby the homogeneity of the electroconductibility in each parts is high, can make it show high-quality printing characteristic.In addition, because toughness, resistance to bend(ing), flexibility are excellent, therefore in chance long-time with other material or that contact at a high speed, the distortion, friction loss, breakage of self or contact object etc. can not take place, can keep initial good order and condition.
Embodiment
Composition shown in the table 1 below using according to the blending ratio of (a)～(c) composition shown in the below table 2, is made the conductive resin composition of embodiment and comparative example.
Embodiment 1
In advance with mixing machines such as rotary drums with the EMS-CHEMIE (Japan) of 11 quality % as (a) composition; Ltd. (strain) ELY60 of producing (below be called PAE12 (i)), 15% quality % are as the Polyplastics Co. of (b) composition; Ltd. the Duranex 600FP that produces (below be called PBT) mixes; Be made as the main hopper of 240～260 ℃ parallel dual-screw extruding machine (NR-II57mm, two-story valley machinery (strain) is produced) from bowl temperature and die temperature, supply with this mixture with batch feeder.Fully after the fusion; Respectively from the side feeding machine; Ensaco250G that 14 quality % is produced as the TIMCAL company of (c) composition through batch feeder (below be called CB (i)) and 60 quality % supply to forcing machine as the PAE12 (i) of (a) composition; Mixing, carry out prilling, obtain the conductive resin composition of embodiment 1.
Embodiment 2
Except that the UBESTAXPA9044X2 that in embodiment 1, the emerging product of space portion (strain) of 11 quality % is produced (below be called PAE12 (ii)) as being used to supply to (a) composition of main hopper, likewise operates the conductive composition that obtains embodiment 2 with embodiment 1.
Embodiment 3
In embodiment 1 with 28 quality %PAE12 (ii) as (a) composition that is used to supply to main hopper, with the PAE12 (i) of 43 quality % as (a) composition that is used for supplying with from the side feeding machine; In addition, likewise operate the conductive composition that obtains embodiment 3 with embodiment 1.
Embodiment 4
In embodiment 1 with 6 quality %PAE12 (i) and 4 quality %PAE12 mixture (ii) as (a) composition that is used to supply to main hopper, with the PAE12 (i) of 37 quality % and 24 quality %PAE12 mixture (ii) as (a) composition that is used for supplying with from the side feeding machine; In addition, likewise operate the conductive composition that obtains embodiment 4 with embodiment 1.
Embodiment 5
Except that CB (i) in embodiment 4 is the 8 quality %, likewise operate the conductive composition that obtains embodiment 5 with embodiment 4.
Embodiment 6
Except that in embodiment 1 with PAE12 (ii) as the composition (a), likewise operate the conductive composition that obtains embodiment 6 with embodiment 1.
Embodiment 7
In embodiment 1; (a) composition PAE12 (i) that is used to supply to main hopper is that 18 quality %, (b) composition PBT are 8 quality %; With 60 quality %PAE12 (i) as (a) composition that is used for supplying with from the side feeding machine; In addition, likewise operate the conductive composition that obtains embodiment 7 with embodiment 1.
Embodiment 8
In embodiment 1; (a) composition PAE12 (i) that is used to supply to main hopper is that 16 quality %, (b) composition PBT are 25 quality %; With the PAE12 (i) of 45 quality % as (a) composition that is used for supplying with from the side feeding machine; In addition, likewise operate the conductive composition that obtains embodiment 8 with embodiment 1.
Embodiment 9
In embodiment 1 with 10 quality %PBT and 5 quality %MITSUBISHIRAYON CO.; LTD. the mixture of the DIANITE MA-521H-D25 that produces (below be called PET) is as (b) composition; In addition, likewise operate the conductive composition that obtains embodiment 9 with embodiment 1.
Embodiment 10
In embodiment 1; The Ketjen black EC300J that (a) composition PAE12 (i) that is used to supply to main hopper is 11 quality %, produce 8 quality %Lion corpoation (below be called CB (ii)) is as (c) composition; With 60 quality %PAE12 (i) as (a) composition that is used for supplying with from the side feeding machine; In addition, likewise operate the conductive composition that obtains embodiment 10 with embodiment 1.
Embodiment 11
Except that CB in embodiment 5 (ii) is 8 quality %, likewise operate the conductive composition that obtains embodiment 11 with embodiment 5.
Embodiment 12
In embodiment 1; The mixture of the composition that is used to the to supply to main hopper Irgastat P18 that to be 15 quality % (b) composition PBT and 10 quality % produce as the macroion static eliminator CibaSpecialty Chemicals Inc. of (d) composition; Being used for from (a) composition that the side feeding machine is supplied with is 40 quality %PAE12 (i) and 27 quality %PAE12 mixture (ii); (c) composition that is used for supplying with from the side feeding machine is 8 quality %CB (i); In addition, likewise operate the conductive composition that obtains embodiment 12 with embodiment 1.
Embodiment 13
In embodiment 1; The composition that is used to supply to main hopper for (a) composition 6 quality %PAE12 (i) and 4 quality %PAE12 (ii) with the mixture of 15 quality % (b) composition PBT; The composition that is used for supplying with from the side feeding machine for (a) composition 32 quality %PAE12 (i) and 21 quality %PAE12 (ii) and the mixture of 15 quality % (d) composition IrgastatP18; (c) composition that is used for supplying with from the side feeding machine is 7 quality %CB (i); In addition, likewise operate the conductive composition that obtains embodiment 13 with embodiment 1.
Embodiment 14
In embodiment 13; The composition that is used for supplying with from the side feeding machine for (a) composition 37 quality %PAE12 (i) and 24 quality %PAE12 (ii) and the mixture of 5 quality % (d) composition Irgastat P18; (c) composition that is used for supplying with from the side feeding machine is 9 quality %CB (i); In addition, likewise operate the conductive composition that obtains embodiment 14 with embodiment 13.
Comparative example 1
In embodiment 1, (a) composition PAE12 (i) that is used to supply to main hopper is 26 quality %, and does not use (b) composition, in addition, likewise operates the conductive composition that obtains comparative example 1 with embodiment 1.
Comparative example 2
In embodiment 1; Do not use (a) composition that is used to supply to main hopper, (b) PBT of composition is 50 quality %, and (a) composition that is used for supplying with from the side feeding machine is 36 quality %PAE12 (i); In addition, likewise operate the conductive composition that obtains comparative example 2 with embodiment 1.
Comparative example 3
In embodiment 1, CB (i) is 30 quality %, and 44 quality %PAE12 (i) as (a) composition that is used for supplying with from the side feeding machine, in addition, are likewise operated the conductive composition that obtains comparative example 3 with embodiment 1.
Table 1
| Composition (a) | Be called for short | Trade(brand)name | Shore D hardness | Fusing point (℃) |
| Polymeric amide 12 elastomericss | PAE12(i) | EMS-GRIVORY produces ELY60 | 63 | 160 |
| Polymeric amide 12 elastomericss | PAE12(ii) | The emerging product of space portion (strain) is produced UBESTAXPA9044X2 | 44 | 150 |
| Composition (b) | Be called for short | Trade(brand)name | Intrinsicviscosity |
| Polybutylene terephthalate | PBT | Polyplastics Co., Ltd. produces Duranex 600FP | 1.0 |
| Polyethylene terephthalate | PET | MITSUBISHI RAYONCO., LTD. produces DIANITEMA-521H-D25 | 0.78 |
| Composition (c) | Be called for short | Trade(brand)name | The DBP oil number |
| Carbon black | CB(i) | TIMCAL company produces Ensaco250G | 190 |
| Carbon black | CB(ii) | Lion corpoation produces Ketjen black EC300J | 360 |
| Composition (d) | Be called for short | Trade(brand)name |
| The macroion static eliminator | Irgastat?P18 | The Irgastat P18 (mixture of polyphenylene ether-polyamide based copolymer and sodium perchlorate) that Ciba Specialty Chemicals Inc. produces |
Table 2
| (a) composition | (b) composition | (c) composition | Other composition | ||||
| PAE12(i) | PAE12(ii) | PBT | ?PET | CB(i) | CB(ii) | Irgastat?P18 | |
| Embodiment 1 | 71 | 15 | 14 | ||||
| Embodiment 2 | 60 | 11 | 15 | 14 | |||
| Embodiment 3 | 43 | 28 | 15 | 14 | |||
| Embodiment 4 | 45 | 30 | 15 | 10 | |||
| Embodiment 5 | 46 | 31 | 15 | 8 | |||
| Embodiment 6 | 71 | 15 | 14 | ||||
| Embodiment 7 | 78 | 8 | 14 | ||||
| Embodiment 8 | 61 | 25 | 14 | ||||
| Embodiment 9 | 71 | 10 | ?5 | 14 | |||
| Embodiment 10 | 77 | 15 | 8 | ||||
| Embodiment 11 | 46 | 31 | 15 | 8 | |||
| Embodiment 12 | 40 | 27 | 15 | 8 | 10 | ||
| Embodiment 13 | 38 | 25 | 15 | 7 | 15 | ||
| Embodiment 14 | 43 | 28 | 15 | 9 | 5 | ||
| Comparative example 1 | 86 | 14 | |||||
| Comparative example 2 | 36 | 50 | 14 | ||||
| Comparative example 3 | 55 | 15 | 30 | ||||
Utilize about 25 ℃ water, cool off resulting conductive resin composition, carry out prilling, and carry out following evaluation.
The opactitas number
Resulting granules is carried out blow molding, obtain the film that thickness is 100 μ m.In addition; Blow molding is that 190 ℃, screw speed are to carry out under the condition of 80rpm in bowl temperature; The control driving part of forcing machine uses the LaboPlastomill ME type of the smart machine manufactured of Japan, and mold is used the 25mm Φ spiral inflating die IND-25 type of the smart machine manufactured of Japan.
Obtain the sample of wide 5cm, long 20cm from this film, for mensuration.
But use vernier callipers to measure the diameter of the condensation prod of Visual Confirmation existence, calculated diameter is the quantity (opactitas number) of the above condensation prod of 0.2mm.
Surface smoothness
To the opactitas number of above-mentioned statistics, according to the surface smoothness of following benchmark evaluation formed body.
◎: below 3
Zero: 4～12
△: 13～20
*: more than 21
Electroconductibility
Resulting granules is carried out injection molding, measure volume specific resistance according to the method for Japan rubber association criterion specification SRIS2301-1969.The denary logarithm value of the volume specific resistance of the compsn of embodiment 1～14 (Ω cm) is 2.5～11.5.
Mechanical characteristics
1) toughness
Resulting granules is carried out injection molding, measure tensile strength, tension fracture nominal strain according to ISO527-2/1A/50.
2) flexibility
Resulting granules is carried out injection molding, measure Shore D hardness according to JIS K7215.
The evaluation result of the foregoing description and comparative example is shown in table 3.
Table 3
| The formed body surface smoothness | The opactitas number | Tensile strength MPa | Tension fracture nominal strain % | Flexibility Shore D hardness | |
| Embodiment 1 | ○ | 6 | 32.4 | 170 | 71 |
| Embodiment 2 | ◎ | 2 | 27.2 | 170 | 70 |
| Embodiment 3 | ◎ | 1 | 25.5 | 190 | 68 |
| Embodiment 4 | ◎ | 0 | 25.5 | 220 | 65 |
| Embodiment 5 | ◎ | 0 | 25.7 | 240 | 63 |
| Embodiment 6 | ◎ | 2 | 20.1 | 210 | 61 |
| Embodiment 7 | ○ | 10 | 32.6 | 170 | 70 |
| Embodiment 8 | ○ | 5 | 34.8 | 140 | 73 |
| Embodiment 9 | ○ | 7 | 24.9 | 100 | 71 |
| Embodiment 10 | ○ | 9 | 34.5 | 130 | 70 |
| Embodiment 11 | ○ | 7 | 30.4 | 150 | 67 |
| Embodiment 12 | ◎ | 0 | 26.2 | 290 | 64 |
| Embodiment 13 | ◎ | 0 | 27.6 | 270 | 64 |
| Embodiment 14 | ◎ | 0 | 25.0 | 230 | 65 |
| Comparative example 1 | × | ＞50 | 33.5 | 170 | 70 |
| Comparative example 2 | ○ | 4 | 42.5 | 50 | 86 |
| Comparative example 3 | △ | 16 | 58.3 | 5 | 92 |
Can know that from the result of above-mentioned table 3 among the embodiment 1～14, the good dispersibility of conductive carbon black, formed body have the characteristic of the such excellence of H.T., high flexibility, high resistance to bend(ing).In contrast, can know that comparative example 1～3 can not satisfy above-mentioned all characteristics.
Embodiment 15
In embodiment 1; The mixture of the composition that is used to the to supply to main hopper Irgastat P18 that to be 15 quality % (b) composition PBT and 5 quality % produce as the macroion static eliminator CibaSpecialty Chemicals Inc. of (d) composition; Being used for from (a) composition that the side feeding machine is supplied with is 43 quality %PAE12 (i) and 28 quality %PAE12 mixture (ii); (c) composition that is used for supplying with from the side feeding machine is 9 quality %CB (i); In addition, likewise operate the saccharoid of the conductive composition that obtains embodiment 1 with embodiment 1.
This saccharoid is supplied in the single screw extrusion machine (the exhaust single screw extrusion machine D2020 type of the smart machine manufactured of Japan), use annular die to extrude, force cooling with fan immediately then, obtain the cylindrical pipe of external diameter 40mm, thick 100 μ m.Cut the cylindrical pipe of gained, the film of gained is used sample as SR and VR mensuration.In addition, the control driving part of this forcing machine uses the LaboPlastomill ME type of the smart machine manufactured of Japan, and mold is used the 25mm Φ spiral inflating die IND-25 type of the smart machine manufactured of Japan.Extrusion temperature all is being to carry out under 240 ℃ from the cylinder melting zone to die temperature, and screw speed carries out under 80rpm.
Embodiment 16,17, comparative example 4
Through making saccharoid with the conductive resin composition of forming shown in the table 4, and use it, use sample with VR mensuration as SR through making film by cylindrical pipe with embodiment 15 same methods with the same methods of embodiment 15.
The mensuration of resistivity
The mensuration of SR and VR is carried out based on ASTM D257-93.Mensuration is through carry out as follows: the sample of under 23 ℃, the condition of 50%RH, making in embodiment 15～17 and comparative example 4 kept 24 hours, used following resistance measurement device and electrode then, and sample is applied voltage, measured the resistance value after 1 minute.SR applies the value that each voltage of 100V, 500V and 1000V obtains, and VR applies the value that the voltage of 100V obtains.Measure the SR of sample outer circumference surface (in the face of the film that the incision cylindrical pipe obtains, being the face of outer circumference surface one side of pipe) and the VR of thickness direction before cutting.Mensuration is carried out 5 points, gets its MV.In addition, the electrically conducting coating (silver coating) that ASTM D257-93 is put down in writing thereby does not use owing to be not to measure necessaryly.
The result is as shown in table 4.Each measures the SR of voltage, and (Ω/) and VR (Ω cm) get the value representation of denary logarithm with measured value.The difference of the denary logarithm value of the SR when the denary logarithm value of the SR of the voltage-dependent of SR when measuring voltage 1000V and 100V is represented.
The resistance measurement machine: ADVANTEST CORPORATION makes electrometer (electrometer) R8340
Electrode: ADVANTEST CORPORATION makes resistivitychamber R12702A
Table 4
| Embodiment | Comparative example | |||||
| 15 | 16 | 17 | 4 | |||
| Form | (a) | PAE12(i) | 43 | 40 | 37 | 46 |
| PAE12(ii) | 28 | 26 | 24 | 30 | ||
| (b) | PBT | 15 | 15 | 15 | 15 | |
| (c) | CB(i) | 9 | 9 | 9 | 9 | |
| (d) | Irgastat?P18 | 5 | 10 | 15 | 0 | |
| Surface resistivity LogSR | 100V | 10.88 | 9.43 | 10.17 | 11.57 | |
| 500V | 11.58 | 10.00 | 10.41 | 13.00 | ||
| 1000V | 11.85 | 10.28 | 10.67 | 13.33 | ||
| LogSR voltage-dependent (100-1000V) (figure place) | 0.97 | 0.85 | 0.50 | 1.76 | ||
| Volume specific resistance LogVR (100V) | 5.68 | 5.68 | 6.75 | 10.13 | ||
Claims (9)
1. conductive resin composition, it comprises:
(a) polyamide thermoplastic 12 elastomericss,
(b) with respect to 100 mass parts compsns be 1～30 mass parts the thermoplasticity aromatic polyester or with aliphatic polyether or aliphatic polyester import multipolymer that this thermoplasticity aromatic polyester obtains and
(c) be the conductive carbon black of 1～25 mass parts with respect to 100 mass parts compsns.
2. conductive resin composition according to claim 1 is characterized in that (b) composition is the polybutylene terephthalate or derivatives thereof.
3. conductive resin composition according to claim 1 and 2 is characterized in that, (c) composition is the conductive carbon black that the positive dibutylester oil number of phthalic acid is 100～500ml/100g.
4. conductive resin composition according to claim 1 and 2 is characterized in that, also contains (d) ionic conductive agent.
5. conductive resin composition according to claim 3 is characterized in that, also contains (d) ionic conductive agent.
6. electroconductive resin molding body, wherein, this electroconductive resin molding body is formed by each described conductive resin composition manufacturing of claim 1～5.
7. formed body according to claim 6, the Shore D hardness of this formed body is below 80.
8. according to claim 6 or 7 described formed bodys, this formed body is the form of film or sheet.
9. according to claim 6 or 7 described formed bodys, this formed body is the form of pipe.
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| CN109385073A (en) * | 2018-10-19 | 2019-02-26 | 沧州旭阳科技有限公司 | Electrically conductive polyamide elastic composition and preparation method thereof |
| WO2021048123A1 (en) * | 2019-09-11 | 2021-03-18 | Basf Se | Polyamide composition comprising carbon black |
| CN111253733B (en) * | 2020-04-07 | 2022-09-02 | 长沙五犇新材料科技有限公司 | Modified nylon elastomer and preparation method and application thereof |
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