JP2009102634A - Method and apparatus for performing surface treatment of rubber member - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for performing surface treatment of a rubber member, the method realizing production of a rubber member which has low hardness and thus can respond to deformation and which does not cause staining of an OPC and the like and leakage. <P>SOLUTION: The method for performing surface treatment of the rubber member comprises impregnating a rubber member with a first surface-treatment liquid containing an isocyanate component and an organic solvent to form a first impregnation layer, and sequentially treating the surface of the rubber member, without exposure to air, with a second surface-treatment liquid for partially removing the isocyanate component present in the first impregnation layer. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a charging roll, a developing roll, a cleaning roll, a toner supply roll, a toner regulating roll, a transfer roll, and an intermediate transfer of an image forming apparatus such as an electrophotographic copying machine and printer, or a toner jet copying machine and printer. The present invention relates to a rubber member surface treatment method and a rubber member surface treatment apparatus suitably used for a roll, a cleaning blade, a belt, and the like.

  Charging rolls, developing rolls, cleaning rolls, toner supply rolls, toner regulating rolls, and transfer rolls, intermediate transfer rolls, and cleaning blades for image forming apparatuses such as electrophotographic copying machines and printers, or toner jet copying machines and printers The belt and the like are required to have predetermined conductivity, a coefficient of friction and the like in addition to non-contamination to the photoreceptor. Conventionally, polyurethane and silicone rubber are used, but those having a coating layer are used for reasons such as contamination of the photoreceptor and charging properties.

  In recent years, toner binders used in electrophotographic copying machines have been lowered in melting point, and accordingly, developing rolls have a low hardness to form a sufficient nip to ensure toner charging. Is required. In order to satisfy the above-described requirements, there has been proposed a developing roll composed of an elastic layer, a coat layer made of urethane resin, and a thin cured layer made of isocyanate, and having a hard surface while keeping the whole soft (for example, Patent Documents) 1).

On the other hand, the formation of the coating layer has the disadvantage that the process becomes complicated and the production cost increases, and as a means for easily solving this problem, a method of chemically treating the roll surface layer has been proposed. (For example, refer to Patent Document 2). Although this treatment method is effective, the conductive roll subjected to the surface treatment tends to have a hard surface treatment layer. In the case of a roll having a reduced hardness, the surface layer portion of the roll is greatly deformed during use, so that it is necessary to follow the deformation. However, a roll having a hard surface treatment layer has a poor followability, such as OPC. There was a risk of damage.
JP-A-2005-283913 JP-A-5-158341

  In view of such circumstances, the present invention is free from the problem of contamination such as OPC and leakage, and has a rubber member surface treatment method and a rubber member that can obtain a low-hardness rubber member that can follow deformation. It is an object to provide a surface treatment apparatus.

  According to a first aspect of the present invention for solving the above-mentioned problems, a first surface treatment liquid containing an isocyanate component and an organic solvent is impregnated into a rubber member to form an impregnated layer, and then continuously without contact with air. Further, the rubber member surface treatment method is characterized in that the surface of the rubber member is treated with a second surface treatment liquid for removing a part of the isocyanate component in the impregnated layer.

  According to a second aspect of the present invention, in the rubber member surface treatment method according to the first aspect, after the rubber member is immersed in a layer made of the first surface treatment liquid to form an impregnation layer. In the rubber member surface treatment method, the rubber member is moved to a layer made of the second surface treatment liquid formed by phase separation from the layer made of the first surface treatment liquid.

  According to a third aspect of the present invention, in the method for surface treatment of a rubber member according to the second aspect, the rubber member is immersed in the first surface treatment liquid, and then the first surface treatment liquid. The rubber member surface treatment method is characterized in that a layer made of the second surface treatment liquid is formed on the layer, and the rubber member is pulled up via the second surface treatment liquid.

  According to a fourth aspect of the present invention, in the rubber member surface treatment method according to any one of the first to third aspects, the organic solvent is an aprotic polar solvent. Is in the way.

  According to a fifth aspect of the present invention, in the rubber member surface treatment method according to any one of the first to fourth aspects, the second surface treatment liquid is made of a nonpolar solvent. There is a surface treatment method.

  According to a sixth aspect of the present invention, in the surface treatment method for a rubber member according to any one of the first to fifth aspects, a second impregnation layer is further formed after the treatment with the second surface treatment liquid. A rubber member characterized in that after the rubber member is impregnated with the third surface treatment liquid, the surface of the rubber member is continuously treated with the second surface treatment liquid without being brought into contact with air. In the surface treatment method.

  According to a seventh aspect of the present invention, in the surface treatment method for a rubber member according to any one of the first to fifth aspects, after the treatment with the second surface treatment liquid, one of the isocyanate components in the impregnated layer. The rubber member surface treatment method is characterized in that the surface of the rubber member is treated with a fourth surface treatment liquid that further removes the part.

  According to an eighth aspect of the present invention, in the rubber member surface treatment method according to the sixth aspect, the third surface treatment liquid comprises an isocyanate compound, a conductivity-imparting material, an acrylic fluorine-based polymer, and an acrylic silicone. It is in the surface treatment method of the rubber member characterized by containing at least one selected from a system polymer.

  According to a ninth aspect of the present invention, the rubber member is immersed in a first surface treatment liquid containing an isocyanate component and an organic solvent, and then the second surface treatment liquid phase-separated from the first surface treatment liquid. A container for treating the surface of the rubber member by moving the rubber member, and containing the first surface treatment liquid and the second surface treatment liquid in a phase-separated state, and at least an upper layer And a means for discharging the surface treatment liquid constituting the outside of the container.

  In a tenth aspect of the present invention, the rubber member is immersed in a first surface treatment liquid containing an isocyanate component and an organic solvent, and then the rubber member is phase-separated from the first surface treatment liquid. For treating the surface of the rubber member by moving to the third surface treatment liquid phase-separated from the second surface treatment liquid, provided from the bottom to the middle in the height direction. And a container for storing the second surface treatment liquid in the upper part of the first surface treatment liquid and the third surface treatment liquid in a state where the lower part is divided into two parts by the partition plate and the first surface treatment liquid and the third surface treatment liquid are separated. And a means for discharging the surface treatment liquid to be out of the container.

  According to an eleventh aspect of the present invention, in the surface treatment apparatus for a rubber member according to the ninth or tenth aspect, the apparatus includes an introduction unit that introduces the surface treatment liquid discharged from the discharge unit into the container. A surface treatment apparatus for a rubber member.

  According to the present invention, it is possible to obtain a low-hardness rubber member that is free from problems of contamination such as OPC and leakage, and that can follow deformation.

  In the rubber member surface treatment method of the present invention, a first surface treatment liquid containing an isocyanate component and an organic solvent is impregnated into a rubber member to form an impregnated layer, and then impregnated continuously without contact with air. The surface of the rubber member is treated with a second surface treatment liquid that removes part of the isocyanate component in the layer. According to this surface treatment method, since the first surface treatment liquid impregnated in the rubber member does not volatilize, the treatment with the second surface treatment liquid is performed uniformly over the entire surface of the rubber member. be able to.

  An impregnation layer is formed by impregnating the rubber member with the first surface treatment liquid, a part of the isocyanate component in the impregnation layer is removed by the second surface treatment liquid, and then dried and cured, whereby the rubber member A surface treatment layer integrated with the rubber member is formed on the surface layer portion. In the surface treatment layer, the density of the isocyanate component is larger in the interior than the surface in the upper layer portion on the surface side, and the density of the isocyanate component is gradually decreased toward the inside in the lower layer portion on the lower side of the upper layer portion. .

  That is, according to the surface treatment method for a rubber member of the present invention, a lower layer portion that functions to prevent leakage and adjust electrical resistance as well as to prevent bleeding from the inside of the pollutant as in the past, and hardness Thus, it is possible to obtain a rubber member having a surface treatment layer composed of an upper layer portion in which the rise of the thickness is suppressed. For this reason, the rubber member obtained by the surface treatment method of the rubber member of the present invention is a low-hardness rubber member that is free from contamination and leakage problems such as OPC and has a followability to deformation.

  As described above, the surface treatment method for the rubber member is formed by impregnating the rubber member with the first surface treatment liquid containing the isocyanate component and the organic solvent to form an impregnated layer, and then continuously without contacting the air. What is necessary is just to process the surface of the said rubber member with the 2nd surface treatment liquid which removes a part of isocyanate component of the surface layer part in an impregnation layer. For example, a rubber member is immersed in a layer made of a first surface treatment liquid to form an impregnated layer, and then the rubber member is phase-separated from a layer made of the first surface treatment liquid. There is a method of treating the surface of the rubber member by moving it to a layer made of the surface treatment liquid (hereinafter referred to as phase separation treatment). As described above, the rubber member is moved between the two phase-separated layers composed of the first surface treatment liquid and the second surface treatment liquid, so that continuous treatment without contact with air can be easily performed. Can do.

  When such a phase separation treatment is performed, the first surface treatment liquid and the second surface treatment liquid are used which have low compatibility and phase separation, but the first surface treatment liquid is an upper layer. May be a lower layer. The specific gravity of the first surface treatment liquid may be smaller or larger than the specific gravity of the second surface treatment liquid, but the first surface treatment liquid is higher in specific gravity than the second surface treatment liquid, It is preferable that 1 surface treatment liquid is used as a lower layer. In this case, after immersing the rubber member in the first surface treatment liquid, a layer made of the second surface treatment liquid is formed on the layer made of the first surface treatment liquid, and the second surface treatment By pulling up the rubber member through the liquid, it is possible to more easily perform a continuous process without contacting the air. According to this method, when the rubber member is pulled up, the surface of the rubber member is wiped by the second surface treatment liquid, and the excess isocyanate component adhering to the surface of the rubber member is removed. Further, a part of the isocyanate component in the impregnated layer is uniformly removed. This surface treatment method differs from the conventional method of impregnating with an isocyanate component and then wiping with a sponge or the like, so that the first surface treatment liquid impregnated in the rubber member does not volatilize and the second surface When the treatment liquid uniformly contacts the surface of the rubber member, a uniform surface treatment can be performed over the entire surface of the rubber member.

  Further, the surface treatment method of the rubber member is not limited to the phase separation treatment. For example, after the rubber member is immersed in the first surface treatment liquid, the second surface is pulled up while the rubber member is pulled up from the first surface treatment liquid. A method of continuously treating the surface of the rubber member without spraying with the treatment liquid by spraying the treatment liquid may be used. Note that the spraying of the second surface treatment liquid is preferably performed under dry air or an inert gas (such as nitrogen or argon). It is because it can suppress that the water | moisture content in air and an isocyanate compound react.

  Here, the first surface treatment liquid and the second surface treatment liquid according to the present invention will be described.

  As described above, the first surface treatment liquid contains an isocyanate component and an organic solvent. As isocyanate components, 2,6-tolylene diisocyanate (TDI), 4,4'-diphenylmethane diisocyanate (MDI), paraphenylene diisocyanate (PPDI), 1,5-naphthalene diisocyanate (NDI) and 3,3-dimethyldiphenyl Examples thereof include isocyanate compounds such as -4,4'-diisocyanate (TODI) and hexamethylene diisocyanate (HDI), and the aforementioned multimers and modified products. Furthermore, the prepolymer which consists of a polyol and isocyanate can be mentioned.

  Moreover, the organic solvent used for the first surface treatment liquid is particularly limited as long as it dissolves an isocyanate component, a polyether polymer, an acrylic fluorine polymer, and an acrylic silicone polymer, which will be described later, contained as necessary. However, it is preferable to use a rubber member which is relatively easily impregnated into the rubber member and swells the rubber member, and varies depending on the type of rubber base material constituting the rubber member, but ethyl acetate, methyl ethyl ketone (MEK), methyl isobutyl ketone ( MIBK) and an organic solvent such as toluene may be used. In the case of the phase separation treatment, an aprotic polar solvent that undergoes phase separation with respect to a nonpolar solvent such as hexane is used as the first surface treatment liquid, although it varies depending on the type of solvent used in the second surface treatment liquid. For example, an organic solvent such as N-methylpyrrolidone, N, N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), or acetonitrile may be used.

  The first surface treatment liquid may contain a polyether polymer. Here, the polyether polymer is preferably soluble in an organic solvent, and preferably has active hydrogen and can be chemically bonded by reacting with an isocyanate component.

  Examples of suitable polyether polymers having active hydrogen include epichlorohydrin rubber. The epichlorohydrin rubber here refers to an unvulcanized state. Epichlorohydrin rubber is preferable because it can impart elasticity to the surface treatment layer as well as conductivity. The epichlorohydrin rubber has an active hydrogen (hydroxyl group) at the terminal, but preferably has a unit having an active hydrogen such as a hydroxyl group or an allyl group. Examples of the epichlorohydrin rubber include an epichlorohydrin homopolymer, an epichlorohydrin-ethylene oxide copolymer, an epichlorohydrin-allyl glycidyl ether copolymer, an epichlorohydrin-ethylene oxide-allyl glycidyl ether terpolymer and a derivative thereof. it can.

  Examples of other suitable polyether polymers having active hydrogen include polymers having a hydroxyl group or an allyl group, such as polyols and glycols. Such a polyether polymer preferably has only one terminal rather than one having active hydrogen groups at both terminals. Moreover, it is preferable that a number average molecular weight is 300-1000. This is because elasticity can be imparted to the surface treatment layer formed on the surface layer portion of the rubber member. Examples of such polyether polymers include polyalkylene glycol monomethyl ether, polyalkylene glycol dimethyl ether, allylated polyether, polyalkylene glycol diol, polyalkylene glycol triol, and the like.

  Thus, by adding a polyether polymer to the first surface treatment liquid, the flexibility and strength of the surface treatment layer formed on the surface layer portion of the rubber member are improved, and as a result, the surface of the desired rubber member There is no risk of wear or damage to the surface of the photosensitive member that comes into contact.

  Further, the first surface treatment liquid may contain a polymer selected from an acrylic fluorine polymer and an acrylic silicone polymer.

  The acrylic fluorine-based polymer and the acrylic silicone-based polymer used in the first surface treatment liquid are soluble in a predetermined solvent and can be chemically bonded by reacting with an isocyanate component. The acrylic fluorine-based polymer is, for example, a solvent-soluble fluorine-based polymer having a hydroxyl group, an alkyl group, or a carboxyl group, and examples thereof include block copolymers of acrylic acid esters and fluorinated alkyl acrylates and derivatives thereof. . The acrylic silicone polymer is a solvent-soluble silicone polymer, and examples thereof include block copolymers of acrylic acid esters and acrylic acid siloxane esters, and derivatives thereof.

  In addition, the first surface treatment liquid is further used as a conductivity-imparting material such as carbon black such as acetylene black, ketjen black (manufactured by Lion), Toka Black (manufactured by Tokai Carbon Co., Ltd.), or a conventional surface treatment liquid. A conductivity imparting material that is used (see, for example, JP-A-2007-31703) may be added. When carbon black is used for the first surface treatment liquid, it is preferably 0 to 40% by mass with respect to the isocyanate component. If the amount is too large, problems such as dropout and deterioration of physical properties occur, which is not preferable.

  In addition, the acrylic fluorine-based polymer and the acrylic silicone-based polymer in the first surface treatment liquid are such that the total amount of the acrylic fluorine-based polymer and the acrylic silicone-based polymer is 2 to 30 parts by mass with respect to 100 parts by mass of the isocyanate component. It is preferable to do this. When the amount is less than 2 parts by mass, the effect of retaining carbon black or the like in the surface treatment layer is reduced. On the other hand, when the polymer amount is too large, there are problems that the electric resistance value of the charging roll is increased and the discharge characteristics are lowered, and there is a problem that an effective surface treatment layer cannot be formed due to relatively less isocyanate component.

  On the other hand, the second surface treatment liquid is not particularly limited as long as it can remove the isocyanate component of the outermost layer portion of the impregnated layer of the rubber member, but the one containing no isocyanate component or the concentration of the isocyanate component is the first. The organic solvent-based one that is remarkably smaller than the surface treatment liquid is preferred.

  The organic solvent that can be used for the second surface treatment liquid may dissolve the isocyanate component in the same manner as the organic solvent used for the first surface treatment liquid. Those that do not dissolve the components and those that hardly swell the rubber member are preferred. Using an organic solvent that dissolves the isocyanate component or equivalently swells the rubber member than the organic solvent of the first surface treatment liquid, prevents contamination inside the rubber member corresponding to the lower layer part as well as the outermost layer part. This is because there is a high risk of removing the isocyanate component for this purpose, and precise temperature management and time management are required in the process.

  In the case of the phase separation treatment, as the second surface treatment liquid, a nonpolar solvent which is a poor solvent for the isocyanate component can be used, and examples thereof include hexane and cyclohexane. Such treatment has an advantage that the upper layer portion of the surface treatment layer can be formed relatively thin and uniformly. Further, since hexane and cyclohexane are less likely to absorb moisture in the air, when the phase separation state occurs, the influence of moisture on the isocyanate component in the first surface treatment liquid is suppressed, and the first surface There is an advantage that the life of the treatment liquid becomes long.

  On the other hand, when it is not a phase separation treatment, a polar solvent that is a good solvent for the isocyanate component can be used as the second surface treatment liquid, and ethyl acetate or methyl ethyl ketone (like the organic solvent of the first surface treatment liquid) MEK). When processing is performed using such an organic solvent, the upper layer portion can be formed relatively thick, and the thicker the upper layer portion, the lower the hardness of the rubber member.

  Dry curing is not particularly limited as long as the isocyanate component can be cured inside the rubber member. After cooling to a temperature below the freezing point of the isocyanate, a method of curing with moisture in the atmosphere or under reduced pressure After volatilizing the solvent, there is a method of curing with heat or moisture. Generally, after drying at room temperature, heat treatment is performed as necessary. In addition, the heating temperature at this time is 40-150 degreeC, for example.

  The rubber member is not particularly limited, and is formed and vulcanized by adding a conductivity-imparting material to a rubber base as necessary. Here, examples of the rubber base material include polyurethane, epichlorohydrin rubber, nitrile rubber (NBR), styrene rubber (SBR), and chloroprene rubber.

  Further, as the conductivity imparting material, an electron conductivity imparting material such as carbon black or metal powder, an ionic conductivity imparting material, or a mixture of both can be used. Examples of the ionic conductivity-imparting material include organic salts, inorganic salts, metal complexes, ionic liquids, and the like. Examples of organic salts and inorganic salts include lithium perchlorate, quaternary ammonium salts, and sodium trifluoride acetate. Moreover, as a metal complex, halogenated ferric-ethylene glycol etc. can be mentioned, Specifically, what was described in the patent 3655364 can be mentioned. On the other hand, the ionic liquid is a molten salt that is liquid at room temperature, and is also called a room temperature molten salt, and particularly refers to a melting point of 70 ° C. or lower, preferably 30 ° C. or lower. Specific examples include those described in JP-A No. 2003-202722.

  Fig.1 (a) is sectional drawing of an example of the rubber roll obtained by the surface treatment method of the rubber member of this invention, FIG.1 (b) is an expanded sectional view of this rubber roll. A rubber roll 10 shown in FIG. 1 (a) has an elastic layer (rubber member) 12 that is obtained by adding a conductivity-imparting material or the like to a rubber base material on a core metal 11 and heat-curing it. The surface layer portion is a surface treatment layer 12a. Here, the surface treatment layer 12a is composed of an upper layer portion 12c on the surface side and a lower layer portion 12b below it. The upper layer portion 12c is a region in which the density of the impregnated isocyanate component is larger in the interior than in the surface, for example, gradually increases from the surface toward the interior. The lower layer portion 12b is a region where the density of the isocyanate component gradually decreases from the surface side toward the inside. The presence of the upper layer portion 12c means that there is a region where the density of the isocyanate component is larger on the inside than on the surface side, and conversely, it is sufficient that there is a region where the density of the isocyanate component is smaller on the surface side. The isocyanate component may be substantially absent on the outermost surface of the portion 12c. Further, such an upper layer portion 12c does not have a problem with the boundary with the lower layer portion 12b, and the presence of the upper layer portion 12c forms a state in which the surface layer has a lower hardness than the inside. Since the upper layer part 12c exists in order to make the hardness of the outermost layer low (lower hardness than the lower layer part 12b), for example, the thickness is at least 1 μm or more, preferably 10 μm or more. It is particularly preferable that the upper layer portion 12c exists up to a region where a nip is formed by deformation when used, and for example, the thickness is preferably about 10 to 100 μm. Moreover, it is preferable that the lower layer part 12b is about 100-1000 micrometers in thickness. The thicknesses of the upper layer part 12c and the lower layer part 12b can be predicted from, for example, the rubber hardness and electrical resistance value at each part by polishing the surface of the conductive rubber member. Here, the rubber roll in which a part of the isocyanate component in the impregnated layer is removed together with the excess isocyanate component adhering to the surface of the rubber roll in the treatment of the second surface treatment liquid has been described as an example, but the present invention is not limited thereto. For example, when only the excess isocyanate component adhering to the surface of the rubber roll is removed in the second surface treatment liquid, the upper layer portion 12c is not formed, and the surface treatment layer 12a becomes the lower layer portion. It becomes a rubber roll consisting only of 12b.

  In the rubber roll 10 formed by the surface treatment method for a rubber member of the present invention, the surface treatment layer 12 a provided on the surface layer portion of the elastic layer 12 is composed of an upper layer portion 12 c and a lower layer portion 12 b, and these are the surface layer portions of the elastic layer 12. Are integrally provided. The lower layer portion 12b of the surface treatment layer 12a is formed integrally by mainly curing the isocyanate component so that the density of the isocyanate component gradually decreases from the surface toward the inside. As a result, bleeding of contaminants such as a plasticizer on the surface of the rubber roll can be prevented, and the rubber roll is excellent in resistance to contamination of the photoreceptor.

  In addition, although the surface treatment of the rubber roll 10 which has the elastic layer 12 of one layer was performed here, the rubber member concerning this invention is not specifically limited. For example, the rubber member may have a structure of two or more layers, and may be a foamed layer or a non-foamed layer, and may have a blade shape, a brush shape, a belt shape, a film shape, a sheet shape, and a chip shape. .

  After the treatment with the second surface treatment liquid, the rubber member is further impregnated with the third surface treatment liquid for forming the second impregnation layer, and then the second surface treatment liquid is continuously brought into contact with the air without contact with the air. The surface of the rubber member may be treated with the surface treatment liquid to obtain a rubber member. With the third surface treatment liquid, new performance can be imparted to the rubber member, the followability to deformation of the rubber member can be further improved, or the rubber member can be further reduced in hardness. The third surface treatment liquid here is not particularly limited as long as it can form the second impregnation layer, and is appropriately selected according to the purpose.

  The second impregnation layer is preferably formed in a shallow surface layer region of the above-described impregnation layer (hereinafter referred to as the first impregnation layer), for example, a region from which a part of the isocyanate component has been removed. A region overlapping with the impregnated layer may be formed up to a region deeper than the first surface layer portion.

  Here, FIG. 1C and FIG. 1D are cross-sectional views showing an example of a rubber roll in which a second impregnation layer is formed and cured in a shallow surface layer region of the first impregnation layer. The rubber rolls shown in FIGS. 1C and 1D are cured by forming a second impregnation layer in a shallow surface layer region of the first impregnation layer using a third surface treatment liquid containing an isocyanate component. It has been made. By forming the second impregnation layer in the shallow surface layer region of the first impregnation layer, the lower layer portion 12d where the density of the isocyanate component gradually decreases from the surface side toward the inside, and the density of the isocyanate component is the surface The upper layer portion 12e having a higher density of the isocyanate component is formed inside than on the side. That is, in this rubber member, the surface treatment layer 12a is composed of the lower layer portion 12b, the lower layer portion 12d, and the upper layer portion 12e. Here, the rubber roll from which a part of the isocyanate component in the impregnated layer is removed together with the excess isocyanate component adhering to the surface of the rubber roll in the second treatment of the second surface treatment liquid has been described as an example. For example, when only the excess isocyanate component adhering to the surface of the rubber roll is removed in the second surface treatment liquid for the second time, the upper layer portion 12e is not formed, and the surface is not formed. The treatment layer 12a is a rubber roll including a lower layer portion 12b and a lower layer portion 12d.

  As the third surface treatment liquid, for example, the same one as the first surface treatment liquid may be used. That is, after the treatment with the second surface treatment liquid, the second surface treatment liquid is further impregnated with the first surface treatment liquid to form a second impregnation layer, and then the second surface treatment is continuously performed without contact with air. The rubber member may be obtained by treating the surface layer of the rubber member with a liquid.

  Of course, the third surface treatment liquid may be different from the first surface treatment liquid. Examples of the third surface treatment liquid include those containing an isocyanate component. The third surface treatment liquid may further contain at least one selected from the group consisting of a polyether polymer, an acrylic fluorine polymer, an acrylic silicone polymer, and a conductivity imparting material.

  The isocyanate component used in the third surface treatment liquid is not particularly limited, and the same or different one may be used as the isocyanate component of the first surface treatment liquid. Moreover, when using the same isocyanate component as a 1st surface treatment liquid, it is preferable that the density | concentration of an isocyanate component is lower than a 1st surface treatment liquid in a 3rd surface treatment liquid. This is because the density of the isocyanate component on the surface side of the rubber member is reduced, and it is easy to ensure flexibility.

  As described above, a desired rubber member can be obtained by appropriately selecting the third surface treatment liquid. For example, an isocyanate component (such as MDI) having an excellent anti-contamination effect is used as the first surface treatment liquid, and an isocyanate component (such as a prepolymer) that can impart flexibility is used as the third surface treatment liquid. Thus, it is possible to obtain a rubber member having excellent contamination and more flexibility. In addition, for example, by using a carbon black-free material as the first surface treatment liquid and using a carbon black-containing material as the third surface treatment liquid, carbon black can be applied to a particularly shallow surface layer region of the surface layer portion. A rubber member having excellent electrical conductivity can be obtained. In addition, for example, an isocyanate component (MDI or the like) having an excellent anti-contamination effect is used as the first surface treatment liquid, and an acrylic fluorine-based polymer, an acrylic silicone polymer, a polyisocyanate together with the isocyanate component as the third surface treatment liquid. By using an ether polymer, it is possible to obtain a rubber member excellent in adhesion preventing performance of toner components and the like, and particularly in the flexibility of the surface layer portion.

  Further, the third surface treatment liquid does not contain an isocyanate component, and includes at least one polymer selected from the group consisting of a polyether-based polymer, an acrylic fluorine-based polymer, and an acrylic silicone-based polymer, and an organic solvent. It may be. By using this third surface treatment liquid, a rubber member having further improved flexibility and strength can be obtained.

  The organic solvent used for the third surface treatment liquid described above is not particularly limited and may be appropriately selected depending on the purpose, but the same solvents as those mentioned for the first surface treatment liquid can be used.

  Further, after the treatment with the second surface treatment liquid, the surface layer portion of the rubber member may be treated with a fourth surface treatment liquid that further removes a part of the isocyanate component in the impregnated layer. The fourth surface treatment liquid is made of an organic solvent. The fourth surface treatment liquid is not particularly limited, but is preferably one that can dissolve the isocyanate component than the second surface treatment liquid. In the case of the phase separation treatment, the fourth surface treatment liquid (organic solvent) can be the same as that mentioned in the first surface treatment liquid, and is higher than the organic solvent of the first surface treatment liquid. Those that do not dissolve the isocyanate component and those that hardly swell the rubber member are preferred. In addition, when it is not a phase separation process, the thing similar to what was mentioned by the 2nd surface treatment liquid can be used.

  According to the surface treatment method for a rubber member of the present invention, it is possible to obtain a rubber member having a low hardness that is free from contamination and leakage problems such as OPC, and that can follow deformation.

  The rubber member obtained by the surface treatment method of the present invention includes, for example, a charging roll, a developing roll, a cleaning roll, a toner supply roll, an image forming apparatus such as an electrophotographic copying machine and printer, or a toner jet copying machine and printer. It is suitable for toner regulating rolls, transfer rolls / intermediate transfer rolls, cleaning blades, belts and the like.

  In the rubber member surface treatment apparatus of the present invention, the second surface treatment liquid phase-separated from the first surface treatment liquid after the rubber member is immersed in the first surface treatment liquid containing the isocyanate component and the organic solvent. The surface of the rubber member is treated by moving the rubber member.

  Here, the details of the surface treatment apparatus for a rubber member of the present invention will be described based on the embodiment. In addition, embodiment shown below is one Embodiment of this invention, and does not limit this invention.

(Embodiment 1)
FIG. 2 is a cross-sectional view of the rubber member surface treatment apparatus according to the first embodiment.

  The container 50 serving as the main body of the rubber member surface treatment apparatus has, for example, a cylindrical shape or a polygonal tubular shape, and includes a first surface treatment liquid containing an isocyanate component and an organic solvent, and the first organic solvent. And contain the second surface treatment liquid to be phase-separated in a two-layer state.

  A discharge pipe 21 for discharging the surface treatment liquid constituting the upper layer A is inserted into the container 50, and the discharge port 21 a of the discharge pipe 21 is disposed below the interface between the upper layer A and the lower layer B. ing. Here, the discharge pipe 21 is composed of a plurality of cylindrical bodies, and can be expanded and contracted vertically so as to be lower than the liquid level of the lower layer B supplied into the container 50.

  The discharge pipe 21 is provided with a pump for discharging the surface treatment liquid constituting the upper layer A, and is connected to a tank 20 provided outside the container 50 via the pump. The tank 20 is connected to the container 50 via the introduction path 22. In the introduction path 22, the introduction port 22 a is provided above the discharge port 21 a on the side wall of the container 50, and the surface treatment liquid constituting the upper layer A (and the surface treatment liquid constituting the lower layer B) stored in the tank 20. ) Is introduced into the container 50. The introduction path 22 is provided with an openable / closable valve and a pump for feeding the surface treatment liquid constituting the upper layer A (and the surface treatment liquid constituting the lower layer B).

  On the other hand, the bottom wall of the container 50 is provided with a discharge passage 31 for discharging the surface treatment liquid constituting the lower layer B. The discharge path 31 is connected to a tank 30 provided outside the container 50. The tank 30 is connected to the container 50 via the introduction path 32. The introduction path 32 is provided so that the introduction port 32 a is below the discharge port 21 a on the side wall of the container 50, and introduces the surface treatment liquid constituting the lower layer B stored in the tank 30 into the container 50. It is like that. The introduction path 32 is provided with an openable / closable valve and a pump for discharging the surface treatment liquid constituting the upper layer A (and the surface treatment liquid constituting the lower layer B).

  In the present embodiment, the discharge pipe 21 can be expanded and contracted, but the discharge pipe 21 may not be expanded and contracted. In this case, the surface treatment liquid constituting the upper layer A and the surface treatment liquid constituting the lower layer B are placed in the container. When introducing, it adjusts so that the surface treatment liquid which comprises the lower layer B may become below the discharge port 21a.

  In the present embodiment, the surface treatment liquid constituting the upper layer A is discharged from the discharge pipe 21 by a pump. However, the discharge means for discharging the surface treatment liquid forming the upper layer A is not limited to this. For example, the discharge port of the discharge path is provided so as to be below the interface between the upper layer A and the lower layer B of the side wall of the container 50, and when discharging, the upper layer A is removed from the discharge path by the weight of the surface treatment liquid constituting the upper layer A. You may make it discharge | emit the surface treatment liquid which comprises.

  The positions of the introduction port 22a of the introduction path 22 and the introduction port 32a of the introduction path 32 are not particularly limited. In this embodiment, the openings of the introduction path 22 and the introduction path 32 are connected to the side surface of the container 50, but the introduction path 22 and the introduction path 32 may be inserted into the container 50.

  In the present embodiment, the tank 20, the introduction path 22, the discharge path 31, the tank 30, and the introduction path 32 are provided, but it is not always necessary to provide them.

  A rubber member surface treatment method using the rubber member surface treatment apparatus 100A having the above-described configuration will be described with reference to FIG. FIG. 3 is a view for explaining an example of a surface treatment method and a surface treatment apparatus for a rubber member according to the present invention. In the present embodiment, the upper layer A is a second surface treatment liquid, and the lower layer B is a first surface treatment liquid.

  First, the first surface treatment liquid constituting the lower layer B is supplied into the container 50 from a supply path (not shown) so that the liquid level of the lower layer B is higher than the discharge port 21 a of the discharge pipe 21. At this time, the liquid level of the lower layer B is made high enough to immerse the rubber member. In addition, when the liquid level of the lower layer B becomes higher than a desired height, the first surface treatment liquid is discharged from the discharge path 31 to adjust the liquid level.

  And as shown to Fig.3 (a), the rubber member 1 is immersed in this lower layer B (1st surface treatment liquid). Thereby, the rubber member 1 is impregnated with the first surface treatment liquid.

  Next, a second surface treatment liquid (upper layer A) that is phase-separated from the first surface treatment liquid is supplied to a predetermined height from a supply path (not shown) into the lower layer B in which the rubber member 1 is immersed. Thereby, in the container 50, the 1st surface treatment liquid and the 2nd surface treatment liquid are prepared in a two-layer state.

  Then, as shown in FIG. 3B, the rubber member 1 is slowly pulled up from the lower layer B (first surface treatment liquid) through the upper layer A (second surface treatment liquid). Thereby, a part of surface layer of the isocyanate component impregnated in the rubber member 1 is removed. The rubber member mentioned above is obtained by carrying out heat hardening etc. of this.

  When a new surface treatment is performed on the rubber member, the second surface treatment liquid and a small amount of the first surface treatment liquid are discharged from the container 50 by a pump provided in the discharge pipe 21.

  Here, when the first surface treatment liquid is decreased, the first surface treatment liquid stored in the tank 30 is introduced from the introduction path 32 by a pump, or from the supply path (not shown). By supplying the liquid, the first surface treatment liquid (lower layer B) in the container 50 is replenished.

  Then, after the rubber member is immersed in the lower layer B, the second surface treatment liquid and a small amount of the first surface treatment liquid stored in the tank 20 are introduced into the container 50 from the introduction path 22. As a result, two layers are formed by the second surface treatment liquid and the first surface treatment liquid. Thereafter, similarly, the rubber member is slowly pulled up from the lower layer B (first surface treatment liquid) through the upper layer A (second surface treatment liquid).

  A rubber member surface treatment method using the rubber member surface treatment apparatus 100A when the first surface treatment liquid is the upper layer A and the second surface treatment liquid is the lower layer B will be described. 4 and 5 are views for explaining an example of the rubber member surface treatment method and surface treatment apparatus of the present invention.

  First, after supplying the second surface treatment liquid (lower layer B) from a supply path (not shown), the first surface treatment liquid (upper layer A) is supplied from a supply path (not shown) to form two layers. As shown in a), the rubber member is immersed in the upper layer A.

  Then, the rubber member 1 is moved from the upper layer A to the lower layer B as shown in FIG.

  Thereafter, as shown in FIG. 5 (a), the first surface treatment liquid and a small amount of the second surface treatment liquid are discharged from the container 50 by the pump provided in the discharge pipe 21 and stored in the tank 20. To do. Finally, the rubber member 1 is pulled up from the lower layer B as shown in FIG.

  When a new surface treatment is performed on the rubber member, the first surface treatment liquid and a small amount of the second surface treatment liquid stored in the tank 20 are introduced into the container 50 by a pump provided in the introduction path 22.

  Thus, the rubber member surface treatment apparatus of the present embodiment can reuse the first surface treatment liquid and the second surface treatment liquid, and not only can manufacture the rubber member at low cost. This will prevent environmental pollution.

(Embodiment 2)
FIG. 6 is a cross-sectional view of a rubber member surface treatment apparatus according to a second embodiment. The same parts as those in the first embodiment are denoted by the same reference numerals, and redundant description is omitted.

  A container 50 serving as a main body of a surface treatment apparatus for a rubber member can accommodate two layers in the lower portion by a partition plate 51 provided from the bottom to the middle in the height direction. This partition plate 51 divides the lower part of the container 50 and may be any one that can regulate the movement of the solution. Such a container 50 can accommodate the lower layer B and the lower layer C in a separated state, and can accommodate the upper layer A in the upper part. Note that the interface between the upper layer A and the lower layer B and between the upper layer A and the lower layer C is set lower than the upper end portion of the partition plate 51.

  Further, a discharge pipe 21B for discharging the surface treatment liquid constituting the upper layer A is inserted into the container 50. The discharge port 21b of the discharge pipe 21B is disposed below the upper end portion of the partition plate 51 and below the interface between the upper layer A and the lower layer B.

  The discharge pipe 21B is provided with a pump for discharging the first surface treatment liquid constituting the upper layer A, and is connected to a tank 20B provided outside the container 50 via the pump. . The tank 20B is connected to the container 50 through the introduction path 22B. In the introduction path 22B, the introduction port 22b is provided above the discharge port 21b on the side wall of the container 50, and the surface treatment liquid constituting the upper layer A (and the surface treatment liquid constituting the lower layer B) stored in the tank 20B. ) Is introduced into the container 50. In addition, the introduction path 22B is provided with the introduction port 22b above the discharge port 21b on the side wall of the container 50, and the surface treatment liquid constituting the upper layer A (and the surface constituting the lower layer B) stored in the tank 20B. Treatment liquid) is introduced into the container 50. The introduction path 22B is provided with an openable / closable valve and a pump for feeding the surface treatment liquid constituting the upper layer A (and the surface treatment liquid constituting the lower layer C).

  Further, on the side surface of the container 50 on the lower layer C side, a discharge path 40 provided with an openable / closable valve is provided. The discharge port 40c of the discharge path 40 is provided at the same height as the discharge port 21b, and discharges the surface treatment liquid in the vicinity of the interface between the upper layer A and the lower layer C.

  A rubber member surface treatment method using the rubber member surface treatment apparatus 100B having the above-described configuration will be described with reference to FIGS. 7 and 8 are views for explaining an example of the rubber member surface treatment method and surface treatment apparatus of the present invention. In this embodiment, the upper layer A is a second surface treatment liquid, the lower layer B is a first surface treatment liquid, and the lower layer C is a third surface treatment liquid.

  First, the first surface treatment liquid constituting the lower layer B is supplied into the container 50 from a supply path (not shown). At this time, the liquid level of the lower layer B is set to a position higher than the discharge port 21b of the discharge pipe 21B and lower than the partition plate 51. Further, the liquid level of the lower layer B is set to a height sufficient to immerse the rubber member. Further, the third surface treatment liquid constituting the lower layer C is supplied, and the lower layer C is formed by the same method. At this time, the liquid level of the lower layer C is made high enough to immerse the rubber member. Note that the liquid level of the lower layer B and the liquid level of the lower layer C are not necessarily the same height, but are preferably the same level.

  Then, as shown in FIG. 7A, the rubber member 1 is immersed in the lower layer B (first surface treatment liquid). Thereby, the rubber member 1 is impregnated with the first surface treatment liquid.

  Next, the second surface treatment liquid phase-separated from the first surface treatment liquid is supplied to a predetermined height from the supply path (not shown) into the lower layer B in which the rubber member 1 is immersed. As a result, the first surface treatment liquid and the second surface treatment liquid are brought into a phase-separated state in the container 50, and at the same time, the third surface treatment liquid and the second surface treatment liquid are in phase with each other. It can be given a state of separation. At this time, the upper layer A is made high enough to immerse the rubber member.

  Then, as shown in FIG. 7B, the rubber member 1 is slowly pulled up from the lower layer B (first surface treatment liquid) to the upper layer A (second surface treatment liquid). When it is pulled up from the interface of A, it is moved upward above the lower layer C while rotating in the radial direction.

  Next, as shown in FIG. 8A, the rubber member 1 is immersed in the lower layer C. When the first surface treatment liquid eluted from the rubber member 1 is present near the interface between the upper layer A and the lower layer C, at least the first surface treatment liquid is discharged from the discharge port 40c.

  Finally, as shown in FIG. 8B, the rubber member 1 is slowly pulled up through the upper layer A. A rubber member is obtained by heat-curing this.

  When a new surface treatment is performed on the rubber member, the second surface treatment liquid and a small amount of the first surface treatment liquid are discharged from the container 50 by a pump provided in the discharge pipe 21B. At this time, the second surface treatment liquid (a part of the upper layer A) may remain on the lower layer C side of the container 50.

  Here, when the first surface treatment liquid is decreased, the first surface treatment liquid (lower layer B) in the container 50 is supplied by supplying the first surface treatment liquid from a supply path (not shown). refill. When the third surface treatment liquid is decreasing, the third surface treatment liquid (lower layer C) in the container 50 is replenished by supplying the third surface treatment liquid from a supply path (not shown). At this time, the liquid level of the lower layer B and the liquid level of the lower layer C are set to be lower than the upper end portion of the partition plate 51.

  Then, after the rubber member is immersed in the lower layer B, the second surface treatment liquid and a small amount of the first surface treatment liquid stored in the tank 20B are introduced into the container 50 from the introduction path 22B. Thereafter, the same operation as described above is performed.

  As described above, the surface treatment apparatus for the rubber member according to the second embodiment can reuse the first surface treatment liquid, the second surface treatment liquid, and the third surface treatment liquid. Not only can it be manufactured, it also prevents environmental pollution.

  In the second embodiment, the discharge port 21b of the discharge pipe 21B is disposed below the upper end of the partition plate 51 and below the interface between the upper layer A and the lower layer B, but further on the lower layer C side. A discharge pipe may be provided to discharge the surface treatment liquid constituting the upper layer A and the third surface treatment liquid constituting the lower layer C. When the discharge pipe is provided on the lower layer C side, the discharge port is disposed below the upper end portion of the partition plate 51 and below the interface between the upper layer A and the lower layer C.

  Further, the partition plate 51 may be provided up to the upper portion of the container 50, and the upper layer A may be accommodated in a divided state. In this case, when the rubber member 1 is pulled up from the second surface treatment liquid, the inside of the container 50 is replaced with dry air or an inert gas (such as nitrogen or argon) so that it does not come into contact with moisture in the air. . The immersion of the rubber member 1 in the third surface treatment liquid is performed after confirming that the surface of the rubber member 1 is not partially dried or uniformly dried. This is because if the rubber member 1 is immersed in the third surface treatment liquid while being in a semi-dry state, unevenness occurs in the treatment depending on the dry state.

  By using the rubber member surface treatment apparatus as described above, it is possible to obtain a low-hardness rubber member that is free from contamination and leakage problems such as OPC and that can follow deformation.

  EXAMPLES Hereinafter, although this invention is demonstrated based on an Example, this invention is not limited to this.

(Example 1)
<Manufacture of rolls>
3 parts by weight of Ketjen Black EC (made by Ketjen Black International) and 5 parts by weight of Asahi # 60 (Asahi Carbon) are added to 100 parts by weight of MN-3050 (made by Mitsui Takeda Chemical), which is a trifunctional polyether polyol. The mixture was dispersed to a particle size of 20 μm or less, adjusted to 80 ° C., and then defoamed and dehydrated for 6 hours under reduced pressure to obtain solution A. On the other hand, 10 parts by mass of Coronate C-HX (manufactured by Nippon Polyurethane) was added to and mixed with 22 parts by mass of prepolymer adiprene L100 (manufactured by Uniroyal), and the temperature was adjusted to 80 ° C. to obtain a liquid B. This A liquid and B liquid are mixed and poured into a steel pipe mold with a diameter of 23 mm preheated to 120 ° C. in which a shaft (φ: 8 mm, l: 270 mm) is arranged in the center in advance. It heated for 120 minutes and obtained the roll by which the conductive polyurethane layer was formed in the shaft surface except both ends. The surface of this roll was polished 1.5 mm, the outer diameter was adjusted to 20 mm, and a roll (untreated) was obtained.

<Preparation of first surface treatment liquid>
An isocyanate compound (MDI) 10 parts by mass was added to and mixed with 100 parts by mass of N, N-dimethylformamide (DMF) to prepare a first surface treatment liquid.

<Surface treatment of roll>
After immersing the roll produced in the first surface treatment liquid maintained at 23 ° C. for 30 seconds, 100 parts by mass of n-hexane was gently added as the second surface treatment liquid to obtain a phase separation state, and 250 mm / min. The surface treatment layer was formed by heating at a speed and heating in an oven maintained at 120 ° C. for 1 hour to obtain a conductive roll.

(Example 2)
<Preparation of first surface treatment liquid>
An isocyanate compound (HDI) 10 parts by mass was added to and dissolved in 100 parts by mass of N-methylpyrrolidone to prepare a first surface treatment liquid.

<Surface treatment of roll>
After the roll (untreated) produced in Example 1 was immersed in the first surface treatment liquid maintained at 23 ° C. for 30 seconds, 100 parts by mass of n-hexane was gently added to the surface treatment liquid to obtain a phase-separated state, 250 mm The surface treatment layer was formed by pulling up at a speed of / min and heating in an oven maintained at 120 ° C. for 1 hour to obtain a conductive roll.

(Example 3)
<Manufacture of rolls>
With respect to 100 parts by mass of epichlorohydrin rubber (Epichromer CG-102; manufactured by Daiso Corporation), 0.5 parts by mass of tetraethylammonium perchlorate (manufactured by Kanto Chemical Co., Ltd.) as a conductive material and di (2-ethylhexyl) phthalate (as a plasticizer) 3 parts by mass of DOP), 5 parts by mass of zinc oxide (ZnO), and 2 parts by mass of 2-mercaptoimidazoline (Axel-22) as a vulcanizing agent were kneaded with a roll mixer on the surface of a metal shaft having a diameter of 6 mm. A roll (untreated) in which a rubber elastic member was formed on the surface of the shaft by press molding and polishing to a diameter of 12 mm was obtained.

<Preparation of first surface treatment liquid>
To 100 parts by mass of acetonitrile, 10 parts by mass of prepolymer adiprene L100 (manufactured by Uniroyal) was added, mixed and dissolved to prepare a first surface treatment liquid.

<Surface treatment of roll>
After immersing the produced roll in the first surface treatment liquid maintained at 23 ° C. for 60 seconds, 100 parts of cyclohexane is gently added as the second surface treatment liquid to obtain a phase separation state, and pulled up at a speed of 250 mm / min. A surface treatment layer was formed by heating in an oven maintained at 120 ° C. for 1 hour to obtain a conductive roll.

Example 4
<Preparation of third surface treatment liquid>
100 parts by mass of acetonitrile, 3 parts by mass of acetylene black (manufactured by Denki Kagaku), 1 part by mass of an acrylic fluoropolymer (Modiper F600; manufactured by NOF Corporation), 1 part by mass of an acrylic silicone polymer (MODIPER FS700; manufactured by NOF Corporation) 3 parts by weight, 1.5 parts by weight of polyethylene glycol diallyl ether (molecular weight 450) are dispersed and mixed in a ball mill for 3 hours, and then 10 parts by weight of prepolymer adiprene L100 (manufactured by Uniroyal) are added, mixed and dissolved, and the third surface treatment A liquid was prepared.

<Surface treatment of roll>
After the manufactured roll was immersed in the first surface treatment liquid of Example 1 maintained at 23 ° C. for 60 seconds, 100 parts by mass of cyclohexane was gently added as the second surface treatment liquid to obtain a phase separation state, and 250 mm / min. It pulled up from the 1st surface treatment liquid at the speed of, and was kept in the 2nd surface treatment liquid for 10 seconds. Next, the roll was moved from the second surface treatment liquid to the third surface treatment liquid and immersed for 60 seconds. Thereafter, the roll is pulled up again from the third surface treatment liquid and the second surface treatment liquid at a speed of 250 mm / min, and heated in an oven maintained at 120 ° C. for 1 hour to form a surface treatment layer. A sex roll was obtained.

(Comparative Example 1)
A conductive roll was obtained in the same manner as in Example 1 except that n-hexane was not added.

(Comparative Example 2)
A conductive roll was obtained in the same manner as in Comparative Example 1, except that the surface of the roll was wiped with a sponge soaked with n-hexane after being immersed in the first surface treatment solution.

(Comparative Example 3)
A conductive roll was obtained in the same manner as in Example 3 except that cyclohexane was not added.

(Comparative Example 4)
A conductive roll was obtained in the same manner as in Example 3, except that the roll was immersed in the first surface treatment solution and then taken out and immersed in cyclohexane maintained at 23 ° C. for 60 seconds.

(Comparative Example 5)
A conductive roll was obtained in the same manner as in Comparative Example 4 except that acetonitrile was used instead of cyclohexane.

(Test Example 1): Micro hardness measurement of roll The micro hardness (Hs) of the conductive roll of each untreated product, the conductive roll of each example and each comparative example was measured with a micro hardness meter (MD-1: polymer meter). Measured using a product manufactured by Co., Ltd. The results are shown in Tables 1 and 2.

(Test example 2): Measurement of electrical resistance value of roll The electrical resistance value when the applied voltage was 100 V was measured for the conductive rolls of each untreated product, the conductive rolls of the examples and the comparative examples. The electrical resistance value was measured by applying a voltage for 30 seconds under a NN environment (23 ° C., 55% RH) with a roll placed on an electrode member made of a SUS304 plate and a load of 500 g applied to both ends of the roll. Then, the resistance value between a metal core and an electrode member was measured using ULTRAHIGH REISTANCE METER R8340A (made by Advantest Corporation). In addition, it rotated by 45 degree | times to the circumferential direction, measured 8 places over the rotation direction, and measured the maximum value, the minimum value, and the average value at that time, respectively. The results are shown in Tables 1 and 2.

(Test example 3): Observation of surface condition About the electroconductive roll of each Example and each comparative example, the surface condition of the roll was confirmed visually. In addition, when the surface state was good, it was evaluated as ◯, when the surface state was normal, Δ, and when the surface state was poor, it was evaluated as x. The results are shown in Tables 1 and 2 below.

(Test Example 4): Image Evaluation Commercially available lasers using the conductive rolls of Examples 1 and 2 and Comparative Examples 1 and 2 as developing rolls and the conductive rolls of Example 3 and Comparative Examples 3 to 5 as charging rolls, respectively. It was mounted on a printer (MICROLINE 9600PS, manufactured by Oki Data Co., Ltd.), and the image change of the printed matter after passing 10,000 sheets was visually confirmed under an NN environment (23 ° C., 55% RH). In addition, when the image was good, “◯”, when the image was normal, “Δ”, and when the image was bad, “X”. The results are shown in Tables 1 and 2.

(Summary of test results)
Implementation in which a rubber member was impregnated with a first surface treatment liquid containing an isocyanate compound and an organic solvent, and then the surface of the rubber member was continuously treated with the second surface treatment liquid without being brought into contact with air. It was confirmed that the conductive rolls of Examples 1 to 3 had lower microhardness and electrical resistance than the conductive rolls of Comparative Examples 1 and 3 subjected to conventional surface treatment. Similarly, in the conductive roll of Example 4, which was treated with the first and second surface treatment liquids and further treated with the third surface treatment liquid, the micro hardness and the electrical resistance value were similarly lowered. It was confirmed that In addition, in all of the conductive rolls of Examples 1 to 4, the image of the printed matter was good in image evaluation after passing 10,000 sheets, whereas the conductive roll of Comparative Example 1 was cracked on the roll surface. As a result, the conductive roll of Comparative Example 3 was also scratched on the photoreceptor, and the image of the printed matter was both poor.

  The conductive roll of Comparative Example 2 in which the surface of the roll was wiped with a sponge soaked with n-hexane after being immersed in the first surface treatment solution had a microhardness and an electrical resistance of Example 1. Although it was confirmed that the level was reduced to the same level as the conductive rolls No. 2 and No. 2, there was a large variation in the electric resistance value due to uneven wiping. Further, in the image evaluation, density unevenness was observed in the printed image, which was a failure evaluation.

  After the roll was immersed in the first surface treatment solution, the conductive roll of Comparative Example 4 immersed in cyclohexane for 60 seconds was lower in both the microhardness and the electrical resistance value than Comparative Example 3 in which the conventional surface treatment was performed. However, a slight variation was observed in the electric resistance value because the unevenness of the treatment occurred on the surface because the semi-dried roll was immersed again in the solvent. Further, in the image evaluation, some density unevenness was seen in the printed image, which was a slightly poor evaluation.

  On the other hand, the conductive roll of Comparative Example 5 immersed in acetonitrile for 60 seconds after immersing the roll in the first surface treatment solution was further reduced in micro hardness and electrical resistance value than the conductive roll of Comparative Example 4. However, as in the case of the conductive roll of Comparative Example 4, treatment unevenness was observed, and the electrical resistance value was slightly varied. In the image evaluation, density unevenness was observed in the image of the printed matter, which was a failure evaluation. Moreover, the OPC contamination by the plasticizer was seen whether the density | concentration of the isocyanate of the surface treatment layer fell more than necessary by being immersed in acetonitrile.

  As described above, after the rubber member is impregnated with the first surface treatment liquid containing the isocyanate component and the organic solvent to form the impregnated layer, a part of the isocyanate component in the impregnated layer is continuously formed without contact with air. By treating the surface of the rubber member with the second surface treatment liquid that removes the problem, it is possible to obtain a low-hardness rubber member that is free from problems of contamination such as OPC and leaks and that can follow deformation. I understood.

It is sectional drawing of an example of the rubber roll obtained by the surface treatment method of the rubber member of this invention. It is sectional drawing of the surface treatment apparatus of the rubber member concerning Embodiment 1 of this invention. It is a figure explaining an example of the surface treatment method and surface treatment apparatus of a rubber member of the present invention. It is a figure explaining an example of the surface treatment method and surface treatment apparatus of a rubber member of the present invention. It is a figure explaining an example of the surface treatment method and surface treatment apparatus of a rubber member of the present invention. It is sectional drawing of the surface treatment apparatus of the rubber member concerning Embodiment 2 of this invention. It is a figure explaining an example of the surface treatment method and surface treatment apparatus of a rubber member of the present invention. It is a figure explaining an example of the surface treatment method and surface treatment apparatus of a rubber member of the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Rubber member 20 Tank 21 Discharge pipe 22 Introductory path 30 Tank 31 Discharge path 32 Introductory path 50 Container 100A, 100B Surface treatment apparatus

Claims (11)

After impregnating a rubber member with a first surface treatment liquid containing an isocyanate component and an organic solvent to form an impregnated layer, a portion of the isocyanate component in the impregnated layer is continuously removed without contacting with air. A surface treatment method for a rubber member, wherein the surface of the rubber member is treated with a second surface treatment liquid. 2. The surface treatment method for a rubber member according to claim 1, wherein an impregnation layer is formed by immersing the rubber member in a layer made of the first surface treatment liquid, and then the rubber member is formed on the first surface. A method for treating a surface of a rubber member, comprising: moving to a layer made of a second surface treatment liquid formed by phase separation from a layer made of a treatment liquid. 3. The surface treatment method for a rubber member according to claim 2, wherein the second surface treatment is performed on the layer made of the first surface treatment liquid after the rubber member is immersed in the first surface treatment liquid. A method for treating a surface of a rubber member, comprising forming a layer made of a liquid and pulling up the rubber member through the second surface treatment liquid. 4. The rubber member surface treatment method according to claim 1, wherein the organic solvent is an aprotic polar solvent. The surface treatment method for a rubber member according to any one of claims 1 to 4, wherein the second surface treatment liquid comprises a nonpolar solvent. 6. The rubber member surface treatment method according to claim 1, wherein after the treatment with the second surface treatment liquid, a third surface treatment liquid for forming a second impregnation layer is further added to the rubber. A method for treating a surface of a rubber member, comprising: impregnating the member, and continuously treating the surface of the rubber member with the second surface treatment liquid without contacting the air. 6. The surface treatment method for a rubber member according to claim 1, wherein after the treatment with the second surface treatment liquid, a part of the isocyanate component in the impregnated layer is further removed. A surface treatment method for a rubber member, characterized by treating a surface layer portion of the rubber member with a liquid. The surface treatment method for a rubber member according to claim 6, wherein the third surface treatment liquid comprises an isocyanate compound and at least one selected from a conductivity imparting material, an acrylic fluorine-based polymer, and an acrylic silicone-based polymer. A surface treatment method for a rubber member, comprising: After immersing a rubber member in a first surface treatment liquid containing an isocyanate component and an organic solvent, the rubber member is moved to a second surface treatment liquid phase-separated from the first surface treatment liquid, thereby forming a rubber. A container for treating the surface of a member, containing a container in which the first surface treatment liquid and the second surface treatment liquid are phase-separated, and at least a surface treatment liquid constituting an upper layer. A surface treatment apparatus for a rubber member, characterized by comprising: means for discharging to the outside. After immersing the rubber member in the first surface treatment liquid containing an isocyanate component and an organic solvent, the rubber member is phase-separated from the first surface treatment liquid, the second surface treatment liquid, the second It is for treating the surface of the rubber member by moving to a third surface treatment liquid phase-separated from the surface treatment liquid, and the lower part is divided into two parts by a partition plate provided from the bottom to the middle of the height direction. The first surface treatment liquid and the third surface treatment liquid are accommodated in a separated state, and a container containing the second surface treatment liquid is provided on the upper portion thereof, and at least the surface treatment liquid constituting the upper layer is disposed outside the container. A surface treatment apparatus for a rubber member. 11. The rubber member surface treatment apparatus according to claim 9, further comprising an introduction unit that introduces the surface treatment liquid discharged from the discharge unit into the container.

Images