JP3747209B2 - Charge control agent containing a novel polyhydroxyalkanoate containing a unit having a carboxyl group in the side chain in the molecule, toner binder and toner, and image forming method and image forming apparatus using the toner - Google Patents

Description

  The present invention relates to a charge control agent, a toner binder, an electrostatic charge image developing toner, an image forming method using the toner, and an image thereof using the electrophotographic method, electrostatic recording method, magnetic recording method and the like. The present invention relates to a forming apparatus. In particular, electronic devices such as copiers, printers, and fax machines that form a toner image on an electrostatic latent image carrier (hereinafter simply referred to as an image carrier) and then transfer it onto a transfer material to form an image. The present invention relates to a charge control agent used in photography, electrostatic recording, electrostatic printing, a toner binder, an electrostatic image developing toner, an image forming method using the toner, and an image forming apparatus thereof. More specifically, a negatively chargeable charge control agent that is safer to the human body / environment, a toner binder using the same, an electrostatic charge image developing toner, an image forming method using the toner, and an image forming apparatus thereof About.

  Conventionally, many methods are known as electrophotographic methods.In general, an electric latent image is formed on an image carrier (photosensitive member) by various means using a photoconductive substance. Next, the latent image is developed with toner to form a visible image. If necessary, the toner image is transferred to a transfer material such as paper, and then the toner image is fixed on the transfer material by heat and / or pressure. To obtain a copy. As a method for visualizing an electric latent image, a cascade development method, a magnetic brush development method, a pressure development method, and the like are known. Further, there is also used a method in which a magnetic toner and a rotating developing sleeve having a magnetic pole at the center are used, and the magnetic toner is ejected from the developing sleeve onto the photoreceptor by a magnetic field.

  Development methods used when developing an electrostatic latent image include a two-component development method using a two-component developer composed of a toner and a carrier, and a one-component developer composed only of a toner not using a carrier. There is a one-component development system to be used.

  Here, the colored fine particles generally referred to as toner are composed of a binder resin and a coloring material as essential components, and are composed of magnetic powder or the like as necessary.

  As a method for imparting charge to the toner, the charging characteristics of the binder resin itself can be used without using a charge control agent. Absent. Therefore, a charge control agent is usually added for the purpose of charge retention and charge control of the toner.

  Known charge control agents known in the art today include, for example, azo dye metal complexes, aromatic dicarboxylic acid metal complexes, and salicylic acid derivative metal complexes as negative triboelectric charging properties. Further, as the positive charge control agent, nigrosine dyes, triphenylmethane dyes, various tin compounds such as quaternary ammonium salts dibutyltin oxide, etc. are known. Toners containing these as charge control agents are, Depending on the composition, the quality characteristics required for the toner, such as chargeability and stability over time, may not always be sufficiently satisfied.

  For example, a toner containing an azo dye metal complex known as a negative charge control agent has a reasonable level of charge, but the azo dye metal complex is a low-molecular crystal. Depending on the case, the dispersibility may be inferior. In that case, the negative charge control agent is not uniformly distributed in the binder resin, and the charge amount distribution of the obtained toner is extremely sharp, and the obtained image has low gradation and inferior image forming ability. It is. Furthermore, since the azo dye metal complex has a unique color tone, it is currently used only for toners of a limited hue centered on black. When used as a color toner, the demand for color tone is required. The problem is that it does not have the sharpness of the colorant required to obtain a high-quality image.

  Also, examples of negatively charged negative charge control agents include metal complexes of aromatic dicarboxylic acids, but they are also not completely colorless, and low dispersibility due to low molecular crystals is a problem. There is.

  On the other hand, nigrosine dyes and triphenylmethane dyes, which are known as positive charge control agents, are colored themselves, so they are currently used only for toners with a limited hue centered on black. In addition, the stability over time of continuous copying of toner may not be good. Further, the conventional quaternary ammonium salt may have insufficient moisture resistance when it is made into a toner, in which case the stability over time is inferior, and a high-quality image may not be provided by repeated use.

  In recent years, from the viewpoint of environmental protection, reduction of waste and improvement of safety of waste are regarded as problems worldwide. Such a problem also applies to the field of electrophotography. In other words, with the widespread use of imaging devices, the volume of printed paper, used waste toner, and copy paper is increasing year by year. From the standpoint of protecting the global environment, the safety of such waste Sex is also an important issue.

  In consideration of such points, polymer charge control agents have been studied. USP 4480021 (Patent Document 1), USP 4442189 (Patent Document 2), USP 4925765 (Patent Document 3), JP-A-60-108861 (Patent Document 4), JP-A 61-3149 (Patent Document 5) ), JP-A 63-38958 (Patent Document 6) and JP-A 63-88564 (Patent Document 7). Further, as a polymer charge control agent in general when toner exhibits negative chargeability, styrene and / or α-methylstyrene, alkyl (meth) acrylate ester or alkyl (meth) acrylate amide having a sulfonic acid group, and Copolymers (Japanese Patent Laid-Open No. 7-72658 (Patent Document 8), Japanese Patent Laid-Open No. 8-179564 (Patent Document 9), Japanese Patent No. 2114410 (Patent Document 10), Japanese Patent No. 2262684 (Patent Document 11) Patent No. 280795 (Patent Document 12)) is often used. Such a material is advantageous in that it is colorless, but a large amount of addition is required in order to obtain a target charge amount.

  As described above, these compounds do not have sufficient performance as a charge control agent, and have problems in charge amount, charge rising characteristics, temporal stability, environmental stability, and the like. In addition to functional aspects, when considering the effects on the human body and the environment, the compounds and organic solvents used in the synthesis are also safer compounds, safer and milder synthesis processes, reduced use of organic solvents, etc. A feasible charge control agent is highly desired.

  From the viewpoint of environmental protection, resins that can be decomposed over time by the action of microorganisms, that is, biodegradable resins, are being developed, and many microorganisms have biodegradable resins (polyhydroxyalkanoates having a polyester structure). Ate: hereinafter abbreviated as PHA) and is reported to accumulate in the fungus body. It is known that such PHA can have various compositions and structures depending on the type of microorganism used for production, medium composition, culture conditions, and so on, mainly from the viewpoint of improving physical properties, Research has been conducted on the control of the composition and structure of the produced PHA, and there is already considerable achievement, particularly in the field of medical materials. In the field of agriculture, biodegradable resins are used for multi-films, horticultural materials, etc., and for sustained-release agricultural chemicals and fertilizers. In the field of leisure industry, biodegradable resins are used for fishing lines, fishing equipment, golf equipment, and the like.

  However, when considering a wide range of applications as plastics, the physical properties are still not sufficient. In order to further expand the range of use of PHA, it is important to consider the improvement of physical properties more broadly. To that end, development and search for PHA containing monomer units with various structures is essential. is there. On the other hand, a PHA of a type in which a substituent is introduced into the side chain is a very useful function or property resulting from the properties of the introduced substituent by selecting the introduced substituent according to the desired properties. Development as a “functional polymer” comprising That is, the development and search of an excellent PHA that can achieve both such functionality and biodegradability is also an important issue.

  Also in the field of electrophotography, the application of biodegradable resins to binder resins has been proposed, particularly in toner production. USP 5004664 (Patent Document 13) discloses a toner having a composition composed of a biodegradable resin, particularly polyhydroxybutyric acid, polyhydroxyvaleric acid, a copolymer or a blend thereof. In JP-A-6-289644 (Patent Document 14), at least the binder resin contains a vegetable wax and a biodegradable resin, and the vegetable wax is contained in the binder resin in an amount of 5-50. An electrophotographic toner, particularly for hot roll fixing, is disclosed, characterized in that it is added in an amount of mass%.

  JP-A-7-120975 (Patent Document 15) discloses an electrophotographic toner characterized by containing a lactic acid resin as a binder resin. Further, JP-A-9-274335 (Patent Document 16) contains a polyester resin and a colorant obtained by dehydration polycondensation of a composition containing lactic acid and a tri- or higher functional oxycarboxylic acid. Disclosed is a toner for developing an electrostatic charge image.

  JP-A-8-262796 (Patent Document 17) discloses an electrophotographic toner containing a binder resin and a colorant, wherein the binder resin is made of a biodegradable resin, and the colorant is water-insoluble. An electrophotographic toner characterized by comprising a functional dye is disclosed. Further, JP-A-9-281746 (Patent Document 18) contains a urethanized polyester resin obtained by crosslinking polylactic acid with a trifunctional or higher polyvalent isocyanate and a colorant. A toner for developing a charge image is disclosed.

  In any of the electrophotographic toners described above, it is understood that a biodegradable resin is used as the binder resin, which contributes to environmental preservation and the like.

  However, reports of examples of using biodegradable resins as charge control agents are not yet known, and there is room for further improvement in contribution to environmental conservation and the like.

The technology related to the present invention relates to a technology for obtaining a carboxylic acid by oxidizing a carbon-carbon double bond with an oxidizing agent (Japanese Patent Laid-Open No. 59-190945 (Patent Document 19)). J. Chem. Soc., Perkin. Trans. 1, 806 (1973) (Non-Patent Document 1), Org. Synth., 4, 698 (1963) (Non-Patent Document 2), J. Org. Chem., 46, 19 (1981) (non-patent document 3), J. Am. Chem. Soc., 81, 4273 (1959) (non-patent document 4), Macromolecular Chemistry, 4, 289-293 (2001) (non-patent document) 5)). Japanese Patent Laid-Open No. 2002-80751 (Patent Document 20) describes a microorganism that has been separated and identified by the inventors.
USP 4480021 USP 4442189 USP 4925765 JP 60-108861 A JP 61-3149 Japanese Unexamined Patent Publication No. 63-38958 JP 63-88564 A Japanese Unexamined Patent Publication No. 7-72658 JP-A-8-179564 Japanese Patent No. 2114410 Japanese Patent No.2623684 Japanese Patent No. 280795 USP 5004664 JP-A-6-289644 JP 7-120975 A JP-A-9-274335 JP-A-8-262796 JP-A-9-281746 JP 59-190945 JP 2002-80751 A J. Chem. Soc., Perkin. Trans. 1, 806 (1973) Org. Synth., 4, 698 (1963) J. Org. Chem., 46, 19 (1981) J. Am. Chem. Soc., 81, 4273 (1959) Macromolecular chemistry, 4, 289-293 (2001)

  In order to solve the above-mentioned problems, the present invention has a higher contribution to environmental conservation and the like in terms of function, and high performance (high charge amount, quick rise of charge, excellent temporal stability, environmental stability. A negatively chargeable charge control agent with improved dispersibility, a toner binder containing the charge control agent, an electrostatic image developing toner containing the charge control agent, and the electrostatic image An image forming method and an image forming apparatus using a developing toner are provided.

  The present inventors have intensively studied to develop a charge control agent having a high contribution to environmental preservation and the like, and have reached the present invention. That is, the outline of the present invention is as follows.

  [1] A charge control agent for controlling a charged state of a granular material contains a polyhydroxyalkanoate having at least one unit among 3-hydroxy-ω-carboxyalkanoic acid units represented by chemical formula (1). A charge control agent characterized by comprising:

(n is an integer selected from the range shown in the chemical formula; R ₁ is an H atom, an Na atom, a K atom, or

When there are multiple units, n and R ₁ may be different for each unit. )
[2] A toner binder for use in an electrostatic charge image developing toner, comprising the charge control agent according to [1].
[3] An electrostatic charge image developing toner, comprising at least a binder resin, a colorant, and the charge control agent according to [1].
[4] A step of charging the electrostatic latent image carrier by applying a voltage to the charging member from the outside, a step of forming an electrostatic charge image on the charged electrostatic latent image carrier, and Development process for developing with electrostatic charge image developing toner to form toner image on electrostatic latent image carrier, transfer process for transferring toner image on electrostatic latent image carrier to recording material, and recording material An image forming method comprising at least a fixing step for heat-fixing the above toner image, comprising: an electrostatic charge image developing toner comprising at least a binder resin, a colorant, and a charge control agent according to [1]. An image forming method characterized by being used.
[5] means for applying a voltage to the charging member from the outside to charge the electrostatic latent image carrier, means for forming an electrostatic image on the charged electrostatic latent image carrier, and Developing means for developing with an electrostatic charge image developing toner to form a toner image on the electrostatic latent image carrier, transfer means for transferring the toner image on the electrostatic latent image carrier to the recording material, and recording material An image forming apparatus having at least a fixing unit for heating and fixing the above toner image, comprising: an electrostatic charge image developing toner containing at least a binder resin, a colorant, and a charge control agent according to [1]. An image forming apparatus for use.

  INDUSTRIAL APPLICABILITY According to the present invention, there is provided a charge control agent using polyhydroxyalkanoate with PHA “unusual PHA” having at least one type of monomer units having a protected or unprotected carboxyl group at the end of the side chain. .

  In addition, according to the present invention, by adding one or more polyhydroxyalkanoates represented by the chemical formula (1) as a charge control agent to the toner composition for developing an electrostatic image, the charging property is excellent and the toner resin is incorporated. Electrostatic charge images that improve the dispersibility and spent property of the compound, and that do not generate image fogging when output on an image forming apparatus, have excellent transferability, and are highly applied to electrophotographic processes. It is possible to provide a developing toner. Further, since the charge control agent used in the present invention is colorless or weakly colored, any colorant can be selected according to the hue required for the color toner, and the original hue of the dye or pigment can be selected. It is also a feature that there is no hindrance. In addition, the electrostatic image developing toner of the present invention is extremely safe and biodegradable, so there is no need to perform a combustion treatment, and from the viewpoint of environmental conservation such as prevention of air pollution and global warming. It has a great effect on the industry.

  Hereinafter, the present invention will be described in more detail with reference to preferred embodiments. As a result of intensive studies to achieve the above object, the present inventors have found that the above polyhydroxyalkanoate has extremely excellent characteristics as a charge control agent and is highly safe to the human body and the environment. Furthermore, it has been found that the electrostatic charge image developing toner containing the charge control agent and the electrostatic charge image developing toner are remarkably effective when used in an image forming apparatus having a certain development system. Was completed.

  That is, the present invention is a charge control agent containing the above-mentioned polyhydroxyalkanoate, and further an electrostatic charge image developing toner containing the charge control agent. Further, the electrostatic charge image developing toner is applied with a voltage from the outside to the charging member to uniformly charge the electrostatic latent image carrier, and a toner image is formed on the electrostatic latent image carrier. A developing step, a transfer step in which the toner image on the electrostatic latent image carrier is transferred to the transfer material with or without the intermediate transfer member, and the toner image on the transfer material is fixed by heat. And an image forming apparatus having each means corresponding to each step of the method, that is, a charging means, a developing means, a transfer means, and a heat fixing means.

  Here, the polyhydroxyalkanoate used in the present invention has a basic skeleton as a biodegradable resin, and therefore can be used for production of various products by melt processing or the like, as in the case of conventional plastics. At the same time, unlike petroleum-derived synthetic polymers, it has the outstanding characteristic of being decomposed by living organisms and taken into the natural material circulation. 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.

  The polyhydroxyalkanoate suitable for the charge control agent used in the electrostatic image developing toner of the present invention will be specifically described.

  The polyhydroxyalkanoate used in the present invention is a polyester resin containing 3-hydroxyalkanoate as a monomer unit, and is at least one of 3-hydroxy-ω-carboxyalkanoic acid units represented by the chemical formula (1). A polyhydroxyalkanoate having units.

(n is an integer selected from the range shown in the chemical formula; R ₁ is an H atom, an Na atom, a K atom, or

When there are multiple units, n and R ₁ may be different for each unit. )
Further, in addition to the 3-hydroxy-ω-carboxyalkanoic acid unit represented by chemical formula (1), a 3-hydroxy-ω-substituted alkanoic acid unit represented by chemical formula (6),

(m is an integer selected from the range shown in the chemical formula; R ₆ contains a residue having either a phenyl structure or a thienyl structure; and m and R ₆ may be different for each unit) or chemical formula (7):

3-hydroxy-ω-cyclohexylalkanoic acid unit (wherein R ₇ represents a substituent to the cyclohexyl group, R ₇ 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, k is an integer selected from the range shown in the chemical formula, and there are a plurality of units. May be different for each unit.) May be included independently or both.

  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.

  An example of a method for producing the polyhydroxyalkanoate used in the present invention will be described below.

  The target polyhydroxyalkanoate represented by the chemical formula (1) in the present invention is the oxidation of the double bond portion of the polyhydroxyalkanoate containing the 3-hydroxy-ω-alkenoic acid unit represented by the chemical formula (19) as a starting material. Manufactured by.

(p is an integer selected from the range shown in the chemical formula, and when there are a plurality of units, they may be different for each unit.)
Thus, as a method for obtaining a carboxylic acid by oxidative cleavage of a carbon-carbon double bond with an oxidizing agent, for example, a method using 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. Org) Chem., 46, 19 (1981); Non-patent document 3), a method using nitric acid (JP 59-190945 A; patent document 19), a method using ozone (J. Am. Chem. Soc., 81, 4273 (1959); Non-Patent Document 4), and the like. Furthermore, regarding polyhydroxyalkanoates, Macromolecular Chemistry, 4, 289-293 (2001) (Non-Patent Document 5), Carboxylic acid is obtained by performing the reaction under acidic conditions using potassium permanganate with the carbon-carbon double bond at the side chain end of the alkanoate as the oxidizing agent. A method has been reported. A similar method can be used in the present invention.

  Although not particularly limited, a permanganate is particularly preferable as the oxidizing agent used in the present invention. The permanganate used as the oxidizing agent is generally potassium permanganate. Since the oxidative cleavage reaction is a stoichiometric reaction, the amount of permanganate used is usually 1 molar equivalent or more, preferably 2 to 10 molar equivalents per 1 mol of the unit represented by chemical formula (19). It is good to do.

  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 (19). When the amount is less than 0.2 molar equivalent, the yield is low, and when it exceeds 2000 molar equivalent, a decomposition product due to the acid is by-produced.

  In addition, crown-ether can be used for the purpose of promoting the reaction. In this case, the crown-ether and 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 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 hydrocarbons such as benzene; hexane And aliphatic hydrocarbons such as heptane; halogenated hydrocarbons such as methyl chloride, dichloromethane, and chloroform. Among these solvents, halogenated hydrocarbons such as methyl chloride, dichloromethane, chloroform, and acetone are preferable in consideration of the solubility of polyhydroxyalkanoate.

  In the oxidation reaction of the present invention, the polyhydroxyalkanoate copolymer containing the unit represented by the chemical formula (19), the permanganate and the acid may be charged together with the solvent from the beginning and reacted. Or you may make it react, adding in the system intermittently. 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. The reaction time depends on the stoichiometric ratio of the ω-alkenoic acid unit and permanganate represented by the chemical formula (19) and the reaction temperature, but it is usually preferably 2 to 48 hours.

  In addition to the 3-hydroxy-ω-alkenoic acid unit represented by the chemical formula (19), a 3-hydroxy-ω-substituted alkanoic acid unit represented by the chemical formula (6), or a 3-hydroxy represented by the chemical formula (7). In the case of using a polyhydroxyalkanoate containing a -ω-cyclohexylalkanoic acid unit, the reaction can be performed under the same conditions.

  As described above, the polyhydroxyalkanoate containing the unit represented by the chemical formula (1) aimed at in the present invention contains a carbon-carbon double bond at the end of the side chain represented by the chemical formula (19) used as a starting material. Manufactured from polyhydroxyalkanoates containing -hydroxy-ω-alkenoic acid units.

  The polyhydroxyalkanoate containing the unit represented by the chemical formula (19) used as a starting material of the present invention is not particularly limited, but a method of producing by a microbial production process, a method of producing by a genetically manipulated plant crop system, It can manufacture using the method of superposing | polymerizing and manufacturing. Preferably, a method of producing by a microbial production process is used.

  In the present invention, a production method in the case where a polyhydroxyalkanoate containing a 3-hydroxy-ω-alkenoic acid unit represented by the chemical formula (19) is used as a starting material will be described.

  The polyhydroxyalkanoate as a starting material is based on a production method characterized by culturing the microorganism in a medium containing ω-alkenoic acid represented by chemical formula (20).

(q is an integer selected from the range shown in the chemical formula)
The microorganism used in the method for producing a polyhydroxyalkanoate containing a unit represented by chemical formula (19) as a starting material of the present invention is a microorganism having PHA-producing ability, that is, a medium containing ω-alkenoic acid represented by chemical formula (20) Among them, any microorganism may be used as long as it can produce a PHA-type polyester containing the 3-hydroxy-ω-alkenoic acid unit represented by the general formula (19) by culturing the microorganism. As a preferable example of the microorganism having an available PHA producing ability, a microorganism belonging to the genus Pseudomonas can be mentioned. Examples include microorganisms belonging to the genus Pseudomonas. More specifically, Pseudomonas cichorii, Pseudomonas putida, Pseudomonas fluorecense, Pseudomonas oleovorans, Pseudomonas steumonas, Pseudomonas Pseudomonas jessenii) is desirable. More specifically, in more detail, Pseudomonas chicory eye YN2 strain (Pseudomonas cichorii YN2; FERM BP-7375), Pseudomonas chicory eye H45 strain (Pseudomonas cichorii H45, FERM BP-7374), Pseudomonas jeseniii P161s P161B 7376) and Pseudomonas putida P91 strain (Pseudomonas putida P91, FERM BP-7373). These four types of microorganisms are deposited in the National Institute of Advanced Industrial Science and Technology (formerly the Ministry of International Trade and Industry, Institute of Industrial Science and Technology), Biotechnology Institute of Technology, Patent Microorganism Depositary Center, Japanese Patent Laid-Open No. 2002-80751 (Patent Document 20) ).

  These microorganisms are ω-substituted-straight chain in which a 6-membered ring group of any one of a substituted or unsubstituted phenyl group, a substituted or unsubstituted phenoxy group, and a substituted or unsubstituted cyclohexyl group is substituted at the chain end. Polysiloxanes containing alkanoic acid or ω-substituted straight-chain alkanoic acid substituted with a 5-membered ring group such as thienyl group as raw materials and the corresponding ω-substituted-3-hydroxy-alkanoic acid as monomer units Has the ability to produce hydroxyalkanoates.

  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 thereof can be added in the form of a water-soluble salt and 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 0.1% to 5% (w / v) per medium. It is desirable to select a 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.

  The substrate for producing the target polyhydroxyalkanoate, that is, the content ratio of ω-alkenoic acid represented by the general formula (20) is more preferably in the range of 0.01% to 1% (w / v) per medium. Is preferably selected in the range of 0.02% to 0.2% (w / v).

  The culture temperature may be a temperature at which the microbial 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 produced PHA-type polyester has a hydrophobic atomic group such as a vinylalkyl group derived from a 3-hydroxy-ω-alkenoic acid unit in the side chain, so that it is poor in water solubility and has a PHA-producing ability. Therefore, it is easily separated from the culture medium by collecting the cells that have been grown and cultured to produce / accumulate the target PHA-type polyester. 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 the 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 improve the growth of the bacterial cells and improve the productivity of the PHA accordingly, 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)
Further, the substrate for producing the desired polyhydroxyalkanoate, that is, not only the ω-alkenoic acid represented by the chemical formula (20) but also the ω-substituted alkanoic acid compound represented by the chemical formula (21), or the chemical formula ( In addition to the 3-hydroxy-ω-alkenoic acid unit represented by the chemical formula (19), the 3-hydroxy-ω represented by the chemical formula (6) can be obtained by coexisting the ω-cyclohexylalkanoic acid compound represented by 22) during the culture. It is possible to produce a polyhydroxyalkanoate containing a substituted alkanoic acid unit or a 3-hydroxy-ω-cyclohexylalkanoic acid unit represented by the chemical formula (7). In this case, the content ratio of the ω-alkenoic acid represented by the chemical formula (20), the ω-substituted alkanoic acid compound represented by the chemical formula (21) and the ω-cyclohexylalkanoic acid compound represented by the chemical formula (22) It is desirable to select each in the range of 0.01% to 1% (w / v), more preferably in the range of 0.02% to 0.2% (w / v).

(r is an integer selected from the range shown in the chemical formula; R ₂₄ contains a residue having a ring structure of either a phenyl structure or a thienyl structure, and the chemical formula (8), ( 9), (10), (11), (12), (13), (14), (15), (16), (17), (18), and there are multiple units (It may be different for each unit)

(In the formula, R ₂₅ represents a substituent to the cyclohexyl group, and R ₂₅ 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, a CF ₃ group. Group, C ₂ F ₅ group or C ₃ F ₇ group, and s is an integer selected from the range shown in the chemical formula)
Further, a polyhydroxyalkanoate containing the 3-hydroxy-ω-carboxyalkanoic acid unit of the present invention in the molecule at the same time,
Chemical formula (23):

(n is an integer selected from the range shown in the chemical formula; R ₂₆ is any of the residues shown in the formula; when there are multiple units, n and R ₂₆ are units (It may be different for each.)
A 3-hydroxy-ω-alkoxycarbonylalkanoic acid unit shown in
Chemical formula (6):

(m is an integer selected from the range shown in the chemical formula; R ₆ contains a residue having either a phenyl structure or a thienyl structure; and m and R ₆ may be different for each unit) or chemical formula (7):

(Wherein R ₇ represents a substituent to the cyclohexyl group, and R ₇ 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, a CF ₃ group, A group, a C ₂ F ₅ group or a C ₃ F ₇ group, k is an integer selected from the range shown in the chemical formula, and when a plurality of units are present, they may be different for each unit.) A polyhydroxyalkanoate copolymer containing a 3-hydroxy-ω-cyclohexylalkanoic acid unit in the molecule at the same time as a raw material, and the polyhydroxyalkanoate represented by the chemical formula (23) is hydrolyzed in the presence of an acid or an alkali. By the method of decomposing, or the method of hydrocracking including catalytic reduction,
Chemical formula (1):

(n is an integer selected from the range shown in the chemical formula; R ₁ is an H atom, an Na atom, a K atom, or

When there are multiple units, n and R ₁ may be different for each unit. )
3-hydroxy-ω-carboxyalkanoic acid shown in
Chemical formula (6):

(m is an integer selected from the range shown in the chemical formula; R ₆ contains a residue having either a phenyl structure or a thienyl structure; and m and R ₆ may be different for each unit) or chemical formula (7):

(Wherein R ₇ represents a substituent to the cyclohexyl group, and R ₇ 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, a CF ₃ group, A group, a C ₂ F ₅ group or a C ₃ F ₇ group, k is an integer selected from the range shown in the chemical formula, and when a plurality of units are present, they may be different for each unit.) It may be produced as a polyhydroxyalkanoate copolymer containing the 3-hydroxy-ω-cyclohexylalkanoic acid unit shown in FIG.

  What is important in the structure of the polyhydroxyalkanoate used in the present invention is that it has a structure in which an aliphatic carboxylic acid or a derivative thereof is substituted on the side chain like the monomer unit represented by the chemical formula (1). is there. These anionic or electron-withdrawing functional group-containing units are preferable for further improving the negative chargeability. In fact, the charge control agent of the present invention has an excellent negative chargeability.

  The polyhydroxyalkanoate used in the present invention has a good compatibility with the binder resin, and particularly has a very good compatibility with the polyester binder resin. Since the toner containing the polyhydroxyalkanoate of the present invention has a high specific charge amount and good stability over time, it can be stably and clearly formed in electrostatic recording image formation even if the toner is stored for a long time. Since it gives an image and has a colorless negative charging performance, both black negatively charged toner and color toner can be produced.

Furthermore, wide compatibility control is possible by appropriately selecting the type / composition ratio of the monomer units constituting the polyhydroxyalkanoate of the present invention.
Here, when the resin composition is selected so that the charge control agent has a microphase separation structure in the toner binder, the electric continuity of the toner does not occur, so that the charge can be stably held. In addition, since the polyhydroxyalkanoate of the present invention does not contain heavy metals, when a toner is prepared by a suspension polymerization method or an emulsion polymerization method, the polymerization inhibiting action by heavy metals, such as that seen in metal-containing charge control agents, is exhibited. Therefore, the toner can be produced stably.

<Addition of PHA to toner>
In the present invention, as a method of incorporating the above-described compound into the toner, there are a method of internally adding to the toner and a method of externally adding to the toner. In the case of internal addition, the addition amount is usually 0.1 to 50% by mass, preferably 0.2 to 20% by mass, as the mass ratio of the toner binder and the charge control agent. If it is less than 0.1% by mass, the degree of improvement in the chargeability of the toner is not noticeable, which is not preferable. On the other hand, when it exceeds 50 mass%, it is not preferable from an economical viewpoint. In the case of external addition, the mass ratio of the toner binder and the charge control agent is preferably 0.01 to 5% by mass, and particularly preferably mechanochemically fixed to the toner surface. Furthermore, the polyhydroxyalkanoate of the present invention can be used in combination with a known charge control agent.

  The number average molecular weight of the polyhydroxyalkanoate of the present invention is usually 1,000 to 1,000,000, preferably 1,000 to 300,000. If it is less than 1,000, it becomes difficult to form a discontinuous domain due to complete compatibility with the toner binder, so that the charge amount becomes insufficient and the fluidity of the toner is adversely affected. If it exceeds 500,000, it will be difficult to disperse in the toner.

  The molecular weight of the polyhydroxyalkanoate of the present invention was measured by GPC (gel permeation chromatography). As a specific GPC measurement method, the polyhydroxyalkanoate is dissolved in a soluble solvent in advance, and measurement is performed with the same mobile phase. As a detector, a differential refraction detector (RI), an ultraviolet detector (UV) or the like was used, and a molecular weight distribution was obtained from a standard polystyrene resin calibration curve. The solvent may be selected from those in which the polymer is soluble such as 0.1% by mass LiBr-containing dimethylformamide (DMF), dimethyl sulfoxide (DMSO), chloroform, tetrahydrofuran (THF), toluene, hexafluoroisopropanol (HFIP).

  In the present invention, the polyhydroxyalkanoate having a ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) measured as described above is in the range of 1 to 10. Is preferably used.

  The polyhydroxyalkanoate used in the present invention has a melting point of 20 to 150 ° C., particularly 40 to 150 ° C., or has no melting point but a glass transition point of 10 to 150 ° C., particularly 20 to 150 ° C. Is preferred. When the melting point is less than 20 ° C. or has no melting point and the glass transition point is less than 20 ° C., the flowability and storage stability of the toner are liable to be adversely affected. When the melting point exceeds 150 ° C. or the glass transition point does not have a melting point and exceeds 150 ° C., it becomes difficult to knead the charge control agent in the toner, and the charge amount distribution tends to be widened.

  In this case, the melting point Tm and the glass transition point Tg may be measured using, for example, a highly accurate internal heat input compensation type differential scanning calorimeter such as DSC-7 manufactured by PerkinElmer. .

  In the toner binder and the electrostatic image developing toner of the present invention, the mass ratio of the toner binder and the charge control agent is usually 0.1 to 50% by mass, preferably 0.2 to 20% by mass. The composition ratio of the electrostatic charge image developing toner of the present invention is usually 0.1 to 50% by mass of the charge control agent, 20 to 95% by mass of the toner binder, and 0 to 15% by mass of the coloring material based on the toner mass. If necessary, magnetic powder (ferromagnetic metal powder such as iron, cobalt, nickel or a compound such as magnetite, hematite, ferrite) may be contained in an amount of 60% by mass or less in order to function as a coloring material. In addition, various additives (such as lubricants (polytetrafluoroethylene, low molecular weight polyolefins, fatty acids, or metal salts or amides thereof) and other charge control agents (metal-containing azo dyes, salicylic acid metal salts, etc.) are included. Can do. Also, hydrophobic colloidal silica fine powder or the like can be used to improve toner fluidity. The amount of these additives is usually 10% by mass or less based on the toner mass.

  In the toner of the present invention, it is preferable that at least a part of the toner binder forms a continuous phase and at least a part of the charge control agent forms a discontinuous domain. Compared with the case where the charge control agent is completely compatible in the toner binder without forming discontinuous domains, the added charge control agent is more easily exposed on the toner surface, and the effect is exhibited with a small amount of addition. The dispersed particle size of the domain is preferably 0.01 to 4 μm, more preferably 0.05 to 2 μm. If it exceeds 4 μm, dispersibility is insufficient, the charge amount distribution becomes wide, and the transparency of the toner becomes poor. On the other hand, when the dispersed particle size is less than 0.01 μm, it is the same as in the case of complete compatibility in the toner binder without forming discontinuous domains, and it is necessary to add a large amount of charge control agent. The fact that at least a part of the charge control agent forms a discontinuous domain and the dispersed particle size thereof can be confirmed by observing a section of the toner with a transmission electron microscope or the like. In order to clearly observe the interface, it is also effective to observe the electron microscope after dyeing the toner slice with ruthenium tetroxide, osmium tetroxide or the like.

  In addition, for the purpose of reducing the particle size of the discontinuous domain formed by the polyhydroxyalkanoate of the present invention, it is compatible with the polyhydroxyalkanoate of the present invention and also compatible with the toner binder. The polymer which has it can also be contained as a compatibilizing agent. As the compatibilizing agent, a polymer chain containing 50 mol% or more of a monomer having substantially the same structure as the constituent monomer of the polyhydroxyalkanoate of the present invention, a constituent monomer of the toner binder, In particular, a polymer in which polymer chains containing 50 mol% or more of monomers having the same structure are combined in a graft or block form can be mentioned. The use amount of the compatibilizing agent is usually 30% by mass or less, preferably 1 to 10% by mass with respect to the polyhydroxyalkanoate of the present invention.

<Other components>
Hereinafter, other constituent materials constituting the toner for developing an electrostatic charge image of the present invention will be described.

(Binder resin)
First, any binder resin can be used as long as it is usually used when producing toner, and is not particularly limited. In addition, the charge control agent of the present invention can be mixed with a binder resin in advance before being used as a toner and used as a toner binder composition of the present invention having charge control ability. For example, examples of the binder resin include styrene-based polymers, polyester-based polymers, epoxy-based polymers, polyolefin-based polymers, and polyurethane-based polymers, which can be used alone or in combination.

  Styrene polymers include copolymers of styrene and (meth) acrylic acid esters and copolymers of other monomers copolymerizable with these, styrene and diene monomers (butadiene, isoprene, etc.) And copolymers of other monomers copolymerizable therewith. Examples of polyester polymers include polycondensates of aromatic dicarboxylic acids and alkylene oxide adducts of aromatic diols. Examples of the epoxy polymer include a reaction product of an aromatic diol and epichlorohydrin and a modified product thereof. Examples of polyolefin-based polymers include polyethylene, polypropylene, and copolymer chains of these and other copolymerizable monomers. Examples of the polyurethane polymer include a polyaddition product of an aromatic diisocyanate and an alkylene oxide adduct of an aromatic diol.

  Specific examples of the binder resin used in the present invention are obtained by using two or more kinds of polymerizable monomers listed below, a mixture thereof, or a mixture thereof, or the following polymerizable monomers. A copolymerization product is mentioned. Specifically, for example, a styrene polymer such as a styrene-acrylic acid copolymer or a styrene-methacrylic acid copolymer, a polyester polymer, an epoxy polymer, and a polyolefin polymer. And polyurethane polymers, and the like can be preferably used.

  Specific examples of the polymerizable monomer include, for example, styrene, o-methylstyrene, p-methylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, 3,4-dichlorostyrene, p- Styrene such as ethyl styrene, 2,4-dimethyl styrene, pn-butyl styrene, p-tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, and Derivatives thereof; ethylenically unsaturated monoolefins such as ethylene, propylene, butylene, isobutylene; unsaturated polyenes such as butadiene; vinyl halides such as vinyl chloride, vinylidene chloride, vinyl bromide, vinyl fluoride; vinyl acetate; Vinyl ester acids such as vinyl propionate and vinyl benzoate; methyl methacrylate, methacrylic acid Chill, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, methacryl Α-methylene aliphatic monocarboxylic acid esters such as diethylaminoethyl acid; methyl acrylate, ethyl acrylate, -n-butyl acrylate, isobutyl acrylate, propyl acrylate, n-octyl acrylate, dodecyl acrylate, acrylic Acrylic acid esters such as 2-ethylhexyl acid, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether; Vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and methyl isopropenyl ketone; N-vinyl compounds such as N-vinyl pyrrole, N-vinyl carbazole, N-vinyl indole and N-vinyl pyrrolidone; vinyl naphthalenes; acrylonitrile, methacrylate Acrylic acid or methacrylic acid derivatives such as nitrile, acrylamide; esters of the aforementioned α, β-unsaturated acids, diesters of dibasic acids; maleic acid, methyl maleate, butyl maleate, dimethyl maleate, phthalic acid, Dicarboxylic acids such as succinic acid and terefluic acid; ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, bisphenol A, Polyol compounds such as hydrogenated bisphenol A and polyoxyethylenated bisphenol A; isocyanates such as p-phenylene diisocyanate, p-xylylene diisocyanate, and 1,4-tetramethylene diisocyanate; ethylamine, butylamine, ethylenediamine, and 1,4-diamino Examples include amines such as benzene, 1,4-diaminobutane, and monoethanolamine; epoxy compounds such as diglycidyl ether, ethylene glycol diglycidyl ether, bisphenol A glycidyl ether, and hydroquinone diglycidyl ether.

(Crosslinking agent)
When forming the binder resin used in the present invention, the following crosslinking agents may be used as necessary. For example, as a bifunctional crosslinking agent, divinylbenzene, bis (4-acryloxypolyethoxyphenyl) propane, ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5 -Pentanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 200, # 400, # 600 Acrylate, dipropylene glycol diacrylate, polypropylene glycol diacrylate, polyester-type diacrylate (MANDA Nippon Kayaku), and the above acrylates replaced with methacrylates, etc. Is mentioned.

  Examples of the bifunctional or higher polyfunctional crosslinking agent include pentaerythritol triacrylate, trimethylol ethane triacrylate, trimethylol propane triacrylate, tetramethylol methane tetraacrylate, oligoester acrylate and methacrylate thereof, and 2,2-bis ( 4-methacryloxy, polyethoxyphenyl) propane, diallyl phthalate, triallyl cyanurate, triallyl isocyanurate, triallyl trimellitate, diaryl chlorendate and the like.

(Polymerization initiator)
Moreover, when forming binder resin used in this invention, the following polymerization initiators can be used as needed. For example, t-butylperoxy-2-ethylhexanoate, cumin perpivalate, t-butylperoxylaurate, benzoyl peroxide, lauroyl peroxide, octanoyl peroxide, di-t-butyl peroxide, t -Butylcumyl peroxide, dicumyl peroxide, 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), 2,2'-azobis (2,4-dimethyl) Valeronitrile), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 1,4-bis (t-butylperoxycarbonyl) cyclohexane, 2,2-bis (t-butylperoxy) octane, n-butyl-4,4-bis (t-butylperoxy) Ii) valerate, 2,2-bis (t-butylperoxy) butane, 1,3-bis (t-butylperoxy-isopropyl) benzene, 2,5-dimethyl-2,5-di (t-butylper) Oxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, di-t-butyldiperoxy Isophthalate, 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane, di-t-butylperoxy α-methylsuccinate, di-t-butylperoxydimethylglutarate, di- t-Butylperoxyhexahydroterephthalate, di-t-butylperoxyazelate, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, diethylene glycol-bis (t-butylperoxycarbonate) , Di-t-butylperoxytrimethyladipate, Squirrel (t-butylperoxy) triazine, vinyltris (t-butylperoxy) silane. These can be used alone or in combination. The amount used is 0.05 parts by mass or more (preferably 0.1 to 15 parts by mass) with respect to 100 parts by mass of the monomer.

(Other biodegradable plastics)
Furthermore, in the present invention, biodegradable plastics can also be preferably used. Biodegradable plastics include `` Ecostar '', `` Ecostar Plus '' (Ebara Kogyo), `` Biopole '' (Monsanto), `` Aji Coat '' (Ajinomoto), `` Selgrain '' (Daicel Chemical), `` Shorex '', `` Bionore '' (Showa Denko) ) “Lacty” (Shimadzu Corporation) “Lacia” (Mitsui Chemicals), “Biogreen” (Mitsubishi Gas Chemical), etc.

  In the combination of the binder resin and the charge control agent of the present invention, the polymer structure of the binder resin and the polymer structure of the polymer chain of the charge control agent are preferably as similar as possible. If the polymer structure of the binder resin and the polymer structure of the polymer chain of the charge control agent are greatly different, the dispersion of the charge control agent in the binder resin tends to be insufficient.

  The mass proportion for internally adding the charge control agent of the present invention to the binder resin is usually 0.1 to 50 mass%, preferably 0.2 to 20 mass%. Here, when the mass ratio of the charge control agent to be internally added is less than 0.1 mass%, the charge amount is low, and when it exceeds 50 mass%, the charging stability of the toner is deteriorated.

<Colorant>
As the colorant constituting the toner for developing an electrostatic charge image of the present invention, any colorant can be used as long as it is usually used in the production of toner, and is not particularly limited. For example, carbon black, titanium white, and any other pigments and / or dyes can be used.

  For example, when the electrostatic charge image developing toner of the present invention is used as a magnetic color toner, examples of the colorant include C.I. Direct Red 1, C.I. Direct Red 4, and C.I. Acid. Red 1, C.I.Basic Red 1, C.I.Modern Red 30, C.I.Direct Blue 1, C.I.Direct Blue 2, C.I. Acid Blue 9, C.I. Acid Blue 15, C.I.Basic Blue 3, C.I.Basic Blue 5, C.I.Modern Blue 7, C.I.Direct Green 6, C.I.Basic Green 4, C.I.Basic Green 6 Etc. As pigments, chrome yellow, cadmium yellow, mineral fast yellow, navel yellow, naphthol yellow S, Hansa yellow G, permanent yellow NCG, tartrage rake, red mouth yellow lead, molybdenum orange, permanent orange GTR, pyrazolone orange, benzidine orange G , Cadmium Red, Permanent Red 4R, Watching Red Calcium Salt, Eosin Lake, Brilliant Carmine 3B, Manganese Purple, Fast Violet B, Methyl Violet Lake, Bitumen, Cobalt Blue, Alkaline Blue Lake, Victoria Blue Lake, Phthalocyanine Blue, Fast Sky Blue, Indanthrene Blue BC, Chrome Green, Chrome Oxide, Pigment Green B, Malachite Green Lake, It is possible to use the § Lee Naru yellow green G and the like.

  When the electrostatic image developing toner of the present invention is used as a two-component full color toner, the following can be used as a colorant. For example, as pigments for magenta toner, CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 39, 40, 41, 48, 49, 50, 51, 52, 53, 54, 55, 57, 58, 60, 63, 64, 68, 81, 83, 87, 88, 89, 90, 112, 114, 122, 123, 163, 202, 206, 207, 209, C.I. Pigment Violet 19, C.I. 1, 2, 10, 13, 15, 23, 29, 35 and the like.

  In the present invention, the above-mentioned pigments may be used alone, but it is more preferable from the viewpoint of the image quality of a full-color image to improve the sharpness by using a dye and a pigment together. Examples of magenta dyes that can be used in this case include CI Solvent Red 1, 3, 8, 23, 24, 25, 27, 30, 49, 81, 82, 83, 84, 100, 109, 121, C.I. disperse thread 9, C.I. solvent violet 8, 13, 14, 21, 27, oil-soluble dyes such as C.I. disperse violet 1, C.I. basic red 1, 2, 9, 12, 13, 14, 15, 17, 18, 22, 23, 24, 27, 29, 32, 34, 35, 36, 37, 38, 39, 40, C.I.Basic Violet 1, 3, 7, Basic dyes such as 10, 14, 15, 21, 25, 26, 27, 28 and the like can be mentioned.

  As other coloring pigments, as cyan coloring pigments, CI Pigment Blue 2, 3, 15, 16, 17, CI Bat Blue 6, CI Acid Blue 45, or a phthalocyanine skeleton And copper phthalocyanine pigments substituted with 1 to 5 phthalimidomethyl groups.

  As pigments for yellow, CI pigment yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 16, 17, 23, 65, 73, 83 C.I. Vat Yellow 1, 3, 20 and the like.

  The dyes and pigments as described above may be used alone or else may be used in any mixture in order to obtain a desired toner color tone. In addition, various food colorings can be suitably used in consideration of environmental protection and safety for the human body. The content of the colorant in the toner as described above can be widely changed according to a desired coloring effect. Usually, in order to obtain the best toner characteristics, that is, when considering the coloring power of printing, toner shape stability, toner scattering, etc., these colorants are usually based on 100 parts by mass of binder resin. 0.1 to 60 parts by mass, preferably 0.5 to 20 parts by mass is used.

<Other components of toner>
In the toner for developing an electrostatic charge image of the present invention, in addition to the binder resin and the colorant component described above, the following (in a proportion smaller than the content of the binder resin component) within the range that does not adversely affect the effect of the present invention: A compound may be contained. For example, silicone resin, polyester, polyurethane, polyamide, epoxy resin, polyvinyl butyral, rosin, modified rosin, terpene resin, phenol resin, aliphatic or alicyclic hydrocarbon resin such as low molecular weight polyethylene or low molecular weight polypropylene, aromatic Petroleum resin, chlorinated paraffin, paraffin wax and the like. Specific examples of the waxes preferably used include low molecular weight polypropylene and its by-products, low molecular weight polyesters and ester waxes, and aliphatic derivatives. Of these waxes, waxes obtained by fractionating waxes by molecular weight by various methods are also preferably used in the present invention. Further, oxidation, block copolymerization, and graft modification may be performed after fractionation.

  In particular, the electrostatic charge image developing toner of the present invention contains the wax component as described above, and when the tomographic observation of the toner is performed using a transmission electron microscope (TEM), these wax components are: When the toner is dispersed in a substantially spherical and / or spindle-shaped island shape in the binder resin, the toner has excellent characteristics.

<Toner creation method>
As a specific method for producing the toner for developing an electrostatic charge image of the present invention having the above-described configuration, any conventionally known method can be used. The electrostatic image developing toner of the present invention can be produced by, for example, a so-called pulverization method in which a toner is obtained by the following steps. Specifically, the above polyhydroxyalkanoate, resins such as a binder resin, and other waxes added as necessary are sufficiently mixed by a mixer such as a Henschel mixer or a ball mill, and then heated rolls. Pigments, dyes, or magnetic substances as colorants, and metal compounds that are added as needed, while melt-kneading using a thermal kneader such as a kneader or extruder to make the resins compatible with each other Or the like, and after cooling and solidifying, the solidified product is pulverized by a pulverizer such as a jet mill or a ball mill, and then classified to obtain the electrostatic image developing toner of the present invention having a desired particle size. Obtainable. In the classification step, it is preferable to use a multi-division classifier in terms of production efficiency.

  In addition, the binder resin and the above polyhydroxyalkanoate are used in a solvent solution (aromatic hydrocarbons such as toluene and xylene, halides such as chloroform and ethylene dichloride, ketones such as acetone and methyl ethyl ketone, and amides such as dimethylformamide). After mixing, stirring treatment, re-precipitation in water, filtration, drying, pulverization of the solidified product by a pulverizer such as a jet mill or a ball mill, classification is performed, and the static of the present invention having a desired particle size is obtained. A toner for developing a charge image can also be obtained. In the classification step, it is preferable to use a multi-division classifier in terms of production efficiency.

  The electrostatic image developing toner of the present invention can also be produced by the so-called polymerization method as described below. That is, in this case, the polyhydroxyalkanoate, a polymerizable monomer, a pigment as a colorant, a dye, or a magnetic material, and if necessary, a crosslinking agent, a polymerization initiator, a wax, and other additives. In the presence of a surfactant or the like, the polymerizable colored resin particles are synthesized by suspension polymerization in an aqueous dispersion medium, and the obtained particles are solid-liquid separated and then dried. Classification can be performed as necessary to obtain the electrostatic image developing toner of the present invention.

  Furthermore, colored fine particles containing no charge control agent are prepared by the above method, and then the polyhydroxyalkanoate is fixed to the particle surface by a mechanochemical method or the like alone or with an external additive such as colloidal silica. You can also

(Silica external additive)
In the present invention, it is preferable to externally add fine silica powder to the toner produced by the above method in order to improve charging stability, developability, fluidity and durability. As the silica fine powder used at this time, those having a specific surface area of 20 m ² / g or more (particularly 30 to 400 m ² / g) by nitrogen adsorption measured by the BET method give good results. In this case, the amount of fine silica powder is 0.01 to 8 parts by mass, preferably about 0.1 to 5 parts by mass, based on 100 parts by mass of toner particles. The silica fine powder used at this time includes silicone varnish, various modified silicone varnishes, silicone oil, various modified silicone oils, silane coupling agents, and functional groups as necessary for the purpose of hydrophobicity and chargeability control. It is preferable to use those treated with a treating agent such as a silane coupling agent or other organosilicon compound. These treatment agents may be used as a mixture.

(Inorganic powder)
In order to improve the developability and durability of the toner, it is also preferable to add the following inorganic powder. For example, oxides of metals such as magnesium, zinc, aluminum, cerium, cobalt, iron, zirconium, chromium, manganese, strontium, tin, antimony; complex metal oxides such as calcium titanate, magnesium titanate, strontium titanate; Metal salts such as calcium carbonate, magnesium carbonate, and aluminum carbonate; clay minerals such as kaolin; phosphate compounds such as apatite; silicon compounds such as silicon carbide and silicon nitride; and carbon powders such as carbon black and graphite. Among these, it is preferable to use fine powders of zinc oxide, aluminum oxide, cobalt oxide, manganese dioxide, strontium titanate and magnesium titanate.

(Lubricant)
Further, a lubricant powder as described below may be added to the toner. Examples thereof include fluorine resins such as Teflon and polyvinylidene fluoride; fluorine compounds such as carbon fluoride; fatty acid metal salts such as zinc stearate; fatty acid derivatives such as fatty acids and fatty acid esters; molybdenum sulfide and the like.

<About Career>
The electrostatic image developing toner of the present invention having the above-described configuration is used alone as a non-magnetic one-component developer, or constitutes a magnetic two-component developer together with a magnetic carrier, or a single toner And can be applied to various conventionally known toners such as a magnetic toner used as a magnetic one-component toner. Here, as the carrier for use in the two-component development method, any conventionally known carrier can be used. Specifically, particles having an average particle size of 20 to 300 μm formed of surface oxidized or unoxidized metal such as iron, nickel, cobalt, manganese, chromium, rare earth and their alloys or oxides are used as carrier particles. it can. In addition, the carrier used in the present invention is such that the surface of the carrier particles described above is attached or coated with a substance such as a styrene resin, an acrylic resin, a silicone resin, a fluorine resin, or a polyester resin. preferable.

<Magnetic toner>
The toner for developing an electrostatic charge image of the present invention may be a magnetic toner containing a magnetic material in toner particles. In this case, the magnetic material can also serve as a colorant. Magnetic materials used at this time include iron oxides such as magnetite, hematite and ferrite; metals such as iron, cobalt and nickel or these metals and aluminum, cobalt, copper, lead, magnesium, tin, zinc and antimony , Alloys with metals such as beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten, vanadium and mixtures thereof. These magnetic materials that can be used in the present invention preferably have an average particle diameter of 2 μm or less, preferably about 0.1 to 0.5 μm. The amount to be contained in the toner is preferably 20 to 200 parts by mass, particularly preferably 40 to 150 parts by mass with respect to 100 parts by mass of the binder resin.

  Furthermore, in order to achieve high image quality, it is necessary to be able to faithfully develop finer latent image dots. For this purpose, for example, the weight of toner particles for electrostatic image development according to the present invention is required. It is preferable to adjust so that an average diameter may be in the range of 4 μm to 9 μm. That is, toner particles having a weight average diameter of less than 4 μm are not preferable because the transfer efficiency is lowered, and a large amount of residual toner tends to remain on the photoconductor, which easily causes uneven image unevenness due to fog and transfer failure. . Further, when the weight average diameter of the toner particles exceeds 9 μm, characters and line images are likely to be scattered.

  In the present invention, the average particle size and the particle size distribution of the toner are a Coulter Counter TA-II type or Coulter Multisizer (manufactured by Coulter), etc. 9801 Measurement was performed by connecting a personal computer (NEC). A 1% NaCl aqueous solution is prepared using first-grade sodium chloride as the electrolytic solution used at that time. As the electrolytic solution, for example, commercially available ISOTON R-II (manufactured by Coulter Scientific Japan) can also be used. As a specific measurement method, 0.1 to 5 ml of a surfactant (preferably using an alkylbenzene sulfonate) is added as a dispersant to 100 to 150 ml of the above electrolytic aqueous solution, and 2 to 20 mg of a measurement sample is further added. To make a measurement sample. At the time of measurement, the electrolyte solution in which the measurement sample is suspended is subjected to a dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes, and then the Coulter counter TA-II type is used as a 100 μm aperture as an aperture. The volume and number of toners of 2 μm or more were measured, and the volume distribution and number distribution were calculated. Then, the volume-based weight average particle diameter (D4) obtained from the volume distribution according to the present invention and the number-based length average particle diameter (D1) obtained from the number distribution were obtained.

<Charge amount>
The toner for developing an electrostatic charge image of the present invention has a charge amount per unit mass (two-component method) of −10 to −80 μC / g, more preferably −15 to −70 μC / g. This is preferable for improving transfer efficiency in a transfer method using an applied transfer member.

A method for measuring the charge amount (two-component tribo) by the two-component method used in the present invention is shown below. For the measurement, the charge amount measuring apparatus shown in FIG. 7 was used. First, EFV 200/300 (manufactured by Powdertech) was used as a carrier in a fixed environment, and a mixture obtained by adding 0.5 g of toner to be measured to 9.5 g of the carrier was added to a polyethylene bottle having a capacity of 50 to 100 ml. And place it on a shaker with a constant amplitude. Set the shaking conditions to 100 mm amplitude and 100 rounds per minute, and shake for a certain period of time. Next, 1.0 to 1.2 g of the mixture is put in a metal measuring container 42 having a 500 mesh screen 43 at the bottom of the charge amount measuring apparatus shown in FIG. The total mass of the measuring container 42 at this time is weighed and is defined as W1 (g). Next, suction is performed from the suction port 47 with a suction device (not shown) (at least the part in contact with the measurement container 22), and the air flow control valve 46 is adjusted so that the pressure of the vacuum gauge 45 becomes 2450 Pa (250 mmAq). To do. In this state, suction is performed for 1 minute to remove the toner by suction. The potential of the electrometer 49 at this time is V (volt). Here, 48 is a capacitor, and the capacity is C (μF). Moreover, the mass of the whole measuring machine after suction is weighed and is defined as W2 (g). The triboelectric charge amount (μC / g) of the toner is calculated from these measured values according to the following equation.

Frictional charge (μC / g) = C × V / (W1-W2)

<Molecular weight distribution of binder resin>
In addition, the binder resin used for the constituent material of the toner for developing an electrostatic charge image of the present invention has a peak in the low molecular weight region in the range of 3,000 to 15,000 in the molecular weight distribution by GPC, particularly when produced by a pulverization method. It is preferable to have it. In other words, if the GPC peak in the low molecular weight region exceeds 15,000, it may be difficult to obtain a product with sufficiently improved transfer efficiency. In addition, it is not preferable to use a binder resin having a GPC peak of less than 3,000 in the low molecular weight region because fusion is likely to occur during the surface treatment.

  In the present invention, the molecular weight of the binder resin was measured by GPC (gel permeation chromatography). As a specific GPC measurement method, a sample obtained by previously extracting toner with a THF (tetrahydrofuran) solvent for 20 hours using a Soxhlet extractor was used for measurement, and the column configuration was A-801, 802 manufactured by Showa Denko. 803, 804, 805, 806, and 807 were connected, and a molecular weight distribution was measured using a standard polystyrene resin calibration curve. In the present invention, a binder resin in which the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured as described above is in the range of 2 to 100 is used. It is preferable.

<Glass transition point of toner>
Further, the toner of the present invention has a glass transition point Tg of 40 ° C. to 75 ° C., more preferably 52 ° C. to 70 ° C., from the viewpoint of fixability and storage stability by using an appropriate material. It is preferable to be prepared. In this case, the glass transition point Tg may be measured, for example, using a highly accurate internal heating input compensation type differential scanning calorimeter such as DSC-7 manufactured by PerkinElmer. The measurement is performed according to ASTM D 3418-82. In the present invention, when measuring the glass transition point Tg, the measurement sample is heated once and the entire history is taken, then rapidly cooled, and again at a temperature rate of 10 ° C / min and a temperature of 0 to 200 ° C. A DSC curve measured when the temperature is raised may be used.

<Image forming method>
The electrostatic charge developing toner of the present invention having the above-described configuration includes at least a charging step in which a voltage is applied to the charging member from the outside to charge the electrostatic latent image carrier, and a charged electrostatic latent image. A step of forming an electrostatic charge image on the image carrier, a development step of developing the electrostatic charge image with toner to form a toner image on the electrostatic latent image carrier, and a toner image on the electrostatic latent image carrier An image forming method having a transfer step for transferring the toner image onto the recording material and a heat fixing step for heating and fixing the toner image on the recording material, or the transfer step intermediates the toner image on the electrostatic latent image carrier. It is particularly preferable to apply to an image forming method comprising a first transfer step for transferring to a transfer member and a second transfer step for transferring a toner image on the intermediate transfer member to a recording material.

  Next, although an Example and a comparative example are given and this invention is demonstrated still in detail, this Example does not limit this invention at all. Moreover, all the parts in the following mixing | blending are a mass part. “%” Is based on mass unless otherwise specified.

  First, as an example of a method for producing a charge control agent according to the present invention, a method for producing a polyhydroxyalkanoate according to the present invention and a subsequent chemical treatment step are shown below (Examples 1 to 5).

(Example 1)
<Preparation 1: Biosynthesis of ω-alkene PHA (1)>
Twenty 500 ml shake flasks are prepared. For each, 0.5 wt% of polypeptone (Wako Pure Chemical Industries), 5-phenoxyvaleric acid 6 mmol / L and 10-undecenoic acid 3.75 mmol / L are dissolved in 200 ml of the M9 medium. The mixture was sterilized by autoclaving in a shake flask and then cooled to room temperature. To the prepared medium, 2 ml of Pseudomonas chicory eye strain YN2 cultured in advance in M9 medium containing 0.5% polypeptone for 8 hours was added to each medium and cultured at 30 ° C. for 64 hours. After culturing, the culture broth was collected, and 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 72 hours. The chloroform from which the polymer was extracted was filtered through a 0.45 μm membrane filter, concentrated by an evaporator, and then reprecipitated in cold methanol to recover the polymer. Then, it dried under reduced pressure and obtained the target polymer.

As a result of weighing the obtained polymer , in this example, 1528 mg (dry weight) of PHA was obtained. The average molecular weight of the obtained PHA was evaluated by gel permeation chromatography (GPC: Tosoh HLC-8220, column: Tosoh TSK-GEL Super HM-H, solvent: chloroform, converted to polystyrene). As a result, the number average molecular weight Mn = 104000 and the weight average molecular weight Mw = 231000.

Furthermore, in order to specify the structure of the obtained PHA, NMR analysis was performed under the following conditions.
<Measurement equipment> FT-NMR: Bruker DPX400
Resonance frequency: ¹ H = 400 MHz
<Measurement conditions> Measurement nuclide: ¹ H
Solvent: TMS / CDCl ₃
Measurement temperature: room temperature As a result, as a monomer unit, 3-hydroxy-5-phenoxyvaleric acid represented by the following chemical formula (24), 3-hydroxy-10-undecenoic acid represented by the chemical formula (25), 3 represented by the chemical formula (26) It was confirmed to be a polyhydroxyalkanoate copolymer containing -hydroxy-8-nonenoic acid and 3-hydroxy-6-heptenoic acid represented by the chemical formula (27).

Further, the unit ratio is 69 mol% 3-hydroxy-5-phenoxyvaleric acid, 3-hydroxy-10-undecenoic acid, 3-hydroxy-8-nonenoic acid, 3-hydroxy-6-, based on ¹ H-NMR spectrum. It was confirmed that the total of 3 units of heptenoic acid was 23 mol%, and the others (linear 3-hydroxyalkanoic acid having 4 to 12 carbon atoms and 3-hydroxyalk-5-enoic acid having 10 or 12 carbon atoms) were 8 mol%. .

  From this result, it was confirmed that the PHA was represented by the chemical formula (19) containing a 3-hydroxy-10-undecenoic acid unit.

<Synthesis of aliphatic carboxy PHA by oxidation reaction (1)>
303 mg of the polyhydroxyalkanote obtained in Preparatory Preparation 1 was added to a 200 ml eggplant flask and dissolved by adding 20 ml of dichloromethane. This was placed in an ice bath, and 3 ml of acetic acid and 300 mg of 18-crown-6-ether were added and stirred. Next, 241 mg of potassium permanganate was slowly added in an ice bath and stirred at room temperature for 20 hours. After completion of the reaction, 50 ml of water and sodium bisulfite were added. Thereafter, the liquidity was adjusted to pH 1 with 1.0 mol / L (1.0 N) hydrochloric acid. Dichloromethane in the mixed solution was distilled off with an evaporator, and then the polymer in the solution was recovered. This was washed with 100 ml of methanol, and further washed with 100 ml of pure water three times, and then the polymer was recovered. 247 mg of the intended PHA was obtained by drying under reduced pressure.

  The average molecular weight of the obtained PHA was evaluated by gel permeation chromatography (GPC: Tosoh HLC-8220, column: Tosoh TSK-GEL Super HM-H, solvent: chloroform, polystyrene conversion). As a result, the number average molecular weight Mn = 29400 and the weight average molecular weight Mw = 102800.

  In order to specify the structure of the obtained PHA, NMR analysis was performed under the above-mentioned conditions.

  As a result, 3-hydroxy-5-phenoxyvaleric acid represented by the following chemical formula (24), 3-hydroxy-9-carboxynonanoic acid represented by chemical formula (28), and 3-hydroxy- It was confirmed to be a polyhydroxyalkanoate copolymer containing 7-carboxyheptanoic acid and 3-hydroxy-5-carboxyvaleric acid represented by the chemical formula (30).

  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 (50 mg) was added to a 100 ml eggplant flask, and chloroform (3.5 ml) and methanol (0.7 ml) were added and dissolved. To this, 2 ml of 0.63 mol / L trimethylsilyldiazomethane-hexane solution (Tokyo Kasei) was added and stirred at room temperature for 30 minutes. After the completion of the reaction, the polymer was recovered after distilling off with an evaporator. The polymer was recovered after washing with 50 ml of methanol. 49 mg of PHA was obtained by drying under reduced pressure.

  NMR analysis was performed using the same method as described above. As a result, the ratio of units was 83 mol% of 3-hydroxy-5-phenoxyvaleric acid, 3-hydroxy-9-carboxynonanoic acid, 3-hydroxy-7-heptanoic acid, and 3-hydroxy-5-valeric acid. It was confirmed that the total of the units was 8 mol%, and the others were 9 mol% (linear 3-hydroxyalkanoic acid having 4 to 12 carbon atoms and 3-hydroxyalk-5-enoic acid having 10 or 12 carbon atoms).

  By scaling up the above method, 50 g of PHA was obtained, and this was designated as PHA (1).

[Example 2]
<Preparation 2: Biosynthesis of ω-alkene PHA (2)>
Twenty 500 ml shake flasks were prepared, each containing 0.5 wt% polypeptone (Wako Pure Chemical), 4-cyclohexylbutyric acid 6 mmol / L and 10-undecenoic acid 3 mmol / L in 200 ml of the M9 medium, and a 500 ml shake flask. The mixture was sterilized by autoclaving and then cooled to room temperature. Into the prepared medium, 2 ml each of Pseudomonas chicory eye strain YN2 cultured in M9 medium containing 0.5% polypeptone in advance for 8 hours was added and cultured at 30 ° C. for 60 hours. After culturing, the culture broth was collected, and 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 25 ° C. for 72 hours. The chloroform from which the polymer was extracted was filtered through a 0.45 μm membrane filter, concentrated by an evaporator, and then reprecipitated in cold methanol to recover the polymer. Then, it dried under reduced pressure and obtained the target polymer.

As a result of weighing the obtained polymer, 1433 mg (dry weight) of PHA was obtained in this example. The average molecular weight of the obtained PHA was evaluated under the same GPC conditions as in Example 1. As a result, the number average molecular weight Mn = 143000 and the weight average molecular weight Mw = 458000. Furthermore, in order to specify the structure of the obtained PHA, NMR analysis was performed under the same conditions as in Example 1.

  As a result, as a monomer unit, 3-hydroxy-4-cyclohexylbutyric acid represented by the following chemical formula (31), 3-hydroxy-10-undecenoic acid represented by the chemical formula (25), 3-hydroxy-8- represented by the chemical formula (26) It was confirmed that it was a polyhydroxyalkanoate copolymer containing nonenoic acid and 3-hydroxy-6-heptenoic acid represented by chemical formula (27).

Further, the ratio of the unit was determined from the ¹ H-NMR spectrum. The total of three units of 3-hydroxy-10-undecenoic acid, 3-hydroxy-8-nonenoic acid and 3-hydroxy-6-heptenoic acid was 37 mol%, 3- It was confirmed that the content was 63 mol% of hydroxy-4-cyclohexylbutyric acid and other (linear 3-hydroxyalkanoic acid having 4 to 12 carbon atoms and 3-hydroxyalk-5-enoic acid having 10 or 12 carbon atoms).

<Synthesis of aliphatic carboxy PHA by oxidation reaction (2)>
301 mg of the polyhydroxyalkanoate obtained in Preparatory Preparation 2 was added to a 200 ml eggplant flask and dissolved by adding 20 ml of dichloromethane. This was placed in an ice bath, 3 ml of acetic acid and 541 mg of 18-crown-6-ether were added and stirred. Next, 430 mg of potassium permanganate was slowly added in an ice bath and stirred at room temperature for 20 hours. After completion of the reaction, 50 ml of water and sodium bisulfite were added. Thereafter, the liquidity was adjusted to pH 1 with 1.0 mol / L (1.0 N) hydrochloric acid. Dichloromethane in the mixed solution was distilled off with an evaporator, and then the polymer in the solution was recovered. This was washed with 100 ml of methanol, and further washed with 100 ml of pure water three times, and then the polymer was recovered. 184 mg of the intended PHA was obtained by drying under reduced pressure.

  The average molecular weight of the obtained PHA was evaluated in the same manner as in Example 1. As a result, the number average molecular weight Mn = 111800 and the weight average molecular weight Mw = 272800 were obtained.

  In order to specify the structure of the obtained PHA, NMR analysis was performed under the same conditions as in Example 1.

  As a result, 3-hydroxy-4-cyclohexylbutanoic acid represented by the following chemical formula (31), 3-hydroxy-9-carboxynonanoic acid represented by the chemical formula (28), and 3-hydroxy-7 represented by the chemical formula (29) as monomer units. It was confirmed to be a polyhydroxyalkanoate copolymer containing -carboxyheptanoic acid and 3-hydroxy-5-carboxyvaleric acid represented by the chemical formula (30).

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

  30 mg of PHA as the target product was added to a 100 ml eggplant flask, and 2.1 ml of chloroform and 0.4 ml of methanol were added and dissolved. To this, 0.9 ml of 0.63 mol / L trimethylsilyldiazomethane-hexane solution (Tokyo Kasei) was added and stirred at room temperature for 30 minutes. After the completion of the reaction, the polymer was recovered after distilling off with an evaporator. The polymer was recovered after washing with 50 ml of methanol. 31 mg of PHA was obtained by drying under reduced pressure.

NMR analysis was performed using the same method as described above. As a result, the unit ratio was 9 mol% in total of three units of 3-hydroxy-9-carboxynonanoic acid, 3-hydroxy-7-heptanoic acid and 3-hydroxy-5-valeric acid, from ¹ H-NMR spectrum. It was confirmed that 3-hydroxy-4-cyclohexylbutyric acid and others (linear 3-hydroxyalkanoic acid having 4 to 12 carbon atoms and 3-hydroxyalk-5-enoic acid having 10 or 12 carbon atoms) total 91 mol%. .

By scaling up the above method, 50 g of PHA was obtained, and this was designated as PHA (2).
Example 3
<Preparation 3: Biosynthesis of ω-alkene PHA (3)>
Three 2000 ml shake flasks were prepared, and polypeptone (Wako Pure Chemical Industries) 0.5 wt% 5- (phenylsulfanyl) valeric acid 4.8 mmol / L and 10-undecenoic acid 2 mmol / L were dissolved in 1000 ml of the M9 medium. The mixture was sterilized by autoclaving in a 2000 ml shake flask and then cooled to room temperature. To the prepared medium, 10 ml each of Pseudomonas chicory eye strain YN2 cultured in M9 medium containing 0.5% polypeptone in advance for 8 hours was added and cultured at 30 ° C. for 38 hours. After culturing, the culture broth was collected, and 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 25 hours. The chloroform from which the polymer was extracted was filtered through a 0.45 μm membrane filter, concentrated by an evaporator, and then reprecipitated in cold methanol to recover the polymer. Then, it dried under reduced pressure and obtained the target polymer.

As a result of weighing the obtained polymer, 1934 mg (dry weight) of PHA was obtained in this example.
The average molecular weight of the obtained PHA was evaluated in the same manner as in Example 1. As a result, the number average molecular weight Mn = 430000 and the weight average molecular weight Mw = 1500,000. Furthermore, in order to specify the structure of the obtained PHA, NMR analysis was performed under the same conditions as in Example 1.

  As a result, 3-hydroxy-5- (phenylsulfanyl) valeric acid represented by the following chemical formula (32), 3-hydroxy-10-undecenoic acid represented by chemical formula (25), and 3- It was confirmed to be a polyhydroxyalkanoate copolymer containing hydroxy-8-nonenoic acid and 3-hydroxy-6-heptenoic acid represented by the chemical formula (27).

The unit ratio is 78 mol% 3-hydroxy-5- (phenylsulfanyl) valeric acid, 3-hydroxy-10-undecenoic acid, 3-hydroxy-8-nonenoic acid, 3-hydroxy based on ¹ H-NMR spectrum. The total of the 3 units of -6-heptenoic acid is 19 mol%, and the others (linear 4-hydroxyalkanoic acid having 4 to 12 carbon atoms and 3-hydroxyalk-5-enoic acid having 10 or 12 carbon atoms) are 3 mol%. It was confirmed.

<Synthesis of aliphatic carboxy PHA by oxidation reaction (3)>
302 mg of the polyhydroxyalkanote obtained in Preparatory Preparation 3 was added to a 200 ml eggplant flask and dissolved by adding 20 ml of dichloromethane. This was placed in an ice bath, and 3 ml of acetic acid and 1154 mg of 18-crown-6-ether were added and stirred. Next, 917 mg of potassium permanganate was slowly added in an ice bath and stirred at room temperature for 19 hours. After completion of the reaction, 50 ml of water and 3010 mg of sodium bisulfite were added. Thereafter, the liquidity was adjusted to pH 1 with 1.0 N hydrochloric acid. Dichloromethane in the mixed solution was distilled off with an evaporator, and then the polymer in the solution was recovered. This was washed with 100 ml of methanol, and further washed with 100 ml of pure water three times, and then the polymer was recovered. By drying under reduced pressure, 311 mg of the intended PHA was obtained.

  As a result of evaluation in the same manner as in Example 1, the average molecular weight of the obtained PHA was a number average molecular weight Mn = 62000 and a weight average molecular weight Mw = 260,000.

  In order to specify the structure of the obtained PHA, NMR analysis was performed under the same conditions as in Example 1.

  As a result, as a monomer unit, 3-hydroxy-5- (phenylsulfonyl) valeric acid represented by the following chemical formula (33), 3-hydroxy-9-carboxynonanoic acid represented by the chemical formula (28), and 3 represented by the chemical formula (29) It was confirmed to be a polyhydroxyalkanoate copolymer containing -hydroxy-7-carboxyheptanoic acid and 3-hydroxy-5-carboxyvaleric acid represented by the chemical formula (30).

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

  30 mg of PHA, which was the target product, was added to a 100 ml eggplant flask, and dissolved by adding 2.1 ml of chloroform and 0.7 ml of methanol. To this, 0.5 ml of a 0.63 mol / L trimethylsilyldiazomethane-hexane solution (Aldrich) was added and stirred at room temperature for 30 minutes. After the completion of the reaction, the polymer was recovered after distilling off with an evaporator. The polymer was recovered after washing with 50 ml of methanol. 31 mg of PHA was obtained by drying under reduced pressure.

NMR analysis was performed using the same method as described above. As a result, the ratio of the unit was determined from the ¹ H-NMR spectrum to be 89 mol% 3-hydroxy-5- (phenylsulfonyl) valeric acid, 3-hydroxy-9-carboxynonanoic acid, 3-hydroxy-7-heptanoic acid, 3 3-hydroxy-5-valeric acid 3 units total 8mol%, others (linear 3-hydroxyalkanoic acid having 4 to 12 carbon atoms and 3-hydroxyalk-5-enoic acid having 10 or 12 carbon atoms) total 3mol% It was confirmed that.

  By scaling up the above method, 50 g of PHA was obtained, and this was designated as PHA (3).

Example 4
<Preparation 4: Biosynthesis of ω-alkene PHA (4)>
Three 2000 ml shake flasks are prepared, and 0.5 wt% of polypeptone (Wako Pure Chemical Industries, Ltd.), 5-phenylvaleric acid 6 mmol / L and 10-undecenoic acid 1.5 mmol / L are dissolved in 1000 ml of the M9 medium. The mixture was sterilized by autoclaving in a shake flask and then cooled to room temperature. Into the prepared medium, 10 ml each of Pseudomonas chicory eye strain YN2 cultured in M9 medium containing 0.5% polypeptone in advance for 8 hours was added and cultured at 30 ° C. for 60 hours. After culture, each culture solution was collected, and 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 25 ° C. for 72 hours. The chloroform from which the polymer was extracted was filtered through a 0.45 μm membrane filter, concentrated by an evaporator, and then reprecipitated in cold methanol to recover the polymer. Then, it dried under reduced pressure and obtained the target polymer.

  As a result of weighing the obtained polymer, PHA1533 mg (dry weight) was obtained in this example.

  The average molecular weight of the obtained PHA was evaluated under the same conditions as in Example 1. As a result, the number average molecular weight Mn = 72000 and the weight average molecular weight Mw = 1700 were obtained.

  Furthermore, in order to specify the structure of the obtained PHA, NMR analysis was performed under the same conditions as in Example 1.

  As a result, as a monomer unit, 3-hydroxy-5-phenylvaleric acid represented by the following chemical formula (34), 3-hydroxy-10-undecenoic acid represented by the chemical formula (25), and 3-hydroxy-8 represented by the chemical formula (26) -Nonenoic acid, a polyhydroxyalkanoate copolymer containing 3-hydroxy-6-heptenoic acid represented by the chemical formula (27) was confirmed.

Further, the proportion of the unit was determined from the ¹ H-NMR spectrum. The total of the three units of 3-hydroxy-10-undecenoic acid, 3-hydroxy-8-nonenoic acid and 3-hydroxy-6-heptenoic acid was 12 mol%, 3- It was confirmed that it was 85 mol% of hydroxy-5-phenylvaleric acid and 3 mol% of others (linear 3-hydroxyalkanoic acid having 4 to 12 carbon atoms and 3-hydroxyalk-5-enoic acid having 10 or 12 carbon atoms). .

<Synthesis of aliphatic carboxy PHA by oxidation reaction (4)>
1002 mg of the polyhydroxyalkanoate obtained in Preparatory Preparation 4 was added to a 500 ml eggplant flask and dissolved by adding 60 ml of acetone. This was placed in an ice bath, 10 ml of acetic acid and 537 mg of 18-crown-6-ether were added and stirred. Next, 429 mg of potassium permanganate was slowly added in an ice bath, stirred for 2 hours in an ice bath, and further stirred for 18 hours at room temperature. After completion of the reaction, 40 ml of ethyl acetate, 30 ml of water and 1000 mg of sodium bisulfite were added. Thereafter, the liquidity was adjusted to pH = 1 with 1.0 N hydrochloric acid. The polymer was extracted and the polymer was recovered by evaporating the solvent. This was washed with 200 ml of pure water, further washed with 200 ml of methanol, further washed with 200 ml of pure water three times, and finally washed with 200 ml of methanol to recover the polymer. The polymer obtained here was dissolved in 10 ml of tetrahydrofuran and dialyzed for 1 day in a 1 L beaker containing 500 ml of methanol using a dialysis membrane (Spectra / Por Standard Regenerative Cellulose Dialysis Membrane 3 manufactured by Spectrum). It was. The polymer in the dialysis membrane was collected and dried under reduced pressure to obtain 953 mg of the intended PHA.

  The average molecular weight of the obtained PHA was evaluated under the same conditions as in Example 1. As a result, the number average molecular weight Mn = 43000 and the weight average molecular weight Mw = 94000 were obtained.

  In order to specify the structure of the obtained PHA, NMR analysis was performed under the same conditions as in Example 1.

  As a result, 3-hydroxy-5-phenylvaleric acid represented by the following chemical formula (34) as a monomer unit, 3-hydroxy-9-carboxynonanoic acid represented by the chemical formula (28), and 3-hydroxy- represented by the chemical formula (29) It was confirmed to be a polyhydroxyalkanoate copolymer containing 7-carboxyheptanoic acid and 3-hydroxy-5-carboxyvaleric acid shown in chemical formula (30).

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

  30 mg of PHA, which is the target product, was added to a 100 ml eggplant flask and dissolved by adding 2.1 ml of chloroform and 0.7 ml of methanol. To this was added 0.3 ml of a 2.0 mol% / L trimethylsilyldiazomethane-hexane solution (manufactured by Aldrich), 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. After further washing with 50 ml of methanol, the polymer was recovered. 30 mg of PHA was obtained by drying under reduced pressure.

  NMR analysis was performed under the same conditions as in Example 1. As a result, the unit ratio was 86 mol% 3-hydroxy-5-phenylvaleric acid, 3-hydroxy-9-carboxynonanoic acid, 3-hydroxy-7-carboxyheptanoic acid, and 3-hydroxy-5-carboxyvaleric acid. It was confirmed that the total of the three units was 9 mol%, and the other was 5 mol% (linear 3-hydroxyalkanoic acid having 4 to 12 carbon atoms and 3-hydroxyalk-5-enoic acid having 10 or 12 carbon atoms).

  By scaling up the above method, 50 g of PHA was obtained, and this was designated as PHA (4).

(Example 5)
<Preparation 5: Biosynthesis of ω-alkene PHA (5)>
Twenty 2000 ml shake flasks were prepared, each containing 0.5 wt% polypeptone (Wako Pure Chemical Industries), 5 benzoylvaleric acid 6 mmol / L and 10-undecenoic acid 1 mmol / L in 1000 ml of the M9 medium, and shaken 2000 ml. The flask was sterilized by autoclaving and then cooled to room temperature. Into the prepared medium, 10 ml each of Pseudomonas chicory eye strain YN2 cultured in M9 medium containing 0.5% polypeptone in advance for 8 hours was added and cultured at 30 ° C. for 60 hours. After culture, each culture solution was collected, and 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 25 ° C. for 72 hours. The chloroform from which the polymer was extracted was filtered through a 0.45 μm membrane filter, concentrated by an evaporator, and then reprecipitated in cold methanol to recover the polymer. Then, it dried under reduced pressure and obtained the target polymer.

  As a result of weighing the obtained polymer, 1027 mg (dry weight) of PHA was obtained in this example.

  The average molecular weight of the obtained PHA was evaluated under the same conditions as in Example 1. As a result, the number average molecular weight Mn = 120,000 and the weight average molecular weight Mw = 370,000.

  Furthermore, in order to specify the structure of the obtained PHA, NMR analysis was performed under the same conditions as in Example 1.

  As a result, 3-hydroxy-5-benzoylvaleric acid represented by the following chemical formula (35), 3-hydroxy-10-undecenoic acid represented by chemical formula (25), and 3-hydroxy-8 represented by chemical formula (26) as monomer units. -Nonenoic acid, a polyhydroxyalkanoate copolymer containing 3-hydroxy-6-heptenoic acid represented by the chemical formula (27) was confirmed.

The ratio of the unit is 11 mol% in total for the three units of 3-hydroxy-10-undecenoic acid, 3-hydroxy-8-nonenoic acid and 3-hydroxy-6-heptenoic acid, according to ¹ H-NMR spectrum. It was confirmed that it was 82 mol% of hydroxy-5-benzoylvaleric acid and 7 mol% of others (linear 3-hydroxyalkanoic acid having 4 to 12 carbon atoms and 3-hydroxyalk-5-enoic acid having 10 or 12 carbon atoms). .
1003 mg of the polyhydroxyalkanoate obtained in Preparatory Preparation 5 was added to a 500 ml eggplant flask and dissolved by adding 20 ml of dichloromethane. This was placed in an ice bath, 10 ml of acetic acid and 410 mg of 18-crown-6-ether were added and stirred. Next, 327 mg of potassium permanganate was slowly added in an ice bath, stirred for 2 hours in an ice bath, and further stirred for 18 hours at room temperature. After completion of the reaction, 100 ml of water and 1000 mg of sodium bisulfite were added. Thereafter, the liquidity was adjusted to pH = 1 with 1.0 N hydrochloric acid. After the dichloromethane in the mixed solvent was distilled off by an evaporator, the polymer in the solution was recovered. This was washed with 200 ml of pure water, further washed with 200 ml of methanol, further washed with 200 ml of pure water three times, and finally washed with 200 ml of methanol to recover the polymer. The polymer obtained here was dissolved in 10 ml of tetrahydrofuran and dialyzed for 1 day in a 1 L beaker containing 500 ml of methanol using a dialysis membrane (Spectra / Por Standard Regenerative Cellulose Dialysis Membrane 3 manufactured by Spectrum). It was. The polymer in the dialysis membrane was collected and dried under reduced pressure to obtain 948 mg of the intended PHA.

  The average molecular weight of the obtained PHA was evaluated under the same conditions as in Example 1. As a result, the number average molecular weight Mn = 76000 and the weight average molecular weight Mw = 235000 were found.

  In order to specify the structure of the obtained PHA, NMR analysis was performed under the same conditions as in Example 1.

  As a result, 3-hydroxy-5-benzoylvaleric acid represented by chemical formula (35) as a monomer unit, 3-hydroxy-9-carboxynonanoic acid represented by chemical formula (28), and 3-hydroxy-7- represented by chemical formula (29). It was confirmed to be a polyhydroxyalkanoate copolymer containing carboxyheptanoic acid and 3-hydroxy-5-carboxyvaleric acid represented by the chemical formula (30).

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

  30 mg of PHA, which is the target product, was added to a 100 ml eggplant flask and dissolved by adding 2.1 ml of chloroform and 0.7 ml of methanol. To this was added 0.3 ml of a 2.0 mol% / L trimethylsilyldiazomethane-hexane solution (manufactured by Aldrich), 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. After further washing with 50 ml of methanol, the polymer was recovered. 29 mg of PHA was obtained by drying under reduced pressure.

  NMR analysis was performed under the same conditions as in Example 1. As a result, the proportion of units was 84 mol% of 3-hydroxy-5-benzoylvaleric acid, 3-hydroxy-9-carboxynonanoic acid, 3-hydroxy-7-carboxyheptanoic acid, and 3-hydroxy-5-carboxyvaleric acid. It was confirmed that the total of the three units was 9 mol%, and the others were 7 mol% (linear 3-hydroxyalkanoic acid having 4 to 12 carbon atoms and 3-hydroxyalk-5-enoic acid having 10 or 12 carbon atoms).

  By scaling up the above method, 50 g of PHA was obtained, and this was designated as PHA (5).

Example 6
To 1000 ml of the M9 medium, 5.0 g of polypeptone (Wako Pure Chemical Industries) and 5-phenylvaleric acid and sebacic acid monomethyl ester are added to a final concentration of 4 mmol / L and 1 mmol / L, respectively, and placed in a 2000 ml shake flask. The mixture was sterilized by autoclaving and then cooled to room temperature. Into the prepared medium, 5 ml of a culture solution of Pseudomonas chicory eye strain YN2 previously cultured with shaking in M9 medium containing 0.5% polypeptone at 30 ° C. for 8 hours was added and cultured at 30 ° C. for 40 hours. After culturing, the cells were harvested by centrifugation, washed with methanol, and lyophilized. After weighing the dried cells, chloroform was added, and the polymer was extracted by stirring at 50 ° C. for 48 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. As a result of weighing the obtained polymer, 671 mg (dry weight) of PHA was obtained in this example.

  The structure of the resulting polymer was determined using the following methylolysis-GC / MS method. That is, 5 mg of the polymer was dissolved in 2 ml of chloroform, 2 ml of methanol-3% sulfuric acid solution was further added, and the mixture was refluxed at 100 ° C. for 3.5 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, 10 ml of deionized water was added, and the mixture was stirred and separated, and the organic layer was dehydrated with magnesium sulfate (anhydrous). -5050A: Column: DB-WAXETR 0.32 mm × 30 m). The main peaks were 35.6 minutes, 38.0 minutes, and 45.8 minutes. As a result of measuring the mass spectrum (MS) of each peak, the peak at 35.6 minutes is the chemical formula (36):

  The peak of 38.0 minutes is derived from the chemical formula (34):

  The peak from 45.8 minutes is derived from the chemical formula (37):

  It was derived from the unit shown in. The ratio of each unit calculated from the TIC peak area ratio was 12.0%, 77.7%, and 6.7%, respectively.

  The average molecular weight of the obtained PHA was evaluated under the same conditions as in Example 1. As a result, the number average molecular weight Mn = 81000 and the weight average molecular weight Mw = 159000.

  By scaling up the above method, 50 g of PHA was obtained, and this was designated as PHA (6).

(Example 7)
Two 2000 ml shake flasks were prepared, each containing 0.5 p% polypeptone (Wako Pure Chemicals), 5 phenoxyvaleric acid 4 mmol / L, and dodecanedioic acid monoethyl ester 1 mmol / L in 1000 ml of the M9 medium. The mixture was placed in a shake flask and sterilized by autoclaving, and then cooled to room temperature. Into the prepared medium, 5 ml of Pseudomonas chicory eye strain YN2 cultured in an M9 medium containing 0.5% polypeptone in advance at 30 ° C. for 8 hours was added and cultured at 30 ° C. for 41 hours. After culturing, the cells were harvested by centrifugation, washed with methanol, and lyophilized. After weighing the dried cells, chloroform was added, and the polymer was extracted by stirring at 50 ° C. for 48 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. As a result of weighing the obtained polymer, 680 mg (dry weight) of PHA was obtained in this example.

  The average molecular weight of the obtained PHA was evaluated under the same conditions as in Example 1. As a result, the number average molecular weight Mn = 69000 and the weight average molecular weight Mw = 135000.

  Furthermore, in order to specify the structure of the obtained PHA, NMR analysis was performed under the same conditions as in Example 1.

  As a result, 74 mol% of 3-hydroxy-5-phenoxyvaleric acid represented by the chemical formula (24), 3-hydroxy-11-ethoxycarbonylundecanoic acid represented by the chemical formula (38), and 3-hydroxy represented by the chemical formula (39) -9-ethoxycarbonylnonanoic acid, 17 mol% in total of three units of 3-hydroxy-7-ethoxycarbonylheptanoic acid represented by the chemical formula (40), other (linear C3-C12 linear 3-hydroxyalkanoic acid and This was confirmed to be a polyhydroxyalkanoate copolymer containing 9 mol% of 3-hydroxyalk-5-enoic acid having 10 or 12 carbon atoms.

  By scaling up the above method, 50 g of PHA was obtained, and this was designated as PHA (7).

  The compounds obtained as in Examples 1 to 7 were designated as Exemplified Compounds (1) to (7) and used in Example 8 and later.

  Next, various toners were manufactured using the charge control agents manufactured as in Examples 1 to 7 by a method selected from the methods of the present invention, and evaluated.

(Example 8)
First, an aqueous Na ₃ PO ₄ solution was added to a 2-liter four-necked flask equipped with a high-speed stirrer TK-homomixer, the rotation speed was adjusted to 10,000 rpm, and the mixture was heated to 60 ° C. An aqueous CaCl ₂ solution was gradually added thereto to prepare an aqueous dispersion medium containing a minute hardly water-soluble dispersant Ca ₃ (PO ₄ ) ₂ .

On the other hand, after dispersing for 3 hours using a ball mill according to the following composition, 10 parts by weight of a release agent (ester wax) and 10 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator. A polymerizable monomer composition was prepared by adding parts.
-82 parts by weight of styrene monomer-18 parts by weight of ethylhexyl acrylate monomer-0.1 part by weight of divinylbenzene monomer-6 parts by weight of cyan colorant (C.I. Pigment Blue 15)-Polyethylene oxide resin (molecular weight 3200, Acid value 8) 5 parts by mass. Illustrative compound (1) 2 parts by mass.

Next, the polymerizable monomer composition obtained above was put into the previously prepared aqueous dispersion medium and granulated while maintaining the rotational speed of 10,000 rpm. Thereafter, while stirring with a paddle stirring blade, the mixture was reacted at 65 ° C. for 3 hours and then polymerized at 80 ° C. for 6 hours to complete the polymerization reaction. After completion of the reaction, the suspension was cooled and acid was added to dissolve the poorly water-soluble dispersant Ca ₃ (PO ₄ ) ₂ , followed by filtration, washing with water and drying to obtain blue polymer particles (1). The particle size of the resulting blue polymer particles (1) measured using a Coulter Counter Multisizer (manufactured by Coulter Inc.) is a weight average particle size of 6.8 μm, and the amount of fine powder (the proportion of particles having a particle distribution of 3.17 μm or less in the number distribution) Was 5.1% by number.

To 100 parts by weight of the blue polymer particles (1) prepared above, 1.3 parts by weight of hydrophobic silica fine powder (BET: 270 m ^{2 /} g) treated with hexamethyldisilazane as a flow improver is dry-mixed with a Henschel mixer. Thus, the blue toner (1) of this example was obtained. Further, 7 parts by weight of this blue toner (1) and 93 parts by weight of a resin-coated magnetic ferrite carrier (average particle size: 45 μm) were mixed to prepare a two-component blue developer (1) for magnetic brush development. .

(Examples 9 to 14)
The blue toners (2) to (7) of Examples 9 to 14 were prepared in the same manner as in Example 8, except that 2.0 parts by mass of the exemplified compounds (2) to (7) were used instead of the exemplified compound (1). Got. The characteristics of these toners were measured in the same manner as in Example 8, and the results are shown in Table 1. In addition, using this, in the same manner as in Example 8, two-component blue developers (2) to (7) were obtained.

(Comparative Example 1)
A blue toner (8) of Comparative Example 1 was obtained in the same manner as in Example 8 except that the exemplified compound was not used. The characteristics of this toner were measured in the same manner as in Example 8. The results are shown in Table 1. In addition, using this, the two-component blue developer (8) of Comparative Example 1 was obtained in the same manner as in Example 8.

<Evaluation>
Regarding the two-component blue developers (1) to (7) obtained in Examples 8 to 14 and the two-component blue developer (8) obtained in Comparative Example 1, normal temperature and normal humidity (25 ° C., 60 % RH) and high-temperature and high-humidity (30 ° C., 80% RH), the charge amount of the toner after stirring for 10 seconds and 300 seconds is measured using the charge amount measurement method described above. It was measured. And the second decimal place was rounded off from the measured value of the two-component blow-off charge amount, and the following criteria were used for evaluation. The results are summarized in Table 1.

[Charging]
◎: Very good (-20μC / g or less)
○: Good (-19.9 to -10.0μC / g)
Δ: Practical use possible (-9.9 to -5.0μC / g)
X: Not practical (-4.9 μC / g or more).

(Example 15 to Example 21)
Examples 15 to 21 were prepared in the same manner as in Example 8, except that 2.0 parts by mass of Exemplified Compounds (1) to (7) were used and a yellow colorant (Hansa Yellow G) was used instead of the cyan colorant. Yellow toners (1) to (7) were obtained. The characteristics of these toners were measured in the same manner as in Example 3, and the results are summarized in Table 1. Using this, in the same manner as in Example 8, two-component yellow developers (1) to (7) were obtained.

(Comparative Example 2)
A yellow toner (8) of Comparative Example 2 was obtained in the same manner as in Example 8, except that the exemplified compound was not used and a yellow colorant (Hansa Yellow G) was used instead of the cyan colorant. The toner characteristics were measured in the same manner as in Example 8. The results are summarized in Table 1. In addition, using this, the two-component yellow developer (8) of Comparative Example 2 was obtained in the same manner as in Example 8.

<Evaluation>
With respect to the two-component yellow developers (1) to (7) obtained in Examples 15 to 21 and the two-component yellow developer (8) obtained in Comparative Example 2, normal temperature and normal humidity (25 ° C., 60% RH) and high-temperature and high-humidity (30 ° C, 80% RH) environments using the above-mentioned method for measuring the charge amount, and the charge amount of the toner after stirring for 10 seconds and 300 seconds. Was measured. Then, the second decimal place was rounded off from the measured value of the two-component blow-off charge amount, and the evaluation was made according to the same criteria as in Examples 8-14. The results are summarized in Table 1.

(Example 22 to Example 28)
Example 22 was carried out in the same manner as in Example 8, except that 2.0 parts by mass of Exemplified Compounds (1) to (7) were used, and carbon black (DBP oil absorption 110 ml / 100 g) was used instead of the cyan colorant. -28 black toners (1) to (7) were obtained. The characteristics of these toners were measured in the same manner as in Example 8. The results are summarized in Table 1. Using this, in the same manner as in Example 8, two-component black developers (1) to (7) were obtained.

(Comparative Example 3)
A black toner (8) of Comparative Example 3 was obtained in the same manner as in Example 8, except that the exemplified compound was not used and carbon black (DBP oil absorption 110 ml / 100 g) was used instead of the cyan colorant. . The toner characteristics were measured in the same manner as in Example 8. The results are summarized in Table 1. In addition, using this, the two-component black developer (8) of Comparative Example 3 was obtained in the same manner as in Example 8.

<Evaluation>
For the two-component black developers (1) to (7) obtained in Examples 22 to 28 and the two-component black developer (8) obtained in Comparative Example 3, normal temperature and normal humidity (25 ° C., 60% RH) and high-temperature and high-humidity (30 ° C, 80% RH) environments using the above-mentioned method for measuring the charge amount, and the charge amount of the toner after stirring for 10 seconds and 300 seconds. Was measured. Then, the second decimal place was rounded off from the measured value of the two-component blow-off charge amount, and the evaluation was made according to the same criteria as in Examples 8-14. The results are summarized in Table 1.

(Example 29)
-100 parts by weight of styrene-butyl acrylate copolymer resin (glass transition temperature 70 ° C)-5 parts by weight of magenta pigment (C.I. Pigment Red 114)-2 parts by weight of Exemplified Compound (1) The mixture was melt kneaded with an extruder (L / D = 30). The kneaded product was cooled, coarsely pulverized with a hammer mill, finely pulverized with a jet mill, and classified to obtain magenta colored particles ( 1 ) by a pulverization method. The magenta colored particles ( 1 ) had a weight average particle size of 6.8 μm and a fine powder amount of 5.2% by number.

To 100 parts by mass of the magenta colored particles ( 1 ), 1.5 parts by mass of a hydrophobic silica fine powder (BET: 250 m ^{2 /} g) treated with hexamethyldisilazane as a flow improver was dry-mixed with a Henschel mixer. A magenta toner ( 1 ) of this example was obtained. Further, 7 parts by mass of the obtained magenta toner ( 1 ) and 93 parts by mass of a resin-coated magnetic ferrite carrier (average particle size: 45 μm) are mixed to prepare a two-component magenta developer ( 1 ) for magnetic brush development. Prepared.

(Examples 30 to 35)
The magenta toners ( 2 ) to ( 7 ) of Examples 30 to 35 were prepared in the same manner as in Example 29 except that 2.0 parts by mass of the exemplified compounds ( 2 ) to ( 7 ) were used instead of the exemplified compound ( 1 ). Got. The characteristics of these toners were measured in the same manner as in Example 8. The results are shown in Table 2. Using this, in the same manner as in Example 29, two-component magenta developers ( 2 ) to ( 7 ) were obtained.

(Comparative Example 4)
A magenta toner ( 8 ) of Comparative Example 4 was obtained in the same manner as in Example 29 except that the exemplified compound was not used. The characteristics of this toner were measured in the same manner as in Example 8. The results are summarized in Table 2. In addition, using this, the two-component magenta developer ( 8 ) of Comparative Example 4 was obtained in the same manner as in Example 29.

<Evaluation>
For the two-component magenta developers ( 1 ) to ( 7 ) obtained in Examples 29 to 35 and the two-component magenta developer ( 8 ) obtained in Comparative Example 4, normal temperature and normal humidity (25 ° C., 60% RH) and high-temperature and high-humidity (30 ° C, 80% RH) environments using the above-mentioned method for measuring the charge amount, and the charge amount of the toner after stirring for 10 seconds and 300 seconds. Was measured. And the second decimal place was rounded off from the measured value of the two-component blow-off charge amount, and the following criteria were used for evaluation. The results are summarized in Table 2.

[Charging]
◎: Very good (-20μC / g or less)
○: Good (-19.9 to -10.0μC / g)
Δ: Practical use possible (-9.9 to -5.0μC / g)
X: Not practical (-4.9 μC / g or more).

(Examples 36 to 42)
Except for using 2.0 parts by mass of Exemplified Compounds (1) to (7) and using carbon black (DBP oil absorption 110 ml / 100 g) in place of the magenta pigment, Example 36 to 42 black toners (9) to (15) were obtained. The characteristics of these toners were measured in the same manner as in Example 6. The results are summarized in Table 2. In addition, using this, in the same manner as in Example 29, two-component black developers (9) to (15) were obtained.

(Comparative Example 5)
A black toner (16) of Comparative Example 5 was obtained in the same manner as in Example 29 except that the exemplified compound was not used and carbon black (DBP oil absorption: 110 ml / 100 g) was used instead of the magenta pigment. The characteristics of this toner were measured in the same manner as in Example 8. The results are summarized in Table 2. In addition, using this, the two-component black developer (16) of Comparative Example 5 was obtained in the same manner as in Example 29.

<Evaluation>
Regarding the two-component black developers (9) to (15) obtained in Examples 36 to 42 and the two-component black developer (16) obtained in Comparative Example 5, normal temperature and normal humidity (25 ° C., 60% RH) and high-temperature and high-humidity (30 ° C, 80% RH) environments using the above-mentioned method for measuring the charge amount, and the charge amount of the toner after stirring for 10 seconds and 300 seconds. Was measured. Then, the second decimal place was rounded off from the measured value of the two-component blow-off charge amount, and evaluation was performed according to the same criteria as in Examples 29 to 35. The results are summarized in Table 2.

(Example 43)
Polyester resin 100 parts by mass Carbon black (DBP oil absorption 110 ml / 100 g) 5 parts by mass Illustrative compound (1) 2 parts by mass The polyester resin was synthesized as follows. Bisphenol A propylene oxide 2-mole adduct 751 parts, terephthalic acid 104 parts, trimellitic anhydride 167 parts, and dibutyltin oxide 2 parts were subjected to polycondensation to obtain a polyester resin having a softening point of 125 ° C.

  The above compositions were mixed and melt kneaded with a biaxial extruder (L / D = 30). The kneaded product was cooled, coarsely pulverized with a hammer mill, finely pulverized with a jet mill, and classified to obtain black colored particles (17) by a pulverization method. The black colored particles (17) had a weight average particle size of 7.6 μm and a fine powder amount of 4.7% by number.

To 100 parts by mass of the black colored particles (17), 1.5 parts by mass of a hydrophobic silica fine powder (BET: 250 m ^{2 /} g) treated with hexamethyldisilazane as a flow improver was dry-mixed with a Henschel mixer. As a result, a black toner (17) of this example was obtained. Further, 7 parts by mass of the obtained black toner (17) and 93 parts by mass of a resin-coated magnetic ferrite carrier (average particle size: 44 μm) were mixed to prepare a two-component black developer (17) for magnetic brush development. Prepared.

(Examples 44 to 49)
The black toners (18) to (23) of Examples 44 to 49 were prepared in the same manner as in Example 43 except that 2.0 parts by mass of the exemplified compounds (2) to (7) were used instead of the exemplified compound (1). Got. The characteristics of these toners were measured in the same manner as in Example 8. The results are shown in Table 3. In addition, using this, in the same manner as in Example 43, two-component black developers (18) to (23) were obtained.

(Comparative Example 6)
A black toner (24) of Comparative Example 6 was obtained in the same manner as in Example 43 except that the exemplified compound was not used. The characteristics of this toner were measured in the same manner as in Example 8. The results are shown in Table 6. Further, using this, the two-component black developer (24) of Comparative Example 6 was obtained in the same manner as in Example 43.

<Evaluation>
For the two-component black developers (17) to (23) obtained in Examples 43 to 49 and the two-component black developer (24) obtained in Comparative Example 6, normal temperature and normal humidity (25 ° C., 60% RH) and high-temperature and high-humidity (30 ° C., 80% RH) in each environment, the charge amount of the toner after stirring for 10 seconds and 300 seconds using the charge amount measurement method described above. Was measured. And the second decimal place was rounded off from the measured value of the two-component blow-off charge amount, and the following criteria were used for evaluation. The results are summarized in Table 3.

[Charging]
◎: Very good (-20μC / g or less)
○: Good (-19.9 to -10.0μC / g)
Δ: Practical use possible (-9.9 to -5.0μC / g)
×: Not practical (-4.9μC / g or more)

(Examples 50 to 76 and Comparative Examples 7 to 12)
First, image forming apparatuses used in the image forming methods of Examples 50 to 76 and Comparative Examples 7 to 12 will be described. FIG. 1 is a schematic explanatory view of a cross section of an image forming apparatus for executing the image forming methods of the examples and comparative examples of the present invention. The photosensitive drum 1 shown in FIG. 1 has a photosensitive layer 1a having an organic optical semiconductor on a substrate 1b and is configured to rotate in the direction of the arrow, but faces the photosensitive drum 1 and The surface of the charging roller 2 which is a charging member rotating in contact with the drum is charged to a surface potential of about −600V. As shown in FIG. 1, the charging roller 2 is configured by covering a cored bar 2b with a conductive elastic layer 2a.

Next, exposure 3 is performed toward the photosensitive drum 1 whose surface is charged. At that time, the exposure portion potential is set to −100 V by turning on and off the photoconductor on the photoconductor according to digital image information. An electrostatic charge image having a dark part potential of −600 V is formed. Subsequently, the electrostatic charge image on the photosensitive drum 1 is developed by reversal using a plurality of developing devices 4-1, 4-2, 4-3, 4-4, and is made visible on the photosensitive drum 1. A toner image is formed. At that time, the two-component developers obtained in Examples 8 to 16, 22, 23, 25, 27, 29 to 32, 35 to 37, 39, 41 to 45, 48 and Comparative Examples 1 to 6 were used as developers. Each was used to form a toner image with yellow toner, magenta toner, cyan toner or black toner. FIG. 2 is an enlarged cross-sectional view of the main part of each developing device 4 for the two-component developer used at that time.

  Next, the toner image on the photosensitive drum 1 is transferred onto an intermediate transfer member 5 rotating in contact with the photosensitive drum 1. As a result, a four-color superimposed developed image is formed on the intermediate transfer member 5. The transfer residual toner remaining without being transferred onto the photosensitive drum 1 is collected in the residual toner container 9 by the cleaner member 8.

As shown in FIG. 1, the intermediate transfer member 5 is composed of a cored bar 5b as a support and an elastic layer 5a laminated thereon. In this embodiment, an intermediate transfer body in which an elastic layer 5b in which carbon black is used as a conductive material and is sufficiently dispersed in nitrile-butadiene rubber (NBR) is coated on a pipe-shaped metal core 5b. 5 was used. The hardness of the elastic layer 5b measured in accordance with “JIS K-6301” was 30 degrees, and the volume resistance value was 10 ⁹ Ω · cm. The transfer current required for transfer from the photosensitive drum 1 to the intermediate transfer member 5 is about 5 μA, which was obtained by applying +500 V to the core metal 5b from the power source.

The four-color toner color developed image formed on the intermediate transfer member 5 is transferred onto a transfer material such as paper by a transfer roller 7, and then fixed and fixed by a heat fixing device H. . The transfer roller 7 has an enough diameter of carbon in a foam of ethylene-propylene-diene-based three-dimensional copolymer (EPDM) on a metal core 7b having an outer diameter of 10 mm and carbon as a conductivity-imparting material. Thus, an elastic layer 7a coated with a dispersion in a state is formed. The volume resistivity value is 10 ⁶ Ω · cm, and the hardness measured in accordance with “JIS K-6301” shows a value of 35 degrees. A voltage was applied to the transfer roller 7 to flow a transfer current of 15 μA.

  In the apparatus shown in FIG. 1, a heat roll type fixing apparatus without an oil application mechanism as shown in FIGS. At this time, an upper roller and a lower roller having a fluororesin surface layer were used. The roller diameter was 60 mm. The fixing temperature during fixing was 160 ° C., and the nip width was set to 7 mm. The transfer residual toner on the photosensitive drum 1 collected by cleaning was transported to the developing device by the reuse mechanism and reused.

<Evaluation>
Under the above-described conditions, Examples 8 to 8 were performed at a printout speed of 8 sheets (A4 size) / min in an environment of normal temperature and normal humidity (25 ° C., 60% RH) and high temperature and high humidity (30 ° C., 80% RH). A two-component developer produced using 49 toners and a two-component developer produced using the toners of Comparative Examples 1 to 6 were used, respectively, and a single color intermittent mode ( In other words, the developer is paused for 10 seconds each time a single printout is made, and a mode in which the preliminary operation at the time of restarting promotes the deterioration of toner) performs a printout test. evaluated. The evaluation results are summarized in Table 4.

[Printout image evaluation]
1. Image density A predetermined number of printouts were made on ordinary copying machine plain paper (75 g / m ² ), and the evaluation was based on the degree of image density maintenance at the end of printing of the initial image. For the image density, a Macbeth reflection densitometer (manufactured by Macbeth) was used, and the relative density with respect to the printout image of the white background portion where the original density was 0.00 was measured and used for evaluation.
◎: Excellent (Image density at the end is 1.40 or more)
○: Good (image density at the end is 1.35 or more and less than 1.40)
△: Yes (image density at the end is 1.00 or more and less than 1.35)
×: Impossible (image density at the end is less than 1.00).

2. Image fog A predetermined number of printouts were made on ordinary copying machine plain paper (75 g / m ² ), and evaluation was performed using a solid white image at the end of printing. Specifically, the evaluation was performed by the following method. The worst value of the white background reflection density after printing measured using a reflection densitometer (TOKYO DENSHOKU CO., LTD, REFECTOMETER ODEL TC-6DS) is Ds, and the average reflection density value of the paper before printing is Dr. (Ds-Dr) was determined from these values, and this was taken as the amount of fogging and evaluated according to the following criteria.
A: Very good (fogging amount of 0% to less than 1.5%)
○: Good (fogging amount 1.5% or more and less than 3.0%)
△: Practical use (fogging amount is 3.0% or more and less than 5.0%)
×: Not practical (fogging amount is 5.0% or more).

3. Transferability A predetermined number of black solid images were printed on ordinary copying machine plain paper (75 g / m ² ), and the amount of image omission at the end of printing was visually observed and evaluated according to the following criteria. .
A: Very good (almost no occurrence)
○: Good (slight)
Δ: Practical use ×: Impractical use

  Also, in Example 50 to Example 76 and Comparative Example 7 to Comparative Example 12, when a 5000-sheet image is output, the surface of the photosensitive drum and the intermediate transfer member is damaged and the residual toner is fixed and the printed image is displayed. When the two-component developer in Examples 50 to 76 was visually evaluated for the influence of the toner (matching with the image forming apparatus), scratches on the surface of the photosensitive drum and the intermediate transfer member, and residual toner Adherence could not be confirmed at all, and matching with the image forming apparatus was very good. On the other hand, in each of the systems using the two-component developers of Comparative Examples 7 to 12, the toner was fixed on the surface of the photosensitive drum. Further, in the system using the two-component developer of Comparative Examples 7 to 12, an image in which toner adhesion and surface flaws can be confirmed on the surface of the intermediate transfer member, and vertical streak-like image defects are also generated on the image. There was a problem in matching with the forming device.

(Example 77 to Example 91, Comparative Example 13 to Comparative Example 15)
In carrying out the image forming methods of Examples 77 to 91 and Comparative Examples 13 to 15, Examples 8 , 9, 11, 13 , 15 to 23, 26, 27 and Comparative Examples 1 to 9 were used as developers. The toner obtained in 3 was used. Further, as a means for forming an image, as shown in FIG. 3, an image forming apparatus which was remodeled by attaching a reuse mechanism to a commercially available laser beam printer LBP-EX (manufactured by Canon Inc.) was used. That is, in the image forming apparatus shown in FIG. 3, the untransferred toner remaining on the photosensitive drum 20 after the transfer is scraped off by the elastic blade 22 of the cleaner 21 in contact with the photosensitive drum 20, and then the cleaner is cleaned. It is fed into the cleaner 21 by a roller, passes through the cleaner reuse 23, and is returned to the developing device 26 through the hopper 25 by a supply pipe 24 provided with a conveying screw, and a system that uses the collected toner is installed again. .

  In the image forming apparatus shown in FIG. 3, the surface of the photosensitive drum 20 is charged by the primary charging roller 27. The primary charging roller 27 uses a rubber roller (diameter 12 mm, contact pressure 50 g / cm) coated with nylon resin and dispersed with conductive carbon, and an electrostatic latent image carrier (photosensitive drum 20). On the top, an electrostatic latent image having a dark portion potential VD = −700 V and a bright portion potential VL = −200 V was formed by laser exposure (600 dpi, not shown). As the toner carrier, a developing sleeve 28 having a surface roughness Ra of 1.1, the surface of which is coated with a resin in which carbon black is dispersed, was used.

  FIG. 4 shows an enlarged cross-sectional view of a main part of the developing device for one-component developer used in Example 77 to Example 91 and Comparative Example 13 to Comparative Example 15. As a condition for developing the electrostatic latent image, the speed of the developing sleeve 28 is set to be 1.1 times the moving speed of the opposing photosensitive drum 20 surface, and further, the developing speed of the photosensitive drum 20 The distance α (between SD) with the sleeve 28 was 270 μm. As the toner layer thickness regulating member, a urethane rubber blade 29 was used in contact therewith. The set temperature of the heat fixing device for fixing the toner image was 160 ° C. The fixing device shown in FIGS. 5 and 6 was used as the fixing device.

  As described above, in a normal temperature and normal humidity (25 ° C., 60% RH) environment, at a printout speed of 8 sheets (A4 size) / min. In this mode, the toner consumption was promoted without printing), up to 30,000 sheets were printed, the image density of the obtained printout image was measured, and the durability was evaluated according to the following criteria. The 10,000th image was observed and image fogging was evaluated according to the following criteria. At the same time, the appearance of each apparatus constituting the image forming apparatus after the durability test was observed, and the matching between each apparatus and each toner was also evaluated. The above results are summarized in Table 5.

[Image density transition during durability]
A predetermined number of printouts were made on ordinary copying machine plain paper (75 g / m ² ), and evaluation was made based on the degree of image density maintenance at the end of printing of the initial image. For the image density, a Macbeth reflection densitometer (manufactured by Macbeth) was used, and the relative density with respect to the printout image of the white background portion where the original density was 0.00 was measured and used for evaluation.
◎: Excellent (Image density at the end is 1.40 or more)
○: Good (image density at the end is 1.35 or more and less than 1.40)
△: Yes (image density at the end is 1.00 or more and less than 1.35)
×: Impossible (image density at the end is less than 1.00).

[Image fog]
A predetermined number of printouts were made on ordinary copying machine plain paper (75 g / m ² ), and evaluation was performed using a solid white image at the end of printing. Specifically, the evaluation was performed by the following method. The worst value of the white background reflection density after printing measured using a reflection densitometer (TOKYO DENSHOKU CO., LTD, REFECTOMETER ODEL TC-6DS) is Ds, and the average reflection density value of the paper before printing is Dr. (Ds-Dr) was determined from these values, and this was taken as the amount of fogging and evaluated according to the following criteria.
A: Very good (fogging amount of 0% to less than 1.5%)
○: Good (fogging amount 1.5% or more and less than 3.0%)
△: Practical use (fogging amount is 3.0% or more and less than 5.0%)
×: Not practical (fogging amount is 5.0% or more)
[Image forming device matching evaluation]
1. Matching with developing sleeve After completion of the printout test, the appearance of the residual toner on the surface of the developing sleeve and the effect on the printout image were visually evaluated.
◎: Very good (not generated)
○: Good (almost no occurrence)
Δ: Practical use possible (although there is sticking, there is little effect on the image)
×: Impractical use (many sticking and image unevenness occurs).

2. Matching with the photosensitive drum The appearance of scratches on the surface of the photosensitive drum and sticking of residual toner and the effect on the printed image were visually evaluated.
◎: Very good (not generated)
○: Good (slight scratches are seen, but there is no effect on the image)
△: Practical (possibly stuck or scratched, but has little effect on the image)
×: Impractical (non-fixed, causing vertical streak-like image defects).

3. Matching with fixing device The surface of the fixing film was observed, and the results of surface properties and residual toner fixation were averaged, and the durability was evaluated.

(1) Surface property The appearance of scratches or abrasions on the surface of the fixing film after completion of the printout test was visually observed and evaluated.
◎: Very good (not generated)
○: Good (almost no occurrence)
Δ: Practical use ×: Impractical use

(2) Residual Toner Fixing Status The residual toner fixing status on the surface of the fixing film after the printout test was visually observed and evaluated.
◎: Very good (not generated)
○: Good (almost no occurrence)
△: Practical use ×: Impractical use

(Example 92)
While removing the toner reuse mechanism of the image forming apparatus of FIG. 3 and changing the printout speed to 16 sheets (A4 size) / min, the same as in Example 77, while sequentially supplying blue toner (1) in Example 8 The printout test was conducted in a continuous mode (ie, a mode that promotes toner consumption without pausing the developer). The same items as in Example 77 to Example 91 and Comparative Example 13 to Comparative Example 15 were evaluated for the obtained printout image evaluation and matching with the image evaluation apparatus used. As a result, good results were obtained for all items.

(Examples 93 to 95)
The type of toner was changed from the blue toner (1) of Example 8 to the blue toners (2), (4) and (6) of Examples 9, 11 and 13, and evaluation was performed in the same manner as in Example 92. As a result, good results were obtained for all items.

FIG. 6 is a schematic explanatory diagram of an image forming apparatus used in Examples 50 to 76 and Comparative Examples 7 to 12. FIG. 10 is a cross-sectional view of a main part of a developing device for a two-component developer used in Example 50 to Example 76 and Comparative Example 7 to Comparative Example 12; FIG. 7 is a schematic explanatory diagram of an image forming apparatus having a toner reuse mechanism used in Examples 77 to 91 and Comparative Examples 13 to 15. FIG. 10 is a cross-sectional view of a main part of a developing device for a one-component developer used in Example 77 to Example 91 and Comparative Example 13 to Comparative Example 15; FIG. 2 is an exploded perspective view of a main part of a fixing device used in an embodiment of the present invention. FIG. 3 is an enlarged cross-sectional view of a main part showing a film state when the fixing device used in the embodiment of the present invention is not driven. It is a schematic diagram showing a blow-off charge amount measuring device for measuring the charge amount of toner.

Explanation of symbols

1, 20: Photoconductor (electrostatic latent image carrier)
2, 27: Charging roller 3: Exposure 4, 26: Developing device (4-1, 4-2, 4-3, 4-4)
5: Intermediate transfer member 6: Transfer material 7: Transfer roller
13: Photosensitive drum
11, 28: Developer carrier
30: Stay
31: Heating body
31a: Heater board
31b: Heating element
31c: Surface protective layer
31d: Temperature detector
32: Fixing film
33: Heating roller
34: Coil spring
35: Film edge regulating flange
36: Power connector
37: Insulating material
38: Entrance guide
39: Exit guide (separation guide)
43: Screen
45: Vacuum gauge
47: Suction port
49: Electrometer

Claims (7)

A charge control agent for controlling the charged state of a granular material, comprising a polyhydroxyalkanoate having at least one unit among 3-hydroxy-ω-carboxyalkanoic acid units represented by chemical formula (1) A charge control agent characterized by comprising:

(n is an integer selected from the range shown in the chemical formula; R ₁ is an H atom, an Na atom, a K atom, or

When there are multiple units, n and R ₁ may be different for each unit. ) In addition to the 3-hydroxy-ω-carboxyalkanoic acid shown in chemical formula (1),
Chemical formula (6):

3-hydroxy-ω- substituted alkanoic acid unit (wherein m is an integer selected from the range shown in the chemical formula; R ₆ contains a residue having either a phenyl structure or a thienyl structure) When there are multiple units, m and R ₆ may be different for each unit.)
Or chemical formula (7):

3-hydroxy-ω-cyclohexylalkanoic acid unit (wherein R ₇ represents a substituent to the cyclohexyl group, R ₇ 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, k is an integer selected from the range shown in the chemical formula, and there are a plurality of units. 2. The charge control agent according to claim 1, wherein the charge control agent comprises a polyhydroxyalkanoate that may be different for each unit. R ₆ in the chemical formula (6) is at least one selected from the group consisting of a phenyl group, a phenoxy group, a benzoyl group, and a phenylsulfonyl group , and when there are a plurality of units, they are different for each unit. The charge control agent according to claim 1, further comprising a polyhydroxyalkanoate . A toner binder for use in an electrostatic charge image developing toner, comprising the charge control agent according to any one of claims 1 to 3. An electrostatic charge image developing toner, comprising at least a binder resin, a colorant, and the charge control agent according to claim 1. A step of charging the electrostatic latent image carrier by applying a voltage to the charging member from the outside, a step of forming an electrostatic charge image on the charged electrostatic latent image carrier, and the electrostatic charge image as an electrostatic charge image A developing process for developing with a developing toner to form a toner image on the electrostatic latent image carrier, a transfer process for transferring the toner image on the electrostatic latent image carrier to a recording material, and a toner on the recording material An image forming method comprising at least a fixing step of fixing an image by heating,
An image forming method using the electrostatic image developing toner according to claim 5. Means for charging the electrostatic latent image carrier by applying a voltage to the charging member from the outside; means for forming an electrostatic image on the charged electrostatic latent image carrier; and Developing means for developing with a developing toner to form a toner image on the electrostatic latent image carrier, transfer means for transferring the toner image on the electrostatic latent image carrier to the recording material, and toner on the recording material An image forming apparatus having at least a fixing unit that heat-fixes an image,
The image forming apparatus according to claim 5, wherein the electrostatic charge image developing toner is the electrostatic charge image developing toner according to claim 5.

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