JP5608956B2 - Polyether based multi-component copolymer and cross-linked product thereof - Google Patents

Description

  The present invention relates to a polyether-based multi-component copolymer for a semiconductive rubber material and a semiconductive rubber material comprising a cross-linked product obtained by cross-linking the copolymer.

  Conventionally, in image forming apparatuses such as copiers and printers, a non-contact charging method in which a high voltage is applied by performing corona discharge has been used. However, since corona discharge uses a high-voltage power source, it is expensive and includes problems such as generation of ozone as a product.

  In recent years, a contact-type charging system has been adopted as a substitute for corona discharge. In the contact-type charging system, a rubber roll having a structure in which a rubber layer is formed on a roll surface such as a charging roll or a developing roll is generally used. In such a contact-type charging system, the rubber roll and the photosensitive member are always in contact with each other, so that the physical properties of the rubber layer on the surface have a great influence on the improvement in image quality.

As a material for a rubber layer in a charging roll, a developing roll, etc., a material having an electric resistance value of about 10 ⁵ to 10 ⁹ Ωcm and showing a stable electric resistance value is required. Usually, a charging roll, a developing roll, and the like are provided with a coating layer on the surface of a rubber layer in consideration of releasability from toner and durability of the roll itself. Accordingly, the resistance value of the roll as a whole is increased, so that the resistance value of the rubber layer itself is preferably low. In order to satisfy this requirement, a method of adding a conductive additive to a rubber component has been conventionally devised.

  However, the electrical resistance of the rubber material obtained in this way greatly depends on the amount of conductive additive added and the state of dispersion. For example, when carbon black is added to the rubber component, there is a problem that the electrical resistance changes remarkably due to a slight difference in addition amount, poor dispersion of carbon black, and the like, and the resulting rubber material becomes rigid. . In addition, a method of adding an ionic conductive agent to a rubber component is also known, but there are essential drawbacks such as a decrease in rubber physical properties due to the addition and surface contamination due to bleeding from the rubber material.

  In addition, epichlorohydrin rubber (for example, see Patent Document 1 and Patent Document 2) is disclosed as a proposal using a rubber having a relatively low electrical resistance, and is excellent in electrical resistance and environmental dependency.

  On the other hand, as part of countermeasures against environmental problems in recent years, there has been an active movement to avoid using polymer materials containing a large amount of halogen as much as possible. However, at present, a polyether polymer rubber having any of the above-mentioned excellent characteristics that can replace epichlorohydrin rubber has not yet been found.

On the other hand, various polyether polymer rubbers that use little or no halogen-containing compounds such as epichlorohydrin have been proposed, such as ethylene oxide and oxirane monomers copolymerizable therewith. The copolymer is used for rubber parts of OA equipment (for example, see Patent Document 3), used for a water-swellable sealing material (for example, see Patent Document 4), and used for a polymer solid electrolyte ( For example, see Patent Document 5).
JP-A-10-97118 JP 2000-63656 A JP 2002-105246 A JP 2002-194202 A However, the polyether polymers described in these prior documents have performances that can be used only in the above-mentioned specific fields, and are polymers containing structural units derived from specific oxirane monomers. There is no description or suggestion that ether copolymers have excellent semiconducting properties.

  In view of the environmental problems in recent years, an object of the present invention is to provide a polyether copolymer that can be used as a rubber having excellent semiconducting properties without using a halogen-containing compound such as epichlorohydrin as a main constituent unit. There is an attempt to provide a coalescence and a cross-linked product thereof.

  As a result of various studies to solve the above problems, the present inventors have used a specific glycidyl ester as a monomer, the same monomer, and a crosslinkable oxirane monomer having a crosslinkable functional group. It is found that a multi-component copolymer having a specific composition obtained by copolymerizing with an alkylene oxide substantially randomly if necessary exhibits a performance as a rubber having excellent semiconducting characteristics by crosslinking the copolymer. The present invention has been completed.

The present invention includes a constitutional unit derived from 10 to 99 mol% of a structural unit represented by the following general formula (I), 0 to 89 mol% of a structural unit represented by the following general formula (II), and a crosslinkable oxirane monomer From a cross-linked product obtained by cross-linking a semiconductive multi-component copolymer containing 1 to 10 mol% of units
Provide electrical or electronic equipment material .

[Wherein, R ¹ represents an alkyl group having 1 to 6 carbon atoms. ]

[Wherein R ² represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a phenyl group or —CH ₂ OR ³ , and R ³ represents an alkyl group having 1 to 6 carbon atoms or a phenyl group. ]
Hereinafter, the configuration of the present invention will be described in detail.

A polyether multicomponent comprising 10 to 99 mol% of the structural unit (I), 0 to 89 mol% of the structural unit (II), and 1 to 10 mol% of the structural unit derived from a crosslinkable oxirane monomer. Regarding the molecular weight of the polymer (hereinafter abbreviated as polyether multi-component copolymer), Mooney viscosity (ML _{1 + 4} ) measured at 100 ° C. according to the method described in JIS K 6300-1 from the viewpoint of processability of the rubber material. Is in the range of 10 to 200, preferably 20 to 100. Such a high molecular weight polyether multi-component copolymer is prepared by using a solution capable of ring-opening polymerization of an oxirane compound as a catalyst, and by a solution polymerization method, a slurry polymerization method, or the like within a temperature range of -20 to 100 ° C. Can do. As such a catalyst, for example, a catalyst system obtained by reacting organic aluminum mainly with water or phosphorus oxo acid compound or acetylacetone, and obtained by reacting water mainly with organic zinc. Examples thereof include a catalyst system and an organic tin-phosphate ester condensate catalyst system. For example, polyether multicomponent copolymers can be prepared using the organotin-phosphate ester condensate catalyst system described in US Pat. No. 3,773,694 by the present applicant.

  In addition, in such a manufacturing method, it has 10-99 mol% of said structural units (I), 0-89 mol% of said structural units (II), and 1-10 mol% of structural units derived from a crosslinkable oxirane monomer. In addition, in order to produce a polyether multi-component copolymer having rubber-like properties that is the object of the present invention, it is preferable to copolymerize monomer components corresponding to these structural units substantially randomly. .

  The proportion of each structural unit in the polyether multi-component copolymer is 10 to 99 mol% of the structural unit (I), 0 to 89 mol% of the structural unit (II), and the structural unit 1 derived from the crosslinkable oxirane monomer. It is in the range of -10 mol%. The proportion of the structural unit (I) is preferably in the range of 10 to 80 mol%, more preferably 20 to 75 mol%.

  When the proportion of the structural unit (I) is less than 10 mol%, a rubber-like polymer cannot be obtained due to crystallization of alkylene oxide units. On the other hand, if this ratio exceeds 99 mol%, a sufficient crosslinking density cannot be obtained when the polyether multi-component copolymer of the present invention is crosslinked, and as a result, a crosslinked product having sufficient physical properties can be obtained. Can not. Further, as the proportion of the structural unit (I) increases, the heat resistance and fuel oil resistance of the resulting crosslinked product are improved, but the low-temperature flexibility tends to decrease. Therefore, the proportion of the structural unit (I) is preferably in the range of 10 to 80 mol%, more preferably 20 to 75 mol%.

  Examples of the monomer oxirane compound used to constitute the structural unit (I) include glycidyl esters such as glycidyl acetate, glycidyl propionate, and glycidyl butyrate. Two or more of these may be used in combination. However, when a glycidyl ester having a large number of carbon atoms is used, the semiconductivity of the resulting crosslinked product of the polyether multi-component copolymer tends to decrease. Therefore, the oxirane compounds preferably used in the present invention are glycidyl acetate and glycidyl propionate. Particularly preferred is glycidyl propionate.

  The proportion of the structural unit (II) may be 0 mol%, but conversely if the proportion exceeds 89 mol%, the proportion of the structural unit (I) will be less than 10 mol%. A rubber-like polymer cannot be obtained by the conversion. A preferred range of the proportion of the structural unit (II) is 10 to 80 mol%.

  Examples of the monomer used to constitute the structural unit (II) include alkylene oxides such as ethylene oxide, propylene oxide, isobutylene oxide, n-butylene oxide, methyl glycidyl ether, and styrene oxide. Two or more of these may be used in combination. However, when an alkylene oxide having a large number of carbon atoms is used, the semiconductivity of the resulting crosslinked product of the polyether multi-component copolymer tends to be lowered. Therefore, the alkylene oxides preferably used as monomers are ethylene oxide and propylene oxide, Particularly preferred is ethylene oxide.

 The proportion of the structural unit derived from the crosslinkable oxirane monomer used in the polyether multi-component copolymer of the present invention is in the range of 1 to 10 mol%, preferably 1 to 6 mol%. When this ratio is less than 1 mol%, a sufficient crosslinking density cannot be obtained when the polyether copolymer of the present invention is crosslinked, and as a result, a crosslinked product having sufficient physical properties cannot be obtained. Moreover, when the ratio of the structural unit derived from a crosslinkable oxirane monomer exceeds 10 mol%, there is a possibility of causing a problem of so-called scorch and a decrease in heat resistance, such being undesirable.

  The crosslinkable oxirane monomer may be any oxirane monomer capable of crosslinking the copolymer of the structural unit (I) and the structural unit (II), such as allyl glycidyl ether, glycidyl acrylate, methacrylic acid. Ethylenically unsaturated group-containing oxiranes such as glycidyl, glycidyl crotonic acid, 3,4-epoxy-1-butene, 2,3-epoxypropyl-2 ′, 3′-epoxy-2′-methylpropyl ether, metaglycidic acid Examples thereof include diepoxy compounds such as glycidyl ester, glycidyl metaglycidyl ester, and 1,2,3,4-diepoxy-2-methylbutane. In addition, as halogen-containing oxirane monomers, epihalohydrins such as epichlorohydrin, epibromohydrin, epiiodohydrin, p-chlorostyrene oxide, dibromoglycidylmethyl carbonate, m-chloromethylstyrene oxide, p-chloromethylstyrene oxide, chloro Illustrative are halogen-substituted oxiranes other than epihalohydrins such as glycidyl acetate and chloromethyl glycidate. Two or more of these crosslinkable oxirane monomers may be used in combination.

  As a crosslinking agent when an ethylenically unsaturated group-containing oxirane such as allyl glycidyl ether or glycidyl methacrylate is applied to the polyether multi-component copolymer of the present invention as a crosslinkable oxirane monomer, it is usually used for diene rubbers. For example, sulfur-based crosslinking (vulcanizing) agents such as sulfur, tetramethylthiuram disulfide, dipentamethylenethiuram tetrasulfide, morpholine disulfide, parabenzoquinone dioxime, benzoylquinone dioxime, etc. Quinonedioxime crosslinker, polymethylolphenol, resin phenolic crosslinker such as alkylphenol formaldehyde resin, bromide alkylphenol formaldehyde resin, dicumyl peroxide, 1,3-bis (ter-butylperoxyisopropyl) Organic peroxide crosslinking agents such as benzene, n-butyl-4,4-bis (ter-butylperoxy) valerate, 2,5-dimethyl-2,5-di (ter-butylperoxy) hexane, etc. Can be mentioned. It is optional to use these crosslinking agents in combination with vulcanization accelerators, vulcanization acceleration assistants, crosslinking assistants, and retarders known for diene rubbers.

  Furthermore, as a crosslinking agent when the above-described diepoxy compounds are applied to the polyether multi-component copolymer of the present invention, alkyldithiocarbamate-based crosslinking agents such as zinc dimethyldithiocarbamate and iron dimethyldithiocarbamate, ethylenediamine, diethylenetriamine, Amine-based crosslinking agents such as triethylenetetramine, p-phenylenediamine and hexamethylenediamine carbamate, active sulfur-releasing organic vulcanizing agents such as dipentamethylene thiuram tetrasulfide, ammonium benzoate, isocyanuric acid, ammonium salts of organic acids, etc. Can be mentioned. Also in this case, the use of a crosslinking accelerator and a retarder is optional, and examples of the accelerator include imidazoles and onium salts, and examples of the retarder include phthalic anhydride.

  Among these crosslinkable oxirane monomers, as a crosslinking agent when epihalohydrins such as epichlorohydrin and epibromohydrin are applied to the polyether copolymer of the present invention, those usually used for halogen-containing rubbers are used. For example, amine-based crosslinking agents such as ethylenediamine, diethylenetriamine, triethylenetetramine, p-phenylenediamine, hexamethylenediamine carbamate, thiourea-based crosslinking agents such as ethylenethiourea, 1,3-diethylthiourea, trimethylthiourea, Thiadiazole-based crosslinking agents such as 2,5-dimercapto-1,3,4-thiadiazole, 2,5-dimercapto-1,3,4-thiadiazole-5-thiobenzoate, 2,4,6-trimercapto-1, 3,5-triazine, Triazine-based crosslinking agents such as 1-hexylamino-3,5-dimercaptotriazine, 1-dibutylamino-3,5-dimercaptotriazine, 1-phenylamino-3,5-dimercaptotriazine, quinoxaline-2,3 -2,3-dimercaptoquinoxaline derivative-based crosslinking agents such as dithiocarbonate, 6-methylquinoxaline-2,3-dithiocarbonate, 5,6-dimethylquinoxaline-2,3-dithiocarbonate, pyrazine-2,3-dithio 2,3-Dimercaptopyrazine derivatives such as carbonate, 5-methyl-2,3-dimercaptopyrazine, 5,6-dimethyl-2,3-dimercaptopyrazine, 5-methylpyrazine-2,3-dithiocarbonate Crosslinker, bisphenol A, bisphenol AF, bisphenol S, etc. And the like bisphenol-based crosslinking agent. In addition, it is optional to use a known vulcanization accelerator, vulcanization acceleration assistant, crosslinking assistant and retarder which are usually used together with these crosslinking agents.

 In addition, when halogen-substituted oxiranes other than epihalohydrins such as p-chloromethylstyrene oxide, glycidyl chloroacetate, and chloromethyl glycidate are applied as the crosslinkable oxirane monomer to the polyether copolymer of the present invention, In addition to the crosslinking agent exemplified when epihalohydrins are applied, sulfur, active sulfur releasing organic vulcanizing agent, ammonium benzoate and the like can be exemplified as the crosslinking agent. Further, similarly, it is optional to use a known vulcanization accelerator, vulcanization accelerator, crosslinking assistant, and retarder in combination.

  In the polyether multi-component copolymer, additives other than those usually used in the art, for example, lubricants, fillers, reinforcing agents, plasticizers, anti-aging agents, processing aids, flame retardants, foaming agents , Foaming aids, conductive agents, antistatic agents, pigments, tackifiers and the like can be blended as necessary. Furthermore, it is also possible to perform blending with rubber, resin and the like, which is usually performed in the technical field.

  In order to produce a rubber product by crosslinking the polyether multi-component copolymer, a polyether multi-component is appropriately used by using a mixing means conventionally used in the field of polymer processing, for example, a mixing roll, a Banbury mixer, various kneaders and the like. A crosslinker and other compounding agents are blended into the copolymer to crosslink the polyether multi-component copolymer. The temperature and time required for crosslinking are appropriately set depending on the crosslinkable oxirane compound, the crosslinking agent, etc. used in the production of the polyether multi-component copolymer. Usually, the temperature is 100 to 250 ° C., and the time is 0.5 to 300 minutes. Is in range. As a method of cross-linking molding, methods such as compression molding using a mold, injection molding, steam can, air bath, infrared ray, or heating using microwaves can be appropriately used.

  The cross-linked product of the polyether multi-component copolymer according to the present invention thus obtained can be applied to the field where the polyether rubber represented by epichlorohydrin rubber is used. The polyether multi-component copolymer according to the present invention has a low electric resistance value, and is useful as a semiconductive rubber part such as a charging roll and a transfer roll used in OA equipment, taking advantage of its excellent environmental dependency. Application to rubber parts is expected.

  Furthermore, when a crosslinkable oxirane monomer that does not contain a halogen atom (non-halogen) is used, it is possible to reduce environmental pollution such as generation of a halogen-containing gas due to combustion.

  Hereinafter, the present invention will be specifically described by way of examples. However, the present invention is not limited to the following examples without departing from the gist thereof.

Production of polymerization catalyst 10 g of tributyltin chloride and 35 g of tributyl phosphate were put into a three-necked flask equipped with a stirrer, a thermometer, and a condenser, and heated at 250 ° C. for 20 minutes with stirring under a nitrogen stream. The product was distilled off and a solid condensate was obtained as a residue at room temperature. Thereafter, this was used as a polymerization catalyst.

Analysis of Polymer The copolymer composition of the polyether copolymer obtained in the following examples was determined by ¹ H-NMR spectrum. The Mooney viscosity (ML _{1 + 4} ) of the polyether copolymer was measured at 100 ° C. using an L rotor according to the method described in JIS K 6300.

Example 1
The inside of a jacketed stainless steel reactor having an internal volume of 5 L was purged with nitrogen, charged with 6 g of the above condensate catalyst, 428 g of glycidyl propionate, 56 g of allyl glycidyl ether, and 2250 g of normal hexane as a solvent, and 266 g of ethylene oxide was glycidyl propionate. The polymerization rate was successively added while monitoring the polymerization rate by gas chromatography. The polymerization reaction was stopped by adding 1 g of methanol after 4 hours while maintaining the reaction temperature at 20 ° C. After taking out the polymer by decantation, it was dried at 80 ° C. under reduced pressure for 8 hours to obtain 715 g of a polyether copolymer. The copolymer composition of the obtained polyether copolymer was 30 mol% glycidylpropionate units, 66 mol% ethylene oxide units, and 4 mol% allyl glycidyl ether units. The Mooney viscosity measured at 100 ° C. was 37.

(Example 2)
The inside of a jacketed stainless steel reactor with an internal volume of 5 L was purged with nitrogen, charged with 6 g of the condensate catalyst, 436 g of glycidyl butionate, 77 g of allyl glycidyl ether, and 2250 g of normal hexane as a solvent, and 237 g of ethylene oxide was glycidyl propionate. While the polymerization rate was monitored by gas chromatography, it was added successively. The polymerization reaction was stopped by adding 1 g of methanol after 4 hours while maintaining the reaction temperature at 20 ° C. After taking out the polymer by decantation, it was dried at 80 ° C. under reduced pressure for 8 hours to obtain 684 g of a polyether copolymer. The copolymer composition of the obtained polyether copolymer was 30 mol% of glycidylpropionate units, 64 mol% of ethylene oxide units, and 6 mol% of allyl glycidyl ether units. The Mooney viscosity measured at 100 ° C. was 31.

(Example 3)
The inside of a jacketed stainless steel reactor having an internal volume of 5 L was purged with nitrogen, charged with 6 g of the above condensate catalyst, 646 g of glycidyl propionate, 36 g of allyl glycidyl ether, and 2250 g of normal hexane as a solvent, and 68 g of ethylene oxide was glycidyl propionate. The polymerization rate was successively added while monitoring the polymerization rate by gas chromatography. The polymerization reaction was stopped by adding 1 g of methanol after 4 hours while maintaining the reaction temperature at 20 ° C. After taking out the polymer by decantation, it was dried at 80 ° C. under reduced pressure for 8 hours to obtain 702 g of a polyether copolymer. The copolymer composition of the obtained polyether copolymer was 70 mol% glycidyl propionate units, 26 mol% ethylene oxide units, and 4 mol% allyl glycidyl ether units. The Mooney viscosity measured at 100 ° C. was 22.

Example 4
The inside of a jacketed stainless steel reactor having an internal volume of 5 L was purged with nitrogen, charged with 6 g of the above condensate catalyst, 593 g of glycidyl propionate, 36 g of allyl glycidyl ether, and 2250 g of normal hexane as a solvent, and 120 g of propylene oxide was glycidyl propio The polymerization rate was successively added while monitoring the polymerization rate of the nate by gas chromatography. The polymerization reaction was stopped by adding 1 g of methanol after 4 hours while maintaining the reaction temperature at 20 ° C. The polymer was taken out by decantation and then dried at 80 ° C. for 8 hours under reduced pressure to obtain 696 g of a polyether copolymer. The copolymer composition of the obtained polyether copolymer was 64 mol% glycidylpropionate units, 32 mol% ethylene oxide units, and 4 mol% allyl glycidyl ether units. The Mooney viscosity measured at 100 ° C. was 24.

(Example 5)
The inside of a jacketed stainless steel reactor with an internal volume of 5 L is purged with nitrogen, and the above condensate catalyst 6 g, glycidyl propionate 553 g, 2,3-epoxypropyl-2 ′, 3′-epoxy-2′-methylpropyl ether 44 g and 2250 g of normal hexane as a solvent were charged, and 153 g of ethylene oxide was sequentially added while monitoring the polymerization rate of glycidyl propionate by gas chromatography. The polymerization reaction was stopped by adding 1 g of methanol after 4 hours while maintaining the reaction temperature at 20 ° C. After taking out the polymer by decantation, it was dried at 80 ° C. for 8 hours under reduced pressure to obtain 703 g of a polyether copolymer. The copolymer composition of the obtained polyether copolymer was 49 mol% glycidyl propionate units, 48 mol% ethylene oxide units, 2,3-epoxypropyl-2 ', 3'-epoxy-2'-methylpropyl ether. The unit was 3 mol%. The Mooney viscosity measured at 100 ° C. was 27.

(Example 6)
The inside of a jacketed stainless steel reactor with an internal volume of 5 L was purged with nitrogen, and 6 g of the above condensate catalyst, 281 g of glycidyl propionate, 2,3-epoxypropyl-2 ′, 3′-epoxy-2′-methylpropyl ether 69 g and 2250 g of normal hexane as a solvent were charged, and 401 g of ethylene oxide was sequentially added while monitoring the polymerization rate of glycidyl propionate by gas chromatography. The polymerization reaction was stopped by adding 1 g of methanol after 4 hours while maintaining the reaction temperature at 20 ° C. The polymer was taken out by decantation and then dried at 80 ° C. under reduced pressure for 8 hours to obtain 727 g of a polyether copolymer. The copolymer composition of the obtained polyether copolymer was 16 mol% glycidyl propionate units, 81 mol% ethylene oxide units, 2,3-epoxypropyl-2 ', 3'-epoxy-2'-methylpropyl ether. The unit was 3 mol%. The Mooney viscosity measured at 100 ° C. was 65.

Preparation of a cross-linked product The following compounding agents were added to the polyether copolymer obtained in the examples, and a cross-linked product was prepared according to a conventional method.

Calcium carbonate: Light calcium carbonate “Akadama”, Shiraishi Kogyo Co., Ltd. Lubricant: “Splendor R-300”, Kao Co., Ltd. Anti-aging agent: “Nocrack MB”, Ouchi Shinsei Chemical Co., Ltd. Acid acceptor: Magnesium oxide "Kyowa Mag 150", Kyowa Chemical Industry Co., Ltd.
Sulfur: Vulcanizing agent, Vulcanization accelerator ETU: Vulcanizing agent, Ethylenethiourea DM: Vulcanization accelerator, “Noxeller DM”, manufactured by Ouchi Shinsei Chemical Co., Ltd. TS: Vulcanization accelerator, “Noxeller TS”, large Uchisei Shin Chemical Co., Ltd. (Examples 7 to 12) Procedure for making a cross-linked product After masticating 100 parts by weight of a polyether copolymer in a 1 liter kneader set at 120 ° C., it is shown in Table 1. The A kneading compounding agent was added in the amount shown in Table 1. After kneading these for 5 minutes, the kneaded product was taken out from the kneader and formed into a sheet with a 7-inch roll set at 70 ° C. to prepare a rubber A kneaded sheet.

Next, using a 7 inch roll set at a temperature of 70 ° C., the B kneading compound shown in Table 1 was added to the A kneading sheet of the rubber in the amount shown in Table 1, and kneaded for about 5 minutes. B kneaded roll sheet was created.

  This B-kneaded roll sheet is heated and pressed for 15 minutes with a press set at a temperature of 170 ° C. to form a 2 mm thick crosslinked rubber sheet, and a sheet having a predetermined shape is punched by a punching die, as shown in JIS K 6251. A dumbbell-shaped No. 3 test piece was obtained. For Example 12, a 2 mm thick crosslinked rubber sheet was heat treated (so-called secondary vulcanization) for 2 hours in an oven set at a temperature of 150 ° C., and then a test piece was obtained.

Performance Test A performance test was performed on the following items for each test piece obtained in Examples 7-12. The measurement results are as shown in Table 2.

a) Hardness Surface hardness was measured based on the method described in JIS K 6253.

b) Volume resistivity: Test piece and insulation resistance meter (Hiresta HP, manufactured by Mitsubishi Yuka Co., Ltd.) at 10 ° C x 23% RH, 23 ° C x 50% RH, 35 ° C x 85% RH The sample was left in a constant temperature and humidity chamber set to, and allowed to stand for 48 hours or longer. Then, 10V was applied, the resistance value after 1 minute was read, and the volume specific resistance value was calculated.

c) Environment dependency (LL / HH [log])
The environmental dependence of the volume resistivity is defined by the difference between the volume resistivity in the low temperature and low humidity environment and the volume resistivity in the high temperature and high humidity environment. Environmental Dependence (LL / HH [log]) is calculated by log ₁₀ (volume resistivity of RH 10 ℃ × 23%) -log 10 ( volume resistivity of RH 35 ℃ × 85%). In addition, the one where LL / HH [log] is low shows that the fluctuation | variation of the volume resistivity with respect to environmental fluctuation | variation is small.

In Table 2, the crosslinked product of the example has a volume specific resistivity generally called a semiconductive region. The semiconductive region in the rubber material is usually in the range of about 10 ⁶ to 10 ¹⁰ Ω · cm.

The polyether-based copolymer of the present invention is constituted as described above, and the cross-linked product also has excellent semiconductivity. Therefore, it can be widely applied to the field where polyether rubber represented by epichlorohydrin rubber is used. For example, it is useful as a rubber material for semiconductive rubber parts such as rubber parts for electrical or electronic equipment, charging rolls and transfer rolls used in OA equipment, and excellent application of semiconductive rubber parts is expected.

  Furthermore, because the polyether copolymer of the present invention contains little or no halogen atoms due to its chemical structure, it is possible to reduce environmental pollution such as generation of halogen-containing gas due to combustion.

Claims (6)

10 to 99 mol% of structural units represented by the following general formula (I), 0 to 89 mol% of structural units represented by the following general formula (II), and 1 to structural units derived from a crosslinkable oxirane monomer.
It is characterized by comprising a cross-linked product obtained by cross-linking a semiconductive multi-component copolymer containing 10 mol%.
Electric or electronic equipment material.

[Wherein R ¹ represents an alkyl group having 1 to 6 carbon atoms. ]

[Wherein R ² represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a phenyl group, or —CH _2.
Represents O—R ³ , and R ³ represents an alkyl group having 1 to 6 carbon atoms or a phenyl group. ] Formula according to claim 1 electric or electronic device materials according to structural units represented by in the range of 20 to 75 mole percent (I). Electrical or electronic device materials according to claim 1 or 2 crosslinkable oxirane monomer is of non-halogen. The electric or electronic device material according to any one of claims 1 to 3, wherein the structural unit represented by the general formula (II) is an ethylene oxide unit, and the crosslinkable oxirane monomer is allyl glycidyl ether. Fee. Half Mooney viscosity (ML _{1 + 4} ) measured at 100 ° C. in the range of 10-200
Electrical or electronic device materials according to any one of 請 Motomeko 1 to 4 comprising a conductive multicomponent copolymer crosslinked product obtained by crosslinking. Charging using the electrical or electronic equipment material according to any one of claims 1 to 5 ,
Image or transfer roll.