JP2008045031A - Electroconductive thermoplastic elastomer composition, its manufacturing method and molded product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electroconductive thermoplastic elastomer composition that exhibits both elasticity and flexibility like a rubber and good moldability and recyclability like a resin and has an electrically semiconductive resistance value with excellent dispersibility of contained components, and therefore exhibits excellent mechanical properties and finish properties. <P>SOLUTION: The electroconductive thermoplastic elastomer composition comprises a component (A) comprising a thermoplastic resin and/or a thermoplastic elastomer, a component (B) comprising an ion-conductive electroconductive agent comprised of an ethylene oxide-propylene oxide copolymer and/or an ethylene oxide-propylene oxide-allyl glycidyl ether copolymer having a metal salt incorporated therewith, and a component (C) comprising an ethylene-acrylate ester-maleic anhydride copolymer. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a conductive thermoplastic elastomer composition, a method for producing the same, and a molded product obtained by molding the composition. More specifically, the present invention is effective as a conductive roller used in an image forming apparatus such as a copying machine, a printer, or a facsimile machine. The present invention relates to a thermoplastic elastomer composition having electrical conductivity used in the above.

  Methods for imparting conductivity to the elastomer include a method using an electronically conductive polymer composition in which a conductive filler such as a metal oxide powder or carbon black is blended in a polymer, urethane rubber, acrylonitrile butadiene rubber, epichlorohydrin. There is a method using an ion conductive polymer composition such as rubber.

When an electronic conductive polymer composition is used for a conductive roller, there is a region where the electrical resistance changes suddenly due to a slight change in the amount of conductive filler added, which makes it very difficult to control the electrical resistance. There's a problem. In addition, since it is difficult to uniformly disperse the conductive filler in the polymer, there is a problem that the electric resistance value varies in the circumferential direction and the width direction of the conductive roller.
Further, there is a problem that the electric resistance value of the conductive roller using the electronic conductive polymer composition depends on the applied voltage. This tendency is particularly noticeable when carbon black is used as the conductive filler. Furthermore, if a conductive filler such as carbon black is added too much, the molding process becomes difficult.

  Since the conductive roller using the electronic conductive polymer composition has the above-mentioned problems, the recent progress in image quality improvement technology such as digitization and colorization is remarkable. However, the ion conductive polymer composition tends to be particularly preferred.

Most of the ionic conductive polymer compositions that have been put to practical use for conductive rollers are vulcanized rubber compositions, but the vulcanized rubber compositions have a drawback that they are not thermoplastic and cannot be recycled.
Therefore, ion conductive polymers that have thermoplasticity and are recyclable have been used. Among them, the conductive roller using epichlorohydrin rubber has a low resistance value and good physical properties. However, ionic conductive thermoplastic elastomers containing chlorine, as typified by epichlorohydrin rubber, have the problem that harmful gases such as hydrogen chloride are generated at the time of disposal, and dioxins are generated in some cases. .

  In order to solve such problems, JP-A-8-183866 (Patent Document 1) discloses a thermoplastic elastomer sheet in which a permanent antistatic agent is added to an olefinic thermoplastic elastomer. Since the sheet-like material has thermoplasticity, it can be recycled, and by using an olefinic thermoplastic elastomer, the olefinic thermoplastic elastomer does not contain chlorine, so that environmental pollution during disposal can be avoided. There is also a bleed type using a conductive plasticizer as an antistatic agent.

In the thermoplastic elastomer sheet-like material, the surface resistance value can be lowered by blending a permanent antistatic agent, but the volume resistivity cannot be reduced and the electrical resistance becomes high. There is. In addition, there is a problem that compression set is large, and good physical properties cannot be obtained as a conductive roller.
In addition, the bleed type also deteriorates the mechanical properties, particularly the compression set is worsened, and the plasticizer bleeds and severely contaminates other parts such as a photoconductor. There is a problem that it cannot be used as a part of a forming apparatus.

Therefore, the present applicants have developed a conductive thermoplastic elastomer having an electrically semiconductive resistance value and good mechanical properties such as a small compression set. Specifically, JP 2004-18984A (Patent Document 2) and JP 2004-272209 A (Patent Document 3) describe polymers and conductive salts represented by polyether polymers in thermoplastic elastomers. An electrically conductive thermoplastic elastomer is provided.
However, in the conductive thermoplastic elastomer, there is room for further improvement in order to further enhance the dispersibility of each component contained and to suppress deterioration in physical properties and molding defects due to insufficient dispersion. .

  Here, in Japanese Patent Application Laid-Open No. 2004-189883 (Patent Document 4), an acid-modified EPDM or an acid-modified hydrogenated styrene system is used to finely disperse a polyamide-based resin in a dynamically crosslinked thermoplastic elastomer. A compatibilizer comprising at least one of a thermoplastic elastomer is used. However, in this document, for example, whether or not the compatibilizer is effective for finely dispersing components other than the polyamide-based resin such as a conductive salt in the thermoplastic elastomer has not been studied. There is no description or suggestion of other compatibilizers other than the compatibilizer.

JP-A-8-183866 Japanese Patent Laid-Open No. 2004-189884 JP 2004-272209 A JP 2004-189883 A

  The present invention has been made in view of the above-mentioned problems, and has both elasticity and flexibility such as rubber and good moldability and recyclability such as resin, and is excellent in dispersibility of contained components, and therefore excellent. It is an object of the present invention to provide a conductive thermoplastic elastomer composition having mechanical properties and processing finish, a method for producing the same, and a molded article such as a conductive roller made of the elastomer composition.

In order to solve the above problems, the present invention provides:
A component (A) comprising a thermoplastic resin and / or a thermoplastic elastomer;
(B) component consisting of an ionic conductive conductive agent containing a metal salt in an ethylene oxide-propylene oxide copolymer and / or an ethylene oxide-propylene oxide-allyl glycidyl ether copolymer;
Component (C) comprising an ethylene-acrylic ester-maleic anhydride copolymer;
An electrically conductive thermoplastic elastomer composition is provided.

The present inventor contains a conductive metal salt to reduce the electric resistance value. When this metal salt is used together with an EO-PO copolymer and / or an EO-PO-AGE copolymer, It has been found that the copolymer stabilizes ions derived from the metal salt, and a remarkable effect is obtained for reducing the electric resistance value.
Furthermore, as a result of repeated studies, the component (A), which becomes a base polymer containing a thermoplastic resin and / or a thermoplastic elastomer, comprises the EO-PO copolymer or / and the EO-PO-AGE copolymer. When the component (B) is blended, the dispersibility of the copolymer may not be sufficient, and when it is extruded into a roll shape in this state, streak marks resulting from the separation of the components are formed on the roll surface. I confirmed that it might be possible. As described above, the EO-PO copolymer and / or the EO-PO-AGE copolymer has a problem that there is room for further fine dispersion in the component (A) of the base polymer. added. As a result, if an ethylene-acrylic acid ester-maleic anhydride copolymer is blended, the copolymer can be finely dispersed in the component (A) of the base polymer, and has excellent dispersibility. It has been found that a thermoplastic elastomer composition can be obtained. Based on this, the present invention has been completed.

First, the component (A) of the base polymer containing a thermoplastic resin and / or a thermoplastic elastomer will be described in detail.
As the thermoplastic elastomer contained in the component (A), a known thermoplastic elastomer can be used.
Specific examples include styrene-based thermoplastic elastomers, vinyl chloride-based thermoplastic elastomers, olefin-based thermoplastic elastomers, urethane-based thermoplastic elastomers, ester-based thermoplastic elastomers, and amide-based thermoplastic elastomers. Among these, it is preferable to use a styrene thermoplastic elastomer.
Moreover, a well-known thing can also be used as a thermoplastic resin contained in a base polymer, for example, polyester resins, such as olefin resin, polyethylene terephthalate (PET) or polybutylene terephthalate (PBT), polystyrene (PS), nylon, etc. Can be mentioned. Among these, it is preferable to use an olefin resin.

Among the thermoplastic elastomers of the component (A), it is particularly preferable to use a mixture of a styrene thermoplastic elastomer and an olefin resin.
Examples of the styrenic thermoplastic elastomer include a block copolymer of a polymer block (A) mainly composed of a styrene monomer and a block (B) mainly composed of a conjugated diene compound, and a conjugated diene polymer unit of the block copolymer. The hydrogenated product can be exemplified. Examples of the styrene monomer include styrene, α-methyl styrene, vinyl toluene, and t-butyl styrene. These monomers may be used alone or in combination of two or more. Of these, styrene is preferable as the styrene monomer. Examples of the conjugated diene compound include butadiene, isoprene, chloroprene, and 2,3-dimethylbutadiene. These may be used alone or in combination of two or more.

Among the styrene thermoplastic elastomers, it is preferable to use a hydrogenated styrene thermoplastic elastomer.
Hydrogenated styrenic thermoplastic elastomers have saturated double bonds by hydrogenation, have low hardness, a high coefficient of friction, a small compressive strain, and excellent durability. Further, when the dynamically crosslinked thermoplastic elastomer composition described below is used as the base polymer, the hydrogenated styrene thermoplastic elastomer as a matrix is not crosslinked by reacting with a crosslinking agent during dynamic crosslinking. Therefore, it is preferable to use a hydrogenated styrenic thermoplastic elastomer from the viewpoint that the elastomer composition after dynamic crosslinking can exhibit desired plasticity without inhibiting the crosslinking of the rubber component.

Specific examples of the styrenic thermoplastic elastomer include styrene-butadiene-styrene copolymer (SBS), styrene-isoprene-styrene copolymer (SIS), and styrene-ethylene / butylene-styrene copolymer (SEBS). Styrene-ethylene / propylene-styrene copolymer (SEPS) or styrene-ethylene-ethylene / propylene-styrene copolymer (SEEPS).
Among these, it is particularly preferable to use a styrene-ethylene-ethylene / propylene-styrene copolymer (SEEPS).

  Examples of the olefin-based resin include polyethylene, polypropylene, ethylene ethyl acrylate resin, ethylene vinyl acetate resin, ethylene-methacrylic acid resin, ionomer resin, chlorinated polyethylene, and the like, among which polypropylene or polyethylene is preferably used. Among these, it is more preferable to use polypropylene from the viewpoint of easy compatibilization.

When a thermoplastic elastomer and a thermoplastic resin are mixed in the component (A), the mixing ratio can be determined as an appropriate mixing ratio depending on the elastomer and resin used, but with respect to 100 parts by mass of the thermoplastic elastomer. The thermoplastic resin is preferably 1 part by mass or more and 100 parts by mass or less.
This is because when the mixing amount of the thermoplastic resin is less than 1 part by mass, an effect of mixing the thermoplastic resin, for example, improvement in processability, etc. is not observed. On the other hand, if the mixing amount of the thermoplastic resin is more than 100 parts by mass, the hardness of the molded product tends to increase.
The mixing amount of the thermoplastic resin is preferably 5 parts by mass, more preferably 10 parts by mass, and particularly preferably 20 parts by mass with respect to 100 parts by mass of the thermoplastic elastomer. The upper limit is preferably 80 parts by mass, more preferably 70 parts by mass, particularly 60 parts by mass.

The component (A) of the base polymer is used as a thermoplastic elastomer composition in which a crosslinkable rubber or / and a thermoplastic elastomer are dynamically crosslinked and dispersed in a thermoplastic resin and / or a thermoplastic elastomer. Particularly preferred.
In the thermoplastic elastomer composition, the thermoplastic resin and / or the thermoplastic elastomer used as the matrix are as described above. Although a well-known thing can be used as a thermoplastic resin, an olefin resin is preferable and a well-known thing can be used also as a thermoplastic elastomer, However, A styrene-type thermoplastic elastomer is preferable. In particular, it is more preferable to use a mixture of a styrene thermoplastic elastomer and an olefin resin.

Examples of the crosslinkable rubber include ethylene-propylene-diene rubber (EPDM), butyl rubber (IIR), halogenated butyl rubber (X-IIR), acrylonitrile butadiene rubber (NBR), acrylic rubber, isobutylene and p-methylstyrene. Brominated isobutylene-p-methylstyrene copolymer (BIMS), fluoro rubber, silicon rubber, chloroprene rubber (CR), natural rubber (NR), butadiene rubber (BR), styrene butadiene Examples thereof include rubber (SBR), isoprene rubber (IR), ethylene propylene rubber, hydrogenated nitrile rubber (HNBR), and chlorosulfonated polyethylene rubber.
These may be used individually by 1 type and may be used in combination of 2 or more types.
Examples of the crosslinkable thermoplastic elastomer include styrene-isoprene-styrene copolymer, styrene-butadiene-styrene copolymer, and styrene-vinylisoprene-styrene copolymer.

The crosslinkable rubber and / or thermoplastic elastomer is selected from the group consisting of EPDM, butyl rubber, halogenated butyl rubber, acrylonitrile butadiene rubber, acrylic rubber, brominated isobutylene-p-methylstyrene copolymer, fluorine rubber and silicone rubber. It is preferable to use one or more rubber components.
Among these, it is particularly preferable to use EPDM. In EPDM, the main chain is composed of saturated hydrocarbons, and the main chain does not contain double bonds. Therefore, even when exposed to an environment such as high-concentration ozone atmosphere or light irradiation including ultraviolet rays, EPDM can cleave the molecular main chain. Hard to happen. Therefore, ozone resistance, ultraviolet resistance, and heat resistance of the conductive thermoplastic elastomer of the present invention can be improved. The EPDM is preferably used alone, but when EPDM and the above-described other rubber components are blended, the ratio of EPDM to the entire crosslinkable rubber is preferably 50% by mass or more, and further 80 More preferably, it is at least mass%.

  The crosslinkable rubber and / or thermoplastic elastomer is preferably blended at a ratio of 50 parts by mass or more and 500 parts by mass or less with respect to 100 parts by mass of the thermoplastic resin or / and the thermoplastic elastomer. This is because if the amount is less than the above range, physical properties such as wear resistance and compression set may be easily lowered. On the other hand, if it exceeds the above range, the resin content becomes too small, and it is difficult to disperse the crosslinkable rubber or / and the thermoplastic elastomer in the thermoplastic resin and / or the thermoplastic elastomer or the mixture in the dynamic crosslinking process. This is because kneading becomes difficult. As for the said compounding quantity, 100 mass parts or more and 500 mass parts or less are more preferable.

In order to dynamically crosslink the crosslinkable rubber and / or thermoplastic elastomer, a crosslinking agent is usually used. As the crosslinking agent, for example, a known crosslinking agent such as a resin crosslinking agent or a peroxide can be used, but a resin crosslinking agent is preferably used.
Resin crosslinking agent is a synthetic resin that causes a crosslinking reaction to rubber or thermoplastic elastomer by heating, etc. Compared to the case where sulfur and vulcanization accelerator are used in combination, bloom is less likely to occur, compression set is small, and physical properties are reduced. It is preferable in that it is small and has excellent accuracy and durability. Furthermore, since the cross-linking time is shorter than that of the sulfur cross-linking system, the dynamic cross-linking can proceed within a short time staying in the extruder.

Examples of the resin cross-linking agent include phenol resin, melamine / formaldehyde resin, triazine / formaldehyde condensate, hexamethoxymethyl / melamine resin, and the like. Among these, it is preferable to use a phenol resin.
Specific examples of the phenol resin include various phenol resins synthesized by reaction of phenols such as phenol, alkylphenol, cresol, xylenol or resorcin with aldehydes such as formaldehyde, acetaldehyde or furfural. A halogenated phenol resin in which at least one halogen atom is bonded to the aldehyde unit of the phenol resin can also be used.
In particular, alkylphenol-formaldehyde resins obtained by the reaction of formaldehyde with alkylphenols with alkyl groups bonded to the ortho or para position of benzene are excellent in compatibility with rubber and have a high reactivity, thus increasing the time for initiation of the crosslinking reaction. This is preferable because it can be done relatively quickly. The alkyl group of the alkylphenol / formaldehyde resin is usually an alkyl group having 1 to 10 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, a propyl group, and a butyl group. Moreover, the halide of this alkylphenol formaldehyde resin is also used suitably.
Furthermore, a modified alkylphenol resin obtained by addition condensation of sulfurized p-tert-butylphenol and aldehydes, or an alkylphenol sulfide resin can also be used as a resin crosslinking agent.

  The blending amount of the resin crosslinking agent is preferably 2 to 20 parts by mass with respect to 100 parts by mass of the crosslinkable rubber and / or thermoplastic elastomer. This is because when the blending amount of the resin cross-linking agent is less than 2 parts by mass, the crosslinking becomes insufficient and the wear resistance is inferior. On the other hand, when the blending amount of the resin cross-linking agent exceeds 20 parts by mass, the hardness of the molded product This is because may become too high. The blending amount is more preferably 5 to 15 parts by mass.

  A crosslinking activator may be used to appropriately perform the dynamic crosslinking reaction. As the crosslinking activator, a metal oxide is used, and zinc oxide and zinc carbonate are particularly preferable. The amount of the crosslinking activator is preferably 0.5 to 10 parts by mass, more preferably 1 to 5 parts by mass with respect to 100 parts by mass of the crosslinkable rubber and / or thermoplastic elastomer. preferable.

Next, the component (B) made of an ion conductive conductive agent will be described below.
The component (B) composed of an ionic conductive conductive agent is preferably included in the conductive thermoplastic elastomer composition of the present invention in a volume fraction of 8% to 45%. More preferably, the lower limit is 10% or more, and further 15% or more, and the upper limit is more preferably 40% or less.
The range is set to be less than 8% because it is difficult to reduce the electrical resistance. On the other hand, if it exceeds 45%, the moldability and compression set are likely to deteriorate, and even if added more than this, the resistance value hardly decreases and the cost increases.
In addition, the volume fraction said here is the volume% in the resin matrix phase of an electroconductive thermoplastic elastomer composition. The volume% in the resin matrix is a ratio when the composition that can be a resin matrix is considered as a whole, excluding rubber and thermoplastic elastomer that are crosslinked by dynamic crosslinking to form domains.

  If it says by mass ratio, it is preferable that (B) component which consists of an ion electroconductive electrically conductive agent is mix | blended in the ratio of 1-20 mass parts with respect to 100 mass parts of conductive thermoplastic elastomer compositions of this invention. Moreover, it is preferable that the compounding quantity of (B) component is 1-35 mass parts with respect to 100 mass parts of (A) component of the said base polymer.

Examples of the metal constituting the metal salt contained in the component (B) made of the ion conductive conductive agent include alkali metals, alkaline earth metals, transition metals, and amphoteric metals. Among these, alkali metals such as lithium and sodium are preferable because they are easily ion-dissociated.
The metal salt is not particularly limited as long as it is a salt that can dissociate the exemplified metal as a cation. Of these, a salt having a metal cation and an anion having a fluoro group and a sulfonyl group is preferably used. In such a salt, since the fluoro group and the sulfonyl group have electron withdrawing properties, the anion is more stabilized, and the ion exhibits a higher degree of dissociation. This has the advantage that a very low electrical resistance value can be obtained with a small amount of addition.

  Preferred examples of the anion having a fluoro group and a sulfonyl group include bis (fluoroalkylsulfonyl) imide ion, tris (fluoroalkylsulfonyl) methide ion, and fluoroalkylsulfonic acid ion. These anions are preferable from the viewpoint of high compatibility with the matrix EO-PO copolymer and / or EO-PO-AGE copolymer.

Specific examples of the metal salt include CF ₃ SO ₃ Li, C ₄ F ₉ SO ₃ Li, (CF ₃ SO ₂ ) ₂ NLi, (C ₂ F ₅ SO ₂ ) ₂ NLi, and (C ₄ F ₉ SO ₂ ) (CF ₃ SO ₂ ) NLi, (FSO ₂ C ₆ F ₄ ) (CF ₃ SO ₂ ) NLi, (C ₈ F ₁₇ SO ₂ ) (CF ₃ SO ₂ ) NLi, (CF ₃ CH ₂ OSO ₂ ) ₂ NLi, (CF ₃ CF ₂ CH ₂ OSO ₂ ) ₂ NLi, (HCF ₂ CF ₂ CH ₂ OSO ₂ ) ₂ NLi, ((CF ₃ ) ₂ CHOSO ₂ ) ₂ NLi, (CF ₃ SO ₂ ) ₃ CLi, CF ₃ CH ₂ OSO ₂ ) ₃ CLi, LiPF _{6 and the} like.

It is preferable that the metal salt is blended at a ratio of 5 to 30 parts by mass with respect to 100 parts by mass of the entire ion conductive conductive agent (B).
This is because if the amount of the metal salt is less than the above range, the conductivity imparting effect cannot be obtained sufficiently. On the other hand, if the amount is larger than the above range, the metal salt tends to be hard, and even if the metal salt is added in a certain level or more, the conductivity hardly changes. On the other hand, the metal salt is expensive, which may be disadvantageous in cost. Because.

By containing the metal salt in the EO-PO copolymer and / or the EO-PO-AGE copolymer, the copolymer stabilizes the ions derived from the metal salt and reduces the electric resistance value. A remarkable effect can be obtained.
In the EO-PO copolymer or EO-PO-AGE copolymer, the ethylene oxide ratio is preferably 55 mol% or more and 95 mol% or less, and more preferably 65 mol% or more and 95 mol% or less. The metal cation of the metal salt is stabilized by an ethylene oxide unit or a propylene oxide unit. In general, the ethylene oxide unit has a higher stabilizing ability than the propylene oxide unit. Therefore, a higher ratio of ethylene oxide units can stabilize more ions. On the other hand, when the ratio of the ethylene oxide unit exceeds 95 mol%, the ethylene oxide unit is crystallized.
When an EO-PO-AGE copolymer is used, the copolymerization ratio of allyl glycidyl ether is preferably 1 mol% or more and 10 mol% or less. If it is less than 1 mol%, bleeding and photoreceptor contamination are likely to occur, whereas if it exceeds 10 mol%, the tensile strength, fatigue characteristics, flex resistance, etc. are likely to deteriorate.
The number average molecular weight of the EO-PO copolymer or EO-PO-AGE copolymer is preferably 10,000 or more, and more preferably 30,000 or more. The reason is to prevent bleed bloom and photoconductor contamination.

The EO-PO copolymer and / or the EO-PO-AGE copolymer may be dynamically cross-linked in the conductive thermoplastic elastomer composition of the present invention.
In order to dynamically crosslink the EO-PO copolymer and / or the EO-PO-AGE copolymer, a crosslinking agent is usually used. As the crosslinking agent, for example, a known crosslinking agent such as a resin crosslinking agent or a peroxide can be used, but it is preferable to use a peroxide.

  Examples of the peroxide include benzoyl peroxide, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, 2,5-dimethyl-2,5-di (benzoylperoxy). Hexane, di (tert-butylperoxy) diisopropylbenzene, 1,4-bis [(tert-butyl) peroxyisopropyl] benzene, di (tert-butylperoxy) benzoate, tert-butylperoxybenzoate, dicumylper Oxide, tert-butylcumyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, ditert-butyl peroxide or 2,5-dimethyl-2,5-di (tert- Butyl peroxy) -3-hexene and the like. These may be used alone or in combination of two or more. Of these, di (tert-butylperoxy) diisopropylbenzene is preferably used.

  It is preferable that the compounding quantity of the said peroxide is 0.1-5 mass parts with respect to 100 mass parts of EO-PO copolymer and / or EO-PO-AGE copolymer. This is because when the amount of peroxide is less than 0.1 parts by mass, crosslinking is insufficient, so that the effect of dynamic crosslinking such as improved wear resistance cannot be obtained, while the amount of peroxide is 5% by mass. If it exceeds the part, the physical properties are lowered due to molecular cutting, and further, the processing becomes difficult due to the occurrence of poor dispersion. The amount of the peroxide is more preferably 0.1 to 5 parts by mass.

A crosslinking aid may be blended with the peroxide. The cross-linking aid itself functions to cross-link and react with rubber molecules to cross-link and polymerize the whole. By co-crosslinking using this crosslinking aid, the crosslinking density can be improved, and various mechanical properties such as wear resistance can be improved and adjusted.
Examples of the crosslinking aid include polyfunctional polymers using functional groups such as metal salts of methacrylic acid or acrylic acid, methacrylic acid esters, aromatic vinyl compounds, heterocyclic vinyl compounds, allyl compounds, and 1,2-polybutadiene. And dioximes. More specifically, triallyl isocyanurate (TAIC), triallyl cyanurate (TAC), trimethylolpropane trimethacrylate (TMPT), ethylene glycol dimethacrylate (EDMA), p-quinone dioxime, p, p'- Examples include dibenzoylquinone dioxime or N, N′-m-phenylene bismaleimide, among which dioximes are preferable, and N, N′-m-phenylene bismaleimide is more preferable.
The amount of the crosslinking aid can be appropriately selected depending on the type of the crosslinking aid or other components used, but EO-PO copolymer and / or EO-PO-AGE copolymer 100 parts by mass Is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 15 parts by mass.

Next, the component (C) composed of an ethylene-acrylic acid ester-maleic anhydride copolymer will be described in detail.
By blending an ethylene-acrylic acid ester-maleic anhydride copolymer, an ion conductive conductive agent can be finely dispersed in the component (A) of the base polymer, and a conductive heat having excellent dispersibility. A plastic elastomer composition is obtained.
The amount of component (C) composed of an ethylene-acrylic acid ester-maleic anhydride copolymer is preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the conductive thermoplastic elastomer composition of the present invention. .
Moreover, it is preferable that the compounding quantity of this (C) component is 0.1-10 mass parts with respect to 100 mass parts of said (A) component, and it is 1-1 with respect to 100 mass parts of ion conductive conductive agent (B) components. It is preferably 50 parts by mass.
The reason for the above range is that if the amount is less than the above range, the effect of compatibilization is not sufficiently exhibited, and there is a risk of deterioration of physical properties, poor molding, or the like. On the other hand, if the amount is larger than the above range, the compatibilizing effect is not greatly affected, and conversely, the strength may decrease or the hardness may increase.

In the ethylene-acrylic acid ester-maleic anhydride copolymer, the acrylic acid ester content is preferably 0.1 to 30% by mass, more preferably 1 to 20% by mass, and 3 to 15% by mass. More preferably it is. The maleic anhydride content is preferably 0.05 to 20% by mass, more preferably 0.1 to 15% by mass, further preferably 0.5 to 10% by mass, It is especially preferable that it is 10 mass%.
In the copolymer, the acrylic ester is preferably methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, or the like. Moreover, you may use the ethylene-methacrylic acid ester-maleic anhydride terpolymer which used the methacrylic acid ester instead of the acrylic acid ester as a component (C).

As the component (C), the ethylene-acrylic acid ester-maleic anhydride copolymer is most preferably used, but one or more terpolymers corresponding to the following definitions are used. May be.
The ternary copolymer that can be contained as the component (C) is a ternary copolymer comprising an olefin component (c1), an acrylic ester or a methacrylic ester (c2), and an unsaturated carboxylic acid unit (c3).
Examples of the olefin component (c1) include ethylene hydrocarbons having 2 to 6 carbon atoms such as ethylene, propylene, isobutylene, 1-butene, 1-pentene and 1-hexene.
Specific examples of the acrylate ester or methacrylate ester (c2) component include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, acrylic Examples thereof include esterified products of acrylic acid such as 2-ethylhexyl acid and 2-ethylhexyl methacrylate or methacrylic acid and alcohol. Among them, methyl acrylate, methyl methacrylate, ethyl acrylate, and ethyl methacrylate are preferable.
Unsaturated carboxylic acid unit (c3) is introduced by unsaturated carboxylic acid or its anhydride, specifically acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, fumaric acid, croton. In addition to acids and the like, unsaturated dicarboxylic acid half esters, half amides and the like can be mentioned. Of these, acrylic acid, methacrylic acid, maleic acid, and maleic anhydride are preferable, and maleic anhydride is particularly preferable. The form of the unsaturated carboxylic acid unit is not limited as long as it is copolymerized in the ternary copolymer, and examples thereof include random copolymerization, block copolymerization, and graft copolymerization.
The content of the acrylic acid ester or methacrylic acid ester (c2) component is preferably 0.1 to 30% by mass, more preferably 1 to 20% by mass, and further preferably 5 to 15% by mass. . The unsaturated carboxylic acid unit (c3) content is preferably 0.05 to 20% by mass, more preferably 0.1 to 15% by mass, and 0.5 to 10% by mass. More preferred is 1 to 10% by mass.

In the conductive thermoplastic elastomer composition of the present invention, other components may be blended in addition to the component (A), the component (B), and the component (C) as long as the object of the present invention is not violated.
For example, a softening agent can be blended to give moderate flexibility and elasticity.
Examples of softeners include oils and plasticizers. As the oil, for example, a paraffinic, naphthenic or aromatic mineral oil or a synthetic oil known per se made of a hydrocarbon oligomer or a process oil can be used. As the synthetic oil, for example, an oligomer with α-olefin, an oligomer of butene, and an amorphous oligomer of ethylene and α-olefin are preferable. Examples of the plasticizer include phthalate-based, adipate-based, separate-based, phosphate-based, polyether-based, and polyester-based plasticizers. More specifically, for example, dioctyl phthalate (DOP), dibutyl phthalate (DBP), dioctyl. Sepacate (DOS), dioctyl adipate (DOA), etc. are mentioned.

It is preferable that the compounding quantity of the said softener is 10-200 mass parts with respect to 100 mass parts of (A) component. If it is smaller than the above range, the hardness tends to be high, whereas if it is larger than the above range, the softener tends to bleed.
When a thermoplastic elastomer and / or thermoplastic elastomer composition in which a crosslinkable rubber and / or thermoplastic elastomer is dynamically crosslinked and dispersed in the thermoplastic elastomer and / or thermoplastic elastomer is used as the component (A), a softener is blended. The amount is preferably 15 to 600 parts by mass, and preferably 25 to 400 parts by mass with respect to 100 parts by mass of the crosslinkable rubber and / or thermoplastic elastomer.
When the blending amount of the softening agent is less than the above range, it is difficult to obtain the effect of adding the softening agent, that is, the effect of further improving the dispersibility of the crosslinkable rubber and / or thermoplastic elastomer at the time of dynamic crosslinking. If the amount of the softening agent is larger than the above range, the softening agent causes cross-linking inhibition, the dynamic cross-linking is not sufficiently performed, and the physical properties are likely to be lowered.
The blending amount of the softener includes the amount of extending oil when oil-extended rubber is used.

Moreover, you may mix | blend a filler etc. in order to improve mechanical strength.
Examples of the filler include powders such as silica, carbon black, clay, talc, calcium carbonate, dibasic phosphite (DLP), basic magnesium carbonate, and alumina.
The filler is preferably blended in an amount of 15% by mass or less based on the total mass of the conductive thermoplastic elastomer composition of the present invention. This is because the blending of the filler is effective in improving the tensile strength and tear strength of the elastomer composition, but if too much is blended, the flexibility of the elastomer composition decreases and the friction coefficient of the roller becomes a roller. This is to show a tendency to decrease.

You may mix | blend a foaming agent for provision of a softness | flexibility etc.
A known foaming agent can be used as the foaming agent, but a microcapsule type foaming agent is preferably used. When a microcapsule type foaming agent is used, a closed cell state can be created, and the size and number of bubble holes can be easily controlled, so that wear performance and the like are not easily lowered. The foaming agent is preferably blended at a ratio of 0.1 to 10 parts by mass, more preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the conductive thermoplastic elastomer composition of the present invention. .
In addition, in the conductive thermoplastic elastomer composition of the present invention, an anti-aging agent, an antioxidant, an ultraviolet absorber, a lubricant, a pigment, an antistatic agent, a flame retardant, a neutralizing agent, a nucleating agent, an anti-bubble agent, etc. These additives may be appropriately blended.

Second, the present invention provides a method for producing the conductive thermoplastic elastomer composition of the present invention described above.
That is, component (A) of a base polymer comprising a thermoplastic elastomer composition in which a crosslinkable rubber and / or thermoplastic elastomer is dynamically crosslinked and dispersed in a thermoplastic resin and / or thermoplastic elastomer,
(B) component consisting of an ion conductive conductive agent containing a metal salt in the EO-PO copolymer and / or EO-PO-AGE copolymer;
(C) component consisting of an ethylene-acrylic acid ester-maleic anhydride copolymer, and a process for producing a conductive thermoplastic elastomer composition comprising:
Before mixing the components (A) to (C), dynamic crosslinking of the crosslinkable rubber and / or thermoplastic elastomer is previously performed in the component (A).

Specifically, first, the crosslinkable rubber or / and the thermoplastic elastomer are dynamically cross-linked by a cross-linking agent, preferably a resin cross-linking agent, in an extruder or a kneader, and the thermoplastic resin or / and the thermoplastic elastomer are mixed. To disperse.
Next, the obtained thermoplastic elastomer composition (A), the ion conductive conductive agent (B) and the ethylene-acrylic ester-maleic anhydride copolymer (C) are kneaded in an extruder or a kneader. Thus, the conductive thermoplastic elastomer composition of the present invention is obtained.

The ion conductive conductive agent (B) has a feature that it hardly enters the dynamically cross-linked domain phase and is selectively mixed into the matrix phase. For this reason, according to the said manufacturing method, an ion conductive conductive agent (B) will be selectively arrange | positioned toward the matrix of a conductive thermoplastic elastomer composition (A), and an ion conductive conductive agent (B ) Can be unevenly distributed in the thermoplastic resin and / or the thermoplastic elastomer (A) as a matrix.
As a result, even if an ion conductive conductive agent is blended, the degree of crosslinking of the rubber is not affected, so that an increase in compression set can be suppressed. In addition, the use amount of the ion conductive conductive agent is not unnecessarily increased, so that an increase in hardness can be suppressed and raw material costs can be suppressed.

  Crosslinkable rubber or / and thermoplastic elastomer, thermoplastic resin or / and thermoplastic elastomer, crosslinking agent, preferably resin crosslinking agent, ionic conductive conductive agent (B), and ethylene-acrylate -The maleic anhydride copolymer (C) is kneaded together, and the crosslinkable rubber and / or thermoplastic elastomer is dynamically cross-linked simultaneously with mixing of the respective components. It is also possible to get things.

There are two production methods for dynamically crosslinking the EO-PO copolymer and / or the EO-PO-AGE copolymer contained in the ion conductive conductive agent (B).
As a first method, first, a crosslinkable rubber or / and a thermoplastic elastomer are dynamically cross-linked by a cross-linking agent, preferably a resin cross-linking agent, and dispersed in the thermoplastic resin or / and the thermoplastic elastomer to be a thermoplastic elastomer. A composition (A) is produced. Subsequently, the obtained thermoplastic elastomer composition (A), an ionic conductive conductive agent (B), an ethylene-acrylate-maleic anhydride copolymer (C), and a crosslinking agent, preferably a peroxide. And the EO-PO copolymer and / or the EO-PO-AGE copolymer contained in the ionic conductive agent (B) at the same time as mixing of the components (A) to (C) , Preferably a method of dynamically crosslinking with a peroxide to obtain the conductive thermoplastic elastomer composition of the present invention.
As a second method, first, a crosslinkable rubber or / and thermoplastic elastomer is dynamically cross-linked by a cross-linking agent, preferably a resin cross-linking agent, and dispersed in the thermoplastic resin or / and the thermoplastic elastomer to be thermoplastic. The elastomer composition (A) is prepared, while the EO-PO copolymer and / or the EO-PO-AGE copolymer is previously crosslinked with a crosslinking agent, preferably a peroxide, in the ion conductive conductive agent (B). Next, the thermoplastic elastomer composition (A) obtained in the step, the ion conductive conductive agent (B) obtained in the step, and an ethylene-acrylate-maleic anhydride copolymer ( C) and kneading to obtain the conductive thermoplastic elastomer composition of the present invention.
In the present invention, the former method is preferred because it requires fewer steps.

The heating temperature for dynamic crosslinking is preferably 160 to 250 ° C., and the heating time is preferably 1 to 20 minutes. Moreover, it is preferable that the heating temperature at the time of mixing of component (A)-(C) is 160-250 degreeC, and heating time is 1 to 20 minutes. For dynamic crosslinking and kneading, a twin screw extruder, a Banbury mixer, a kneader, or the like can be used.
The dynamic crosslinking may be performed in the presence of a halogen such as chlorine, bromine, fluorine or iodine. In order to allow halogen to be present during dynamic crosslinking, the halogenated resin crosslinking agent described above may be used, or a halogen-donating substance may be blended. Examples of the halogen donating substance include tin chloride such as stannic chloride, ferric chloride, and cupric chloride. As the halogen donating substance, one kind of substance may be used alone, or two or more kinds of substances may be used in combination.
The conductive thermoplastic elastomer composition obtained as described above is preferably formed into a pellet for the subsequent process. Thereby, favorable moldability can be obtained.

Furthermore, the present invention provides a molded product obtained by molding the conductive thermoplastic elastomer composition of the present invention.
The molded product of the present invention can be used for various applications, and can be shaped according to it. Among these, it is preferable to use as a conductive member in an image forming apparatus such as a copying machine, a printer, a facsimile, or an ATM. Examples of the conductive member include a roller-shaped conductive roller, an endless belt-shaped conductive belt, and a sheet-shaped pad.

  The conductive roller has a configuration including a cylindrical conductive layer made of the conductive thermoplastic elastomer composition of the present invention and a columnar core, and has a simple structure with only one conductive layer around the core. From the viewpoint of industrial production, it is preferable. However, in addition to the conductive layer, a multi-layer structure such as two or three layers may be used for adjusting the resistance of the roll or protecting the surface. can do. The core metal can be made of metal such as aluminum, aluminum alloy, SUS or iron, or ceramic.

  The conductive roller is used in an image forming apparatus. Specifically, a charging roller for uniformly charging the photosensitive drum, a developing roller for attaching toner to the photosensitive member, and a toner image from the photosensitive member. A transfer roller for transferring to a sheet or an intermediate transfer belt, a toner supply roller for conveying toner, a drive roller for driving the transfer belt from the inside, a paper feed roller that contributes to paper conveyance (more specifically, Are used as a cleaning roller for removing residual toner, and the like.

  The conductive roller can be produced by a conventional method. For example, the conductive thermoplastic elastomer composition of the present invention in the form of pellets is injection-molded by an injection molding machine and formed into a tube shape. After polishing the surface of the molded product, the conductive roller can be manufactured by cutting to a required size, inserting and bonding a cored bar, and polishing the surface as desired. Instead of the injection molding machine, it is possible to form a conductive roller by extruding it into a tube shape by a single screw extruder for resin, etc., polishing it if desired, cutting it, and inserting and bonding a cored bar.

  The conductive belt has a simple structure having only one conductive layer made of the conductive thermoplastic elastomer composition of the present invention, and is preferable from the viewpoint of industrial production. However, in addition to the conductive layer, a layer may be provided on the inner surface or the surface for resistance adjustment, surface protection, and the like, and a multilayer structure such as two layers or three layers may be used. Depending on the required performance, the type, stacking order, stacking thickness, etc. of each layer can be set as appropriate.

The conductive belt is used in an image forming apparatus. Specifically, the conductive belt is used as a transfer belt, an intermediate transfer belt, a fixing belt, a photoreceptor substrate belt, or the like.
The conductive belt can be produced by a conventional method. For example, the conductive thermoplastic elastomer composition of the present invention in the form of pellets can be extruded and molded into a belt shape with an extruder for resin, and then air-cooled to produce a conductive belt.

The conductive member of the present invention can be irradiated with ultraviolet rays to form an oxide film. The oxide film becomes a dielectric layer, and the effect of reducing the dielectric loss tangent of the conductive member, and improving the toner separation by the oxide film becoming a low friction layer can be obtained.
Further, the surface may be coated. Specifically, a known coating material in which urethane, acrylic, rubber latex or the like is a main polymer and a fluororesin is dispersed is applied by a known method such as electrostatic painting, spray painting, dipping, brush painting, etc. A coating layer can be provided. The thickness of the coating layer is preferably 1 to 20 μm. By coating the surface, for example, it is easy to scrape off the toner remaining at the time of transfer, change the detachability of the toner, control the surface energy, prevent the adhesion of paper dust and toner, reduce the friction coefficient, etc. The effect is obtained.

In the conductive member of the present invention, various physical properties can be adjusted according to the application. For example, in a conductive roller, the roller resistance value at an applied voltage of 1000 V is preferably 10 ^4.0 Ω to 10 ^9.0 Ω, and more preferably 10 ⁶ Ω to 10 ⁸ Ω.

According to the present invention, it is possible to obtain a conductive thermoplastic elastomer composition having durability, elasticity, flexibility such as rubber, and good moldability such as resin, and having a semiconductive resistance value.
In the conductive thermoplastic elastomer composition of the present invention, the dispersibility of each component contained is very excellent. As a result, for example, it is possible to reduce the yield of the manufacturing process by suppressing molding defects such as streaks appearing on the surface layer due to separation of components, and also to reduce physical properties particularly in a high temperature and high humidity state. Can be suppressed.
In the present invention, since the EO-PO copolymer and / or the EO-PO-AGE copolymer stabilizes ions derived from the metal salt, the amount of the expensive metal salt is increased carelessly. Since low resistance can be realized, it is advantageous in terms of cost.
Furthermore, since the conductive thermoplastic elastomer composition of the present invention is thermoplastic, it can be recycled.

  The conductive roller formed by molding the semiconductive thermoplastic elastomer composition of the present invention having such characteristics is very useful as a conductive member for image forming apparatuses such as printers, electrostatic copying machines, facsimile machines, and ATMs. Can be suitably used, and a good image can be obtained over a long period of time.

Hereinafter, embodiments of the present invention will be described with reference to the drawings.
In the conductive thermoplastic elastomer composition of the present embodiment, EPDM or / and acrylonitrile butadiene rubber (hereinafter referred to as “NBR”) is dynamically crosslinked and dispersed in a mixture of an olefin resin and a styrene thermoplastic elastomer. (A) component of a base polymer comprising a thermoplastic elastomer composition;
(B) component consisting of an ion conductive conductive agent containing a metal salt consisting of a metal cation and an anion having a fluoro group and a sulfonyl group in an EO-PO-AGE copolymer;
(C) component which consists of an ethylene-acrylic acid ester-maleic anhydride copolymer.
Here, the EO-PO-AGE copolymer in the component (B) made of the ion conductive conductive agent may be dynamically cross-linked.

  In the component (A) of the base polymer, in this embodiment, polypropylene is used as the olefin resin, and styrene-ethylene-ethylene / propylene-styrene copolymer (SEEPS) is used as the styrene thermoplastic elastomer. The mixing ratio of the styrene thermoplastic elastomer and the olefin resin is such that the olefin resin is 30 to 50 parts by mass with respect to 100 parts by mass of the styrene thermoplastic elastomer.

EPDM and / or NBR as a crosslinkable rubber is blended in an amount of 100 to 400 parts by weight, preferably 200 to 400 parts by weight, per 100 parts by weight of the mixture of the styrene thermoplastic elastomer and olefin resin.
As NBR, it is preferable to use low nitrile NBR having a nitrile content of less than 25%.

The EPDM and / or NBR is dynamically cross-linked by a resin cross-linking agent. As the resin crosslinking agent, a halogenated alkylphenol resin crosslinking agent is particularly preferred.
The blending amount of the resin crosslinking agent is 5 to 15 parts by mass, preferably 10 to 15 parts by mass with respect to 100 parts by mass of EPDM and / or NBR.

The component (B) composed of the ion conductive conductive agent is preferably contained in the conductive thermoplastic elastomer composition of the present invention at a volume fraction of 20 to 40%.
In terms of mass ratio, the ion conductive conductive agent (B) is preferably blended at a ratio of 2 to 15 parts by mass with respect to 100 parts by mass of the conductive thermoplastic elastomer composition of the present invention. Moreover, it is preferable that the compounding quantity of an ion conductive electrically conductive agent (B) is 3-25 mass parts with respect to 100 mass parts of base polymers (A).

As the metal salt, lithium fluoroalkyl sulfonate is used. The metal salt is blended at a ratio of 10 to 25 parts by mass, assuming that the total component (B) of the ion conductive conductive agent is 100 parts by mass.
As the EO-PO-AGE copolymer, an EO-PO-AGE copolymer having a content ratio of ethylene oxide: propylene oxide: allyl glycidyl ether of 80 to 95 mol%: 1 to 10 mol%: 1 to 10 mol% Use coalescence. The number average molecular weight Mn of the copolymer is particularly preferably 50,000 or more.

The EO-PO-AGE copolymer may be dynamically crosslinked with a peroxide.
As the peroxide, di (tert-butylperoxy) diisopropylbenzene is preferably used. It is preferable that the compounding quantity of the said peroxide is 0.5-3 mass parts with respect to 100 mass parts of EO-PO-AGE copolymers.
A crosslinking aid may be blended with the peroxide. As the crosslinking aid, dioximes are preferable, and N, N′-m-phenylenebismaleimide is more preferable. The amount of the crosslinking aid is 0.1 to 5 parts by mass, preferably 0.2 to 2 parts by mass with respect to 100 parts by mass of the EO-PO-AGE copolymer.

In the component (C) composed of an ethylene-acrylic acid ester-maleic anhydride copolymer, methyl acrylate or ethyl acrylate is used as the acrylic acid ester, and ethyl acrylate is particularly preferred.
The proportion of the constituent monomers is such that the acrylate content is 3 to 10% by mass and the maleic anhydride content is 1 to 5% by mass.
The copolymer comprising the component (C) has a melt flow rate of 0.5 to 100 g / 10 minutes, preferably 1 to 50 g / 10 minutes.

The amount of component (C) composed of an ethylene-acrylic acid ester-maleic anhydride copolymer is 0.1 to 3 parts by mass with respect to 100 parts by mass of the conductive thermoplastic elastomer composition of the present invention.
Moreover, the compounding quantity of ethylene-acrylic acid ester-maleic anhydride copolymer (C) is 3-30 mass parts with respect to 100 mass parts of (B) component of an ion conductive conductive agent, and (A) component of a base polymer. It is set as 0.5-5 mass parts with respect to 100 mass parts.

The conductive thermoplastic elastomer composition of the present embodiment contains a softener, calcium carbonate and carbon black, and optionally a foaming agent, in addition to the components (A) to (C).
As the softening agent, paraffinic oil is preferable, and paraffin process oil is more preferable. It is preferable that the compounding quantity of a softening agent is 50-200 mass parts with respect to 100 mass parts of components (A). Moreover, it is preferable that it is 50-250 mass parts with respect to 100 mass parts of EPDM or / and NBR in a component (A).
It is preferable that the compounding quantity of calcium carbonate is 5-10 mass parts with respect to 100 mass parts of the whole conductive thermoplastic elastomer composition of this invention.
It is preferable that the compounding quantity of carbon black is 1-10 mass parts with respect to 100 mass parts of the whole conductive thermoplastic elastomer composition of this invention.
As the foaming agent, a microcapsule type foaming agent is preferable. As for the compounding quantity of a foaming agent, it is more preferable that it is 0.5-5 mass parts with respect to 100 mass parts of the whole conductive thermoplastic elastomer composition of this invention.

The conductive thermoplastic elastomer composition of the present invention is produced by the following method.
First, EPDM or / and NBR are previously pelletized. The pellets of EPDM or / and NBR, styrene thermoplastic elastomer, olefin resin, cross-linking agent and softener are kneaded at a temperature of 200 ° C., and pellets of the thermoplastic elastomer composition as component (A) of the base polymer Is made.

(A) component pellets comprising the obtained thermoplastic elastomer composition, (B) component of an ion conductive conductive agent, (C) component of ethylene-acrylic acid ester-maleic anhydride copolymer, calcium carbonate, carbon Black, if necessary, a blowing agent is kneaded at a temperature of 200 ° C. to obtain pellets of the conductive thermoplastic elastomer composition of the present invention.
When the EO-PO-AGE copolymer contained in the component (B) of the ion conductive conductive agent is dynamically cross-linked with a peroxide, the peroxide and the cross-linking aid are used in the subsequent step. What is necessary is just to knead | mix with (B) component etc. which consist of.

The conductive roller of the present invention can be obtained by molding the conductive thermoplastic elastomer composition of the present invention thus obtained.
One embodiment of the conductive roller of the present invention is shown in FIG.
The conductive roller 10 includes a cylindrical roller portion 11 and a columnar core 12 made of the conductive thermoplastic elastomer composition of the present invention.
The conductive roller 10 extrudes a pellet-shaped conductive thermoplastic elastomer composition of the present invention into a tube shape using a single screw extruder under a condition of 180 to 230 ° C., and a metal core 12 in a hollow portion. Can be obtained by press-fitting or fixing both with an adhesive. In addition, it can also be set as a substantially D-shaped rubber roller by press-fitting a substantially D-shaped core material in the hollow part of the roller part shape | molded by the cylindrical shape.
Further, the surface of the conductive roller 10 may be coated (not shown).

The conductive roller 10 of the present invention produced by the above method preferably has a roller resistance value of 10 ⁴ Ω to 10 ⁹ Ω at an applied voltage of 1000 V, more preferably 10 ⁶ Ω to 10 ⁸ Ω. preferable.

Hereinafter, examples and comparative examples of the paper feed roller of the present invention will be described in detail.
A tube-like extruded product was produced using the composition having the composition described in Tables 1 to 3, and this was fitted into the shaft core to produce a conductive roller. Various tests were performed on the obtained conductive roller.

The materials used are as follows.
In addition, although 100% oil-extended EPDM was used for EPDM, the extended oil of oil-extended EPDM is included in the blending amount of the softening agent in the table, and the value of only the rubber component is described in the EPDM column. For example, in the case of 100 parts by mass of EPDM and 174 parts by mass of the softening agent, 100 parts by mass of the extended oil derived from oil-extended EPDM is 174 parts by mass of the softening agent, and the remaining 74 parts by mass are the following commercially available softening agents.

・ EPDM: “Esprene 670F” manufactured by Sumitomo Chemical Co., Ltd. (100% paraffin oil)
・ NBR: "DN401LL" manufactured by Nippon Zeon Co., Ltd.
・ SEEPS: Hydrogenated Styrenic Thermoplastic Elastomer (Septon 4 manufactured by Kuraray Co., Ltd.)
077 ")
PP: Polypropylene resin ("Novatec PP" manufactured by Nippon Polychem Co., Ltd.)
・ Crosslinking agent: Halogenated alkylphenol resin crosslinking agent (Takka Chemical Co., Ltd.
250-III ")
・ Softener: Paraffinic oil (“Diana Process Oil PW-38” manufactured by Idemitsu Kosan Co., Ltd.)
0 ")
・ Calcium carbonate: “BF300” manufactured by Shiraishi Calcium Co., Ltd.
・ Carbon black; “Seast 3” manufactured by Tokai Carbon Co., Ltd.
・ Compatibilizer; ethylene-acrylic acid ester-maleic anhydride copolymer (Arkema Co., Ltd.)
"Bondyne LX4110")
Conductive agent 1; EO-PO-AGE copolymer (“ZSN8030” manufactured by Nippon Zeon Co., Ltd.):
Lithium trifluoromethanesulfonate (manufactured by Sanko Chemical Co., Ltd.) = 9: 1 (quality
Ratio)
-Conductive agent 2; polyether-polyolefin copolymer ("Perez" manufactured by Sanyo Chemical Industries, Ltd.
Tat 300 "): lithium trifluoromethanesulfonate (Sanko Chemical (
Co., Ltd.) = 20: 1 (mass ratio)
・ Conducting agent 3 ： Polyether block amide copolymer (Ciba Specialty Chemical)
"IRGASTAT P18"): trifluoromethanesulfonic acid
Tium (Sanko Chemical Co., Ltd.) = 9: 1 (mass ratio)
・ Peroxide: Di (tert-butylperoxy) diisopropylbenzene (Nippon Yushi Co., Ltd.
) "Perbutyl P")
・ Crosslinking aid: N, N′-m-phenylenebismaleimide (“actor P” manufactured by Kawaguchi Chemical Co., Ltd.
BM-R ")
・ Foaming agent: “MB170EVA65” manufactured by Matsumoto Yushi Seiyaku Co., Ltd.

The manufacturing method was as follows.
Thermoplastic elastomer in which EPDM or / and NBR are dynamically cross-linked by a resin cross-linking agent and dispersed in a mixture of styrenic thermoplastic elastomer (SEEPS) and polypropylene resin (PP) as component (A) of the base polymer The composition was used.
First, EPDM and NBR were previously pelletized. This pellet-shaped EPDM or / and NBR, styrenic thermoplastic elastomer, polypropylene resin, cross-linking agent, and softening agent are blended in the proportions shown in the above table, dry blended with a tumbler, and then a twin screw extruder (IPEC) (HTM38) manufactured) and kneaded at a rotation speed of 200 rpm and a temperature of 200 ° C. to produce pellets of a thermoplastic elastomer composition.

  Pellets of the obtained thermoplastic elastomer composition, calcium carbonate, carbon black, ethylene-acrylic acid ester-maleic anhydride copolymer as a compatibilizing agent, ionic conductive conductive agent, peroxide as required, crosslinking aid The foaming agent was blended at the ratio shown in the above table, dry blended with a tumbler, and then kneaded at a rotational speed of 200 rpm and a temperature of 200 ° C. with a twin-screw extruder (“HTM38” manufactured by Ipec). A pellet of a conductive thermoplastic elastomer composition was obtained.

The obtained pellets of the electrically conductive thermoplastic elastomer composition were extruded into a tube shape at a rotation speed of 20 rpm and a temperature of 200 ° C. using a single-screw extruder (SUNNT φ50 extruder), and extruded with an outer diameter of 12 mm and an inner diameter of 5 mm. A molded product was obtained.
A cored bar was inserted into the hollow part of the obtained tube to obtain a conductive roller of the present invention.
In Examples 7 and 8, the obtained conductive roller was subjected to surface coating. That is, a surface coating agent (“JLY-009” manufactured by Nippon Atisone) was sprayed and baked at 150 ° C. for 10 minutes.

The following tests were performed on the obtained conductive roller.
(Roller resistance value)
As shown in FIG. 2, the roller portion 11 of the conductive roller 10 that has passed through the cored bar 12 is abutted and mounted on a φ30 aluminum drum 13 in an atmosphere of a temperature of 23 ° C. and a relative humidity of 55%. The end of the lead wire with the internal resistance r (100Ω to 10 kΩ) connected to the side is connected to one end surface of the aluminum drum 13 and the tip of the lead wire connected to the negative side of the power supply 14 is connected to one end surface of the core metal 12 to energize Went. The conductive roller 10 was indirectly rotated by applying a load of 500 g to both ends of the core metal 12 and rotating the aluminum drum 13 while applying a voltage of 1000 V between the core metal 12 and the aluminum drum 13. At this time, resistance measurement was performed 36 times in the circumferential direction, and the average value was obtained. The value of the internal resistance was adjusted according to the level of the resistance value of the roller so that the effective number of the measured value was as large as possible. In the apparatus of FIG. 2, when the applied voltage is E, the roller resistance value R is R = r × E / V−r, but this time the term −r is regarded as minute, and R = r × E / V, The roller resistance value R was calculated from the detected voltage V applied to the internal resistance r. In the table, the logarithmic value of the average roller resistance value is shown.

(Stability under high temperature and high humidity)
The conductive roller was stored at a high temperature and high humidity of a temperature of 30 ° C. and a relative humidity of 80%. One week later, the roller resistance value was measured by the above method. Thus, the cycle of storing under high temperature and high humidity and measuring the roller resistance value every week was continued for one month.
The evaluation was “gradual decrease” when the roller resistance value continued to decrease gradually within one month and was not stable, and “no change” when stable.

(Print test)
The conductive rubber rollers of Examples and Comparative Examples were mounted as a transfer roller or a charging roller on a commercially available printer (“C5200n” manufactured by Oki Data Co., Ltd.) or an attached cartridge (black).
50 sheets were printed under the conditions of a temperature of 23 ° C. and a relative humidity of 55%. The obtained printed matter was visually confirmed for printing density, printing unevenness, white spot and the like.

As is apparent from the description in the table, in Comparative Examples 1, 4 and 6, in which the compatibilizing agent ethylene-acrylic ester-maleic anhydride copolymer was not blended, the ionic conductive conductive agent was a phase. It did not melt and could not be extruded into a tube shape.
Further, in Comparative Example 2, Comparative Example 3 and Comparative Example 5 using a polymer other than the EO-PO copolymer and / or the EO-PO-AGE copolymer in the ion conductive conductive agent, extrusion molding can be performed well. However, the stability under high temperature and high humidity was poor, and the roller resistance value gradually decreased. Further, it was found that the printing density gradually increased when it was actually incorporated into a printer as a transfer roller, leaving room for improvement in practice.

On the other hand, in the examples, the extrusion molding was good, the stability under high temperature and high humidity was high, and the roller resistance value did not change. Further, it was found that the printing density was stable even when it was actually incorporated into a printer as a transfer roller or a charging roller, and it was extremely practical.
In addition, in Examples 7 and 8 where the surface coating was applied, the friction coefficient could be further reduced.

It is the schematic of the electroconductive roller of this invention. It is the schematic of the apparatus which measures the roller resistance value of an electroconductive roller.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Conductive roller 11 Roller part 12 Core metal 13 Aluminum drum 14 Power supply

Claims (11)

A component (A) comprising a thermoplastic resin and / or a thermoplastic elastomer;
(B) component consisting of an ionic conductive conductive agent containing a metal salt in an ethylene oxide-propylene oxide copolymer and / or an ethylene oxide-propylene oxide-allyl glycidyl ether copolymer;
Component (C) comprising an ethylene-acrylic ester-maleic anhydride copolymer;
A conductive thermoplastic elastomer composition comprising:   The conductive thermoplastic elastomer composition according to claim 1, wherein a styrene thermoplastic elastomer and an olefin resin are used as the component (A).   The component (A) comprises a thermoplastic elastomer composition in which a crosslinkable rubber or / and thermoplastic elastomer are dynamically crosslinked and dispersed in the thermoplastic resin and / or thermoplastic elastomer. The conductive thermoplastic elastomer composition according to claim 2.   The thermoplastic elastomer composition comprises at least one rubber component selected from general-purpose rubbers such as EPDM, butyl rubber, and NBR as a crosslinkable rubber dispersed by the dynamic crosslinking and / or a thermoplastic elastomer. The conductive thermoplastic elastomer composition according to claim 3, which is used.   The conductive thermoplastic elastomer composition according to claim 3 or 4, wherein the dynamic crosslinking is performed using a resin crosslinking agent.   The ethylene oxide-propylene oxide copolymer and / or the ethylene oxide-propylene oxide-allyl glycidyl ether copolymer as the component (B) are dynamically crosslinked with a peroxide. 2. The conductive thermoplastic elastomer composition according to item 1. A method for producing a conductive thermoplastic elastomer composition according to any one of claims 3 to 6,
The method for producing a conductive thermoplastic elastomer composition, wherein the dynamic crosslinking of (A) is performed before mixing the component (A) and the component (B).   A molded article obtained by molding the conductive thermoplastic elastomer composition according to any one of claims 1 to 6.   A conductive thermoplastic molded article obtained by foaming foam molding the conductive thermoplastic elastomer composition according to any one of claims 1 to 6.   The electroconductive roller obtained by shape | molding the electroconductive thermoplastic-elastomer composition of any one of Claim 1 thru | or 6.   The molded article according to any one of claims 8 to 10, wherein a surface treatment is applied.

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