JP5679717B2 - Elastic roller and manufacturing method thereof - Google Patents

Description

  The present invention relates to an elastic roller and a method for manufacturing the same.

  A developing roller used in an electrophotographic apparatus generally has an elastic layer in order to reduce stress on toner. However, the developing roller may remain in contact with the other contact member for a long period of time in a stationary state, and in such a case, the elastic layer has a permanent deformation (C set) that does not easily recover. May occur. Regarding low compression permanent deformation, Patent Document 1 proposes a method of reducing the amount of compression permanent deformation by dispersing short fibers in a rubber material when a foam layer is present.

JP-A-2005-090627

However, the reduction in the amount of permanent compression deformation of the foamed elastic roller using short fibers may cause the foam layer to be strongly reinforced by the short fibers, which may impair flexibility.
Accordingly, an object of the present invention is to provide an elastic roller that hardly causes permanent compression deformation while achieving the flexibility of the foam layer, and a method for manufacturing the same.

An elastic roller according to the present invention is an elastic roller having a conductive shaft core, a foam layer on the outer peripheral surface of the conductive shaft core, and a coating layer on the outer peripheral surface of the foam layer. The foam layer is made of ethylene-propylene-diene rubber, acrylonitrile-butadiene rubber, hydrogenated acrylonitrile-butadiene rubber, styrene-butadiene rubber, butadiene rubber, isoprene rubber, epichlorohydrin rubber, butyl rubber, chloroprene rubber and norbornene rubber . A crosslinked rubber obtained by crosslinking at least one raw rubber selected from the group consisting of a crosslinking agent, at least one compound selected from the group of compounds represented by the following (1) and (2) , and carbon black: An elastic roller is provided.

(In formula (1), n represents 1 or 2, R1 and R2 each independently represents an alkyl group having 3 or 4 carbon atoms, and R3 represents an alkyl group having 7 to 11 carbon atoms. )

(In the formula (2), t represents 0 or 1, and R4 to R13 each independently represents a hydrogen atom, an alkyl group having 1 to 2 carbon atoms, a halogen atom, a nitro group, or 1 to 2 carbon atoms. Represents an alkoxy group.)

The present invention also provides a method for producing the elastic roller, and at least one compound selected from the group of the formula (1) compounds represented by and (2), and the raw material rubber, and the carbon black, wherein a step of coating the outer peripheral surface of the conductive mandrel uncrosslinked rubber composition comprising a cross-linking agent, a step of obtaining the foam layer by foaming and crosslinking by heating the uncrosslinked rubber composition, A method for producing an elastic roller is provided.

  As described above, according to the present invention, it is possible to provide an elastic roller having good compression permanent deformation and a method for manufacturing the same while achieving flexibility using a foam layer.

It is typical sectional drawing which shows the outline of one form of the elastic roller of this invention. It is explanatory drawing of the electric current measurement method. 1 is a cross-sectional view of an electrophotographic image forming apparatus according to the present invention. 1 is a cross-sectional view of an electrophotographic process cartridge according to the present invention.

  When the elastic roller of the present invention is used as a developing roller, image density unevenness due to compression permanent deformation of the roller, contamination of the photosensitive drum, or reduction in image density due to reduction in roller current value due to repeated image formation is small, and a high-quality image can be obtained. It is possible to obtain.

<< Elastic Roller >>
As shown in FIG. 1, the elastic roller of the present invention has a conductive shaft core 1 and a foam layer 2 on the outer peripheral surface of the conductive shaft core 1, and covers the outer peripheral surface of the foam layer 2. The structure has the layer 3.

<Conductive shaft core>
As the conductive shaft core, those conventionally used for elastic rollers such as a developing roller, a charging roller, and a fixing roller can be used.

<Foam layer>
The foam layer used in the present invention comprises a raw material rubber described later and at least one compound selected from the group consisting of compounds represented by formulas 1 to 3 described later (hereinafter referred to as a network-forming component). Contains plasticizer. In addition, a foam layer means the crosslinked rubber layer containing a bubble. The foam layer is formed on the outer peripheral surface of the conductive shaft core. The foam layer is not necessarily in contact with the outer peripheral surface of the conductive shaft core, and may have a primer treatment layer or the like between the conductive shaft core and the foam layer.

(Raw rubber)
Examples of the raw rubber used for the foam layer 2 include the following. Ethylene-propylene-diene rubber (EPDM), acrylonitrile-butadiene rubber (NBR), hydrogenated acrylonitrile-butadiene rubber (H-NBR), styrene-butadiene rubber (SBR), butadiene rubber (BR), isoprene rubber (IR), epi Chlorohydrin rubber (CO), butyl rubber (IIR), chloroprene rubber (CR) and norbornene rubber (NOR). These raw rubbers may be liquid. These may be used alone or in combination of two or more. Hereinafter, a material obtained by kneading the raw material rubber with a network-forming component and various additives such as a conductive agent and a foaming agent as necessary is expressed as an uncrosslinked rubber composition. Moreover, what crosslinked the said uncrosslinked rubber composition is expressed as a crosslinked rubber in this specification.

(Network forming component)
The network forming component used in the present invention is at least one compound selected from the group consisting of compounds represented by Formula 1, Formula 2, and Formula 3.

(In formula (1), n represents 1 or 2, R1 and R2 each independently represents an alkyl group having 3 or 4 carbon atoms, and R3 represents an alkyl group having 7 to 11 carbon atoms. )

(In the formula (2), t represents 0 or 1, and R4 to R13 each independently represents a hydrogen atom, an alkyl group having 1 to 2 carbon atoms, a halogen atom, a nitro group, or 1 to 2 carbon atoms. Represents an alkoxy group.)

(In formula (3), R14 represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms. M represents the number of methylene groups and represents an integer of 0 to 18 inclusive. 12 or more and 20 or less.)
The network forming component self-assembles in the uncrosslinked rubber composition and the crosslinked rubber by hydrogen bonding, van der Waals force, etc., and forms a network structure. As described above, this network structure is formed by weak bonds such as hydrogen bonds and van der Waals forces. Therefore, when heat is applied, the network structure is destroyed. Form. The following effects are acquired by adding the network formation component which forms these network structures to a foam layer.

  In other words, an elastic roller can be obtained in which the current value is less reduced by repeated image formation. The decrease in current value due to repeated image formation is considered to be caused by agglomeration of carbon black distributed in the cross-linked rubber by energization or repeated stress. It is considered that foamed rubber, which is a crosslinked rubber containing bubbles that forms a foam layer, has a greater amount of deformation due to stress than non-foamed rubber, and is therefore likely to aggregate carbon black. However, by adding a network forming component to the foam layer, a reversible network structure is formed, and changes in the carbon black distribution are reduced. Therefore, an elastic roller can be obtained in which the current value is less reduced by repeated image formation.

In addition, an elastic roller that is flexible and has good compression permanent deformation is obtained. In general, the elastic roller can be made more flexible by increasing the foaming ratio of the foam layer. However, if the foaming ratio is increased, the cell wall made of the crosslinked rubber becomes thinner and the compression permanent deformation property is reduced. The effect is reduced. The expansion ratio is calculated by an equation using the density (g / cm ³ ) before and after foaming as shown below.

Foaming ratio = (density before foaming) / (density after foaming)
However, since the reversible network structure composed of the network forming component reinforces the crosslinked rubber that is the cell wall, low compression permanent deformation can be obtained even if the cell wall is thin. Therefore, when a network-forming component is added to the foam layer, a flexible roller having good compression set can be obtained.

  Furthermore, an elastic roller with less hardness unevenness can be obtained. Foam rubber is cross-linked by mixing non-reactive gas into the liquid rubber using a method such as foaming by heating using a blended foaming agent to form cells and crosslinking the uncrosslinked rubber composition, or using a mixer or the like. Obtained by techniques. Examples of the non-reactive gas include nitrogen, carbon dioxide, and air. However, when temperature unevenness or the like occurs in the uncrosslinked rubber composition during cell formation, a difference in viscosity occurs, making it difficult to obtain a uniform cell diameter, resulting in uneven hardness. By adding a network-forming component that forms a reversible network structure to the foam layer, it is possible to maintain a constant viscosity even during heating, thereby reducing viscosity unevenness and obtaining a fine and uniform cell diameter during heating and foaming. I can do it.

  When there are a plurality of network forming components in the foam layer with respect to 100 parts by mass of the raw rubber in the foam layer, the total mass part is preferably 0.1 parts by mass or more and 10 parts by mass or less. If the added mass part is 0.1 parts by mass or more and 10 parts by mass or less, a reversible network structure composed of a network forming component can be formed sufficiently easily, and good dispersibility to the crosslinked rubber in the foam layer can be achieved. Can be easily obtained. Therefore, a fine and uniform cell diameter can be obtained especially during heating and foaming, the reinforcing effect of the crosslinked rubber due to the network structure and the suppression of changes in the carbon black distribution due to energization are excellent, hardness unevenness is particularly small, and the current value decreases due to energization An elastic roller excellent in image forming property with a particularly small difference can be obtained.

Compound represented by Formula 1 R1 and R2 constituting the compound represented by Formula 1 each independently represent an alkyl group having 3 or 4 carbon atoms, and R3 represents an alkyl group having 7 to 11 carbon atoms. Represent. In addition, the alkyl group of R1, R2, and R3 may be a linear alkyl group or a branched alkyl group.

  When R1, R2 and R3 constituting the compound represented by Formula 1 are less than the specified number of carbon atoms, it may be difficult to uniformly disperse the compound of Formula 1 in the crosslinked rubber. When the dispersibility of the compound of Formula 1 with respect to the crosslinked rubber is reduced, a difference in hardness unevenness in the elastic roller or a decrease in current value due to repeated image formation is likely to occur, and the possibility of adverse image effects increases. In addition, when R1, R2, and R3 constituting the compound represented by Formula 1 exceed the specified number of carbon atoms, the self-assembly effect may be reduced, and it may be difficult to obtain a sufficient network structure. In this case, the suppression of the change in carbon black distribution in the crosslinked rubber due to repeated image formation and the reinforcing effect of the crosslinked rubber due to the network structure are not sufficient, and it is difficult to obtain a fine and uniform cell diameter.

  A compound in which R1 and R2 in Formula 1 each independently represents an alkyl group having 3 to 4 carbon atoms and R3 represents an alkyl group having 7 to 11 carbon atoms is excellent in the following points. . That is, both the dispersibility and the self-assembly effect are good, a fine and uniform cell diameter can be obtained, and the elastic roller produced using the compound is excellent in the effect of suppressing the permanent deformation and the decrease in the current value due to energization.

  The number n of methylene groups in the compound represented by Formula 1 is 1 or 2. If the number n of methylene groups is 1 or 2, glutamic acid or aspartic acid as a raw material for the compound represented by Formula 1 is preferable because it is easily available and inexpensive.

  The compound represented by Formula 1 can be obtained, for example, by the method shown below. In this method, first, N-acylated glutamic acid or N-acylated aspartic acid is obtained by reacting glutamic acid or aspartic acid with a fatty acid halide by a Schotten-Baumann reaction under a basic catalyst such as sodium hydroxide. Subsequently, the carboxyl group of this N-acylated glutamic acid or N-acylated aspartic acid is converted into an active group having high reactivity such as ester, acid halide, acid anhydride, etc., and then reacted with an amine. Alternatively, the N-acylamino acid such as N-acylated glutamic acid and N-acylated aspartic acid and an amine are directly amidated by heat dehydration. The compound shown in Formula 1 can be obtained by these methods.

  The compound represented by Formula 1 may have one or more asymmetric carbons depending on the types of R1 and R2, and the present invention includes optical isomers and diastereomers based on such asymmetric carbons. Stereoisomers, mixtures of any stereoisomers, or racemates may be used. Further, two or more compounds represented by Formula 1 may be used in combination.

Compound represented by Formula 2 The substituents R4 to R13 constituting the compound represented by Formula 2 are each independently a hydrogen atom, an alkyl group having 1 to 2 carbon atoms, a halogen atom, a nitro group, or 1 or more carbon atoms. 2 or less alkoxy groups are represented. The substitution position of the substituent is not particularly limited in R4 to R13. In addition, the alkyl group of R4 to R13 may be a linear alkyl group or a branched alkyl group. When the substituents R4 to R13 of the compound represented by Formula 2 are other than the above-mentioned atoms or functional groups, the self-assembling property is lowered, and it is difficult to obtain a fine and uniform cell diameter, and the current value is reduced due to compression permanent deformation and energization. There is little suppression effect.

  The alkyl group substituted by the substituents R4 to R13 of the compound represented by Formula 2 has 1 to 2 carbon atoms. If the carbon number is 1 or more and 2 or less, the steric hindrance is small, so that the self-assembly property is good.

  The alkoxy group substituted by the substituents R4 to R13 of the compound represented by Formula 2 has 1 to 2 carbon atoms. If the number of carbon atoms of the alkoxy group is 1 or more and 2 or less, the steric hindrance is small, so that self-assembly is good. T of the compound represented by Formula 2 is 0 or 1. When t of the compound represented by Formula 2 is 2 or more, it is difficult to uniformly disperse in the crosslinked rubber, and it is easy to cause a difference in hardness unevenness and a decrease in current value due to energization in the elastic roller. Increases nature.

  The compound represented by Formula 2 is obtained by condensing sorbitol or xylitol with a compound having a formyl group on at least an aromatic ring or a compound obtained by dimethylacetalizing the formyl group under an acid catalyst such as p-toluenesulfonic acid. Can be obtained. These compounds represented by Formula 2 may be used alone or in combination of two or more.

-The compound shown by Formula 3 R14 of Formula 3 represents a hydrogen atom (H) or a C1-C18 alkyl group. The alkyl group of R14 may be a linear alkyl group or a branched alkyl group. M in Formula 3 represents the number of methylene groups and represents an integer of 0 to 18. The total carbon number of the compound represented by Formula 3 is 12 or more and 20 or less. When the total number of carbon atoms of the compound represented by Formula 3 is less than 12, the self-assembly property is weak, a sufficient network structure cannot be obtained, and it is difficult to obtain a fine and uniform cell diameter. In addition, the suppression of the change in the carbon black distribution in the rubber due to energization is not sufficient. If the total number of carbon atoms is greater than 20, the dispersibility in the elastic roller will be reduced, causing unevenness in hardness due to non-uniform cell diameters and a decrease in current value due to energization, causing image defects. There is. Examples of the compound represented by Formula 3 include the following. Hydroxy lauric acid, hydroxy myristic acid, hydroxy pentadecylic acid, hydroxy palmitic acid, hydroxy margaric acid, hydroxy stearic acid, hydroxy nonadecanoic acid, hydroxy arachidic acid. Moreover, these compounds have a carboxyl group and a hydroxy group in one molecule, and the bonding site of the hydroxy group is not limited as long as the structure of Formula 3 is satisfied. These can generally be obtained by hydrolyzing and purifying vegetable oil, wax and the like by conventional methods. These compounds represented by Formula 3 may be used alone or in combination of two or more.

(Plasticizer)
The foam layer used in the present invention need not contain a plasticizer. In general, the plasticizer means a generic term for liquid substances added to improve the processability of raw rubber, soften the crosslinked rubber and reduce the cost. Examples of the plasticizer include the following. Petroleum plasticizers such as paraffinic oil, naphthenic oil and aromatic oil, ester plasticizers such as butyl phthalate, dioctyl phthalate, dioctyl adipate dioctyl sebacate, and vegetable oils such as pine oil and pine tar. In the present invention, as described above, a foam layer having a good flexibility and good compression set can be obtained by adding a network-forming component to the foam layer. Therefore, it is not necessary to add a plasticizer for softening.

(Various additives)
As the foaming agent that can be used in the present invention, for example, a chemical foaming agent is preferably used, and the chemical foaming agent is classified into an organic type and an inorganic type. Organic foaming agents include azo compounds such as azodicarbonamide (ADCA), azobisisobutyronitrile (AIBN), barium azodicarboxylate (Ba / AC), N, N′-dinitrosopentamethylenetetra Nitroso compounds such as amine (DPT), hydrazine derivatives such as benzenesulfonyl hydrazide (BSH), 4,4 oxybis (benzenesulfonyl hydrazide) (OBSH), toluenesulfonyl hydrazide (TSH), hydrazodicarbonamide (HDCA) . Examples of the inorganic foaming agent include sodium bicarbonate (sodium bicarbonate), ammonium bicarbonate, ammonium carbonate, sodium bicarbonate and the like. These foaming agents may be used alone or in combination of two or more. The addition amount of the foaming agent is preferably 2 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the raw rubber. If 2 parts by mass or more is added, flexibility can be easily obtained in the foam layer, and if it is 30 parts by mass or less, the mechanical strength is excellent.

  In the present invention, it is particularly preferable to use azodicarbonamide as a foaming agent. This is because azodicarbonamide can adjust the decomposition temperature and decomposition rate, has a large amount of gas generation, and is less contaminated by decomposition products. Examples of the foaming aid include urea compounds, metal oxides such as zinc oxide and lead oxide, and compounds such as salicylic acid and stearic acid, which can be added corresponding to the foaming agent. Furthermore, the foam layer may contain various additives such as a conductive agent, a filler, a cross-linking agent, a cross-linking aid, an antioxidant, an anti-aging agent, or a processing aid as necessary.

  Examples of the conductive agent include the following. Metal powders and fibers such as aluminum, palladium, iron, copper, silver, etc., conductive metal compound powders such as carbon black, metal oxides, copper sulfide, zinc sulfide, or tin oxide, antimony oxide, Powder in which indium oxide, molybdenum oxide, zinc, aluminum, gold, silver, copper, chromium, cobalt, iron, lead, platinum, rhodium are deposited by electrolytic treatment, spray coating, and mixed shaking. Among these conductive agents, carbon black is particularly preferable in terms of performance, quality, and cost.

  The following are mentioned as a crosslinking agent contained in the non-crosslinked rubber composition used for a foam layer. Organic sulfur-containing compounds such as tetramethylthiuram disulfide (TMTD), tetraethylthiuram disulfide (TETD), N, N'-dithiobismorpholine, and sulfur. An organic peroxide-based crosslinking agent can also be used. Examples of the organic peroxide-based crosslinking agent include the following. tert-butyl hydroperoxide, di-tert-butyl peroxide, dicumyl peroxide, tert-butyl cumyl peroxide, 1,1-bis (tert-butylperoxy) cyclododecane, 2,2-bis (tert-butylperoxy) octane 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, 1,3-bis (tert-butylperoxyisopropyl) benzene, n-butyl-4,4-bis (tert-butylperoxy) valerate, Benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tert-butyl peroxybenzoate.

  The amount of the crosslinking agent used is 0.01 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the raw rubber used for the foam layer.

  Examples of the crosslinking aid include the following compounds. Ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, polyethylene glycol dimethacrylate, 1,4-butanediol diacrylate, 1,6- Hexanediol diacrylate, 2,2'-bis- (4-methacryloyldiethoxyphenyl) propane, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, divinylbenzene, N, N'-methylenebisacrylamide , P-quinonedioxime, p, p'-dibenzoylquinonedioxime, triazinedithiol, triallyl cyanurate, triallyl isocyanurate, bismaleimide

<< Method for Manufacturing Elastic Roller >>
The manufacturing method of the elastic roller of this invention has the kneading | mixing process mentioned later and a shaping | molding process. Moreover, it can also have the heating process mentioned later between a kneading | mixing process and a shaping | molding process.

(Kneading process)
The kneading step of the foam layer used in the present invention is a step of obtaining an uncrosslinked rubber composition by kneading the network forming component, the raw rubber, and, if necessary, the additive.

  The additive and network forming component used in the present invention can be kneaded into the raw material rubber by kneading with a Banbury mixer, kneading with a kneader, kneading with a twin screw extruder, kneading with two rolls, etc. These methods are appropriately selected depending on the type and amount.

  In the present invention, when the network forming component and the raw rubber are kneaded, the network forming component may be kneaded into the raw rubber simultaneously with other additives. Before kneading the network-forming component in the raw rubber, dissolve the network-forming component in a low-boiling solvent (liquid) that has a boiling point of 100 ° C. or less, and add the solution, raw rubber, and various additions as necessary. More preferably, an uncrosslinked rubber composition is obtained by kneading the agent. The low boiling point solvent is a solvent having a boiling point of 100 ° C. or lower, and examples thereof include organic solvents such as ethanol and methyl ethyl ketone. When a solvent having a boiling point of 100 ° C. or lower is used, it is particularly easy to remove the low-boiling solvent from the uncrosslinked rubber composition, and the foaming and crosslinking reaction of the uncrosslinked rubber composition proceeds when the low-boiling solvent is removed by heating. Can be easily prevented.

(Molding process)
The foam layer forming step used in the present invention is a step of obtaining a foam layer by coating an uncrosslinked rubber composition on the outer peripheral surface of a conductive shaft core and foaming and crosslinking the uncrosslinked rubber composition. It is. Specifically, an uncrosslinked rubber composition is extruded using an extruder, heated and foamed and crosslinked to form a foam layer, or the mold is filled with the uncrosslinked rubber composition and foamed and crosslinked. Thus, a method of forming a foam layer can be used. The surface of the foam layer may be polished and the shape may be adjusted.

(Heating process)
When a foaming agent is used as at least one of the additives, the network-forming component is dissolved in the low boiling point solvent during the kneading step, and the solution, raw rubber and various additives are kneaded, the viewpoint of removing the low boiling point solvent Therefore, it is preferable to have a heating step between the kneading step and the molding step. A heating process is a process of heating an uncrosslinked rubber composition below the decomposition temperature of the foaming agent and below the crosslinking temperature of the uncrosslinked rubber composition. Although a heating process can be performed under a normal pressure or pressure reduction, it is preferable to carry out under pressure reduction from a viewpoint of the removability of a low boiling-point solvent, and the workability maintenance of an uncrosslinked rubber composition. The decomposition temperature of the foaming agent used in the present specification is a temperature at which the foaming agent and the foaming aid are decomposed to generate gas. Also the crosslinking temperature of the uncrosslinked rubber composition, scorch time: the temperature at which t ₅ is less than 45 minutes. Scorch time used in this specification: a t ₅ performs a Mooney scorch test according to the provisions of JIS K 6300, a value obtained. The scorch time can be determined by inserting an uncrosslinked rubber composition into a cylindrical die using a Mooney viscometer (manufactured by Shimadzu Corporation), rotating the rotor, and measuring the torque.

In the examples and comparative examples of the present invention, the scorch time t ₅ at 100 ° C. is determined instead of the crosslinking temperature of the uncrosslinked rubber composition. When the scorch time at 100 ° C .: t ₅ is 45 minutes or more, it is obvious that the crosslinking temperature of the uncrosslinked rubber composition is 100 ° C. or more. Therefore, in Examples and Comparative Examples in which the scorch time t ₅ at 100 ° C. is 45 minutes or more, the uncrosslinked rubber composition can be heated up to the decomposition temperature of the foaming agent and up to 100 ° C.

  When a network forming component is dissolved in a low boiling point solvent, a reversible network structure is formed. However, since the low boiling point solvent has a lower viscosity than an uncrosslinked rubber composition, a reversible network structure is easily formed. Therefore, after dissolving the network-forming component in a low-boiling solvent, raw rubber and various additives as necessary are kneaded into the solution to obtain an uncrosslinked rubber composition, and then the low-boiling solvent is removed by heating or reduced pressure. When removed under heat, the formation of a network structure composed of a network-forming component is particularly good. As a result, a finer and more uniform cell diameter can be obtained, compression permanent deformation is small, and the effect of suppressing a decrease in current value due to repeated image formation is excellent, which is preferable.

<Coating layer>
The elastic roller of the present invention has a coating layer on the outer peripheral surface of the foam layer. The coating layer means at least one layer having a non-foaming outer peripheral surface existing on the outer peripheral surface of the foam layer. Examples of the material for the coating layer include thermoplastic resins and thermosetting resins. An inorganic coating layer can also be provided. Examples of the inorganic coating layer include a silica film and a carbon film. The silica film is a silicon oxide film containing carbon atoms chemically bonded to silicon atoms, and the ratio of the total number of elements occupied by silicon atoms and oxygen atoms out of all elements in the silicon oxide film is 60%. The film | membrane which is the above is mentioned. Examples of the carbon film include diamond-like carbon (DLC) which is a carbon thin film having high hardness, electrical insulation, and infrared transmission. The structure of the DLC includes C (carbon atom) as a main skeleton and contains some hydrogen atoms, and is composed of diamond covalent bond (SP ³ hybrid orbital bond) and graphite covalent bond (SP ² hybrid orbital bond). It is an amorphous structure in which both bonds are mixed. Moreover, a coating layer can contain the various additives which can be contained in the above-mentioned foam layer except a foaming agent and foaming adjuvant. Moreover, the preferable addition amount range of various additives is the same as that of a foam layer.

  Examples of the method for forming the coating layer include the following. Conventionally known methods for simultaneous formation of foam layer and coating layer by bi-layer extrusion, method of coating foam layer with coating layer formed into tube shape using injection molding or extruder, dip coating, spray coating Wet methods such as roll coating, plasma CVD methods, vacuum vapor deposition, sputtering, ion plating and other physical vapor deposition (PVD) methods, and chemical vapor deposition (CVD) such as plasma CVD, thermal CVD and laser CVD Dry method.

  In addition, after producing a coating layer on the outer peripheral surface of the foam layer, the surface of the coating layer may be polished to adjust the shape.

  Furthermore, in the case of having two or more coating layers, in order to improve adhesion so that peeling does not occur between the coating layers, the outer periphery of the first coating layer is subjected to surface modification methods such as corona treatment, frame treatment, It may be modified by excimer UV treatment. When the elastic roller of the present invention has two or more coating layers, the foam layer and the coating layer may all be formed simultaneously, or after the foam layer and the first coating layer are formed simultaneously. The remaining coating layers may be formed, or each layer may be formed separately.

The thickness of the coating layer can be appropriately selected depending on the type of coating layer to be formed and the forming method.
In the case of an organic coating layer, the thickness is preferably 3 μm or more and 1000 μm or less. When the thickness is 3 μm or more, a uniform layer thickness can be easily obtained, and when the thickness is 1000 μm or less, it can be easily prevented from causing uneven volume resistance of the elastic roller. The thickness of the inorganic coating layer is preferably 0.01 μm or more and 3 μm or less. When the thickness is 0.01 μm or more, it is possible to easily prevent the foam layer from being difficult to be coated, and to easily prevent the foam layer from being scraped and worn. When the thickness is 3 μm or less, it is possible to easily prevent the coating layer from cracking.

  FIG. 2 is a schematic diagram for explaining a measuring method for evaluating a current value decrease due to energization of the elastic roller of the present invention. A developing roller is brought into contact with the SUS drum 6 having a diameter of 40 mm, and a load 4 of 500 g is applied to both ends of the cored bar for a total load of 1 kg. In this state, the roller is rotated at 45 rpm, the internal resistance 7 of 10 kΩ is arranged on the ground side, and the current value when 100 V is applied for 2 seconds from the DC power source 8 is 21 points every 0.1 second by the multimeter 5. taking measurement. Then, the average value of the current value during one round of the elastic roller is defined as the current value of the elastic roller.

<Electrophotographic image forming apparatus>
FIG. 3 is a schematic view of an example of an electrophotographic image forming apparatus that can use the elastic roller of the present invention.
The photosensitive drum 9 rotates in the direction of the arrow, is uniformly charged by a charging roller 16 for charging the photosensitive drum 9, and the surface of the photosensitive drum 9 is exposed by laser light 15 as an exposure means for writing an electrostatic latent image on the photosensitive drum 9. An electrostatic latent image is formed. The electrostatic latent image is developed by applying toner 12 by a developing roller 10 disposed in contact with the photosensitive drum 9, and is visualized as a toner image. Development is so-called reversal development in which a toner image is formed on the exposed portion. The visualized toner image on the photosensitive drum 9 is transferred to a paper 26 as a recording medium by a transfer roller 21 connected to a bias power source 22. The paper 26 is supplied by a paper feed roller 27 and is transported by being electrostatically adhered onto the transfer transport belt 24 by an adsorption roller 28. The transfer / conveying belt 24 is suspended from the driving roller 20, the driven roller 25, and the tension roller 23. The paper 26 to which the toner image has been transferred is subjected to fixing processing by the fixing device 19 and is discharged out of the device, thus completing the printing operation. On the other hand, the toner remaining on the photosensitive drum 9 without being transferred is scraped off by a cleaning blade 18 which is a cleaning member for cleaning the surface of the photosensitive drum and stored in a waste toner container 17. The above operation is repeated. The developing device 14 includes a developing container that contains non-magnetic toner as a one-component toner, and a developing roller 10 that is located in an opening extending in the longitudinal direction in the developing container and is disposed opposite to the photosensitive drum 9. The electrostatic latent image on the drum 9 is developed and visualized.

<Electrophotographic process cartridge>
FIG. 4 shows a schematic view of an example of an electrophotographic process cartridge that can use the elastic roller of the present invention. The electrophotographic process cartridge includes a developing roller 10, a toner regulating blade 13, a developing device 14, and a charging roller 16. In addition, a toner applying member 11 and a photosensitive drum 9 may be incorporated. The cartridge is formed by integrally holding these members, and is detachably attached to the image forming apparatus.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited at all.

  First, a method for synthesizing compounds A to E, which are one of the compounds of formula 1, and their similar compounds, and compounds F to H that do not fall under formula 1 and are not network-forming components will be described.

[Synthesis of Compound A]
After 20 g of sodium hydroxide was dissolved in 180 g of water, 95.5 g (0.5 mol) of sodium glutamate monohydrate and 100 g of acetone were added to obtain a solution. Thereafter, the solution was cooled to 5 ° C., and 109.4 g (0.5 mol) of lauroyl chloride and 105 g of a 20 mass% aqueous sodium hydroxide solution were added dropwise simultaneously over 2 hours to obtain a reaction solution. The reaction solution was diluted with 80 g of water and cooled to 10 ° C., 63 g of 95% by mass sulfuric acid was added, the aqueous layer of the resulting solution was removed, and the organic layer was concentrated under reduced pressure to obtain an oily substance. This oily substance was dissolved in 740 g of methanol, 6.3 g of 95% by mass sulfuric acid was added and the mixture was refluxed for 10 hours, cooled to 20 ° C., and 8.9 g (0.12 mol) of n-butylamine was added. The methanol was concentrated under reduced pressure to obtain a concentrated material. To this concentrated material, 643 g of toluene and 271 g (3.7 mol) of n-butylamine were added, and the mixture was heated and stirred at 80 ° C. for 10 hours. After cooling, 500 g of water and 130 g of 95% by mass sulfuric acid were added thereto, Removal of the organic layer in which compound A was present was obtained. To the organic layer containing Compound A, 1000 g of water was added, the solvent was removed at normal pressure, and the precipitated white solid was subjected to suction filtration. The resulting white solid was vacuum dried at 50 ° C. to obtain Compound A.

[Synthesis of Compound B]
Lauroyl chloride used for the synthesis of Compound A was changed to 81.3 g (0.5 mol) of 2-ethylhexanoyl chloride. Otherwise, compound B was synthesized in the same manner as compound A.

[Synthesis of Compounds C to H]
Sodium glutamate monohydrate, lauroyl chloride, and n-butylamine used in the synthesis of Compound A were changed to amino acids, carboxylic acid chlorides, and amines having the same mole number corresponding to the structures of Compounds C to H described later. Otherwise, compounds C to H were synthesized in the same manner as the synthesis of compound A.

  Next, a method for synthesizing compounds Q to T, which are one of the compounds of formula 2, and compounds similar thereto, which do not fall under formula 2 and are not network forming components, will be described.

[Synthesis of Compound I]
In a reaction vessel equipped with a Dean-Stark fractionating tube, in addition to 500 ml of toluene, 23.4 g (0.13 mol) of sorbitol, 27.6 (0.26 mol) of benzaldehyde and 0.25 g of p-toluenesulfonic acid And heated under reflux for 6 hours. At the time of heating and refluxing, the produced water was separated by a Dean-Stark type fractionating tube. After heating to reflux, the mixture was cooled to 20 ° C., neutralized with a 10% by mass aqueous sodium hydroxide solution, and the precipitated white solid was suction filtered. The obtained white solid was washed with 500 ml of ethanol and suction filtered. The resulting white solid was vacuum dried at 50 ° C. to obtain Compound I.

[Synthesis of Compound J]
The benzaldehyde used for the synthesis of Compound I was changed to 31.2 g (0.26 mol) of 4-methylbenzaldehyde. Otherwise, Compound J was synthesized in the same manner as Compound I.

[Synthesis of Compounds K to T]
The sorbitol and benzaldehyde used in the synthesis of Compound I are changed to polyhydric alcohol and substituted benzaldehyde having the same mole number corresponding to the structures of Compounds KT described later, and the other methods are the same as in the synthesis of Compound I. Thus, compounds KT were synthesized.

  In addition, compounds U to W, which are one of the compounds of formula 3, and similar compounds thereof, and compounds X and Y that do not fall under formula 3 and are not network-forming components were used as follows.

[Compounds U to Y]
Compound U: 12-hydroxystearic acid (one of the compounds of formula 3): Wako Pure Chemical Industries, Ltd.
Compound V: 2-hydroxylauric acid (one of the compounds of formula 3): manufactured by Sigma-Aldrich.
Compound W: 2-hydroxyarachidic acid (one of the compounds of formula 3): manufactured by Sigma-Aldrich.
Compound X: 10-hydroxydecanoic acid: manufactured by Sigma-Aldrich.
Compound Y: 22-hydroxy docosanoic acid: INDOFINE Chemical Co.

[Example 1]
[Preparation of uncrosslinked rubber composition for foam layer]
Kneading step: As raw material rubber, 100 parts by mass of Esprene 505 (trade name, manufactured by Sumitomo Chemical Co., Ltd.), which is ethylene-propylene-diene rubber (EPDM), as a processing aid, 2 parts by mass of zinc stearate, as a conductive agent, Compound A (1 of the compound of formula 1) dissolved in 30 parts by mass of MT carbon black Thermax Flow Foam N990 (trade name, manufactured by CANCAB) and ethanol (boiling point: 78.3 ° C.) as a low boiling point solvent. Seed) 1 part by mass was kneaded with a kneader. Subsequently, 1 part by mass of sulfur as a crosslinking agent, 1 part by mass of Noxeller M (trade name, manufactured by Ouchi Shinsei Chemical Co., Ltd.) which is mercaptobenzothiazole (MBT) as a crosslinking aid, and azodicarboxylic as a foaming agent Vinyl paste AC # 3 (trade name, manufactured by Eiwa Kasei Kogyo Co., Ltd., decomposition temperature: 208 ° C.) 5 parts by mass of amide (ADCA), Cell Paste A (trade name, manufactured by Eiwa Kasei Kogyo Co., Ltd.) (Decomposition temperature: 112 ° C.) 5 parts by mass were mixed with an open roll to obtain an uncrosslinked rubber composition for a foam layer.
Heating step: Thereafter, the uncrosslinked rubber composition was heated to 80 ° C. for 30 minutes in an environment of 666 Pa (5 mmHg).
The scorch time t ₅ of the uncrosslinked rubber composition for a foam layer at 100 ° C. was 115 minutes.

[Preparation of uncrosslinked rubber composition for first coating layer]
As raw material rubber, 100 parts by mass of esprene 505 (trade name, manufactured by Sumitomo Chemical Co., Ltd.), an ethylene-propylene-diene rubber, 2 parts by mass of zinc stearate as a processing aid, and MT carbon black as a conductive agent. 30 parts by weight of Kuss Flow Foam N990 (trade name, manufactured by CANCAB) was kneaded with a kneader. Subsequently, 1 part by mass of sulfur as a crosslinking agent and 1 part by mass of Noxeller M (trade name, manufactured by Ouchi Shinsei Chemical Co., Ltd.), which is mercaptobenzothiazole (MBT), are mixed in an open roll. Thus, an uncrosslinked rubber composition for the coating layer was obtained.

[Preparation of foam layer and first coating layer]
Molding step: The obtained uncrosslinked rubber composition for foam layer and uncrosslinked rubber composition for coating layer are formed into a cylindrical conductive shaft core having a diameter of 6 mm and a length of 252 mm using a two-layer extruder. A cylindrical laminate integrated with (made of sulfur composite free-cutting steel, nickel-plated surface) was formed. The thicknesses of the foam layer and the coating layer were adjusted by controlling the rotation speed ratio of each extruder. Next, the obtained cylindrical laminate was inserted into a mold, crosslinked and foamed at 160 ° C., and a foam layer and a coating layer were formed at the same time to obtain an elastic roller. The elastic roller obtained here was randomly cut with a three-point cutter, and the cross section of the foam layer was irradiated with visible light (halogen lamp), and an optical microscope (made by Leica Microsystem Co., Ltd., trade name: DMR). The cell distribution was observed with an HC metal microscope at a magnification of 200 times. As a result, the cells were uniformly distributed throughout.

[Preparation of second coating layer]
Nippon Poly 5033 (trade name, manufactured by Nippon Polyurethane Co., Ltd.), which is a polyol, and Coronate L (trade name, manufactured by Nippon Polyurethane Co., Ltd.), which is an isocyanate as a curing agent, were combined to make 100 parts by mass. At that time, the mixing ratio of both was set so that the molar ratio of [NCO] / [OH] was 1.2. [NCO] is the number of moles of isocyanate groups in the isocyanate, and [OH] is the number of moles of hydroxyl groups in the polyol. Further, 30 parts by mass of carbon black MA100 (trade name, manufactured by Mitsubishi Chemical Corporation) was added thereto as a conductive agent. Methyl ethyl ketone was added to the raw material mixture, and the solid content concentration was adjusted to 25% by mass so that the film thickness of the second coating layer was 20 μm. To this, 5 parts by mass of urethane resin particles CFB-101-40 (trade name, manufactured by Dainippon Ink & Chemicals, Inc.) having an average particle size of 16 μm are added, uniformly dispersed, and mixed together with the raw material liquid for the second coating layer did. The obtained elastic roller is immersed and coated in this resin raw material liquid, and then pulled up, dried, and heat-treated at 160 ° C. for 20 minutes to form a second coating layer having a layer thickness of about 20 μm. An elastic roller provided on the outer periphery was produced.

[Evaluation of compression permanent deformation performance (deformation recovery)]
The obtained elastic roller having the two coating layers was incorporated as a developing roller into an electrophotographic process cartridge for a color laser printer LBP5400 (trade name, manufactured by Canon Inc.) and allowed to stand in a thermostatic bath at a temperature of 40 ° C. for one month. . Further, after being left still for one day in an environment at a temperature of 25 ° C., the developing roller was taken out of the cartridge and incorporated in a new electrophotographic process cartridge and attached to the main body of LBP5400. Then, a solid image having a printing rate of 100% density and a halftone image having a printing rate of 50% density were evaluated based on the following evaluation criteria. Table 2 shows the evaluation of the compression permanent deformation of the elastic roller.

Evaluation criteria A: No pressure contact mark is seen on the image.
B: The press-contact mark is thin on the solid image, but the press-contact mark is not seen on the halftone image.
C: The press-contact mark is clearly seen on the solid image, and the press-contact mark is thin on the halftone image.
D: A press-contact mark is clearly seen on solid and halftone images.

[Evaluation of contamination of photosensitive drum]
The obtained elastic roller having two coating layers is incorporated as a developing roller into an electrophotographic process cartridge for a color laser printer LBP5400 (trade name, manufactured by Canon Inc.), and is placed in a thermostatic chamber at a temperature of 40 ° C. and a relative humidity of 90%. It was left for 1 month. Further, after being left still for one day in an environment of a temperature of 25 ° C. and a relative humidity of 50%, the developing roller was taken out from the cartridge, and a new developing roller was assembled and attached to the LBP 5400 main body. Then, 10 halftone image evaluations with a printing rate of 50% density were output and performed based on the following criteria. Table 2 shows the evaluation of the contamination of the photosensitive drum.

Evaluation criteria A: There is no white image defect due to contamination of the photosensitive drum on the halftone image.
B: A slight white image defect is seen in the first output image, but it cannot be seen after passing three sheets.
C: A slight white image defect is seen in the third output image, but it is not seen after passing 10 sheets.
D: There is a white image defect even after 10 sheets are output.

[Evaluation of change in current value of elastic roller with two coating layers by energization]
The obtained elastic roller provided with the two coating layers is incorporated as a developing roller in an electrophotographic process cartridge for a color laser printer LBP5400 (trade name, manufactured by Canon Inc.) and attached to the main body of the LBP5400. An image was formed. Thereafter, the elastic roller was taken out from the process cartridge and energized for 10 minutes at an applied voltage of 50 v with the evaluation system shown in FIG. The elastic roller after energization was incorporated as a developing roller in an electrophotographic process cartridge for the color laser printer LBP5400, and was attached to the main body of the LBP5400 to form 5000 images with a printing rate of 5%. Thereafter, a halftone image having a printing rate of 50% density was formed. A halftone image with a printing rate of 50% density formed before and after energization was compared and evaluated based on the following evaluation criteria. The evaluation results are shown in Table 2. Note that the image defect due to the change in the current value of the developing roller due to energization is an occurrence of a density unevenness image on the halftone image in conformity with the rotation pitch of the developing roller.
A: Density unevenness does not occur.
B: Minor density unevenness occurs in part.
C: Minor density unevenness occurs on the entire surface.
D: Density unevenness occurs on the entire surface.

[Example 2]
The raw rubber in the uncrosslinked rubber composition for the foam layer used in Example 1 was NBR rubber ((trade name) Nipol DN401: 18% bonded acrylonitrile amount, manufactured by Nippon Zeon Co., Ltd.), and liquid NBR rubber ( (Product name) Nipol 1312: amount of bound acrylonitrile 40.5%, manufactured by Nippon Zeon Co., Ltd.) 20 parts by mass. Moreover, the addition amount of the compound A in the uncrosslinked rubber composition for foam layers used in Example 1 was changed to 3 parts by mass. Otherwise, an elastic roller was prepared and evaluated in the same manner as in Example 1.

[Example 3]
The raw rubber in the uncrosslinked rubber composition for the foam layer used in Example 1 was changed to 100 parts by mass of H-NBR rubber ((trade name) Zetpol 2020: amount of bound acrylonitrile 36.2%, manufactured by Nippon Zeon Co., Ltd.). And the addition amount of the compound A was changed to 0.5 mass part. Otherwise, an elastic roller was prepared and evaluated in the same manner as in Example 1.

[Example 4]
The raw rubber in the uncrosslinked rubber composition for the foam layer used in Example 1 was 80 parts by mass of SBR rubber ((trade name) Nipol NS116R, manufactured by Nippon Zeon) and liquid SBR rubber ((trade name) Poly-bd. CS-15, manufactured by Idemitsu Petrochemical Co., Ltd.). Moreover, the addition amount of the compound A in the uncrosslinked rubber composition for foam layers used in Example 1 was changed to 7 parts by mass. Otherwise, an elastic roller was prepared and evaluated in the same manner as in Example 1.

[Example 5]
The raw material rubber in the uncrosslinked rubber composition for the foam layer used in Example 1 was 80 parts by mass of butadiene rubber ((trade name) BR-150, manufactured by Ube Industries) and liquid butadiene rubber ((trade name) LIR- 300, manufactured by Kuraray Co., Ltd.) and the amount of Compound A added was changed to 5 parts by mass. Otherwise, an elastic roller was prepared and evaluated in the same manner as in Example 1.

[Example 6]
The raw rubber in the uncrosslinked rubber composition for the foam layer used in Example 1 was 80 parts by mass of IR rubber (trade name) Nipol IR2200, manufactured by Nippon Zeon Co., Ltd. and liquid IR rubber ((trade name) LIR-50, The product was changed to 20 parts by mass. Moreover, the addition amount of the compound A in the uncrosslinked rubber composition for foam layers used in Example 1 was changed to 3 parts by mass. Otherwise, an elastic roller was prepared and evaluated in the same manner as in Example 1.

[Example 7]
The raw rubber in the uncrosslinked rubber composition for the foam layer used in Example 1 was changed to 100 parts by mass of epichlorohydrin rubber (CO) (trade name: Hydrin T3106, manufactured by Nippon Zeon). Otherwise, an elastic roller was prepared and evaluated in the same manner as in Example 1.

[Example 8]
The raw material rubber in the uncrosslinked rubber composition for the foam layer used in Example 1 was changed to 100 parts by weight of butyl rubber (IIR) (trade name: Butyl 065, manufactured by Nippon Butyl Co., Ltd.), and the amount of compound A added was changed. The amount was changed to 0.5 parts by mass. Otherwise, an elastic roller was prepared and evaluated in the same manner as in Example 1.

[Example 9]
The raw rubber in the uncrosslinked rubber composition for a foam layer used in Example 1 was changed to 100 parts by mass of chloroprene rubber (CR) ((trade name) Neoprene WRT, Showa Denki, DuPont). Otherwise, an elastic roller was prepared and evaluated in the same manner as in Example 1.

[Example 10]
The raw rubber in the uncrosslinked rubber composition for the foam layer used in Example 1 was 60 parts by mass of ethylene-propylene-diene rubber ((trade name) Esprene 505, manufactured by Sumitomo Chemical Co., Ltd.), norbornene rubber (NOR) ((product Name) Nosolex, manufactured by Nippon Zeon Co., Ltd.) 20 parts by mass and liquid IR rubber (trade name: LIR-50, manufactured by Kuraray Co., Ltd.) 20 parts by mass. Moreover, the addition amount of the compound A in the uncrosslinked rubber composition for foam layers used in Example 1 was changed to 0.1 parts by mass. Otherwise, an elastic roller was prepared and evaluated in the same manner as in Example 1.

[Examples 11 to 14]
The amount of compound A added in the uncrosslinked rubber composition for a foam layer used in Example 1 was changed as described in Table 2. Otherwise, an elastic roller was prepared and evaluated in the same manner as in Example 1.

[Examples 15 to 17]
About each of Examples 2-4, the compound A in the uncrosslinked rubber composition for foam layers was changed to the compound B (one type of the compound of Formula 1) mentioned later. Otherwise, an elastic roller was produced and evaluated in the same manner as in Example 2.

[Examples 18 to 21]
About each of Examples 5-8, the compound A in the uncrosslinked rubber composition for foam layers was changed to the compound C or D (all of which are 1 type of the compound of Formula 1) mentioned later. Otherwise, an elastic roller was produced and evaluated in the same manner as in Example 5.

[Example 22]
Compound A in the uncrosslinked rubber composition for a foam layer used in Example 9 was changed to Compound E (one of the compounds of Formula 1). Otherwise, an elastic roller was produced and evaluated in the same manner as in Example 9.

[Example 23]
Compound A in the uncrosslinked rubber composition for a foam layer used in Example 1 was changed to Compound I (one of the compounds of Formula 2) described later, and the amount added was changed to 0.5 parts by mass. Otherwise, an elastic roller was prepared and evaluated in the same manner as in Example 1.

[Example 24]
Compound A in the uncrosslinked rubber composition for a foam layer used in Example 2 was changed to Compound I described later, and the amount added was changed to 1.5 parts by mass. Otherwise, an elastic roller was produced and evaluated in the same manner as in Example 2.

[Example 25]
Compound A in the uncrosslinked rubber composition for a foam layer used in Example 3 was changed to Compound I described later, and the amount added was changed to 0.1 parts by mass. Otherwise, an elastic roller was prepared and evaluated in the same manner as in Example 3.

[Example 26]
Compound A in the uncrosslinked rubber composition for a foam layer used in Example 4 was changed to Compound I described later, and the amount added was changed to 3 parts by mass. Otherwise, an elastic roller was produced and evaluated in the same manner as in Example 4.

[Example 27]
Compound A in the uncrosslinked rubber composition for a foam layer used in Example 5 was changed to Compound I described later, and the amount added was changed to 2 parts by mass. Otherwise, an elastic roller was produced and evaluated in the same manner as in Example 5.

[Example 28]
Compound A in the uncrosslinked rubber composition for a foam layer used in Example 6 was changed to Compound I described later, and the amount added was changed to 2 parts by mass. Otherwise, an elastic roller was produced and evaluated in the same manner as in Example 6.

[Example 29]
Compound A in the uncrosslinked rubber composition for a foam layer used in Example 7 was changed to Compound I described later, and the amount added was changed to 0.5 parts by mass. Otherwise, an elastic roller was produced and evaluated in the same manner as in Example 7.

[Example 30]
Compound A in the uncrosslinked rubber composition for foam layer used in Example 8 was changed to Compound I described later, and the amount added was changed to 0.2 parts by mass. Otherwise, an elastic roller was prepared and evaluated in the same manner as in Example 8.

[Example 31]
Compound A in the uncrosslinked rubber composition for foam layer used in Example 9 was changed to Compound I described later, and the amount added was changed to 7 parts by mass. Otherwise, an elastic roller was produced and evaluated in the same manner as in Example 9.

[Example 32]
Compound A in the uncrosslinked rubber composition for a foam layer used in Example 10 was changed to Compound I described later. Otherwise, an elastic roller was produced and evaluated in the same manner as in Example 10.

[Examples 33 to 36]
About each of Examples 11-14, the compound A in the uncrosslinked rubber composition for foam layers was changed to the compound I mentioned later. Otherwise, an elastic roller was prepared and evaluated in the same manner as in each of Examples 11-14.

[Examples 37 to 39]
About each of Examples 24-26, the compound I in the uncrosslinked rubber composition for foam layers was changed to the compound J (one type of the compound of Formula 2) mentioned later. Otherwise, an elastic roller was prepared and evaluated in the same manner as in each of Examples 24-26.

[Example 40]
Compound I in the uncrosslinked rubber composition for a foam layer used in Example 27 was changed to Compound K (one of the compounds of Formula 2) described later. Otherwise, an elastic roller was produced and evaluated in the same manner as in Example 27.

[Example 41]
Compound I in the uncrosslinked rubber composition for a foam layer used in Example 28 was changed to Compound L (one of the compounds of Formula 2) described later. Otherwise, an elastic roller was prepared and evaluated in the same manner as in Example 28.

[Example 42]
The amount of compound I in the uncrosslinked rubber composition for a foam layer used in Example 29 was the same and was changed to compound M (one of the compounds of formula 2) described later. Otherwise, an elastic roller was prepared and evaluated in the same manner as in Example 29.

[Example 43]
Compound I in the uncrosslinked rubber composition for a foam layer used in Example 30 was changed to Compound N (one of the compounds of Formula 2) described later. Otherwise, an elastic roller was produced and evaluated in the same manner as in Example 30.

[Example 44]
Compound I in the uncrosslinked rubber composition for a foam layer used in Example 31 was changed to Compound O (one of the compounds of Formula 2) described later. Otherwise, an elastic roller was produced and evaluated in the same manner as in Example 31.
[Example 45]
Compound I in the uncrosslinked rubber composition for a foam layer used in Example 32 was changed to Compound P (one of the compounds of Formula 2) described later. Otherwise, an elastic roller was prepared and evaluated in the same manner as in Example 32.

[Example 46]
Compound A in the uncrosslinked rubber composition for a foam layer used in Example 1 was changed to Compound U (one of the compounds of Formula 3) described later, and the amount added was changed to 1.5 parts by mass. Otherwise, an elastic roller was prepared and evaluated in the same manner as in Example 1.

[Example 47]
Compound B in the uncrosslinked rubber composition for a foam layer used in Example 15 was changed to Compound U described later, and the amount added was changed to 4 parts by mass. Otherwise, an elastic roller was prepared and evaluated in the same manner as in Example 15.

[Example 48]
Compound B in the uncrosslinked rubber composition for a foam layer used in Example 16 was changed to Compound U described later, and the amount added was changed to 0.8 parts by mass. Otherwise, an elastic roller was prepared and evaluated in the same manner as in Example 16.

[Example 49]
Compound B in the uncrosslinked rubber composition for a foam layer used in Example 17 was changed to Compound U described later, and the amount added was changed to 10 parts by mass. Otherwise, an elastic roller was produced and evaluated in the same manner as in Example 17.

[Example 50]
Compound C in the uncrosslinked rubber composition for a foam layer used in Example 18 was changed to Compound U described later, and the amount added was changed to 8 parts by mass. Otherwise, an elastic roller was prepared and evaluated in the same manner as in Example 18.

[Example 51]
Compound C in the uncrosslinked rubber composition for a foam layer used in Example 19 was changed to Compound U described later, and the amount added was changed to 5 parts by mass. Otherwise, an elastic roller was produced and evaluated in the same manner as in Example 19.

[Example 52]
Compound D in the uncrosslinked rubber composition for a foam layer used in Example 20 was changed to Compound U described later, and the amount added was changed to 2 parts by mass. Otherwise, an elastic roller was produced and evaluated in the same manner as in Example 20.

[Example 53]
Compound D in the uncrosslinked rubber composition for a foam layer used in Example 21 was changed to Compound U described later, and the amount added was changed to 1 part by mass. Otherwise, an elastic roller was produced and evaluated in the same manner as in Example 21.

[Example 54]
Compound E in the uncrosslinked rubber composition for foam layer used in Example 22 was changed to Compound U described later, and the amount added was changed to 2 parts by mass. Otherwise, an elastic roller was produced and evaluated in the same manner as in Example 22.

[Example 55]
Compound A in the uncrosslinked rubber composition for a foam layer used in Example 10 was changed to Compound U described later, and the amount added was changed to 0.2 parts by mass. Otherwise, an elastic roller was prepared and evaluated in the same manner as in Example 10.

[Examples 56 to 59]
About each of Examples 11-14, the compound A in the uncrosslinked rubber composition for foam layers was changed to the compound U mentioned later. Otherwise, an elastic roller was prepared and evaluated in the same manner as in each of Examples 11-14.

[Example 60]
Compound U in the uncrosslinked rubber composition for a foam layer used in Example 46 was changed to Compound V (one of the compounds of Formula 3) described later. Otherwise, an elastic roller was prepared and evaluated in the same manner as in Example 46.

[Example 61]
Compound U in the uncrosslinked rubber composition for a foam layer used in Example 47 was changed to Compound W (one of the compounds of Formula 3) described later. Otherwise, an elastic roller was prepared and evaluated in the same manner as in Example 47.

[Example 62]
The addition amount of Compound A in the uncrosslinked rubber composition for foam layer used in Example 1 was changed to 0.5 parts by mass, and 0.3 parts by mass of Compound I described later was further added. Otherwise, an elastic roller was prepared and evaluated in the same manner as in Example 1.

[Example 63]
The addition amount of the compound A in the uncrosslinked rubber composition for a foam layer used in Example 1 was changed to 0.5 parts by mass, and 0.8 parts by mass of the compound U described later was further added. Otherwise, an elastic roller was prepared and evaluated in the same manner as in Example 1.

[Example 64]
Compound A in the uncrosslinked rubber composition for foam layer used in Example 1 was changed to Compound I, the addition amount was changed to 0.3 parts by mass, and 0.8 parts by mass of Compound U was further added. . Otherwise, an elastic roller was prepared and evaluated in the same manner as in Example 1.

[Example 65]
In the uncrosslinked rubber composition for a foam layer used in Example 62, the amount of compound A added was changed to 0.3 parts by mass, the amount of compound I added was changed to 0.1 parts by mass, 5 parts by mass were added. Otherwise, an elastic roller was prepared and evaluated in the same manner as in Example 62.

[Example 66]
When the uncrosslinked rubber composition for the foam layer of Example 1 was prepared (kneading step), the compound A was used without being dissolved in ethanol, which is a low boiling point solvent, and the obtained uncrosslinked rubber for the foam layer was heated. It used for the following forming process, without performing a process. Otherwise, an elastic roller was prepared and evaluated in the same manner as in Example 1.

[Example 67]
After the preparation of the uncrosslinked rubber composition for the foam layer of Example 1, the uncrosslinked rubber composition was used in the next molding step without performing reduced pressure and heating and without performing the heating step. Otherwise, an elastic roller was produced and evaluated in the same manner as in Example 1.

[Example 68]
After producing the uncrosslinked rubber composition for the foam layer of Example 1, the uncrosslinked rubber composition was heated to 80 ° C. at normal pressure without reducing the pressure in the heating step, and used in the next molding step. Otherwise, an elastic roller was produced and evaluated in the same manner as in Example 1.

[Example 69]
Ethanol, which is a low boiling point solvent used in Example 1, was changed to methyl ethyl ketone (boiling point: 79.5 ° C.). Otherwise, an elastic roller was prepared and evaluated in the same manner as in Example 1.

[Comparative Examples 1 to 10]
About each of Examples 1-10, the compound A in the uncrosslinked rubber composition for foam layers was not added. Otherwise, an elastic roller was prepared and evaluated in the same manner as in each of Examples 1 to 10.
[Comparative Examples 11 to 17]
For Examples 1, 2, 3, 26, 27, 29 and 30, the elastic rollers were prepared in the same manner as in each Example except that the compounds were changed to compounds not corresponding to the network forming component as shown in Table 3. Were made and evaluated.

[Comparative Examples 18-19]
An elastic roller was prepared and evaluated in the same manner as in Example 46 except that Compound U in Example 46 was changed to Compound X or Compound Y that does not correspond to the network forming component.

  The compounds A to H used in the examples and comparative examples are shown below. These compounds are compounds of formula 1 or analogs thereof. In addition, the similar compound does not correspond to the compound of Formula 1, and does not correspond to a network formation component.

  Compound A is a compound in which n in Formula 1 represents 2, R1 represents 4, R2 represents 4, and R3 represents 11.

  Compound B is a compound in which n in Formula 1 is 2, R1 is 4, R2 is 4, and R3 is 7.

  Compound C is a compound in which n in Formula 1 is 2, R1 is 3, R2 is 4, and R3 is 7.

  Compound D is a compound in which n in Formula 1 represents 2, R1 represents 3, R2 represents 3, and R3 represents 7.

  Compound E is a compound in which n in Formula 1 is 1, R1 is 4, R2 is 4, and R3 is 11.

  Compound F is a compound in which n in Formula 1 is 1, R1 is 4, R2 is 4, and R3 is 5, and does not correspond to the network-forming component used in the present invention.

  Compound G is a compound in which n in Formula 1 is 2, R1 is 2, R2 is 2, and R3 is 5, and does not correspond to a network forming component.

  Compound H is a compound in which n in Formula 1 is 2, R1 is 7, R2 is 7, and R3 is 15, and does not correspond to a network forming component.

  The compounds I to T used in the above Examples and Comparative Examples are shown below. These compounds are compounds of formula 2 or analogues thereof. The analogous compound does not correspond to the compound of formula 2 and does not correspond to the network forming component. Table 1 shows t and R4 to 13 in Formula 2 of these compounds, and all of the compounds having no description of substituents R4 to R13 represent hydrogen atoms. In the table, Me represents a methyl group, Et represents an ethyl group, and Pr represents a normal propyl group. Compounds Q, R, S, and T do not correspond to network forming components.

The compounds U to Y used in the examples and comparative examples are shown below. These compounds are compounds of formula 3 or analogues thereof. The analogous compound does not correspond to the compound of formula 3 and does not correspond to the network forming component. Compounds X and Y do not correspond to network forming components.
Compound U: 12-hydroxystearic acid (one of the compounds of formula 3)
Compound V: 2-hydroxylauric acid (one of the compounds of formula 3)
Compound W: 2-hydroxyarachidic acid (one of the compounds of formula 3)
Compound X: 10-Hydroxydecanoic acid Compound Y: 22-Hydroxydocosanoic acid For Examples 1 to 69 and Comparative Examples 1 to 19, the scorch time at 100 ° C. and the evaluation results of the uncrosslinked rubber composition for the foam layer Are shown in Tables 2-3 below.

  As described above, according to the present invention, there is provided an elastic roller that is flexible, has little contamination to the photosensitive drum, has a low compression permanent deformation property, and has a small current value decrease due to energization, and a method for manufacturing the elastic roller. Can do.

DESCRIPTION OF SYMBOLS 1 ... Conductive shaft core 2 ... Foam layer 3 ... Cover layer 4 ... Load 5 ... Multimeter

Claims (2)

An elastic roller having a conductive shaft core, a foam layer on the outer peripheral surface of the conductive shaft core, and a coating layer on the outer peripheral surface of the foam layer,
The foam layer is
At least one raw material selected from the group consisting of ethylene-propylene-diene rubber, acrylonitrile-butadiene rubber, hydrogenated acrylonitrile-butadiene rubber, styrene-butadiene rubber, butadiene rubber, isoprene rubber, epichlorohydrin rubber, butyl rubber, chloroprene rubber and norbornene rubber A crosslinked rubber obtained by crosslinking a rubber with a crosslinking agent ;
At least one compound selected from the group of compounds represented by the following formulas (1) and (2) ;
An elastic roller comprising carbon black :
(In formula (1), n represents 1 or 2, R1 and R2 each independently represents an alkyl group having 3 or 4 carbon atoms, and R3 represents an alkyl group having 7 to 11 carbon atoms. ),
(In the formula (2), t represents 0 or 1, and R4 to R13 each independently represents a hydrogen atom, an alkyl group having 1 to 2 carbon atoms, a halogen atom, a nitro group, or 1 to 2 carbon atoms. Represents an alkoxy group) . It is a manufacturing method of the elastic roller of Claim 1, Comprising:
And at least one compound selected from the group of the following formula (1) and the compound represented by (2), wherein the raw material rubber, and the carbon black, the crosslinking agent include uncrosslinked rubber composition in conductive mandrel a step of coating the outer peripheral surface of,
Manufacturing method of the elastic roller, characterized in that and a step of obtaining the foam layer by foaming and crosslinking by heating the uncrosslinked rubber composition:
(In formula (1), n represents 1 or 2, R1 and R2 each independently represents an alkyl group having 3 or 4 carbon atoms, and R3 represents an alkyl group having 7 to 11 carbon atoms. ),
(In the formula (2), t represents 0 or 1, and R4 to R13 each independently represents a hydrogen atom, an alkyl group having 1 to 2 carbon atoms, a halogen atom, a nitro group, or 1 to 2 carbon atoms. Represents an alkoxy group) .