CN101161724A - Conductive resin composition and moulded body produced thereby - Google Patents
Conductive resin composition and moulded body produced thereby Download PDFInfo
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- CN101161724A CN101161724A CNA2007101628395A CN200710162839A CN101161724A CN 101161724 A CN101161724 A CN 101161724A CN A2007101628395 A CNA2007101628395 A CN A2007101628395A CN 200710162839 A CN200710162839 A CN 200710162839A CN 101161724 A CN101161724 A CN 101161724A
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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.In detail, 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 has mixed conductive carbon black in polyamide resin 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 the 2006/049139th brochure that discloses
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 formed body of surface smoothness excellence.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 found that, by adopting specific elastomerics as polyamide resin, it is mixed with thermoplasticity aromatic polyester or derivatives thereof, can access the conductive resin composition of surface smoothness excellence.Promptly, the invention provides conductive resin composition, 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 compositions and (c) are the conductive carbon black of 1～25 mass parts with respect to 100 mass parts compositions.
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 of the formed body that the surface smoothness excellence can be provided.The formed body that is formed by composition manufacturing of the present invention also has high tenacity, 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 list the material that for example obtains by following method: the polyether glycol that will form the omega-lauric lactam of hard segment and dicarboxylic acid, formation soft chain segment is put in the reactive tank simultaneously, make it carry out the lactan ring-opening reaction, generate intermediate, then, under reduced pressure make this intermediate and polyether glycol carry out the method for condensation reaction; The reaction of omega-lauric lactam and dicarboxylic acid is formed after the hard segment, add polyether glycol, the method for under high temperature, decompression, carrying out condensation reaction.Also have other following method, combine by amido linkage with polyether units, use the terminal amino group modified polyether, perhaps make the method for the terminal amino group polycondensation of terminal carboxyl(group) modified polyether and polymeric amide as polyethers in order to make polyamide units.
Aforementioned dicarboxylic acid plays the effect of the molecular weight regulator of hard segment.As dicarboxylic acid, can list the alicyclic dicarboxylic acid, as 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-dicarboxylic acid etc.; Aromatic dicarboxylic acid, as terephthalic acid, m-phthalic acid, phthalic acid, 2,6-naphthalene dicarboxylic acids, 2,7-naphthalene dicarboxylic acids, biphenoxyl ethane dicarboxylic acid, phenylbenzene-4,3-sulfo-m-phthalic acid an alkali metal salts such as 4 '-dicarboxylic acid, 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, particularly preferred material can list hexanodioic acid, sebacic acid, terephthalic acid, m-phthalic acid, 3-sulfo-m-phthalic acid sodium.
The aliphatic polyether composition of soft chain segment can list polyoxyethylene glycol, polyoxy (1,2-or 1,3-) the copolymerization glycol of propylene glycol, 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, and Shore D hardness is that the mechanical characteristics of formed body (particularly flexibility) is better under the situation below 70.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 by 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, at employed polyamide thermoplastic 12 elastomericss is that Shore D hardness is meant the mean value that is calculated by each polyamide thermoplastic 12 elastomeric Shore D hardness and blending ratio under the situation of multiple mixture.
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, and fusing point is that the mechanical characteristics of formed body (particularly flexibility) is better under the situation below 180 ℃.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 by differential scanning calorimeter (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 by known method, also can use EMS-CHEMIE (Japan), the commercially available products 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 high tenacity, flexibility, resistance to bend(ing).In addition, the high dispersive that also helps electroconductibility charcoal in the composition 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 favorable dispersity of electroconductibility charcoal is preferred.
Composition (b) thermoplasticity aromatic polyester or derivatives thereof
In the present invention, the affinity excellence of thermoplasticity aromatic polyester or derivatives thereof and conductive carbon black can improve the dispersiveness of conductive carbon black in the composition of the present invention.Its result can improve the surface smoothness of the formed body that is formed by composition manufacturing of the present invention.Further, when using with polyamide thermoplastic 12 elastomericss, even the amount of conductive carbon black is few, the also electroconductibility that 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 main component is carried out the material that polycondensation generates.The not special restriction of ordered state, random polycondensate, block polycondensate, wire, branch, crosslinked etc. arbitrary all passable.
As operable thermoplasticity aromatic polyester among the present invention, can list 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 list as the derivative 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 intrinsic viscosity be 0.5～1.5 material of (100ml/g, orthomonochlorphenol solution, 25 ℃).By it is used as composition (b), better with the affinity of conductive carbon black, can bring higher dispersiveness.In addition, the aromatic polyester derivative that contains aliphatic polyether also helps the improvement of mechanical characteristics, so preferred.
Especially preferably poly-terephthalic acid butanediol ester or derivatives thereof.This is because it helps to improve the dispersiveness of the conductive carbon black in the composition 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 product.Can enumerate for example Polyplastics Co. as commercially available product, 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 form the material of effective galvanic circle in dispersion medium such as resin.
The not special restriction of operable in the present invention conductive carbon black can suitably be selected according to purpose, for example can list, and utilizes the oil oven method to make the stock 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 by 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 composition of favorable dispersity 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 possibility in the formed body.
Operable in the present invention conductive carbon black also can use commercially available product.Can list 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 favorable dispersity of conductive carbon black in composition, 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 list polyvinyl resin, acrylic resin, ethylene-vinyl acetate copolymer, the multipolymer of acrylate or methacrylic ester and other compound, phenylethylene resin series, composition (a) polyamide resin in addition, polycarbonate resin, aliphatic polyester resin, the polychlorostyrene ethenoid resin, composition (a) thermoplastic elastomer in addition, 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 list, fiber is that metals such as carbon, zinc oxide, titanium oxide are conductive agent, titanate whisker, ionic conductive agent be the such low molion conductive agent of inorganic salt/organic salt or macroion conductive agent etc. for example.The preferred ion conductive agent, especially preferably low molion conductive agent or macroion conductive agent.
As the example of low molion conductive agent, can list 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 conductive agent is meant the polymkeric substance or the multipolymer of ionic conduction.As an example, can list low polyethoxylated acrylate 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 conductive agent and macroion conductive agent 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 conductive agent and/or (C) form of the masterbatch that forms of low molion conductive agent use.
As the example of (A) organic polymer material, can list polyacrylic ester, polymethacrylate, polyacrylonitrile, polyvinyl alcohol, polyvinyl acetate (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 composition 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 being used in combination.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 conductive agent 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 by 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 by 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, sometimes surface resistivity (surface resistivity:SR) changes more than 1.5, with respect to this, use simultaneously in the situation of conductive resin composition of the present invention of ionic conductive agent, the aforementioned variation that applies the SR in the voltage range can be suppressed in 1.By 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.By littler, can suppress the dependency of aforementioned electric resistance to humidity than higher limit.
When making charged roller or intermediate transfer belt by the conductive resin composition that uses ionic conductive agent simultaneously of the present invention, preferably by suitably adjusting (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 preferred semi-conductivity zones of purposes institute, 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 by 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, these method for making is not particularly limited, for example can be manufactured by the following:, use annular die the mixing thing extrusion molding of gained by the resinous principle and the conductive material of the mixing base material of twin-screw mixer machine.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 pattern tool, 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 conductive agent 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 list for example fire retardant, pigment, dyestuff, toughener (carbon fiber 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 by the whole bag of tricks.Can modulate by known continous way or the mixing method of batch-type,, can mixingly under the fused state modulate more than 30 seconds by at thermoplastic resin (a) and (b) being heated for example at above-mentioned (a)～(c) composition all under the coexistence.Particularly, can list 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 supplies 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 by 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, 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, with other position the Electrofax parts of chance long-time or that contact are at a high speed arranged, 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 height of the electroconductibility in each parts, can make it show high-quality printing characteristic.In addition, because toughness, resistance to bend(ing), flexibility excellence, 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
Use the composition shown in the following table 1,, make the conductive resin composition of embodiment and comparative example according to the blending ratio of (a)～(c) composition shown in the following table 2.
Embodiment 1
In advance with mixing machines such as rotary drums with the EMS-CHEMIE (Japan) of 11 quality % as (a) composition, Ltd. ELY60 (hereinafter referred to as PAE12 (i)), the 15% quality % of (strain) production are as the Polyplastics Co. of (b) composition, Ltd. the Duranex 600FP (hereinafter referred to as PBT) of Sheng Chaning mixes, be made as 240～260 ℃ parallel dual-screw extruding machine (NR-II57mm from bowl temperature and die temperature, two-story valley machinery (strain) production) main hopper is supplied with this mixture with batch feeder.Fully after the fusion; respectively from the side feeding machine; Ensaco250G (hereinafter referred to as CB (i)) that 14 quality % is produced as the TIMCAL company of (c) composition by batch feeder and 60 quality % supply to forcing machine as the PAE12 (i) of (a) composition; mixing; carry out granulating, obtain the conductive resin composition of embodiment 1.
Embodiment 2
Except that the UBESTAXPA9044X2 ((ii)) that in embodiment 1, the emerging product of space portion (strain) of 11 quality % is produced hereinafter referred to as PAE12 as being used to supply to (a) composition of main hopper, operate the conductive composition that obtains embodiment 2 similarly to Example 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, operate the conductive composition that obtains embodiment 3 similarly to Example 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, operate the conductive composition that obtains embodiment 4 similarly to Example 1.
Embodiment 5
Except that CB (i) in embodiment 4 was 8 quality %, operation obtained the conductive composition of embodiment 5 similarly to Example 4.
Embodiment 6
Except that in embodiment 1 with PAE12 (ii) as the composition (a), operation obtains the conductive composition of embodiment 6 similarly to Example 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, operate the conductive composition that obtains embodiment 7 similarly to Example 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, operate the conductive composition that obtains embodiment 8 similarly to Example 1.
Embodiment 9
In embodiment 1 with 10 quality %PBT and 5 quality %MITSUBISHIRAYON CO., LTD. the mixture of the DIANITE MA-521H-D25 (hereinafter referred to as PET) of Sheng Chaning is as (b) composition, in addition, operate the conductive composition that obtains embodiment 9 similarly to Example 1.
Embodiment 10
In embodiment 1, the Ketjen black EC300J (hereinafter referred to as CB (ii)) that (a) composition PAE12 (i) that is used to supply to main hopper is 11 quality %, produce 8 quality %Lion corpoation 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, operate the conductive composition that obtains embodiment 10 similarly to Example 1.
Embodiment 11
Except that CB in embodiment 5 (ii) was 8 quality %, operation obtained the conductive composition of embodiment 11 similarly to Example 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 conductive agent 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, operate the conductive composition that obtains embodiment 12 similarly to Example 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, be used for the composition supplied 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, operate the conductive composition that obtains embodiment 13 similarly to Example 1.
Embodiment 14
In embodiment 13, be used for the composition supplied 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, operate the conductive composition that obtains embodiment 14 similarly to Example 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, and in addition, operation obtains the conductive composition of comparative example 1 similarly to Example 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, operate the conductive composition that obtains comparative example 2 similarly to Example 1.
Comparative example 3
In embodiment 1, CB (i) is 30 quality %, and as (a) composition that is used for supplying with from the side feeding machine, in addition, operation obtains the conductive composition of comparative example 3 similarly to Example 1 with 44 quality %PAE12 (i).
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 UBESTA XPA9044X2 | 44 | 150 |
| Composition (b) | Be called for short | Trade(brand)name | Intrinsic viscosity |
| Polybutylene terephthalate | PBT | Polyplastics Co., Ltd. produces Duranex 600FP | 1.0 |
| Polyethylene terephthalate | PET | MITSUBISHI RAYON CO., 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 Ensaco 250G | 190 |
| Carbon black | CB(ii) | Lion corpoation produces Ketjen black EC300J | 360 |
| Composition (d) | Be called for short | Trade(brand)name |
| The macroion conductive agent | 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 granulating, 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 25mm Φ spiral type inflating die IND-25 type that the LaboPlastomill ME type that the control driving part of forcing machine uses Japan smart machine company to make, mold use Japan smart machine company to make.
Obtain the sample of wide 5cm, long 20cm from this film, for mensuration.
But use vernier callipers to measure the diameter of the condensation product of Visual Confirmation existence, calculated diameter is the quantity (opactitas number) of the above condensation product 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 composition 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 |
From the result of above-mentioned table 3 as can be known, among the embodiment 1～14, the favorable dispersity of conductive carbon black, formed body have the characteristic of the such excellence of high tenacity, high flexibility, high resistance to bend(ing).In contrast, comparative example 1～3 can not satisfy above-mentioned all characteristics as can be known.
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 conductive agent 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, operate the saccharoid of the conductive composition that obtains embodiment 1 similarly to Example 1.
This saccharoid is supplied in the single screw extrusion machine (the exhaust single screw extrusion machine D2020 type that Japan smart machine company makes), 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 measured as SR and VR used sample.In addition, the 25mm Φ spiral type inflating die IND-25 type that the LaboPlastomill ME type that the control driving part of this forcing machine uses Japan smart machine company to make, mold use Japan smart machine company to make.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
Make saccharoid by method similarly to Example 15 with the conductive resin composition of forming shown in the table 4, and use its method of passing through similarly to Example 15 to make film, as SR and VR mensuration sample by cylindrical pipe.
The mensuration of resistivity
The mensuration of SR and VR is carried out based on ASTM D257-93.Mensuration is undertaken by following: the sample of making in embodiment 15～17 and comparative example 4 under 23 ℃, the condition of 50%RH 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, before cutting, being the face of outer circumference surface one side of pipe) and the VR of thickness direction.Mensuration is carried out 5 points, gets its mean value.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 (8)
1. conductive resin composition, it comprises:
(a) polyamide thermoplastic 12 elastomericss,
(b) with respect to 100 mass parts compositions be 1～30 mass parts thermoplasticity aromatic polyester or derivatives thereof and
(c) be the conductive carbon black of 1～25 mass parts with respect to 100 mass parts compositions.
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 that the positive dibutylester of phthalic acid (DBP) oil number is the conductive carbon black of 100～500ml/100g.
4. according to each described conductive resin composition of claim 1～3, it is characterized in that, also contain (d) ionic conductive agent.
5. electroconductive resin molding body, wherein, this electroconductive resin molding body is formed by each described conductive resin composition manufacturing of claim 1～4.
6. formed body according to claim 5, the Shore D hardness of this formed body is below 80.
7. according to claim 5 or 6 described formed bodys, this formed body is the form of film or sheet.
8. according to claim 5 or 6 described formed bodys, this formed body is the form of pipe.
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| JP2006280329 | 2006-10-13 | ||
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109320954A (en) * | 2011-06-30 | 2019-02-12 | 艾恩费斯公司 | Halogen-free polymer blend |
| 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 |
| CN111253733A (en) * | 2020-04-07 | 2020-06-09 | 长沙五犇新材料科技有限公司 | Modified nylon elastomer and preparation method and application thereof |
| WO2021048123A1 (en) * | 2019-09-11 | 2021-03-18 | Basf Se | Polyamide composition comprising carbon black |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6500895B1 (en) * | 2000-10-13 | 2002-12-31 | General Electric Company | Thermoplastic blend comprising poly(arylene ether) and polyamide |
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2007
- 2007-10-15 CN CN2007101628395A patent/CN101161724B/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109320954A (en) * | 2011-06-30 | 2019-02-12 | 艾恩费斯公司 | Halogen-free polymer blend |
| CN109320954B (en) * | 2011-06-30 | 2024-02-13 | 艾恩费斯公司 | Halogen-free polymer blends |
| 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 |
| CN114402035A (en) * | 2019-09-11 | 2022-04-26 | 巴斯夫欧洲公司 | Polyamide composition comprising carbon black |
| CN111253733A (en) * | 2020-04-07 | 2020-06-09 | 长沙五犇新材料科技有限公司 | Modified nylon elastomer and preparation method and application thereof |
| 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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