JP2012027122A - Electroconductive roller and picture forming device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electroconductive roller and a picture forming device that can form a fogging-free picture even in a low humidity environment.SOLUTION: An electroconductive roller 1 comprises an elastic layer 3 formed on an outer circumferential face of an axial body 2 and an urethane coating layer 4 formed on an outer circumferential face of the elastic layer 3. The urethane coating layer 4 has, as its main component, an urethane resin containing polyisocyanate and polyester polyol of which the hydroxyl value (OHV) is 40 to 250 KOH mg/g and the average degree of branching represented by the number of hydroxyl groups per 1 g to the number of molecules per 1 g is 2.5 to 8. A picture forming device includes the electroconductive roller 1.

Description

  The present invention relates to a conductive roller and an image forming apparatus, and more particularly to a conductive roller and an image forming apparatus capable of forming an image without fogging even in a low humidity environment.

  Various image forming apparatuses using an electrophotographic system are employed in printers such as laser printers and video printers, copiers, facsimiles, and multi-function machines thereof. An image forming apparatus using an electrophotographic system includes various types of rollers. Examples of the various rollers include a conductive roller having conductivity or semi-conductivity, and an elastic roller having relatively low hardness. Specific examples of the conductive roller include a developing roller that carries and conveys the developer and supplies the developer to the image carrier, and a developer supply roller that supplies the developer while charging the developer. Such a conductive roller may be provided with a coating layer on the outer peripheral surface of the elastic layer, for example, in order to improve the charging property to the developer, the carrying property, and the like.

  As a roller having an elastic layer formed of a urethane composition, for example, Patent Document 1 discloses that “a urethane composition for OA equipment members according to claim 1 or 2 is formed. "OA device member" is described (claim 3). Patent Document 2 states that “in a member for an image forming apparatus produced from a polyether polyol and a polyisocyanate, the polyether polyol has at least one polyether polyol having a terminal structure represented by the following general formula (1): An image forming apparatus portion characterized by containing a seed ”is described (claim 1).

  By the way, when the environment around the image forming apparatus changes, the characteristics of the conductive roller may change, and the initial function may not be exhibited. For example, in the case of the developing roller, when the humidity decreases, a predetermined amount of developer cannot be supplied to the image carrier, and an unnecessary developer is fixed to the formed solid image. Phenomenon (called fogging) may occur, and a desired image may not be obtained.

  In addition, the roller formed with the "urethane composition for OA equipment member" described in Patent Document 1 and the roller provided with the elastic layer containing "Polyether Polyol" described in Patent Document 2 under a low humidity environment. It is presumed that the occurrence of fog cannot be substantially prevented, and a desired high-quality image cannot be formed.

JP 2004-59739 A JP 2006-153951 A

  An object of the present invention is to provide a conductive roller and an image forming apparatus capable of forming an image without fogging even in a low humidity environment.

As means for solving the problems,
Claim 1 is a conductive roller comprising an elastic layer formed on the outer peripheral surface of a shaft body and a urethane coat layer formed on the outer peripheral surface of the elastic layer, wherein the urethane coat layer is made of polyisocyanate. And a urethane resin having a hydroxyl value (OHV) of 40 to 250 KOHmg / g and a polyester polyol having an average degree of branching of 2.5 to 8 expressed by the number of hydroxyl groups per gram with respect to the number of molecules per gram It is a conductive roller characterized by containing as
Claim 2 is the conductive roller according to claim 1, wherein the urethane coat layer satisfies at least one of the following conditions (1) and (2):
The conductive roller according to claim 1 or 2, wherein the elastic layer satisfies at least one of the following conditions (A) and (B):
A fourth aspect of the present invention is an image forming apparatus comprising the conductive roller according to any one of the first to third aspects.

Condition (1): 140-400% elongation condition (2): Break strength of 10-40 MPa The elongation of condition (1) and the break strength of condition (2) are 10 mm × 50 mm × 40 μm test pieces, It is a value when measured according to the measurement method described in JIS K7113 under the conditions where the measurement temperature is 25 ± 2 ° C. and the tensile speed is 100 mm / min.
Condition (A): 300-1200% elongation condition (B): Break strength of 3-25 MPa The elongation of condition (A) and the break strength of condition (B) are 10 mm × 50 mm × 40 μm test pieces, It is a value when measured according to the measurement method described in JIS K7113 under the conditions where the measurement temperature is 25 ± 2 ° C. and the tensile speed is 100 mm / min.

  The conductive roller according to the present invention includes a urethane coat layer containing, as a main component, a urethane resin composed of a polyisocyanate and a polyester polyol having a specific hydroxyl value and an average branching degree. The occurrence of fogging can be substantially suppressed even in a low humidity environment with a relative humidity of 20% as well as a humidity of about 50%. The image forming apparatus according to the present invention includes the conductive roller according to the present invention. Therefore, according to the present invention, it is possible to provide a conductive roller and an image forming apparatus that can form an image without fogging even in a low humidity environment.

FIG. 1 is a perspective view showing an example of a conductive roller according to the present invention. FIG. 2 is a schematic view showing an example of an image forming apparatus according to the present invention.

  The conductive roller according to the present invention includes an elastic layer formed on the outer peripheral surface of the shaft body and a urethane coat layer containing a specific urethane resin as a main component. As described above, when the urethane coat layer containing a specific urethane resin as a main component is provided on the outer peripheral surface of the elastic layer, the object of the present invention can be well achieved. In the present invention, the low humidity environment means that the relative humidity of the environment is, for example, 20% or less, and preferably 10% or less in that the object of the present invention can be satisfactorily achieved.

  An example of the conductive roller according to the present invention will be described. As shown in FIG. 1, a conductive roller 1 that is an example of a conductive roller according to the present invention includes a shaft body 2, an elastic layer 3, and a urethane coat layer 4.

  The shaft body 2 is basically the same as a shaft body in a conventionally known conductive roller. The shaft body 2 is a so-called “core metal” composed of iron, aluminum, stainless steel, brass, or the like, and has good conductive characteristics. The shaft body 2 may be a shaft body made conductive by plating an insulating core body such as a thermoplastic resin or a thermosetting resin.

  The elastic layer 3 is formed by curing a rubber composition described later on the outer peripheral surface of the shaft body 2 and preferably has a JIS A hardness of 20 to 70. When the elastic layer 3 has a JIS A hardness (JIS K6301) of 20 to 70, the contact area between the conductive roller 1 and the contacted body can be increased, and the rebound resilience of the elastic layer 3 can be increased. And compression set is excellent.

The elastic layer 3 preferably has a volume resistivity in the range of 10 ¹ to 10 ⁷ Ω · cm and / or an electrical resistivity in the range of 10 ¹ to 10 ⁹ Ω. When the volume resistivity and / or electrical resistivity of the elastic layer 3 is within the above range, the developer is supported and supplied as desired when the conductive roller 1 is mounted on the image forming apparatus, and the desired quality is obtained. It is possible to contribute to forming an image having The volume resistivity can be measured according to a method defined in JIS K6911 (applied voltage is 100 V). The electrical resistivity is, for example, using an electrical resistance meter (trade name: ULTRA HIGH RESISTANCE METER R8340A, manufactured by Advantest Co., Ltd.), placing the conductive roller 1 horizontally, a thickness of 5 mm, a width of 30 mm, and A gold-plated plate having a length on which the entire elastic layer 3 of the conductive roller 1 can be placed is used as an electrode, and a load of 500 g is supported on both ends of the shaft 2 in the conductive roller 1. Then, DC100V is applied between the shaft body 2 and the electrode, the value of the electric resistance meter after 1 second is read, and the measurement can be performed according to the method of setting this value as the electric resistance value.

  The thickness of the elastic layer 3 is preferably 1 mm or more in that a uniform nip width between the contacted body and the elastic layer 3 can be secured in the contact state with the contacted body. It is particularly preferably 5 mm or more. On the other hand, the upper limit of the thickness of the elastic layer 3 is not particularly limited as long as the outer diameter accuracy of the elastic layer 3 is not impaired. Generally, if the thickness of the elastic layer 3 is excessively increased, the production cost of the elastic layer 3 increases. In consideration of practical production costs, the thickness of the elastic layer 3 is preferably 30 mm or less, and more preferably 20 mm or less. The thickness of the elastic layer 3 is appropriately selected according to the hardness of the elastic layer 3, such as JIS A hardness, in order to achieve a desired nip width.

  The elastic layer 3 has an elongation of 300 to 1200% (condition (A) in that the conductive roller 1 can contribute to forming a fog-free image even in a low humidity environment when the conductive roller 1 is mounted on the image forming apparatus. )) And at least one of the breaking strengths of 3 to 25 MPa (condition (B)) is preferable, and it is particularly preferable that both conditions are satisfied. The elongation is more preferably 400 to 800%, and particularly preferably 500 to 800%. Even if the conductive roller 1 is mounted on the image forming apparatus so that the pressing margin against the abutting member such as the photosensitive drum is increased when the elastic layer 3 has the elongation in the above range, the pressing margin is reduced. This makes it difficult to damage the developer passing therethrough, and can greatly contribute to the formation of a fog-free image even in a low humidity environment. The breaking strength is more preferably 10 to 25 MPa, and particularly preferably 15 to 25 MPa. If the elastic layer 3 has a breaking strength in the above range, the conductive roller 1 can be mounted on the image forming apparatus so that the pressing allowance with the contacted body such as the photosensitive drum is increased. The conductive roller 1 is not loaded to such an extent that the 1 is destroyed, and can greatly contribute to the formation of an image without fogging even in a low humidity environment. The elongation and the breaking strength are the same as those of the urethane coat layer 4 described later, that is, a test piece (10 mm × 50 mm × thickness 40 μm) cut out from the elastic layer 3 of the conductive roller 1 or the elastic layer 3 Using a test piece (10 mm × 50 mm × thickness 40 μm) made of the rubber composition being formed, the measurement temperature is 25 ± 2 ° C., the tensile speed is 100 mm / min, and the distance between the grips of the test piece is 50 mm. It is a value when measured according to the measurement method described in JIS K7113 under conditions. In order to adjust the elongation and breaking strength of the elastic layer 3 to the above ranges, for example, a method of adding an organohydrogenpolysiloxane described later to the rubber composition or adjusting the blending amount, a filler or inorganic material described later in the rubber composition Examples include a method of adding a filler or adjusting the blending amount.

The elastic layer 3 is preferably formed of a silicone rubber composition or a urethane rubber composition among rubber compositions. Preferred examples of the rubber composition capable of forming the elastic layer 3 include addition curable millable conductive silicone rubber compositions, addition curable liquid conductive silicone rubber compositions, and urethane rubber compositions. The addition-curable millable conductive silicone rubber composition has the following (A) average composition formula: R _n SiO _{(4-n) / 2} (R may be the same or different, substituted or unsubstituted monovalent carbonization A hydrogen group, preferably a monovalent hydrocarbon group having 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, and n is a positive number of 1.95 to 2.05). It contains a polysiloxane, (B) a filler, and (C) a conductive material other than those belonging to the component (B). Each of these components (A) to (C) is basically the same as, for example, each component in “The following silicone rubber composition that is a millable type” described in JP-A-2008-058622. The addition-curable liquid conductive silicone rubber composition comprises (D) an organopolysiloxane containing at least two alkenyl groups bonded to silicon atoms in one molecule, and (E) bonded to silicon atoms in one molecule. An organohydrogenpolysiloxane containing at least two hydrogen atoms; (F) an inorganic filler having an average particle size of 1 to 30 μm and a bulk density of 0.1 to 0.5 g / cm ³ ; and (G). An addition-curable liquid conductive silicone rubber composition containing a conductivity imparting agent and (H) an addition reaction catalyst can be mentioned. These components (D) to (H) are basically the same as the components in the “liquid silicone composition” described in, for example, JP-A-2008-058622. The urethane rubber composition comprises at least one polyurethane preparation component selected from the group consisting of a polyol and an isocyanate, a prepolymer obtained by reacting these and a polyurethane obtained by reacting these, a conductivity imparting agent, If necessary, it contains various additives. Examples of the polyurethane preparation component include “polyurethane preparation components” described in JP-A-2008-070420. The conductivity imparting agent and various additives are as described above.

  The urethane coat layer 4 is formed by curing a urethane resin composition, which will be described later, on the outer peripheral surface of the elastic layer 3. It contains as a main component a urethane resin obtained by reacting 5-8 polyester polyol as a main reactant.

  The polyester polyol constituting the urethane resin is formed by polymerizing a polyol and a polycarboxylic acid. The polyol may be a low molecular weight compound or a high molecular weight compound as long as it is a compound containing a plurality of OH groups, and examples thereof include diols and triols. Examples of such polyols include ethylene glycol, propylene glycol, butylene glycol, benzyl glycol, hexylene glycol, octylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, 1,2,4-butanetriol, 1,2,3-propanetriol, 1,2,6-hexanetriol and the like can be mentioned. The polycarboxylic acid is a compound containing a plurality of COOH groups, and examples thereof include dicarboxylic acid, tricarboxylic acid, and tetracarboxylic acid. Such a polycarboxylic acid may be a low molecular weight compound or a high molecular weight compound, and may be an aliphatic polycarboxylic acid or an aromatic polycarboxylic acid. For example, succinic acid, glutaric acid, adipic acid, pimelic acid, suberin Aliphatic saturated polycarboxylic acids such as acid, azelaic acid and sebacic acid, aliphatic unsaturated dicarboxylic acids such as fumaric acid, fragrances such as terephthalic acid, isophthalic acid, phthalic acid, orthophthalic acid, hexahydroterephthalic acid, naphthalenedicarboxylic acid And dimer acids obtained by dimerization of unsaturated dicarboxylic acids and unsaturated fatty acids.

  It is preferable that one of the polyol and the polycarboxylic acid is polyfunctional having 3 or more, particularly trifunctional, in that a polyester polyol satisfying the average degree of branching described later can be prepared. That is, it is particularly preferable that the polyol contains a trifunctional triol and / or contains a trifunctional tricarboxylic acid as the polycarboxylic acid. Specific examples include a combination of a polyol containing a triol and a dicarboxylic acid, a combination of a polycarboxylic acid containing a tricarboxylic acid and a diol, and a combination of a polyol containing a triol and a polycarboxylic acid containing a tricarboxylic acid.

  The polyol can be used alone or in combination of two or more, and it is possible to prepare a polyester polyol satisfying the average degree of branching described below. It is preferable to use a bifunctional polyol and a trifunctional polyol in combination, and it is preferable to use a polyol whose chain is branched and a polyol whose main chain is not branched. As the bifunctional polyol, for example, 1,2-ethanediol, 1,3-propanediol, 1,4-butanediol and 1,6-hexanediol are preferable, and 1,6-hexanediol is particularly preferable. As the trifunctional polyol, for example, 1,2,3-propanetriol, 1,2,4-butanetriol, and 1,2,6-hexanetriol are preferable, and 1,2,4-butanetriol is particularly preferable. . The polyol having a branched main chain is preferably a triol such as 1,2,4-butanetriol, and the polyol having no branched main chain is a diol such as 1,2-ethanediol, 1,3. -Linear diols such as propanediol, 1,4-butanediol and 1,6-hexanediol are preferred. When two or more kinds of polyols are used in combination, the ratio of the combination is determined in consideration of, for example, the molecular weight of each polyol so that the average degree of branching of the polyester polyol falls within the range described below. For example, when the bifunctional polyol and the trifunctional polyol are combined, the merge ratio (mass of the bifunctional polyol: mass of the trifunctional polyol) is 1: 1 to 4: 1, preferably 1. : 1 to 3.5: 1 can be set, and the merge ratio when the polyol whose main chain is not branched and the polyol whose main chain is branched (the main chain is not branched) The mass of the polyol: the mass of the polyol having a branched main chain) can be set to 1: 1 to 4: 1, preferably 1: 1 to 3.5: 1.

  The polycarboxylic acid can be used singly or in combination of two or more, and in the case where the polyol is bifunctional in that a polyester polyol satisfying the average degree of branching described below can be prepared, It is preferable to use a polycarboxylic acid having 3 or more COOH groups and a dicarboxylic acid having 2 COOH groups in combination. For example, tricarboxylic acid is preferable as the polycarboxylic acid having 3 or more COOH groups. The combined ratio of the polycarboxylic acid having 3 or more COOH groups and the dicarboxylic acid having 2 COOH groups is, for example, polycarboxylic acid or It is determined in consideration of the molecular weight of the dicarboxylic acid. The polycarboxylic acid is preferably used in combination with the aliphatic saturated polycarboxylic acid and / or the aliphatic unsaturated dicarboxylic acid and the aromatic dicarboxylic acid. For example, the merge ratio (mass of aliphatic saturated dicarboxylic acid: mass of aromatic dicarboxylic acid) when the aliphatic saturated dicarboxylic acid and the aromatic dicarboxylic acid are merged is set to 1: 1 to 1: 2. can do.

  The polyol and the polycarboxylic acid are polymerized by a conventionally known method to obtain a polyester polyol. At this time, the molar ratio (OH / COOH) between the OH group of the polyol and the COOH group of the polycarboxylic acid is preferably adjusted to 0.7 to 1.3, and is adjusted to 1.0 to 1.2. Is particularly preferred.

  The polyester polyol has a hydroxyl value (OHV) of 40 to 250 KOHmg / g, preferably 45 to 200 KOHmg / g. If the hydroxyl value is less than 40 Hmg / g, the breaking strength may be insufficient and the strength of the surface layer of the conductive roller 1 may be insufficient. On the other hand, if the hydroxyl value exceeds 250 Hmg / g, the elongation may be insufficient. The urethane coat layer 4 itself may become too hard, and in any case, when the conductive roller 1 is attached to the image forming apparatus, it cannot contribute to forming an image without fogging in a low humidity environment. Sometimes. The reason why the conductive roller 1 can contribute to forming a fog-free image in a low-humidity environment when the hydroxyl value (OHV) is in the above range is not clear, but one of the conditions (1) ) And / or a urethane resin that satisfies the condition (2) can be formed. The hydroxyl value (OHV) is defined as the number of mg of potassium hydroxide required to neutralize acetic acid bonded to a hydroxyl group when 1 g of polyester polyol is acetylated. Specifically, the hydroxyl value (OHV) of the polyester polyol is a value measured by a neutralization titration method described in JIS K0070, which is a hydroxyl value measurement method using an acetic anhydride-pyridine acetylating agent. The hydroxyl value (OHV) of the polyester polyol can be adjusted by, for example, the hydroxyl value of the polyol or the molar ratio of the polyol and the polycarboxylic acid. Specifically, when the hydroxyl value of the polyol is increased and when the molar ratio of the polyol is increased, the hydroxyl value (OHV) of the polyester polyol is increased.

The polyester polyol has an average degree of branching represented by the number of hydroxyl groups per gram with respect to the number of molecules per gram is 2.5 to 8, preferably 3 to 6. If the average branching degree is less than 2.5, the breaking strength may be insufficient and the breaking strength as the surface layer of the conductive roller 1 may be insufficient. On the other hand, if the average branching degree exceeds 8, the urethane resin itself In some cases, when the conductive roller 1 is mounted on the image forming apparatus, the elongation as a coating film is insufficient and the breaking strength becomes too large, and the coating film strength of the urethane resin itself may increase. In some cases, it may not contribute to forming an image without fogging in a low humidity environment. The reason why the conductive roller 1 can contribute to forming an image without fogging in a low humidity environment when the average branching degree is in the above range is not clear, but one of them is condition (1) described later. And / or that it is possible to form a urethane resin that satisfies the condition (2). The average degree of branching of the polyester polyol is a value obtained by dividing the number of hydroxyl groups per gram by the number of molecules per gram. Specifically, the formula: (hydroxyl value (OHV) × 10 ⁻³ × number average Molecular weight) /56.1. In this formula, the hydroxyl value (OHV) is the hydroxyl value (KOHmg / g), and 56.1 is the molecular weight of potassium hydroxide. The average branching degree of the polyester polyol can be adjusted by, for example, the number of functional groups of the polyol or the polycarboxylic acid, or the molar ratio of the polyol to the polycarboxylic acid. For example, when the number of functional groups of the polyol or polycarboxylic acid increases, and when the molar ratio of the polyol or polycarboxylic acid having a large number of functional groups is increased, the hydroxyl value (OHV) of the polyester polyol increases.

  The polyester polyol preferably has a number average molecular weight (Mn) of 1400 or more and less than 2000. When the number average molecular weight (Mn) of the polyester polyol is within the above range, a urethane resin satisfying the condition (1) and / or condition (2) described later can be obtained. The occurrence of fogging can be substantially suppressed even in a low humidity environment. The number average molecular weight (Mn) is a value measured by the following method. That is, a polyester polyol is immersed in tetrahydrofuran (hereinafter referred to as THF) (temperature: 25 ° C., immersion time: 1 hour), and a liquid substance (polyester polyol) obtained by solvent extraction with THF is gel permeation chromatography (Gel Permeation Chromatography). (Hereinafter referred to as GPC)) (model name: HLC-8220 GPC manufactured by Tosoh Corporation).

  The polyester polyol may be a polyester polyol obtained by selecting the polyol and the polycarboxylic acid and reacting them in the molar ratio so as to satisfy the average degree of branching and the hydroxyl value. Examples of such polyester polyols include adipate-based polyols, polycaprolactone polyols, aromatic polyester polyols, and polycarbonate diols.

  The polyisocyanate constituting the urethane resin is not particularly limited, and an isocyanate usually used for a urethane resin can be appropriately used. Examples thereof include aliphatic polyisocyanate, alicyclic polyisocyanate, and aromatic polyisocyanate. It is done. The polyisocyanate is preferably an aliphatic polyisocyanate in that the object of the present invention can be satisfactorily achieved.

  Examples of such polyisocyanates include isophorone diisocyanate (IPDI), 4,4′-diphenylmethane diisocyanate (MDI), 2,4-tolylene diisocyanate (2,4-TDI), 2,6-tolylene diisocyanate ( 2,6-TDI), 3,3′-vitrylene-4,4′-diisocyanate, 3,3′-dimethyldiphenylmethane-4,4′-diisocyanate, 2,4-tolylene diisocyanate uretidinedione (2,4 -TDI dimer), 1,5-naphthylene diisocyanate, metaphenylene diisocyanate, hexamethylene diisocyanate (HDI), 4,4'-dicyclohexylmethane diisocyanate (hydrogenated MDI), carbodiimide-modified MDI, orthotoluidine diisocyanate Xylene diisocyanate, paraphenylene diisocyanate, and diisocyanates such as lysine diisocyanate methyl ester, triphenylmethane-4,4 ', 4' '- triisocyanate such triisocyanates, polymeric MDI, etc., and these derivatives. Examples of the derivatives include polynuclear polyisocyanates, urethane-modified products modified with polyols (including urethane prepolymers), dimers formed by uretidione formation, isocyanurate-modified products, carbodiimide-modified products, uretonimine-modified products, and allophanate-modified products. Products, urea-modified products, and burette-modified products. The said polyisocyanate can be used individually by 1 type or 2 or more types.

  The urethane coat layer 4 contains a urethane resin obtained by reacting the polyester polyol and the polyisocyanate as a main component, and may contain various additives usually contained in the urethane resin composition. The urethane resin has a polyester polyol and a polyisocyanate having a molar ratio (NCO / OH) of a hydroxyl group (OH) contained in the polyester polyol and an isocyanate group (NCO) contained in the polyisocyanate of 0.7 to 1.15. It is obtained by reacting at a ratio of The molar ratio (NCO / OH) is more preferably from 0.85 to 1.10 in that the hydrolysis of the polyurethane can be prevented. However, in practice, it can be set to an amount equivalent to 3 to 4 times the appropriate molar ratio in consideration of work environment and work errors. Examples of the various additives include a chain extender, a catalyst, a surfactant, a flame retardant, a colorant, a filler, a plasticizer, a stabilizer, and a release agent. Moreover, you may contain the unreacted polyester polyol and / or polyisocyanate. In addition, the urethane coat layer 4 does not contain an ionic liquid as is apparent from Examples and the like.

  The urethane coat layer 4 may contain a conductivity-imparting agent such as carbon black and small-diameter silica. In particular, when small-diameter silica is contained, the unevenness formed on the surface of the urethane coat layer 4 is reduced, and the state of adhesion of the developer to the surface of the conductive roller 1 becomes even more uniform. The occurrence of fogging below can be further prevented. The small-diameter silica preferably has an average particle size of 0.5 to 3 μm, and particularly preferably 1 to 2 μm, in terms of highly preventing fogging in a low-humidity environment. The average particle diameter (secondary particle diameter) can be measured by a coal counter method. This small-diameter silica is preferably contained in the urethane coat layer 4 in an amount of 1 to 20 parts by mass, particularly preferably 1 to 10 parts by mass with respect to 100 parts by mass of the urethane resin, in that the effect can be exhibited as desired. ing.

  The urethane coat layer 4 contains the urethane resin as a main component, that is, 50% by mass or more, preferably 75% by mass or more. When the urethane resin is contained as a main component, occurrence of fogging in a low humidity environment can be effectively prevented.

  The urethane coat layer 4 containing the urethane resin as a main component can contribute to forming a fog-free image even in a low humidity environment when the conductive roller 1 is mounted on an image forming apparatus. It is preferable that at least one of the elongation of 400% (condition (1)) and the breaking strength of 10 to 40 MPa (condition (2)) is satisfied, and it is particularly preferable that both conditions are satisfied. The elongation is more preferably from 150 to 400%, particularly preferably from 150 to 350%. When the urethane coat layer 4 has an elongation in the above range, it can contribute to forming an image without fogging even in a low humidity environment when the conductive roller 1 is mounted on an image forming apparatus. The urethane coating layer 4 is less likely to be damaged even when a strong load is applied to the outer periphery of the conductive roller 1 due to a high degree of freedom. The breaking strength is more preferably 10 to 35 MPa, and particularly preferably 10 to 30 MPa. When the urethane coat layer 4 has a breaking strength in the above range, it can contribute to forming a fog-free image even in a low humidity environment when the conductive roller 1 is mounted on the image forming apparatus. Even when a strong load is applied to the outer periphery of the conductive roller 1, the urethane coat layer 4 is less likely to be damaged. The elongation and the breaking strength are the test piece (10 mm × 50 mm × 40 μm (thickness)) cut out from the urethane coat layer 4 of the conductive roller 1 or the urethane composition forming the urethane coat layer 4. Using the prepared test piece (10 mm × 50 mm × 40 μm (thickness)), the measurement temperature is 25 ± 2 ° C., the tensile speed is 100 mm / min, and the distance between the grips of the test piece is 50 mm. It is a value when measured according to the described measuring method.

  The urethane coat layer 4 preferably has a difference between the elongation of the elastic layer 3 and the elongation of the elastic layer 3 (elongation of the elastic layer 3−elongation of the urethane coat layer 4) of 100 to 1000%, preferably 100 to 500%. Is particularly preferred. When the difference in elongation between the urethane coat layer 4 and the elastic layer 3 is within the above range, when the conductive roller 1 is mounted on the image forming apparatus, an image without fogging is formed even in a low humidity environment. In addition to making a contribution, the urethane coat layer 4 can sufficiently follow the deformation of the elastic layer 3, and the urethane coat layer 4 becomes more difficult to break.

  Furthermore, the urethane coat layer 4 preferably has a difference between the breaking strength thereof and the breaking strength of the elastic layer 3 (breaking strength of the elastic layer 3−breaking strength of the urethane coat layer 4) of 2 to 37 MPa, More preferably, it is 2-10 MPa. When the difference in breaking strength between the urethane coat layer 4 and the elastic layer 3 is in the above range, when the conductive roller 1 is mounted on the image forming apparatus, an image without fogging is formed even in a low humidity environment. Further, the urethane coat layer 4 can sufficiently follow the deformation of the elastic layer 3, and the urethane coat layer 4 is more difficult to break.

  In general, the urethane coat layer 4 preferably has a layer thickness of 0.1 to 60 μm, and more preferably has a layer thickness of 10 to 30 μm.

  The urethane coat layer 4 includes at least one polyurethane preparation component selected from the group consisting of the polyester polyol and the polyisocyanate, a prepolymer obtained by reacting these, and a urethane resin obtained by reacting these, A urethane resin composition containing the various additives or the conductivity-imparting agent, preferably the small-diameter silica, as desired, is formed on the outer peripheral surface of the elastic layer 3. In the urethane resin composition, the content of the small-diameter silica with respect to 100 parts by mass of the polyurethane preparation component is basically the same as the content of the small-diameter silica with respect to 100 parts by mass of the urethane resin in the urethane coat layer 4.

  The conductive roller 1 is manufactured by forming the elastic layer 3 on the outer peripheral surface of the shaft body 2 and further forming the urethane coat layer 4 on the outer peripheral surface of the elastic layer 3. In order to manufacture the conductive roller 1, first, the shaft body 2 is prepared. For example, the shaft body 2 is prepared in a desired shape by a known method. The shaft body 2 may be coated with a primer before the elastic layer 3 is formed. Although there is no restriction | limiting in particular as a primer apply | coated to the shaft body 2, The resin similar to the material which forms the primer layer which adheres or adheres the said elastic layer 3 and the coating layer 4, and a crosslinking agent are mentioned. The primer is dissolved in a solvent or the like as desired, and is applied to the outer peripheral surface of the shaft body according to a conventional method such as a dipping method or a spray method.

  The elastic layer 3 is formed by heat-curing the rubber composition on the outer peripheral surface of the shaft body 2. For example, the elastic layer 3 is formed on the outer peripheral surface of the shaft body 2 by performing heat curing and molding simultaneously or continuously by a known molding method. The method for curing the rubber composition may be any method that can apply heat necessary for curing the rubber composition, and the molding method for the elastic layer 3 is particularly limited, such as continuous vulcanization by extrusion, pressing, or molding by injection. Is not to be done. When the rubber composition is an addition curable millable conductive silicone rubber composition, for example, extrusion molding or the like can be selected, and when the rubber composition is an addition curable liquid conductive silicone rubber composition For example, a molding method using a mold can be selected. The heating temperature for curing the rubber composition is from 100 to 500 ° C., particularly from 120 to 300 ° C., in the case of an addition-curable millable conductive silicone rubber composition, the time is from several seconds to 1 hour, especially from 10 seconds to It is preferably 35 minutes or less, and in the case of an addition curable liquid conductive silicone rubber composition, it is 100 to 300 ° C., particularly 110 to 200 ° C., and the time is 5 minutes to 5 hours, particularly 1 to 3 hours. Is preferred. In addition, in the case of an addition-curable millable conductive silicone rubber composition, if necessary, the curing conditions are about 100 to 200 ° C. for about 1 to 20 hours, and in the case of an addition-curable liquid conductive silicone rubber composition. Secondary vulcanization may be performed at 120 to 250 ° C. under curing conditions for about 2 to 70 hours. The rubber composition can be foam-cured by a known method to easily form a sponge-like elastic layer having bubbles.

  The elastic layer 3 formed in this way has its surface polished and ground as desired to adjust the outer diameter, surface state, and the like. Further, the primer layer may be formed on the elastic layer 3 formed in this way before the urethane coat layer 4 is formed.

  The urethane coat layer 4 is formed by coating the urethane resin composition on the outer peripheral surface of the elastic layer 3 thus formed or the primer layer formed as desired, and then applying the urethane resin composition. An object is formed by heat curing. The application of the urethane resin composition includes, for example, a coating method in which a coating liquid of the urethane resin composition is applied, a dipping method in which the elastic layer 3 or the like is immersed in the coating liquid, and the coating liquid in the elastic layer 3 or the like. It is carried out by a known coating method such as a spray coating method for spraying on the surface. The urethane resin composition may be applied as it is, or applied to the urethane resin composition, for example, alcohols such as methanol and ethanol, aromatic solvents such as xylene and toluene, and ester solvents such as ethyl acetate and butyl acetate. You may apply the coating liquid which added volatile solvents, such as these, or water. The urethane resin composition thus coated may be cured by any method that can add heat or moisture necessary for curing the urethane resin composition. For example, the urethane resin composition is coated. And a method of heating the elastic layer 3 and the like with a heater, a method of leaving the elastic layer 3 and the like coated with the urethane resin composition under high humidity, and the like. The heating temperature when the urethane resin composition is heat-cured is, for example, 100 to 200 ° C., particularly 120 to 160 ° C., and the heating time is preferably 10 to 120 minutes, particularly preferably 30 to 60 minutes. In addition, instead of the coating, the urethane resin composition was laminated on the outer peripheral surface of the elastic layer 3 or the primer layer by a known molding method such as extrusion molding, press molding, injection molding, or the like. Later, a method of curing the laminated urethane resin composition or the like can be employed.

  The conductive roller 1 includes a urethane coat layer 4 containing, as a main component, a urethane resin composed of polyisocyanate and a polyester polyol having a hydroxyl value of 40 to 250 KOHmg / g and an average degree of branching of 2.5 to 8. Therefore, the occurrence of fogging can be substantially suppressed even in a low humidity environment of 20% relative humidity as well as normal humidity. The reason why the conductive roller 1 has such an excellent effect is that if the conductive roller 1 having the urethane coat layer 4 as a surface layer is used as a developing roller, the elongation and / or breaking strength in the above range can be exhibited. The inventors of the present application speculate that the transferability of the developer is improved and it is possible to avoid the overcharged developer remaining on the conductive roller 1 for a long period of time.

  Thus, since the conductive roller 1 can substantially suppress the occurrence of fog even when the surroundings are at low humidity, for example, a developer charged to a desired charge amount is uniformly applied to its surface. It is particularly preferably used as a developing roller for an image forming apparatus, a developer conveying roller, or the like, which needs to exhibit the function and function of being supplied to an image carrier while being supported in a small thickness.

  Next, an example of an image forming apparatus provided with the conductive roller 1 according to the present invention (hereinafter sometimes referred to as an image forming apparatus according to the present invention) will be described with reference to FIG. As shown in FIG. 2, the image forming apparatus 10 includes a plurality of image carriers 11B, 11C, 11M, and 11Y that are provided in the developing units B, C, M, and Y of the respective colors in series on the transfer conveyance belt 6. Therefore, the developing units B, C, M, and Y are arranged in series on the transfer conveyance belt 6. The developing unit B includes an image carrier 11B such as a photosensitive member (also referred to as a photosensitive drum), a charging unit 12B such as a charging roller, an exposure unit 13B, a developing unit 20B, and an image carrier via the transfer conveyance belt 6. A transfer unit 14B that contacts the body 11B, such as a transfer roller, and a cleaning unit 15B are provided. The developing unit 20B adjusts the thickness of the casing 21B that accommodates the one-component non-magnetic developer 22B, the developer carrier 23B that supplies the developer 22B to the image carrier 11B, such as a developing roller, and the thickness of the developer 22B. Developer amount adjusting means 24B, for example, a blade. The developing units C, M, and Y are basically configured in the same manner as the developing unit B. The fixing unit 30 is disposed on the downstream side of the developing unit Y. The fixing unit 30 includes a fixing roller 31, an endless belt support roller 33 disposed in the vicinity of the fixing roller 31, a fixing roller 31, and an endless belt support roller in a housing having an opening 35 through which the recording medium 16 passes. 33, an endless belt 36 wound around 33, and a pressure roller 32 disposed opposite to the fixing roller 31. The fixing roller 31 and the pressure roller 32 are in contact with or pressed against each other via the endless belt 36. It is a pressure heat fixing device which is supported in a freely rotatable manner. At the bottom of the image forming apparatus 10, a cassette 41 that houses the recording body 16 is installed. The transfer conveyance belt 6 is wound around a plurality of support rollers 42.

  Each of the developers 22B, 22C, 22M and 22Y used in the image forming apparatus 10 may be a dry developer or a wet developer as long as it can be charged by friction, and a non-magnetic developer or a magnetic developer. An agent may be used. One component non-magnetic black developer 22B, cyan developer 22C, magenta developer 22M and yellow developer 22Y are accommodated in the housings 21B, 21C, 21M and 21Y of the developing units. In the image forming apparatus 10, the conductive roller 1 is mounted as a developer carrier 23B, 23C, 23M and 23Y, that is, as a developing roller. Therefore, the developing means 20 is a developing means (also referred to as a developing device) according to the present invention provided with the conductive roller 1 according to the present invention.

  The image forming apparatus 10 forms a color image on the recording body 16 as follows. First, in the developing unit B, an electrostatic latent image is formed by the exposure unit 13B on the surface of the image carrier 11B charged by the charging unit 12B, and the black electrostatic latent image is developed by the developer 22B supplied by the developer carrier 23B. The image is developed. The black electrostatic latent image is transferred to the surface of the recording medium 16B when the recording medium 16 passes between the transfer means 14B and the image carrier 11B. Next, in the same manner as in the developing unit B, a cyan image, a magenta image, and a yellow image are superimposed on the recording medium 16 in which the electrostatic latent image is visualized as a black image by the developing units C, M, and Y, respectively. A color image is visualized. Next, the recording body 16 in which the color image is visualized is fixed to the recording body 16 by the fixing unit 30 as a permanent image. In this way, a color image can be formed on the recording medium 16.

  In the tandem type image forming apparatus 10, when the conductive roller 1 according to the present invention is used as the developer carrying member 23, the relative humidity is particularly 10 even in a low humidity environment of 20% relative humidity as well as normal humidity. %, A high-quality image having substantially no fogging can be formed.

  The image forming apparatus 10 is an image forming apparatus such as a copying machine, a facsimile machine, or a printer. Although the image forming apparatus 10 has been described with reference to the example in which the conductive roller 1 according to the present invention is used as a developing roller as an example of the developer carrier 23, the conductive roller 1 according to the present invention is used as a developer supply roller. Even if the neutral roller 1 is used, a high-quality image having substantially no fogging can be formed even in a low humidity environment.

  The conductive roller and the image forming apparatus according to the present invention are not limited to the above-described embodiments, and various modifications can be made within a range in which the object of the present invention can be achieved.

  For example, the conductive roller 1 may have another layer between the elastic layer 3 and the urethane coat layer 4. Examples of the other layer include a primer layer that adheres or adheres the elastic layer 3 and the urethane coat layer 4 to each other. Examples of materials for forming the primer layer include alkyd resins, phenol-modified / silicone-modified alkyd resin modified products, oil-free alkyd resins, acrylic resins, silicone resins, epoxy resins, fluororesins, phenol resins, polyamide resins, urethanes. Examples thereof include resins and mixtures thereof. Moreover, as a crosslinking agent which hardens and / or bridge | crosslinks these resin, an isocyanate compound, a melamine compound, an epoxy compound, a peroxide, a phenol compound, a hydrogen siloxane compound etc. are mentioned, for example. The primer layer is formed with a thickness of 0.1 to 10 μm, for example.

  The image forming apparatus 10 is an electrophotographic image forming apparatus. However, in the present invention, the image forming apparatus is not limited to the electrophotographic system, and may be, for example, an electrostatic image forming apparatus. Good. Further, the image forming apparatus provided with the conductive roller 1 according to the present invention is not limited to a tandem type color image forming apparatus in which a plurality of image carriers having developing units of respective colors are arranged in series on a transfer conveyance belt. For example, it may be a monochrome image forming apparatus provided with a single developing unit, a 4-cycle color image forming apparatus that sequentially repeats primary transfer of a developer image carried on an image carrier onto an endless belt, and the like. . The developer 22 used in the image forming apparatus 10 is a one-component nonmagnetic developer. However, in the present invention, the developer 22 may be a one-component magnetic developer or a two-component nonmagnetic developer. Or a two-component magnetic developer. The fixing unit 30 may be a heat roller fixing device, a heat fixing device, a pressure fixing device, or the like.

Example 1
An electroless nickel-plated shaft body (SUM22, diameter 10 mm, length 275 mm) was washed with ethanol, and a silicone primer (trade name “Primer No. 16”, manufactured by Shin-Etsu Chemical Co., Ltd.) on its surface. ) Was applied. The primer-treated shaft body 2 was fired at a temperature of 150 ° C. for 10 minutes using a gear oven, and then cooled at room temperature for 30 minutes or more to form a primer layer on the surface of the shaft body 2.

100 parts by weight of methyl vinyl silicone raw rubber (trade name “KE-78VBS”, manufactured by Shin-Etsu Chemical Co., Ltd.), 20 parts by weight of dimethyl silicone raw rubber (trade name “KE-76VBS”, manufactured by Shin-Etsu Chemical Co., Ltd.), and carbon 10 parts by weight of black (trade name “Asahi Thermal”, manufactured by Asahi Carbon Co., Ltd.) and fumed silica-based filler (trade name “AEROSIL OX-50”, average primary particle size 40 nm, bulk density 1.3 g / cm ³ 15 parts by mass of Nippon Aerosil Co., Ltd., 0.5 parts by mass of a platinum-based catalyst (trade name “C-19A”, manufactured by Shin-Etsu Chemical Co., Ltd.), and organohydrogenpolysiloxane (trade name “C-19B”) ”, Manufactured by Shin-Etsu Chemical Co., Ltd.), 2.0 parts by mass, kneaded with a pressure kneader, and addition-curable millable conductive silicone rubber composition It was prepared.

  Next, the shaft body 2 on which the primer layer is formed and the addition-curable millable conductive silicone rubber composition are integrally extracted with a crosshead type extruder, and heated at 250 ° C. for 30 minutes using a gear oven. did. Thereafter, using a gear oven, secondary heating was performed at 200 ° C. for 4 hours, and the mixture was left at room temperature for 24 hours. Next, the surface of the elastic layer 3 was polished by a cylindrical grinder so that the formed elastic layer 3 had a diameter of 18 mm.

  As the elongation and breaking strength of the elastic layer 3 thus formed, the results measured by the above method using test pieces (10 mm × 50 mm × 40 μm) separately prepared with the addition-curable millable conductive silicone rubber composition were used. Table 2 shows.

  Also, the polyol and polycarboxylic acid shown below were prepared, and these were polymerized so that the molar ratio (OH / COOH) of the OH group of the polyol to the COOH group of the polycarboxylic acid was 8/7. A polyol was prepared.

  The polyester polyol was synthesized as follows. That is, 709 parts by mass of 1,6-hexanediol and 212 parts by mass of 1,2,4-butanetriol, adipic acid were added to a separable flask in which a cooling pipe, a thermometer, a moisture receiver, a nitrogen introduction pipe and a decompression device were set. 472 parts by mass, 498 parts by mass of isophthalic acid, 0.5 part by mass of p-toluenesulfonic acid, and 50 parts by mass of toluene were charged, and the mixture was heated to 180 ° C. over 2 hours while stirring nitrogen and stirred. During the heating, the whole was melted and mixed, and the mixture of water and toluene flowed out. After raising the temperature to 180 ° C., dehydration condensation was performed at the same temperature for 2 hours. Subsequently, the pressure in the flask was gradually reduced to 20 mmHg, and dehydration condensation was subsequently performed while toluene was distilled off at this pressure for 1 hour. Thereafter, it was cooled to obtain a polyester polyol.

Next, a urethane resin composition for forming the urethane coat layer 4 having the following composition was prepared.
-28 parts by mass of the polyester polyol (molar ratio of hexamethylene diisocyanate and polyester polyol described later (NCO / OH = 1.1 / 1)
・ 5 parts by mass of carbon black (trade name “Toka Black # 5500”, manufactured by Tokai Carbon Co., Ltd.) ・ 4 parts by mass of small diameter silica (average particle size 1.5 μm, trade name “ACEMATT OK-607”, manufactured by Degussa) (9.5 parts by mass with respect to 100 parts by mass of the polyurethane adjusting component)
・ 0.03 parts by mass of dibutyltin diuraurate (trade name “di-n-butyltin dilaurate”, manufactured by Showa Chemical Co., Ltd.)

  The urethane resin composition thus prepared was applied to the outer peripheral surface of the elastic layer 3 by a spray coating method and heated at 160 ° C. for 30 minutes to form a urethane coat layer 4 having a layer thickness of 22 μm. In this way, the conductive roller of Example 1 was manufactured.

(Examples 2 and 3)
The conductive rollers of Examples 2 and 3 were basically the same as Example 1 except that the mixing ratio (parts by mass) of the polyol and the polycarboxylic acid was changed to the mixing ratio shown in Table 1. Each was manufactured.

Example 4
A conductive roller of Example 4 was produced basically in the same manner as in Example 1 except that the hexamethylene diisocyanate was changed to an elastic polyisocyanate (aliphatic isocyanate).

(Examples 5 and 7)
The conductive rollers of Examples 5 and 7 were produced in substantially the same manner as in Example 1 except that the average particle diameter of the small-diameter silica was changed to 3.0 μm and 1.0 μm, respectively.

(Example 6)
A conductive roller of Example 6 was produced basically in the same manner as Example 1 except that the small diameter silica was not used.

(Comparative Examples 1-4)
The conductive rollers of Comparative Examples 1 to 4 were basically the same as Example 1 except that the mixing ratio (parts by mass) of the polyol and the polycarboxylic acid was changed to the mixing ratio shown in Table 1. Each was manufactured.

(Comparative Example 5)
A conductive roller of Comparative Example 5 was produced basically in the same manner as in Example 1 except that polyether polyol (trade name “P-4000”, manufactured by ADEKA Corporation) was used instead of the polyester polyol. did.

(Characteristics of polyester polyol and urethane coat layer)
The average branching degree, hydroxyl value (OHV) and number average molecular weight (Mn) of each polyester polyol in Examples 1 to 7 and Comparative Examples 1 to 4 or the polyether polyol in Comparative Example 5 were measured by the above methods. The results are shown in Table 1. Further, the elongation and breaking strength of the urethane coat layer 4 in each example and comparative example were measured by the above method using test pieces (10 mm × 50 mm × 40 μm) separately prepared from the respective urethane resin compositions, and the elasticity The difference from layer 3 was calculated. These results are shown in Table 2.

(Evaluation of fogging in a low humidity environment)
Each manufactured conductive roller is used as a developing roller and placed in a non-magnetic one-component electrophotographic printer (trade name “JUSTIO HL-4040CN”, manufactured by Brother Industries, Ltd.) under a low humidity environment (10 ° C., relative humidity). 20%), black solid printing and white solid printing were respectively carried out (pre-printing step). After this pre-printing step, under the same environment, 5,000 A4 sheets were continuously printed in a horizontal line pattern with a printing rate of 1%, and then white solid printing was performed (main printing step). The presence or absence of developer adhesion was visually confirmed on the white solid print portion printed in this printing step. Evaluation is `` ◎ '' when the developer is not attached to the white solid print portion at all, `` ○ '' when the developer is acceptable and slightly visible on the white solid print portion, The case where the developer adhered to the white solid print portion exceeding the allowable amount was marked as “x”. The evaluation results are shown in Table 2.

DESCRIPTION OF SYMBOLS 1 Conductive roller 2 Shaft body 3 Elastic layer 4 Urethane coat layer 6 Transfer conveyance belt 10 Image forming apparatus 11B, 11C, 11M, 11Y Image carrier 12B, 12C, 12M, 12Y Charging means 13B, 13C, 13M, 13Y Exposure means 14B, 14C, 14M, 14Y Transfer means 15B, 15C, 15M, 15Y Cleaning means 20 Developing means 21B, 21C, 21M, 21Y, 34 Housing 22B, 22C, 22M, 22Y Developer 23B, 23C, 23M, 23Y Developer Carriers 24B, 24C, 24M, 24Y Developer regulating member 30 Fixing means 31 Fixing roller 32 Pressure roller 33 Endless belt support roller 36 Endless belt B, C, M, Y Developing unit

Claims (4)

A conductive roller comprising an elastic layer formed on the outer peripheral surface of the shaft body and a urethane coat layer formed on the outer peripheral surface of the elastic layer,
The urethane coat layer is a polyisocyanate and a polyester polyol having a hydroxyl value (OHV) of 40 to 250 KOHmg / g and an average degree of branching expressed by the number of hydroxyl groups per gram with respect to the number of molecules per gram. A conductive roller characterized by containing a urethane resin consisting of The conductive roller according to claim 1, wherein the urethane coat layer satisfies at least one of the following conditions (1) and (2).
(1) 140-400% elongation (2) 10-40 MPa breaking strength The elongation and breaking strength were measured using a 10 mm × 50 mm × 40 μm test piece at a measurement temperature of 25 ± 2 ° C. and a tensile rate of 100 mm / This is the value when measured according to the measurement method described in JIS K7113 under the condition that the distance between the grips of the test piece is 50 mm. The conductive roller according to claim 1, wherein the elastic layer satisfies at least one of the following conditions (A) and (B).
(A) 300 to 1200% elongation (B) 3 to 25 MPa breaking strength The elongation and breaking strength were measured using a 10 mm × 50 mm × 40 μm test piece at a measurement temperature of 25 ± 2 ° C. and a tensile speed of 100 mm / This is the value when measured according to the measurement method described in JIS K7113 under the condition that the distance between the grips of the test piece is 50 mm.   An image forming apparatus comprising the conductive roller according to claim 1.

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