JP4434849B2 - Developer carrier and developing device - Google Patents

Description

  The present invention relates to a developing device for developing a latent image formed on an electrostatic latent image carrier used for electrophotography, electrostatic recording method, magnetic recording method and the like with a developer to visualize it, and development The present invention relates to an agent carrier.

  Conventionally, as a developing device that visualizes an electrostatic latent image formed on the surface of a photosensitive drum as an electrostatic latent image carrier with toner as a one-component developer, friction between toner particles, developer holding The toner particles are charged positively or negatively by friction between the developing sleeve and the toner particles as a body, friction between the toner sleeve and a member that regulates the toner application amount on the developing sleeve (developer layer thickness regulating member), and the like. The charged toner is applied very thinly on the developing sleeve and conveyed to a developing area where the photosensitive drum and the developing sleeve are opposed to each other, and in the developing area, the toner is transferred to the electrostatic latent image on the surface of the photosensitive drum. And an electrostatic latent image on a photosensitive drum is visualized as a toner image.

The developer carrier used in the conventional developing apparatus as described above is formed, for example, by forming a metal, an alloy, or a metal compound into a cylindrical shape, and the surface thereof has a predetermined surface roughness by electrolysis, blast, file, or the like. What was processed in this way is used. On the other hand, in recent years, in order to achieve low-temperature fixing of a developer and high-definition image formation required for energy saving, it is desired to reduce the particle size of toner. In such a toner having a small particle diameter, the surface charge per unit weight is large, so that the surface charge is likely to be large, and the toner is fixed to the developer carrying member by a so-called charge-up phenomenon. The developer supplied on the body is difficult to be charged, and the charge amount of the developer tends to be non-uniform. On the other hand, in Japanese Patent Laid-Open No. 01-277256 (Patent Document 1), in order to prevent the generation of such an excessively charged developer and the strong adhesion of the developer to the developer carrying member, a resin is used. In particular, a method has been proposed in which a film (resin layer) made of a resin composition in which a powder of a conductive material such as carbon or graphite or a solid lubricant is dispersed is formed on a developer carrier. In Japanese Patent Application Laid-Open No. 02-304468 (Patent Document 2), a conductive resin layer in which a conductive lubricant such as a solid lubricant and carbon and spherical particles are dispersed in a resin coating layer is provided on a metal substrate. A developing sleeve has been proposed. In JP-A-08-240981 (Patent Document 3), the spherical particles dispersed in the conductive coating layer are made into conductive spherical particles, thereby further improving the wear resistance and the shape of the surface of the developing sleeve. Development having a surface layer that can further stabilize the toner, further improve the charging of the toner, and can suppress sleeve contamination and fusion by the toner even when the resin layer, which is a conductive coating layer, is somewhat worn. A sleeve has been proposed.
Japanese Patent Laid-Open No. 01-277256 JP 02-304458 A Japanese Patent Laid-Open No. 08-240981 JP 59-190945 A JP 2001-288256 A JP 2002-80571 A J. et al. Chem. Soc. Perkin. Trans. 1,806 (1973) Org. Synth. , 4, 698 (1963) J. et al. Org. Chem. 46, 19 (1981) J. et al. Am. Chem. Soc. , 81, 4273 (1959) Macromolecular chemistry, 4, 289-293 (2001).

  Therefore, the present invention prevents the toner from being overcharged in the developing device, keeps the toner charge amount high, and carries the developer on the developer carrying body that hardly causes toner fusion. And a developing device having the developer carrying member. In addition, the present invention suppresses uneven charging of the toner on the surface of the developer carrying member, which appears particularly when a toner having a small particle diameter is used, and can carry a developer carrying an appropriate charge amount. And a developing device having the developer carrying member.

  That is, the present invention relates to a developer carrier used in a developing device that develops a latent image formed on an electrostatic latent image carrier with a developer carried and conveyed by the developer carrier and visualizes the latent image. And having at least a substrate and a resin layer formed on the surface of the substrate, and the binder resin used in the resin layer includes at least a chemical formula (1):

(In the formula, R represents —A ₁ — (SO ₂ R ₁ ) _x . R ₁ represents OH, a halogen atom, ONa, OK, OR _1a . A ₁ and R _1a represent a substituted or unsubstituted aliphatic group. Represents a hydrocarbon structure, a substituted or unsubstituted aromatic ring structure, a substituted or unsubstituted heterocyclic structure, m is an integer selected from the range of 0 to 7, and x is a range of 1 to 7 (In the case where there are a plurality of units, R, R ₁ , A ₁ , R _1a , m, and x represent the above meanings independently for each unit.)
A developer carrier characterized by containing a polyhydroxyalkanoate containing at least one unit shown in the molecule.

  In the present invention, the developer accommodated in the developer container is supported on the developer carrying member, and the developer carrying member is developed while forming a thin layer of the developer on the developer carrying member by the developer layer thickness regulating member. In the developing device for transporting the developer to a development area facing the latent image carrier, and developing the latent image on the latent image carrier with the developer in the development area, the developer carrier Is a developing device characterized in that

  According to the present invention, there is provided a developer carrier that is more durable than a conventionally used developer carrier and can maintain a state in which a good image can be provided for a long time. . Furthermore, according to the present invention, a positive charge imparting property to toner is stabilized, and the developer layer on the developer carrier is made uniform, thereby providing a highly durable developer carrier.

  Hereinafter, the present invention will be described in detail with reference to preferred embodiments. As a result of intensive studies on the above-described problems of the prior art, the present inventors have found that at least the chemical formula (1) in the binder resin constituting the resin layer formed on the surface of the developer carrier.

(In the formula, R represents —A ₁ — (SO ₂ R ₁ ) _x . R ₁ represents OH, a halogen atom, ONa, OK, OR _1a . A ₁ and R _1a represent a substituted or unsubstituted aliphatic group. Represents a hydrocarbon structure, a substituted or unsubstituted aromatic ring structure, a substituted or unsubstituted heterocyclic structure, m is an integer selected from the range of 0 to 7, and x is a range of 1 to 7 (In the case where there are a plurality of units, R, R ₁ , A ₁ , R _1a , m, and x represent the above meanings independently for each unit.)
Despite the fact that the developer can be quickly charged and kept at a high level by including a polyhydroxyalkanoate characterized in that the unit contains at least one unit as shown in FIG. Knowing that it is difficult to cause the developing sleeve to be contaminated by the developer, and that it is possible to obtain a developer carrying body that can obtain a high charge amount even in a high humidity environment and that does not become overcharged even in a low humidity environment. The present invention has been reached.

  The polyhydroxyalkanoate used in the present invention (hereinafter sometimes abbreviated as PHA) has a basic skeleton as a biodegradable resin. Therefore, as with conventional plastics, various products are produced by melt processing or the like. Unlike petroleum-derived synthetic polymers, it has the outstanding characteristics of being decomposed by living organisms and taken into the natural material cycle. Therefore, it is not necessary to perform a combustion treatment, and is an effective material from the viewpoint of preventing air pollution and global warming, and can be used as a plastic that enables environmental conservation.

  Generally, Tm (melting temperature) and Tg (glass transition temperature) are important physical properties related to the heat resistance and mechanical strength (for example, elastic modulus) of the resin material. For example, a resin material having a high Tm and Tg is excellent in heat resistance and strength. Conversely, a resin material having a low Tm and Tg has advantages such as easy molding, but is inferior in heat resistance and strength. The Many conventional PHAs have relatively low Tm and Tg, and therefore have limitations on extrusion processability, mechanical properties, heat resistance, and the like, and there is a limit to expanding their applications.

  The PHA used in the present invention has improved physical properties such as thermal properties and mechanical properties as compared with conventional ones, and can be applied to applications requiring heat resistance and strength.

  These desired physical properties of PHA can be obtained by selecting culture conditions for microorganisms capable of synthesizing PHA in the present invention. For example, the number average molecular weight can be controlled by controlling the culture time and the like. Further, the number average molecular weight can be controlled by removing low molecular weight components using means such as solvent extraction and reprecipitation. Here, the glass transition temperature and the softening point have a correlation with the molecular weight of PHA. It is also possible to control the glass transition temperature and the softening point by controlling the type / composition ratio of monomer units in PHA.

  The molecular weight of PHA is desirably about 1,000 to 1,000,000 in terms of number average molecular weight.

  Here, when such a compound is produced using microorganisms, the polyester resin is an isotactic polymer composed only of R-form, but if the object of the present invention can be achieved in both physical properties / functions, For example, it is not necessary to be an isotactic polymer, and an atactic polymer can also be used. It is also possible to obtain PHA by a chemical synthesis method in which a lactone compound is subjected to ring-opening polymerization using an organometallic catalyst (for example, an organic catalyst containing aluminum, zinc, tin or the like).

  The polyhydroxyalkanoate represented by the chemical formula (1) intended in the present invention is a polyhydroxyalkanoate containing a 3-hydroxy-ω- (4-carboxyphenyl) alkanoic acid unit represented by the chemical formula (24) used as a starting material. It is produced by the reaction of an ate with at least one compound represented by the chemical formula (25).

(P is an integer selected from the range of 0 to 7. R ₂₄ is an H atom, Na atom or K atom. When a plurality of units are present, p and R ₂₄ are Independently represents the above meaning.)
_{H 2 N-A 25 - (} SO 2 R 25) x (25)
Wherein R ₂₅ is OH, halogen atom, ONa, OK, OR _25a . A ₂₅ is a substituted or unsubstituted aliphatic hydrocarbon structure, a substituted or unsubstituted aromatic ring structure, a substituted or unsubstituted R _25a represents a substituted or unsubstituted aliphatic hydrocarbon structure, a substituted or unsubstituted aromatic ring structure, a substituted or unsubstituted heterocyclic structure, and x is in the range of 1 to 7. When there are a plurality of amine compounds, A ₂₅ , R ₂₅ , R _25a , and x independently represent the above meanings for each amine compound.)

(Method for producing polyhydroxyalkanoate containing a unit represented by chemical formula (24))
A polyhydroxyalkanoate containing a 3-hydroxy-ω- (4-carboxyphenyl) alkanoic acid unit represented by the chemical formula (24) is a 3-hydroxy-ω- (4-vinylphenyl) represented by the chemical formula (28). Oxidative cleavage of double bond portion of polyhydroxyalkanoate containing alkanoic acid unit, or methyl group of polyhydroxyalkanoate containing 3-hydroxy-ω- (4-methylphenyl) alkanoic acid unit represented by chemical formula (54) Manufactured by partial oxidation.

(In the formula, s is an integer selected from the range of 0 to 7. When there are a plurality of units, s represents the above meaning independently for each unit.)

(In the formula, l is an integer selected from the range of 0 to 7. When there are a plurality of units, l represents the above meaning independently for each unit.)

  As described above, as a method for obtaining a carboxylic acid by oxidizing a carbon-carbon double bond or a methyl group using an oxidizing agent, a method using a permanganate (J. Chem. Soc., Perkin. Trans) 1,806 (1973); Non-Patent Document 1), a method using dichromate (Org. Synth., 4,698 (1963); Non-Patent Document 2), a method using periodate (J. Chem., 46, 19 (1981); Non-patent document 3) A method using nitric acid (Japanese Patent Laid-Open No. 59-190945; Patent document 4), a method using ozone (J. Am. Chem. Soc., 81, 4273 (1959); Non-Patent Document 4) and the like. Further, regarding the polyhydroxyalkanoate, the above-mentioned Macromolecular Chemist is used. y, 4, 289-293 (2001) (Non-Patent Document 5), using potassium permanganate with a carbon-carbon double bond at the end of the side chain of polyhydroxyalkanoate as an oxidizing agent, and the reaction under acidic conditions. A method for obtaining a carboxylic acid by performing it has been reported. A similar method can be used in the present invention.

  As the permanganate used as an oxidizing agent, potassium permanganate is common. Since the oxidation reaction is a stoichiometric reaction, the amount of permanganate used is usually 1 mole equivalent or more, preferably 2 to 10 moles per mole of the unit represented by the chemical formula (28) or (54). Molar equivalents should be used.

  In order to bring the reaction system to acidic conditions, various inorganic acids and organic acids such as sulfuric acid, hydrochloric acid, acetic acid and nitric acid are usually used. However, when an acid such as sulfuric acid, nitric acid or hydrochloric acid is used, the ester bond of the main chain of polyhydroxyalkanoate is cleaved, which may cause a decrease in molecular weight. Therefore, it is preferable to use acetic acid. The amount of the acid used is usually 0.2 to 2000 molar equivalents, preferably 0.4 to 1000 molar equivalents, per 1 mol of the unit represented by the chemical formula (28) or (54). When the amount is less than 0.2 molar equivalent, the yield is low, and when the amount exceeds 2000 molar equivalent, an acid decomposition product is by-produced. In addition, crown-ether can be used for the purpose of promoting the reaction. In this case, the crown-ether and the permanganate form a complex, and the effect of increasing the reaction activity is obtained. As the crown-ether, dibenzo-18-crown-6-ether, dicyclo-18-crown-6-ether, or 18-crown-6-ether is generally used. The amount of the crown-ether used is usually 0.005 to 2.0 molar equivalents, preferably 0.01 to 1.5 molar equivalents per mole of permanganate.

  In addition, the solvent in the oxidation reaction of the present invention is not particularly limited as long as it is an inert solvent. For example, water, acetone; ethers such as tetrahydrofuran and dioxane; aromatic carbonization such as benzene, toluene and xylene. Hydrogens; aliphatic hydrocarbons such as hexane and heptane; halogenated hydrocarbons such as methyl chloride, dichloromethane and chloroform can be used. Among these solvents, halogenated hydrocarbons such as methyl chloride, dichloromethane and chloroform are preferable in consideration of the solubility of polyhydroxyalkanoate.

  In the oxidation reaction of the present invention, the polyhydroxyalkanoate, permanganate and acid containing a unit represented by the chemical formula (28) or (54) may be charged together with a solvent from the beginning and reacted. You may make it react, adding continuously or intermittently in a system. Alternatively, only permanganate may be dissolved or suspended in a solvent first, and then polyhydroxyalkanoate and acid may be continuously or intermittently added to the system to react. Alternatively, only permanganate and an acid may be added to the system continuously or intermittently and reacted in advance. Further, the polyhydroxyalkanoate and the acid may be charged first, and then the permanganate may be continuously or intermittently added to the system to react, and the permanganate and the acid may be charged first. Subsequently, the polyhydroxyalkanoate may be continuously or intermittently added to the system to react, and the polyhydroxyalkanoate and permanganate are charged first, followed by the acid continuously or intermittently. You may make it react in addition to the inside of a system.

  The reaction temperature is usually −40 to 40 ° C., preferably −10 to 30 ° C. Although the reaction time depends on the stoichiometric ratio between the unit represented by the chemical formula (28) or (54) and the permanganate and the reaction temperature, it is usually preferably 2 to 48 hours.

  In addition to the 3-hydroxy-ω- (4-vinylphenyl) alkanoic acid unit represented by the chemical formula (28) or the 3-hydroxy-ω- (4-methylphenyl) alkanoic acid unit represented by the chemical formula (54), a chemical formula ( In the case of using a polyhydroxyalkanoate containing a 3-hydroxy-ω-substituted alkanoic acid unit represented by 11) or a 3-hydroxy-ω-cyclohexylalkanoic acid unit represented by chemical formula (12), the same conditions are used. It is possible to carry out the reaction.

(Method for producing polyhydroxyalkanoate containing a unit represented by chemical formula (28) or (54))
The polyhydroxyalkanoate containing a unit represented by the chemical formula (28) or (54) used in the present invention is not particularly limited, but a method of producing by microbial production, a method of producing by a genetically engineered plant crop system, It can be produced using a method such as chemical polymerization and production. Here, when such a compound is produced by a method including a step of producing by a microorganism, the polyhydroxyalkanoate is an isotactic polymer composed only of the R isomer, but the present invention has both physical properties and functions. If the above-mentioned object can be achieved, it is not necessary to be an isotactic polymer, and an atactic polymer can also be used. It is also possible to obtain the polyhydroxyalkanoate by a method in which chemical synthesis utilizing ring-opening polymerization of a lactone compound is included in the process.

  The case where microbial production is used as a method for producing a polyhydroxyalkanoate containing a unit represented by the chemical formula (28) or (54) in the present invention will be described in detail.

  The polyhydroxyalkanoate as a starting material contains at least one of ω- (4-vinylphenyl) alkanoic acid represented by chemical formula (29) or ω- (4-methylphenyl) alkanoic acid represented by chemical formula (55). According to the production method, the microorganism is cultured in a medium.

(T is an integer selected from the range of 0-7.)

(Q is an integer selected from the range of 0-7.)

<PHA producing bacteria>
The microorganism used in the method for producing a polyhydroxyalkanoate containing a unit represented by the chemical formula (28) or (54) as a starting material of the present invention is a microorganism having a PHA-producing ability, that is, an ω− represented by the general formula (29). By culturing in a medium containing (4-vinylphenyl) alkanoic acid or ω- (4-methylphenyl) alkanoic acid represented by the general formula (55), 3-hydroxy-ω- represented by the general formula (28) Any microorganism can be used as long as it is a microorganism capable of producing a PHA-type polyester containing the (4-vinylphenyl) alkanoic acid unit or the 3-hydroxy-ω- (4-methylphenyl) alkanoic acid unit represented by (54). Also good. As a suitable example of the microorganisms which have PHA production ability which can be utilized, the microorganisms which belong to Pseudomonas (Pseudomonas) genus can be mentioned. Among these, strains that have PHA production ability but do not exhibit enzyme reactivity such as oxidation or epoxidation of the vinyl group substituted on the phenyl group are more preferable. .

  More specifically, among the microorganisms belonging to the genus Pseudomonas, the more preferable species as the microorganism used in the production method of the present invention are Pseudomonas chicory, Pseudomonas putida, Pseudomonas, and Pseudomonas.・ Fluoresence (Pseudomonas fluorecense), Pseudomonas oleovorans, Pseudomonas aeruginosa (Pseudomonas aeruginosa), Pseudomonas studomo It can gel.

  Further, as more preferable strains, for example, Pseudomonas chicoryi YN2 strain (Pseudomonas chicory YN2; FERM BP-7375), Pseudomonas chicoryii strain H45 (Pseudomonas chicoryi H45; messenii P161; FERM BP-7376), Pseudomonas putida P91 strain (Pseudomonas putida P91; FERM BP-7373). These four strains are deposited at the Patent Organism Depositary, National Institute of Advanced Industrial Science and Technology, National Institute of Advanced Industrial Science and Technology, Japanese Patent Laid-Open No. 2001-288256 (Patent Document 5) and Japanese Patent Laid-Open No. 2002-80571. It is the microorganism described in the gazette (patent document 6).

  In addition to these Pseudomonas microorganisms, strains belonging to the genus Burkholderia sp., Aeromonas sp., Comamonas sp. And the like and known to produce PHA Many of these are applicable to the PHA biosynthesis of the present invention.

  These microorganisms are ω-substituted linear alkanes in which the chain ends are substituted with 6-membered ring groups such as substituted or unsubstituted phenyl groups, substituted or unsubstituted phenoxy groups, substituted or unsubstituted cyclohexyl groups. A polyhydroxy containing an acid or a ω-substituted straight-chain alkanoic acid substituted with a 5-membered ring group such as a thienyl group as a raw material and a corresponding ω-substituted-3-hydroxy-alkanoic acid as a monomer unit Has the ability to produce alkanoates.

<Culture>
A carbon source serving as a substrate for introduction of the 3-hydroxy-ω- (4-vinylphenyl) alkanoic acid unit or 3-hydroxy-ω- (4-methylphenyl) alkanoic acid unit, and 3 -Hydroxy-ω- (4-vinylphenyl) alkanoic acid unit or carbon source serving as substrate for introduction of desired monomer unit other than 3-hydroxy-ω- (4-methylphenyl) alkanoic acid unit, and microorganism The target PHA can be produced by culturing in a medium containing at least a growth carbon source. Such PHA is an isotactic polymer that is generally composed only of R-isomers.

  In the production method of the present invention, any medium can be used as the medium used in the microorganism culturing step as long as it is an inorganic salt medium containing a phosphate and a nitrogen source such as ammonium salt or nitrate. In the process of producing PHA, it is possible to improve the productivity of PHA by adjusting the nitrogen source concentration in the medium.

  In addition, nutrients such as yeast extract, polypeptone, and meat extract can be added to the medium as a substrate that promotes the growth of microorganisms. That is, peptides can be added as energy sources and carbon sources in the form of nutrients such as yeast extract, polypeptone, and meat extract.

  Alternatively, in the medium, as an energy source consumed by the growth of microorganisms, as a carbon source, sugars such as aldoses such as glyceraldehyde, erythrose, arabinose, xylose, glucose, galactose, mannose, fructose, glycerol, erythritol, xylitol, etc. Aldonic acids such as alditol and gluconic acid, uronic acids such as glucuronic acid and galacturonic acid, disaccharides such as maltose, sucrose and lactose can be used.

  In place of the saccharide, an organic acid or a salt thereof, more specifically, an organic acid involved in the TCA cycle and an organic acid derived from a TCA cycle by one or two less biochemical reactions, or Those water-soluble salts can be used. Examples of organic acids or salts thereof include, for example, pyruvic acid, oxaloacetic acid, citric acid, isocitric acid, ketoglutaric acid, succinic acid, fumaric acid, malic acid, lactic acid and other hydroxycarboxylic acids and oxocarboxylic acids or their water-soluble salts. It is possible to use. Alternatively, an amino acid or a salt thereof, for example, an amino acid such as aspartic acid or glutamic acid or a salt thereof can be used. When adding an organic acid or a salt thereof, one or more kinds from the group consisting of pyruvic acid, oxaloacetic acid, citric acid, isocitric acid, ketoglutaric acid, succinic acid, fumaric acid, malic acid, lactic acid, and salts thereof More preferably, it is selected, added to the medium and dissolved. Or when adding an amino acid or its salt, it is more preferable to select 1 type or multiple types from the group which consists of aspartic acid, glutamic acid, and those salts, add to a culture medium, and to make it melt | dissolve. At that time, if necessary, all or a part of it can be added in the form of a water-soluble salt, and it can be dissolved uniformly without affecting the pH of the medium.

  As a carbon source for microbial growth, and as an energy source for polyhydroxyalkanoate production, the concentration of the coexisting substrate added to the medium is typically 0.05% to 5% (w / w) per medium. It is desirable to select the range of v), more preferably in the range of 0.2% to 2% (w / v). That is, peptides, yeast extracts, organic acids or salts thereof, amino acids or salts thereof, and saccharides, which are used as the coexisting substrate described above, can be added singly or in combination. Thus, it is desirable to add in the range of the total concentration.

  A substrate for producing the desired polyhydroxyalkanoate, that is, ω- (4-vinylphenyl) alkanoic acid represented by the general formula (29) or ω- (4-methylphenyl) represented by the chemical formula (55) The content ratio of alkanoic acid is preferably selected in the range of 0.01% to 1% (w / v), more preferably in the range of 0.02% to 0.2% (w / v) per medium.

  Further, a substrate for producing the desired polyhydroxyalkanoate, that is, ω- (4-vinylphenyl) alkanoic acid represented by the chemical formula (29) or ω- (4-methylphenyl) represented by the chemical formula (55) ) Not only at least one alkanoic acid but also at least one ω-substituted alkanoic acid compound represented by chemical formula (30) or at least one ω-cyclohexyl alkanoic acid compound represented by chemical formula (31) in culture In addition to the 3-hydroxy-ω- (4-vinylphenyl) alkanoic acid unit represented by the chemical formula (28) or the 3-hydroxy-ω- (4-methylphenyl) alkanoic acid unit represented by the chemical formula (55) Or a 3-hydroxy-ω-substituted alkanoic acid unit represented by the chemical formula (11) It is possible to produce a polyhydroxyalkanoate containing a 3-hydroxy -ω- cyclohexyl alkanoic acid unit represented by (12). Furthermore, it is also possible to synthesize copolymers containing other 3-hydroxyalkanoic acid units. Specific examples of such monomer units include 3-hydroxyhexanoic acid units, 3-hydroxyheptanoic acid units, 3-hydroxyoctanoic acid units, 3-hydroxynonanoic acid units, 3-hydroxydecanoic acid units, 3-hydroxy Examples thereof include 3-hydroxyalkanoic acid units constituting mcl-PHA such as dodecanoic acid units and 3-hydroxytetraacid units. It is also possible for PHA to contain a plurality of these monomer units, and it is possible to control the physical properties of PHA using the characteristics of each monomer unit and the functional groups contained therein, to add a plurality of functions, and to use new interactions utilizing functional groups. It is possible to express various functions.

(U is an integer selected from the range of 1 to 8. R ₃₀ includes a ring structure of either a phenyl structure or a thienyl structure, and the chemical formulas (13), (14), (15 ), (16), (17), (18), (19), (20), (21), (22), (23), and when there are a plurality of units, each unit Represents the above meaning independently.

(In the formula, R ₃₁ represents a substituent to the cyclohexyl group, and R ₃₁ represents an H atom, CN group, NO ₂ group, halogen atom, CH ₃ group, C ₂ H ₅ group, C ₃ H ₇ group, CF _3. Group, C ₂ F ₅ group or C ₃ F ₇ group, and v is an integer selected from the range of 0 to 8.)

  The culture temperature may be any temperature as long as the microorganism strain to be used can grow well, and is usually selected within the range of 15 ° C to 37 ° C, more preferably within the range of 20 ° C to 30 ° C. .

  Any culture method can be used for the culture as long as the microorganism grows and produces PHA such as liquid culture and solid culture. Furthermore, the types such as batch culture, fed-batch culture, semi-continuous culture, and continuous culture are not limited. As a form of liquid batch culture, there are a method of supplying oxygen while shaking in a shake flask, and a method of supplying oxygen by stirring aeration using a jar fermenter.

  As a technique for producing and accumulating PHA in a microorganism, the microorganism is cultured in an inorganic salt medium containing a nitrogen source such as a phosphate and an ammonium salt or nitrate to which a substrate is added at a predetermined concentration as described above. In addition to the step culture method, a two-stage culture method in which the culture is divided into two stages can also be employed. In this two-stage culture method, as a primary culture, microorganisms are once sufficiently grown in an inorganic salt medium containing a nitrogen source such as phosphate and ammonium salt or nitrate to which a substrate is added at a predetermined concentration. As a secondary culture, a nitrogen source such as ammonium chloride contained in the medium is restricted, and then the cells obtained in the primary culture are transferred to a medium to which a substrate is added at a predetermined concentration. To produce and accumulate PHA. When this two-stage culture method is employed, the target PHA productivity may be improved.

  In general, the PHA-type polyester produced has a 4-vinylphenyl group or 3-hydroxy-ω- (4-methylphenyl) alkane of 3-hydroxy-ω- (4-vinylphenyl) alkanoic acid unit in the side chain. Since it has a hydrophobic atomic group such as 4-methylphenyl group of the acid unit, it has poor water solubility and accumulates in the cells of microorganisms having PHA-producing ability. By collecting the cells that are produced and accumulated, separation from the medium is facilitated. The collected cultured cells are washed and dried, and then the target PHA-type polyester can be recovered.

  In addition, polyhydroxyalkanoate is usually accumulated in the cells of microorganisms having such PHA producing ability. As a method for recovering the target PHA from the microbial cells, a conventional method can be applied. For example, extraction with an organic solvent such as chloroform, dichloromethane, acetone, and ethyl acetate is the simplest. In addition to the above solvents, dioxane, tetrahydrofuran, and acetonitrile may be used. Also, in working environments where the use of organic solvents is not desirable, instead of solvent extraction methods, treatment with surfactants such as SDS, treatment with enzymes such as lysozyme, and chemicals such as hypochlorite, ammonia, EDTA, etc. Treatment, or after disrupting the microbial cells physically using any of the ultrasonic crushing method, homogenizer method, pressure crushing method, bead impact method, grinding method, crushing method, and freeze-thaw method. It is also possible to adopt a method of removing PHA other than PHA and recovering PHA.

  As an example of the inorganic salt medium that can be used in the production method of the present invention, the composition of an inorganic salt medium (M9 medium) used in Examples described later is shown below.

(Composition of M9 medium)
Na ₂ HPO ₄ : 6.3
KH ₂ PO ₄ : 3.0
NH ₄ Cl: 1.0
NaCl: 0.5
(G / L, pH = 7.0)
Furthermore, in order to achieve good cell growth and the accompanying improvement in PHA productivity, an appropriate amount of an essential trace element such as an essential trace metal element is added to the inorganic salt medium such as the M9 medium. It is extremely effective to add about 0.3% (v / v) of a trace component solution having the following composition. The addition of such a trace component solution supplies trace metal elements used for the growth of microorganisms.

(Composition of trace component solution)
Nitrilotriacetic acid: 1.5
MgSO ₄ : 3.0
MnSO ₄ : 0.5
NaCl: 1.0
FeSO ₄ : 0.1
CaCl ₂ : 0.1
COCl ₂ : 0.1
ZnSO ₄ : 0.1
CuSO ₄ : 0.1
AlK (SO ₄ ) ₂ : 0.1
H ₃ BO ₃ : 0.1
Na ₂ MoO ₄ : 0.1
NiCl _2: 0.1
(G / L)

(Compound shown in chemical formula (25))
As the compound represented by the chemical formula (25) used in the present invention,
_{H 2 N-A 25 - (} SO 2 R 25) x (25)
Wherein R ₂₅ is OH, halogen atom, ONa, OK, OR _25a . A ₂₅ is a substituted or unsubstituted aliphatic hydrocarbon structure, a substituted or unsubstituted aromatic ring structure, a substituted or unsubstituted R _25a represents a substituted or unsubstituted aliphatic hydrocarbon structure, a substituted or unsubstituted aromatic ring structure, a substituted or unsubstituted heterocyclic structure, and x is in the range of 1 to 7. When there are a plurality of amine compounds, A ₂₅ , R ₂₅ , R _25a , and x independently represent the above meanings for each amine compound.)
Is mentioned.

More specifically, A ₂₅ is any one of a linear or branched alkylene group having 1 to 8 carbon atoms, a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, substituted or unsubstituted N, S, and O. Represents a heterocyclic structure containing two or more. When A ₂₅ is a ring structure, the unsubstituted ring may be further condensed.

Examples of the compound in which A ₂₅ is a linear or branched alkylene group having 1 to 8 carbon atoms include 2-aminoethanesulfonic acid (taurine), 3-aminopropanesulfonic acid, 4-aminobutanesulfonic acid, 2-amino-2- Examples thereof include methyl propane sulfonic acid and alkali metal salts thereof.

When A ₂₅ is a substituted or unsubstituted phenyl group, it is represented by the chemical formula (32).

(In the formula, at least one of R _32a , R _32b , R _32c , R _32d and R _32e is SO ₂ R _32f (R _32f is OH, halogen atom, ONa, OK, OR _32h . R _32h is A substituted or unsubstituted aliphatic hydrocarbon structure, a substituted or unsubstituted aromatic ring structure, a substituted or unsubstituted heterocyclic structure, and a hydrogen atom, a halogen atom, and a carbon number of 1 to 20 Alkyl group, alkoxy group having 1 to 20 carbon atoms, OH group, NH ₂ group, NO ₂ group, COOR _32g (R _32g : represents any of H atom, Na atom, K atom), acetamide group, OPh group , NHPh group, CF ₃ group, C ₂ F ₅ group or C ₃ F ₇ group.)

  Examples of the compound represented by the chemical formula (32) include p-aminobenzenesulfonic acid (sulfanilic acid), m-aminobenzenesulfonic acid, o-aminobenzenesulfonic acid, m-toluidine-4-sulfonic acid, and o-toluidine-4. -Sulfonic acid sodium salt, p-toluidine 2-sulfonic acid, 4-methoxyaniline-2-sulfonic acid, o-anisidine-5-sulfonic acid, p-anisidine-3-sulfonic acid, 3-nitroaniline-4-sulfone Acid, 2-nitroaniline-4-sulfonic acid sodium salt, 4-nitroaniline-2-sulfonic acid sodium salt, 1,5-dinitroaniline-4-sulfonic acid, 2-aminophenol-4-hydroxy-5-nitrobenzene Sulfonic acid, 2,4-dimethylaniline-5-sulfonic acid sodium salt, 2,4-dimethyl Aniline-6-sulfonic acid, 3,4-dimethylaniline-5-sulfonic acid, 4-isopropylaniline-6-sulfonic acid, 4-trifluoromethylaniline-6-sulfonic acid, 3-carboxy-4-hydroxyaniline- Various aminobenzenesulfonic acid derivatives such as 5-sulfonic acid, 4-carboxyaniline-6-sulfonic acid, aniline-2,4-disulfonic acid, and salts thereof, as well as 2-aminobenzenesulfonic acid methyl ester, 4-amino Examples include various aminobenzenesulfonic acid derivatives such as benzenesulfonic acid methyl ester, 2-aminobenzenesulfonic acid phenyl ester, and 4-aminobenzenesulfonic acid phenyl ester, and esterified products such as methyl esterified products or phenyl esterified products of the salts thereof.

When A ₂₅ is a substituted or unsubstituted naphthyl group, it is represented by chemical formulas (33a) and (33b).

(In the formula, at least one of R _33A , R _33B , R _33C , R _33D , R _33E , R _33F , R _33G is SO ₂ R _33O (R _33O is OH, halogen atom, ONa, OK, OR _33s . R _33s represents a substituted or unsubstituted aliphatic hydrocarbon structure, a substituted or unsubstituted aromatic ring structure, or a substituted or unsubstituted heterocyclic structure.) In addition, a hydrogen atom or a halogen atom , An alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an OH group, NH ₂ , NO ₂ group, COOR _33P (R _33P represents any one of an H atom, an Nl atom, and a K atom), Acetamide group, OPh group, NHPh group, CF ₃ group, C ₂ F ₅ group or C ₃ F ₇ group)

_{(Wherein, R 33H, R 33I, R} 33J, R 33K, R 33L, R 33M, R 33N , at least one is _SO 2 _{R 33Q (R} 33Q is OH, a halogen atom, ONa, _OK, with _{OR 33t} R _33t represents a substituted or unsubstituted aliphatic hydrocarbon structure, a substituted or unsubstituted aromatic ring structure, or a substituted or unsubstituted heterocyclic structure.) In addition, a hydrogen atom or a halogen atom , An alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an OH group, an NH ₂ group, a NO ₂ group, COOR _33R (R _33R represents one of an H atom, an Nl atom, and a K atom) , An acetamide group, an OPh group, an NHPh group, a CF ₃ group, a C ₂ F ₅ group or a C ₃ F ₇ group)

  Examples of the compounds represented by the chemical formulas (33a) and (33b) include 1-naphthylamine-4-sulfonic acid, 1-naphthylamine-5-sulfonic acid, 1-naphthylamine-6-sulfonic acid, and 1-naphthylamine-7-sulfonic acid. 1-naphthylamine-8-sulfonic acid, 2-naphthylamine-1-sulfonic acid, 2-naphthylamine-5-sulfonic acid, 1-naphthylamine-2-ethoxy-6-sulfonic acid, 1-amino-2-naphthol-4 -Sulfonic acid, 6-amino-1-naphthol-3-sulfonic acid, 1-amino-8-naphthol-2,4-sulfonic acid monosodium salt, 1-amino-8-naphthol-3,6-sulfonic acid mono Various naphthylamine sulfonic acid derivatives such as sodium salts and salts thereof, as well as 1-naphthylamine-8-sulfonic acid Various naphthylamine sulfonic acid derivatives such as 2-ester, 2-naphthylamine-1-sulfonic acid methyl ester, 1-naphthylamine-8-sulfonic acid phenyl ester, 2-naphthylamine-1-sulfonic acid phenyl ester, and methyl esterified products or phenyl thereof Examples include esterified products such as esterified products.

In the case where A ₂₅ is a heterocyclic structure containing any one or more of substituted or unsubstituted N, S, and O, examples thereof include a pyridine ring, a piperazine ring, a furan ring, and a thiol ring.

(Production method of polyhydroxyalkanoate represented by chemical formula (1))
The condensation reaction between the polyhydroxyalkanoate containing a unit represented by the chemical formula (24) and the aminosulfonic acid compound represented by the chemical formula (25) in the present invention will be described in detail. Examples of the condensation reaction of a carboxyl group and an amino group include a method using a condensing agent, a method of forming a salt and performing condensation by a dehydration reaction, a method using a dehydrating agent, a method of converting a carboxyl group into an acid chloride and reacting an amino group, etc. Both are available.

  As the production method of the present invention, a method using a condensing agent will be described in detail.

  As the condensing agent, a phosphoric acid condensing agent, a carbodiimide condensing agent, an acid chloride condensing agent, etc. can be used. For example, as a phosphoric acid condensing agent, a phosphite ester condensing agent, a phosphor chloride It is possible to use a system condensing agent, a phosphoric acid anhydride condensing agent, a phosphoric ester condensing agent, a phosphoric acid amide condensing agent, and a thionyl chloride condensing agent.

  In the reaction of the present invention, a phosphite-based condensing agent is preferably used. The phosphites used here include triphenyl phosphite, trimethyl phosphite, triethyl phosphite, diphenyl phosphite, tri-o-tolyl phosphite, di-o-phosphite. Tolyl, tri-m-tolyl phosphite, di-m-tolyl phosphite, tri-p-tolyl phosphite, di-p-tolyl phosphite, di-o-chlorophenyl phosphite, phosphorous acid Examples thereof include tri-p-chlorophenyl and di-p-chlorophenyl phosphite. Of these, triphenyl phosphite is preferably used. Examples of the carbodiimide condensing agent include dicyclohexylcarbodiimide (DCC), diisopropylcarbodiimide (DIPC), N-ethyl-N′-3-dimethylaminopropylcarbodiimide (EDC = WSCI), and its hydrochloride (WSCI · HCl). can give. DCC or WSCI, N-hydroxysuccinimide (HONSu), 1-hydroxybenzotriazole (HOBt), 3-hydroxy-4-oxo-3,4-dihydro-1,2,3-benzotriazine (HOObt), etc. And may be used in combination. The amount of the condensing agent to be used is in the range of 0.1 times mol or more, preferably 1 times mol or more, relative to the compound represented by chemical formula (25). Further, the condensing agent itself can be used as a reaction solvent.

  The usage-amount of the compound shown to Chemical formula (25) used for this invention is 0.1-50.0 times mole with respect to the unit shown to Chemical formula (24) used as a starting material, Preferably, it is 1.0-20. The range is 0.0 mole.

  In the reaction of the present invention, a solvent can be used as necessary. Solvents used include hydrocarbons such as hexane, cyclohexane and heptane, ketones such as acetone and methyl ethyl ketone, ethers such as dimethyl ether, diethyl ether and tetrahydrofuran, dichloromethane, chloroform, carbon tetrachloride, dichloroethane, trichloroethane and the like. Examples include halogenated hydrocarbons, aromatic hydrocarbons such as benzene and toluene, aprotic polar solvents such as N, N-dimethylformamide and dimethyl sulfoxide, and pyridine derivatives. Particularly preferably, pyridine is used. The amount of the solvent used can be appropriately determined according to the starting material, the type of base, reaction conditions and the like.

  In the method of the present invention, the reaction temperature is not particularly limited, but is usually a temperature in the range of 0 ° C. to the boiling point of the solvent. However, it is desirable to carry out the reaction at an optimum temperature according to the condensing agent used.

  In the method of the present invention, the reaction time cannot be generally specified, but is usually in the range of 1 to 48 hours.

  In the present invention, the reaction solution containing the polyhydroxyalkanoate represented by the chemical formula (1) thus produced can be removed by distillation which is a conventional method. Or using a solvent such as water, alcohols such as methanol and ethanol, and ethers such as dimethyl ether, diethyl ether, and tetrahydrofuran, and a solvent that is homogeneous in the reaction solution and insoluble in the polyhydroxyalkanoate represented by chemical formula (1) It can collect | recover by mixing and reprecipitating the polyhydroxyalkanoate shown to the target Chemical formula (1). The polyhydroxyalkanoate represented by the chemical formula (1) obtained here can be isolated and purified if necessary. The isolation and purification method is not particularly limited, and a method of reprecipitation using a solvent insoluble in the polyhydroxyalkanoate represented by the chemical formula (1) and a method by column chromatography can be used.

(Method for producing polyhydroxyalkanoate represented by chemical formula (27))
As shown in chemical formula (26), when R ₁ in chemical formula (1) is OH, a halogen atom, ONa, or OK, trimethylsilyldiazomethane, which is a methyl esterifying agent, is used. It is possible to synthesize polyhydroxyalkanoates where R is —A ₂₇ — (SO ₃ CH ₃ ) _x (where x is an integer selected from the range of 1 to 7). .

(In the formula, R represents —A ₂₆ — (SO ₂ R ₂₆ ) _x . R ₂₆ represents OH, a halogen atom, ONa, or OK. A ₂₆ represents a substituted or unsubstituted aliphatic hydrocarbon structure, substituted or Represents an unsubstituted aromatic ring structure, a substituted or unsubstituted heterocyclic structure, m is an integer selected from the range of 0 to 7, and x is an integer selected from the range of 1 to 7 When there are a plurality of units, R, R ₂₆ , A ₂₆ , m, and x have the above meanings independently for each unit.)

(Wherein, R _{-A 27 - (SO 3 CH 3} ) .A 27 representing the _x is a substituted or unsubstituted aliphatic hydrocarbon structure, aromatic ring structure substituted or unsubstituted, a substituted or unsubstituted heterocyclic M represents an integer selected from the range of 0 to 7, and x is an integer selected from the range of 1 to 7. When a plurality of units are present, R, A ₂₇ , m, and x represent the above meanings independently for each unit.)

  The reaction is described in detail below.

  In the reaction of the present invention, a solvent can be used as necessary. Solvents used include hydrocarbons such as hexane, cyclohexane and heptane, alcohols such as methanol and ethanol, ethers such as dimethyl ether, diethyl ether and tetrahydrofuran, dichloromethane, chloroform, carbon tetrachloride, dichloroethane, trichloroethane and the like. Examples include halogenated hydrocarbons, aromatic hydrocarbons such as benzene and toluene, aprotic polar solvents such as N, N-dimethylformamide and dimethyl sulfoxide, and pyridine derivatives. Particularly preferably, chloroform and methanol are used. The amount of the solvent used can be appropriately determined according to the starting materials, reaction conditions and the like.

The amount of trimethylsilyl diazomethane, to one _SO 2 _{R 26} group of a compound represented by the chemical formula (26), 0.1 to 50 moles, preferably in the range of 1 to 20 moles, _SO 2 R _When there are a plurality of ₂₆ groups, the amount used may be increased according to the number.

  In the method of the present invention, the reaction temperature is not particularly limited, but is usually in the range of −20 ° C. to 30 ° C.

  In the method of the present invention, the reaction time cannot be generally specified, but is usually in the range of 1 to 48 hours.

  In the present invention, the reaction solution containing the polyhydroxyalkanoate represented by the chemical formula (27) thus produced can be removed by distillation which is a conventional method. Or, using a solvent such as water, alcohols such as methanol and ethanol, ethers such as dimethyl ether, diethyl ether, and tetrahydrofuran, a solvent that is homogeneous in the reaction solution and insoluble in the polyhydroxyalkanoate represented by chemical formula (27) It can collect | recover by mixing and reprecipitating the polyhydroxy alkanoate shown to the target Chemical formula (27). The polyhydroxyalkanoate represented by the chemical formula (27) obtained here can be isolated and purified if necessary. The isolation and purification method is not particularly limited, and a method of reprecipitation using a solvent insoluble in the polyhydroxyalkanoate represented by the chemical formula (27) and a method by column chromatography can be used.

  The polyhydroxyalkanoate polymer produced by the method of the present invention and having a microbially produced polyhydroxyalkanoate as an intermediate raw material contains a unit having a sulfonic acid group or a derivative thereof in the polymer molecule. . These structures strongly promote the localization of electrons in the molecule at the end of such units, and their electrical properties can be significantly different from conventional polyhydroxyalkanoates. In addition, due to such electron localization, the behavior with respect to the solvent also differs from that of the conventional polyhydroxyalkanoate. For example, it can be dissolved in a polar solvent such as dimethylformamide (DMF). In addition, the control of thermal characteristics, particularly the increase in the glass transition temperature derived from hydrogen bonding, is remarkable, and it can be applied to a wide range of uses.

  The PHA used in the present invention contains monomer units of the chemical formula (1) in a ratio of 0.2% to 40% in unit ratio, and has a number average molecular weight of 1,000 to 200,000. Preferably there is. When the proportion of the unit of the chemical formula (1) is less than 0.2%, the ability to induce a positive charge on the toner tends to be inferior. On the other hand, when the proportion of the unit of the chemical formula (1) is more than 40%, it is not preferable because environmental stability such as moisture resistance is deteriorated and film characteristics are deteriorated. On the other hand, when the number average molecular weight of the PHA used is less than 1,000, the amount of low molecular weight components is too large, so that the toner is easily attached or fixed to the sleeve, or the charge imparting property of the resin layer is lowered. On the other hand, if the number average molecular weight of the polymer is larger than 200,000, the compatibility with other resins forming the resin layer is deteriorated, and stable chargeability cannot be obtained due to environmental fluctuations or aging. On the other hand, if the molecular weight is too high, the viscosity of the resin in the solvent will increase, resulting in poor coating, or if pigments are added, it will cause poor dispersion and the composition of the resin layer to be coated will be uneven. Toner charging is not stable, and the surface roughness of the resin coating layer is not stable, resulting in a decrease in wear resistance.

  In general, since the glass transition point of the binder resin for toner is often about 50 ° C. to 70 ° C., when the PHA is used, the toner on the surface of the resin layer formed by coating the substrate is used. In order to avoid adhesion of toner, a material is appropriately selected so as to form a coating PHA so that a coating film (resin layer) having a glass transition point higher than that of the toner is formed. Is preferred.

  Next, another configuration of the developer carrying member of the present invention having the resin layer composed of the above components will be described. The developer carrying member of the present invention has a resin layer formed of the above-mentioned material on the surface of the substrate. Examples of the substrate used for the developer carrying member are made of metal, resin, rubber or a composite material thereof. The columnar member, the cylindrical member, and the belt-shaped member that are formed can be applied. Among these, a cylindrical tube is particularly preferably used. As the cylindrical tube, for example, a non-magnetic metal or alloy such as aluminum, stainless steel, or brass is formed into a cylindrical shape, and then polished and ground is preferably used. These metal cylindrical tubes are used after being molded or processed with high accuracy in order to improve the uniformity of the image. For example, the straightness in the longitudinal direction is preferably 30 μm or less, more preferably 20 μm or less. The gap between the sleeve and the photosensitive drum is swung, for example, abuts against a vertical surface through a uniform spacer, and the sleeve is rotated. In this case, the fluctuation of the gap with the vertical surface is preferably 30 μm or less, more preferably 20 μm or less.

  Further, in the developer carrying member of the present invention, a resin layer is formed by coating the surface of the substrate as described above. As the binder resin used for forming the resin layer, the chemical formula (1):

(In the formula, R represents —A ₁ — (SO ₂ R ₁ ) _x . R ₁ represents OH, a halogen atom, ONa, OK, OR _1a . A ₁ and R _1a represent a substituted or unsubstituted aliphatic group. Represents a hydrocarbon structure, a substituted or unsubstituted aromatic ring structure, a substituted or unsubstituted heterocyclic structure, m is an integer selected from the range of 0 to 7, and x is a range of 1 to 7 (In the case where there are a plurality of units, R, R ₁ , A ₁ , R _1a , m, and x represent the above meanings independently for each unit.)
The polyhydroxyalkanoate characterized by including 1 unit or more in a molecule | numerator is contained. Here, if necessary, the copolymer may be contained in other known resins. Examples of resins that can be used at this time include thermoplastic resins such as styrene resins, vinyl resins, polyethersulfone resins, polycarbonate resins, polyphenylene oxide resins, polyamide resins, fluororesins, fiber resins, and acrylic resins. Thermal or photo-curable resins such as polyester resins, alkyd resins, polyurethane resins, urea resins and silicone resins can be used. Among these, those having releasability such as silicone resin and fluororesin, or those having excellent mechanical properties such as polyethersulfone, polycarbonate, polyphenylene oxide, styrene resin and acrylic resin are used. It is more preferable.

  Furthermore, it is preferable that the resin layer coated on the substrate surface constituting the developer carrying member of the present invention contains a conductive fine powder and / or a solid lubricant to form a conductive resin layer. The lubricating substance is a frictional charge imparting material, and the effect of the present invention can be further promoted by forming a resin layer in which the lubricating substance is dispersed on the substrate surface. Examples of lubricating substances that can be used in this case include graphite, molybdenum disulfide, boron nitride, mica, graphite fluoride, silver-niobium selenide, calcium chloride-graphite, talc, and fatty acids such as zinc stearate. Examples thereof include solid lubricants such as metal salts. Among these, graphite is preferably used because it does not impair the conductivity of the coating resin layer. These solid lubricants preferably have a number average particle diameter of about 0.2 to 20 μm, more preferably 1 to 15 μm.

  When the amount of the solid lubricant as described above is in the range of 10 to 120 parts by weight with respect to 100 parts by weight of the binder resin, particularly preferable results are given. That is, when the addition amount exceeds 120 parts by weight, a decrease in the strength of the coated resin layer and a decrease in the charge amount of the toner are recognized. There is a tendency that the effect of preventing toner adhesion on the surface of the resin layer constituting the developer carrying member is reduced.

  In the present invention, in order to adjust the volume resistance of the resin layer formed on the substrate surface, conductive fine particles may be dispersed in the binder resin in addition to the solid lubricant. The conductive fine particles used at this time preferably have a number average particle size of 20 μm or less. More preferably, the thickness is 10 μm or less, and in order to avoid the formation of irregularities on the surface, it is preferable to use a thickness of 1 μm or less.

  Examples of the conductive fine particles that can be used in the present invention include carbon black such as furnace black, lamp black, thermal black, acetylene black, and channel black; titanium oxide, tin oxide, zinc oxide, molybdenum oxide, potassium titanate. And metal oxides such as antimony oxide and indium oxide; metals such as aluminum, copper, silver and nickel; inorganic fillers such as graphite, metal fibers and carbon fibers. As the addition amount of the conductive fine particles described above, it is particularly preferable to use the conductive fine particles within a range of 100 parts by weight or less based on 100 parts by weight of the binder resin. That is, when the amount exceeds 100 parts by weight, a decrease in the film strength of the resin layer and a decrease in the charge amount of the toner are recognized.

  As a preferred structure of the resin layer of the developer carrying member of the present invention, in addition to the additive substances described above, in order to form irregularities on the surface of the coated resin layer having a number average particle size of 0.3 to 30 μm. In the resin layer, the surface roughness of the developer carrier is stabilized, and the toner coat amount on the developer carrier is optimized. Thereby, it is possible to sufficiently exert the effect of imparting triboelectric charge obtained by the copolymer of the vinyl polymerizable monomer and the sulfonic acid-containing acrylamide monomer. The particles maintain a uniform surface roughness on the surface of the resin layer of the developer carrier, and at the same time, even when the surface of the resin layer is worn, there is little change in the surface roughness of the resin layer. There is an effect to make it difficult to wear.

  The particles used for forming irregularities on the surface of the resin layer coated on the surface of the substrate constituting the developer carrying member of the present invention have a number average diameter of 0.3 to 30 μm, preferably 2 to 20 μm. Good. If the number average particle diameter of the particles is less than 0.3 μm, the effect of imparting uniform roughness to the surface and the effect of improving the charging performance are small, and the rapid and uniform charging to the developer becomes insufficient, and the resin layer It is not preferable because the toner charge up, toner contamination and toner fusion occur due to the wear of the toner, and the ghost is easily deteriorated and the image density is lowered. When the number average particle diameter exceeds 30 μm, the surface roughness of the resin layer becomes too large, and it becomes difficult to sufficiently charge the toner, and the mechanical strength of the resin layer is decreased, which is preferable. Absent.

  In the present invention, the particles for forming irregularities on the surface of the resin layer are preferably spherical. The spherical shape in the spherical particle referred to here means a particle having a major axis / minor axis ratio of about 1.0 to 1.5. In the present invention, the ratio of major axis / minor axis is preferably 1. It is preferred to use 0 to 1.2 particles. When the ratio of the major axis / minor axis of the spherical particles exceeds 1.5, the surface roughness of the resin layer becomes non-uniform, which leads to rapid and uniform charging of the toner and the strength of the conductive resin layer. It is not preferable.

More preferably, the true density of spherical particles, 3 g / cm ³ or less, preferably 2.7 g / cm ³ or less, more preferably be a 0.9~2.3g / cm ^3. That is, when the true density of the spherical particles exceeds ³ g / cm ³ , the dispersibility of the spherical particles in the resin layer becomes insufficient, so that it is difficult to impart uniform roughness to the resin layer surface. In addition, since the storage stability of the paint is not good, it is difficult to obtain the surface of the frictional charge imparting member having uniform surface irregularities. Even when the true density of the spherical particles is smaller than 0.9 g / cm ³ , the dispersibility and storage stability of the spherical particles in the resin layer are insufficient.

  As the spherical particles used in the present invention, known spherical particles can be used. Examples thereof include spherical resin particles, spherical metal oxide particles, and spherical carbonized particles. As the spherical particles, for example, spherical resin particles obtained by suspension polymerization, dispersion polymerization, or the like are used. Among these, it is preferable to use spherical resin particles because a surface roughness suitable for the surface of the developer carrying member can be obtained with a smaller addition amount and a uniform surface state can be easily obtained. Examples of such spherical particles include acrylic resin particles such as polyacrylate and polymethacrylate, polyamide resin particles such as nylon, polyolefin resin particles such as polyethylene and polypropylene, silicone resin particles, phenolic resin particles, Examples include polyurethane resin particles, styrene resin particles, benzoguanamine particles, and the like. The resin particles obtained by the pulverization method may be used after thermally or physically spheroidizing.

Further, an inorganic substance may be attached or fixed to the surface of the spherical particles as mentioned above. Examples of the inorganic fine powder that can be used at this time include oxides such as SiO ₂ , SrTiO ₃ , CeO ₂ , CrO, Al ₂ O ₃ , ZnO and MgO, nitrides such as Si ₃ N ₄ , and SiC. Carbides, sulfates such as CaSO ₄ , BaSO ₄ and CaCO ₃ , carbonates, and the like. Such inorganic fine powder may be organically treated with a coupling agent.

  In particular, for the purpose of improving the adhesion to the binder resin or imparting hydrophobicity to the particles, it is preferable to use an inorganic fine powder treated with a coupling agent. Examples of the coupling agent used at this time include a silane coupling agent, a titanium coupling agent, and a zircoaluminate coupling agent. More specifically, for example, as silane coupling agents, hexamethyldisilazane, trimethylsilane, trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, allylphenyldichlorosilane , Benzyldimethylchlorosilane, bromomethyldimethylchlorosilane, α-chloroethyltrichlorosilane, β-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane, triorganosilylmercaptan, trimethylsilylmercaptan, triorganosilylacrylate, vinyldimethylacetoxysilane, Dimethyldiethoxysilane, dimethyldimethoxysilane, diphenyldiethoxysilane, hexamethyldisiloxane, 1,3-divinylte Tramethyldisiloxane, 1,3-diphenyltetramethyldisiloxane, and 2-12 siloxane units per molecule, each containing a hydroxyl group bonded to one silicon atom in the terminal unit Dimethylpolysiloxane and the like. If spherical resin particles or the like having inorganic fine powder treated with such a coupling agent adhered or fixed to the surface are used, the dispersibility of the spherical particles to be added in the resin layer is improved, and the resin layer to be formed It is possible to improve surface uniformity, contamination resistance, charge imparting property to toner, wear resistance, and the like.

Moreover, it is more preferable that the spherical particles having the above-described configuration used in the present invention have conductivity. That is, by imparting electrical conductivity to the spherical particles, it becomes difficult for charges to accumulate on the surface of the particles due to the electrical conductivity, so that it is possible to reduce toner adhesion to the surface of the developing sleeve and to improve the chargeability of the toner. . The conductivity of the spherical particles suitable in the present invention is preferably a particle having a volume resistance of 10 ⁶ Ω · cm or less, more preferably 10 ⁻³ to 10 ⁶ Ω · cm. That is, when the volume resistance of the spherical particles exceeds 10 ⁶ Ω · cm, the spherical particles are exposed on the surface of the resin layer due to wear and become partially insulating, which causes the toner to be contaminated and fused. In addition to being easy, it may be difficult to perform quick and uniform charging.

  As a method for obtaining conductive spherical particles that can be suitably used in the present invention, the methods described below are preferable, but are not necessarily limited thereto. As a method for obtaining particularly preferable conductive spherical particles used in the present invention, for example, spherical resin particles and mesocarbon microbeads are baked to be carbonized and / or graphitized to form a low concentration and highly conductive spherical particle. A method for obtaining carbon particles may be mentioned. Examples of the resin material used for the spherical resin particles include phenol resin, naphthalene resin, furan resin, xylene resin, divinylbenzene polymer, styrene-divinylbenzene copolymer, and polyacrylonitrile. In addition, mesocarbon microbeads can usually be produced by washing spherical crystals formed in the process of heating and firing the medium pitch with a large amount of a solvent such as tar, medium oil, and quinoline.

  More preferable methods for obtaining conductive spherical particles include a mechanochemical method on the surface of spherical resin particles such as phenol resin, naphthalene resin, furan resin, xylene resin, divinylbenzene polymer, styrene-divinylbenzene copolymer, and polyacrylonitrile. There is a method in which a bulk mesophase pitch is coated, and the coated particles are heat-treated in an oxidizing atmosphere and then calcined to be carbonized and / or graphitized to obtain conductive spherical carbon particles.

The conductive spherical carbon particles obtained by the method described above can control the conductivity of the spherical carbon particles obtained by changing the firing conditions to some extent in any of the methods described above. Can be preferably used as spherical particles having conductivity used in the above. In addition, in some cases, the spherical carbon particles obtained by the above-described method may have a conductive metal and a conductive metal in a range where the true density of the conductive spherical particles does not exceed ³ g / cm ³ in order to further increase the conductivity. Alternatively, metal oxide plating may be applied.

  As another method for obtaining conductive spherical particles suitably used in the present invention, conductive fine particles smaller than the particle diameter of the core particles are mechanically mixed with the core particles made of spherical resin particles at an appropriate blending ratio. After the conductive fine particles are uniformly attached to the periphery of the core particles by the action of van der Waals force and electrostatic force, for example, the core is caused by a local temperature rise caused by applying a mechanical impact force. Examples thereof include a method of obtaining spherical resin particles obtained by softening the particle surface, forming conductive fine particles on the core particle surface, and conducting the conductive treatment.

  For the core particles, spherical resin particles having a small true density made of an organic compound are preferably used. Examples of the resin include PMMA, acrylic resin, polybutadiene resin, polystyrene resin, polyethylene, polypropylene, polybutadiene, or These copolymers, benzoguanamine resin, phenol resin, polyamide resin, nylon, fluorine resin, silicone resin, epoxy resin and polyester resin can be mentioned. As the conductive fine particles (small particles) used when forming a film on the surface of the core particles (mother particles), the particle size of the small particles is the same as the particle size of the mother particles in order to provide a conductive fine particle coating uniformly. It is preferable to use 1/8 or less.

  Furthermore, as another method for obtaining conductive spherical particles that can be used in the present invention, conductive spherical particles in which conductive fine particles are dispersed are obtained by uniformly dispersing conductive fine particles in spherical resin particles. A method is mentioned. As a method for uniformly dispersing the conductive fine particles in the spherical resin particles, for example, the binder resin and the conductive fine particles are kneaded to disperse the conductive fine particles, then cooled and solidified, and pulverized to a predetermined particle size. Then, a method for obtaining conductive spherical particles by spheronizing by mechanical treatment and thermal treatment, or adding a polymerization initiator, conductive fine particles and other additives into a polymerizable monomer, and uniformly using a disperser The dispersed monomer composition is suspended in an aqueous phase containing a dispersion stabilizer so as to have a predetermined particle size by a stirrer, and polymerization is performed to obtain spherical particles in which conductive fine particles are dispersed. A method is mentioned.

  Even in the conductive spherical particles in which the conductive fine particles obtained by various methods as described above are dispersed, mechanically mixed with the conductive fine particles having a particle diameter smaller than the above-described core particles at an appropriate blending ratio, After the conductive fine particles are uniformly adhered around the conductive spherical particles by the action of van der Waals force and electrostatic force, for example, the local temperature rise caused by applying a mechanical impact force causes the conductive spherical particles to The surface may be softened, conductive fine particles may be formed on the surface, and the conductivity may be further increased.

  In the present invention, the number average particle size was measured by attaching a 100 μm aperture (50 μm aperture for particles of 3.0 μm or less) to Multisizer II type (manufactured by Coulter). The conductive particles were measured by attaching a liquid module to a particle size distribution analyzer LS-130 (manufactured by Coulter).

Examples of the material that is added to the resin layer constituting the surface of the developer carrying member of the present invention and imparts conductivity include generally known conductive fine powders. For example, powders of metals or alloys such as copper, nickel, silver and aluminum, metal oxides such as antimony oxide, indium oxide, tin oxide and titanium oxide, carbon-based conductive fine particles such as carbon fiber, carbon black and graphite. A powder etc. are mentioned. The amount of conductive fine powder added varies depending on the development system. For example, when a one-component insulating developer is used in the jumping development method, the volume resistance value of the conductive resin layer is 10 ³ Ω · cm. It is preferable to add so that it may become the following. Carbon black, especially conductive amorphous carbon, is particularly excellent in electrical conductivity, and can be given conductivity by adding a small amount compared to other substances. It is preferable because it can be obtained.

  Next, the developer carried on the surface of the developer carrying member of the present invention having the above-described configuration will be described. The toner constituting the developer is mainly colored with a uniform particle size distribution by melting and kneading a binder resin, a release agent, a charge control agent, a colorant and the like, solidifying and then pulverizing, and then classifying and the like. It is a resin fine powder. As the binder resin used for the toner, generally known resins can be used. For example, styrene such as styrene, α-methylstyrene, p-chlorostyrene, and substituted homopolymers thereof; styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-ethyl acrylate copolymer, styrene -Butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-dimethylaminoethyl copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer Polymer, styrene-dimethylaminoethyl methacrylate copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-maleic acid Copolymer, styrene-maleic acid ester Copolymers such as styrene copolymers; polymethyl methacrylate, polybutyl methacrylate, polyvinyl acetate, polyethylene, polypropylene polyvinyl butyral, polyacrylic acid resin, rosin, modified rosin, temper resin, phenol resin, aliphatic or fat Cyclic hydrocarbon resins and aromatic petroleum resins can be used alone or in combination.

  The toner can contain the pigments listed above as a colorant. For example, carbon black, nigrosine dye, lamp black, Sudan Black SM, First Yellow G, Benzidine Yellow, Pigment Yellow, India First Orange, Irgadin Red, Paranitroaniline Red, Toluidine Red, Carmine FB, Permanent Bordeaux FRR, Pigment Orange R, Risor Red 2G, Lake Red C, Rhodamine FB, Rhodamine B Lake, Methyl Bio Red B Lake, Phthalocyanine Blue, Pigment Blue, Brilliant Green B, Phthalocyanine Green, Oil Yellow GG, Pomelo First Yellow CGG, Kaya Set Y963, Kaya Set YG, Pomelo First Orange RR, Oil Scarlet, Orazole Bra Down B, it is possible to use a Zapon Fast Scarlet CG, and Oil Pink OP or the like.

  In order to obtain a magnetic toner, the toner may contain magnetic powder. As such magnetic powder, a substance that is magnetized in a magnetic field is used, for example, a powder of ferromagnetic metal such as iron, cobalt and nickel, or an alloy or compound such as magnetite, hematite and ferrite. Is mentioned. The content of these magnetic powders is preferably 15 to 70% by weight with respect to the toner weight.

  In addition, the toner can contain waxes for the purpose of improving the releasability during fixing and improving the fixing property. Examples of such waxes include paraffin wax and derivatives thereof, microcrystalline wax and derivatives thereof, Fischer-Tropsch wax and derivatives thereof, polyolefin wax and derivatives thereof, carnauba wax and derivatives thereof, and the like. Here, the derivatives include oxides, block copolymers with vinyl monomers, and graft modified products. In addition, alcohols, fatty acids, acid amides, esters, ketones, hydrogenated castor oil and derivatives thereof, plant waxes, animal waxes, mineral waxes, petrolactams and the like can also be used.

  Further, if necessary, a charge control agent may be contained in the toner. Charge control agents include negative charge control agents and positive charge control agents. Materials that control the toner to be negatively charged include the following substances. For example, organometallic complexes and chelate compounds are effective, and there are monoazo metal complexes, acetylacetone metal complexes, aromatic hydroxycarboxylic acid and aromatic dicarboxylic acid metal complexes. Other examples include aromatic hydroxycarboxylic acids, aromatic mono- and polycarboxylic acids and their metal salts, anhydrides, esters, and phenol derivatives such as bisphenol.

  Examples of substances for positively charging the toner include the following. For example, modified products with nigrosine and fatty acid metal salts, quaternary ammonium salts such as tributylbenzylammonium-1-hydroxy-4-naphthosulfonate, tetrabutylammonium tetrafluoroborate, and phosphonium salts that are analogs thereof Onium salts of these and lake pigments thereof (for example, phosphotungstic acid, phosphomolybdic acid, phosphotungstic molybdic acid, tannic acid, lauric acid, gallic acid, ferricyanide and ferrocyanide) Metal salts; Diorganotin oxides such as dibutyltin oxide, dioctyltin oxide and dicyclohexyltin oxide; Diorganotin volleys such as dibutyltin borate, dioctyltin borate and dicyclohexyltin borate S; guanidine compounds and imidazole compounds.

  If necessary, the toner may be externally added with a powder such as an inorganic fine powder for the purpose of improving fluidity. Examples of such fine powder include silica fine powder, metal oxide such as alumina, titania, germanium oxide and zirconium oxide; carbide such as silicon carbide and titanium carbide; inorganic such as nitride such as silicon nitride and germanium nitride. Fine powder can be used. Further, these fine powders can be used after being organically treated with an organosilicon compound, a titanium coupling agent or the like. Examples of the organic silicon compound that can be used in this case include hexamethyldisilazane, trimethylsilane, trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, and allylphenyldichlorosilane. , Benzyldimethylchlorosilane, bromomethyldimethylchlorosilane, α-chloroethyltrichlorosilane, β-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane, triorganosilylmercaptan, trimethylsilylmercaptan, triorganosilylacrylate, vinyldimethylacetoxysilane, Dimethylethoxysilane, dimethyldimethoxysilane, diphenyldiethoxysilane, hexamethyldisiloxane, 1,3-divinyl Rutetramethyldisiloxane, 1,3-diphenyltetramethyldisiloxane, and 2-12 siloxane units per molecule, each containing a hydroxyl group bonded to one Si at each terminal unit Dimethylpolysiloxane can be used.

  Moreover, you may use what processed the untreated fine powder with the nitrogen-containing silane coupling agent. In particular, it is suitable for a positive toner. Examples of such treating agents include aminopropyltrimethoxysilane, aminopropyltriethoxysilane, dimethylaminopropyltrimethoxysilane, diethylaminopropyltrimethoxysilane, dipropylaminopropyltrimethoxysilane, dibutylaminopropyltrimethoxysilane, Monobutylaminopropyltrimethoxysilane, dioctylaminopropyltrimethoxysilane, dibutylaminopropyldimethoxysilane, dibutylaminopropylmonomethoxysilane, dimethylaminophenyltrimethoxysilane, trimethoxysilyl-γ-propylphenylamine, trimethoxysilyl-γ -Propylbenzylamine, trimethoxysilyl-γ-propylpiperidine, trimethoxysilyl-γ-propylmorpholine and Methoxysilyl -γ- propyl imidazole, and the like.

  Examples of methods for treating inorganic fine powder with various silane coupling agents as mentioned above include 1) spray method, 2) organic solvent method, and 3) aqueous solution method. The treatment by the spray method is generally a method of stirring the pigment, spraying an aqueous solution or solvent solution of the coupling agent, and then removing and drying the water or solvent at about 120 to 130 ° C. The treatment by the organic solvent method is a method in which a coupling agent is dissolved in an organic solvent (for example, alcohol, benzene or halogenated hydrocarbon) containing a hydrolysis catalyst together with a small amount of water, and a pigment is immersed therein. Then, solid-liquid separation is performed by filtration or squeezing and dried at about 120 to 130 ° C. In the aqueous solution method, a coupling agent of about 0.5% is hydrolyzed in water or water-organic solvent at a constant pH, and after pigment is immersed therein, solid-liquid separation is similarly performed and dried. Is.

As another organic processing method, it is also possible to use fine powder treated with silicone oil. Preferred silicone oils that can be used at this time include those having a viscosity at 25 ° C. of about 0.5 to 10,000 mm ² / s, preferably 1 to 1,000 mm ² / s. Such as, for example, methyl hydrogen silicone oil, dimethyl silicone oil, phenyl methyl silicone oil, chlorophenyl methyl silicone oil, alkyl modified silicone oil, fatty acid modified silicone oil, polyoxyalkylene modified silicone oil and fluorine modified silicone. An oil etc. are mentioned. Moreover, you may use the silicone oil which has a nitrogen atom in a side chain.

  In particular, in the case of a positive toner, it is preferable to use one that has been organically treated with silicone oil. The treatment with silicone oil can be performed, for example, as follows. If necessary, the pigment is vigorously agitated while heating, and sprayed or vaporized with the silicone oil or its solution as mentioned above, or the pigment is made into a slurry and stirred. However, it can be easily treated by a method of dripping silicone oil or a solution thereof. These silicone oils are used alone, in a mixture of two or more, or in combination or in multiple treatments. Moreover, you may use together with the process by a silane coupling agent.

  Furthermore, it is more preferable that the toner formed as described above is subjected to spheroidizing treatment or surface smoothening treatment by various methods because transferability is improved. As a method of spheroidizing treatment or surface smoothing treatment, an apparatus having a stirring blade or a blade and a liner or a casing or the like is used, for example, when a toner is passed through a minute gap between the blade and the liner. There are a method of smoothing the surface by force or spheroidizing the toner, a method of spheroidizing by suspending the toner in warm water, a method of spheroidizing by exposing the toner to a hot air current, and the like.

  In addition, as a method for producing a spherical toner, for example, there is a method in which a mixture containing a monomer as a raw material for a toner binder resin is suspended in water and polymerized to form a toner. As a general method, for example, a polymerizable monomer, a colorant, a polymerization initiator, and, if necessary, a crosslinking agent, a charge control agent, a release agent and other additives are uniformly dissolved or dispersed. Then, the polymerizable monomer composition is dispersed in an appropriate particle size using a suitable stirrer in a continuous layer containing a dispersion stabilizer, for example, an aqueous phase. Further, there is a method of obtaining a toner comprising toner particles having a desired particle diameter by performing a polymerization reaction.

  Next, an example of the developing device of the present invention constituted by incorporating the developer carrying member of the present invention capable of exhibiting the excellent effects as described above will be described with reference to the drawings. FIG. 1 is a schematic diagram showing an example of the developing device of the present invention. In FIG. 1, an electrostatic latent image carrier, for example, an electrophotographic photosensitive drum 7 that carries an electrostatic latent image formed by a known process is rotated in the direction of arrow B. The developing sleeve 14 as a developer carrying member carries, for example, a magnetic toner 10 which is supplied by the hopper 9 and is, for example, a one-component magnetic developer, and rotates in the direction of arrow A. The magnetic toner 10 is transported to the developing section D (developing area) facing 7. A magnet 11 for magnetically attracting and holding the magnetic toner 10 on the developing sleeve 14 is disposed in the developing sleeve 14. The magnetic toner 10 carried on the developing sleeve 14 obtains a triboelectric charge that enables the electrostatic latent image on the photosensitive drum 7 to be developed by friction with the developing sleeve 14.

  Further, in the developing device illustrated in FIG. 1, in order to regulate the layer thickness of the magnetic toner 10 conveyed to the developing unit D, a regulating blade 8 that is a developer layer thickness regulating member made of a ferromagnetic metal is provided with a hopper. 9 from the surface of the developing sleeve 14 so as to face the developing sleeve 14 with a gap width of about 200 to 300 μm. As a result, the magnetic lines of force from the magnetic pole N 1 of the magnet 11 in the developing sleeve 14 concentrate on the blade 8, whereby a thin layer of the magnetic toner 10 is formed on the developing sleeve 14. As the blade 8, a nonmagnetic blade can be used.

  In the present invention, the thickness of the thin layer of the magnetic toner 10 formed on the developing sleeve 14 as described above is thinner than the minimum gap between the developing sleeve 14 and the photosensitive drum 7 in the developing portion D. It is preferable. The present invention is particularly effective for a developing device that develops an electrostatic latent image with such a thin toner layer, that is, a non-contact developing device. However, of course, in the developing unit, the developer carrying member of the present invention is also applied to a developing device in which the thickness of the toner layer is equal to or greater than the minimum gap between the developing sleeve 14 and the photosensitive drum 7, that is, a contact type developing device. Can be applied. Hereinafter, in order to avoid complicated explanation, a non-contact type developing device will be described in more detail as an example.

  In the developing sleeve 14 having the above-described configuration suitable for the present invention, a developing bias voltage is applied by the power source 15 in order to fly the magnetic toner 10 carried on the surface thereof. In the present invention, when a DC voltage is used as the developing bias voltage, a value between the potential of the image portion of the electrostatic latent image (the region visualized by the adhesion of the magnetic toner 10) and the potential of the background portion. Is preferably applied to the developing sleeve 14. On the other hand, in order to increase the density of the developed image or improve the gradation, an alternating bias voltage may be applied to the developing sleeve 14 to form an oscillating electric field whose direction is alternately reversed in the developing portion D. In this case, it is preferable to apply to the developing sleeve 14 an alternating bias voltage in which a DC voltage component having a value between the image portion potential and the background portion potential is superimposed.

  In the so-called regular development in which toner is attached to a high potential portion of an electrostatic latent image having a high potential portion and a low potential portion for visualization, toner charged to a polarity opposite to that of the electrostatic latent image is used. On the other hand, in the so-called reversal development in which the toner is made visible by attaching the toner to the low potential portion of the electrostatic latent image, it is preferable to use the toner charged with the same polarity as the polarity of the electrostatic latent image. The high potential and the low potential are expressed by absolute values. In any case, the magnetic toner 10 is charged to a polarity for developing the electrostatic latent image by friction with the developing sleeve 14. Silica externally added to the magnetic toner 10 is also charged by friction with the developing sleeve 14.

  Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. First, PHA used in Examples and Comparative Examples was produced by the following method.

  First, the manufacturing method which has the microbe production process of the polyhydroxyalkanoate in this invention, and a subsequent chemical treatment process is shown below (preparation example AC).

(Preparation Example A-1)
As 0.5% polypeptone (Wako Pure Chemical Industries), 6 mmol / L 5-phenylvaleric acid, and ω- (4-vinylphenyl) alkanoic acid, 5- (4-vinylphenyl) valeric acid 1.5 mmol / L Was dissolved in 1000 mL of the M9 medium, placed in a 2000 mL shake flask and sterilized by autoclave, and then cooled to room temperature. To the prepared medium, 2 mL of a culture solution of Pseudomonas chicoryai YN2 strain previously cultured in an M9 medium containing 0.5% polypeptone at 30 ° C. for 8 hours was added and cultured at 30 ° C. for 64 hours. After cultivation, the cells were collected by centrifugation, washed with methanol, and dried. After weighing the dry cells, chloroform was added and the polymer was extracted by stirring at 35 ° C. for 88 hours. The chloroform from which the polymer was extracted was filtered and concentrated with an evaporator, and then the precipitated and solidified portion was collected with cold methanol and dried under reduced pressure to obtain the desired polymer.

The structure of the obtained polymer was determined by ¹ H-NMR (FT-NMR: Bruker DPX400; ¹ H resonance frequency: 400 MHz; measurement nuclide: ¹ H; solvent used: CDCl ₃ ; measurement temperature: room temperature). As a result, the following formula (34):

It was confirmed that it was a polyhydroxyalkanoate copolymer containing the units shown in (1) at a content ratio (mol%) A: B = 80: 20.

The molecular weight of the polymer was measured by gel permeation chromatography (GPC) (Tosoh HLC-8220 GPC, column: Tosoh TSK-GEL Super HM-H, solvent: chloroform, polystyrene conversion). The weight (PDW) of the obtained polymer was 0.44 g / L, the number average molecular weight M _n of the obtained polymer was 86000, and the weight average molecular weight M _w was 242,000.

(Preparation Example A-2)
1.0017 g of polyester containing 20 mol% of 3-hydroxy-ω- (4-vinylphenyl) valeric acid unit obtained in Preparation Example A-1 in a 200 mL flask, 0.8710 g of 18-crown-6-ether, 60.000 dichloromethane. 0 mL and 10 ml of acetic acid were added and stirred. The flask was placed in an ice bath and the reaction system was brought to 0 ° C. After 45 minutes, 0.6932 g of potassium permanganate was added and stirred for 15 hours. After completion of the reaction, 5% aqueous sodium hydrogen sulfite solution was added and stirred, and the liquidity was adjusted to pH = 1 with 1.0 N hydrochloric acid. After distilling off dichloromethane in the mixed solution with an evaporator, the polymer in the solution was recovered. Further, the washing was repeated twice with 100 ml of pure water, and then washed with 100 ml of methanol to recover the polymer. 0.8053g of target PHA was obtained by drying under reduced pressure.

The structure of the obtained polymer was determined by ¹ H-NMR (FT-NMR: Bruker DPX400; resonance frequency: 400 MHz; measurement nuclide: ¹ H; solvent used: CDCl ₃ ; measurement temperature: room temperature), Fourier transform-infrared absorption Analysis was performed by (FT-IR) spectrum (Nicolet AVATAR360FT-IR). As a result of IR measurement, absorption derived from a carboxylic acid was newly observed at 1693 cm ⁻¹ , and thus the obtained PHA was found to have a 3-hydroxy-ω- (4-carboxyphenyl) valeric acid unit. .

  Furthermore, in order to calculate the ratio of the obtained PHA unit, the calculation was performed by methyl esterifying the carboxyl group at the side chain end of PHA using trimethylsilyldiazomethane.

  The target product, PHA 18.7 mg, was added to a 100 ml eggplant flask, and chloroform 1.4 ml and methanol 0.35 ml were added and dissolved. To this was added 0.4 ml of a 2.0 mol / L trimethylsilyldiazomethane-hexane solution, and the mixture was stirred at room temperature for 30 minutes. After completion of the reaction, the solvent was removed by an evaporator, and then the polymer was recovered. The polymer was recovered after washing with 50 ml of methanol. By drying under reduced pressure, 8.9 mg of PHA was obtained.

  NMR analysis was performed using the same method as described above. As a result, the following formula (35):

It was confirmed that it was a polyhydroxyalkanoate copolymer containing the units shown in (5) in a content ratio (mol%) A: B = 83: 17.

The average molecular weight of PHA obtained by methyl esterification of the carboxyl group at the side chain end of PHA using trimethylsilyldiazomethane was determined by gel permeation chromatography (GPC; Tosoh, Column; Tosoh PLgel 5μ MIXED-C). , Solvent: DMF / LiBr 0.1% (w / v), polystyrene conversion). As a result, the number average molecular weight M _n = 61000 and the weight average molecular weight M _w = 82000.

(Preparation Example A-3)
Under a nitrogen atmosphere, 0.2007 g of a polymer containing 17 mol% of 3-hydroxy-ω- (4-carboxyphenyl) valeric acid unit obtained in Preparation Example A-2 and 54.7 mg of p-toluidine-2-sulfonic acid were added. After putting into a 50 ml two-necked flask and adding 10 ml of pyridine and stirring, 0.08 ml of triphenyl phosphite was added and heated at 100 ° C. for 6 hours. After completion of the reaction, it was reprecipitated in 250 ml of ethanol and collected by centrifugation. The obtained polymer was washed by stirring in water for 3 days, further washed with 1N hydrochloric acid for 1 day, and then dried under reduced pressure for 1 day.

The structure of the obtained polymer was determined by ¹ H-NMR (FT-NMR: Bruker DPX400; resonance frequency: 400 MHz; measurement nuclide: ¹ H; solvent used: heavy DMSO; measurement temperature: room temperature), Fourier transform-infrared absorption Analysis was performed by (FT-IR) spectrum (Nicolet AVATAR360FT-IR). As a result of the IR measurement, the peak at 1693 cm ⁻¹ derived from carboxylic acid decreased, and a new peak derived from the amide group was observed at 1668 cm ⁻¹ .

Next, from the result of ¹ H-NMR of the obtained polymer, the peak derived from the methyl group of p-toluidine-2-sulfonic acid structure is shifted from the peak of the methyl group of p-toluidine-2-sulfonic acid. Therefore, the obtained PHA has the following formula (36):

It was confirmed that it was a polyhydroxyalkanoate copolymer containing 13 mol% of the unit shown in FIG.

The average molecular weight of the obtained PHA was evaluated by gel permeation chromatography (GPC; Tosoh, column; Tosoh PLgel 5μ MIXED-C, solvent; DMF / LiBr 0.1% (w / v), polystyrene conversion). did. As a result, the number average molecular weight M _n = 18000 and the weight average molecular weight M _w = 38000.

(Preparation Example A-4)
0.1005 g of the polymer obtained in Preparation Example A-3 containing 13 mol% of the unit represented by chemical formula (36) is added to a 50 ml eggplant flask, and 7 ml of chloroform and 1.8 ml of methanol are added to dissolve it. Cooled down. To this was added 2.7 ml of a 2 mol / L trimethylsilyldiazomethane-hexane solution (manufactured by Aldrich), and the mixture was stirred for 4 hours. After completion of the reaction, the solvent was removed by an evaporator, and then the polymer was recovered.

  Further, 7 ml of chloroform and 1.8 ml of methanol were added to redissolve the polymer, and the solvent was distilled off with an evaporator. This operation was repeated three times, and 0.0845 g of PHA was obtained by drying under reduced pressure.

The structure of the obtained polymer was determined by ¹ H-NMR (FT-NMR: Bruker DPX400; resonance frequency: 400 MHz; measurement nuclide: ¹ H; solvent used: heavy DMSO; measurement temperature: room temperature). ^From the result of ¹ H-NMR, since a peak derived from methyl sulfonate is observed at 3 to 4 ppm, the obtained PHA has the following formula (37):

It was confirmed that it was a polyhydroxyalkanoate copolymer containing 11 mol% of the units shown in FIG.

  In addition, the acid value titration using the potentiometric titrator AT510 (manufactured by Kyoto Electronics Co., Ltd.) revealed that the sulfonic acid was methyl sulfonate because no peak derived from sulfonic acid was observed. .

The average molecular weight of the obtained PHA was evaluated by gel permeation chromatography (GPC; Tosoh, column; Tosoh PLgel 5μ MIXED-C, solvent; DMF / LiBr 0.1% (w / v), polystyrene conversion). did. As a result, the number average molecular weight M _n = 17000 and the weight average molecular weight M _w = 36000.

  The preparation method was scaled up, and this compound was used as a copolymer (a).

(Preparation Example B-1)
3-hydroxy-ω- (4-vinylphenyl) was prepared in exactly the same manner as Preparation Example A-1, except that 1.5 mmol / L of 5- (4-vinylphenyl) valeric acid was changed to 0.75 mmol / L. ) 2999 mg of polyhydroxyalkanoate containing 9 mol% of valeric acid unit and 91 mol% of 3-hydroxy-5-phenylvaleric acid unit was obtained.

(Preparation Example B-2)
The polyhydroxyalkanoate synthesized in Preparation Example B-1 was converted into 3-hydroxy-ω- (4-carboxyphenyl) valeric acid unit 7 mol% and 3-hydroxy-5 using the same method as Preparation Example A-2. -2990 mg of polyhydroxyalkanoates containing 93 mol% of phenylvaleric acid units were obtained.

(Preparation Example B-3)
Under a nitrogen atmosphere, 1.5002 g of a polymer containing 7 mol% of 3-hydroxy-ω- (4-carboxyphenyl) valeric acid unit obtained in Preparation Example B-2, 2-amino-2-methylpropanesulfonic acid 448. 6 mg was put into a 100 ml three-necked flask, 56.5 ml of pyridine was added and stirred, 1.53 ml of triphenyl phosphite was added, and the mixture was heated at 100 ° C. for 6 hours.

  After completion of the reaction, it was reprecipitated in 565 ml of ethanol and collected by filtration. The obtained polymer was washed by stirring in 565 ml of pure water for 5.5 hours. The polymer was collected by filtration, dried under reduced pressure, dissolved in 150 ml of THF, and mixed and stirred with 150 ml of 1N hydrochloric acid. After 14 hours, THF in the mixed solution was distilled off by an evaporator, and then the polymer in the solution was recovered.

The structure of the obtained polymer was determined by ¹ H-NMR (FT-NMR: Bruker DPX400; resonance frequency: 400 MHz; measurement nuclide: ¹ H; solvent used: heavy DMSO; measurement temperature: room temperature), Fourier transform-infrared absorption Analysis was performed by (FT-IR) spectrum (Nicolet AVATAR360FT-IR).

As a result of the IR measurement, the peak at 1693 cm ⁻¹ derived from carboxylic acid decreased, and a new peak derived from the amide group was observed at 1669 cm ⁻¹ . In addition, from the result of ¹ H-NMR of the obtained polymer, the introduction of 2-amino-2-methylpropanesulfonic acid shifts the peak at 1.46 ppm derived from the methyl group. Following formula (58):

It was confirmed that this was a polyhydroxyalkanoate copolymer containing 7 mol% of the units shown in FIG.

The average molecular weight of the obtained PHA was determined by gel permeation chromatography (GPC; Tosoh, column; Polymer Laboratories PLgel 5μ MIXED-C, solvent; DMF / LiBr 0.1% (w / v), polystyrene conversion). evaluated. As a result, the number average molecular weight M _n = 21,000 and the weight average molecular weight M _w = 33000.

  The preparation method was scaled up, and this compound was used as a copolymer (b).

(Preparation Example C-1)
As 0.5% polypeptone (Wako Pure Chemical Industries), 6 mmol / L 5-phenylvaleric acid, and ω- (4-vinylphenyl) alkanoic acid, 5- (4-vinylphenyl) valeric acid 0.5 mmol / L Was dissolved in 1000 mL of the M9 medium, placed in a 2000 mL shake flask and sterilized by autoclave, and then cooled to room temperature. To the prepared medium, 2 mL of a Pseudomonas chicory eye strain YN2 cultured in advance in a M9 medium containing 0.5% polypeptone at 30 ° C. for 8 hours was added and cultured at 30 ° C. for 40 hours. After cultivation, the cells were collected by centrifugation, washed with methanol, and dried. After weighing the dried cells, chloroform was added and the polymer was extracted by stirring at 35 ° C. for 15 hours. The chloroform from which the polymer was extracted was filtered and concentrated with an evaporator, and then the precipitated and solidified portion was collected with cold methanol and dried under reduced pressure to obtain the desired polymer.

The structure of the obtained polymer was determined by ¹ H-NMR (FT-NMR: Bruker DPX400; ¹ H resonance frequency: 400 MHz; measurement nuclide: ¹ H; solvent used: CDCl ₃ ; measurement temperature: room temperature).

  As a result, the following formula (45):

It was confirmed that it was a polyhydroxyalkanoate copolymer containing the unit shown in (4) in a content ratio (mol%) A: B = 94: 6.

  The molecular weight of the polymer was measured by gel permeation chromatography (GPC) (Tosoh HLC-8220 GPC, column: Tosoh TSK-GEL Super HM-H, solvent: chloroform, polystyrene conversion).

The weight (PDW) of the obtained polymer was 0.56 g / L, the number average molecular weight M _n of the obtained polymer was 61000, and the weight average molecular weight M _w was 197000.

(Preparation Example C-2)
3.3006 g of polyester containing 6 mol% of 3-hydroxy-ω- (4-vinylphenyl) valeric acid unit obtained in Preparation Example C-1 in a 500 mL flask, 0.8824 g of 18-crown-6-ether, 200 mL of dichloromethane, 33 ml of acetic acid was added and stirred. The flask was placed in an ice bath and the reaction system was brought to 0 ° C. After 120 minutes, 0.7061 g of potassium permanganate was added and stirred for 15 hours. After completion of the reaction, 4.044 g of sodium bisulfite was added and stirred, and the liquidity was adjusted to pH = 1 with 1.0 N hydrochloric acid. After distilling off dichloromethane in the mixed solution with an evaporator, the polymer in the solution was recovered. The polymer obtained here was washed with 450 ml of pure water and then washed with 300 ml of methanol. Furthermore, after washing twice with 300 ml of pure water and once with 100 ml of methanol, the polymer was recovered. By drying under reduced pressure, 2.9168 g of the intended PHA was obtained.

The structure of the obtained polymer was determined by ¹ H-NMR (FT-NMR: Bruker DPX400; resonance frequency: 400 MHz; measurement nuclide: ¹ H; solvent used: CDCl ₃ ; measurement temperature: room temperature), Fourier transform-infrared absorption Analysis was performed by (FT-IR) spectrum (Nicolet AVATAR360FT-IR). As a result, absorption derived from carboxylic acid was newly observed at 1693 cm ⁻¹ , and thus the obtained PHA was found to have a 3-hydroxy-ω- (4-carboxyphenyl) valeric acid unit.

  Further, in order to calculate the ratio of the obtained PHA unit, calculation was performed by methyl esterifying the carboxyl group at the side chain end of PHA using trimethylsilyldiazomethane in the same manner as in Preparation Example A-2. It was.

  As a result, the following formula (46):

It was confirmed that it was a polyhydroxyalkanoate copolymer containing the unit shown in (5) in a content ratio (mol%) A: B = 95: 5.

The average molecular weight of PHA obtained by methyl esterification of the carboxyl group at the side chain end of PHA using trimethylsilyldiazomethane was determined by gel permeation chromatography (GPC; Tosoh, Column; Tosoh PLgel 5μ MIXED-C). , Solvent: DMF / LiBr 0.1% (w / v), polystyrene conversion). As a result, the number average molecular weight M _n = 65000 and the weight average molecular weight M _w = 88000.

(Preparation Example C-3)
Under a nitrogen atmosphere, 1.3013 g of a polymer containing 5 mol% of 3-hydroxy-ω- (4-carboxyphenyl) valeric acid unit obtained in Preparation Example C-2, 401.9 mg of 2-amino-1-naphthalenesulfonic acid Was placed in a 100 ml three-necked flask, 50 ml of pyridine was added and stirred, 0.94 ml of triphenyl phosphite was added, and the mixture was heated at 100 ° C. for 6 hours. After completion of the reaction, it was reprecipitated in 500 ml of ethanol and collected by centrifugation. The obtained polymer was washed by stirring in 250 ml of pure water for 2 hours, and the polymer was collected by filtration, dried under reduced pressure, dissolved in 130 ml of THF, and mixed and stirred with 130 ml of 1N hydrochloric acid. After 14 hours, THF in the mixed solution was distilled off by an evaporator, and then the polymer in the solution was recovered. The polymer obtained here was washed three times with 100 ml of pure water and then dried under reduced pressure to obtain 1.0059 g of the intended PHA.

The structure of the obtained polymer was determined by ¹ H-NMR (FT-NMR: Bruker DPX400; resonance frequency: 400 MHz; measurement nuclide: ¹ H; solvent used: heavy DMSO; measurement temperature: room temperature), Fourier transform-infrared absorption Analysis was performed by (FT-IR) spectrum (Nicolet AVATAR360FT-IR).

As a result of the IR measurement, the peak at 1693 cm ⁻¹ derived from carboxylic acid decreased, and a new peak derived from the amide group was observed at 1669 cm ⁻¹ . Moreover, from the result of ¹ H-NMR of the obtained polymer, the following formula (47):

It was confirmed that this was a polyhydroxyalkanoate copolymer containing 4 mol% of the units shown in FIG.

The average molecular weight of the obtained PHA was evaluated by gel permeation chromatography (GPC; Tosoh, column; Tosoh PLgel 5μ MIXED-C, solvent; DMF / LiBr 0.1% (w / v), polystyrene conversion). did. As a result, the number average molecular weight _Mn = 22000 and the weight average molecular weight _Mw = 32000.

  The preparation method was scaled up, and this compound was used as a copolymer (c).

<Example 1>
-1 part by weight of carbon black-9 parts by weight of crystalline graphite-25 parts by weight of copolymer (a)-65 parts by weight of toluene Add zirconia beads having a diameter of 1 mm to the above materials as media particles and disperse in a sand mill for 2 hours. The beads were separated using a sieve to obtain a coating solution. Using this coating solution, a coating layer is formed on the surface of the developing sleeve of NP-6035 (manufactured by Canon Inc.) by spraying, followed by heating at 150 ° C. for 30 minutes in a hot air drying oven to cure, A developer carrier of this example having a resin layer on the sleeve surface was prepared. Table 1 shows the structure of the resin layer of the obtained developer carrying member. Further, the developer carrier of this example was evaluated by the following methods and standards, and the results are shown in Tables 3 and 4.

In the evaluation, a toner prepared using the following raw materials was used.
-Styrene-acrylic resin (Tg 56 ° C) 100 parts by weight-Magnetite 80 parts by weight-Positive charge control agent 2 parts by weight-Low molecular weight polypropylene 4 parts by weight Weight obtained by melt-kneading, grinding and dispersing the above constituent materials To the positively charged toner having an average particle diameter of 6 μm, 0.9% by weight of colloidal silica coupled with trimethoxysilyl-γ-propylbenzylamine as a positively chargeable external additive was externally added to obtain a positively chargeable toner. Component system magnetic toner A was obtained.

  Using the developer carrying member of this example and the toner A described above, an image was output using Canon NP-6035 in an H / H (high temperature and high humidity) and N / L (normal temperature and low humidity) environment. And tested. The evaluation results under the N / L environment are shown in Table 3, and the evaluation results under the H / H environment are shown in Table 4, respectively.

[Evaluation]
(1) Image density The density of a solid black portion of the obtained image was measured with a reflection densitometer RD918 (manufactured by Macbeth), and the decrease in the image density was evaluated based on the measured value.

(2) Tribo The developer tribo on the developer carrying member was measured by the following suction method. For the measurement of the tribo value by the suction method, first, using a measuring container having a cylindrical filter paper, a metal suction port is attached along the shape of the surface of the developer carrier, and immediately after image formation (preferably within 5 minutes). The suction pressure is adjusted so that the developer layer on the surface of the developer carrying member can be sucked uniformly without excess and deficiency, and the developer is sucked. Then, the charge Q of the developer sucked at this time is measured with a 616 digital electrometer (manufactured by KEITHLEY), and the tribo value is obtained by calculating with Q / M (mC / kg) where M is the mass.

(3) Reversal fog Measure the reflectance of the solid white image in the aptitude image, and further measure the reflectance of the unused transfer paper, (the worst value of the reflectance of the solid white image−the reflectance of the unused transfer paper The maximum fog) was set as the reverse fog density, and both images were observed visually, and these were evaluated together according to the following criteria. As the transfer paper, a 127.9 g / m 2 thick paper was used, and the reflectance was measured with TC-6DS (manufactured by Tokyo Denshoku).
A: Reversal fog density is 1.5 or less, and the difference is hardly understood.
○: The reversal fog density is 1.5 to 2.5, and the difference cannot be understood unless carefully observed.
(Triangle | delta): A reversal fog density | concentration is 2.5-3.5, and it becomes possible to recognize fog gradually as the image is printed.
Δ ×: The reverse fog density is 3.5 to 4.0, and the fog can be confirmed at a glance at the practical level lower limit.
X: Reversal fog density is 4.0 to 5.0, which is very bad.

(4) Image defects (streaks, unevenness, blotches)
Check various images such as solid black, halftone, and line images, and visually check the toner coat defects on the sleeve, such as streaks, wavy irregularities, and blotches (spotted irregularities) on the developing sleeve. Observed and evaluated according to the following criteria with reference to the results.
A: Neither image nor sleeve can be confirmed at all.
○: Slightly confirmed on the sleeve, but hardly confirmed on the image.
○ △: About one to several tens of images can be confirmed by looking through the image.
Δ: Confirmed on the first half-tone image or solid black image and on the first round of the sleeve cycle.
(Triangle | delta): It can confirm with a halftone image or a solid black image. Practical level lower limit.
Δ: Image defect can be confirmed in the entire solid black image. Unusable level.
X: It can confirm also on a solid white image.

(5) Abrasion amount of conductive resin layer (film scraping)
After evaluating the image under each environment, the developing sleeve was removed, and the outer diameter was measured with a laser measuring instrument Y-CTF type (manufactured by True Pattern Measurement Development). The amount of abrasion of the conductive resin layer was calculated from this measured value and the measured outer diameter of the developing sleeve before image formation, and the average value of 30 points was taken as the film abrasion (μm).

<Example 2>
In Example 1, a developer carrying member of this example was prepared in the same manner as in Example 1 except that the copolymer (a) was changed to the copolymer (b). Table 1 shows the structure of the resin layer of the obtained developer carrying member. Then, using the developer carrier thus obtained, an image output test was performed while supplying toner A in the same manner as in Example 1, and the results are shown in Tables 3 and 4. It was.

<Example 3>
A developer carrying member of this example was prepared in the same manner as in Example 1, except that the copolymer (a) was changed to the copolymer (c). Table 1 shows the structure of the resin layer of the obtained developer carrying member. Then, using the developer carrier thus obtained, an image output test was performed while supplying toner A in the same manner as in Example 1, and the results are shown in Tables 3 and 4. It was.

<Example 4>
After the same material as in Example 1 was dispersed by the same operation, 5 parts of conductive spherical carbon particles having a number average particle diameter of 5 μm were further added and dispersed over 3 hours using glass beads having a diameter of 3 mm. The beads were separated using a sieve to obtain a coating solution. Next, a resin layer was formed by the same operation as in Example 1 to prepare a developer carrying member of this example. Table 1 shows the structure of the resin layer of the obtained developer carrying member.

Further, using the developer carrier thus obtained, an image output test was conducted while supplying toner A in the same manner as in Example 1, and the results are shown in Tables 3 and 4. Indicated. The conductive spherical carbon particles used in this example had a number average particle diameter of 1. on the surface of 100 parts by weight of a spherical phenol resin having a number average particle diameter of 5.5 μm using a raikai machine (automatic mortar, manufactured by Ishikawa Factory). 14 parts by weight of coal-based bulk mesophase pitch powder of 5 μm or less was uniformly coated, heat-treated in an oxidizing atmosphere, and then calcined at 2,200 ° C. to obtain graphitized. The obtained conductive spherical carbon particles have a number average particle diameter of 5 μm, a true density of 1.50 g / cm ³ , a volume resistance of 7.5 × 10 ⁻² Ω · cm, and a major axis / minor axis ratio of 1.15. Met.

<Example 5>
-1 part by weight of carbon black-9 parts by weight of crystalline graphite-25 parts by weight of PMMA resin-5 parts by weight of copolymer (a)-65 parts by weight of toluene Dispersing was performed in the same manner as in Example 1 using the above materials. Thereafter, a resin layer was formed by the same operation, and a developer carrying member of this example was produced. Table 1 shows the structure of the resin layer of the obtained developer carrying member. Then, using the developer carrier thus obtained, an image output test was performed while supplying toner A in the same manner as in Example 1, and the results are shown in Tables 3 and 4. It was.

<Example 6>
In Example 5, a resin layer was formed in the same manner as in Example 5 except that the copolymer (a) was changed to the copolymer (b) to prepare a developer carrying member of this example. Table 1 shows the structure of the resin layer of the obtained developer carrying member. Then, using the developer carrier thus obtained, an image output test was performed while supplying toner A in the same manner as in Example 1, and the results are shown in Tables 3 and 4. It was.

<Example 7>
In Example 5, a resin layer was formed in the same manner as in Example 5 except that the copolymer (a) was changed to the copolymer (c), and a developer carrier of this example was prepared. Table 1 shows the structure of the resin layer of the obtained developer carrying member. Then, using the developer carrier thus obtained, an image output test was performed while supplying toner A in the same manner as in Example 1, and the results are shown in Tables 3 and 4. It was.

<Example 8>
Using the same material as in Example 5 and dispersing by the same operation, 5 parts of conductive spherical carbon particles having a number average particle diameter of 5 μm were added, and dispersed for 1 hour using glass beads having a diameter of 3 mm, The beads were separated using a sieve to obtain a coating solution. Next, a resin layer was formed by the same operation as in Example 1 to prepare a developer carrying member of this example. Table 1 shows the structure of the resin layer of the obtained developer carrying member.

Then, using the obtained developer carrying member, an image output test was performed while supplying toner A in the same manner as in Example 1, and the results are shown in Tables 3 and 4. Indicated. The conductive spherical carbon particles used in the present example have a number average particle diameter of 1.5 μm or less using 100 parts by weight of a spherical phenol resin having a number average particle diameter of 5.5 μm using a reika machine (automatic mortar, manufactured by Ishikawa Factory). 14 parts by weight of coal-based bulk mesophase pitch powder was uniformly coated, heat-stabilized in an oxidizing atmosphere, and then calcined at 2,200 ° C. to obtain graphitized. The obtained conductive spherical carbon particles had a number average particle diameter of 5 μm, a true density of 1.50 g / cm ³ , a volume resistance of 7.5 × 10 ⁻² Ω · cm, and a major axis / minor axis ratio of 1.15.

<Example 9>
Resin was prepared in the same manner as in Example 8, except that 7.5 parts of conductive spherical carbon particles having a number average particle diameter of 2 μm were added instead of the conductive spherical carbon particles having a number average particle diameter of 5 μm used in Example 8. A layer was formed to prepare a developer carrier of this example. Table 1 shows the structure of the resin layer of the obtained developer carrying member. Then, using the obtained developer carrier, an image image output test was performed while supplying toner A, and the results were shown in Tables 3 and 4. The spherical carbon particles having a number average particle diameter of 2 μm used in this example are prepared by using 100 parts of a spherical phenol resin having a number average particle diameter of 2.3 μm and using a laika machine (automatic mortar, manufactured by Ishikawa Factory). .14 [mu] m or less coal-based bulk mesophase pitch powder was uniformly coated, heat-stabilized in an oxidizing atmosphere, and then calcined at 2,200 [deg.] C. to obtain graphitized. The obtained conductive spherical carbon particles had a true density of 1.52 g / cm ³ , a volume resistance of 7.2 × 10 ⁻² Ω · cm, and a major axis / minor axis ratio of 1.12.

<Example 10>
In place of the conductive spherical carbon particles having a number average particle size of 5 μm used in Example 8, 2.5 parts of conductive spherical carbon particles having a number average particle size of 20 μm were added. A layer was formed to prepare a developer carrier of this example. Table 1 shows the structure of the resin layer of the obtained developer carrying member. Then, using the obtained developer carrier, an image image output test was performed while supplying toner A, and the results were shown in Tables 3 and 4. This spherical carbon particle having a number average particle diameter of 20 μm is obtained by using a kaikai machine (automatic mortar, manufactured by Ishikawa Factory) on 100 parts of a spherical phenol resin having a number average particle diameter of 24 μm, and a coal-based bulk mesophase pitch having a number average particle diameter of 3 μm or less. 14 parts of the powder was uniformly coated, heat-stabilized in an oxidizing atmosphere, and then fired at 2,200 ° C. to graphitize. The obtained conductive spherical carbon particles had a true density of 1.45 g / cm ³ , a volume resistance of 9.6 × 10 ⁻² Ω · cm, and a major axis / minor axis ratio of 1.18.

<Example 11>
A resin layer was formed in the same manner as in Example 8 except that carbon black-coated PMMA particles having a number average particle size of 5 μm were used instead of the conductive spherical carbon particles having a number average particle size of 5 μm used in Example 8. A developer carrier of this example was prepared. Table 1 shows the structure of the resin layer of the obtained developer carrying member. Then, using the obtained developer carrier, an image image output test was performed while supplying toner A, and the results were shown in Tables 3 and 4. The carbon black-coated PMMA particles having a number average particle size of 5 μm used were obtained by coating 5 parts of conductive carbon black with a hybridizer (manufactured by Nara Machinery Co., Ltd.) on 100 parts of spherical PMMA particles having a number average particle diameter of 4.8 μm. The obtained conductive spherical PMMA particles had a true density of 1.20 g / cm ³ , a volume resistance of 6.8 × 10 ⁻¹ Ω · cm, and a major axis / minor axis ratio of 1.06.

<Example 12>
A resin layer is formed in the same manner as in Example 8 except that carbon black-dispersed resin particles having a number average particle diameter of 5 μm are used instead of the conductive spherical carbon particles having a number average particle diameter of 5 μm used in Example 8. Thus, a developer carrier of this example was prepared. Table 1 shows the structure of the resin layer of the obtained developer carrying member. Then, using the obtained developer carrier, an image image output test was performed while supplying toner A, and the results were shown in Tables 3 and 4. The carbon black resin particles having a number average particle diameter of 5 μm used were kneaded, pulverized, and classified using the following materials to obtain conductive resin particles having a number average particle diameter of 5.3 μm, and then a hybridizer ( It was obtained by carrying out a spheroidizing process using Nara Machinery Co., Ltd. The obtained conductive spherical carbon particles had a true density of 1.21 g / cm ³ , a volume resistance of 5.2 Ω · cm, and a major axis / minor axis ratio of 1.20.
Styrene-dimethylaminoethyl methacrylate-divinylbenzene copolymer (copolymerization ratio = 90: 10: 0.05) 100 parts by weight Carbon black 25 parts by weight

<Example 13>
A resin layer was formed in the same manner as in Example 8 except that PMMA particles having a number average particle diameter of 5 μm were used instead of the conductive spherical carbon particles having a number average particle diameter of 5 μm used in Example 8. An example developer carrier was prepared. Table 1 shows the structure of the resin layer of the obtained developer carrying member. Then, using the obtained developer carrying member, an image output test was performed while supplying toner A in the same manner as in Example 1, and the results are shown in Tables 3 and 4. Indicated.

<Example 14>
A resin layer was formed in the same manner as in Example 8 except that a silicone resin was used instead of the PMMA resin used in Example 8, and a developer carrier of this example was prepared. Table 1 shows the structure of the resin layer of the obtained developer carrying member. Then, using the obtained developer carrying member, an image output test was performed while supplying toner A in the same manner as in Example 1, and the results are shown in Tables 3 and 4. Indicated.

<Example 15>
A resin layer was formed in the same manner as in Example 8 except that a styrene-acrylic resin was used instead of the PMMA resin used in Example 8, and a developer carrier of this example was prepared. Table 1 shows the structure of the resin layer of the obtained developer carrying member. Then, using the obtained developer carrying member, an image output test was performed while supplying toner A in the same manner as in Example 1, and the results are shown in Tables 3 and 4. Indicated.

<Example 16>
A resin layer was formed in the same manner as in Example 8 except that a polyester resin was used instead of the PMMA resin used in Example 8, and a developer carrier of this example was prepared. Table 1 shows the structure of the resin layer of the obtained developer carrying member. Then, using the obtained developer carrying member, an image output test was performed while supplying toner A in the same manner as in Example 1, and the results are shown in Tables 3 and 4. Indicated.

<Comparative Example 1>
In Example 1, the developer carrying of this comparative example was carried out in the same manner as in Example 1 except that the resin layer was not formed but the glass beads having a particle size of # 300 were used and the FGB sleeve in which the substrate surface was sandblasted was used. Created the body. Table 2 shows the structure of the resin layer of the obtained developer carrying member. Then, using the obtained developer carrying member, an image output test was performed while supplying toner A in the same manner as in Example 1, and the results are shown in Tables 3 and 4. Indicated.

<Comparative example 2>
A resin layer was formed in the same manner as in Example 5 except that the copolymer (a) used in Example 5 was omitted, and a developer carrier of this comparative example was prepared. Table 2 shows the structure of the resin layer of the obtained developer carrying member. Then, using the obtained developer carrying member, an image output test was performed while supplying toner A in the same manner as in Example 1, and the results are shown in Tables 3 and 4. Indicated.

<Comparative Example 3>
A resin layer was formed in the same manner as in Example 14 except that the copolymer (a) and conductive spherical carbon particles used in Example 14 were removed, and a developer carrier of this comparative example was prepared. Table 2 shows the structure of the resin layer of the obtained developer carrying member. Then, using the obtained developer carrying member, an image output test was performed while supplying toner A in the same manner as in Example 1, and the results are shown in Tables 3 and 4. Indicated.

<Comparative example 4>
A resin layer was formed in the same manner as in Example 16 except that the copolymer (a) and conductive spherical carbon particles used in Example 16 were removed, and a developer carrier of this comparative example was prepared. Table 2 shows the structure of the resin layer of the obtained developer carrying member. Then, using the obtained developer carrying member, an image output test was performed while supplying toner A in the same manner as in Example 1, and the results are shown in Tables 3 and 4. Indicated.

<Comparative Example 5>
In Example 4, PMMA was used in place of the copolymer (a), and an azonaphthol chromium complex (S) containing chlorophenol was used instead of the conductive spherical carbon particles. Thus, a resin layer was formed to prepare a developer carrier of this comparative example. Table 2 shows the structure of the resin layer of the obtained developer carrying member. Then, using the obtained developer carrying member, an image output test was performed while supplying toner A in the same manner as in Example 1, and the results are shown in Tables 3 and 4. Indicated.

<Comparative Example 6>
In Example 5, a resin layer was formed in the same manner as in Example 4 except that the quaternary ammonium salt was used instead of the copolymer (a) to prepare a developer carrying member of this comparative example. Table 2 shows the structure of the resin layer of the obtained developer carrying member. Then, using the obtained developer carrying member, an image output test was performed while supplying toner A in the same manner as in Example 1, and the results are shown in Tables 3 and 4. Indicated.

It is sectional drawing which shows an example of the image development apparatus using the developing agent carrier of this invention.

Explanation of symbols

7 Photosensitive drum 8 Regulating blade 9 Hopper 10 Toner 11 Magnet 12 Cylindrical substrate 13 Resin layer 14 Developer carrier (developing sleeve)
DESCRIPTION OF SYMBOLS 15 Power supply 16 Stirrer 17 Elastic board A Rotating direction of the developing sleeve 14 B Rotating direction of the photosensitive drum 7 D Developing area

Claims (10)

A developer carrier used in a developing device that develops a latent image formed on an electrostatic latent image carrier with a developer carried and conveyed by the developer carrier and visualizes the latent image, comprising at least a substrate and It has a resin layer formed on the substrate surface, and the binder resin used for the resin layer has at least the chemical formula (1):

(In the formula, R represents —A ₁ — (SO ₂ R ₁ ) _x . R ₁ represents OH, a halogen atom, ONa, OK, OR _1a . A ₁ and R _1a represent a substituted or unsubstituted aliphatic group. Represents a hydrocarbon structure, a substituted or unsubstituted aromatic ring structure, a substituted or unsubstituted heterocyclic structure, m is an integer selected from the range of 0 to 7, and x is a range of 1 to 7 (In the case where there are a plurality of units, R, R ₁ , A ₁ , R _1a , m, and x represent the above meanings independently for each unit.)
A developer carrier characterized by containing a polyhydroxyalkanoate containing at least one unit shown in the molecule. The unit represented by the chemical formula (1) is represented by the chemical formula (2):

(In the formula, R represents —A ₂ — (SO ₂ R ₂ ) _x . R ₂ represents OR _2a . A ₂ represents a substituted or unsubstituted aliphatic hydrocarbon structure, a substituted or unsubstituted aromatic ring. R _2a represents a linear or branched alkyl group having 1 to 8 carbon atoms or a substituted or unsubstituted phenyl group, and m is in the range of 0 to 7. X is an integer selected from the range of 1 to 7. When there are a plurality of units, R, R ₂ , R _2a , A ₂ , m, x are each unit Each of the above meanings is expressed independently.)
The developer carrying member according to claim 1, which is a unit shown in FIG. The unit represented by the chemical formula (1) is represented by the chemical formula (3):

(In the formula, R _3a is OH, a halogen atom, ONa, OK, OR _3b . A ₃ represents a linear or branched alkylene group having 1 to 8 carbon atoms. R _3b is a linear or branched carbon number. Represents an alkyl group of 1 to 8 or a substituted or unsubstituted phenyl group, m is an integer selected from the range of 0 to 7, and x is an integer selected from the range of 1 to 7. When there are a plurality of units, A ₃ , R _3a , x and m have the above meanings independently for each unit.)
The developer carrying member according to claim 1, which is a unit shown in FIG. The unit represented by the chemical formula (1) is represented by the chemical formula (4):

(In the formula, at least one of R _4a , R _4b , R _4c , R _4d and R _4e is SO ₂ R _4f (R _4f is OH, a halogen atom, ONa, OK, OR _4h . R _4h is direct) A chain or branched alkyl group having 1 to 8 carbon atoms and a substituted or unsubstituted phenyl group.), Hydrogen atom, halogen atom, alkyl group having 1 to 20 carbon atoms, and 1 to 20 carbon atoms Alkoxy group, OH group, NH ₂ group, NO ₂ group, COOR _4g (R _4g : represents any of H atom, Na atom, K atom), acetamide group, OPh group, NHPh group, CF ₃ group, C Represents ₂ F ₅ group or C ₃ F ₇ group, and m is an integer selected from the range of 0 to _{7. When} a plurality of units are present, R _4a , R _4b , R _4c , R _4d , R _4e , R _4f , R _4g , R _4h and m represent the above meanings independently for each unit.)
The developer carrying member according to claim 1, which is a unit shown in FIG. The unit represented by the chemical formula (1) is represented by the chemical formula (5a):

(In the formula, at least one of R _5A , R _5B , R _5C , R _5D , R _5E , R _5F , R _5G is SO ₂ R _5O (R _5O is OH, halogen atom, ONa, OK, OR _5s . R _5s represents a linear or branched alkyl group having 1 to 8 carbon atoms or a substituted or unsubstituted phenyl group, and a hydrogen atom, a halogen atom, or an alkyl group having 1 to 20 carbon atoms. , An alkoxy group having 1 to 20 carbon atoms, OH group, NH ₂ group, NO ₂ group, COOR _5P (R _5P represents any one of an H atom, a Na atom, and a K atom), an acetamide group, an OPh group, and an NHPh group , CF ₃ group, C ₂ F ₅ group or C ₃ F ₇ group, and m is an integer selected from the range of 0 to _{7. When} a plurality of units are present, R _5A and R _5B , R _5C , R _5D , R _5E , R _5F , R _5G , R _5O , R _5P , R _5s , and m have the above meanings independently for each unit.
Chemical formula (5b):

(In the formula, at least one of R _5H , R _5I , R _5J , R _5K , R _5L , R _5M , R _5N is SO ₂ R _5Q (R _5Q is OH, halogen atom, ONa, OK, OR _5t R _5t represents a linear or branched alkyl group having 1 to 8 carbon atoms or a substituted or unsubstituted phenyl group, and a hydrogen atom, a halogen atom, or an alkyl group having 1 to 20 carbon atoms. , An alkoxy group having 1 to 20 carbon atoms, OH group, NH ₂ group, NO ₂ group, COOR _5R (R _5R represents any one of H atom, Na atom and K atom), acetamide group, OPh group, NHPh group , CF ₃ group, C ₂ F ₅ group or C ₃ F ₇ group, and m is an integer selected from the range of 0 to _{7. When} a plurality of units are present, R _5H , R _5I , R _5J , R _5K , R _5L , R _5M , R _5N , R _5Q , R _5R , R _5t , and m have the above meanings independently for each unit.)
The developer carrying member according to claim 1, which is a unit shown in at least one of the above. In addition to the unit represented by the chemical formula (1), the polyhydroxyalkanoate has the chemical formula (11):

(In the formula, n is an integer selected from the range of 1 to 8. R ₁₁ contains a residue having a ring structure of either a phenyl structure or a thienyl structure; when a plurality of units are present. , N and R ₁₁ independently represent the above-mentioned meaning for each unit.) Or a 3-hydroxy-ω-substituted alkanoic acid unit represented by formula (12):

(In the formula, R ₁₂ represents a substituent to the cyclohexyl group, and R ₁₂ represents an H atom, a CN group, a NO ₂ group, a halogen atom, a CH ₃ group, a C ₂ H ₅ group, a C ₃ H ₇ group, CF _3. Group, C ₂ F ₅ group or C ₃ F ₇ group, k is an integer selected from the range of 0 to 8, and when a plurality of units are present, each unit has the above meaning independently Represents.)
The developer carrier according to claim 1, comprising at least one of the 3-hydroxy-ω-cyclohexylalkanoic acid units shown in FIG. R ₁₁ in the chemical formula (11), that is, a residue having a phenyl structure or a thienyl structure is represented by the chemical formulas (13), (14), (15), (16), (17), (18), (19), ( 20), (21), (22), (23), and when a plurality of units are present, the developer carrying according to claim 6, which represents the above meaning independently for each unit. body.
Chemical formula (13):

(In the formula, R ₁₃ represents a substituent to the aromatic ring, and R ₁₃ represents an H atom, a halogen atom, a CN group, a NO ₂ group, a CH ₃ group, a C ₂ H ₅ group, a C ₃ H ₇ group, CH = CH ₂ group, COOR _13a (R _13a : represents any one of H atom, Na atom and K atom), CF ₃ group, C ₂ F ₅ group or C ₃ F ₇ group, and when there are a plurality of units And each unit has the above meanings independently), and a group of unsubstituted or substituted phenyl groups represented by formula (14):

(In the formula, R ₁₄ represents a substituent to the aromatic ring, and R ₁₄ represents an H atom, a halogen atom, a CN group, a NO ₂ group, a CH ₃ group, a C ₂ H ₅ group, a C ₃ H ₇ group, an SCH _3). Group, CF ₃ group, C ₂ F ₅ group or C ₃ F ₇ group, and when a plurality of units are present, each unit independently represents the above meaning)) or unsubstituted or substituted phenoxy Group of groups and chemical formula (15):

(In the formula, R ₁₅ represents a substituent to the aromatic ring, and R ₁₅ represents an H atom, a halogen atom, a CN group, a NO ₂ group, a CH ₃ group, a C ₂ H ₅ group, a C ₃ H ₇ group, a CF ₃ group. A group, a C ₂ F ₅ group or a C ₃ F ₇ group, and when a plurality of units are present, each unit independently represents the above meaning)), a group of unsubstituted or substituted benzoyl groups And the chemical formula (16):

(In the formula, R ₁₆ represents a substituent to the aromatic ring, and R ₁₆ represents an H atom, a halogen atom, a CN group, a NO ₂ group, COOR _16a , SO ₂ R _16b (R _16a : H, Na, K, CH ₃ or C ₂ H ₅ , R _16b represents OH, ONa, OK, a halogen atom, OCH ₃ or OC ₂ H ₅ ), CH ₃ group, C ₂ H ₅ group, C ₃ H ₇ group, (CH ₃ ) ₂ —CH group or (CH ₃ ) ₃ —C group, and when a plurality of units are present, each unit independently represents the above meaning). Group of substituted or substituted phenylsulfanyl groups and the chemical formula (17):

(In the formula, R ₁₇ represents a substituent on the aromatic ring, and R ₁₇ represents an H atom, a halogen atom, a CN group, a NO ₂ group, COOR _17a , SO ₂ R _17b (R _17a : H, Na, K, CH ₃ or C ₂ H ₅ , R _17b represents OH, ONa, OK, a halogen atom, OCH ₃ or OC ₂ H ₅ ), CH ₃ group, C ₂ H ₅ group, C ₃ H ₇ group, (CH ₃ ) ₂ —CH group or (CH ₃ ) ₃ —C group, and when a plurality of units are present, each unit independently represents the above meaning). Group of substituted or substituted (phenylmethyl) sulfanyl groups and chemical formula (18):

A 2-thienyl group represented by the formula (19):

2-thienylsulfanyl group represented by the formula (20):

A 2-thienylcarbonyl group represented by the formula (21):

(In the formula, R ₂₁ represents a substituent on the aromatic ring, and R ₂₁ represents an H atom, a halogen atom, a CN group, a NO ₂ group, COOR _21a , SO ₂ R _21b (R _21a : H, Na, K, CH ₃ or C ₂ H ₅ , R _21b represents OH, ONa, OK, a halogen atom, OCH ₃ or OC ₂ H ₅ ), CH ₃ group, C ₂ H ₅ group, C ₃ H ₇ group, (CH ₃ ) ₂ —CH group or (CH ₃ ) ₃ —C group, and when a plurality of units are present, each unit independently represents the above meaning). Group of substituted or substituted phenylsulfinyl groups and chemical formula (22):

(In the formula, R ₂₂ represents a substituent to the aromatic ring, and R ₂₂ represents an H atom, a halogen atom, a CN group, a NO ₂ group, COOR _22a , SO ₂ R _22b (R _22a : H, Na, K, CH ₃ and C ₂ H ₅ , R _22b represents OH, ONa, OK, a halogen atom, OCH ₃ and OC ₂ H ₅ ), CH ₃ group, C ₂ H ₅ group, C ₃ H ₇ group, (CH ₃ ) ₂ —CH group or (CH ₃ ) ₃ —C group, and when a plurality of units are present, each unit independently represents the above meaning). Group chemical formula of substituted or substituted phenylsulfonyl group (23):

(Phenylmethyl) oxy group represented by   The developer carrier according to any one of claims 1 to 7, wherein the number average molecular weight of the polyhydroxyalkanoate is selected in the range of 1000 to 1000000. A developer accommodated in a developer container is carried on a developer carrying member, and a developer thin layer is formed on the developer carrying member by a developer layer thickness regulating member. In the developing device for transporting to a developing area opposite to the developing area and developing the latent image on the latent image carrying body with a developer in the developing area to make a visible image, the developer carrying body comprises at least a substrate and a substrate The binder resin having a resin layer formed on the surface and used in the resin layer has at least the chemical formula (1):

(In the formula, R represents —A ₁ — (SO ₂ R ₁ ) _x . R ₁ represents OH, a halogen atom, ONa, OK, OR _1a . A ₁ and R _1a represent a substituted or unsubstituted aliphatic group. Represents a hydrocarbon structure, a substituted or unsubstituted aromatic ring structure, a substituted or unsubstituted heterocyclic structure, m is an integer selected from the range of 0 to 7, and x is a range of 1 to 7 (In the case where there are a plurality of units, R, R ₁ , A ₁ , R _1a , m, and x represent the above meanings independently for each unit.)
A developing apparatus comprising polyhydroxyalkanoate characterized in that the unit contains at least one unit represented by   The developing device according to claim 9, wherein the developer carrying member is the developer carrying member according to claim 2.

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