JP4455412B2 - Charge control agent, electrostatic image developing toner, image forming method and image forming apparatus - Google Patents

Description

  The present invention relates to a charge control agent used in a recording method utilizing an electrophotographic method, an electrostatic recording method, a magnetic recording method, etc., an electrostatic charge image developing toner, an image forming method using the toner, and an image using the toner. The present invention relates to a forming apparatus.

  In recent years, biodegradable polymer materials have been widely applied to medical materials, drug delivery systems, environmentally compatible materials, and the like. In recent years, in addition to these, new functions have been required, and various studies have been conducted.

  In particular, for polyhydroxyalkanoates typified by polylactic acid, it has been studied to introduce functional groups that can be chemically modified into the molecule, and there have been reports on compounds having a carboxyl group or a vinyl group introduced therein. For example, polymalic acid is known as a polyhydroxyalkanoate having a carboxyl group in the side chain. As the polymalic acid polymer, an α type represented by the chemical formula (14) and a β type represented by the chemical formula (15) are known depending on the structure of the monomer unit.

  Among these, for β-type polymalic acid and copolymers thereof, Patent Document 1 discloses a polymer obtained by ring-opening polymerization of a benzyl ester of β-malolactone represented by chemical formula (16).

(In the formula, R16 represents a benzyl group.)

  Moreover, about the alpha-type polymalic acid-glycolic acid copolymer and the copolymer containing other hydroxy alkanoic acids including glycolic acid, patent document 2 is 6-membered represented by Chemical formula (17). A copolymer obtained by copolymerizing a cyclic diester monomer with glycolide and lactide, which are cyclic diesters, and lactones, which are intramolecular ring-closing reaction esters of ω-hydroxycarboxylic acid, is disclosed.

(In the formula, R17 represents a lower alkyl group such as methyl group, ethyl group, n-propyl group, isopropyl group, t-butyl group, and benzyl group)

As polyhydroxyalkanoate having a carboxyl group in the side chain, a polymer having an ester group in the side chain is produced by ring-opening polymerization of 7-oxo-4-oxepanecarboxylic acid ester in Non-Patent Document 1. Further, it is disclosed that a polymer having a carboxylic acid in the side chain was further hydrocracked. Non-Patent Document 2 discloses that by reacting poly (ε-caprolactone) with lithium diisopropylamide and further with benzyl chloroformate, the α-position of the carbonyl group in the main chain of poly (ε-caprolactone) is obtained. A polymer in which a benzyloxycarbonyl group is introduced into the methylene group is disclosed.
Non-Patent Document 3 discloses that by reacting polylactic acid with lithium diisopropylamide and further reacting with benzyl bromoacetate, the carbonyl group in the main chain of polylactic acid has an α-position methylene group (benzyloxycarbonyl). ) Polymers having methyl groups introduced therein are disclosed.

  As polyhydroxyalkanoate having a vinyl group in the side chain, Non-Patent Document 4 discloses a polymer obtained by ring-opening polymerization of α-allyl (δ-valerolactone).

  Similarly, as a polyhydroxyalkanoate having a vinyl group in the side chain, Non-Patent Document 5 discloses the ring opening of 6,6-diallyl-1,4-dioxane-2,5-dione, which is a 6-membered ring diester monomer. A polymerized polymer is disclosed.

  As described above, there is a report on a polymer having a new function, in which a structure that imparts functionality to a polyhydroxyalkanoate having a functional group that can be chemically modified is introduced. In Non-Patent Document 6, an α-type malic acid and glycolic acid copolymer is obtained by ring-opening polymerization of a cyclic dimer of α-malic acid and glycolic acid, and the resulting polymer is deprotected. A polyester having a carboxyl group in the side chain is obtained. When the tripeptide was chemically modified to the carboxyl group of this side chain and the resulting polymer was evaluated for cell adhesiveness, good results were obtained.

  Conventionally, many methods are known as electrophotographic methods. Generally, an electro latent image is formed on an image carrier (photoreceptor) using a photoconductive substance by various means. 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 other components such as a charge control agent and magnetic powder as required.

As a method for imparting a charge to the toner, the charging characteristics of the binder resin itself can be used without using a charge control agent. However, it is difficult to obtain good image quality due to poor charging stability over time and moisture resistance. . 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 technical field today include, for example, azo dye metal complexes, aromatic dicarboxylic acid metal complexes, salicylic acid derivative metal complexes and the like as negative triboelectric charging agents. . 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, which is known as a negative charge control agent, has a certain level of charge, but the azo dye metal complex is a low-molecular crystal. Depending on the type, 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. A big problem is that the colorant required for obtaining a high-quality image has low sharpness.

An example of a negatively charged negative charge control agent is a metal complex of an aromatic dicarboxylic acid, but it is not completely colorless, and the dispersibility may be low due to low molecular weight crystals.
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. The compounds described in Patent Documents 3 to 5 are listed. Furthermore, as a polymer charge control agent in general when a toner exhibits negative chargeability, styrene and / or α-methylstyrene, an alkyl (meth) acrylate ester or alkyl (meth) acrylate amide having a sulfonic acid group, and Are 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 charge control agent itself, as well as the compounds and organic solvents used in the synthesis, are safer compounds, safer and milder synthesis processes, organic solvents There is a strong demand for a charge control agent that can realize a reduction in the amount used. However, reports of such charge control agents and their synthesis processes are not yet known, and there is room for further improvement in terms of contribution to functional aspects and environmental preservation.

U.S. Pat. No. 4,265,247 JP-A-2-3415 US Pat. No. 4,448,0021 U.S. Pat. No. 4,442,189 U.S. Pat. No. 4,925,765 “Macromolecules” 2000, Vol. 33, No. 13, p. 4619 “Biomacromolecules” 2000, Vol. 1, p. 275 “Macromolecular Bioscience” 2004, Vol. 4, p. 232 “Polymeric Materials Science & Engineering” 2002, Vol. 87, p. 254 “Polymer Preprints” 2002, Vol. 43, No. 2, p. 727 “International Journal of Biological Macromolecules” 1999, Vol. 25, p. 265

  The present invention solves the above-described problems, and includes a sulfonic acid group that is a hydrophilic group or a polar group and a derivative thereof, or a polyhydroxyalkanoate into which a carboxyl group and a derivative thereof are introduced in order to improve various functions. In terms of functionality, it contributes more to environmental conservation, etc., and has a high performance (high charge amount, quick rise of charge, excellent stability over time, high environmental stability) and improved dispersibility. The present invention provides a chargeable charge control agent, an electrostatic charge image developing toner containing the charge control agent, and an image forming method and an image forming apparatus using the electrostatic charge image developing toner.

  Therefore, the present inventors have found that the above polyhydroxyalkanoate has extremely excellent characteristics as a charge control agent and has high safety to the human body and the environment, and further contains the charge control agent. It has been found that there is a remarkable effect when the electrostatic charge image developing toner and the electrostatic charge image developing toner are used in an image forming apparatus having a certain development system.

  That is, the present invention relates to a charge control agent that controls the charge state of a powder, wherein the unit contains at least one unit represented by the following chemical formula (1) in the molecule.

(Wherein, R represents -A1-SO ₂ R1,
R1 represents OH, a halogen atom, ONa, OK or OR1a;
R1a and A1 each independently represents a group having a substituted or unsubstituted aliphatic hydrocarbon structure, a substituted or unsubstituted aromatic ring structure, or a substituted or unsubstituted heterocyclic structure.
In addition, about l, m, Z1a, Z1b in the formula,
When l is an integer selected from 2 to 4, Z1a is not selected or is a linear alkylene chain having 1 to 4 carbon atoms, Z1b is a hydrogen atom, and m is selected from 0 to 8 An integer,
When l is 1 and Z1a is a linear alkylene chain having 1 to 4 carbon atoms, Z1b is a hydrogen atom, m is an integer selected from 0 to 8,
When l is 1 and Z1a is not selected, Z1b is a hydrogen atom, m is 0,
When l is 0 and Z1a is a linear alkylene chain having 1 to 4 carbon atoms, the linear alkylene chain has a linear or branched alkyl group or a phenyl structure, thienyl structure, or cyclohexyl structure at the terminal. Among them, it may be substituted with an alkyl group containing a residue having any structure, and Z1b is substituted with a hydrogen atom, or a linear or branched alkyl group, aryl group, aryl group. An aralkyl group, m is an integer selected from 0 to 8;
When l is 0 and Z1a is not selected, Z1b is a hydrogen atom or a linear or branched alkyl group, aryl group, aryl group optionally substituted with an aryl group, and m is It is an integer selected from 0-8.
When there are a plurality of units, R, R 1, R 1a, A 1, Z 1a, Z 1b, l, m have the above meanings independently for each unit. )

  The present invention also relates to a charge control agent for controlling a charged state of a granular material, wherein the unit contains at least one unit represented by the following chemical formula (5) in a molecule.

(Wherein R5 represents hydrogen, a salt-forming group or R5a, and R5a represents a linear or branched alkyl group having 1 to 12 carbon atoms or an aralkyl group.
Also, for l, m, Z5a, Z5b in the formula,
When l is an integer selected from 2 to 4, Z5a is not selected or is a linear alkylene chain having 1 to 4 carbon atoms, Z5b is a hydrogen atom, and m is selected from 0 to 8 An integer,
When l is 1 and Z5a is a linear alkylene chain having 1 to 4 carbon atoms, Z5b is a hydrogen atom, m is an integer selected from 0 to 8,
When l is 1 and no Z5a is selected, Z5b is a hydrogen atom, m is 0,
When l is 0 and Z5a is a linear alkylene chain having 1 to 4 carbon atoms, the linear alkylene chain has a linear or branched alkyl group or a phenyl structure, a thienyl structure, or a cyclohexyl structure at the terminal. Of these, Z5b may be substituted with an alkyl group including a residue having any structure, and Z5b is substituted with a hydrogen atom, or a linear or branched alkyl group, aryl group, or aryl group. An aralkyl group, m is an integer selected from 0 to 8;
When l is 0 and Z5a is not selected, Z5b is a hydrogen atom or an aralkyl group which may be substituted with a linear or branched alkyl group, aryl group or aryl group, and m is It is an integer selected from 0-8.
Further, when there are a plurality of units, R5, R5a, Z5a, Z5b, l, and m have the above meanings independently for each unit. )

The present invention also relates to an electrostatic charge image developing toner comprising at least a binder resin, a colorant, and the charge control agent of the present invention in the electrostatic charge image developing toner.
The present invention also includes a step of applying a voltage to the charging member from the outside to charge the electrostatic latent image carrier, a step of forming an electrostatic charge image on the charged electrostatic latent image carrier, and the electrostatic A development step of developing the charge image with an electrostatic image developing toner to form a toner image on the electrostatic latent image carrier; a transfer step of transferring the toner image on the electrostatic latent image carrier to a recording material; The present invention relates to an image forming method using the electrostatic charge image developing toner of the present invention in an image forming method having at least a fixing step of heat-fixing a toner image on a recording material.

  The present invention also includes 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 a charge image 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 a recording material; The present invention relates to an image forming apparatus using the electrostatic charge image developing toner of the present invention in an image forming apparatus having at least a fixing unit for fixing a toner image on a recording material by heating.

  According to the present invention, by adding one or more polyhydroxyalkanoates represented by the chemical formula (1) or (5) as a charge control agent into the toner composition for developing an electrostatic image, excellent charging characteristics can be obtained. This improves the dispersibility and spent property of the compound. Further, it is possible to provide a toner for developing an electrostatic charge image that is reduced in occurrence of image fog, excellent in transferability, and highly applied to an electrophotographic process even when output by an image forming apparatus. 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. Can be inhibited. In addition, safety can be improved by configuring the electrostatic charge developing toner so as not to contain heavy metals. In addition, when a biodegradable material is used, it is not necessary to perform a combustion treatment, and it has a great industrial effect in terms of environmental protection such as prevention of air pollution and global warming.

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. Further, the present invention has found that there is a remarkable effect when the electrostatic charge image developing toner containing the charge control agent and the electrostatic charge image developing toner are used in an image forming apparatus having a certain development system. Was completed.

  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 target polyhydroxyalkanoate represented by the chemical formula (1) in the present invention is a polyhydroxyalkanoate containing a unit represented by the chemical formula (11) used as a starting material and an aminosulfonic acid compound represented by the chemical formula (13). Manufactured by reaction with one species.

(Wherein R 11 represents hydrogen or a group forming a salt.
In addition, about l, m, Z11a, Z11b in the formula,
When l is an integer selected from 2 to 4, Z11a is not selected or is a linear alkylene chain having 1 to 4 carbon atoms, Z11b is a hydrogen atom, and m is selected from 0 to 8 An integer,
When l is 1 and Z11a is a linear alkylene chain having 1 to 4 carbon atoms, Z11b is a hydrogen atom, m is an integer selected from 0 to 8,
When l is 1 and Z11a is not selected, Z11b is a hydrogen atom, m is 0,
When l is 0 and Z11a is a linear alkylene chain having 1 to 4 carbon atoms, the linear alkylene chain has a linear or branched alkyl group, or a phenyl structure, a thienyl structure, or a cyclohexyl structure at the terminal. Among them, it may be substituted with an alkyl group containing a residue having any structure, and Z11b is substituted with a hydrogen atom, or a linear or branched alkyl group, aryl group, or aryl group. An aralkyl group, m is an integer selected from 0 to 8;
When l is 0 and Z11a is not selected, Z11b is a hydrogen atom or a linear or branched alkyl group, aryl group, aryl group optionally substituted with an aryl group, and m is It is an integer selected from 0-8.
Further, when there are a plurality of units, R11, Z11a, Z11b, l, and m represent the above meanings independently for each unit. )

  More specifically, in the compound represented by the chemical formula (11) used in the present invention, when l is 0 and Z11a is a linear alkylene chain having 1 to 4 carbon atoms, the linear alkylene chain is linear or It may be substituted with a branched alkyl group or an alkyl group containing a residue having any one of a phenyl structure, a thienyl structure, and a cyclohexyl structure at the end, specifically, substituted or unsubstituted Cyclohexyl structure, substituted or unsubstituted phenyl structure, substituted or unsubstituted phenoxy structure, substituted or unsubstituted benzoyl structure, substituted or unsubstituted phenylsulfanyl structure, substituted or unsubstituted phenylsulfinyl structure, substituted or unsubstituted Phenylsulfonyl structure, substituted or unsubstituted (phenylmethyl) sulfanyl structure (Phenylmethyl) oxy structure, 2-thienyl structure, 2-dithienyl Alpha sulfonyl structure, such as 2-thienylcarbonyl structure.

  In addition, in the compound represented by the chemical formula (11) used in the present invention, when l is 0, Z11b is an aralkyl substituted with a hydrogen atom or a linear or branched alkyl group, aryl group or aryl group It is a group. Specifically, the linear or branched alkyl group includes a methyl group, ethyl group, propyl group, isopropyl group (2-methylpropyl group), butyl group, 1-methylpropyl group, pentyl group, isopropyl group (3 -Methylbutyl group), hexyl group, isohexyl group (4-methylpentyl group), heptyl group and the like. In addition, examples of the aryl group include a phenyl group and a methylphenyl group. Examples of the aralkyl group include a phenylmethyl group (benzyl group), a phenylethyl group, a phenylpropyl group, a phenylbutyl group, a phenylpentyl group, and a methylbenzyl group. In the present invention, Z11b is preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, a pentyl group, a hexyl group, a phenyl group, or a phenylmethyl group in consideration of productivity regarding the synthesis of the polymer.

(Wherein R13 represents OH, a halogen atom, ONa, OK or OR13a;
R13a and A3 each independently represents a substituted or unsubstituted aliphatic hydrocarbon structure, a substituted or unsubstituted aromatic ring structure, or a substituted or unsubstituted heterocyclic structure. When there are a plurality of units, R13, R13a, and A3 represent the above meanings independently for each unit. )

  More specifically, R13 is OH, a halogen atom, ONa, OK or OR13a. R13a represents a linear or branched alkyl group having 1 to 8 carbon atoms or a substituted or unsubstituted phenyl group.

  A3 is any one of C1 to C8 linear or branched substituted or unsubstituted alkylene group, substituted or unsubstituted phenylene group, substituted or unsubstituted naphthalene group, substituted or unsubstituted N, S, or O. Represents a heterocyclic structure containing one or more. When A3 is a ring structure, the unsubstituted ring may be further condensed. When there are a plurality of units, R13, R13a and A3 represent the above meanings independently for each unit.

  When A3 is a linear substituted or unsubstituted alkylene group, examples of the compound represented by the chemical formula (13) include a compound represented by the following chemical formula (18).

(Wherein R18 represents OH, a halogen atom, ONa, OK or OR18a, and R18a represents a linear or branched alkyl group having 1 to 8 carbon atoms or a substituted or unsubstituted phenyl group. A4 Represents a C1-C8 linear or branched substituted or unsubstituted alkylene group, which may be substituted with an alkyl group having 1 to 20 carbon atoms, an alkoxy group, or the like.

  Examples of the compound represented by the chemical formula (18) include 2-aminoethanesulfonic acid (taurine), 3-aminopropanesulfonic acid, 4-aminobutanesulfonic acid, 2-amino-2-methylpropanesulfonic acid, and alkali metals thereof. Examples include salts and esterified products.

  When A3 is a substituted or unsubstituted phenylene group, examples of the compound represented by the chemical formula (13) include a compound represented by the following chemical formula (19).

(In the formula, at least one of R 3a, R 3b, R 3c, R 3d and R 3e is SO ₂ R 3f (where R 3f represents OH, halogen atom, ONa, OK or OR 3f 1, and R 3f 1 is linear or branched) Represents an alkyl group having 1 to 8 carbon atoms or a substituted or unsubstituted phenyl group.) Others are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, or 1 to 20 carbon atoms. Alkoxy group, OH group, NH ₂ group, NO ₂ group, COOR 3g (where R 3g represents H atom, Na atom or K atom), acetamide group, OPh group, NHPh group, CF ₃ group, C ₂ F ₅ group or C ₃ F ₇ group, and when there are a plurality of units, R 3a, R 3b, R 3c, R 3d, R 3e, R 3f, R 3f 1, R 3g have the above meanings independently for each unit. To express.)

  Examples of the compound represented by the chemical formula (19) include p-aminobenzenesulfonic acid (sulfanilic acid), m-aminobenzenesulfonic acid, o-aminobenzenesulfonic acid, m-toluidine-4-sulfonic acid, and o-toluidine-4. -Sulfonic acid sodium salt, p-toluidine-2-sulfonic acid, 4-methoxyaniline-2-sulfonic acid, o-anisidine-5-sulfonic acid, p-anisidine-3-sulfonic acid, 3-nitroaniline-4- Sulfonic acid, 2-nitroaniline-4-sulfonic acid sodium salt, 4-nitroaniline-2-sulfonic acid sodium salt, 1,5-dinitroaniline-4-sulfonic acid, 2-aminophenol-4-hydroxy-5 Nitrobenzenesulfonic acid, 2,4-dimethylaniline-5-sulfonic acid sodium salt, 2,4-dimethyl Ruaniline-6-sulfonic acid, 3,4-dimethylaniline-5-sulfonic acid, 4-isopropylaniline-6-sulfonic acid, 4-trifluoromethylaniline-6-sulfonic acid, 3-carboxy-4-hydroxyaniline- Examples include 5-sulfonic acid, 4-carboxyaniline-6-sulfonic acid, and alkali metal salts and esterified products thereof.

  When A3 is a substituted or unsubstituted naphthalene group, examples of the compound represented by the chemical formula (13) include compounds represented by the following chemical formula (20A) or chemical formula (20B).

(At least one of R4a, R4b, R4c, R4d, R4e, R4f and R4g in formula (20A), or at least of R4h, R4i, R4j, R4k, R4l, R4m and R4n in formula (20B) One is SO ₂ R4o (wherein R4o represents OH, a halogen atom, ONa, OK or OR4o1, and R4o1 represents a linear or branched alkyl group having 1 to 8 carbon atoms or a substituted or unsubstituted group. And the others are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an OH group, an NH ₂ group, an NO ₂ group, COOR4p (wherein R4p represents an H atom, Na atom or K atom), an acetamide group, an OPh group, an NHPh group, a CF3 group, a C2F5 group or a C3F7 group, and when there are a plurality of units. , R4a R4b, R4c, represents R4d, R4e, R4f, R4g, R4h, R4i, R4j, R4k, R4l, R4m, R4n, R4o, R4o1, R4p, m is the aforementioned meanings independently for each unit.)

  Examples of the compound represented by the chemical formula (20A) or (20B) include 1-naphthylamine-5-sulfonic acid, 1-naphthylamine-4-sulfonic acid, 1-naphthylamine-8-sulfonic acid, and 2-naphthylamine-5-sulfonic acid. 1-naphthylamine-6-sulfonic acid, 1-naphthylamine-7-sulfonic acid, 1-naphthylamine-2-ethoxy-6-sulfonic acid, 1-amino-2-naphthol-4-sulfonic acid, 6-amino-1 Naphthol-3-sulfonic acid, 1-amino-8-naphthol-2,4-sulfonic acid monosodium salt, 1-amino-8-naphthol-3,6-sulfonic acid monosodium salt, etc., sulfonic acid, or its Examples include alkali metal salts and esterified products.

  When A3 is a heterocyclic structure containing any one or more of substituted, unsubstituted N, S, and O, the heterocyclic ring may be any of a pyridine ring, a piperazine ring, a furan ring, a thiol ring, and the like. Examples of the compound represented by the chemical formula (13) include 2-aminopyridine-6-sulfonic acid, 2-aminopiperazine-6-sulfonic acid and the like, sulfonic acid, alkali metal salts thereof, esterified products, and the like.

Examples of the sulfonic acid ester include a substituted or unsubstituted aliphatic hydrocarbon structure, a substituted or unsubstituted aromatic ring structure, and a substituted or unsubstituted heterocyclic structure. In particular, a linear or branched alkyl group having 1 to 8 carbon atoms, a substituted or unsubstituted phenyl group, and the like are preferable. From the point of easiness of esterification, OCH ₃ , OC ₂ H ₅ , OC ₆ H ₅ , OC ₃ H ₇ , OC ₄ H ₉ , OCH (CH ₃ ) ₂ , OCH ₂ C (CH ₃ ) ₃ , OC Those having a group such as (CH ₃ ) ₃ are more preferred.

(Production method of polyhydroxyalkanoate represented by chemical formula (1))
The reaction of the polyhydroxyalkanoate containing a unit represented by the chemical formula (11) and the aminosulfonic acid compound represented by the chemical formula (13) in the present invention will be described in detail.
The usage-amount of the compound shown to Chemical formula (13) used for this invention is 0.1-50.0 times mole with respect to the unit shown to Chemical formula (11) used as a starting material, Preferably, it is 1.0-20. The range is 0.0 mole.

  The method for producing an amide bond from a carboxylic acid and an amine in the present invention includes a condensation reaction by heat dehydration. In particular, from the viewpoint of mild reaction conditions in which the ester bond of the polymer main chain is not cleaved, it is effective to activate the carboxylic acid moiety with an activator to produce an active acyl intermediate and then react with the amine. It is. Examples of the active acyl intermediate include an acid halide, an acid anhydride, and an active ester. In particular, a method of forming an amide bond in the same reaction field using a condensing agent is preferable from the viewpoint of simplifying the production process. If necessary, it can be isolated as an acid halide and then subjected to a condensation reaction with an amine.

  As the condensing agent to be used, a phosphoric acid condensing agent used for polycondensation of aromatic polyamide, a carbodiimide condensing agent used for peptide synthesis, an acid chloride condensing agent and the like are represented by chemical formulas (13) and (11). It is possible to select appropriately depending on the combination of the compounds.

  Examples of the phosphoric acid-based condensing agent include a phosphite-based condensing agent, a phosphoric chloride-based condensing agent, a phosphoric anhydride-based condensing agent, a phosphoric ester-based condensing agent, and a phosphoric acid amide-based condensing agent.

  In the reaction of the present invention, a condensing agent such as phosphite can be used. Phosphites used at this time include triphenyl phosphite, diphenyl phosphite, tri-o-tolyl phosphite, di-o-tolyl phosphite, tri-m-tolyl phosphite , Di-m-tolyl phosphite, tri-p-tolyl phosphite, di-p-tolyl phosphite, di-o-chlorophenyl phosphite, tri-p-chlorophenyl phosphite, diphosphite -P-chlorophenyl, trimethyl phosphite, triethyl phosphite and the like. Of these, triphenyl phosphite is preferably used. In order to improve the solubility and reactivity of the polymer, a metal salt such as lithium chloride or calcium chloride may be added.

  Examples of the carbodiimide condensing agent include dicyclohexylcarbodiimide (may be represented as DCC), N-ethyl-N′-3-dimethylaminopropylcarbodiimide (may be represented as EDC = WSCI), and diisopropylcarbodiimide (may be represented as DIPC). There are). DCC or WSCI and N-hydroxysuccinimide (sometimes referred to as HONSu), 1-hydroxybenzotriazole (sometimes referred to as HOBt), or 3-hydroxy-4-oxo-3,4-dihydro-1,2 , 3-benzotriazine (sometimes referred to as HOObt).

  The usage-amount of a condensing agent is 0.1-50 times mole with respect to the compound shown in Chemical formula (11), Preferably, it is the range of 1-20 times mole.

  In the reaction, a solvent can be used as necessary. Solvents that can be used include hydrocarbons such as hexane, cyclohexane and heptane, ketones such as acetone and methyl ethyl ketone, ethers such as dimethyl ether, diethyl ether and tetrahydrofuran, dichloromethane, chloroform, carbon tetrachloride, dichloroethane. , Halogenated hydrocarbons such as trichloroethane, aromatic hydrocarbons such as benzene and toluene, aprotic polar solvents such as N, N-dimethylformamide, dimethyl sulfoxide, dimethylacetamide and hexamethylphosphoramide, pyridine and picoline And pyridine derivatives such as N-methylpyrrolidone. Particularly preferably, pyridine, N-methylpyrrolidone or the like is used. The amount of the solvent used can be appropriately determined according to the starting material, the type of base, reaction conditions and the like. In the method of the present invention, the reaction temperature is not particularly limited, but is usually in the range of −20 ° C. to the boiling point of the solvent. However, it is desirable to carry out the reaction at an optimum temperature according to the condensing agent used. In the method of the present invention, the reaction time is usually in the range of 1 to 48 hours. In particular, 1 to 10 hours are preferable.

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

  As another production method of the present invention, when the R moiety in the chemical formula (1) is -A1-SO3CH3, a methyl esterifying agent is used after the condensation reaction with the amine to convert the R moiety in the chemical formula (1) to -A1. -SO3CH3 can also be methylesterified. As the methyl esterifying agent, a method of methyl esterification of fatty acid in gas chromatography analysis can be used.

  Examples of the acid catalyst method such as hydrochloric acid-methanol method, boron trifluoride-methanol method, and sulfuric acid-methanol method include base catalyst methods such as sodium methoxide method, tetramethylguanidine method, and trimethylylsilyldiazomethane method. Among them, the trimethylsilyldiazomethane method is preferable because methylation can be performed under mild conditions.

  Solvents used in the reaction are hydrocarbons such as hexane, cyclohexane and heptane, alcohols such as methanol and ethanol, halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, dichloroethane and trichloroethane, benzene and toluene. And aromatic hydrocarbons. Particularly preferably, halogenated hydrocarbons are used. The amount of the solvent used can be appropriately determined according to the starting materials, reaction conditions and the like. In the method of the present invention, the reaction temperature is not particularly limited, but is usually a temperature in the range of -20 to 30 ° C. However, it is desirable to carry out the reaction at an optimum temperature according to the condensing agent and reagent to be used.

  In the present invention, the step of reacting a polyhydroxyalkanoate having a unit represented by the chemical formula (G) with a base, and the step of reacting the compound obtained in the above step with the compound represented by the chemical formula (E) are performed. Thus, a polyhydroxyalkanoate containing a unit represented by the chemical formula (H) can be produced.

(In the formula, R _Gc is a linear alkylene chain having 0 to 4 carbon atoms (provided that no linear alkylene chain having 0 carbon atoms is selected). -4 linear alkylene chain, the linear alkylene chain has a linear or branched alkyl group, or a residue having any one of a phenyl structure, a thienyl structure, and a cyclohexyl structure at the terminal. R _Gb is a hydrogen atom or an aralkyl group which may be substituted with a linear or branched alkyl group, aryl group or aryl group. When there are a plurality of units, R _Gb and R _Gc represent the above meanings independently for each unit.)

More specifically, when R _Gc is a linear alkylene chain having 1 to 4 carbon atoms in the polyhydroxyalkanoate comprising a unit of a substituted hydroxy acid represented by the chemical formula (G) used in the present invention, the linear alkylene The chain may be substituted with a linear or branched alkyl group, or an alkyl group containing a residue having any one of a phenyl structure, a thienyl structure, and a cyclohexyl structure at the end, specifically, Is substituted or unsubstituted cyclohexyl structure, substituted or unsubstituted phenyl structure, substituted or unsubstituted phenoxy structure, substituted or unsubstituted benzoyl structure, substituted or unsubstituted phenylsulfanyl structure, substituted or unsubstituted phenylsulfinyl Structure, substituted or unsubstituted phenylsulfonyl structure, substituted The unsubstituted (phenylmethyl) sulfanyl structure, (phenylmethyl) oxy structure, 2-thienyl structure, 2-dithienyl Alpha sulfonyl structure, such as 2-thienylcarbonyl structure. R _Gb is a hydrogen atom or an aralkyl group substituted with a linear or branched alkyl group, aryl group, or aryl group. Specifically, the linear or branched alkyl group includes a methyl group, ethyl group, propyl group, isopropyl group (2-methylpropyl group), butyl group, 1-methylpropyl group, pentyl group, isopropyl group (3 -Methylbutyl group), hexyl group, isohexyl group (4-methylpentyl group), heptyl group and the like. In addition, examples of the aryl group include a phenyl group and a methylphenyl group. Examples of the aralkyl group include a phenylmethyl group (benzyl group), a phenylethyl group, a phenylpropyl group, a phenylbutyl group, a phenylpentyl group, and a methylbenzyl group. In the present invention, _RGb is preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, a pentyl group, a hexyl group, a phenyl group, or a phenylmethyl group in consideration of productivity regarding the synthesis of the polymer.

(Wherein, R _E is .R _E1 representing the -A _E -SO ₂ R _E1 is OH, a halogen atom, ONa, OK or OR _Ea. Also, R _Ea and A _E are each independently a substituted or Selected from a group having an unsubstituted aliphatic hydrocarbon structure, a substituted or unsubstituted aromatic ring structure, or a substituted or unsubstituted heterocyclic structure, and when there are a plurality of units, R _E , R _E1 , R _Ea and A _E represent the above meanings independently for each unit.)

(Wherein, R _H is .R _H1 that represents the -A _H -SO ₂ R _H1 is OH, a halogen atom, ONa, OK or OR _Ha .R _Ha and A _H are each independently a substituted or unsubstituted Represents a group having an aliphatic hydrocarbon structure, a substituted or unsubstituted aromatic ring structure, or a substituted or unsubstituted heterocyclic structure, wherein R _Hc is a linear alkylene chain having 0 to 4 carbon atoms. When the linear alkylene chain is a linear alkylene chain having 1 to 4 carbon atoms, the linear alkylene chain is a linear or branched alkyl group, or a phenyl structure, a thienyl structure, or a cyclohexyl structure at the terminal, Any residue having a structure may be optionally substituted with an alkyl group, and R _Hb may be substituted with a hydrogen atom, or a linear or branched alkyl group, aryl group, or aryl group. Ara you may have When there are a plurality of units, R _H , R _H1 , R _Ha , R _Hb , R _Hc , and A _H have the above meanings independently for each unit.)

For example, in the chemical formula (H), a polyhydroxyalkanoate having a unit represented by the chemical formula (F) in which the linear alkylene chain of R _Hc is unsubstituted and R _Hb is a hydrogen atom is represented by the chemical formula (A ) Using a polyhydroxyalkanoate having a unit represented by) and a step of reacting with a base and a step of reacting the compound obtained in the above step with the compound represented by the chemical formula (E). it can.

(Wherein, n, is .R _F is an integer selected from 0 to 4 .R _F1 representing the -A _F -SO ₂ R _F1 OH, a halogen atom, ONa, OK or OR _Fa .R _Fa And A _F each independently represents a group having a substituted or unsubstituted aliphatic hydrocarbon structure, a substituted or unsubstituted aromatic ring structure, or a substituted or unsubstituted heterocyclic structure. When present, R _F , R _F1 , R _Fa , A _F and n represent the above meanings independently for each unit.)

(In the formula, n is an integer selected from 0 to 4. When a plurality of units are present, the above meanings are independently represented for each unit.)

(Wherein, R _E is .R _E1 representing the -A _E -SO ₂ R _E1 is OH, a halogen atom, ONa, OK or OR _Ea. Also, R _Ea and A _E are each independently a substituted or Selected from a group having an unsubstituted aliphatic hydrocarbon structure, a substituted or unsubstituted aromatic ring structure, or a substituted or unsubstituted heterocyclic structure, and when there are a plurality of units, R _E , R _E1 , R _Ea and A _E represent the above meanings independently for each unit.)

  Examples of the compound represented by the chemical formula (E) include 2-acrylamido-2-methylpropanesulfonic acid, its alkali metal salt, and its esterified product.

The reaction between the polyhydroxyalkanoate containing the unit represented by the chemical formula (A) and the compound represented by the chemical formula (E) will be described in detail.
The present invention can be achieved by Michael addition reaction of the compound represented by the chemical formula (E) to the α-methylene group adjacent to the carbonyl group in the polymer main chain. Specifically, under the reaction conditions of Michael addition, a polyhydroxyalkanoate containing a unit represented by the chemical formula (A) and a carbonyl group in the polymer main chain of the polyhydroxyalkanoate containing a unit represented by the chemical formula (A) This is achieved by reacting the adjacent α-methylene group with a base capable of anion formation, and subsequently reacting with the compound represented by the chemical formula (E). In the present invention, the compound used represented by the chemical formula (E) is used in an amount of 0.001 to 100 times, preferably 0.01 to 10 times the amount of the unit represented by the chemical formula (A). is there.

  The solvent used in the reaction is a solvent inert to the reaction and is not particularly limited as long as it dissolves the starting material to some extent. For example, an aliphatic such as hexane, cyclohexane, heptane, ligroin or petroleum ether. Hydrocarbons; aromatic hydrocarbons such as benzene, toluene or xylene; ethers such as diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, dimethoxyethane or diethylene glycol dimethyl ether; or formamide, N, N-dimethylformamide, Amides such as N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylpyrrolidinone or hexamethylphosphorotriamide are preferred, and tetrahydrofuran is preferred.

  The reaction is carried out in the presence of a base. Bases used include alkyllithiums such as methyllithium and butyllithium; alkali metal disilazides such as lithium hexamethyldisilazide, sodium hexamethyldisilazide and potassium hexamethyldisilazide; lithium diisopropylamide Lithium amides such as lithium dicyclohexylamide, preferably lithium diisopropylamide. Moreover, the usage-amount of a base is 0.001-100 times mole amount with respect to the unit shown to Chemical formula (A), Preferably, it is 0.01-10 times mole amount.

  The reaction temperature is usually −78 ° C. to 40 ° C., preferably −78 ° C. to 30 ° C. The reaction time is usually in the range of 10 minutes to 24 hours. In particular, 10 minutes to 4 hours are preferable.

  In the polyhydroxyalkanoate represented by the chemical formula (5) of the present invention, the polyhydroxyalkanoate represented by the chemical formula (21) is obtained by using the polyhydroxyalkanoate represented by the chemical formula (6) as a starting material. It is produced by a method of oxidizing the side chain double bond moiety.

(For l, m, and n in the formula,
when l is an integer selected from 0 and 2-4, and n is an integer selected from 0 to 4, m is an integer selected from 0 to 8;
when l is 1 and n is an integer selected from 1 to 4, m is an integer selected from 0 to 8;
when l is 1 and n is 0, m is 0;
When there are a plurality of units, l, m, and n represent the above meanings independently for each unit. )

(Wherein R21 represents hydrogen or a group forming a salt.
In addition, for l, m, and n in the formula,
when l is an integer selected from 0 and 2-4, and n is an integer selected from 0 to 4, m is an integer selected from 0 to 8;
when l is 1 and n is an integer selected from 1 to 4, m is an integer selected from 0 to 8;
When l is 1 and n is 0, m is 0.
In addition, when there are a plurality of units, R21, l, m, and n represent the above meanings independently for each unit. )

  As a method for obtaining a carboxylic acid by oxidative cleavage of a carbon-carbon double bond as described above with an oxidizing agent, for example, a method using permanganate (J. Chem. Soc., Perkin. Trans. 1,806 (1973)), a method using dichromate (Org. Synth., 4, 698 (1963)), a method using periodate (J. Org. Chem., 46, 19 (1981)). ) A method using nitric acid (Japanese Patent Laid-Open No. 59-190945), a method using ozone (J. Am. Chem. Soc., 81, 4273 (1959)) and the like are known, and Macromolecular chemistry, 4, 289-293 (2001) oxidized the carbon-carbon double bond at the end of the side chain of microbially produced polyhydroxyalkanoate As used potassium permanganate, the reaction is be carried out in acidic conditions, a method of obtaining a carboxylic acid have been reported. A similar method can be used in the present invention.

  As the permanganate used as the oxidizing agent, potassium permanganate is common. 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 the chemical formula (6). 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 in the main chain 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 (6). If it is 0.2 molar equivalent or more, a preferable yield is obtained, and if it is 2000 molar equivalent or less, it is preferable because a decomposition product of an acid can be reduced as a by-product. In addition, crown-ether can be used for the purpose of promoting the reaction. In this case, the crown-ether and the permanganate form a complex, and the effect of increasing the reaction activity is obtained. As the crown-ether, dibenzo-18-crown-6-ether, dicyclo-18-crown-6-ether, or 18-crown-6-ether is generally used. The amount of the crown-ether used is usually 0.005 to 2.0 molar equivalents, preferably 0.01 to 1.5 molar equivalents per mole of permanganate.

  In addition, the solvent in the oxidation reaction 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, heptane and the like Aliphatic hydrocarbons such as: methyl chloride, dichloromethane, chloroform, and other halogenated hydrocarbons. 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, the polyhydroxyalkanoate, permanganate and acid containing the unit represented by the chemical formula (6) may be charged together with the solvent from the beginning and reacted, and each of them may be continuously or intermittently contained in the system. You may make it react, adding to. 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. Furthermore, polyhydroxyalkanoate and acid may be charged first, and then permanganate may be added to the system continuously or intermittently to react, and the permanganate and acid are charged first. The polyhydroxyalkanoate may be continuously or intermittently added to the system and allowed to react, and the polyhydroxyalkanoate and permanganate are charged first, followed by the acid continuously or intermittently. The reaction may be carried out in addition to the system. The reaction temperature is usually −40 to 40 ° C., preferably −10 to 30 ° C. The reaction time depends on the stoichiometric ratio between the unit represented by the chemical formula (6) and the permanganate and the reaction temperature, but it is usually 2 to 48 hours.

  In addition, in the polyhydroxyalkanoate represented by the chemical formula (5), the polyhydroxyalkanoate represented by the chemical formula (11) uses the polyhydroxyalkanoate represented by the chemical formula (23) as a starting material, and the side chain ester portion is converted to an acid. Or it manufactures by the method of hydrolyzing in the presence of an alkali, or the method of hydrocracking including catalytic reduction.

(Wherein R 11 represents hydrogen or a group forming a salt.
In addition, about l, m, Z11a, Z11b in the formula,
When l is an integer selected from 0 and 2 to 4, Z11a is not selected or is a linear alkylene chain having 1 to 4 carbon atoms, Z11b is a hydrogen atom, and m is selected from 0 to 8 Integer,
When l is 1 and Z11a is a linear alkylene chain having 1 to 4 carbon atoms, Z11b is a hydrogen atom, m is an integer selected from 0 to 8,
When l is 1 and Z11a is not selected, Z11b is a hydrogen atom, m is 0,
When l is 0 and Z11a is a linear alkylene chain having 1 to 4 carbon atoms, the linear alkylene chain has a linear or branched alkyl group, or a phenyl structure, a thienyl structure, or a cyclohexyl structure at the terminal. Among them, it may be substituted with an alkyl group containing a residue having any structure, and Z11b is substituted with a hydrogen atom, or a linear or branched alkyl group, aryl group, or aryl group. An aralkyl group, m is an integer selected from 0 to 8;
When l is 0 and Z11a is not selected, Z11b is a hydrogen atom or a linear or branched alkyl group, aryl group, aryl group optionally substituted with an aryl group, and m is It is an integer selected from 0-8.
Further, when there are a plurality of units, R11, Z11a, Z11b, l, and m represent the above meanings independently for each unit. )

(In formula, R23 represents a C1-C12 linear or branched alkyl group and aralkyl group.
In addition, about l, m, Z23a, Z23b in the formula,
When l is an integer selected from 0 and 2 to 4, Z23a is not selected or a linear alkylene chain having 1 to 4 carbon atoms, Z23b is a hydrogen atom, and m is selected from 0 to 8 Integer,
When l is 1 and Z23a is a linear alkylene chain having 1 to 4 carbon atoms, Z23b is a hydrogen atom, m is an integer selected from 0 to 8,
When l is 1 and no Z23a is selected, Z23b is a hydrogen atom, m is 0,
When l is 0 and Z23a is a linear alkylene chain having 1 to 4 carbon atoms, the linear alkylene chain has a linear or branched alkyl group, or a phenyl structure, thienyl structure, or cyclohexyl structure at the terminal. Of these, Z23b may be substituted with an alkyl group containing a residue having any structure, and Z23b is substituted with a hydrogen atom, or a linear or branched alkyl group, aryl group, or aryl group. An aralkyl group, m is an integer selected from 0 to 8;
When l is 0 and Z23a is not selected, Z23b is a hydrogen atom or an aralkyl group which may be substituted with a linear or branched alkyl group, aryl group or aryl group, and m is It is an integer selected from 0-8.
Further, when there are a plurality of units, R23, Z23a, Z23b, l, and m represent the above meanings independently for each unit. )

  More specifically, in the compound represented by the chemical formula (23) used in the present invention, when l is 0 and Z23a is a linear alkylene chain having 1 to 4 carbon atoms, the linear alkylene chain is linear or It may be substituted with a branched alkyl group or an alkyl group containing a residue having any one of a phenyl structure, a thienyl structure, and a cyclohexyl structure at the end, specifically, substituted or unsubstituted Cyclohexyl structure, substituted or unsubstituted phenyl structure, substituted or unsubstituted phenoxy structure, substituted or unsubstituted benzoyl structure, substituted or unsubstituted phenylsulfanyl structure, substituted or unsubstituted phenylsulfinyl structure, substituted or unsubstituted Phenylsulfonyl structure, substituted or unsubstituted (phenylmethyl) sulfanyl structure (Phenylmethyl) oxy structure, 2-thienyl structure, 2-dithienyl Alpha sulfonyl structure, such as 2-thienylcarbonyl structure.

  Further, in the compound represented by the chemical formula (23) used in the present invention, when l is 0, Z23b is substituted with a hydrogen atom, or a linear or branched alkyl group, aryl group, or aryl group. It is an aralkyl group. Specifically, examples of the linear or branched alkyl group include methyl group, ethyl group, propyl group, isopropyl group (2-methylpropyl group), butyl group, 1-methylpropyl group, pentyl group, isopropyl group ( 3-methylbutyl group), hexyl group, isohexyl group (4-methylpentyl group), heptyl group and the like. In addition, examples of the aryl group include a phenyl group and a methylphenyl group. Examples of the aralkyl group include a phenylmethyl group (benzyl group), a phenylethyl group, a phenylpropyl group, a phenylbutyl group, a phenylpentyl group, and a methylbenzyl group. In the present invention, Z23b is preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, a pentyl group, a hexyl group, a phenyl group, or a phenylmethyl group in consideration of productivity regarding the synthesis of the polymer.

  When using the method of hydrolysis in the presence of an acid or an alkali, hydrochloric acid, sulfuric acid, nitric acid in an aqueous solution as a solvent or in an aqueous organic solvent such as methanol, ethanol, tetrahydrofuran, dioxane, dimethylformamide, dimethylsulfoxide, etc. Or an aqueous solution of an inorganic acid such as phosphoric acid or an organic acid such as trifluoroacetic acid, trichloroacetic acid, p-toluenesulfonic acid, methanesulfonic acid, or an aqueous caustic alkali such as sodium hydroxide or potassium hydroxide, It can be carried out using an aqueous solution of an alkali carbonate such as sodium carbonate or potassium carbonate, or an alcohol solution of a metal alkoxide such as sodium methoxide or sodium ethoxide. The reaction temperature is usually 0 to 40 ° C, preferably 0 to 30 ° C. The reaction time is usually 0.5 to 48 hours. However, when hydrolyzed with an acid or alkali, the ester bond of the main chain may be cleaved in any case, and a decrease in molecular weight may be observed.

  When using the method of obtaining carboxylic acid using the method of hydrocracking including catalytic reduction, it is performed as follows. That is, in an appropriate solvent, catalytic reduction is carried out by allowing hydrogen to act at normal pressure or under pressure in the presence of a reduction catalyst at a temperature in the range of -20 ° C to the boiling point of the solvent used, preferably 0 to 50 ° C. Do it. Examples of the solvent used include water, methanol, ethanol, propanol, hexafluoroisopropanol, ethyl acetate, diethyl ether, tetrahydrofuran, dioxane, benzene, toluene, dimethylformamide, pyridine, and N-methylpyrrolidone. Moreover, it can also be used as said mixed solvent. As the reduction catalyst, a catalyst such as palladium, platinum, rhodium or the like supported on a carrier or Raney nickel is used. The reaction time is usually preferably 0.5 to 72 hours. The reaction solution containing the polyhydroxyalkanoate represented by the chemical formula (11) thus produced is recovered as a crude polymer by removing the catalyst by filtration and removing the solvent by distillation or the like. The polyhydroxyalkanoate represented by the chemical formula (11) obtained here can be isolated and purified if necessary. The isolation and purification method is not particularly limited, and a reprecipitation method using a solvent insoluble in the polyhydroxyalkanoate represented by the chemical formula (11), a column chromatography method, a dialysis method, and the like can be used. However, even when catalytic reduction is used, the ester bond of the main chain is also cleaved, and a decrease in molecular weight may be observed.

  Further, in the polyhydroxyalkanoate represented by the chemical formula (5) of the present invention, the polyhydroxyalkanoate represented by the chemical formula (23) uses the polyhydroxyalkanoate represented by the chemical formula (11) as a starting material, and an esterifying agent. Produced by esterification.

(In formula, R23 represents a C1-C12 linear or branched alkyl group and aralkyl group.
In addition, about l, m, Z23a, Z23b in the formula,
When l is an integer selected from 2 to 4, Z23a is not selected or a linear alkylene chain having 1 to 4 carbon atoms, Z23b is a hydrogen atom, and m is selected from 0 to 8 An integer,
When l is 1 and Z23a is a linear alkylene chain having 1 to 4 carbon atoms, Z23b is a hydrogen atom, m is an integer selected from 0 to 8,
When l is 1 and no Z23a is selected, Z23b is a hydrogen atom, m is 0,
When l is 0 and Z23a is a linear alkylene chain having 1 to 4 carbon atoms, the linear alkylene chain has a linear or branched alkyl group, or a phenyl structure, thienyl structure, or cyclohexyl structure at the terminal. Of these, Z23b may be substituted with an alkyl group containing a residue having any structure, and Z23b is substituted with a hydrogen atom, or a linear or branched alkyl group, aryl group, or aryl group. An aralkyl group, m is an integer selected from 0 to 8;
When l is 0 and Z23a is not selected, Z23b is a hydrogen atom or an aralkyl group which may be substituted with a linear or branched alkyl group, aryl group or aryl group, and m is It is an integer selected from 0-8.
Further, when there are a plurality of units, R23, Z23a, Z23b, l, and m represent the above meanings independently for each unit. )

(Wherein R 11 represents hydrogen or a group forming a salt.
In addition, about l, m, Z11a, Z11b in the formula,
When l is an integer selected from 2 to 4, Z11a is not selected or is a linear alkylene chain having 1 to 4 carbon atoms, Z11b is a hydrogen atom, and m is selected from 0 to 8 An integer,
When l is 1 and Z11a is a linear alkylene chain having 1 to 4 carbon atoms, Z11b is a hydrogen atom, m is an integer selected from 0 to 8,
When l is 1 and Z11a is not selected, Z11b is a hydrogen atom, m is 0,
When l is 0 and Z11a is a linear alkylene chain having 1 to 4 carbon atoms, the linear alkylene chain has a linear or branched alkyl group, or a phenyl structure, a thienyl structure, or a cyclohexyl structure at the terminal. Among them, it may be substituted with an alkyl group containing a residue having any structure, and Z11b is substituted with a hydrogen atom, or a linear or branched alkyl group, aryl group, or aryl group. An aralkyl group, m is an integer selected from 0 to 8;
When l is 0 and Z11a is not selected, Z11b is a hydrogen atom or a linear or branched alkyl group, aryl group, aryl group optionally substituted with an aryl group, and m is It is an integer selected from 0-8.
Further, when there are a plurality of units, R11, Z11a, Z11b, l, and m represent the above meanings independently for each unit. )

More specifically, in the compound represented by the chemical formula (11) used in the present invention, when l is 0 and Z11a is a linear alkylene chain having 1 to 4 carbon atoms, the linear alkylene chain is linear or It may be substituted with a branched alkyl group or an alkyl group containing a residue having any one of a phenyl structure, a thienyl structure, and a cyclohexyl structure at the end, specifically, substituted or unsubstituted Cyclohexyl structure, substituted or unsubstituted phenyl structure, substituted or unsubstituted phenoxy structure, substituted or unsubstituted benzoyl structure, substituted or unsubstituted phenylsulfanyl structure, substituted or unsubstituted phenylsulfinyl structure, substituted or unsubstituted Phenylsulfonyl structure, substituted or unsubstituted (phenylmethyl) sulfanyl structure (Phenylmethyl) oxy structure, 2-thienyl structure, 2-dithienyl Alpha sulfonyl structure, such as 2-thienylcarbonyl structure.
In the compound represented by the chemical formula (11) used in the present invention, when 11 is 0, Z11b is substituted with a hydrogen atom or a linear or branched alkyl group, aryl group, or aryl group. It is an aralkyl group. Specifically, examples of the linear or branched alkyl group include methyl group, ethyl group, propyl group, isopropyl group (2-methylpropyl group), butyl group, 1-methylpropyl group, pentyl group, isopropyl group ( 3-methylbutyl group), hexyl group, isohexyl group (4-methylpentyl group), heptyl group and the like. In addition, examples of the aryl group include a phenyl group and a methylphenyl group. Examples of the aralkyl group include a phenylmethyl group (benzyl group), a phenylethyl group, a phenylpropyl group, a phenylbutyl group, a phenylpentyl group, and a methylbenzyl group. In the present invention, Z11b is preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, a pentyl group, a hexyl group, a phenyl group, or a phenylmethyl group in consideration of productivity regarding the synthesis of the polymer.

  As the esterifying agent used, diazomethane and DMF dimethylacetals can be used. For example, it easily reacts with trimethylsilyldiazomethane, DMF dimethyl acetal, DMF diethyl acetal, DMF dipropyl acetal, DMF diisopropyl acetal, DMF-n-butyl acetal, DMF-tert-butyl acetal, DMF dineopentyl acetal, etc. Give an ester. Alcohols such as methanol, ethanol, propanol, isopropyl alcohol, butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, pentyl alcohol, neopentyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol , Lauryl alcohol, and other saccharides such as D-glucose, D-fructose, and other saccharides are reacted with a method using an acid catalyst or a condensing agent such as DCC to produce esterified poly. Hydroxyalkanoates are obtained.

  In the present invention, the step of reacting a polyhydroxyalkanoate having a unit represented by the chemical formula (G) with a base, and the step of reacting the compound obtained in the above step with the compound represented by the chemical formula (K) are performed. Thus, a polyhydroxyalkanoate containing a unit represented by the chemical formula (J) can be produced.

(In the formula, R _Gc is a linear alkylene chain having 0 to 4 carbon atoms. When the linear alkylene chain is a linear alkylene chain having 1 to 4 carbon atoms, the linear alkylene chain is linear. or branched alkyl groups, or terminal phenyl structure, a thienyl structure, among the cyclohexyl structure, optionally may be substituted with an alkyl group that contains a residue having any one of structures. in addition, R _Gb is hydrogen An aralkyl group which may be substituted with an atom or a linear or branched alkyl group, aryl group or aryl group, and when there are a plurality of units, R _Gb and R _Gc are independent for each unit; Represents the above meaning.)

(Wherein, m is .X an integer selected from 0-8 is a halogen atom .R _K represents a linear or branched alkyl group having 1 to 12 carbon atoms, or is an aralkyl group .)

(In the formula, m is an integer selected from 0 to 8. R _J is a linear or branched alkyl group having 1 to 12 carbon atoms or an aralkyl group. R _Jc is a carbon number. A linear alkylene chain of 0 to 4. When the linear alkylene chain is a linear alkylene chain having 1 to 4 carbon atoms, the linear alkylene chain is a linear or branched alkyl group or a terminal phenyl group. R _Jb may be optionally substituted with an alkyl group containing a residue having any one of a structure, a thienyl structure, and a cyclohexyl structure, and R _Jb is a hydrogen atom or a linear or branched alkyl group Group, aryl group, aralkyl group optionally substituted with an aryl group, and when there are a plurality of units, R _J , R _Jb , R _Jc, and m independently represent the above-mentioned meanings for each unit. .)

More specifically, in the compound represented by the chemical formula (G) used in the present invention, when R _Gc is a linear alkylene chain having 1 to 4 carbon atoms, the linear alkylene chain is a linear or branched alkyl group. Group or terminal may be substituted with an alkyl group containing a residue having any one of a phenyl structure, a thienyl structure, and a cyclohexyl structure, specifically, a substituted or unsubstituted cyclohexyl structure, Substituted or unsubstituted phenyl structure, substituted or unsubstituted phenoxy structure, substituted or unsubstituted benzoyl structure, substituted or unsubstituted phenylsulfanyl structure, substituted or unsubstituted phenylsulfinyl structure, substituted or unsubstituted phenylsulfonyl structure Substituted or unsubstituted (phenylmethyl) sulfanyl structure, (phenylmethyl) ) Oxy structure, 2-thienyl structure, 2-dithienyl Alpha sulfonyl structure, such as 2-thienylcarbonyl structure.

In the compound represented by the chemical formula (G) used in the present invention, R _Gb is a hydrogen atom or an aralkyl group substituted with a linear or branched alkyl group, aryl group, or aryl group. Specifically, examples of the linear or branched alkyl group include methyl group, ethyl group, propyl group, isopropyl group (2-methylpropyl group), butyl group, 1-methylpropyl group, pentyl group, isopropyl group ( 3-methylbutyl group), hexyl group, isohexyl group (4-methylpentyl group), heptyl group and the like. In addition, examples of the aryl group include a phenyl group and a methylphenyl group. Examples of the aralkyl group include a phenylmethyl group (benzyl group), a phenylethyl group, a phenylpropyl group, a phenylbutyl group, a phenylpentyl group, and a methylbenzyl group. In the present invention, _RGb is preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, a pentyl group, a hexyl group, a phenyl group, or a phenylmethyl group in consideration of productivity regarding the synthesis of the polymer.

For example, in the chemical formula (J), a polyhydroxyalkanoate having a unit represented by the chemical formula (C) in which the alkylene chain is unsubstituted and R _Jb is a hydrogen atom is a unit represented by the chemical formula (A) as a starting material. It can manufacture by passing through the process made to react with a base using the polyhydroxy alkanoate which has, and the process made to react the compound shown by the said process, and the compound shown by Chemical formula (B).

(In the formula, n is an integer selected from 0 to 4, and m is an integer selected from 0 to 8. R _c is a linear or branched alkyl group having 1 to 12 carbon atoms, aralkyl. When there are a plurality of units, R _c , m and n have the above meanings independently for each unit.)

(In the formula, n is an integer selected from 0 to 4. When a plurality of units are present, the above meanings are independently represented for each unit.)

(Wherein, m is .X an integer selected from 0-8 is a halogen atom .R _B represents a linear or branched alkyl group having 1 to 12 carbon atoms, or is an aralkyl group .)

  Examples of the compound represented by the chemical formula (B) include methyl chloroformate, ethyl chloroformate, propyl chloroformate, isopropyl chloroformate, butyl chloroformate, cyclohexyl chloroformate, benzyl chloroformate, methyl bromate, ethyl bromate, and propyl bromate. , Bromobromoformate, butyl bromoformate, cyclohexyl bromoformate, benzyl bromoformate, methyl chloroacetate, ethyl chloroacetate, propyl chloroacetate, isopropyl chloroacetate, butyl chloroacetate, cyclohexyl chloroacetate, benzyl chloroacetate, methyl bromoacetate, bromo Ethyl acetate, propyl bromoacetate, isopropyl bromoacetate, butyl bromoacetate, cyclohexyl bromoacetate, benzyl bromoacetate, methyl 3-chloropropionate, 3-chloropropionic acid Chill, propyl 3-chloropropionate, isopropyl 3-chloropropionate, butyl 3-chloropropionate, cyclohexyl 3-chloropropionate, benzyl 3-chloropropionate, methyl 3-bromopropionate, ethyl 3-bromopropionate Propyl 3-bromopropionate, isopropyl 3-bromopropionate, butyl 3-bromopropionate, cyclohexyl 3-bromopropionate, benzyl 3-bromopropionate, methyl 4-chlorobutyrate, ethyl 4-chlorobutyrate, 4- Propyl chlorobutyrate, isopropyl 4-chlorobutyrate, butyl 4-chlorobutyrate, cyclohexyl 4-chlorobutyrate, benzyl 4-chlorobutyrate, methyl 4-bromobutyrate, ethyl 4-bromobutyrate, propyl 4-bromobutyrate, 4-bromobutyric acid Isopro Butyl 4-bromobutyrate, cyclohexyl 4-bromobutyrate, benzyl 4-bromobutyrate, methyl 5-chlorovalerate, ethyl 5-chlorovalerate, propyl 5-chlorovalerate, isopropyl 5-chlorovalerate, 5- Butyl chlorovalerate, cyclohexyl 5-chlorovalerate, benzyl 5-chlorovalerate, methyl 5-bromovalerate, ethyl 5-bromovalerate, propyl 5-bromovalerate, isopropyl 5-bromovalerate, 5-bromo Butyl valerate, cyclohexyl 5-bromovalerate, benzyl 5-bromovalerate, methyl 6-chlorohexanoate, ethyl 6-chlorohexanoate, propyl 6-chlorohexanoate, isopropyl 6-chlorohexanoate, 6-chlorohexane Acid butyl, 6-chlorohexanoic acid cyclohexyl, 6-chlorohexanoic acid benzyl, Methyl 6-bromohexanoate, ethyl 6-bromohexanoate, propyl 6-bromohexanoate, isopropyl 6-bromohexanoate, butyl 6-bromohexanoate, cyclohexyl 6-bromohexanoate, benzyl 6-bromohexanoate, 7 -Methyl chloroheptanoate, ethyl 7-chloroheptanoate, propyl 7-chloroheptanoate, isopropyl 7-chloroheptanoate, butyl 7-chloroheptanoate, cyclohexyl 7-chloroheptanoate, benzyl 7-chloroheptanoate, 7- Methyl bromoheptanoate, ethyl 7-bromoheptanoate, propyl 7-bromoheptanoate, isopropyl 7-bromoheptanoate, butyl 7-bromoheptanoate, cyclohexyl 7-bromoheptanoate, benzyl 7-bromooctanoate, 8-chloro Octanoic acid meth , Ethyl 8-chlorooctanoate, propyl 8-chlorooctanoate, isopropyl 8-chlorooctanoate, butyl 8-chlorooctanoate, cyclohexyl 8-chlorooctanoate, benzyl 8-chlorooctanoate, methyl 8-bromooctanoate, Ethyl 8-bromooctanoate, propyl 8-bromooctanoate, isopropyl 8-bromooctanoate, butyl 8-bromooctanoate, cyclohexyl 8-bromooctanoate, benzyl 8-bromooctanoate, methyl 9-chlorononanoate, 9- Ethyl chlorononanoate, propyl 9-chlorononanoate, isopropyl 9-chlorononanoate, butyl 9-chlorononanoate, cyclohexyl 9-chlorononanoate, benzyl 9-chlorononanoate, methyl 9-bromononanoate, ethyl 9-bromononanoate, 9-bromo Nan propyl, 9-bromononane isopropyl, butyl 9-bromononane acid, 9-bromononane cyclohexyl, 9-bromononane benzyl and the like.

The reaction between the polyhydroxyalkanoate containing a unit represented by the chemical formula (A) and the compound represented by the chemical formula (B) in the present invention will be described in detail.
The present invention can be achieved by subjecting a compound represented by the chemical formula (B) to an addition reaction with an α-methylene group adjacent to a carbonyl group in the polymer main chain. Specifically, under the conditions of the addition reaction, a polyhydroxyalkanoate containing a unit represented by the chemical formula (A) and a polyhydroxyalkanoate containing a unit represented by the chemical formula (A) are adjacent to the carbonyl group in the polymer main chain. It is achieved by reacting the α-methylene group in the base with a base capable of anion formation and subsequently reacting with a compound represented by the chemical formula (B). In the present invention, the amount of the compound represented by the chemical formula (B) to be used is 0.001 to 100-fold molar amount, preferably 0.01 to 10-fold molar amount relative to the unit represented by the chemical formula (A). is there.

  The solvent used in the reaction is a solvent inert to the reaction and is not particularly limited as long as it dissolves the starting material to some extent. For example, an aliphatic such as hexane, cyclohexane, heptane, ligroin or petroleum ether. Hydrocarbons; aromatic hydrocarbons such as benzene, toluene or xylene; ethers such as diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, dimethoxyethane or diethylene glycol dimethyl ether; or formamide, N, N-dimethylformamide, Amides such as N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylpyrrolidinone or hexamethylphosphorotriamide are preferred, and tetrahydrofuran is preferred.

  The reaction is carried out in the presence of a base. Bases used include alkyllithiums such as methyllithium and butyllithium; alkali metal disilazides such as lithium hexamethyldisilazide, sodium hexamethyldisilazide and potassium hexamethyldisilazide; lithium diisopropylamide Lithium amides such as lithium dicyclohexylamide, preferably lithium diisopropylamide. Moreover, the usage-amount of the base in this invention is 0.001-100 times mole amount with respect to the unit shown to Chemical formula (A), Preferably, it is 0.01-10 times mole amount.

  The reaction temperature is usually −78 ° C. to 40 ° C., preferably −78 ° C. to 30 ° C. The reaction time is usually in the range of 10 minutes to 24 hours. In particular, 10 minutes to 4 hours are preferable.

  By the above production method, a polyhydroxyalkanoate having a unit represented by the chemical formula (C) can be produced.

  Moreover, the polymer manufactured by a well-known method can also be arbitrarily used for the polyhydroxyalkanoate containing the unit shown to Chemical formula (G) used for this invention. Examples thereof include microbial-produced polyhydroxyalkanoates represented by poly-3-hydroxybutyric acid, poly-3-hydroxyvaleric acid and the like. For example, Japanese Patent Publication Nos. 7-14352 and 8-19227 disclose a method for producing a copolymer of 3-hydroxybutyric acid and 3-hydroxyvaleric acid. JP-A-5-93049 and JP-A-7-265065 disclose a method for producing a copolymer of 3-hydroxybutyric acid and 3-hydroxyhexanoic acid. Japanese Patent Publication No. 2642937 discloses a method for producing a copolymer containing 3-hydroxyalkanoate having 6 to 12 carbon atoms (ie, 3-hydroxyhexanoic acid to 3-hydroxyundecanoic acid). . Japanese Patent Application Laid-Open No. 2002-306190 discloses a method for producing a homopolymer of poly-3-hydroxybutyric acid. In the present invention, polyhydroxyalkanoate can be produced by the same method. Other microorganism-produced polyhydroxyalkanoates can also be produced by the methods disclosed in International Journal of Biological Macromolecules 12 (1990) 92, JP 2001-288256 A, JP 2003-319792 A, and the like.

Further, a polyhydroxyalkanoate composed of a substituted α-hydroxy acid unit represented by a chemical formula (G) in which R _Gc is a linear alkylene chain having 0 carbon atoms (RG _Gc is not selected at all) is also known in the art. Can be synthesized. For example, a polyester can be produced directly from a substituted α-hydroxy acid. Alternatively, prior to the polymerization step, the substituted α-hydroxy acid can be converted to a derivative having high polymerization activity and then produced by ring-opening polymerization.

(Method for producing polyhydroxyalkanoate comprising substituted α-hydroxy acid units from substituted α-hydroxy acid)
A polyhydroxyalkanoate composed of a substituted α-hydroxy acid unit is formed by refluxing a substituted α-hydroxy acid and a polymerization catalyst in an organic solvent, and removing condensation water generated in the polymerization process from the reaction system. Can be advanced.

(A) Polymerization catalyst In the condensation polymerization of a substituted α-hydroxy acid, examples of the polymerization catalyst include metals such as tin powder and zinc powder, and metal oxides such as tin oxide, zinc oxide, magnesium oxide, titanium oxide, and aluminum oxide. Use metal halides such as tin dichloride, tin tetrachloride, tin dibromide, tin bromide, zinc chloride, magnesium chloride, aluminum chloride, tetraphenyltin, tin octylate, p-toluenesulfonic acid, etc. Can do. The usage-amount of a polymerization catalyst is 0.001-10 mass% with respect to substituted alpha-hydroxy acid, Preferably, it is 0.01-5 mass%.

(A) Polymerization solvent In the condensation polymerization of the substituted α-hydroxy acid, a polymerization solvent that can be easily separated from water is preferable. For example, toluene, xylene, mesitylene, 1,2,3,5-tetramethylbenzene, chlorobenzene, 1,2-dichlorobenzene, 1,3-dichlorobenzene, bromobenzene, 1,2-dibromobenzene, 1,3- Solvents such as dibromobenzene, iodobenzene, 1,2-diiodobenzene, diphenyl ether and dibenzyl ether can be used, and these may be used in combination. The amount of the polymerization solvent used is preferably such that the concentration of the substituted α-hydroxy acid is 5 to 50% by mass.

(C) Polymerization conditions In the condensation polymerization of the substituted α-hydroxy acid, the polymerization temperature is 50 to 200 ° C., preferably 110 to 180 ° C., taking into consideration the polymer production rate and the thermal decomposition rate of the polymer produced. . The condensation polymerization reaction is usually performed at the distillation temperature of the organic solvent used under normal pressure. When using a high-boiling organic solvent, it may be carried out under reduced pressure. The condensation polymerization of the substituted α-hydroxy acid is preferably performed in an inert gas atmosphere, and may be performed while replacing the reaction apparatus with an inert gas or while bubbling with an inert gas. Moreover, the water produced | generated in the polymerization reaction process is removed from a reaction apparatus suitably. The number average molecular weight of the polyester obtained by polymerization can be obtained with various molecular weights by changing the conditions such as the type of polymerization solvent, the type and amount of the polymerization catalyst, the polymerization temperature, the polymerization time, etc. In consideration, it is preferably 1000 to 1,000,000 in terms of polystyrene.

(Production method of polyhydroxyalkanoate comprising units of substituted α-hydroxy acid from cyclic dimer of substituted α-hydroxy acid)
Two molecules of the substituted α-hydroxy acid are dehydrated to form a cyclic diester, and a cyclic dimer lactide is produced as a derivative of the substituted α-hydroxy acid. Can be manufactured. Ring-opening polymerization generally has a high polymerization rate and can produce a polyester having a high degree of polymerization. As a method for carrying out cyclic diesterification by dehydrating two molecules of a substituted α-hydroxy acid, for example, using a reactor equipped with DeanStarktrap, a substituted α-hydroxy acid and a condensation catalyst such as p-toluenesulfonic acid are mixed in toluene. The cyclic dimer lactide can be obtained in a high yield by performing azeotropic dehydration for 30 hours in a nitrogen atmosphere and appropriately removing water accumulated in the DeanStarktrap. The target polyester can also be obtained by adding a polymerization catalyst to cyclic dimer lactide and subjecting it to ring-opening polymerization in an inert gas atmosphere.

(A) Polymerization catalyst In the ring-opening polymerization of the cyclic dimer lactide, examples of the polymerization catalyst include metals such as tin powder and zinc powder, metal oxides such as tin oxide, zinc oxide, magnesium oxide, titanium oxide, and aluminum oxide. Further, metal halides such as tin dichloride, tin tetrachloride, tin dibromide, tin bromide, tin bromide, zinc chloride, magnesium chloride, and aluminum chloride, tetraphenyltin, tin octylate, and the like can be used. Among these, since the catalytic activity of tin or a tin compound is excellent, these are particularly preferable. The usage-amount of a polymerization catalyst is 0.001-10 mass% with respect to cyclic | annular dimer lactide, Preferably, it is 0.01-5 mass%.

(A) Polymerization conditions In the ring-opening polymerization of the cyclic dimer lactide, the polymerization temperature is 100 to 200 ° C., preferably 120 to 180 ° C., taking into consideration the production rate of the polymer and the thermal decomposition rate of the produced polymer. is there. The ring-opening polymerization of the cyclic dimer lactide is preferably performed in an inert gas atmosphere. For example, nitrogen gas or argon gas can be used as the inert gas. The number average molecular weight of the polyester obtained by polymerization can be obtained with various molecular weights by changing conditions such as the type and amount of the polymerization catalyst, the polymerization temperature, and the polymerization time. In consideration of the reaction in the next step of polyhydroxyalkanoate composed of substituted α-hydroxy acid units used in the present invention, 1000 to 1,000,000 is preferable in terms of polystyrene.

  The polyhydroxyalkanoate represented by the chemical formula (6), which is a raw material of the polyhydroxyalkanoate represented by the chemical formula (1) or the chemical formula (5), is an intramolecular cyclized compound of ω-hydroxycarboxylic acid represented by the chemical formula (8) Is polymerized in the presence of a catalyst.

(For l, m and n in the formula,
when l is an integer selected from 0 and 2-4, and n is an integer selected from 0 to 4, m is an integer selected from 0 to 8;
When l is 1 and n is an integer selected from 1 to 4, m is an integer selected from 0 to 8.
When there are a plurality of units, l, m, and n represent the above meanings independently for each unit. )

(For l, m and n in the formula,
when l is an integer selected from 0 and 2-4, and n is an integer selected from 0 to 4, m is an integer selected from 0 to 8;
When l is 1 and n is an integer selected from 1 to 4, m is an integer selected from 0 to 8. )

  In the production of the polyhydroxyalkanoate containing the unit represented by the chemical formula (6) using the chemical formula (8) which is the intramolecular ring-closing compound of ω-hydroxycarboxylic acid, the polymerization method is not particularly limited. A polymerization method, a slurry polymerization method, a bulk polymerization method, or the like can be adopted. When a polymerization solvent is used, the solvent is not particularly limited. For example, an inert solvent such as an aliphatic hydrocarbon having 5 to 18 carbon atoms or a cyclic hydrocarbon, or an aromatic hydrocarbon having 6 to 20 carbon atoms, Tetrahydrofuran, chloroform, orthodichlorobenzene, dioxane and the like can be used.

  As the catalyst used for the polymerization, a known ring-opening polymerization catalyst can be used. Examples include tin dichloride, tin tetrachloride, stannous fluoride, stannous acetate, stannous stearate, stannous octoate, stannous oxide, stannic oxide, and other tin salts. . Also, triethoxyaluminum, tri-n-propoxy-aluminum, tri-iso-propoxyaluminum, tri-n-butoxyaluminum, tri-iso-butoxyaluminum, aluminum chloride, di-iso-propylzinc, dimethylzinc, diethyl Zinc, zinc chloride, tetra-n-butoxy titanium, tetra-n-butoxy titanium, tetra-t-butoxy titanium, antimony trifluoride, lead oxide, lead stearate, titanium tetrachloride, boron trifluoride, trifluoride Boron ether complexes, triethylamine, tributylamine and the like can be mentioned.

  The usage-amount of these catalysts is the range of 0.0001-10 mass% with respect to the total amount of a monomer compound, More preferably, it is the range of 0.001-5 mass%.

  In the ring-opening polymerization, a known polymerization initiator can be used as a polymerization initiator. Specifically, the aliphatic alcohol may be mono-, di- or polyhydric alcohol, and may be saturated or unsaturated. Specifically, monoalcohols such as methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, nonanol, decanol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, p-tert-butylbenzyl alcohol, ethylene glycol, Dialcohols such as butanediol, hexanediol, nonanediol, and tetramethylene glycol, polyhydric alcohols such as glycerol, sorbitol, xylitol, ribitol, and erythritol, and methyl lactate and ethyl lactate can be used. These aliphatic alcohols are used in a proportion of 0.01 to 10% by mass with respect to the total amount of monomers, although there are some differences depending on the conditions such as the type of alcohol used.

  The ring-opening polymerization reaction temperature is in the range of 25 to 200 ° C, preferably 50 to 200 ° C, more preferably 100 to 180 ° C. The ring-opening polymerization reaction may be carried out under an inert atmosphere such as nitrogen or argon, or under reduced pressure or under pressure. In this case, a catalyst and alcohol may be added successively.

  In order to change various physical properties such as mechanical properties and decomposition properties, the second component may be copolymerized. Specifically, a cyclic diester of α-hydroxycarboxylic acid or a lactone which is an intramolecular ring-closing compound of ω-hydroxycarboxylic acid can be copolymerized. Furthermore, specific examples of cyclic diesters of α-hydroxycarboxylic acid include glycolic acid, lactic acid, α-hydroxybutyric acid, α-hydroxyisobutyric acid, α-hydroxyvaleric acid, α-hydroxyisovaleric acid, α-hydroxy- Examples include intermolecular cyclic diesters such as α-methylbutyric acid, α-hydroxycaproic acid, α-hydroxyisocaproic acid, α-hydroxy-β-methylvaleric acid, α-hydroxyheptanoic acid, mandelic acid, β-phenyllactic acid and the like. . Moreover, what has asymmetric carbon may be any of L-form, D-form, racemic form, and meso form. In addition, the cyclic diester may be formed by different α-oxyacid molecules. Specifically, it is a cyclic diester between glycolic acid and lactic acid, such as 3-methyl-2,5-diketo-1,4-dioxane. Further, lactones which are intramolecular ring-closing compounds of ω-hydroxycarboxylic acid include β-propiolactone, β-butyrolactone, β-isovalerolactone, β-caprolactone, β-isocaprolactone, β-methyl-β- Intramolecular ring-closing compounds such as valerolactone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, δ-caprolactone, 11-oxydecanoic acid lactone, p-dioxanone and 1,5-dioxeban-2-one It is not limited to these.

  The number average molecular weight of the polyester obtained by polymerization can be obtained with various number average molecular weights by changing the conditions such as the type and amount of the polymerization catalyst, the polymerization temperature, and the polymerization time. 000 is preferred.

  The polyhydroxyalkanoate represented by the chemical formula (10) is produced by polymerizing an intramolecular cyclized compound of ω-hydroxycarboxylic acid represented by the chemical formula (9) in the presence of a catalyst.

(In formula, R9 represents a C1-C12 linear or branched alkyl group and aralkyl group.
In addition, for l, m, and n in the formula,
when l is an integer selected from 0 and 2-4, and n is an integer selected from 0 to 4, m is an integer selected from 0 to 8;
when l is 1 and n is an integer selected from 1 to 4, m is an integer selected from 0 to 8;
When l is 1 and n is 0, m is 0. )

(In formula, R10 represents a C1-C12 linear or branched alkyl group and an aralkyl group.
In addition, for l, m, and n in the formula,
when l is an integer selected from 0 and 2-4, and n is an integer selected from 0 to 4, m is an integer selected from 0 to 8;
when l is 1 and n is an integer selected from 1 to 4, m is an integer selected from 0 to 8;
When l is 1 and n is 0, m is 0.
When there are a plurality of units, l, m, n, and R ₁₀ have the above meanings independently for each unit. )

  In the production of a polyhydroxyalkanoate containing a unit represented by the chemical formula (10) using the chemical formula (9) which is an intramolecular ring-closing compound of ω-hydroxycarboxylic acid, the polymerization method is not particularly limited. A polymerization method, a slurry polymerization method, a bulk polymerization method, or the like can be adopted. When a polymerization solvent is used, the solvent is not particularly limited. For example, an inert solvent such as an aliphatic hydrocarbon having 5 to 18 carbon atoms or a cyclic hydrocarbon, or an aromatic hydrocarbon having 6 to 20 carbon atoms, Tetrahydrofuran, chloroform, orthodichlorobenzene, dioxane and the like can be used.

  As the catalyst used for the polymerization, a known ring-opening polymerization catalyst can be used. Examples include tin dichloride, tin tetrachloride, stannous fluoride, stannous acetate, stannous stearate, stannous octoate, stannous oxide, stannic oxide, and other tin salts. . Also, triethoxyaluminum, tri-n-propoxy-aluminum, tri-iso-propoxyaluminum, tri-n-butoxyaluminum, tri-iso-butoxyaluminum, aluminum chloride, di-iso-propylzinc, dimethylzinc, diethyl Zinc, zinc chloride, tetra-n-propoxy titanium, tetra-n-butoxy titanium, tetra-n-butoxy titanium, tetra-t-butoxy titanium, antimony trifluoride, lead oxide, lead stearate, titanium tetrachloride, three Examples thereof include boron fluoride, boron trifluoride ether complex, triethylamine, and tributylamine.

  The usage-amount of these catalysts is the range of 0.0001-10 mass% with respect to the total amount of a monomer compound, More preferably, it is the range of 0.001-5 mass%.

  In the ring-opening polymerization, a known polymerization initiator can be used as a polymerization initiator. Specifically, the aliphatic alcohol may be mono-, di- or polyhydric alcohol, and may be saturated or unsaturated. Specifically, monoalcohols such as methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, nonanol, decanol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, p-tert-butylbenzyl alcohol, ethylene glycol, Dialcohols such as butanediol, hexanediol, nonanediol, and tetramethylene glycol, polyhydric alcohols such as glycerol, sorbitol, xylitol, ribitol, and erythritol, and methyl lactate and ethyl lactate can be used. These aliphatic alcohols are used in a proportion of 0.01 to 10% by mass with respect to the total amount of monomers, although there are some differences depending on the conditions such as the type of alcohol used.

  The ring-opening polymerization reaction temperature is in the range of 25 to 200 ° C, preferably 50 to 200 ° C, more preferably 100 to 180 ° C. The ring-opening polymerization reaction may be carried out under an inert atmosphere such as nitrogen or argon, or under reduced pressure or under pressure. In this case, a catalyst and alcohol may be added successively.

  In order to change various physical properties such as mechanical properties and decomposition properties, the second component may be copolymerized. Specifically, a cyclic diester of α-hydroxycarboxylic acid or a lactone which is an intramolecular ring-closing compound of ω-hydroxycarboxylic acid can be copolymerized. Furthermore, specific examples of cyclic diesters of α-hydroxycarboxylic acid include glycolic acid, lactic acid, α-hydroxybutyric acid, α-hydroxyisobutyric acid, α-hydroxyvaleric acid, α-hydroxyisovaleric acid, α-hydroxy- Examples include intermolecular cyclic diesters such as α-methylbutyric acid, α-hydroxycaproic acid, α-hydroxyisocaproic acid, α-hydroxy-β-methylvaleric acid, α-hydroxyheptanoic acid, mandelic acid, β-phenyllactic acid and the like. . Moreover, what has asymmetric carbon may be any of L-form, D-form, racemic form, and meso form. In addition, the cyclic diester may be formed by different α-oxyacid molecules. Specifically, it is a cyclic diester between glycolic acid and lactic acid, such as 3-methyl-2,5-diketo-1,4-dioxane. Further, lactones which are intramolecular ring-closing compounds of ω-hydroxycarboxylic acid include β-propiolactone, β-butyrolactone, β-isovalerolactone, β-caprolactone, β-isocaprolactone, β-methyl-β- Intramolecular ring-closing compounds such as valerolactone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, ε-caprolactone, 11-oxydecanoic acid lactone, p-dioxanone, 1,5-dioxepan-2-one and the like can be mentioned. It is not limited to these.

  The number average molecular weight of the polyhydroxyalkanoate obtained by polymerization can be obtained with various molecular weights by changing conditions such as the type and amount of the polymerization catalyst, the polymerization temperature, and the polymerization time. 1,000 is preferred.

  The molecular weight of the polyhydroxyalkanoate of the present invention can be measured as a relative molecular weight or an absolute molecular weight. It can be conveniently measured by, for example, gel permeation chromatography (sometimes referred to as GPC). 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 the detector, a differential refraction (RI) detector or an ultraviolet (UV) detector can be used according to the polyhydroxyalkanoate to be measured. The molecular weight is determined as a relative comparison with a standard sample (polystyrene, polymethyl methacrylate, etc.). Examples of the solvent include dimethylformamide (sometimes represented as DMF), dimethyl sulfoxide (sometimes represented as DMSO), chloroform, tetrahydrofuran (sometimes represented as THF), toluene, hexafluoroisopropanol (sometimes represented as HFIP). )) Or the like in which the polymer is soluble. In the case of a polar solvent, it can also be measured by adding a salt.

  Moreover, in this invention, the ratio (Mw / Mn) of the weight average molecular weight (Mw) measured as mentioned above and a number average molecular weight (Mn) is in the range of 1-10, The said polyhydroxyalkanoate Is preferably used.

[Application to toner]
Applications of the polyhydroxyalkanoate according to the present invention include an electrostatic charge image developing toner and an application to an image forming process using the toner. Specifically, it can be used as a charge control agent that is internally or externally added to the toner.

  That is, the charge control agent of the present invention is the above-mentioned polyhydroxyalkanoate, and at least a toner for developing an electrostatic image containing a binder resin, a colorant, and the charge control agent.

  Furthermore, 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 image 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 using the above-described electrostatic charge image developing toner, and an electrostatic latent image by applying a voltage to the charging member from the outside. Means for charging the carrier, means for forming an electrostatic image on the charged electrostatic latent image carrier, and developing the electrostatic image with an electrostatic image developing toner to carry the toner image as an electrostatic latent image The developing means formed on the body and the toner image on the electrostatic latent image carrier are recorded. A transfer unit for transferring the at least having an image forming apparatus and a fixing means for heat-fixing the toner image on the recording material, an image forming apparatus using an electrostatic image developing toner described above.

<Use as charge control agent>
What is important in the structure of the polyhydroxyalkanoate used as the charge control agent of the present invention is that a sulfonic acid group or a derivative thereof, or a carboxyl group is present in the side chain like the monomer unit represented by the chemical formula (1) or (5). Or it has the structure containing the derivative. 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 excellent negative chargeability.

  The polyhydroxyalkanoate used as the charge control agent of the present invention has a good compatibility with the binder resin, and particularly has a very good compatibility with the polyester-based binder resin. The electrostatic charge image developing toner containing the polyhydroxyalkanoate of the present invention has a high charge amount and good stability over time. In image formation, a stable and clear image is given, and colorless or colored is extremely thin and has a good negative charging performance. Therefore, 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 which is the charge control agent 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 that is the charge control agent of the present invention does not contain heavy metals, heavy metals such as those found in metal-containing charge control agents can be used when preparing toners by suspension polymerization or emulsion polymerization. Therefore, the toner can be produced stably.

(Addition of polyhydroxyalkanoate 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. When added internally, the addition amount is usually 0.1 to 50% by mass, preferably 0.2 to 20% by mass, as the mass ratio of the binder resin and the charge control agent. When the amount is more than 0.1% by mass, the degree of improvement in the chargeability of the toner becomes remarkable, which is preferable. On the other hand, if it is 50 mass% or less, it is preferable from an economical viewpoint. In addition, when externally added, the mass ratio of the binder resin and the charge control agent is preferably 0.01 to 5% by mass, and is particularly preferably mechanochemically fixed to the toner surface. Furthermore, the polyhydroxyalkanoate of the charge control agent of the present invention can be used in combination with a known charge control agent.

  When used as a charge control agent, the polyhydroxyalkanoate has a number average molecular weight of usually 1,000 to 1,000,000, preferably 1,000 to 300,000. When the number average molecular weight is 1,000 or more, the charge amount is sufficient to form discontinuous domains that are not completely compatible with the binder resin, and the fluidity of the toner is favorably affected. Further, when the number average molecular weight is 1,000,000 or less, it becomes easy to disperse in the toner.

  The molecular weight of the polyhydroxyalkanoate can be measured by GPC (gel permeation chromatography). As a specific GPC measurement method, the polyhydroxyalkanoate is dissolved in advance in 0.1% by mass LiBr-containing dimethylformamide (DMF), chloroform, etc., and multiple samples are measured with the same mobile phase. The molecular weight distribution was determined from the calibration curve.

  When used as a charge control agent, in the present invention, the ratio (Mw / Mn) between the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured as described above is in the range of 1 to 10. It is preferable to use the above polyhydroxyalkanoates in

  The polyhydroxyalkanoate used as a charge control agent in the present invention has a melting point of 20 to 150 ° C., particularly 40 to 150 ° C., or no melting point but a glass transition of 10 to 150 ° C., particularly 20 to 150 ° C. It is preferable to have a point. When the melting point is 20 ° C. or higher or has no melting point and the glass transition point is 10 ° C. or higher, it preferably affects the fluidity and storage stability of the toner. Further, when the melting point is 150 ° C. or lower or the glass transition point is 150 ° C. or lower without having a melting point, it becomes easy to knead the charge control agent in the toner and the charge amount distribution becomes uniform, which is preferable. 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 electrostatic charge image developing toner of the present invention, the mass ratio of the binder resin to the charge control agent is usually 0.1 to 50 mass%, preferably 0.2 to 20 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 binder resin, and 0 to 15% by mass of the coloring material based on the toner mass. If necessary, magnetic powder (a powder of a ferromagnetic metal 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 lubricant (polytetrafluoroethylene, low molecular weight polyolefin, fatty acid, or metal salt or amide thereof) and other charge control agents (metal-containing azo dye, salicylic acid metal salt, etc.)) 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 binder resin 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 diameter of the domain is preferably 0.01 to 4 μm, more preferably 0.05 to 2 μm. When the thickness is 4 μm or less, the dispersibility is good, the charge amount distribution is uniform, and the transparency of the toner is good. Further, when the dispersed particle diameter is 0.01 μm or more, discontinuous domains are easily formed, and the addition of a small amount of a charge control agent is preferable because the effect is exhibited. 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 domains formed by the polyhydroxyalkanoate of the electrostatic control agent of the present invention, it is compatible with the polyhydroxyalkanoate and compatible with the binder resin. A soluble polymer can also be included as a compatibilizing agent. As a compatibilizing agent, a polymer chain containing 50 mol% or more of a monomer having substantially the same structure as that of the constituent monomer of polyhydroxyalkanoate, and substantially the same as the constituent monomer of the binder resin Examples thereof include a polymer in which a polymer chain containing a monomer having a structure of 50 mol% or more is bonded in a graft or block form. The amount of the compatibilizer used is usually 30% by mass or less, preferably 1 to 10% by mass with respect to the polyhydroxyalkanoate.

<Other components>
Hereinafter, other constituent materials constituting the toner for developing an electrostatic charge image of the present invention will be described. The toner for developing an electrostatic image of the present invention is composed of a binder resin, a colorant, and other additives added as necessary, in addition to the above charge control agent.

(Binder resin)
First, as the binder resin, a general thermoplastic resin can be used as the binder resin. For example, polystyrene, polyacrylate ester, styrene-acrylate ester copolymer, polyvinyl chloride, polyvinyl acetate, polyvinylidene chloride, phenol resin, epoxy resin, polyester resin, etc. can be used. Any material can be used as long as it is used for producing toner, and it 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.

(Specific examples of binder resin)
Examples of styrenic polymers include copolymers of styrene and (meth) acrylic acid esters, 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 the polyolefin-based polymer include polyethylene, polypropylene, and copolymers of these with 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 combination with the charge control agent of the present invention include polymers of the following polymerizable monomers, mixtures thereof, or two types of polymerizable monomers listed below. The copolymerization product obtained by using above 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-methyl styrene, m-methyl styrene, p-methyl styrene, p-methoxy styrene, p-phenyl styrene, p-chloro styrene, 3,4-distyrene. Chlorostyrene, p-ethylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p-tert-butylstyrene, pn-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, styrene and its derivatives such as pn-decylstyrene and pn-dodecylstyrene; ethylenically unsaturated monoolefins such as ethylene, propylene, butylene and isobutylene; unsaturated polyenes such as butadiene; vinyl chloride and vinylidene chloride , Vinyl bromides, vinyl fluorides such as vinyl fluoride; vinyl acetate, propio Vinyl ester acids such as vinyl acid and vinyl benzoate; methyl methacrylate, ethyl methacrylate, propyl methacrylate, methacrylate-n-butyl, isobutyl methacrylate, methacrylate-n-octyl, dodecyl methacrylate, methacrylate-2 -Α-methylene aliphatic monocarboxylic esters such as ethylhexyl, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate; methyl acrylate, ethyl acrylate, n-butyl acrylate, acrylic Acids such as isobutyl acid, propyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate Vinyl esters such as vinyl methyl ether, vinyl ethyl ether and vinyl isobutyl ether; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and methyl isopropenyl ketone; N-vinyl pyrrole, N-vinyl carbazole, N- N-vinyl compounds such as vinylindole and N-vinylpyrrolidone; vinyl naphthalenes; acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile, acrylamide; esters of the aforementioned α, β-unsaturated acids, dibasic acids Diesters: Dicarboxylic acids such as maleic acid, methyl maleate, butyl maleate, dimethyl maleate, phthalic acid, succinic acid, terephthalic acid; ethylene glycol, diethylene glycol, triethylene glycol Polyol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, bisphenol A, hydrogenated bisphenol A, polyoxyethylenated bisphenol A, etc .; p -Isocyanates such as phenylene diisocyanate, p-xylylene diisocyanate, 1,4-tetramethylene diisocyanate; amines such as ethylamine, butylamine, ethylenediamine, 1,4-diaminobenzene, 1,4-diaminobutane, monoethanolamine; Examples thereof include 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 to be used in combination with the charge control agent of 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 diacrylate (MANDA, manufactured by Nippon Kayaku; trade name), and And the like obtained by changing the acrylate to methacrylate.

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

(Polymerization initiator)
Moreover, when forming binder resin used in combination with the charge control agent of this invention, a polymerization initiator as listed below 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) valerate, 2,2-bis (t-butylperoxy) butane, 1,3-bis (T-butylperoxy-isopropyl) benzene, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, di-t-butyldiperoxyisophthalate, 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane Di-t-butylperoxy α-methylsuccinate, di-t-butylperoxydimethylglutarate, di-t-butylperoxyhexahydroterephthalate, di-t-butyl Peroxyazelate, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, diethylene glycol-bis (t-butylperoxycarbonate), di-t-butylperoxytrimethyladipate, tris (t -Butylperoxy) triazine, vinyltris (t-butylperoxy) silane and the like. 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 Co., Ltd .; trade name), “Biopol” (Monsanto Co., Ltd .; trade name), “Aji Coat” (Ajinomoto Co., Ltd .; trade name) ), "Selgrain" (manufactured by Daicel Chemical Industries; product name), "Bionore" (manufactured by Showa Polymer Co., Ltd .; product name), "Ecoplastic" (manufactured by Toyota Motor Corporation; product name), "Lacia" (Mitsui Chemicals) Product name), “Biogreen” (Mitsubishi Gas Chemical Co., Ltd. product name), “NatureWorks” (Cargill Dow; product name), “Biomax” (manufactured by DuPont; product name), etc. .
Among these, polycaprolactone (that is, a polymer of ε-caprolactone) or polylactic acid is completely easily decomposed by lipase, esterase, etc., and physical properties such as blending or copolymerization with other resins. It is particularly preferable in that it is easy to modify the mechanical properties.

  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 0.1% by mass or more, the charge amount is high, and when it is 50% by mass or less, the charging stability of the toner is preferable.

<Other charge control agents>
In addition to the charge control agent of the present invention, a conventionally used charge control agent can be used together with the charge control agent of the present invention. Specific examples include nigrosine dyes, quaternary ammonium salts, monoazo metal complex salt dyes, and the like. The addition amount of the charge control agent can be determined in consideration of the chargeability of the binder resin, the production method including the addition amount / dispersion method of the colorant, and the chargeability of other additives. It is 0.1-20 mass parts with respect to 100 mass parts, Preferably it can be used in the ratio of 0.5-10 mass parts. In addition, inorganic particles such as metal oxides or inorganic materials surface-treated with the organic materials may be used. These charge control agents may be mixed and added to the binder resin, or may be used in a form adhered to the toner particle surface.

<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, all other pigments and / or dyes such as carbon black, titanium white, monoazo red pigment, disazo yellow pigment, quinacridone magenta pigment, anthraquinone dye, and the like can be used.

  More specifically, when the electrostatic image developing toner of the present invention is used as a magnetic color toner, examples of the colorant include C.I. I. Direct Red 1, C.I. I. Direct Red 4, C.I. I. Acid Red 1, C.I. I. Basic Red 1, C.I. I. Modern Tread 30, C.I. I. Direct Blue 1, C.I. I. Direct Blue 2, C.I. I. Acid Blue 9, C.I. I. Acid Blue 15, C.I. I. Basic Blue 3, C.I. I. Basic Blue 5, C.I. I. Modern Blue 7, C.I. I. Direct Green 6, C.I. I. Basic Green 4, C.I. 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 a coloring pigment for magenta toner, C.I. I. 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. I. Pigment violet 19, C.I. I. Bat red 1, 2, 10, 13, 15, 23, 29, 35, etc. are mentioned.

  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 C.I. I. Solvent Red 1, 3, 8, 23, 24, 25, 27, 30, 49, 81, 82, 83, 84, 100, 109, 121, C.I. I. Disper thread 9, C.I. I. Solvent Violet 8, 13, 14, 21, 27, C.I. I. Oil-soluble dyes such as disperse violet 1, C.I. 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. I. Basic dyes such as basic violet 1, 3, 7, 10, 14, 15, 21, 25, 26, 27, and 28 are listed.

  Examples of other color pigments include C.I. I. Pigment blue 2, 3, 15, 16, 17, C.I. I. Bat Blue 6, C.I. I. Acid Blue 45, or a copper phthalocyanine pigment having 1 to 5 phthalimidomethyl groups substituted on the phthalocyanine skeleton.

  Examples of the color pigment for yellow include C.I. I. Pigment yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 16, 17, 23, 65, 73, 83, C.I. I. Bat yellow 1, 3, 20 etc. are mentioned.

  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 consideration of environmental protection and safety to human body, various food colors such as edible lakes can be suitably used. For example, edible red No. 40 aluminum lake, edible red No. 2 aluminum lake, edible Examples include red No. 3 aluminum rake, edible red No. 106 aluminum rake, edible yellow No. 5 aluminum rake, edible yellow No. 4 aluminum rake, edible blue No. 1 aluminum rake, and edible blue No. 2 aluminum rake.

  Moreover, said water-insoluble food coloring matter can function also as a charge control agent. In that case, the above-described aluminum lake can be suitably used for negative charging. As described above, when the water-insoluble food coloring matter has a function of a charge control agent, not only the environmental safety of the toner is improved but also the cost of the toner can be reduced.

  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 the binder resin. 0.1 to 60 parts by mass, preferably about 0.5 to 20 parts by mass.

<Other components of toner>
In the toner for developing an electrostatic image of the present invention, in addition to the binder resin and the colorant component described above, the following compounds may be contained as long as the effects of the present invention are not adversely affected. 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 toner for developing an electrostatic charge image of the present invention contains a wax component as described above, and when the tomographic observation of the toner is performed using a transmission electron microscope (sometimes referred to as TEM). When the wax component 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 electrostatic image developing toner 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. That is, specifically, a resin such as a binder resin, other charge control agents added as necessary, and wax are sufficiently mixed by a mixer such as a Henschel mixer or a ball mill, and then heated rolls, kneaders, Addition of pigment, dye, or magnetic substance as a colorant, and metal compounds added as necessary, while melt-kneading using a heat kneader such as an extruder to make the resins compatible with each other After dispersing or dissolving the agent, 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. it can. In the classification step, it is preferable to use a multi-division classifier in terms of production efficiency.

  In addition, binder resins and charge control agents, etc. are mixed in solvents using aromatic solvents 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. Then, after the stirring treatment, it is poured into water for re-precipitation, filtered, dried, ground the solidified product by a pulverizer such as a jet mill, a ball mill, etc., and then classified to obtain the electrostatic charge of the present invention having a desired particle size. An image developing toner 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, a polymerizable monomer of the binder resin, a charge control agent, a pigment, a dye, or a magnetic material as a colorant, and if necessary, a crosslinking agent, a polymerization initiator, a wax, and other binders Polymeric colored resin particles are synthesized by mixing and dispersing materials such as resin and other additives, and suspension polymerization in an aqueous dispersion medium in the presence of a surfactant and the like, and solid-liquid separation of the resulting particles Then, it is dried and classified 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, a fine powder 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 gives good results. In this case, the amount of the silica fine powder is preferably 0.01 to 8 parts by mass, preferably about 0.1 to 5 parts by mass with respect to 100 parts by mass of the 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 (registered trademark) 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 metals such as surface-oxidized or unoxidized 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 with respect to 100 parts by mass of the binder resin, and 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 particle size distribution of the toner is an interface (Nikka machine) that outputs a number distribution and a volume distribution using a Coulter Counter TA-II type or Coulter Multisizer (manufactured by Beckman Coulter, Inc .; trade name). Bios) and a personal computer were connected for measurement. A 1% NaCl aqueous solution is prepared using first-grade sodium chloride as an electrolytic solution used at that time. As the electrolytic solution, for example, commercially available ISOTONR-II (manufactured by Coulter Scientific Japan; trade name) can also be used. As a specific measurement method, 0.1 to 5 ml of a surfactant (preferably, alkylbenzene sulfonate is used) is added as a dispersant to 100 to 150 ml of the above electrolytic aqueous solution, and further, a measurement sample is added to 2 to 2 ml. Add 20 mg to make a sample for measurement. 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 a 100 μm aperture is used as an aperture by the Coulter counter TA-II type. 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 in 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, EFV200 / 300 (Powder Tech Co., Ltd .; trade name) was used as a carrier under a constant environment, and a mixture obtained by adding 0.5 g of the toner to be measured to 9.5 g of the carrier had a capacity of 50 to 100 ml. Place it in a polyethylene bottle and place it on a shaker with constant amplitude. Set the shaking conditions to 100 mm amplitude and 100 rounds per minute, and shake for a certain time. Next, 1.0 to 1.2 g of the mixture is put into a metal measuring container 42 having a 500 mesh screen 43 at the bottom of the charge amount measuring apparatus shown in FIG. The mass of the entire measurement 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 machine (not shown) (at least a portion in contact with the measurement container 22), and the air volume 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 set to 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)

<Method for measuring molecular weight and molecular weight distribution of binder resin>
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 of 3,000 to 15, particularly in the molecular weight distribution by GPC, when produced by a pulverization method. It is preferable to be in the range of 000. That is, when the GPC peak in the low molecular weight region is 15,000 or less, it becomes easy to obtain a product with sufficient improvement in transfer efficiency. Further, it is preferable that the GPC peak in the low molecular weight region is 3000 or more because fusion hardly occurs during the surface treatment.
In the present invention, the molecular weight of the binder resin can be measured by GPC (gel permeation chromatography). As a specific GPC measurement method, a sample obtained by previously extracting toner with a THF (tetrahydrofuran) solvent using a Soxhlet extractor for 20 hours was used for measurement, and the column configuration was manufactured by Showa Denko A −801, 802, 803, 804, 805, 806, 807 (trade names) can be connected, and the molecular weight distribution can be measured using a standard polystyrene resin calibration curve. Moreover, in this invention, the ratio (Mw / Mn) of the weight average molecular weight (Mw) and number average molecular weight (Mn) measured as mentioned above uses the binder resin in the range of 2-100. It is preferable.

<Glass transition point of toner>
In addition, 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 can be measured by using a differential scanning calorimeter of high accuracy internal heat input compensation type such as DSC-7 (trade name) manufactured by PerkinElmer. Good. The measurement is performed according to ASTM D 3418-82. In the present invention, when the glass transition point Tg is measured, 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 and Apparatus>
The electrostatic charge developing toner of the present invention having the configuration described above includes a charging step in which a voltage is applied to the charging member from the outside to charge the electrostatic latent image carrier, and the charged electrostatic latent image carrier. Forming an electrostatic image on the surface, developing the electrostatic image with an electrostatic image developing toner to form a toner image on the electrostatic latent image carrier, and toner on the electrostatic latent image carrier An image forming method having at least a transfer step for transferring an image to a recording material and a heat fixing step for heating and fixing a toner image on the recording material, and an electrostatic latent image carrier by applying a voltage to a charging member from the outside A means for charging the electrostatic latent image carrier, a means for forming an electrostatic image on the charged electrostatic latent image carrier, and developing the electrostatic image with an electrostatic image developing toner to form a toner image on the electrostatic latent image carrier. Development means formed on the toner and the toner image on the electrostatic latent image carrier to a recording material. An image forming apparatus having at least a transfer unit for fixing and a fixing unit for heating and fixing a toner image on a recording material, or a transfer step transfers the toner image on the electrostatic latent image carrier to an intermediate transfer member. An image forming method comprising a first transfer step and a second transfer step for transferring a toner image on the intermediate transfer member onto a recording material, and a transfer means comprising: a toner image on an electrostatic latent image carrier; It is particularly preferable to apply to an apparatus having first transfer means for transferring the toner image to an intermediate transfer member and second transfer means for transferring a toner image on the intermediate transfer member to a recording material.

  The reaction solvent, reaction temperature, reaction time, purification method, etc. in the chemical reaction of the polyhydroxyalkanoate of the present invention are not limited to the above methods. Further, the toner preparation method is not limited to the above method.

The present invention will be described in more detail with reference to the following examples. However, the method of the present invention is not limited to these examples.
First, a polyhydroxyalkanoate used in the present invention was prepared.

(Preparation Example A-1)
[Polyester synthesis using 3,6-di (3-butenyl) -1,4-dioxane-2,5-dione and L-lactide]
3,6-di (3-butenyl) -1,4-dioxane-2,5-dione 0.11 g (0.5 mmol), L-lactide 0.65 g (4.5 mmol), 0.01 M tin octylate 2 ml of a toluene solution of (2-ethylhexanoate) and 2 ml of a 0.01 M p-tert-butylbenzyl alcohol toluene solution were charged into a polymerization ampule, dried under reduced pressure for 1 hour and purged with nitrogen. And heated to 150 ° C. to perform ring-opening polymerization. The reaction was terminated after 1 hour and cooled. The obtained polymer was dissolved in chloroform and reprecipitated in 10 times the amount of chloroform required for dissolution. The precipitate was collected and dried under reduced pressure to obtain 0.63 g of polymer.
In order to specify the structure of the obtained polymer, 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 used: TMS / CDCl ₃
Measurement temperature: room temperature As a result, it was confirmed that the monomer unit was a polyhydroxyalkanoate copolymer containing a unit represented by the following chemical formula (24). Moreover, it was confirmed that the ratio of the monomer unit is 9 mol% of A unit and 91 mol% of B unit.

  The average molecular weight of the obtained polyhydroxyalkanoate was determined by gel permeation chromatography (GPC; Tosoh HLC-8220; trade name, column; Tosoh TSK-GEL Super HM-H; trade name, solvent; chloroform, It was evaluated by polystyrene conversion. As a result, the number average molecular weight was Mn = 18200, and the weight average molecular weight was Mw = 24000.

(Preparation Example A-2)
Oxidation reaction of polyhydroxyalkanoate composed of unit represented by chemical formula (24) synthesized in Preparation Example A-1

0.50 g of a polyhydroxyalkanoate copolymer (A: 9 mol%, B: 91 mol%) comprising the unit represented by the chemical formula (24) obtained in Preparation Example A-1 was added to an eggplant flask, and 30 ml of acetone was added. In addition, it was dissolved. This was placed in an ice bath, 5 ml of acetic acid and 0.47 g of 18-crown-6-ether were added and stirred. Next, 0.38 g 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, 60 ml of ethyl acetate was added and 45 ml of water was further added. Sodium bisulfite was then added until the peracid was removed. Thereafter, the liquid property was adjusted to pH = 1 with 1.0 N hydrochloric acid. The organic layer was extracted and washed 3 times with 1.0N hydrochloric acid. After recovering the organic layer, the solvent was distilled off to recover the crude polymer. Next, it was washed with 50 ml of water and 50 ml of methanol, and further washed with 50 ml of water three times, and then the polymer was recovered. Next, it was dissolved in 3 ml of THF, and reprecipitated in 50 times the amount of THF required for dissolution. The precipitate was collected and dried under reduced pressure to obtain 0.44 g of polymer.
As a result of conducting NMR analysis under the same conditions as in Preparation Example A-1 to identify the structure of the obtained polymer, it is a polyhydroxyalkanoate containing a unit represented by the following chemical formula (25) as a monomer unit. Was confirmed.

Moreover, the average molecular weight of the obtained polyhydroxyalkanoate was evaluated by the same method as in Preparation Example A-1. As a result, the number average molecular weight Mn was 13200, and the weight average molecular weight Mw was 18200.
Furthermore, in order to calculate the unit of the obtained polyhydroxyalkanoate, it calculated by methyl-esterifying the carboxyl group in the side chain terminal of polyhydroxyalkanoate using trimethylsilyldiazomethane.
30 mg of the target polyhydroxyalkanoate 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 0.5 ml of a 2 mol / L trimethylsilyldiazomethane-hexane solution, and the mixture was stirred at room temperature for 1 hour. After completion of the reaction, the solvent was distilled off and the polymer was recovered. The polymer was recovered after washing with 50 ml of methanol. 31 mg of polyhydroxyalkanoate was obtained by drying under reduced pressure.
NMR analysis was performed using the same method as in Preparation Example A-1. As a result, it was confirmed that the unit of the polyhydroxyalkanoate represented by the chemical formula (25) was a copolymer of 8 mol% for the C unit and 92 mol% for the D unit.

(Preparation Example A-3)
Condensation reaction of polyhydroxyalkanoate composed of the unit represented by chemical formula (25) synthesized in Preparation Example A-2 and 2-aminobenzenesulfonic acid

0.40 g of polyhydroxyalkanoate copolymer (C: 8 mol%, D: 92 mol%) composed of the unit represented by chemical formula (25) obtained in Preparation Example A-2 under a nitrogen atmosphere, 2-aminobenzenesulfone 0.36 g of acid was placed in a 100 ml three-necked flask, 15.0 ml of pyridine was added and stirred, and then 1.09 ml of triphenyl phosphite was added and heated at 120 ° C. for 6 hours. After completion of the reaction, it was recovered by reprecipitation in 150 ml of ethanol. The obtained polymer was washed with 1N hydrochloric acid for 1 day, then washed by stirring in water for 1 day, and dried under reduced pressure to obtain 0.32 g of polymer.
The structure of the obtained polymer was determined by ¹ H-NMR (FT-NMR: Bruker DPX400; resonance frequency: 400 MHz; measurement nuclide: ¹ H; solvent used: heavy DMSO; measurement temperature: room temperature), Fourier transform-infrared absorption Analysis was performed by (FT-IR) spectrum (Nicolet AVATAR 360FT-IR). As a result of IR measurement, the peak at 1695 cm ⁻¹ derived from the carboxylic acid decreased, and a new peak derived from the amide group was observed at 1658 cm ⁻¹ .
^From the result of ¹ H-NMR, since the peak derived from the aromatic ring having a 2-aminobenzenesulfonic acid structure is shifted, the obtained polymer has a unit represented by the following chemical formula (26) as a monomer unit. It was confirmed to be a polyhydroxyalkanoate containing.

Further, it was confirmed that the unit of the polyhydroxyalkanoate represented by the chemical formula (26) was a copolymer of 8 mol% for the E unit and 92 mol% for the F unit.
The average molecular weight of the obtained polymer was determined by gel permeation chromatography (GPC: HLC-8120; trade name, column; Polymer Laboratories PLgel 5μ MIXED-C, solvent; DMF / LiBr 0.1% (w / v) , Polystyrene conversion). As a result, the number average molecular weight M _n = 11300 and the weight average molecular weight M _w = 16000.

(Preparation Example A-4)
Esterification reaction of polyhydroxyalkanoate comprising unit represented by chemical formula (26) synthesized in Preparation Example A-3

To the eggplant flask, 0.30 g of a polyhydroxyalkanoate copolymer (E: 8 mol%, F: 92 mol%) composed of the unit represented by the chemical formula (26) obtained in Preparation Example A-3 was added. It melt | dissolved by adding 0 ml and methanol 7.0 ml, and cooled to 0 degreeC. To this, 1.35 ml of a 2 mol / L trimethylsilyldiazomethane-hexane solution (manufactured by Aldrich) was added and stirred for 4 hours. After completion of the reaction, the solvent was removed by an evaporator, and then the polymer was recovered.
Further, 21.0 ml of chloroform and 7.0 ml of methanol were added to redissolve the polymer, and the solvent was distilled off by an evaporator. This operation was repeated three times.
The polymer collected here was dried under reduced pressure to obtain 0.30 g of polymer.
The structure of the obtained polymer was determined by ¹ H-NMR (FT-NMR: Bruker DPX400; resonance frequency: 400 MHz; measurement nuclide: ¹ H; solvent used: heavy DMSO; measurement temperature: room temperature). ^From the result of ¹ H-NMR, since a peak derived from methyl sulfonate is observed at 3 to 4 ppm, the obtained polymer is a polyhydroxyalkanoate containing a unit represented by the following chemical formula (27) as a monomer unit. It was confirmed that.

Further, it was confirmed that the unit of the polyhydroxyalkanoate represented by the chemical formula (27) was a copolymer of 8 mol% for the G unit and 92 mol% for the H unit.
In addition, since no peak derived from sulfonic acid was observed by acid value titration using potentiometric titrator AT510 (manufactured by Kyoto Electronics; trade name), it is clear that sulfonic acid is methyl sulfonate. Became.
The average molecular weight of the obtained polymer was evaluated by the same method as in Preparation Example A-3. As a result, the number average molecular weight M _n = 10900 and the weight average molecular weight M _w = 15600. A series of preparation methods were scaled up, and a large amount of polyhydroxyalkanoate represented by the chemical formula (27) was obtained to give Exemplified Compound A.

(Preparation Example B-1)
[Polyester synthesis using 3,6-di (6-heptenyl) -1,4-dioxane-2,5-dione and L-lactide]
3,6-di (6-heptenyl) -1,4-dioxane-2,5-dione 0.15 g (0.5 mmol), L-lactide 0.65 g (4.5 mmol), 0.01 M tin octylate 2 ml of a toluene solution of (tin 2-ethylhexanoate) and 2 ml of a 0.01 M p-tert-butylbenzyl alcohol toluene solution were charged into a polymerization ampule, and then the polymer was prepared in the same manner as in Preparation Example A-1. 0.64 g was obtained.
As a result of conducting NMR analysis under the same conditions as in Preparation Example A-1 to identify the structure of the obtained polymer, a polyhydroxyalkanoate copolymer containing a unit represented by the following chemical formula (28) as a monomer unit It was confirmed that. Moreover, it was confirmed that the ratio of the monomer unit is A unit 7 mol% and B unit 93 mol%.

  Moreover, the average molecular weight of the obtained polyhydroxyalkanoate was evaluated by the same method as in Preparation Example A-1. As a result, the number average molecular weight was Mn = 15700, and the weight average molecular weight was Mw = 21800.

(Preparation Example B-2)
Oxidation reaction of polyhydroxyalkanoate composed of unit represented by chemical formula (28) synthesized in Preparation Example B-1

0.50 g of a polyhydroxyalkanoate copolymer (A: 7 mol%, B: 93 mol%) consisting of the unit represented by the chemical formula (28) obtained in Preparation Example B-1 was added to an eggplant flask, and 30 ml of acetone was added. In addition, it was dissolved. This was placed in an ice bath, 5 ml of acetic acid and 0.35 g of 18-crown-6-ether were added and stirred. Next, 0.28 g of potassium permanganate was slowly added in an ice bath, stirred for 2 hours in an ice bath, and further stirred at room temperature for 18 hours. After completion of the reaction, 0.42 g of polymer was obtained by the same method as in Preparation Example A-2.
As a result of conducting NMR analysis under the same conditions as in Preparation Example A-1 to identify the structure of the obtained polymer, it is a polyhydroxyalkanoate containing a unit represented by the following chemical formula (29) as a monomer unit. Was confirmed.

Moreover, the average molecular weight of the obtained polyhydroxyalkanoate was evaluated by the same method as in Preparation Example A-1. As a result, the number average molecular weight was Mn = 11400, and the weight average molecular weight was Mw = 16300.
Furthermore, in order to calculate the unit of the obtained polyhydroxyalkanoate, 30 mg of the polyhydroxyalkanoate obtained by the same method as in Preparation Example A-2 was subjected to NMR analysis using the same method as in Preparation Example A-1. went. As a result, it was confirmed that the unit of the polyhydroxyalkanoate represented by the chemical formula (29) was a copolymer in which the C unit was 7 mol% and the D unit was 93 mol%.

(Preparation Example B-3)
Condensation reaction of polyhydroxyalkanoate composed of the unit represented by chemical formula (29) synthesized in Preparation Example B-2 and 2-aminobenzenesulfonic acid

0.40 g of polyhydroxyalkanoate copolymer (C: 7 mol%, D: 93 mol%) composed of the unit represented by chemical formula (29) obtained in Preparation Example B-2 under a nitrogen atmosphere, 2-aminobenzenesulfone 0.31 g of acid was placed in a 100 ml three-necked flask, 15.0 ml of pyridine was added and stirred, 0.92 ml of triphenyl phosphite was added, and the mixture was heated at 120 ° C. for 6 hours. After completion of the reaction, 0.33 g of polymer was obtained in the same manner as in Preparation Example A-3.
The structure of the obtained polymer was analyzed by the same method as in Preparation Example A-3. As a result of IR measurement, the peak at 1695 cm ⁻¹ derived from the carboxylic acid decreased, and a new peak derived from the amide group was observed at 1658 cm ⁻¹ .
^From the result of ¹ H-NMR, since the peak derived from the aromatic ring of 2-aminobenzenesulfonic acid structure is shifted, the obtained polymer has a unit represented by the following chemical formula (30) as a monomer unit. It was confirmed to be a polyhydroxyalkanoate containing.

Further, it was confirmed that the unit of polyhydroxyalkanoate represented by the chemical formula (30) was a copolymer of 7 mol% for E unit and 93 mol% for F unit.
The average molecular weight of the obtained polymer was evaluated by the same method as in Preparation Example A-3. As a result, the number average molecular weight M _n = 9900 and the weight average molecular weight M _w = 14400. A series of preparation methods were scaled up to obtain a large amount of the polyhydroxyalkanoate represented by the chemical formula (30) to give Exemplified Compound B.

(Preparation Example C-1)
[Polyester synthesis using 3,6-di (2-propenyl) -1,4-dioxane-2,5-dione and L-lactide]
3,6-di (2-propenyl) -1,4-dioxane-2,5-dione 0.98 g (5.0 mmol), L-lactide 6.49 g (45.0 mmol), 0.01 M tin octylate 20 ml of toluene solution of (tin 2-ethylhexanoate) and 20 ml of 0.01 M toluene solution of p-tert-butylbenzyl alcohol were charged into a polymerization ampule, and then the polymer was prepared in the same manner as in Preparation Example A-1. 6.55 g was obtained.
As a result of conducting NMR analysis under the same conditions as in Preparation Example A-1 to specify the structure of the obtained polymer, a polyhydroxyalkanoate copolymer containing a unit represented by the following chemical formula (31) as a monomer unit It was confirmed that. Moreover, it was confirmed that the ratio of the monomer unit is 9 mol% of A unit and 91 mol% of B unit.

  Moreover, the average molecular weight of the obtained polyhydroxyalkanoate was evaluated by the same method as in Preparation Example A-1. As a result, the number average molecular weight was Mn = 17400, and the weight average molecular weight was Mw = 23300.

(Preparation Example C-2)
Oxidation reaction of polyhydroxyalkanoate comprising unit represented by chemical formula (31) synthesized in Preparation Example C-1

To the eggplant flask, 6.00 g of a polyhydroxyalkanoate copolymer (A: 9 mol%, B: 91 mol%) composed of the unit represented by the chemical formula (31) obtained in Preparation Example C-1 was added, and 360 ml of acetone was added. In addition, it was dissolved. This was placed in an ice bath, 60 ml of acetic acid and 5.75 g of 18-crown-6-ether were added and stirred. Next, 4.59 g 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, 5.30 g of polymer was obtained by the same method as in Preparation Example A-2.
As a result of conducting NMR analysis under the same conditions as in Preparation Example A-1 to identify the structure of the obtained polymer, it is a polyhydroxyalkanoate containing a unit represented by the following chemical formula (32) as a monomer unit. Was confirmed.

Moreover, the average molecular weight of the obtained polyhydroxyalkanoate was evaluated by the same method as in Preparation Example A-1. As a result, the number average molecular weight Mn was 13200, and the weight average molecular weight Mw was 18300.
Further, in order to calculate the unit of the obtained polyhydroxyalkanoate, 28 mg of the polyhydroxyalkanoate obtained by the same method as in Preparation Example A-2 was subjected to NMR analysis using the same method as in Preparation Example A-1. went. As a result, it was confirmed that the unit of the polyhydroxyalkanoate represented by the chemical formula (32) was a copolymer of 8 mol% for the C unit and 92 mol% for the D unit.

(Preparation Example C-3)
Condensation reaction of polyhydroxyalkanoate comprising unit represented by chemical formula (32) synthesized in Preparation Example C-2 and p-toluidine-2-sulfonic acid

Under a nitrogen atmosphere, 0.40 g of a polyhydroxyalkanoate copolymer (C: 8 mol%, D: 92 mol%) comprising the unit represented by the chemical formula (32) obtained in Preparation Example C-2, p-toluidine-2 -0.39 g of sulfonic acid was put in a 100 ml three-necked flask, 15.0 ml of pyridine was added and stirred, and then 1.10 ml of triphenyl phosphite was added, followed by heating at 120 ° C for 6 hours. After completion of the reaction, 0.33 g of polymer was obtained in the same manner as in Preparation Example A-3.
The structure of the obtained polymer was analyzed by the same method as in Preparation Example A-3. As a result of IR measurement, the peak at 1695 cm ⁻¹ derived from the carboxylic acid decreased, and a new peak derived from the amide group was observed at 1658 cm ⁻¹ .
^From the result of ¹ H-NMR, since the peak derived from the aromatic ring having a p-toluidine-2-sulfonic acid structure is shifted, the obtained polymer is represented by the following chemical formula (33) as a monomer unit. It was confirmed to be a polyhydroxyalkanoate containing unit.

Further, it was confirmed that the units of the polyhydroxyalkanoate represented by the chemical formula (33) were 8 mol% of the E unit and 92 mol% of the F unit.
The average molecular weight of the obtained polymer was evaluated by the same method as in Preparation Example A-3. As a result, the number average molecular weight M _n = 11000 and the weight average molecular weight M _w = 15700.

(Preparation Example C-4)
Condensation reaction of polyhydroxyalkanoate comprising unit represented by chemical formula (32) synthesized in Preparation Example C-2 and 4-aminobenzenesulfonic acid

0.40 g of polyhydroxyalkanoate copolymer (C: 8 mol%, D: 92 mol%) composed of the unit represented by the chemical formula (32) obtained in Preparation Example C-2 under a nitrogen atmosphere, 4-aminobenzenesulfone 0.37 g of acid was placed in a 100 ml three-necked flask, and 15.0 ml of pyridine was added and stirred. Then, 1.10 ml of triphenyl phosphite was added and heated at 120 ° C. for 6 hours. After completion of the reaction, 0.31 g of polymer was obtained by the same method as in Preparation Example A-3.
The structure of the obtained polymer was analyzed by the same method as in Preparation Example A-3. As a result of IR measurement, the peak at 1695 cm ⁻¹ derived from the carboxylic acid decreased, and a new peak derived from the amide group was observed at 1658 cm ⁻¹ .
^From the result of ¹ H-NMR, since the peak derived from the aromatic ring having a 4-aminobenzenesulfonic acid structure is shifted, the obtained polymer has a unit represented by the following chemical formula (34) as a monomer unit. It was confirmed to be a polyhydroxyalkanoate containing.

In addition, it was confirmed that the units of the polyhydroxyalkanoate represented by the chemical formula (34) were 8 mol% of the E unit and 92 mol% of the F unit.
The average molecular weight of the obtained polymer was evaluated by the same method as in Preparation Example A-3. As a result, the number average molecular weight M _n = 10700 and the weight average molecular weight M _w = 15700. A series of preparation methods were scaled up, and a large amount of polyhydroxyalkanoate represented by the chemical formula (34) was obtained to give Exemplified Compound C-4.

(Preparation Example C-5)
Condensation reaction of polyhydroxyalkanoate comprising unit represented by chemical formula (32) synthesized in Preparation Example C-2 and 4-aminobenzenesulfonic acid phenyl ester

0.40 g of polyhydroxyalkanoate copolymer (C: 8 mol%, D: 92 mol%) composed of the unit represented by the chemical formula (32) obtained in Preparation Example C-2 under a nitrogen atmosphere, 4-aminobenzenesulfone 0.53 g of acid phenyl ester was placed in a 100 ml three-necked flask, 15.0 ml of pyridine was added and stirred, and then 1.10 ml of triphenyl phosphite was added and heated at 120 ° C. for 6 hours. After completion of the reaction, 0.35 g of polymer was obtained by the same method as in Preparation Example A-3.
The structure of the obtained polymer was analyzed by the same method as in Preparation Example A-3. As a result of IR measurement, the peak at 1695 cm ⁻¹ derived from the carboxylic acid decreased, and a new peak derived from the amide group was observed at 1658 cm ⁻¹ .
^From the result of ¹ H-NMR, since the peak derived from the aromatic ring of the 4-aminobenzenesulfonic acid phenyl ester structure is shifted, the obtained polymer is represented by the following chemical formula (35) as a monomer unit. It was confirmed to be a polyhydroxyalkanoate containing unit.

Further, it was confirmed that the unit of the polyhydroxyalkanoate represented by the chemical formula (35) was a copolymer of 8 mol% for the E unit and 92 mol% for the F unit.
The average molecular weight of the obtained polymer was evaluated by the same method as in Preparation Example A-3. As a result, the number average molecular weight M _n = 11500 and the weight average molecular weight M _w = 17100. A series of preparation methods were scaled up, and a large amount of polyhydroxyalkanoate represented by the chemical formula (35) was obtained to give Exemplified Compound C-5.

(Preparation Example C-6)
Condensation reaction of polyhydroxyalkanoate comprising unit represented by chemical formula (32) synthesized in Preparation Example C-2 and 2-amino-1-naphthalenesulfonic acid

Under a nitrogen atmosphere, 0.40 g of a polyhydroxyalkanoate copolymer (C: 8 mol%, D: 92 mol%) composed of the unit represented by the chemical formula (32) obtained in Preparation Example C-2, 2-amino-1 -Naphtalenesulfonic acid 0.47g was put into a 100 ml three necked flask, 15.0 ml of pyridine was added and stirred, then 1.10 ml of triphenyl phosphite was added, and the mixture was heated at 120 ° C for 6 hours. After completion of the reaction, 0.37 g of polymer was obtained in the same manner as in Preparation Example A-3.
The structure of the obtained polymer was analyzed by the same method as in Preparation Example A-3. As a result of IR measurement, the peak at 1695 cm ⁻¹ derived from the carboxylic acid decreased, and a new peak derived from the amide group was observed at 1658 cm ⁻¹ .
^From the result of ¹ H-NMR, since the peak derived from the aromatic ring having the 2-amino-1-naphthalenesulfonic acid structure is shifted, the obtained polymer is represented by the following chemical formula (36) as a monomer unit. It was confirmed that this was a polyhydroxyalkanoate containing unit.

Further, it was confirmed that the unit of the polyhydroxyalkanoate represented by the chemical formula (36) was a copolymer of 8 mol% for the E unit and 92 mol% for the F unit.
The average molecular weight of the obtained polymer was evaluated by the same method as in Preparation Example A-3. As a result, the number average molecular weight M _n = 11000 and the weight average molecular weight M _w = 16600.

(Preparation Example C-7)
Condensation reaction of polyhydroxyalkanoate composed of the unit represented by chemical formula (32) synthesized in Preparation Example C-2 and 2-amino-2-methylpropanesulfonic acid

Under a nitrogen atmosphere, 0.40 g of a polyhydroxyalkanoate copolymer (C: 8 mol%, D: 92 mol%) comprising the unit represented by the chemical formula (32) obtained in Preparation Example C-2, 2-amino-2 -0.32 g of methylpropanesulfonic acid was placed in a 100 ml three-necked flask, 15.0 ml of pyridine was added and stirred, and then 1.10 ml of triphenyl phosphite was added and heated at 120 ° C for 6 hours. After completion of the reaction, 0.33 g of polymer was obtained in the same manner as in Preparation Example A-3.
The structure of the obtained polymer was analyzed by the same method as in Preparation Example A-3. As a result of IR measurement, the peak at 1695 cm ⁻¹ derived from carboxylic acid decreased, and a new peak derived from the amide group was observed at 1668 cm ⁻¹ .
^From the result of ¹ H-NMR, since the peak derived from methylene having a 2-amino-2-methylpropanesulfonic acid structure is shifted, the obtained polymer is represented by the following chemical formula (37) as a monomer unit. It was confirmed that this was a polyhydroxyalkanoate containing unit.

Further, it was confirmed that the unit of the polyhydroxyalkanoate represented by the chemical formula (37) was a copolymer of 8 mol% for the E unit and 92 mol% for the F unit.
The average molecular weight of the obtained polymer was evaluated by the same method as in Preparation Example A-3. As a result, the number average molecular weight M _n = 10300 and the weight average molecular weight M _w = 14700.

(Preparation Example C-8)
Esterification reaction of polyhydroxyalkanoate composed of unit represented by chemical formula (33) synthesized in Preparation Example C-3

To the eggplant flask, 0.30 g of a polyhydroxyalkanoate copolymer (E: 8 mol%, F: 92 mol%) composed of the unit represented by the chemical formula (33) obtained in Preparation Example C-3 was added. It melt | dissolved by adding 0 ml and methanol 7.0 ml, and cooled to 0 degreeC. To this, 1.35 ml of a 2 mol / L trimethylsilyldiazomethane-hexane solution (manufactured by Aldrich) was added and stirred for 4 hours. After completion of the reaction, 0.30 g of polymer was obtained in the same manner as in Preparation Example A-4.
The structure of the obtained polymer was determined by the same method as in Preparation Example A-4. ^From the result of ¹ H-NMR, since a peak derived from methyl sulfonate is observed at 3 to 4 ppm, the obtained polymer is a polyhydroxyalkanoate containing a unit represented by the following chemical formula (38) as a monomer unit. It was confirmed that.

Further, it was confirmed that the unit of the polyhydroxyalkanoate represented by the chemical formula (38) was a copolymer of 8 mol% for the G unit and 92 mol% for the H unit.
In addition, since no peak derived from sulfonic acid was observed by acid value titration using potentiometric titrator AT510 (manufactured by Kyoto Electronics; trade name), it is clear that sulfonic acid is methyl sulfonate. Became.
The average molecular weight of the obtained polymer was evaluated by the same method as in Preparation Example A-3. As a result, the number average molecular weight M _n = 10500 and the weight average molecular weight M _w = 15500. A series of preparation methods were scaled up, and a large amount of polyhydroxyalkanoate represented by the chemical formula (38) was obtained to give Exemplified Compound C-8.

(Preparation Example C-9)
Esterification reaction of polyhydroxyalkanoate comprising unit represented by chemical formula (36) synthesized in Preparation Example C-6

To the eggplant flask, 0.30 g of a polyhydroxyalkanoate copolymer (E: 8 mol%, F: 92 mol%) composed of the unit represented by the chemical formula (36) obtained in Preparation Example C-6 was added. It melt | dissolved by adding 0 ml and methanol 7.0 ml, and cooled to 0 degreeC. To this, 1.30 ml of a 2 mol / L trimethylsilyldiazomethane-hexane solution (manufactured by Aldrich) was added and stirred for 4 hours. After completion of the reaction, 0.30 g of polymer was obtained in the same manner as in Preparation Example A-4.
The structure of the obtained polymer was determined by the same method as in Preparation Example A-4. ^From the result of ¹ H-NMR, since a peak derived from methyl sulfonate is seen at 3 to 4 ppm, the obtained polymer is a polyhydroxyalkanoate containing a unit represented by the following chemical formula (39) as a monomer unit. It was confirmed that.

Further, it was confirmed that the unit of the polyhydroxyalkanoate represented by the chemical formula (39) was a copolymer of 8 mol% for the G unit and 92 mol% for the H unit.
In addition, since no peak derived from sulfonic acid was observed by acid value titration using potentiometric titrator AT510 (manufactured by Kyoto Electronics; trade name), it is clear that sulfonic acid is methyl sulfonate. Became.
The average molecular weight of the obtained polymer was evaluated by the same method as in Preparation Example A-3. As a result, the number average molecular weight M _n = 10900 and the weight average molecular weight M _w = 17200. A series of preparation methods were scaled up, and a large amount of polyhydroxyalkanoate represented by the chemical formula (39) was obtained to give Exemplified Compound C-9.

(Preparation Example C-10)
Esterification reaction of polyhydroxyalkanoate composed of unit represented by chemical formula (37) synthesized in Preparation Example C-7

To the eggplant flask, 0.30 g of a polyhydroxyalkanoate copolymer (E: 8 mol%, F: 92 mol%) composed of the unit represented by the chemical formula (37) obtained in Preparation Example C-7 was added. It melt | dissolved by adding 0 ml and methanol 7.0 ml, and cooled to 0 degreeC. To this, 1.39 ml of a 2 mol / L trimethylsilyldiazomethane-hexane solution (Aldrich) was added and stirred for 4 hours. After completion of the reaction, 0.31 g of polymer was obtained by the same method as in Preparation Example A-4.
The structure of the obtained polymer was determined by the same method as in Preparation Example A-4. ^From the result of ¹ H-NMR, since a peak derived from methyl sulfonate is observed at 3 to 4 ppm, the obtained polymer is a polyhydroxyalkanoate containing a unit represented by the following chemical formula (40) as a monomer unit. It was confirmed that.

Further, it was confirmed that the unit of the polyhydroxyalkanoate represented by the chemical formula (40) was a copolymer of 8 mol% for the G unit and 92 mol% for the H unit.
In addition, since no peak derived from sulfonic acid was observed by acid value titration using potentiometric titrator AT510 (manufactured by Kyoto Electronics; trade name), it is clear that sulfonic acid is methyl sulfonate. Became.
The average molecular weight of the obtained polymer was evaluated by the same method as in Preparation Example A-3. As a result, the number average molecular weight M _n = 9900 and the weight average molecular weight M _w = 14500. A series of preparation methods were scaled up to obtain a large amount of polyhydroxyalkanoate represented by the chemical formula (40) to give Exemplified Compound C-10.

(Preparation Example D-1)
[Polyester synthesis using 3,6-di (2-propenyl) -1,4-dioxane-2,5-dione and mandelide (3,6-diphenyl-1,4-dioxane-2,5-dione)]
0.10 g (0.5 mmol) of 3,6-di (2-propenyl) -1,4-dioxane-2,5-dione, 1.21 g (4.5 mmol) of mandelide, 0.01 M tin octylate (2 -Tin ethylhexanoate) in toluene 2 ml and 0.01 M p-tert-butylbenzyl alcohol in toluene 2 ml were charged into the polymerization ampule, and then the polymer was prepared in the same manner as in Preparation Example A-1. 05 g was obtained.
As a result of conducting NMR analysis under the same conditions as in Preparation Example A-1 to specify the structure of the obtained polymer, a polyhydroxyalkanoate copolymer containing a unit represented by the following chemical formula (41) as a monomer unit It was confirmed that. Moreover, it was confirmed that the ratio of the monomer unit is 8 mol% A unit and 92 mol% B unit.

  Moreover, the average molecular weight of the obtained polyhydroxyalkanoate was evaluated by the same method as in Preparation Example A-1. As a result, the number average molecular weight was Mn = 17000 and the weight average molecular weight was Mw = 31500.

(Preparation Example D-2)
Oxidation reaction of polyhydroxyalkanoate composed of unit represented by chemical formula (41) synthesized in Preparation Example D-1

0.50 g of a polyhydroxyalkanoate copolymer (A: 8 mol%, B: 92 mol%) composed of the unit represented by chemical formula (41) obtained in Preparation Example D-1 was added to an eggplant flask, and 30 ml of acetone was added. In addition, it was dissolved. This was placed in an ice bath, 5 ml of acetic acid and 0.24 g of 18-crown-6-ether were added and stirred. Next, 0.19 g 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, 0.44 g of polymer was obtained by the same method as in Preparation Example A-2.
As a result of conducting NMR analysis under the same conditions as in Preparation Example A-1 to specify the structure of the obtained polymer, it is a polyhydroxyalkanoate containing a unit represented by the following chemical formula (42) as a monomer unit. Was confirmed.

Moreover, the average molecular weight of the obtained polyhydroxyalkanoate was evaluated by the same method as in Preparation Example A-1. As a result, the number average molecular weight was Mn = 12,500 and the weight average molecular weight was Mw = 24300.
Further, in order to calculate the unit of the obtained polyhydroxyalkanoate, 29 mg of the polyhydroxyalkanoate obtained by the same method as in Preparation Example A-2 was subjected to NMR analysis using the same method as in Preparation Example A-1. went. As a result, it was confirmed that the unit of the polyhydroxyalkanoate represented by the chemical formula (42) was a copolymer of 7 mol% for the C unit and 93 mol% for the D unit.

(Preparation Example D-3)
Condensation reaction of polyhydroxyalkanoate composed of unit represented by chemical formula (42) synthesized in Preparation Example D-2 and 2-aminobenzenesulfonic acid

Under a nitrogen atmosphere, 0.40 g of a polyhydroxyalkanoate copolymer (C: 7 mol%, D: 93 mol%) consisting of the unit represented by the chemical formula (42) obtained in Preparation Example D-2, 2-aminobenzenesulfone 0.18 g of acid was placed in a 100 ml three-necked flask, 15.0 ml of pyridine was added and stirred, 0.55 ml of triphenyl phosphite was added, and the mixture was heated at 120 ° C. for 6 hours. After completion of the reaction, 0.34 g of polymer was obtained by the same method as in Preparation Example A-3.
The structure of the obtained polymer was analyzed by the same method as in Preparation Example A-3. As a result of IR measurement, the peak at 1695 cm ⁻¹ derived from the carboxylic acid decreased, and a new peak derived from the amide group was observed at 1658 cm ⁻¹ .
^From the result of ¹ H-NMR, since the peak derived from the aromatic ring having a 2-aminobenzenesulfonic acid structure is shifted, the obtained polymer has a unit represented by the following chemical formula (43) as a monomer unit. It was confirmed to be a polyhydroxyalkanoate containing.

Further, it was confirmed that the unit of polyhydroxyalkanoate represented by the chemical formula (43) was a copolymer of 7 mol% for the E unit and 93 mol% for the F unit.
The average molecular weight of the obtained polymer was evaluated by the same method as in Preparation Example A-3. As a result, the number average molecular weight M _n = 11400 and the weight average molecular weight M _w = 23100.

(Preparation Example D-4)
Esterification reaction of polyhydroxyalkanoate composed of unit represented by chemical formula (43) synthesized in Preparation Example D-3

To the eggplant flask, 0.30 g of a polyhydroxyalkanoate copolymer (E: 7 mol%, F: 93 mol%) consisting of the unit represented by the chemical formula (43) obtained in Preparation Example D-3 was added. It melt | dissolved by adding 0 ml and methanol 7.0 ml, and cooled to 0 degreeC. To this was added 0.73 ml of a 2 mol / L trimethylsilyldiazomethane-hexane solution (manufactured by Aldrich), and the mixture was stirred for 4 hours. After completion of the reaction, 0.30 g of polymer was obtained in the same manner as in Preparation Example A-4.
The structure of the obtained polymer was determined by the same method as in Preparation Example A-4. ^From the result of ¹ H-NMR, since a peak derived from methyl sulfonate is seen at 3 to 4 ppm, the obtained polymer is a polyhydroxyalkanoate containing a unit represented by the following chemical formula (44) as a monomer unit. It was confirmed that.

Further, it was confirmed that the unit of the polyhydroxyalkanoate represented by the chemical formula (44) was a copolymer of 7 mol% for the G unit and 93 mol% for the H unit.
In addition, since no peak derived from sulfonic acid was observed by acid value titration using potentiometric titrator AT510 (manufactured by Kyoto Electronics; trade name), it is clear that sulfonic acid is methyl sulfonate. Became.
The average molecular weight of the obtained polymer was evaluated by the same method as in Preparation Example A-3. As a result, the number average molecular weight M _n = 11200 and the weight average molecular weight M _w = 23000. A series of preparation methods were scaled up, and a large amount of polyhydroxyalkanoate represented by the chemical formula (44) was obtained to give Exemplified Compound D.

(Preparation Example E-1)
[Polyester synthesis using tetrahydro-6- (2-propenyl) -2H-pyran-2-one and L-lactide]
Tetrahydro-6- (2-propenyl) -2H-pyran-2-one 0.28 g (2.0 mmol), L-lactide 1.15 g (8.0 mmol), 2M di-iso-propylzinc in toluene 20 μl of solution, 8 ml of 0.01 M p-tert-butylbenzyl alcohol in toluene was charged into the polymerization ampule, and 1.06 g of polymer was obtained in the same manner as in Preparation Example A-1.
As a result of conducting NMR analysis under the same conditions as in Preparation Example A-1 to identify the structure of the obtained polymer, a polyhydroxyalkanoate copolymer containing a unit represented by the following chemical formula (45) as a monomer unit It was confirmed that. Moreover, it was confirmed that the ratio of the monomer unit is A unit 11 mol% and B unit 89 mol%.

  Moreover, the average molecular weight of the obtained polyhydroxyalkanoate was evaluated by the same method as in Preparation Example A-1. As a result, the number average molecular weight was Mn = 142500, and the weight average molecular weight was Mw = 233700.

(Preparation Example E-2)
Oxidation reaction of polyhydroxyalkanoate composed of unit represented by chemical formula (45) synthesized in Preparation Example E-1

0.50 g of a polyhydroxyalkanoate copolymer (A: 11 mol%, B: 89 mol%) comprising the unit represented by the chemical formula (45) obtained in Preparation Example E-1 was added to an eggplant flask, and 30 ml of acetone was added. In addition, it was dissolved. This was placed in an ice bath, 5 ml of acetic acid and 0.55 g of 18-crown-6-ether were added and stirred. Next, 0.44 g 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, 0.43 g of polymer was obtained in the same manner as in Preparation Example A-2.
As a result of conducting NMR analysis under the same conditions as in Preparation Example A-1 to identify the structure of the obtained polymer, it is a polyhydroxyalkanoate containing a unit represented by the following chemical formula (46) as a monomer unit. Was confirmed.

Moreover, the average molecular weight of the obtained polyhydroxyalkanoate was evaluated by the same method as in Preparation Example A-1. As a result, the number average molecular weight was Mn = 98500, and the weight average molecular weight was Mw = 166400.
Furthermore, in order to calculate the unit of the obtained polyhydroxyalkanoate, 29 mg of the polyhydroxyalkanoate obtained by the same method as in Preparation Example A-2 was subjected to NMR analysis using the same method as in Preparation Example A-1. went. As a result, it was confirmed that the unit of the polyhydroxyalkanoate represented by the chemical formula (46) was a copolymer of 10 mol% for the C unit and 90 mol% for the D unit.
A series of preparation methods were scaled up to obtain a large amount of the polyhydroxyalkanoate represented by the chemical formula (46), and it was designated as Exemplified Compound E.

(Preparation Example F-1)
[Polyester Synthesis Using Tetrahydro-6- (2-propenyl) -2H-pyran-2-one and Mandelide]
Tetrahydro-6- (2-propenyl) -2H-pyran-2-one 0.28 g (2.0 mmol), mandelide 2.15 g (8.0 mmol), 2 M di-iso-propylzinc in toluene solution 20 μl Then, 8 ml of 0.01M p-tert-butylbenzyl alcohol in toluene was charged into the polymerization ampule, and then 1.59 g of polymer was obtained by the same method as in Preparation Example A-1.
As a result of conducting NMR analysis under the same conditions as in Preparation Example A-1 to specify the structure of the obtained polymer, a polyhydroxyalkanoate copolymer containing a unit represented by the following chemical formula (47) as a monomer unit It was confirmed that. Moreover, it was confirmed that the ratio of the monomer unit is 12 mol% of A unit and 88 mol% of B unit.

  Moreover, the average molecular weight of the obtained polyhydroxyalkanoate was evaluated by the same method as in Preparation Example A-1. As a result, the number average molecular weight was Mn = 12000 and the weight average molecular weight was Mw = 24200.

(Preparation Example F-2)
Oxidation reaction of polyhydroxyalkanoate comprising unit represented by chemical formula (47) synthesized in Preparation Example F-1

0.50 g of a polyhydroxyalkanoate copolymer (A: 12 mol%, B: 88 mol%) comprising the unit represented by the chemical formula (47) obtained in Preparation Example F-1 was added to an eggplant flask, and 30 ml of acetone was added. In addition, it was dissolved. This was placed in an ice bath, 5 ml of acetic acid and 0.35 g of 18-crown-6-ether were added and stirred. Next, 0.28 g of potassium permanganate was slowly added in an ice bath, stirred for 2 hours in an ice bath, and further stirred at room temperature for 18 hours. After completion of the reaction, 0.44 g of polymer was obtained by the same method as in Preparation Example A-2.
As a result of conducting NMR analysis under the same conditions as in Preparation Example A-1 to identify the structure of the obtained polymer, it is a polyhydroxyalkanoate containing a unit represented by the following chemical formula (48) as a monomer unit. Was confirmed.

Moreover, the average molecular weight of the obtained polyhydroxyalkanoate was evaluated by the same method as in Preparation Example A-1. As a result, the number average molecular weight was Mn = 8400, and the weight average molecular weight was Mw = 16300.
Furthermore, in order to calculate the unit of the obtained polyhydroxyalkanoate, 30 mg of the polyhydroxyalkanoate obtained by the same method as in Preparation Example A-2 was subjected to NMR analysis using the same method as in Preparation Example A-1. went. As a result, it was confirmed that the unit of the polyhydroxyalkanoate represented by the chemical formula (48) was a copolymer of 11 mol% for the C unit and 89 mol% for the D unit.
A series of preparation methods were scaled up to obtain a large amount of the polyhydroxyalkanoate represented by the chemical formula (48) to give Exemplified Compound F.

(Preparation Example G-1)
[Polyester synthesis using β-malolactone benzyl ester and L-mandelide]
β-malolactone benzyl ester 0.82 g (4.0 mmol), mandelide 2.68 g (10.0 mmol), 2 M diethylzinc in toluene 28 μl, 0.01 M p-tert-butylbenzyl alcohol in toluene 11.2 ml Was charged into a polymerization ampule, and thereafter, 1.27 g of a polymer was obtained by the same method as in Preparation Example A-1.
As a result of conducting NMR analysis under the same conditions as in Preparation Example A-1 to specify the structure of the obtained polymer, a polyhydroxyalkanoate copolymer containing a unit represented by the following chemical formula (49) as a monomer unit It was confirmed that. Moreover, it was confirmed that the ratio of the monomer unit is 8 mol% A unit and 92 mol% B unit.

  Moreover, the average molecular weight of the obtained polyhydroxyalkanoate was evaluated by the same method as in Preparation Example A-1. As a result, the number average molecular weight Mn was 6500, and the weight average molecular weight Mw was 11200.

(Preparation Example G-2)
1.00 g of the polyhydroxyalkanoate copolymer represented by the chemical formula (49) obtained in Preparation Example G-1 was dissolved in 100 ml of a mixed solvent of dioxane-ethanol (75:25), and 5% palladium / carbon was added thereto. 0.22 g of catalyst was added, the reaction system was filled with hydrogen, and the mixture was stirred at room temperature for 1 day. After completion of the reaction, 0.81 g of polymer was obtained by the same method as in Preparation Example A-2.
As a result of conducting NMR analysis under the same conditions as in Preparation Example A-1 to specify the structure of the obtained polymer, a polyhydroxyalkanoate copolymer containing a unit represented by the following chemical formula (50) as a monomer unit It was confirmed that. Moreover, it was confirmed that the ratio of the monomer unit is C unit 8 mol% and D unit 92 mol%.

Moreover, the average molecular weight of the obtained polyhydroxyalkanoate was evaluated by the same method as in Preparation Example A-1. As a result, the number average molecular weight was Mn = 6400, and the weight average molecular weight was Mw = 10900.
A series of preparation methods were scaled up, and a large amount of polyhydroxyalkanoate represented by the chemical formula (50) was obtained to give Exemplified Compound G.

  (Preparation Example H-1)

[Polyester Synthesis Using 7- (3-Butenyl) -2-oxeppanone represented by Chemical Formula (51) and L-lactide]
7- (3-Butenyl) -2-oxepanone 0.34 g (2.0 mmol), L-lactide 1.15 g (8.0 mmol), 2 M di-iso-propylzinc in toluene solution 20 μl, 0.01 M 8 ml of a toluene solution of p-tert-butylbenzyl alcohol was charged into a polymerization ampule, and then 1.05 g of a polymer was obtained in the same manner as in Preparation Example A-1.
As a result of conducting NMR analysis under the same conditions as in Preparation Example A-1 to specify the structure of the obtained polymer, a polyhydroxyalkanoate copolymer containing a unit represented by the following chemical formula (52) as a monomer unit It was confirmed that. Moreover, it was confirmed that the ratio of the monomer unit is 8 mol% A unit and 92 mol% B unit.

  Moreover, the average molecular weight of the obtained polyhydroxyalkanoate was evaluated by the same method as in Preparation Example A-1. As a result, the number average molecular weight was Mn = 43500, and the weight average molecular weight was Mw = 67400.

(Preparation Example H-2)
Oxidation reaction of polyhydroxyalkanoate composed of unit represented by chemical formula (52) synthesized in Preparation Example H-1

0.50 g of a polyhydroxyalkanoate copolymer (A: 8 mol%, B: 92 mol%) comprising the unit represented by the chemical formula (52) obtained in Preparation Example H-1 was added to an eggplant flask, and 30 ml of acetone was added. In addition, it was dissolved. This was placed in an ice bath, 5 ml of acetic acid and 0.40 g of 18-crown-6-ether were added and stirred. Next, 0.32 g 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, 0.44 g of polymer was obtained by the same method as in Preparation Example A-2.
As a result of conducting NMR analysis under the same conditions as in Preparation Example A-1 to identify the structure of the obtained polymer, it is a polyhydroxyalkanoate containing a unit represented by the following chemical formula (53) as a monomer unit. Was confirmed.

Moreover, the average molecular weight of the obtained polyhydroxyalkanoate was evaluated by the same method as in Preparation Example A-1. As a result, the number average molecular weight was Mn = 37500, and the weight average molecular weight was Mw = 59600.
Further, in order to calculate the unit of the obtained polyhydroxyalkanoate, 28 mg of the polyhydroxyalkanoate obtained by the same method as in Preparation Example A-2 was subjected to NMR analysis using the same method as in Preparation Example A-1. went. As a result, it was confirmed that the unit of the polyhydroxyalkanoate represented by the chemical formula (53) was a copolymer of 8 mol% for the C unit and 92 mol% for the D unit.

(Preparation Example H-3)
Condensation reaction of polyhydroxyalkanoate composed of the unit represented by the chemical formula (53) synthesized in Preparation Example H-2 and 2-amino-2-methylpropanesulfonic acid

Under nitrogen atmosphere, 0.40 g of polyhydroxyalkanoate copolymer (C: 8 mol%, D: 92 mol%) composed of the unit represented by chemical formula (53) obtained in Preparation Example H-2, 2-amino-2 -0.30 g of methylpropanesulfonic acid was placed in a 100 ml three-necked flask, 15.0 ml of pyridine was added and stirred, then 1.03 ml of triphenyl phosphite was added, and the mixture was heated at 120 ° C for 6 hours. After completion of the reaction, 0.32 g of polymer was obtained in the same manner as in Preparation Example A-3.
The structure of the obtained polymer was analyzed by the same method as in Preparation Example A-3. As a result of IR measurement, the peak at 1695 cm ⁻¹ derived from carboxylic acid decreased, and a new peak derived from the amide group was observed at 1668 cm ⁻¹ .
^From the result of ¹ H-NMR, since the peak derived from methylene having a 2-amino-2-methylpropanesulfonic acid structure is shifted, the obtained polymer is represented by the following chemical formula (54) as a monomer unit. It was confirmed that this was a polyhydroxyalkanoate containing unit.

In addition, it was confirmed that the unit of the polyhydroxyalkanoate represented by the chemical formula (54) was a copolymer of 8 mol% for the E unit and 92 mol% for the F unit.
The average molecular weight of the obtained polymer was evaluated by the same method as in Preparation Example A-3. As a result, the number average molecular weight M _n = 37500 and the weight average molecular weight M _w = 59600. A series of preparation methods were scaled up, and a large amount of polyhydroxyalkanoate represented by the chemical formula (54) was obtained to give Exemplified Compound H.

(Preparation Example I-1)
[Polyester synthesis using 3- (2-propenyl) -2-oxetanone and L-lactide]
3- (2-propenyl) -2-oxetanone 0.22 g (2.0 mmol), L-lactide 1.44 g (10.0 mmol), 0.01 M tin octylate (tin 2-ethylhexanoate) in toluene 4.8 ml of toluene solution of 0.01M p-tert-butylbenzyl alcohol 4.8 ml was charged into the polymerization ampule, and then 1.20 g of polymer was obtained by the same method as in Preparation Example A-1.
As a result of conducting NMR analysis under the same conditions as in Preparation Example A-1 to specify the structure of the obtained polymer, a polyhydroxyalkanoate copolymer containing a unit represented by the following chemical formula (55) as a monomer unit It was confirmed that. Moreover, it was confirmed that the ratio of the monomer unit is 9 mol% of A unit and 91 mol% of B unit.

  Moreover, the average molecular weight of the obtained polyhydroxyalkanoate was evaluated by the same method as in Preparation Example A-1. As a result, the number average molecular weight was Mn = 28500, and the weight average molecular weight was Mw = 38500.

(Preparation Example I-2)
Oxidation reaction of polyhydroxyalkanoate comprising unit represented by chemical formula (55) synthesized in Preparation Example I-1

0.50 g of a polyhydroxyalkanoate copolymer (A: 9 mol%, B: 91 mol%) comprising the unit represented by the chemical formula (55) obtained in Preparation Example I-1 was added to an eggplant flask, and 30 ml of acetone was added. In addition, it was dissolved. This was placed in an ice bath, 5 ml of acetic acid and 0.47 g of 18-crown-6-ether were added and stirred. Next, 0.38 g 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, 0.43 g of polymer was obtained in the same manner as in Preparation Example A-2.
As a result of conducting NMR analysis under the same conditions as in Preparation Example A-1 to identify the structure of the obtained polymer, it is a polyhydroxyalkanoate containing a unit represented by the following chemical formula (56) as a monomer unit. Was confirmed.

Moreover, the average molecular weight of the obtained polyhydroxyalkanoate was evaluated by the same method as in Preparation Example A-1. As a result, the number average molecular weight was Mn = 22300, and the weight average molecular weight was Mw = 30600.
Furthermore, in order to calculate the unit of the obtained polyhydroxyalkanoate, 29 mg of the polyhydroxyalkanoate obtained by the same method as in Preparation Example A-2 was subjected to NMR analysis using the same method as in Preparation Example A-1. went. As a result, it was confirmed that the unit of the polyhydroxyalkanoate represented by the chemical formula (56) was a copolymer of 9 mol% for the C unit and 91 mol% for the D unit.

(Preparation Example I-3)
Condensation reaction of polyhydroxyalkanoate comprising unit represented by chemical formula (56) synthesized in Preparation Example I-2 and 2-aminobenzenesulfonic acid

Under a nitrogen atmosphere, 0.40 g of a polyhydroxyalkanoate copolymer (C: 9 mol%, D: 91 mol%) composed of the unit represented by the chemical formula (56) obtained in Preparation Example I-2, 2-aminobenzenesulfone 0.40 g of acid was placed in a 100 ml three-necked flask, 15.0 ml of pyridine was added and stirred, 1.21 ml of triphenyl phosphite was added, and the mixture was heated at 120 ° C. for 6 hours. After completion of the reaction, 0.34 g of polymer was obtained by the same method as in Preparation Example A-3.
The structure of the obtained polymer was analyzed by the same method as in Preparation Example A-3. As a result of IR measurement, the peak at 1695 cm ⁻¹ derived from the carboxylic acid decreased, and a new peak derived from the amide group was observed at 1658 cm ⁻¹ .
^From the result of ¹ H-NMR, since the peak derived from the aromatic ring of 2-aminobenzenesulfonic acid structure is shifted, the obtained polymer has a unit represented by the following chemical formula (57) as a monomer unit. It was confirmed to be a polyhydroxyalkanoate containing.

Further, it was confirmed that the unit of polyhydroxyalkanoate represented by the chemical formula (57) was a copolymer of 9 mol% for the E unit and 91 mol% for the F unit.
The average molecular weight of the obtained polymer was evaluated by the same method as in Preparation Example A-3. As a result, the number average molecular weight M _n = 19800 and the weight average molecular weight M _w = 28100.

(Preparation Example I-4)
Esterification reaction of polyhydroxyalkanoate comprising unit represented by chemical formula (57) synthesized in Preparation Example I-3

To the eggplant flask, 0.30 g of a polyhydroxyalkanoate copolymer (E: 9 mol%, F: 91 mol%) composed of the unit represented by the chemical formula (57) obtained in Preparation Example I-3 was added. It melt | dissolved by adding 0 ml and methanol 7.0 ml, and cooled to 0 degreeC. To this, 1.48 ml of a 2 mol / L trimethylsilyldiazomethane-hexane solution (manufactured by Aldrich) was added and stirred for 4 hours. After completion of the reaction, 0.30 g of polymer was obtained in the same manner as in Preparation Example A-4.
The structure of the obtained polymer was determined by the same method as in Preparation Example A-4. ^From the result of ¹ H-NMR, since a peak derived from methyl sulfonate is observed at 3 to 4 ppm, the obtained polymer is a polyhydroxyalkanoate containing a unit represented by the following chemical formula (58) as a monomer unit. It was confirmed that.

Further, it was confirmed that the unit of the polyhydroxyalkanoate represented by the chemical formula (58) was a copolymer of 9 mol% for the G unit and 91 mol% for the H unit.
In addition, since no peak derived from sulfonic acid was observed by acid value titration using potentiometric titrator AT510 (manufactured by Kyoto Electronics; trade name), it is clear that sulfonic acid is methyl sulfonate. Became.
The average molecular weight of the obtained polymer was evaluated by the same method as in Preparation Example A-3. As a result, the number average molecular weight M _n = 18600 and the weight average molecular weight M _w = 27000. A series of preparation methods were scaled up, and a large amount of polyhydroxyalkanoate represented by the chemical formula (58) was obtained to give Exemplified Compound I.

(Preparation Example J-1)
[Polyester synthesis using 3- (2-propenyl) -2-oxetanone and mandelide (3,6-diphenyl-1,4-dioxane-2,5-dione)]
3. Toluene solution of 2- (2-propenyl) -2-oxetanone 0.22 g (2.0 mmol), mandelide 2.68 g (10.0 mmol), 0.01 M tin octylate (tin 2-ethylhexanoate) 8 ml of a toluene solution of 0.01 M p-tert-butylbenzyl alcohol in an amount of 4.8 ml was charged into a polymerization ampule, and then 1.88 g of a polymer was obtained in the same manner as in Preparation Example A-1.
As a result of conducting NMR analysis under the same conditions as in Preparation Example A-1 to specify the structure of the obtained polymer, a polyhydroxyalkanoate copolymer containing a unit represented by the following chemical formula (59) as a monomer unit It was confirmed that. Moreover, it was confirmed that the ratio of the monomer unit is 10 mol% of A unit and 90 mol% of B unit.

  Moreover, the average molecular weight of the obtained polyhydroxyalkanoate was evaluated by the same method as in Preparation Example A-1. As a result, the number average molecular weight was Mn = 23500, and the weight average molecular weight was Mw = 35000.

(Preparation Example J-2)
Oxidation reaction of polyhydroxyalkanoate composed of unit represented by chemical formula (59) synthesized in Preparation Example J-1

0.50 g of a polyhydroxyalkanoate copolymer (A: 10 mol%, B: 90 mol%) composed of the unit represented by the chemical formula (59) obtained in Preparation Example J-1 was added to an eggplant flask, and 30 ml of acetone was added. In addition, it was dissolved. This was placed in an ice bath, 5 ml of acetic acid and 0.30 g of 18-crown-6-ether were added and stirred. Next, 0.24 g 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, 0.44 g of polymer was obtained by the same method as in Preparation Example A-2.
As a result of conducting NMR analysis under the same conditions as in Preparation Example A-1 to identify the structure of the obtained polymer, it is a polyhydroxyalkanoate containing a unit represented by the following chemical formula (60) as a monomer unit. Was confirmed.

Moreover, the average molecular weight of the obtained polyhydroxyalkanoate was evaluated by the same method as in Preparation Example A-1. As a result, the number average molecular weight was Mn = 20100 and the weight average molecular weight was Mw = 30400.
Further, in order to calculate the unit of the obtained polyhydroxyalkanoate, 28 mg of the polyhydroxyalkanoate obtained by the same method as in Preparation Example A-2 was subjected to NMR analysis using the same method as in Preparation Example A-1. went. As a result, it was confirmed that the unit of the polyhydroxyalkanoate represented by the chemical formula (60) was a copolymer of 10 mol% for the C unit and 90 mol% for the D unit.

(Preparation Example J-3)
Condensation reaction of polyhydroxyalkanoate comprising unit represented by chemical formula (60) synthesized in Preparation Example J-2 and 2-amino-2-methylpropanesulfonic acid

Under nitrogen atmosphere, 0.40 g of polyhydroxyalkanoate copolymer (C: 10 mol%, D: 90 mol%) composed of the unit represented by chemical formula (60) obtained in Preparation Example J-2, 2-amino-2 -0.23 g of methylpropanesulfonic acid was put in a 100 ml three-necked flask, 15.0 ml of pyridine was added and stirred, 0.78 ml of triphenyl phosphite was added, and the mixture was heated at 120 ° C for 6 hours. After completion of the reaction, 0.32 g of polymer was obtained in the same manner as in Preparation Example A-3.
The structure of the obtained polymer was analyzed by the same method as in Preparation Example A-3. As a result of IR measurement, the peak at 1695 cm ⁻¹ derived from carboxylic acid decreased, and a new peak derived from the amide group was observed at 1668 cm ⁻¹ .
^From the result of ¹ H-NMR, since the peak derived from methylene having a 2-amino-2-methylpropanesulfonic acid structure is shifted, the obtained polymer is represented by the following chemical formula (61) as a monomer unit. It was confirmed that this was a polyhydroxyalkanoate containing unit.

Further, it was confirmed that the unit of the polyhydroxyalkanoate represented by the chemical formula (61) was a copolymer of 10 mol% for the E unit and 90 mol% for the F unit.
The average molecular weight of the obtained polymer was evaluated by the same method as in Preparation Example A-3. As a result, the number average molecular weight M _n = 17600 and the weight average molecular weight M _w = 27100. A series of preparation methods were scaled up to obtain a large amount of the polyhydroxyalkanoate represented by the chemical formula (61) to give Exemplified Compound J.

(Preparation Example K-1)
[Polyester synthesis using 3- (2-propenyl) -2-oxetanone and δ-valerolactone]
3- (2-propenyl) -2-oxetanone 0.22 g (2.0 mmol), δ-valerolactone 1.00 g (10.0 mmol), 0.01 M tin octylate (tin 2-ethylhexanoate) in toluene 4.8 ml of solution and 4.8 ml of 0.01 M p-tert-butylbenzyl alcohol in toluene were charged into the polymerization ampule, and then 0.80 g of polymer was obtained in the same manner as in Preparation Example A-1.
As a result of conducting NMR analysis under the same conditions as in Preparation Example A-1 to specify the structure of the obtained polymer, a polyhydroxyalkanoate copolymer containing a unit represented by the following chemical formula (62) as a monomer unit It was confirmed that. Moreover, it was confirmed that the ratio of the monomer unit is A unit 16 mol% and B unit 84 mol%.

  Moreover, the average molecular weight of the obtained polyhydroxyalkanoate was evaluated by the same method as in Preparation Example A-1. As a result, the number average molecular weight was Mn = 19800, and the weight average molecular weight was Mw = 28900.

(Preparation Example K-2)
Oxidation reaction of polyhydroxyalkanoate comprising unit represented by chemical formula (62) synthesized in Preparation Example K-1

0.50 g of a polyhydroxyalkanoate copolymer (A: 16 mol%, B: 84 mol%) composed of the unit represented by the chemical formula (62) obtained in Preparation Example K-1 was added to an eggplant flask, and 30 ml of acetone was added. In addition, it was dissolved. This was placed in an ice bath, 5 ml of acetic acid and 0.62 g of 18-crown-6-ether were added and stirred. Next, 0.50 g 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, 0.42 g of polymer was obtained by the same method as in Preparation Example A-2.
As a result of conducting NMR analysis under the same conditions as in Preparation Example A-1 to specify the structure of the obtained polymer, it is a polyhydroxyalkanoate containing a unit represented by the following chemical formula (63) as a monomer unit. Was confirmed.

Moreover, the average molecular weight of the obtained polyhydroxyalkanoate was evaluated by the same method as in Preparation Example A-1. As a result, the number average molecular weight was Mn = 15700, and the weight average molecular weight was Mw = 23700.
Furthermore, in order to calculate the unit of the obtained polyhydroxyalkanoate, 27 mg of the polyhydroxyalkanoate obtained by the same method as in Preparation Example A-2 was subjected to NMR analysis using the same method as in Preparation Example A-1. went. As a result, it was confirmed that the unit of the polyhydroxyalkanoate represented by the chemical formula (63) was a copolymer of 15 mol% for the C unit and 85 mol% for the D unit.

(Preparation Example K-3)
Condensation reaction of polyhydroxyalkanoate composed of unit represented by chemical formula (63) synthesized in Preparation Example K-2 and 2-aminobenzenesulfonic acid phenyl ester

Under a nitrogen atmosphere, 0.40 g of a polyhydroxyalkanoate copolymer (C: 15 mol%, D: 85 mol%) consisting of the unit represented by the chemical formula (63) obtained in Preparation Example K-2, 2-aminobenzenesulfone 0.71 g of acid phenyl ester was placed in a 100 ml three-necked flask, 15.0 ml of pyridine was added and stirred, and then 1.50 ml of triphenyl phosphite was added and heated at 120 ° C. for 6 hours. After completion of the reaction, 0.37 g of polymer was obtained in the same manner as in Preparation Example A-3.
The structure of the obtained polymer was analyzed by the same method as in Preparation Example A-3. As a result of IR measurement, the peak at 1695 cm ⁻¹ derived from the carboxylic acid decreased, and a new peak derived from the amide group was observed at 1658 cm ⁻¹ .
^From the result of ¹ H-NMR, since the peak derived from the aromatic ring of the 2-aminobenzenesulfonic acid phenyl ester structure is shifted, the obtained polymer is represented by the following chemical formula (64) as a monomer unit. It was confirmed to be a polyhydroxyalkanoate containing unit.

Further, it was confirmed that the unit of the polyhydroxyalkanoate represented by the chemical formula (64) was a copolymer of 15 mol% for the E unit and 85 mol% for the F unit.
The average molecular weight of the obtained polymer was evaluated by the same method as in Preparation Example A-3. As a result, the number average molecular weight M _n = 14000 and the weight average molecular weight M _w = 22,000. A series of preparation methods were scaled up, and a large amount of polyhydroxyalkanoate represented by the chemical formula (64) was obtained to give Exemplified Compound K.

(Preparation Example L-1)
[Polyester synthesis using 3- (9-decenyl) -2-oxetanone and L-lactide represented by chemical formula (65)]

3- (9-decenyl) -2-oxetanone represented by the chemical formula (65) 0.36 g (2.0 mmol), L-lactide 1.44 g (10.0 mmol), 0.01 M tin octylate (2-ethyl) 4.8 ml of tin hexanoate in toluene solution and 4.8 ml of 0.01M p-tert-butylbenzyl alcohol in toluene were charged into the polymerization ampule, and then the polymer was prepared in the same manner as in Preparation Example A-1. 0.75 g was obtained.
As a result of performing NMR analysis under the same conditions as in Preparation Example A-1 to specify the structure of the obtained polymer, a polyhydroxyalkanoate copolymer containing a unit represented by the following chemical formula (66) as a monomer unit It was confirmed that. Moreover, it was confirmed that the ratio of the monomer unit is 4 mol% of A unit and 96 mol% of B unit.

(Preparation Example L-2)
Oxidation reaction of polyhydroxyalkanoate comprising unit represented by chemical formula (66) synthesized in Preparation Example L-1

0.50 g of a polyhydroxyalkanoate copolymer (A: 4 mol%, B: 96 mol%) composed of the unit represented by the chemical formula (66) obtained in Preparation Example L-1 was added to an eggplant flask, and 30 ml of acetone was added. In addition, it was dissolved. This was placed in an ice bath, 5 ml of acetic acid and 0.21 g of 18-crown-6-ether were added and stirred. Next, 0.17 g 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, 0.44 g of polymer was obtained by the same method as in Preparation Example A-2.
As a result of conducting NMR analysis under the same conditions as in Preparation Example A-1 to identify the structure of the obtained polymer, it is a polyhydroxyalkanoate containing a unit represented by the following chemical formula (67) as a monomer unit. Was confirmed.

Moreover, the average molecular weight of the obtained polyhydroxyalkanoate was evaluated by the same method as in Preparation Example A-1. As a result, the number average molecular weight was Mn = 13100 and the weight average molecular weight was Mw = 19100.
Furthermore, in order to calculate the unit of the obtained polyhydroxyalkanoate, 29 mg of the polyhydroxyalkanoate obtained by the same method as in Preparation Example A-2 was subjected to NMR analysis using the same method as in Preparation Example A-1. went. As a result, it was confirmed that the unit of the polyhydroxyalkanoate represented by the chemical formula (67) was a copolymer of 4 mol% for the C unit and 96 mol% for the D unit.

(Preparation Example L-3)
Condensation reaction of polyhydroxyalkanoate composed of the unit represented by chemical formula (67) synthesized in Preparation Example L-2 with 4-methoxyaniline-2-sulfonic acid

In a nitrogen atmosphere, 0.40 g of a polyhydroxyalkanoate copolymer (C: 4 mol%, D: 96 mol%) obtained from the unit represented by the chemical formula (67) obtained in Preparation Example L-2, 4-methoxyaniline- After putting 0.21 g of 2-sulfonic acid into a 100 ml three-necked flask and adding 15.0 ml of pyridine and stirring, 0.53 ml of triphenyl phosphite was added and heated at 120 ° C. for 6 hours. After completion of the reaction, 0.34 g of polymer was obtained by the same method as in Preparation Example A-3.
The structure of the obtained polymer was analyzed by the same method as in Preparation Example A-3. As a result of IR measurement, the peak at 1695 cm ⁻¹ derived from the carboxylic acid decreased, and a new peak derived from the amide group was observed at 1658 cm ⁻¹ .
^From the result of ¹ H-NMR, since the peak derived from the aromatic ring having a 4-methoxyaniline-2-sulfonic acid structure is shifted, the obtained polymer is represented by the following chemical formula (68) as a monomer unit. It was confirmed that this was a polyhydroxyalkanoate containing unit.

Further, it was confirmed that the unit of polyhydroxyalkanoate represented by the chemical formula (68) was a copolymer of 4 mol% for E unit and 96 mol% for F unit.
The average molecular weight of the obtained polymer was evaluated by the same method as in Preparation Example A-3. As a result, the number average molecular weight M _n = 11900 and the weight average molecular weight M _w = 18800. A series of preparation methods were scaled up, and a large amount of polyhydroxyalkanoate represented by the chemical formula (68) was obtained to give Exemplified Compound L.

(Preparation Example M-1)
[Synthesis of polyester using 3- (2-propenyl) dihydro-2 (3H) -furanone and mandelide]
3- (2-propenyl) dihydro-2 (3H) -furanone 0.25 g (2.0 mmol), mandelide 2.68 g (10.0 mmol), 2 M diethylzinc in toluene 24 μl, 0.01 M p -9.6 ml of a toluene solution of tert-butylbenzyl alcohol was charged into a polymerization ampule, and then 1.59 g of a polymer was obtained by the same method as in Preparation Example A-1.
As a result of conducting NMR analysis under the same conditions as in Preparation Example A-1 to specify the structure of the obtained polymer, a polyhydroxyalkanoate copolymer containing a unit represented by the following chemical formula (69) as a monomer unit It was confirmed that. Moreover, it was confirmed that the ratio of the monomer unit is 6 mol% of A unit and 94 mol% of B unit.

  Moreover, the average molecular weight of the obtained polyhydroxyalkanoate was evaluated by the same method as in Preparation Example A-1. As a result, the number average molecular weight was Mn = 7500, and the weight average molecular weight was Mw = 11000.

(Preparation Example M-2)
Oxidation reaction of polyhydroxyalkanoate comprising unit represented by chemical formula (69) synthesized in Preparation Example M-1

0.50 g of a polyhydroxyalkanoate copolymer (A: 6 mol%, B: 94 mol%) comprising the unit represented by the chemical formula (69) obtained in Preparation Example M-1 was added to an eggplant flask, and 30 ml of acetone was added. In addition, it was dissolved. This was placed in an ice bath, 5 ml of acetic acid and 0.18 g of 18-crown-6-ether were added and stirred. Next, 0.14 g 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, 0.44 g of polymer was obtained by the same method as in Preparation Example A-2.
As a result of conducting NMR analysis under the same conditions as in Preparation Example A-1 to identify the structure of the obtained polymer, it is a polyhydroxyalkanoate containing a unit represented by the following chemical formula (70) as a monomer unit. Was confirmed.

Moreover, the average molecular weight of the obtained polyhydroxyalkanoate was evaluated by the same method as in Preparation Example A-1. As a result, the number average molecular weight was Mn = 7300, and the weight average molecular weight was Mw = 11100.
Further, in order to calculate the unit of the obtained polyhydroxyalkanoate, 28 mg of the polyhydroxyalkanoate obtained by the same method as in Preparation Example A-2 was subjected to NMR analysis using the same method as in Preparation Example A-1. went. As a result, it was confirmed that the unit of the polyhydroxyalkanoate represented by the chemical formula (70) was a copolymer of 6 mol% for the C unit and 94 mol% for the D unit.

(Preparation Example M-3)
Condensation reaction between polyhydroxyalkanoate comprising unit represented by chemical formula (70) synthesized in Preparation Example M-2 and taurine

Under a nitrogen atmosphere, 0.40 g of a polyhydroxyalkanoate copolymer (C: 6 mol%, D: 94 mol%) consisting of the unit represented by the chemical formula (70) obtained in Preparation Example M-2, and 0.11 g of taurine were added. In a 100 ml three-necked flask, 15.0 ml of pyridine was added and stirred, and then 0.46 ml of triphenyl phosphite was added and heated at 120 ° C. for 6 hours. After completion of the reaction, 0.30 g of polymer was obtained by the same method as in Preparation Example A-3.
The structure of the obtained polymer was analyzed by the same method as in Preparation Example A-3. As a result of IR measurement, the peak at 1695 cm ⁻¹ derived from carboxylic acid decreased, and a new peak derived from the amide group was observed at 1668 cm ⁻¹ .
^From the result of ¹ H-NMR, since the peak derived from methylene having a taurine structure is shifted, the obtained polymer is a polyhydroxyalkanoate containing a unit represented by the following chemical formula (71) as a monomer unit. It was confirmed that there was.

Further, it was confirmed that the unit of polyhydroxyalkanoate represented by the chemical formula (71) was a copolymer of 6 mol% for E unit and 94 mol% for F unit.
The average molecular weight of the obtained polymer was evaluated by the same method as in Preparation Example A-3. As a result, the number average molecular weight M _n = 6800 and the weight average molecular weight M _w = 10900.

(Preparation Example M-4)
Esterification reaction of polyhydroxyalkanoate composed of unit represented by chemical formula (71) synthesized in Preparation Example M-3

To the eggplant flask, 0.30 g of a polyhydroxyalkanoate copolymer (E: 6 mol%, F: 94 mol%) composed of the unit represented by the chemical formula (71) obtained in Preparation Example M-3 was added. It melt | dissolved by adding 0 ml and methanol 7.0 ml, and cooled to 0 degreeC. To this, 0.64 ml of a 2 mol / L trimethylsilyldiazomethane-hexane solution (Aldrich) was added and stirred for 4 hours. After completion of the reaction, 0.29 g of polymer was obtained by the same method as in Preparation Example A-4.
The structure of the obtained polymer was determined by the same method as in Preparation Example A-4. ^From the result of ¹ H-NMR, since a peak derived from methyl sulfonate is seen at 3 to 4 ppm, the obtained polymer is a polyhydroxyalkanoate containing a unit represented by the following chemical formula (72) as a monomer unit. It was confirmed that.

Further, it was confirmed that the unit of the polyhydroxyalkanoate represented by the chemical formula (72) was a copolymer of 6 mol% for the G unit and 94 mol% for the H unit.
In addition, it was clear that the sulfonic acid was methyl sulfonate because no peak derived from sulfonic acid was observed by acid value titration using potentiometric titrator AT510 (manufactured by Kyoto Electronics; product name). Became.
The average molecular weight of the obtained polymer was evaluated by the same method as in Preparation Example A-3. As a result, the number average molecular weight M _n = 6800 and the weight average molecular weight M _w = 10900. A series of preparation methods were scaled up, and a large amount of polyhydroxyalkanoate represented by the chemical formula (72) was obtained to give Exemplified Compound M.

(Preparation Example N-1)
[Polyester synthesis using tetrahydro-3- (2-propenyl) -2H-pyran-2-one and mandelide]
Tetrahydro-3- (2-propenyl) -2H-pyran-2-one 0.28 g (2.0 mmol), mandelide 2.68 g (10.0 mmol), 0.01 M tin octylate (tin 2-ethylhexanoate) ) In toluene solution (4.8 ml) and 0.01 M p-tert-butylbenzyl alcohol in toluene solution (4.8 ml) were charged into a polymerization ampule, and then 2.06 g of polymer was prepared in the same manner as in Preparation Example A-1. Obtained.
As a result of conducting NMR analysis under the same conditions as in Preparation Example A-1 to specify the structure of the obtained polymer, a polyhydroxyalkanoate copolymer containing a unit represented by the following chemical formula (73) as a monomer unit It was confirmed that. Moreover, it was confirmed that the ratio of the monomer unit is 12 mol% of A unit and 88 mol% of B unit.

  Moreover, the average molecular weight of the obtained polyhydroxyalkanoate was evaluated by the same method as in Preparation Example A-1. As a result, the number average molecular weight was Mn = 48000, and the weight average molecular weight was Mw = 97200.

(Preparation Example N-2)
Oxidation reaction of polyhydroxyalkanoate composed of unit represented by chemical formula (73) synthesized in Preparation Example N-1

0.50 g of a polyhydroxyalkanoate copolymer (A: 12 mol%, B: 88 mol%) comprising the unit represented by the chemical formula (73) obtained in Preparation Example N-1 was added to an eggplant flask, and 30 ml of acetone was added. In addition, it was dissolved. This was placed in an ice bath, 5 ml of acetic acid and 0.35 g of 18-crown-6-ether were added and stirred. Next, 0.28 g of potassium permanganate was slowly added in an ice bath, stirred for 2 hours in an ice bath, and further stirred at room temperature for 18 hours. After completion of the reaction, 0.44 g of polymer was obtained by the same method as in Preparation Example A-2.
As a result of conducting NMR analysis under the same conditions as in Preparation Example A-1 to specify the structure of the obtained polymer, it is a polyhydroxyalkanoate containing a unit represented by the following chemical formula (74) as a monomer unit. Was confirmed.

Moreover, the average molecular weight of the obtained polyhydroxyalkanoate was evaluated by the same method as in Preparation Example A-1. As a result, the number average molecular weight was Mn = 38600, and the weight average molecular weight was Mw = 69100.
Further, in order to calculate the unit of the obtained polyhydroxyalkanoate, 28 mg of the polyhydroxyalkanoate obtained by the same method as in Preparation Example A-2 was subjected to NMR analysis using the same method as in Preparation Example A-1. went. As a result, it was confirmed that the unit of the polyhydroxyalkanoate represented by the chemical formula (74) was a copolymer of 11 mol% for the C unit and 89 mol% for the D unit.

(Preparation Example N-3)
Condensation reaction of polyhydroxyalkanoate comprising unit represented by chemical formula (74) synthesized in Preparation Example N-2 and 3-aminobenzenesulfonic acid

Under a nitrogen atmosphere, 0.40 g of a polyhydroxyalkanoate copolymer (C: 11 mol%, D: 89 mol%) composed of the unit represented by chemical formula (74) obtained in Preparation Example N-2, 3-aminobenzenesulfone 0.28 g of acid was put in a 100 ml three-necked flask, 15.0 ml of pyridine was added and stirred, 0.84 ml of triphenyl phosphite was added, and the mixture was heated at 120 ° C. for 6 hours. After completion of the reaction, 0.33 g of polymer was obtained in the same manner as in Preparation Example A-3.
The structure of the obtained polymer was analyzed by the same method as in Preparation Example A-3. As a result of IR measurement, the peak at 1695 cm ⁻¹ derived from the carboxylic acid decreased, and a new peak derived from the amide group was observed at 1658 cm ⁻¹ .
^From the result of ¹ H-NMR, since the peak derived from the aromatic ring of 3-aminobenzenesulfonic acid structure is shifted, the obtained polymer has a unit represented by the following chemical formula (75) as a monomer unit. It was confirmed to be a polyhydroxyalkanoate containing.

Further, it was confirmed that the unit of the polyhydroxyalkanoate represented by the chemical formula (75) was a copolymer of 11 mol% for the E unit and 89 mol% for the F unit.
The average molecular weight of the obtained polymer was evaluated by the same method as in Preparation Example A-3. As a result, the number average molecular weight M _n = 32600 and the weight average molecular weight M _w = 59000. A series of preparation methods were scaled up, and a large amount of polyhydroxyalkanoate represented by the chemical formula (75) was obtained to give Exemplified Compound N.

(Preparation Example O-1)
[Polyester Synthesis Using 3- (2-propenyl) -2-oxepanone represented by Chemical Formula (76) and L-lactide]

3- (2-propenyl) -2-oxepanone represented by the chemical formula (76) 0.31 g (2.0 mmol), L-lactide 1.44 g (10.0 mmol), 0.01 M tin octylate (2-ethyl) 4.8 ml of tin hexanoate in toluene solution and 4.8 ml of 0.01M p-tert-butylbenzyl alcohol in toluene were charged into the polymerization ampule, and then the polymer was prepared in the same manner as in Preparation Example A-1. 1.32 g was obtained.
As a result of conducting NMR analysis under the same conditions as in Preparation Example A-1 to specify the structure of the obtained polymer, a polyhydroxyalkanoate copolymer containing a unit represented by the following chemical formula (77) as a monomer unit It was confirmed that. Moreover, it was confirmed that the ratio of the monomer unit is 10 mol% of A unit and 90 mol% of B unit.

  Moreover, the average molecular weight of the obtained polyhydroxyalkanoate was evaluated by the same method as in Preparation Example A-1. As a result, the number average molecular weight was Mn = 132000, and the weight average molecular weight was Mw = 220400.

(Preparation Example O-2)
Oxidation reaction of polyhydroxyalkanoate composed of unit represented by chemical formula (77) synthesized in Preparation Example O-1

0.50 g of a polyhydroxyalkanoate copolymer (A: 10 mol%, B: 90 mol%) comprising the unit represented by the chemical formula (77) obtained in Preparation Example O-1 was added to an eggplant flask, and 30 ml of acetone was added. In addition, it was dissolved. This was placed in an ice bath, 5 ml of acetic acid and 0.45 g of 18-crown-6-ether were added and stirred. Next, 0.36 g 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, 0.44 g of polymer was obtained by the same method as in Preparation Example A-2.
As a result of conducting NMR analysis under the same conditions as in Preparation Example A-1 to identify the structure of the obtained polymer, it is a polyhydroxyalkanoate containing a unit represented by the following chemical formula (78) as a monomer unit. Was confirmed.

Moreover, the average molecular weight of the obtained polyhydroxyalkanoate was evaluated by the same method as in Preparation Example A-1. As a result, the number average molecular weight was Mn = 115400, and the weight average molecular weight was Mw = 202000.
Further, in order to calculate the unit of the obtained polyhydroxyalkanoate, 28 mg of the polyhydroxyalkanoate obtained by the same method as in Preparation Example A-2 was subjected to NMR analysis using the same method as in Preparation Example A-1. went. As a result, it was confirmed that the unit of the polyhydroxyalkanoate represented by the chemical formula (78) was a copolymer of 9 mol% for the C unit and 91 mol% for the D unit.

(Preparation Example O-3)
Condensation reaction of polyhydroxyalkanoate comprising unit represented by chemical formula (78) synthesized in Preparation Example O-2 and p-toluidine-2-sulfonic acid

Under nitrogen atmosphere, 0.40 g of polyhydroxyalkanoate copolymer (C: 9 mol%, D: 91 mol%) composed of the unit represented by chemical formula (78) obtained in Preparation Example O-2, p-toluidine-2 -0.41 g of sulfonic acid was put in a 100 ml three-necked flask, 15.0 ml of pyridine was added and stirred, 1.16 ml of triphenyl phosphite was added, and the mixture was heated at 120 ° C for 6 hours. After completion of the reaction, 0.36 g of polymer was obtained in the same manner as in Preparation Example A-3.
The structure of the obtained polymer was analyzed by the same method as in Preparation Example A-3. As a result of IR measurement, the peak at 1695 cm ⁻¹ derived from the carboxylic acid decreased, and a new peak derived from the amide group was observed at 1658 cm ⁻¹ .
^From the result of ¹ H-NMR, since the peak derived from the aromatic ring having a p-toluidine-2-sulfonic acid structure is shifted, the obtained polymer is represented by the following chemical formula (79) as a monomer unit. It was confirmed to be a polyhydroxyalkanoate containing unit.

Further, it was confirmed that the unit of the polyhydroxyalkanoate represented by the chemical formula (79) was a copolymer of 9 mol% for the E unit and 91 mol% for the F unit.
The average molecular weight of the obtained polymer was evaluated by the same method as in Preparation Example A-3. As a result, the number average molecular weight M _n = 98500 and the weight average molecular weight M _w = 176300. A series of preparation methods were scaled up, and a large amount of polyhydroxyalkanoate represented by the chemical formula (79) was obtained to give Exemplified Compound O.

(Preparation Example P-1)
[Polyester synthesis using tetrahydro-4- (2-propenyl) -2H-pyran-2-one and L-lactide]
Tetrahydro-4- (2-propenyl) -2H-pyran-2-one 0.28 g (2.0 mmol), L-lactide 1.44 g (10.0 mmol), 0.01 M tin octylate (2-ethylhexane) 4.8 ml of toluene solution of tin oxide) and 4.8 ml of toluene solution of 0.01 M p-tert-butylbenzyl alcohol were charged into the polymerization ampule, and then polymer 1 was prepared in the same manner as in Preparation Example A-1. .19 g was obtained.
As a result of conducting NMR analysis under the same conditions as in Preparation Example A-1 to specify the structure of the obtained polymer, a polyhydroxyalkanoate copolymer containing a unit represented by the following chemical formula (80) as a monomer unit It was confirmed that. Moreover, it was confirmed that the ratio of the monomer unit is A unit 7 mol% and B unit 93 mol%.

  Moreover, the average molecular weight of the obtained polyhydroxyalkanoate was evaluated by the same method as in Preparation Example A-1. As a result, the number average molecular weight was Mn = 21,500, and the weight average molecular weight was Mw = 29900.

(Preparation Example P-2)
Oxidation reaction of polyhydroxyalkanoate composed of unit represented by chemical formula (80) synthesized in Preparation Example P-1

0.50 g of a polyhydroxyalkanoate copolymer (A: 7 mol%, B: 93 mol%) comprising the unit represented by the chemical formula (80) obtained in Preparation Example P-1 was added to an eggplant flask, and 30 ml of acetone was added. In addition, it was dissolved. This was placed in an ice bath, 5 ml of acetic acid and 0.36 g of 18-crown-6-ether were added and stirred. Next, 0.28 g of potassium permanganate was slowly added in an ice bath, stirred for 2 hours in an ice bath, and further stirred at room temperature for 18 hours. After completion of the reaction, 0.43 g of polymer was obtained in the same manner as in Preparation Example A-2.
As a result of conducting NMR analysis under the same conditions as in Preparation Example A-1 to specify the structure of the obtained polymer, it is a polyhydroxyalkanoate containing a unit represented by the following chemical formula (81) as a monomer unit. Was confirmed.

Moreover, the average molecular weight of the obtained polyhydroxyalkanoate was evaluated by the same method as in Preparation Example A-1. As a result, the number average molecular weight was Mn = 17400, and the weight average molecular weight was Mw = 23800.
Furthermore, in order to calculate the unit of the obtained polyhydroxyalkanoate, 30 mg of the polyhydroxyalkanoate obtained by the same method as in Preparation Example A-2 was subjected to NMR analysis using the same method as in Preparation Example A-1. went. As a result, it was confirmed that the unit of the polyhydroxyalkanoate represented by the chemical formula (81) was a copolymer in which the C unit was 7 mol% and the D unit was 93 mol%.
A series of preparation methods were scaled up, and a large amount of polyhydroxyalkanoate represented by the chemical formula (81) was obtained to give Exemplified Compound P.

(Preparation Example Q-1)
[Polyester synthesis using tetrahydro-4- (2-propenyl) -2H-pyran-2-one and mandelide (3,6-diphenyl-1,4-dioxane-2,5-dione)]
Tetrahydro-4- (2-propenyl) -2H-pyran-2-one 0.28 g (2.0 mmol), mandelide 2.68 g (10.0 mmol), 0.01 M tin octylate (tin 2-ethylhexanoate) ) In toluene solution (4.8 ml) and 0.01 M p-tert-butylbenzyl alcohol in toluene (4.8 ml) were charged into a polymerization ampule, and then 1.79 g of polymer was prepared in the same manner as in Preparation Example A-1. Obtained.
As a result of conducting NMR analysis under the same conditions as in Preparation Example A-1 to specify the structure of the obtained polymer, a polyhydroxyalkanoate copolymer containing a unit represented by the following chemical formula (82) as a monomer unit It was confirmed that. Moreover, it was confirmed that the ratio of the monomer unit is 10 mol% of A unit and 90 mol% of B unit.

  Moreover, the average molecular weight of the obtained polyhydroxyalkanoate was evaluated by the same method as in Preparation Example A-1. As a result, the number average molecular weight was Mn = 18700, and the weight average molecular weight was Mw = 28800.

(Preparation Example Q-2)
Oxidation reaction of polyhydroxyalkanoate composed of unit represented by chemical formula (82) synthesized in Preparation Example Q-1

0.50 g of a polyhydroxyalkanoate copolymer (A: 10 mol%, B: 90 mol%) comprising the unit represented by the chemical formula (82) obtained in Preparation Example Q-1 was added to an eggplant flask, and 30 ml of acetone was added. In addition, it was dissolved. This was placed in an ice bath, 5 ml of acetic acid and 0.29 g of 18-crown-6-ether were added and stirred. Next, 0.23 g 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, 0.41 g of polymer was obtained by the same method as in Preparation Example A-2.
As a result of conducting NMR analysis under the same conditions as in Preparation Example A-1 to identify the structure of the obtained polymer, it is a polyhydroxyalkanoate containing a unit represented by the following chemical formula (83) as a monomer unit. Was confirmed.

Moreover, the average molecular weight of the obtained polyhydroxyalkanoate was evaluated by the same method as in Preparation Example A-1. As a result, the number average molecular weight was Mn = 15500, and the weight average molecular weight was Mw = 20300.
Further, in order to calculate the unit of the obtained polyhydroxyalkanoate, 28 mg of the polyhydroxyalkanoate obtained by the same method as in Preparation Example A-2 was subjected to NMR analysis using the same method as in Preparation Example A-1. went. As a result, it was confirmed that the unit of the polyhydroxyalkanoate represented by the chemical formula (83) was a copolymer of 10 mol% for the C unit and 90 mol% for the D unit.

(Preparation Example Q-3)
Condensation reaction of polyhydroxyalkanoate composed of the unit represented by chemical formula (83) synthesized in Preparation Example Q-2 and 3-aminobenzenesulfonic acid

Under a nitrogen atmosphere, 0.40 g of a polyhydroxyalkanoate copolymer (C: 10 mol%, D: 90 mol%) composed of the unit represented by the chemical formula (83) obtained in Preparation Example Q-2, 3-aminobenzenesulfone 0.25 g of acid was placed in a 100 ml three-necked flask, 15.0 ml of pyridine was added and stirred, 0.76 ml of triphenyl phosphite was added, and the mixture was heated at 120 ° C. for 6 hours. After completion of the reaction, 0.33 g of polymer was obtained in the same manner as in Preparation Example A-3.
The structure of the obtained polymer was analyzed by the same method as in Preparation Example A-3. As a result of IR measurement, the peak at 1695 cm ⁻¹ derived from the carboxylic acid decreased, and a new peak derived from the amide group was observed at 1658 cm ⁻¹ .
^From the result of ¹ H-NMR, since the peak derived from the aromatic ring of 3-aminobenzenesulfonic acid structure is shifted, the obtained polymer has a unit represented by the following chemical formula (84) as a monomer unit. It was confirmed to be a polyhydroxyalkanoate containing.

Further, it was confirmed that the unit of polyhydroxyalkanoate represented by the chemical formula (84) was a copolymer of 10 mol% for the E unit and 90 mol% for the F unit.
The average molecular weight of the obtained polymer was evaluated by the same method as in Preparation Example A-3. As a result, the number average molecular weight M _n = 13100 and the weight average molecular weight M _w = 17700. A series of preparation methods were scaled up to obtain a large amount of polyhydroxyalkanoate represented by the chemical formula (84) to give Exemplified Compound Q.

(Preparation Example R-1)
[Polyester synthesis using 7-oxo-3-oxepanecarboxylic acid phenylmethyl ester represented by chemical formula (85) and ε-caprolactone]

7-oxo-3-oxepanecarboxylic acid phenylmethyl ester represented by the chemical formula (85) 0.50 g (2.0 mmol), ε-caprolactone 1.14 g (10.0 mmol), 0.01 M tin octylate (2 -Tin ethylhexanoate) 4.8 ml, 0.01 M p-tert-butylbenzyl alcohol toluene solution 4.8 ml was charged into the polymerization ampule, and thereafter, in the same manner as in Preparation Example A-1. 1.23 g of polymer was obtained.
As a result of conducting NMR analysis under the same conditions as in Preparation Example A-1 to specify the structure of the obtained polymer, a polyhydroxyalkanoate copolymer containing a unit represented by the following chemical formula (86) as a monomer unit It was confirmed that. Moreover, it was confirmed that the ratio of the monomer unit is 14 mol% of A unit and 86 mol% of B unit.

  Moreover, the average molecular weight of the obtained polyhydroxyalkanoate was evaluated by the same method as in Preparation Example A-1. As a result, the number average molecular weight was Mn = 12000 and the weight average molecular weight was Mw = 16000.

(Preparation Example R-2)
1.00 g of the polyhydroxyalkanoate copolymer represented by the chemical formula (86) obtained in Preparation Example R-1 was dissolved in 100 ml of a mixed solvent of dioxane-ethanol (75:25), and 5% palladium / carbon was added thereto. 0.22 g of catalyst was added, the reaction system was filled with hydrogen, and the mixture was stirred at room temperature for 1 day. After the reaction, in order to remove the catalyst, the reaction solution was collected by filtration through a 0.25 μm membrane filter. The solution was concentrated, dissolved in chloroform, and reprecipitated in 10 times the amount of methanol. The obtained polymer was collected and dried under reduced pressure to obtain 0.75 g of polymer.
As a result of conducting NMR analysis under the same conditions as in Preparation Example A-1 to identify the structure of the obtained polymer, a polyhydroxyalkanoate copolymer containing a unit represented by the following chemical formula (87) as a monomer unit It was confirmed that. Moreover, it was confirmed that the ratio of the monomer unit is C unit 14 mol% and D unit 86 mol%.

  The average molecular weight of the obtained polyhydroxyalkanoate 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 was Mn = 10600, and the weight average molecular weight was Mw = 14700.

(Preparation Example R-3)
Condensation reaction of polyhydroxyalkanoate comprising unit represented by chemical formula (87) synthesized in Preparation Example R-2 and 2-aminobenzenesulfonic acid

Under a nitrogen atmosphere, 0.40 g of a polyhydroxyalkanoate copolymer (C: 14 mol%, D: 86 mol%) composed of the unit represented by the chemical formula (87) obtained in Preparation Example R-2, 2-aminobenzenesulfone 0.40 g of acid was placed in a 100 ml three-necked flask, 15.0 ml of pyridine was added and stirred, 1.21 ml of triphenyl phosphite was added, and the mixture was heated at 120 ° C. for 6 hours. After completion of the reaction, 0.36 g of polymer was obtained in the same manner as in Preparation Example A-3.
The structure of the obtained polymer was analyzed by the same method as in Preparation Example A-3. As a result of IR measurement, the peak at 1695 cm ⁻¹ derived from the carboxylic acid decreased, and a new peak derived from the amide group was observed at 1658 cm ⁻¹ .
^From the result of ¹ H-NMR, since the peak derived from the aromatic ring of 2-aminobenzenesulfonic acid structure is shifted, the obtained polymer has a unit represented by the following chemical formula (88) as a monomer unit. It was confirmed to be a polyhydroxyalkanoate containing.

Further, it was confirmed that the unit of the polyhydroxyalkanoate represented by the chemical formula (88) was a copolymer of 14 mol% for the E unit and 86 mol% for the F unit.
The average molecular weight of the obtained polymer was evaluated by the same method as in Preparation Example A-3. As a result, the number average molecular weight M _n = 9400 and the weight average molecular weight M _w = 13400. A series of preparation methods were scaled up, and a large amount of polyhydroxyalkanoate represented by the chemical formula (88) was obtained to give Exemplified Compound R.

(Preparation Example S-1)
[Polyester synthesis using 7-oxo-4-oxepanecarboxylic acid phenylmethyl ester represented by chemical formula (89) and ε-caprolactone]

  7-oxo-4-oxepanecarboxylic acid phenylmethyl ester represented by the chemical formula (89) 2.48 g (10.0 mmol), L-lactide 7.21 g (50.0 mmol), 0.1 M tin octylate (2 -Tin ethylhexanoate) 2.4 ml, 0.1 M p-tert-butylbenzyl alcohol in toluene 2.4 ml was charged into the polymerization ampule, and thereafter, in the same manner as in Preparation Example A-1. 7.08 g of polymer was obtained. As a result of conducting NMR analysis under the same conditions as in Preparation Example A-1 to specify the structure of the obtained polymer, a polyhydroxyalkanoate copolymer containing a unit represented by the following chemical formula (90) as a monomer unit It was confirmed that. Moreover, it was confirmed that the ratio of the monomer unit is 8 mol% A unit and 92 mol% B unit.

  Moreover, the average molecular weight of the obtained polyhydroxyalkanoate was evaluated by the same method as in Preparation Example A-1. As a result, the number average molecular weight was Mn = 10300, and the weight average molecular weight was Mw = 14800.

(Preparation Example S-2)
5.00 g of the polyhydroxyalkanoate copolymer represented by the chemical formula (90) obtained in Preparation Example S-1 was dissolved in 500 ml of a mixed solvent of dioxane-ethanol (75:25), and 5% palladium / carbon was added thereto. 1.10 g of catalyst was added, the reaction system was filled with hydrogen, and the mixture was stirred at room temperature for 1 day. After completion of the reaction, 3.70 g of polymer was obtained in the same manner as in Preparation Example R-2.
As a result of conducting NMR analysis under the same conditions as in Preparation Example A-1 to specify the structure of the obtained polymer, a polyhydroxyalkanoate copolymer containing a unit represented by the following chemical formula (91) as a monomer unit It was confirmed that. Moreover, it was confirmed that the ratio of the monomer unit is C unit 8 mol% and D unit 92 mol%.

  The average molecular weight of the obtained polyhydroxyalkanoate 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 was Mn = 9500, and the weight average molecular weight was Mw = 1900.

(Preparation Example S-3)
Condensation reaction of polyhydroxyalkanoate comprising unit represented by chemical formula (91) synthesized in Preparation Example S-2 and 1-naphthylamine-8-sulfonic acid

Under a nitrogen atmosphere, 0.40 g of a polyhydroxyalkanoate copolymer (C: 8 mol%, D: 92 mol%) composed of the unit represented by the chemical formula (91) obtained in Preparation Example S-2, 1-naphthylamine-8 -0.45 g of sulfonic acid was put in a 100 ml three-necked flask, 15.0 ml of pyridine was added and stirred, then 1.06 ml of triphenyl phosphite was added, and the mixture was heated at 120 ° C for 6 hours. After completion of the reaction, 0.33 g of polymer was obtained in the same manner as in Preparation Example A-3.
The structure of the obtained polymer was analyzed by the same method as in Preparation Example A-3. As a result of IR measurement, the peak at 1695 cm ⁻¹ derived from the carboxylic acid decreased, and a new peak derived from the amide group was observed at 1658 cm ⁻¹ .
^From the result of ¹ H-NMR, since the peak derived from the aromatic ring having a 1-naphthylamine-8-sulfonic acid structure is shifted, the obtained polymer is represented by the following chemical formula (92) as a monomer unit. It was confirmed to be a polyhydroxyalkanoate containing unit.

Further, it was confirmed that the units of the polyhydroxyalkanoate represented by the chemical formula (92) were 8 mol% of the E unit and 92 mol% of the F unit.
The average molecular weight of the obtained polymer was evaluated by the same method as in Preparation Example A-1. As a result, the number average molecular weight M _n = 8200 and the weight average molecular weight M _w = 12400.

(Preparation Example S-4)
Esterification reaction of polyhydroxyalkanoate composed of unit represented by chemical formula (92) synthesized in Preparation Example S-3

To the eggplant flask, 0.30 g of a polyhydroxyalkanoate copolymer (E: 8 mol%, F: 92 mol%) composed of the unit represented by the chemical formula (92) obtained in Preparation Example S-3 was added. It melt | dissolved by adding 0 ml and methanol 7.0 ml, and cooled to 0 degreeC. To this, 1.34 ml of a 2 mol / L trimethylsilyldiazomethane-hexane solution (manufactured by Aldrich) was added and stirred for 4 hours. After completion of the reaction, 0.30 g of polymer was obtained in the same manner as in Preparation Example A-4.
The structure of the obtained polymer was determined by the same method as in Preparation Example A-4. ^From the result of ¹ H-NMR, since a peak derived from methyl sulfonate is observed at 3 to 4 ppm, the obtained polymer is a polyhydroxyalkanoate containing a unit represented by the following chemical formula (93) as a monomer unit. It was confirmed that.

Further, it was confirmed that the unit of the polyhydroxyalkanoate represented by the chemical formula (93) was a copolymer of 8 mol% for the G unit and 92 mol% for the H unit.
In addition, it was clear that the sulfonic acid was methyl sulfonate because no peak derived from sulfonic acid was observed by acid value titration using potentiometric titrator AT510 (manufactured by Kyoto Electronics; product name). Became.
The average molecular weight of the obtained polymer was evaluated by the same method as in Preparation Example A-1. As a result, the number average molecular weight M _n = 7500 and the weight average molecular weight M _w = 11400. A series of preparation methods were scaled up, and a large amount of polyhydroxyalkanoate represented by chemical formula (93) was obtained to give Exemplified Compound S.

(Preparation Example T-1)
[Synthesis of Polyester Using Tetrahydro-6-oxo-2H-pyran-3-carboxylic acid phenylmethyl ester represented by Chemical Formula (94) and Mandelide]

Tetrahydro-6-oxo-2H-pyran-3-carboxylic acid phenylmethyl ester represented by the chemical formula (94) 0.47 g (2.0 mmol), mandelide 2.68 g (10.0 mmol), 0.01 M tin octylate (Toluene solution of 2-ethylhexanoate) 4.8 ml, 0.01 M p-tert-butylbenzyl alcohol toluene solution 4.8 ml was charged into a polymerization ampule, and then the same as in Preparation Example A-1 2.06 g of polymer was obtained by the method.
As a result of conducting NMR analysis under the same conditions as in Preparation Example A-1 to identify the structure of the obtained polymer, a polyhydroxyalkanoate copolymer containing a unit represented by the following chemical formula (95) as a monomer unit It was confirmed that. Moreover, it was confirmed that the ratio of the monomer unit is A unit 7 mol% and B unit 93 mol%.

  Moreover, the average molecular weight of the obtained polyhydroxyalkanoate was evaluated by the same method as in Preparation Example A-1. As a result, the number average molecular weight was Mn = 12000 and the weight average molecular weight was Mw = 16000.

(Preparation Example T-2)
1.00 g of the polyhydroxyalkanoate copolymer represented by the chemical formula (95) obtained in Preparation Example T-1 was dissolved in 100 ml of a mixed solvent of dioxane-ethanol (75:25), and 5% palladium / carbon was added thereto. 0.22 g of catalyst was added, the reaction system was filled with hydrogen, and the mixture was stirred at room temperature for 1 day. After completion of the reaction, 0.73 g of polymer was obtained by the same method as in Preparation Example R-2.
As a result of conducting NMR analysis under the same conditions as in Preparation Example A-1 to specify the structure of the obtained polymer, a polyhydroxyalkanoate copolymer containing a unit represented by the following chemical formula (96) as a monomer unit It was confirmed that. Moreover, it was confirmed that the ratio of the monomer unit is C unit 7 mol% and D unit 93 mol%.

  The average molecular weight of the obtained polyhydroxyalkanoate 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 was Mn = 8700, and the weight average molecular weight was Mw = 1900.

(Preparation Example T-3)
Condensation reaction of polyhydroxyalkanoate comprising unit represented by chemical formula (96) synthesized in Preparation Example T-2 and 4-methoxyaniline-2-sulfonic acid

In a nitrogen atmosphere, 0.40 g of a polyhydroxyalkanoate copolymer (C: 7 mol%, D: 93 mol%) composed of the unit represented by the chemical formula (96) obtained in Preparation Example T-2, 4-methoxyaniline- After putting 0.21 g of 2-sulfonic acid into a 100 ml three-necked flask, adding 15.0 ml of pyridine and stirring, 0.54 ml of triphenyl phosphite was added and heated at 120 ° C. for 6 hours. After completion of the reaction, 0.32 g of polymer was obtained in the same manner as in Preparation Example A-3.
The structure of the obtained polymer was analyzed by the same method as in Preparation Example A-3. As a result of IR measurement, the peak at 1695 cm ⁻¹ derived from the carboxylic acid decreased, and a new peak derived from the amide group was observed at 1658 cm ⁻¹ .
^From the result of ¹ H-NMR, since the peak derived from the aromatic ring having a 4-methoxyaniline-2-sulfonic acid structure is shifted, the obtained polymer is represented by the following chemical formula (97) as a monomer unit. It was confirmed that this was a polyhydroxyalkanoate containing unit.

Further, it was confirmed that the unit of polyhydroxyalkanoate represented by the chemical formula (97) was a copolymer of 7 mol% for E unit and 93 mol% for F unit.
The average molecular weight of the obtained polymer was evaluated by the same method as in Preparation Example A-1. As a result, the number average molecular weight M _n = 6900 and the weight average molecular weight M _w = 10100. A series of preparation methods were scaled up, and a large amount of polyhydroxyalkanoate represented by the chemical formula (97) was obtained to give Exemplified Compound T.

(Preparation Example 2A-1)
[Synthesis of L-3- (2-benzyloxycarbonyl) ethyl-1,4-dioxane-2,5-dione represented by the chemical formula (98)]

A crude product containing a compound represented by the chemical formula (99) in which 20 g of L-glutamic acid was dissolved in 200 ml of 80% sulfuric acid and 500 g of benzyl alcohol was added and reacted while maintaining at 70 ° C. to protect the carboxyl group at the γ-position. Obtained. 100 g of this crude product was added to 1400 ml of 1N sulfuric acid, and while stirring at 0 to 5 ° C., 100 ml of an aqueous solution containing 45.2 g of sodium nitrite was dropped over about 3 hours, and stirring was continued for 30 minutes. Further, 30 ml of an aqueous solution containing 9.4 g of sodium nitrite was dropped over about 30 minutes and left at room temperature overnight. The mixture was extracted with ether, the extract was dried over sodium sulfate, concentrated, and the remaining crude crystals were purified by silica gel column chromatography and recrystallization to obtain the compound represented by the chemical formula (100). 20 g of this compound and 17.4 g of bromoacetyl chloride were dissolved in 300 ml of ether, cooled to 5 ° C. or less, and 50 ml of an ether solution containing 9.5 g of 1.1-fold molar amount of triethylamine was added dropwise over 30 minutes. The reaction mixture was further stirred at room temperature for 6 hours, filtered, 50 ml of water was added to the filtrate, and the mixture was stirred for 30 minutes. Water was added several times for liquid separation, sodium sulfate was added to the ether layer, dried, and concentrated to obtain 28.3 g of the compound represented by the chemical formula (101). The yield was 94%.
A compound represented by the chemical formula (101), 10 g of DMF in 50 ml, was dropped into a DMF in 950 ml (heterogeneous solution) in 3.6 g of sodium hydrogencarbonate at room temperature over about 8 hours. The mixture was further reacted at the same temperature for 12 hours, filtered, DMF was concentrated, and the residue was washed with 50 ml of isopropanol. After filtration, the obtained white powder was dissolved in 200 ml of acetone, insoluble matter was removed by filtration, and the filtrate was concentrated. The residue was washed with a small amount of isopropanol, filtered and dried thoroughly. This white powder was sublimated and recrystallized from 400 ml of isopropanol to give 1.9 g of L-3- (2-benzyloxycarbonyl) ethyl-1,4-dioxane-2,5-dione represented by the chemical formula (98) ( Yield 24%).

(Preparation Example 2A-2)
[L-3- (2-Benzyloxycarbonyl) ethyl-1,4-dioxane-2,5-dione represented by the chemical formula (98) and phenyl lactide (3,6-bis (phenylmethyl) -1,4- Polyester synthesis using dioxane-2,5-dione)
L-3- (2-benzyloxycarbonyl) ethyl-1,4-dioxane-2,5-dione represented by the chemical formula (98) synthesized in Preparation Example 2A-1 0.56 g (2.0 mmol), phenyl lactide Polymerization of 2.96 g (10.0 mmol), 0.01 M tin octylate (tin tin 2-ethylhexanoate) 4.8 ml, 0.01 M p-tert-butylbenzyl alcohol toluene solution 4.8 ml The ampule was charged, dried under reduced pressure for 1 hour and purged with nitrogen, then sealed under reduced pressure and heated to 180 ° C. to perform ring-opening polymerization. The reaction was terminated after 2 hours and cooled. The obtained polymer was dissolved in chloroform and reprecipitated in 10 times the amount of chloroform required for dissolution. The precipitate was collected and dried under reduced pressure to obtain 2.98 g. As a result of conducting NMR analysis under the same conditions as in Preparation Example A-1 to identify the structure of the obtained polymer, a polyhydroxyalkanoate copolymer containing a unit represented by the following chemical formula (102) as a monomer unit It was confirmed that. Moreover, it was confirmed that the ratio of the monomer unit is 12 mol% of A unit and 88 mol% of B unit.

Moreover, the average molecular weight of the obtained polyhydroxyalkanoate was evaluated by the same method as in Preparation Example A-1. As a result, the number average molecular weight was Mn = 37500, and the weight average molecular weight was Mw = 53300.
1.00 g of the polyhydroxyalkanoate copolymer represented by the chemical formula (102) obtained here was dissolved in 100 ml of a mixed solvent of dioxane-ethanol (75:25), and 0.22 g of 5% palladium / carbon catalyst was added thereto. The reaction system was filled with hydrogen and stirred at room temperature for 1 day. After the reaction, in order to remove the catalyst, the reaction solution was collected by filtration through a 0.25 μm membrane filter. The solution was concentrated, dissolved in chloroform, and reprecipitated in 10 times the amount of methanol. The obtained polymer was collected and dried under reduced pressure to obtain 0.75 g of polymer. As a result of conducting NMR analysis under the same conditions as in Preparation Example A-1 to identify the structure of the obtained polymer, a polyhydroxyalkanoate copolymer containing a unit represented by the following chemical formula (103) as a monomer unit It was confirmed that. Moreover, it was confirmed that the ratio of the monomer unit is C unit 12 mol% and D unit 88 mol%.

  The average molecular weight of the obtained polyhydroxyalkanoate 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 was Mn = 31200, and the weight average molecular weight was Mw = 46800.

(Preparation Example 2A-3)
[Condensation reaction of polyhydroxyalkanoate comprising unit represented by chemical formula (103) synthesized in Preparation Example 2A-2 and 2-aminobenzenesulfonic acid]

0.40 g of a polymer synthesized with a polyhydroxyalkanoate copolymer (C: 12 mol%, D: 88 mol%) composed of the unit represented by the chemical formula (103) obtained in Preparation Example 2A-2 under a nitrogen atmosphere, After putting 0.27 g of 2-aminobenzenesulfonic acid in a 100 ml three-necked flask and adding 15.0 ml of pyridine and stirring, 0.82 ml of triphenyl phosphite was added and heated at 120 ° C. for 6 hours. After completion of the reaction, it was recovered by reprecipitation in 150 ml of ethanol. The obtained polymer was washed with 1N hydrochloric acid for 1 day, then washed by stirring in water for 1 day, and dried under reduced pressure to obtain 0.36 g of polymer. The structure of the obtained polymer was determined by 1H-NMR (FT-NMR: Bruker DPX400; resonance frequency: 400 MHz; measurement nuclide: 1H; solvent used: heavy DMSO; measurement temperature: room temperature), Fourier transform-infrared absorption (FT) -IR) The spectrum was analyzed (Nicolet AVATAR360FT-IR). As a result of IR measurement, the peak at 1695 cm −1 derived from the carboxylic acid decreased, and a new peak derived from the amide group was observed at 1658 cm −1.
From the result of 1H-NMR, since the peak derived from the aromatic ring having a 2-aminobenzenesulfonic acid structure is shifted, the obtained polymer contains a unit represented by the following chemical formula (104) as a monomer unit. It was confirmed to be a polyhydroxyalkanoate.

  Further, it was confirmed that the unit of the polyhydroxyalkanoate represented by the chemical formula (104) was a copolymer of 11 mol% for the E unit and 89 mol% for the F unit. The average molecular weight of the obtained polymer was gel permeation chromatography (GPC; Tosoh HLC-8120, column; Polymer Laboratories PLgel 5μ MIXED-C, solvent; DMF / LiBr 0.1% (w / v), polystyrene. (Conversion). As a result, the number average molecular weight Mn = 26800 and the weight average molecular weight Mw = 42900. A series of preparation methods were scaled up, and a large amount of polyhydroxyalkanoate represented by the chemical formula (104) was obtained to give Exemplified Compound 2A.

(Preparation Example 2B-1)
[Polyester synthesis using tetrahydro-3- (2-propenyl) -2H-pyran-2-one and phenyl lactide (3,6-bis (phenylmethyl) -1,4-dioxane-2,5-dione)]
Tetrahydro-3- (2-propenyl) -2H-pyran-2-one 0.28 g (2.0 mmol), phenyl lactide 2.96 g (10.0 mmol), 0.01 M tin octylate (2-ethylhexanoic acid) Tin) 4.8 ml of toluene solution and 4.8 ml of 0.01 M p-tert-butylbenzyl alcohol in toluene were charged into the polymerization ampule, and then the polymer was added in the same manner as in Preparation Example A-1. 06 g was obtained. As a result of conducting NMR analysis under the same conditions as in Preparation Example A-1 to specify the structure of the obtained polymer, a polyhydroxyalkanoate copolymer containing a unit represented by the following chemical formula (105) as a monomer unit It was confirmed that. Moreover, it was confirmed that the ratio of the monomer unit is 13 mol% of A unit and 87 mol% of B unit.

  Moreover, the average molecular weight of the obtained polyhydroxyalkanoate was evaluated by the same method as in Preparation Example A-1. As a result, the number average molecular weight Mn = 32000 and the weight average molecular weight Mw = 56000.

(Preparation Example 2B-2)
[Oxidation reaction of polyhydroxyalkanoate comprising unit represented by chemical formula (105) synthesized in Preparation Example 2B-1]

  0.50 g of a polyhydroxyalkanoate copolymer (A: 13 mol%, B: 87 mol%) comprising the unit represented by the chemical formula (105) obtained in Preparation Example 2B-1 was added to an eggplant flask, and 30 ml of acetone was added. In addition, it was dissolved. This was placed in an ice bath, 5 ml of acetic acid and 0.35 g of 18-crown-6-ether were added and stirred. Next, 0.28 g of potassium permanganate was slowly added in an ice bath, stirred for 2 hours in an ice bath, and further stirred at room temperature for 18 hours. After completion of the reaction, 0.45 g of polymer was obtained by the same method as in Preparation Example A-2. As a result of conducting NMR analysis under the same conditions as in Preparation Example A-1 to specify the structure of the obtained polymer, it is a polyhydroxyalkanoate containing a unit represented by the following chemical formula (106) as a monomer unit. Was confirmed.

Moreover, the average molecular weight of the obtained polyhydroxyalkanoate was evaluated by the same method as in Preparation Example A-1. As a result, the number average molecular weight Mn = 30100 and the weight average molecular weight Mw = 54200.
Furthermore, in order to calculate the unit of the obtained polyhydroxyalkanoate, 29 mg of the polyhydroxyalkanoate obtained by the same method as in Preparation Example A-2 was subjected to NMR analysis using the same method as in Preparation Example A-1. went. As a result, it was confirmed that the unit of the polyhydroxyalkanoate represented by the chemical formula (106) was a copolymer of 12 mol% for the C unit and 88 mol% for the D unit.

(Preparation Example 2B-3)
[Condensation reaction of polyhydroxyalkanoate comprising unit represented by chemical formula (106) synthesized in Preparation Example 2B-2 and 4-methoxyaniline-2-sulfonic acid]

Under a nitrogen atmosphere, 0.40 g of a polyhydroxyalkanoate copolymer (C: 12 mol%, D: 88 mol%) composed of the unit represented by the chemical formula (106) obtained in Preparation Example 2B-2, 4-methoxyaniline- After putting 0.33 g of 2-sulfonic acid into a 100 ml three-necked flask and adding 15.0 ml of pyridine and stirring, 0.84 ml of triphenyl phosphite was added and heated at 120 ° C. for 6 hours. After completion of the reaction, 0.33 g of polymer was obtained by the same method as in Preparation Example A-3. The structure of the obtained polymer was analyzed by the same method as in Preparation Example A-3. As a result of IR measurement, the peak at 1695 cm ⁻¹ derived from the carboxylic acid decreased, and a new peak derived from the amide group was observed at 1658 cm ⁻¹ . ^From the result of ¹ H-NMR, since the peak derived from the aromatic ring having a 4-methoxyaniline-2-sulfonic acid structure is shifted, the obtained polymer is represented by the following chemical formula (107) as a monomer unit. It was confirmed that this was a polyhydroxyalkanoate containing unit.

Further, it was confirmed that the unit of the polyhydroxyalkanoate represented by the chemical formula (107) was a copolymer of 11 mol% for the E unit and 89 mol% for the F unit. The average molecular weight of the obtained polymer was evaluated by the same method as in Preparation Example A-3. As a result, the number average molecular weight M _n = 29500 and the weight average molecular weight M _w = 53700. A series of preparation methods were scaled up to obtain a large amount of the polyhydroxyalkanoate represented by the chemical formula (107) to give Exemplified Compound 2B.

(Preparation Example 2C-1)
[Polyester synthesis using phenyl lactide]
Phenyl lactide 29.63 g (100.0 mmol), 0.1 M tin octylate (tin 2-ethylhexanoate) in toluene 4.0 ml, 0.1 M p-tert-butylbenzyl alcohol in toluene 4.0 ml Was placed in a polymerization ampule, dried under reduced pressure for 1 hour and purged with nitrogen, sealed under reduced pressure, and heated to 180 ° C. to perform ring-opening polymerization. The reaction was terminated after 10 hours and cooled. The obtained polymer was dissolved in chloroform and reprecipitated in 10 times the amount of chloroform required for dissolution. The precipitate was collected and dried under reduced pressure to obtain 24.00 g of polymer. In order to specify the structure of the obtained compound, 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 used: TMS / CDCl ₃
Measurement temperature: room temperature As a result, it was confirmed that the obtained compound was a polyhydroxyalkanoate containing a unit represented by the following chemical formula (108) as a monomer unit.

  The average molecular weight of the obtained polyhydroxyalkanoate 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 was Mn = 35000 and the weight average molecular weight was Mw = 49000.

(Preparation Example 2C-2)
10.00 g of polyhydroxyalkanoate composed of the unit represented by the chemical formula (108) obtained in Preparation Example 2C-1 was added to an eggplant flask, and 500 ml of THF was added and dissolved. This was placed under a nitrogen atmosphere and stirred at -78 ° C. Next, 33.75 ml (67.5 mmol) of 2M lithium diisopropylamide in THF was slowly added, and the mixture was stirred at −78 ° C. for 30 minutes. Next, after adding 11.58 g (130.5 mmol) of benzyl chloroformate, it stirred at room temperature for 30 minutes. After completion of the reaction, the reaction solution was poured into 1000 ml of an aqueous ammonium chloride solution, and 500 ml of dichloromethane was added to extract the organic layer. After washing with 250 ml of water three times, the organic layer was recovered. The crude polymer was recovered by distilling off the solvent. Next, it melt | dissolved in THF and reprecipitated in 50 times amount methanol of THF required for melt | dissolution. The precipitate was collected and dried under reduced pressure to obtain 8.03 g of a polymer. As a result of conducting NMR analysis under the same conditions as in Preparation Example 2C-1 to identify the structure of the obtained polymer, it is a polyhydroxyalkanoate containing a unit represented by the following chemical formula (109) as a monomer unit. Was confirmed. Moreover, it was confirmed that the ratio of the monomer unit is A unit 11 mol% and B unit 89 mol%.

The average molecular weight of the obtained polyhydroxyalkanoate 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 was Mn = 28500, and the weight average molecular weight was Mw = 41000.
5.00 g of the polyhydroxyalkanoate copolymer represented by the chemical formula (109) obtained here was dissolved in 500 ml of a mixed solvent of dioxane-ethanol (75:25), and 1.10 g of 5% palladium / carbon catalyst was dissolved therein. The reaction system was filled with hydrogen and stirred at room temperature for 1 day. After the reaction, in order to remove the catalyst, the reaction solution was collected by filtration through a 0.25 μm membrane filter. The solution was concentrated, dissolved in chloroform, and reprecipitated in 10 times the amount of methanol. The obtained polymer was collected and dried under reduced pressure to obtain 3.66 g of polymer. As a result of performing NMR analysis under the same conditions as in Preparation Example 2C-1 to identify the structure of the obtained polymer, a polyhydroxyalkanoate copolymer containing a unit represented by the following chemical formula (110) as a monomer unit It was confirmed that. Moreover, it was confirmed that the ratio of the monomer unit is C unit 11 mol% and D unit 89 mol%.

The average molecular weight of the obtained polyhydroxyalkanoate 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 was Mn = 2500 and the weight average molecular weight was Mw = 33800.
Further, 30 mg of the polyhydroxyalkanoate obtained here 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 0.5 ml of a 2 mol / L trimethylsilyldiazomethane-hexane solution, and the mixture was stirred at room temperature for 1 hour. After completion of the reaction, the solvent was distilled off and the polymer was recovered. The polymer was recovered after washing with 50 ml of methanol. 29 mg of polyhydroxyalkanoate was obtained by drying under reduced pressure.
The polyhydroxyalkanoate obtained here was subjected to NMR analysis using the same method as in Preparation Example 2C-1. As a result, it was confirmed that the carboxyl group of the C unit was carboxylic acid methyl ester, and it was confirmed that the obtained polymer could be esterified again.

(Preparation Example 2C-3)
0.40 g of a polyhydroxyalkanoate copolymer (C: 11 mol%, D: 89 mol%) composed of the unit represented by the chemical formula (110) obtained in Preparation Example 2C-2 under a nitrogen atmosphere, 2-aminobenzene Add 0.25 g (1.4 mmol) of sulfonic acid into a 100 ml three-necked flask, add 15.0 ml of pyridine, stir, add 0.75 ml (2.8 mmol) of triphenyl phosphite, and heat at 120 ° C. for 6 hours. did. After completion of the reaction, it was recovered by reprecipitation in 150 ml of ethanol. The obtained polymer was washed with 1N hydrochloric acid for 1 day, then washed by stirring in water for 1 day, and dried under reduced pressure to obtain 0.35 g of polymer. The structure of the obtained polymer was determined by ¹ H-NMR (FT-NMR: Bruker DPX400; resonance frequency: 400 MHz; measurement nuclide: ¹ H; solvent used: heavy DMSO; measurement temperature: room temperature), Fourier transform-infrared absorption Analysis was performed by (FT-IR) spectrum (Nicolet AVATAR360FT-IR). As a result of IR measurement, the peak at 1695 cm ⁻¹ derived from the carboxylic acid decreased, and a new peak derived from the amide group was observed at 1658 cm ⁻¹ .
^From the result of ¹ H-NMR, since the peak derived from the aromatic ring having a 2-aminobenzenesulfonic acid structure is shifted, the obtained polymer has a unit represented by the following chemical formula (111) as a monomer unit. It was confirmed to be a polyhydroxyalkanoate containing.

It was also confirmed that the polyhydroxyalkanoate unit represented by the chemical formula (111) was a copolymer containing 11 mol% of the E unit. The average molecular weight of the obtained polymer was gel permeation chromatography (GPC; Tosoh HLC-8120, column; Polymer Laboratories PLgel 5μ MIXED-C, solvent; DMF / LiBr 0.1% (w / v), polystyrene. (Conversion). As a result, the number average molecular weight M _n = 20500 and the weight average molecular weight M _w = 30800.

(Preparation Example 2C-4)
Add 0.30 g of the polyhydroxyalkanoate copolymer consisting of the unit represented by the chemical formula (111) obtained in Preparation Example 2C-3 to an eggplant flask, and dissolve by adding 21.0 ml of chloroform and 7.0 ml of methanol. And cooled to 0 ° C. To this was added 0.78 ml of a 2 mol / L trimethylsilyldiazomethane-hexane solution (manufactured by Aldrich), and the mixture was stirred for 4 hours. After completion of the reaction, the solvent was distilled off with an evaporator to recover the polymer. Further, 21.0 ml of chloroform and 7.0 ml of methanol were added to redissolve the polymer, and the solvent was distilled off by an evaporator. This operation was repeated three times. The polymer collected here was dried under reduced pressure to obtain 0.30 g of polymer. The structure of the obtained polymer was determined by ¹ H-NMR (FT-NMR: Bruker DPX400; resonance frequency: 400 MHz; measurement nuclide: ¹ H; solvent used: heavy DMSO; measurement temperature: room temperature). ^From the result of ¹ H-NMR, since a peak derived from methyl sulfonate is seen at 3 to 4 ppm, the obtained polymer is a polyhydroxyalkanoate containing a unit represented by the following chemical formula (112) as a monomer unit. It was confirmed that.

Further, it was confirmed that the polyhydroxyalkanoate unit represented by the chemical formula (112) contained 11 mol% of the G unit. In addition, the acid value titration using the potentiometric titrator AT510 (manufactured by Kyoto Electronics Co., Ltd.) revealed that the sulfonic acid was methyl sulfonate because no peak derived from sulfonic acid was observed. . The average molecular weight of the obtained polymer was determined by gel permeation chromatography (GPC; Tosoh HLC-8120, column; Polymer Laboratories PLgel 5μ MIXED-C, solvent: DMF / LiBr 0.1% (w / v), polystyrene. (Conversion). As a result, the number average molecular weight _Mn = 20000 and the weight average molecular weight _Mw = 30400. A series of preparation methods were scaled up to obtain a large amount of polyhydroxyalkanoate represented by the chemical formula (112) to give Exemplified Compound 2C.

(Preparation Example 2D-1)
Other than using 14.41 g (130.5 mmol) of ethyl 5-bromovalerate instead of benzyl chloroformate using the polyhydroxyalkanoate consisting of the unit represented by chemical formula (108) obtained in Preparation Example 2C-1. Produced 8.02 g of polymer in the same manner as in Preparation Example 2C-2. The obtained polymer was subjected to NMR analysis under the same conditions as in Preparation Example 2C-1, and as a result, was a polyhydroxyalkanoate containing a unit represented by the following chemical formula (113). It was confirmed that they were 8 mol% and B unit was 92 mol%.

Moreover, the average molecular weight of the obtained polyhydroxyalkanoate was measured under the same conditions as in Preparation Example 2C-1. As a result, the number average molecular weight Mn = 28500 and the weight average molecular weight Mw = 39600 were obtained.
The polymer was hydrocracked in the same manner as in Preparation Example 2C-2 to obtain 3.94 g of polymer. The obtained polymer was subjected to NMR analysis under the same conditions as in Preparation Example 2C-1. As a result, it was confirmed that the polymer was a polyhydroxyalkanoate copolymer containing a unit represented by the following chemical formula (114) as a monomer unit. It was done. Moreover, it was confirmed that the ratio of the monomer unit is C unit 8 mol% and D unit 92 mol%.

  Moreover, the average molecular weight of the obtained polyhydroxyalkanoate was measured under the same conditions as in Preparation Example 2C-1, and as a result, the number average molecular weight Mn = 24900 and the weight average molecular weight Mw = 35400.

(Preparation Example 2D-2)
Under a nitrogen atmosphere, 0.40 g of a polyhydroxyalkanoate copolymer (C: 8 mol%, D: 92 mol%) comprising the unit represented by the chemical formula (114) obtained in Preparation Example 2D-1 and 0.13 g of taurine (1.0 mmol) was placed in a 100 ml three-necked flask, 15.0 ml of pyridine was added and stirred, 0.53 ml (1.0 mmol) of triphenyl phosphite was added, and the same method as in Preparation Example A-3 was performed. 0.31 g of polymer was obtained. The obtained polymer was a polyhydroxyalkanoate containing a unit represented by the following chemical formula (115) as a result of performing NMR analysis and Fourier transform-infrared absorption spectrum analysis under the same conditions as in Preparation Example A-3. It was confirmed to be a copolymer containing 6 mol% of E units.

Moreover, the average molecular weight of the obtained polymer was measured under the same conditions as in Preparation Example A-3. As a result, the number average molecular weight M _n = 19800 and the weight average molecular weight M _w = 31700 were obtained. A series of preparation methods were scaled up to obtain a large amount of polyhydroxyalkanoate represented by the chemical formula (115) to give Exemplified Compound 2D.

(Preparation Example 2E-1)
[Polyester synthesis using L-lactide]
L-lactide 14.41 g (100.0 mmol), 0.1 M tin octylate (tin 2-ethylhexanoate) in toluene 4.0 ml, 0.1 M p-tert-butylbenzyl alcohol in toluene 4. 0 ml was charged into a polymerization ampule, dried under reduced pressure for 1 hour and purged with nitrogen, then sealed under reduced pressure and heated to 160 ° C. to perform ring-opening polymerization. The reaction was terminated after 10 hours and cooled. The obtained polymer was dissolved in chloroform and reprecipitated in 10 times the amount of chloroform required for dissolution. The precipitate was collected and dried under reduced pressure to obtain 12.68 g of polymer. As a result of conducting NMR analysis under the same conditions as in Preparation Example 2C-1 to identify the structure of the obtained polymer, it was confirmed that the polymer was a polyhydroxyalkanoate containing a unit represented by the following chemical formula (116). .

  Moreover, the average molecular weight of the obtained polyhydroxyalkanoate was measured under the same conditions as in Preparation Example 2C-1. As a result, the number average molecular weight Mn = 42800 and the weight average molecular weight Mw = 59100 were obtained.

(Preparation Example 2E-2)
10.00 g of polyhydroxyalkanoate composed of the unit represented by the chemical formula (116) obtained in Preparation Example 2E-1 was added to an eggplant flask, and 500 ml of THF was added and dissolved. This was placed under a nitrogen atmosphere and stirred at -78 ° C. Next, 69.38 ml (138.8 mmol) of 2M lithium diisopropylamide in THF was slowly added, and the mixture was stirred at −78 ° C. for 30 minutes. Next, 23.81 g (277.5 mmol) of benzyl chloroformate was added, and 9.55 g of a polymer was obtained in the same manner as in Preparation Example 2C-2. The obtained polymer was subjected to NMR analysis under the same conditions as in Preparation Example 2C-1, and as a result, was a polyhydroxyalkanoate containing a unit represented by the following chemical formula (117). It was confirmed that they were 12 mol% and B units were 88 mol%.

Moreover, the average molecular weight of the obtained polyhydroxyalkanoate was measured under the same conditions as in Preparation Example 2C-1. As a result, the number average molecular weight Mn = 32100 and the weight average molecular weight Mw = 46500.
The polymer was hydrocracked in the same manner as in Preparation Example 2C-2 to obtain 3.47 g of polymer. As a result of conducting NMR analysis under the same conditions as in Preparation Example 2C-1, the obtained polymer was confirmed to be a polyhydroxyalkanoate copolymer containing a unit represented by the following chemical formula (118) as a monomer unit. It was done. Moreover, it was confirmed that the ratio of the monomer unit is C unit 12 mol% and D unit 88 mol%.

  Moreover, the average molecular weight of the obtained polyhydroxyalkanoate was measured under the same conditions as in Preparation Example 2C-1. As a result, the number average molecular weight Mn = 30100 and the weight average molecular weight Mw = 45200.

(Preparation Example 2E-3)
In a nitrogen atmosphere, 0.40 g of 2-hydroxy-polyhydroxyalkanoate copolymer (C: 12 mol%, D: 88 mol%) composed of the unit represented by the chemical formula (118) obtained in Preparation Example 2E-2 was obtained. 0.69 g (3.1 mmol) of 1-naphthalenesulfonic acid was placed in a 100 ml three-necked flask, 15.0 ml of pyridine was added and stirred, and then 1.62 ml (6.2 mmol) of triphenyl phosphite was added, and Preparation Example 2C In the same manner as in -3, 0.37 g of polymer was obtained. The obtained polymer was a polyhydroxyalkanoate containing a unit represented by the following chemical formula (119) as a result of NMR analysis and Fourier transform-infrared absorption spectrum analysis under the same conditions as in Preparation Example 2C-3. It was confirmed that the copolymer contained 8 mol% of E units.

Further, the average molecular weight of the obtained polymer was measured under the same conditions as in Preparation Example 2C-3. As a result, the number average molecular weight M _n = 27200 and the weight average molecular weight M _w = 43000 were obtained.

(Preparation Example 2E-4)
Add 0.30 g of the polyhydroxyalkanoate copolymer consisting of the unit represented by the chemical formula (119) obtained in Preparation Example 2E-3 into the eggplant flask, and dissolve by adding 21.0 ml of chloroform and 7.0 ml of methanol. And cooled to 0 ° C. To this, 0.90 ml of a 2 mol / L trimethylsilyldiazomethane-hexane solution (manufactured by Aldrich) was added and stirred for 4 hours. After completion of the reaction, the solvent was distilled off with an evaporator to recover the polymer. Further, 21.0 ml of chloroform and 7.0 ml of methanol were added to redissolve the polymer, and the solvent was distilled off by an evaporator. This operation was repeated three times. The polymer collected here was dried under reduced pressure to obtain 0.30 g of polymer. The structure of the obtained polymer was determined by ¹ H-NMR (FT-NMR: Bruker DPX400; resonance frequency: 400 MHz; measurement nuclide: ¹ H; solvent used: heavy DMSO; measurement temperature: room temperature). ^From the result of ¹ H-NMR, since a peak derived from methyl sulfonate is seen at 3 to 4 ppm, the obtained polymer is a polyhydroxyalkanoate containing a unit represented by the following chemical formula (120) as a monomer unit. It was confirmed that.

Further, it was confirmed that the polyhydroxyalkanoate unit represented by the chemical formula (120) contained 8 mol% of the G unit. In addition, the acid value titration using the potentiometric titrator AT510 (manufactured by Kyoto Electronics Co., Ltd.) revealed that the sulfonic acid was methyl sulfonate because no peak derived from sulfonic acid was observed. . The average molecular weight of the obtained polymer was measured under the same conditions as in Preparation Example 2C-4. As a result, the number average molecular weight M _n = 27000 and the weight average molecular weight M _w = 43700 were obtained. A series of preparation methods were scaled up to obtain a large amount of the polyhydroxyalkanoate represented by the chemical formula (120) to obtain Exemplified Compound 2E.

(Preparation Example 2F-1)
Except for using 34.85 g (277.5 mmol) of ethyl 8-bromooctanoate instead of benzyl chloroformate, 8.63 g of polymer was obtained in the same manner as in Preparation Example 2E-2. The obtained polymer was subjected to NMR analysis under the same conditions as in Preparation Example 2C-1, and as a result, was a polyhydroxyalkanoate containing a unit represented by the following chemical formula (121). 7 mol% and B unit 93 mol% were confirmed.

Moreover, the average molecular weight of the obtained polyhydroxyalkanoate was measured under the same conditions as in Preparation Example 2C-1. As a result, the number average molecular weight Mn was 35500 and the weight average molecular weight Mw was 52500.
Further, the above polymer was subjected to hydrogenolysis in the same manner as in Preparation Example 2C-2 to obtain 4.10 g of a polymer. As a result of conducting NMR analysis under the same conditions as in Preparation Example 2C-1, the obtained polymer was confirmed to be a polyhydroxyalkanoate copolymer containing a unit represented by the following chemical formula (122) as a monomer unit. It was done. Moreover, it was confirmed that the ratio of the monomer unit is C unit 7 mol% and D unit 93 mol%.

  Moreover, the average molecular weight of the obtained polyhydroxyalkanoate was measured under the same conditions as in Preparation Example 2C-1. As a result, the number average molecular weight Mn = 31000 and the weight average molecular weight Mw = 48100 were obtained.

(Preparation Example 2F-2)
0.40 g of polyhydroxyalkanoate copolymer (C: 7 mol%, D: 93 mol%) composed of the unit represented by chemical formula (122) obtained in Preparation Example 2F-1 in a nitrogen atmosphere, 2-aminobenzene After adding 0.43 g (1.7 mmol) of sulfonic acid phenyl ester to a 100 ml three-necked flask, adding 15.0 ml of pyridine and stirring, 0.89 ml (3.4 mmol) of triphenyl phosphite was added, and Preparation Example 2C- In the same manner as in Example 3, 0.39 g of polymer was obtained. The obtained polymer was a polyhydroxyalkanoate containing a unit represented by the following chemical formula (123) as a result of NMR analysis and Fourier transform-infrared absorption spectrum analysis under the same conditions as in Preparation Example 2C-3. It was confirmed that the copolymer contained 7 mol% of E units.

Further, the average molecular weight of the obtained polymer was measured under the same conditions as in Preparation Example 2C-3. As a result, the number average molecular weight M _n = 27500 and the weight average molecular weight M _w = 44600 were obtained. A series of preparation methods were scaled up to obtain a large amount of polyhydroxyalkanoate represented by the chemical formula (123) to give Exemplified Compound 2F.

(Preparation Example 2G-1)
[Polyester synthesis using diisopropyl glycolide (3,6-diisopropyl-1,4-dioxane-2,5-dione)]
14.15 g of a polymer was obtained in the same manner as in Preparation Example 2E-1, except that 22.83 g (100.0 mmol) of diisopropyl glycolide was used instead of L-lactide. The obtained polymer was subjected to NMR analysis under the same conditions as in Preparation Example 2C-1, and as a result, it was confirmed that the polymer was a polyhydroxyalkanoate containing a unit represented by the following chemical formula (124).

  Moreover, the average molecular weight of the obtained polyhydroxyalkanoate was measured under the same conditions as in Preparation Example 2C-1. As a result, the number average molecular weight Mn = 32800 and the weight average molecular weight Mw = 48500.

(Preparation Example 2G-2)
10.00 g of polyhydroxyalkanoate consisting of the unit represented by the chemical formula (124) obtained in Preparation Example 2G-1 was added to an eggplant flask, and 500 ml of THF was added and dissolved. This was placed under a nitrogen atmosphere and stirred at -78 ° C. Next, 43.81 ml (87.6 mmol) of 2M lithium diisopropylamide in THF was slowly added, and the mixture was stirred at −78 ° C. for 30 minutes. Next, after adding 18.32 g (175.2 mmol) of ethyl 5-bromovalerate, 7.64 g of a polymer was obtained in the same manner as in Preparation Example 2C-2. The obtained polymer was subjected to NMR analysis under the same conditions as in Preparation Example 2C-1, and as a result, was a polyhydroxyalkanoate containing a unit represented by the following chemical formula (125). It was confirmed that they were 8 mol% and B unit was 92 mol%.

Further, the average molecular weight of the obtained polyhydroxyalkanoate was measured under the same conditions as in Preparation Example 2C-1, and as a result, the number average molecular weight Mn = 26500 and the weight average molecular weight Mw = 41100 were obtained.
Further, the above polymer was subjected to hydrogenolysis in the same manner as in Preparation Example 2C-2 to obtain 4.05 g of a polymer. As a result of conducting NMR analysis under the same conditions as in Preparation Example 2C-1, the obtained polymer was confirmed to be a polyhydroxyalkanoate copolymer containing a unit represented by the following chemical formula (126) as a monomer unit. It was done. Moreover, it was confirmed that the ratio of the monomer unit is C unit 11 mol% and D unit 89 mol%.

  Moreover, the average molecular weight of the obtained polyhydroxyalkanoate was measured under the same conditions as in Preparation Example 2C-1, and as a result, the number average molecular weight Mn = 2200 and the weight average molecular weight Mw = 33700 were obtained.

(Preparation Example 2G-3)
In a nitrogen atmosphere, 0.40 g of 2-hydroxy-polyhydroxyalkanoate copolymer (C: 11 mol%, D: 89 mol%) composed of the unit represented by chemical formula (126) obtained in Preparation Example 2G-2 was obtained. 2-methylpropanesulfonic acid 0.27 g (1.8 mmol) was placed in a 100 ml three-necked flask, 15.0 ml of pyridine was added and stirred, and then 0.92 ml (3.5 mmol) of triphenyl phosphite was added. In the same manner as in 2C-3, 0.33 g of a polymer was obtained. The obtained polymer was a polyhydroxyalkanoate containing a unit represented by the following chemical formula (127) as a result of NMR analysis and Fourier transform-infrared absorption spectrum analysis under the same conditions as in Preparation Example 2C-3. It was confirmed to be a copolymer containing 9 mol% of E units.

Moreover, the average molecular weight of the obtained polymer was measured under the same conditions as in Preparation Example 2C-3, and as a result, the number average molecular weight M _n = 20900 and the weight average molecular weight M _w = 35500 were obtained.

(Preparation Example 2G-4)
The polyhydroxyalkanoate represented by the chemical formula (127) obtained in Preparation Example 2G-3 was used in place of the polyhydroxyalkanoate represented by the chemical formula (111) in Preparation Example 2C-4, and 2 mol / L of trimethylsilyl was used. Except for using 0.70 ml of diazomethane-hexane solution (manufactured by Aldrich), 0.29 g of polymer was obtained by the same method as in Preparation Example 2C-4. The obtained polymer was subjected to NMR analysis under the same conditions as in Preparation Example 2C-4. As a result, the polymer was a polyhydroxyalkanoate containing a unit represented by the following chemical formula (128) and a copolymer containing 9 mol% of G unit. It was confirmed that.
Further, the acid value titration similar to that of Preparation Example 2C-4 revealed that no sulfonic acid-derived peak was observed, and that sulfonic acid was methyl sulfonate.

Further, the average molecular weight of the obtained polymer was measured under the same conditions as in Preparation Example 2C-4. As a result, the number average molecular weight M _n = 19500 and the weight average molecular weight M _w = 33200 were obtained. A series of preparation methods were scaled up, and a large amount of polyhydroxyalkanoate represented by the chemical formula (128) was obtained to give Exemplified Compound 2G.

(Preparation Example 2H-1)
[Polyester synthesis using hexyl glycolide (3,6-dihexyl-1,4-dioxane-2,5-dione)]
16.66 g of polymer was obtained in the same manner as in Preparation Example 2E-1, except that 25.63 g (100.0 mmol) of hexyl glycolide was used instead of L-lactide. As a result of conducting an NMR analysis under the same conditions as in Preparation Example 2C-1, the obtained polymer was confirmed to be a polyhydroxyalkanoate containing a unit represented by the following chemical formula (129).

  Moreover, the average molecular weight of the obtained polyhydroxyalkanoate was measured under the same conditions as in Preparation Example 2C-1. As a result, the number average molecular weight Mn = 28900 and the weight average molecular weight Mw = 42200.

(Preparation Example 2H-2)
10.00 g of a polyhydroxyalkanoate composed of a unit represented by the chemical formula (129) obtained in Preparation Example 2H-1 was added to an eggplant flask, and 500 ml of THF was added and dissolved. This was placed under a nitrogen atmosphere and stirred at -78 ° C. Next, 39.01 ml (78.0 mmol) of 2M lithium diisopropylamide in THF was slowly added and stirred at −78 ° C. for 30 minutes. Next, after adding 17.95 g (156.0 mmol) of benzyl bromoacetate, 8.40 g of a polymer was obtained in the same manner as in Preparation Example 2C-2. The obtained polymer was subjected to NMR analysis under the same conditions as in Preparation Example 2C-1, and as a result, was a polyhydroxyalkanoate containing a unit represented by the following chemical formula (130). 9 mol% and B unit 91 mol% were confirmed.

Moreover, the average molecular weight of the obtained polyhydroxyalkanoate was measured under the same conditions as in Preparation Example 2C-1. As a result, the number average molecular weight Mn = 23,000 and the weight average molecular weight Mw = 34500 were obtained.
Further, the above polymer was subjected to hydrogenolysis in the same manner as in Preparation Example 2C-2 to obtain 3.68 g of a polymer. As a result of conducting NMR analysis under the same conditions as in Preparation Example 2C-1, the obtained polymer was confirmed to be a polyhydroxyalkanoate copolymer containing a unit represented by the following chemical formula (131) as a monomer unit. It was done. Moreover, it was confirmed that the ratio of the monomer unit is 9 mol% for C unit and 91 mol% for D unit.

  Further, the average molecular weight of the obtained polyhydroxyalkanoate was measured under the same conditions as in Preparation Example 2C-1, and as a result, the number average molecular weight Mn = 19800 and the weight average molecular weight Mw = 30900.

(Preparation Example 2H-3)
0.40 g of a polyhydroxyalkanoate copolymer (C: 9 mol%, D: 91 mol%) composed of the unit represented by the chemical formula (131) obtained in Preparation Example 2H-2 under a nitrogen atmosphere, 2-aminobenzene Add 0.23 g (1.3 mmol) of sulfonic acid to a 100 ml three-necked flask, add 15.0 ml of pyridine and stir, then add 0.70 ml (1.3 mmol) of triphenyl phosphite, and Preparation Example 2C-3 0.35g of polymer was obtained by the same method. The resulting polymer was subjected to NMR analysis and Fourier transform-infrared absorption spectrum analysis under the same conditions as in Preparation Example 2C-3, and as a result, was a polyhydroxyalkanoate containing a unit represented by the following chemical formula (132). It was confirmed that the copolymer contained 8 mol% of E units.

The average molecular weight of the obtained polymer was measured under the same conditions as in Preparation Example 2C-3. As a result, the number average molecular weight M _n = 18900 and the weight average molecular weight M _w = 30400 were obtained. A series of preparation methods were scaled up, and a large amount of polyhydroxyalkanoate represented by the chemical formula (132) was obtained to give Exemplified Compound 2H.

(Preparation Example 2I-1)
2.00 g of a polyhydroxyalkanoate composed of the unit represented by the chemical formula (108) obtained in Preparation Example 2C-1 was added to an eggplant flask, and dissolved by adding 100 ml of THF. This was placed under a nitrogen atmosphere and stirred at -78 ° C. Next, 18.9 ml of 2M lithium diisopropylamide in THF was slowly added and stirred at −78 ° C. for 30 minutes. Next, after adding 5.91 g of methyl 2-acrylamido-2-methylpropanesulfonate, the mixture was stirred at room temperature for 30 minutes. After completion of the reaction, the reaction solution was poured into 400 ml of an aqueous ammonium chloride solution, and 200 ml of dichloromethane was added to extract the organic layer. After washing with 100 ml of water three times, the organic layer was recovered. The crude polymer was recovered by distilling off the solvent. Next, it melt | dissolved in THF and reprecipitated in 50 times amount methanol of THF required for melt | dissolution. The precipitate was collected and dried under reduced pressure to obtain 1.22 g of polymer. The structure of the obtained polymer was determined by ¹ H-NMR (FT-NMR: Bruker DPX400; resonance frequency: 400 MHz; measurement nuclide: ¹ H; solvent used: heavy DMSO; measurement temperature: room temperature). As a result, it was confirmed that the monomer unit was a polyhydroxyalkanoate containing a unit represented by the following chemical formula (133). Moreover, it was confirmed that the ratio of the monomer unit is E unit 7 mol% and F unit 93 mol%.

  Moreover, the average molecular weight of the obtained polyhydroxyalkanoate was measured under the same conditions as in Preparation Example 2C-4. As a result, the number average molecular weight Mn = 25500 and the weight average molecular weight Mw = 38200. A series of preparation methods were scaled up, and a large amount of polyhydroxyalkanoate represented by the chemical formula (133) was obtained to give Exemplified Compound 2I.

(Preparation Example 2J-1)
In this preparation example, polyhydroxyalkanoate is produced using microorganisms. The microorganism used in this preparation example is Ralstonia eutropha strain TB64 (Ralstonia eutropha TB64, disclosed in Japanese Patent Application Laid-Open No. 2000-166687). This microorganism is deposited in the Patent Organism Depositary, National Institute of Advanced Industrial Science and Technology.
Moreover, the inorganic salt medium (M9 medium) used in this preparation example has the following composition.
M9 medium composition (in 1 liter):
Na ₂ HPO ₄ 6.2g
KH ₂ PO ₄ 3.0g
NaCl 0.5g
NH ₄ Cl 1.0g
Water balance
(pH 7.0)
In addition, about 0.3% (volume / volume) of the following trace component solution is added to the above-mentioned inorganic salt medium for further microbial growth and polyhydroxyalkanoate production during culture. .

(Trace component solution composition: Unit g / L)
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

(Synthesis of poly-3-hydroxybutyric acid represented by chemical formula (134))

Poly-3-hydroxybutyric acid (PHB) represented by the chemical formula (134) was synthesized by the method disclosed in Example 1 of JP-A-2002-306190.
A colony of the TB64 strain on M9 agar medium containing 0.1% sodium malate was inoculated into 50 mL of M9 medium containing 0.5% sodium malate in a 500 mL shake flask and cultured at 30 ° C. with shaking. . After 24 hours, 5 mL of the culture solution was added to 1 L of production medium containing 0.5% sodium malate in M9 medium prepared with 1/10 concentration of only NH ₄ Cl as a nitrogen source, and shaken in the same manner. PHB was accumulated. After 48 hours, PHB-accumulating cells were harvested by centrifugation, washed with methanol after centrifugation, and then lyophilized. After weighing the dry cells, chloroform was added and the polymer was extracted by stirring at 60 ° C. for 24 hours. Chloroform from which the polymer was extracted was filtered and concentrated with an evaporator, and then the portion precipitated and solidified with cold methanol was collected and dried under reduced pressure to obtain 1.83 g of polymer per liter of production medium. In order to specify the structure of the obtained polymer, 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 used: TMS / CDCl ₃
Measurement temperature: room temperature As a result, it was confirmed to be a polyhydroxyalkanoate composed of units of 3-hydroxybutyric acid represented by chemical formula (134). The average molecular weight of the obtained polyhydroxyalkanoate 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 was Mn = 549500, and the weight average molecular weight was Mw = 1263900.
By the above method, 45.6 g of polyhydroxyalkanoate used in the following preparation examples was prepared from 50 L of the production medium.

(Preparation Example 2J-2)
10.00 g of a polyhydroxyalkanoate comprising the unit represented by the chemical formula (134) obtained in Preparation Example 2J-1 was added to an eggplant flask, and 500 ml of THF was added and dissolved. This was placed under a nitrogen atmosphere and stirred at -78 ° C. Next, 58.08 ml (116.2 mmol) of 2M lithium diisopropylamide in THF was slowly added and stirred at −78 ° C. for 30 minutes. Next, after adding 19.82 g (232.3 mmol) of benzyl chloroformate, the mixture was stirred at room temperature for 30 minutes. After completion of the reaction, the reaction solution was poured into 1000 ml of an aqueous ammonium chloride solution, and 500 ml of dichloromethane was added to extract the organic layer. After washing with 250 ml of water three times, the organic layer was recovered. The crude polymer was recovered by distilling off the solvent. Next, it melt | dissolved in THF and reprecipitated in 50 times amount methanol of THF required for melt | dissolution. The precipitate was collected and dried under reduced pressure to obtain 8.44 g of polymer. As a result of conducting NMR analysis under the same conditions as in Preparation Example 2J-1 to identify the structure of the obtained polymer, it is a polyhydroxyalkanoate containing a unit represented by the following chemical formula (135) as a monomer unit. Was confirmed. Moreover, it was confirmed that the ratio of the monomer unit is 10 mol% of A unit and 90 mol% of B unit.

The average molecular weight of the obtained polyhydroxyalkanoate 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 was Mn = 325400, and the weight average molecular weight was Mw = 764700.
5.00 g of the polyhydroxyalkanoate copolymer represented by the chemical formula (135) obtained here was dissolved in 500 ml of a mixed solvent of dioxane-ethanol (75:25), and 1.10 g of 5% palladium / carbon catalyst was dissolved therein. The reaction system was filled with hydrogen and stirred at room temperature for 1 day. After the reaction, in order to remove the catalyst, the reaction solution was collected by filtration through a 0.25 μm membrane filter. The solution was concentrated, dissolved in chloroform, and reprecipitated in 10 times the amount of methanol. The obtained polymer was collected and dried under reduced pressure to obtain 3.59 g of polymer. As a result of performing NMR analysis under the same conditions as in Preparation Example 2J-1 to identify the structure of the obtained polymer, a polyhydroxyalkanoate copolymer containing a unit represented by the following chemical formula (136) as a monomer unit It was confirmed that. Moreover, it was confirmed that the ratio of the monomer unit is 10 mol% for C unit and 90 mol% for D unit.

The average molecular weight of the obtained polyhydroxyalkanoate 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 was Mn = 298000, and the weight average molecular weight was Mw = 715200.
Further, 30 mg of the polyhydroxyalkanoate obtained here 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 0.5 ml of a 2 mol / L trimethylsilyldiazomethane-hexane solution, and the mixture was stirred at room temperature for 1 hour. After completion of the reaction, the solvent was distilled off and the polymer was recovered. The polymer was recovered after washing with 50 ml of methanol. 29 mg of polyhydroxyalkanoate was obtained by drying under reduced pressure.
The polyhydroxyalkanoate obtained here was subjected to NMR analysis in the same manner as in Preparation Example 2J-1. As a result, it was confirmed that the carboxyl group of the C unit was carboxylic acid methyl ester, and it was confirmed that the obtained polymer could be esterified again.

(Preparation Example 2J-3)
0.40 g of polyhydroxyalkanoate copolymer (C: 10 mol%, D: 90 mol%) composed of the unit represented by the chemical formula (136) obtained in Preparation Example 2J-3, under a nitrogen atmosphere, 2-aminobenzene Add 0.24 g (1.4 mmol) of sulfonic acid into a 100 ml three-necked flask, add 15.0 ml of pyridine and stir, then add 0.71 ml (2.7 mmol) of triphenyl phosphite and heat at 120 ° C. for 6 hours. did. After completion of the reaction, it was recovered by reprecipitation in 150 ml of ethanol. The obtained polymer was washed with 1N hydrochloric acid for 1 day, then washed by stirring in water for 1 day, and dried under reduced pressure to obtain 0.35 g of polymer. The structure of the obtained polymer was determined by ¹ H-NMR (FT-NMR: Bruker DPX400; resonance frequency: 400 MHz; measurement nuclide: ¹ H; solvent used: heavy DMSO; measurement temperature: room temperature), Fourier transform-infrared absorption Analysis was performed by (FT-IR) spectrum (Nicolet AVATAR 360FT-IR). As a result of IR measurement, the peak at 1695 cm ⁻¹ derived from the carboxylic acid decreased, and a new peak derived from the amide group was observed at 1658 cm ⁻¹ .
^From the result of ¹ H-NMR, since the peak derived from the aromatic ring having a 2-aminobenzenesulfonic acid structure is shifted, the obtained polymer has a unit represented by the following chemical formula (137) as a monomer unit. It was confirmed to be a polyhydroxyalkanoate containing.

Further, it was confirmed that the polyhydroxyalkanoate represented by the chemical formula (137) is a copolymer containing 10 mol% of the E unit. The average molecular weight of the obtained polymer was determined by gel permeation chromatography (GPC; Tosoh, column; Polymer Laboratories PLgel 5μ MIXED-C, solvent; DMF / LiBr 0.1% (w / v), polystyrene conversion). evaluated. As a result, the number average molecular weight M _n = 226000 and the weight average molecular weight M _w = 497200.

(Preparation Example 2J-4)
Add 0.30 g of a polyhydroxyalkanoate copolymer consisting of the unit represented by the chemical formula (137) obtained in Preparation Example 2J-3 to an eggplant flask, and dissolve by adding 21.0 ml of chloroform and 7.0 ml of methanol. And cooled to 0 ° C. To this was added 0.93 ml of a 2 mol / L trimethylsilyldiazomethane-hexane solution (manufactured by Aldrich), and the mixture was stirred for 4 hours. After completion of the reaction, the solvent was distilled off with an evaporator to recover the polymer. Further, 21.0 ml of chloroform and 7.0 ml of methanol were added to redissolve the polymer, and the solvent was distilled off by an evaporator. This operation was repeated three times. The polymer collected here was dried under reduced pressure to obtain 0.30 g of polymer. The structure of the obtained polymer was determined by ¹ H-NMR (FT-NMR: Bruker DPX400; resonance frequency: 400 MHz; measurement nuclide: ¹ H; solvent used: heavy DMSO; measurement temperature: room temperature). ^From the result of ¹ H-NMR, since a peak derived from methyl sulfonate is observed at 3 to 4 ppm, the obtained polymer is a polyhydroxyalkanoate containing a unit represented by the following chemical formula (138) as a monomer unit. It was confirmed that.

Further, it was confirmed that the polyhydroxyalkanoate unit represented by the chemical formula (138) contains 10 mol% of the G unit. In addition, the acid value titration using the potentiometric titrator AT510 (manufactured by Kyoto Electronics Co., Ltd.) revealed that the sulfonic acid was methyl sulfonate because no peak derived from sulfonic acid was observed. . The average molecular weight of the obtained polymer was determined by gel permeation chromatography (GPC; Tosoh HLC-8120, column; Polymer Laboratories PLgel 5μ MIXED-C, solvent: DMF / LiBr 0.1% (w / v), polystyrene. (Conversion). As a result, the number average molecular weight M _n = 228000 and the weight average molecular weight M _w = 513,000. A series of preparation methods were scaled up to obtain a large amount of the polyhydroxyalkanoate represented by the chemical formula (138) to give Exemplified Compound 2J.

(Preparation Example 2K-1)
9.40 g of polymer was obtained in the same manner as in Preparation Example 2J-2 except that 26.61 g (232.3 mmol) of benzyl bromoacetate was used instead of benzyl chloroformate. The obtained polymer was subjected to NMR analysis under the same conditions as in Preparation Example 2J-1, and as a result, was a polyhydroxyalkanoate containing a unit represented by the following chemical formula (139). 11 mol% and B unit 89 mol% were confirmed.

Moreover, the average molecular weight of the obtained polyhydroxyalkanoate was measured under the same conditions as in Preparation Example 2J-1. As a result, the number average molecular weight Mn = 300300 and the weight average molecular weight Mw = 723700.
Further, the above polymer was subjected to hydrogenolysis in the same manner as in Preparation Example 2J-2 to obtain 3.66 g of a polymer. The obtained polymer was subjected to NMR analysis under the same conditions as in Preparation Example 2J-1. As a result, it was confirmed that the polymer was a polyhydroxyalkanoate copolymer containing a unit represented by the following chemical formula (140) as a monomer unit. It was done. Moreover, it was confirmed that the ratio of the monomer unit is C unit 11 mol% and D unit 89 mol%.

  Moreover, the average molecular weight of the obtained polyhydroxyalkanoate was measured under the same conditions as in Preparation Example 2J-1. As a result, the number average molecular weight Mn = 286000 and the weight average molecular weight Mw = 700700.

(Preparation Example 2K-2)
In a nitrogen atmosphere, 0.40 g of a polyhydroxyalkanoate copolymer (C: 11 mol%, D: 89 mol%) composed of the unit represented by the chemical formula (140) obtained in Preparation Example 2K-1 was obtained, and 2-amino-2 -Put 0.23 g (1.5 mmol) of methylpropanesulfonic acid in a 100 ml three-necked flask, add 15.0 ml of pyridine and stir, then add 0.78 ml (3.0 mmol) of triphenyl phosphite to prepare Preparation Example 2J. In the same manner as in -3, 0.31 g of a polymer was obtained. The resulting polymer was subjected to NMR analysis and Fourier transform-infrared absorption spectrum analysis under the same conditions as in Preparation Example 2J-3, and as a result, was a polyhydroxyalkanoate containing a unit represented by the following chemical formula (141). It was confirmed to be a copolymer containing 9 mol% of E units.

Moreover, the average molecular weight of the obtained polymer was measured under the same conditions as in Preparation Example 2J-3. As a result, the number average molecular weight M _n = 225000 and the weight average molecular weight M _w = 540000.

(Preparation Example 2K-3)
The polyhydroxyalkanoate represented by the chemical formula (141) obtained in Preparation Example 2K-2 was used in place of the polyhydroxyalkanoate represented by the chemical formula (137) in Preparation Example 2J-4, and 2 mol / L of trimethylsilyl was used. 0.29 g of polymer was obtained by the same method as Preparation Example 2J-4, except that 0.83 ml of diazomethane-hexane solution (Aldrich) was used. The obtained polymer was subjected to NMR analysis under the same conditions as in Preparation Example 2J-4. As a result, the polymer was a polyhydroxyalkanoate containing a unit represented by the following chemical formula (142), and a copolymer containing 9 mol% of G unit. It was confirmed that.
Further, the acid value titration similar to that of Preparation Example 2J-4 revealed that no sulfonic acid-derived peak was observed, and that sulfonic acid was methyl sulfonate.

Further, the average molecular weight of the obtained polymer was measured under the same conditions as in Preparation Example 2J-4. As a result, the number average molecular weight M _n = 228500 and the weight average molecular weight M _w = 548400 were obtained. A series of preparation methods were scaled up, and a large amount of polyhydroxyalkanoate represented by the chemical formula (142) was obtained to give Exemplified Compound 2K.

(Preparation Example 2L-1)
Except for using 29.17 g (232.3 mmol) of ethyl 8-bromooctanoate instead of benzyl chloroformate, 8.83 g of a polymer was obtained in the same manner as in Preparation Example 2J-2. The obtained polymer was subjected to NMR analysis under the same conditions as in Preparation Example 2J-1, and as a result, it was a polyhydroxyalkanoate containing a unit represented by the following chemical formula (143). 9 mol% and B unit 91 mol% were confirmed.

Moreover, the average molecular weight of the obtained polyhydroxyalkanoate was measured under the same conditions as in Preparation Example 2J-1. As a result, the number average molecular weight Mn = 321000 and the weight average molecular weight Mw = 776800 were obtained.
Further, the above polymer was subjected to hydrogenolysis in the same manner as in Preparation Example 2J-2 to obtain 3.85 g of a polymer. The obtained polymer was subjected to NMR analysis under the same conditions as in Preparation Example 2J-1. As a result, it was confirmed that the polymer was a polyhydroxyalkanoate copolymer containing a unit represented by the following chemical formula (144) as a monomer unit. It was done. Moreover, it was confirmed that the ratio of the monomer unit is 9 mol% for C unit and 91 mol% for D unit.

  Moreover, the average molecular weight of the obtained polyhydroxyalkanoate was measured under the same conditions as in Preparation Example 2J-1. As a result, the number average molecular weight Mn = 298100 and the weight average molecular weight Mw = 715400 were obtained.

(Preparation Example 2L-2)
0.40 g of polyhydroxyalkanoate copolymer (C: 9 mol%, D: 91 mol%) composed of the unit represented by the chemical formula (144) obtained in Preparation Example 2L-1 in a nitrogen atmosphere, p-toluidine-2 -Put 0.22 g (1.2 mmol) of sulfonic acid in a 100 ml three-necked flask, add 15.0 ml of pyridine and stir, then add 0.60 ml (2.3 mmol) of triphenyl phosphite to prepare Preparation Example 2J-3. In the same manner as above, 0.32 g of a polymer was obtained. The obtained polymer was a polyhydroxyalkanoate containing a unit represented by the following chemical formula (145) as a result of NMR analysis and Fourier transform-infrared absorption spectrum analysis under the same conditions as in Preparation Example 2J-3. It was confirmed that the copolymer contained 8 mol% of E units.

Further, the average molecular weight of the obtained polymer was measured under the same conditions as in Preparation Example 2J-3. As a result, the number average molecular weight M _n = 215500 and the weight average molecular weight M _w = 538800 were obtained.

(Preparation Example 2L-3)
The polyhydroxyalkanoate represented by the chemical formula (145) obtained in Preparation Example 2L-2 was used in place of the polyhydroxyalkanoate represented by the chemical formula (137) in Preparation Example 2J-4, and 2 mol / L of trimethylsilyl was used. Except for using 0.71 ml of diazomethane-hexane solution (manufactured by Aldrich), 0.30 g of polymer was obtained by the same method as in Preparation Example 2J-4. The obtained polymer was subjected to NMR analysis under the same conditions as in Preparation Example 2J-4. As a result, it was a polyhydroxyalkanoate containing a unit represented by the following chemical formula (146), and a copolymer containing 8 mol% of G unit. It was confirmed that.
Further, the acid value titration similar to that of Preparation Example 2J-4 revealed that no sulfonic acid-derived peak was observed, and that sulfonic acid was methyl sulfonate.

Further, the average molecular weight of the obtained polymer was measured under the same conditions as in Preparation Example 2J-4. As a result, the number average molecular weight M _n = 218000 and the weight average molecular weight M _w = 555900 were obtained. A series of preparation methods were scaled up to obtain a large amount of polyhydroxyalkanoate represented by the chemical formula (146) to give Exemplified Compound 2L.

(Preparation Example 2M-1)
In this preparation example, polyhydroxyalkanoate is produced using microorganisms. The microorganism used in this preparation example is Pseudomonas chicory eye YN2 strain (Pseudomonas cichorrii YN2; FERM BP-7375, disclosed in JP 2001-288256 A). This microorganism is deposited in the Patent Organism Depositary, National Institute of Advanced Industrial Science and Technology.
Moreover, the inorganic salt medium (M9 medium) and the trace component solution used in this Preparation Example have the same composition as that used in Preparation Example 2J-1.

(Synthesis of poly-3-hydroxy-5-phenylvaleric acid represented by chemical formula (147))

Poly-3-hydroxy-5-phenylvaleric acid represented by the chemical formula (147) was synthesized by the method disclosed in Example 1 of JP-A-2003-319792.
As a production medium, 200 mL of M9 medium containing 0.5% (mass / volume (w / v)) of polypeptone (Wako Pure Chemical Industries) and 0.1% (w / v) of 5-phenylvaleric acid was prepared. 1 mL of a culture solution of Pseudomonas chicory eye strain YN2 previously cultured with shaking at 30 ° C. for 8 hours in M9 medium containing 0.5% polypeptone was added, and cultured in a 500 mL shake flask at 30 ° C. for 24 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 24 hours. Chloroform from which the polymer was extracted was filtered and concentrated with an evaporator, and then the portion precipitated and solidified with cold methanol was collected and dried under reduced pressure to obtain 0.60 g of polymer per liter of production medium. As a result of conducting NMR analysis under the same conditions as in Preparation Example 2J-1 to specify the structure of the obtained polymer, poly-3-hydroxy-5-phenylvaleric acid represented by the general chemical formula (147) was obtained as a monomer unit. Of the unit. The average molecular weight of the obtained polyhydroxyalkanoate was measured under the same conditions as in Preparation Example 2J-1. As a result, the number average molecular weight Mn = 91000 and the weight average molecular weight Mw = 172900 were obtained.
By the above method, 60.1 g of polyhydroxyalkanoate used in the following preparation examples was prepared from 100 L of the production medium.

(Preparation Example 2M-2)
In Preparation Example 2J-2, 10.00 g of a polyhydroxyalkanoate composed of a unit represented by the chemical formula (147) obtained in Preparation Example 2M-2 instead of the polyhydroxyalkanoate composed of a unit represented by the chemical formula (134) The polymer was prepared in the same manner as in Preparation Example 2J-2, except that 28.38 ml (56.8 mmol) of 2M lithium diisopropylamide in THF and 9.68 g (113.5 mmol) of benzyl chloroformate were used. .51 g was obtained. The obtained polymer was subjected to NMR analysis under the same conditions as in Preparation Example 2J-1, and as a result, it was a polyhydroxyalkanoate containing a unit represented by the following chemical formula (148). It was confirmed that they were 12 mol% and B units were 88 mol%.

Moreover, the average molecular weight of the obtained polyhydroxyalkanoate was measured under the same conditions as in Preparation Example 2J-1. As a result, the number average molecular weight Mn was 72500 and the weight average molecular weight Mw was 141400.
The polymer was hydrocracked in the same manner as in Preparation Example 2J-2 to obtain 3.72 g of polymer. The obtained polymer was subjected to NMR analysis under the same conditions as in Preparation Example 2J-1. As a result, it was confirmed that the polymer was a polyhydroxyalkanoate copolymer containing a unit represented by the following chemical formula (149) as a monomer unit. It was done. Moreover, it was confirmed that the ratio of the monomer unit is C unit 12 mol% and D unit 88 mol%.

  Moreover, the average molecular weight of the obtained polyhydroxyalkanoate was measured under the same conditions as in Preparation Example 2J-1. As a result, the number average molecular weight Mn = 69500 and the weight average molecular weight Mw = 139700 were obtained.

(Preparation Example 2M-3)
0.40 g of polyhydroxyalkanoate copolymer (C: 12 mol%, D: 88 mol%) composed of the unit represented by the chemical formula (149) obtained in Preparation Example 2M-2, under a nitrogen atmosphere, 2-aminobenzene Put 0.23 g (1.3 mmol) of sulfonic acid in a 100 ml three-necked flask, add 15.0 ml of pyridine and stir, then add 0.69 ml (2.6 mmol) of triphenyl phosphite, and Preparation Example 2J-3 0.33g of polymer was obtained by the same method. The obtained polymer was a polyhydroxyalkanoate containing a unit represented by the following chemical formula (150) as a result of performing NMR analysis and Fourier transform-infrared absorption spectrum analysis under the same conditions as in Preparation Example 2J-3. It was confirmed that the copolymer contained 11 mol% of E units.

Further, the average molecular weight of the obtained polymer was measured under the same conditions as in Preparation Example 2J-3. As a result, the number average molecular weight M _n = 55300 and the weight average molecular weight M _w = 113400 were obtained.

(Preparation Example 2M-4)
The polyhydroxyalkanoate represented by the chemical formula (150) obtained in Preparation Example 2M-3 was used instead of the polyhydroxyalkanoate represented by the chemical formula (137) in Preparation Example 2J-4, and 2 mol / L of trimethylsilyl was used. 0.29 g of polymer was obtained by the same method as Preparation Example 2J-4, except that 0.83 ml of diazomethane-hexane solution (Aldrich) was used. The obtained polymer was subjected to NMR analysis under the same conditions as in Preparation Example 2J-4. As a result, it was a polyhydroxyalkanoate containing a unit represented by the following chemical formula (151), and a copolymer containing 11 mol% of G unit. It was confirmed that.
Further, the acid value titration similar to that of Preparation Example 2J-4 revealed that no sulfonic acid-derived peak was observed, and that sulfonic acid was methyl sulfonate.

Further, the average molecular weight of the obtained polymer was measured under the same conditions as in Preparation Example 2J-4. As a result, the number average molecular weight M _n = 54500 and the weight average molecular weight M _w = 114500 were obtained. A series of preparation methods were scaled up, and a large amount of polyhydroxyalkanoate represented by the chemical formula (151) was obtained to give Exemplified Compound 2M.

(Preparation Example 2N-1)
Except for using 12.86 g (113.5 mmol) of ethyl 6-bromohexanoate instead of benzyl chloroformate, 7.87 g of a polymer was obtained in the same manner as in Preparation Example 2M-2. The obtained polymer was subjected to NMR analysis under the same conditions as in Preparation Example 2J-1, and as a result, was a polyhydroxyalkanoate containing a unit represented by the following chemical formula (152). It was confirmed that they were 8 mol% and B unit was 92 mol%.

Moreover, the average molecular weight of the obtained polyhydroxyalkanoate was measured under the same conditions as in Preparation Example 2J-1. As a result, the number average molecular weight Mn = 71000 and the weight average molecular weight Mw = 134900.
The polymer was hydrocracked in the same manner as in Preparation Example 2J-2 to obtain 3.95 g of polymer. As a result of conducting NMR analysis under the same conditions as in Preparation Example 2J-1, the obtained polymer was confirmed to be a polyhydroxyalkanoate copolymer containing a unit represented by the following chemical formula (153) as a monomer unit. It was done. Moreover, it was confirmed that the ratio of the monomer unit is C unit 8 mol% and D unit 92 mol%.

  Moreover, the average molecular weight of the obtained polyhydroxyalkanoate was measured under the same conditions as in Preparation Example 2J-1. As a result, the number average molecular weight Mn = 68500 and the weight average molecular weight Mw = 133600 were obtained.

(Preparation Example 2N-2)
0.40 g of polyhydroxyalkanoate copolymer (C: 8 mol%, D: 92 mol%) composed of the unit represented by the chemical formula (153) obtained in Preparation Example 2N-1 in a nitrogen atmosphere, 2-aminobenzene Add 0.15 g (0.9 mmol) of sulfonic acid to a 100 ml three-necked flask, add 15.0 ml of pyridine and stir, then add 0.45 ml (1.7 mmol) of triphenyl phosphite, and Preparation Example 2J-3 0.34g of polymer was obtained by the same method. The obtained polymer was a polyhydroxyalkanoate containing a unit represented by the following chemical formula (154) as a result of NMR analysis and Fourier transform-infrared absorption spectrum analysis under the same conditions as in Preparation Example 2J-3. It was confirmed that the copolymer contained 7 mol% of E units.

Moreover, the average molecular weight of the obtained polymer was measured under the same conditions as in Preparation Example 2J-3. As a result, the number average molecular weight M _n = 54200 and the weight average molecular weight M _w = 108400 were obtained.

(Preparation Example 2N-3)
The polyhydroxyalkanoate represented by the chemical formula (154) obtained in Preparation Example 2N-2 was used in place of the polyhydroxyalkanoate represented by the chemical formula (137) in Preparation Example 2J-4, and 2 mol / L of trimethylsilyl was used. Except for using 0.54 ml of a diazomethane-hexane solution (manufactured by Aldrich), 0.30 g of a polymer was obtained in the same manner as in Preparation Example 2J-4. The obtained polymer was subjected to NMR analysis under the same conditions as in Preparation Example 2J-4. As a result, it was a polyhydroxyalkanoate containing a unit represented by the following chemical formula (155) and a copolymer containing 7 mol% of G unit. It was confirmed that.
Further, the acid value titration similar to that of Preparation Example 2J-4 revealed that no sulfonic acid-derived peak was observed, and that sulfonic acid was methyl sulfonate.

Moreover, the average molecular weight of the obtained polymer was measured under the same conditions as in Preparation Example 2J-4. As a result, the number average molecular weight M _n = 52500 and the weight average molecular weight M _w = 110300 were obtained. A series of preparation methods were scaled up, and a large amount of polyhydroxyalkanoate represented by the chemical formula (155) was obtained to give Exemplified Compound 2N.

(Preparation Example 2O-1)
(Synthesis of poly-3-hydroxy-5-phenoxyvaleric acid represented by chemical formula (156))

Poly-3-hydroxy-5-phenylvaleric acid represented by the chemical formula (156) was synthesized by the method disclosed in Example 4 of JP-A-2003-319792.
As a production medium, polypeptone 0.5% (w / v), 5-phenoxyvaleric acid 0.1% (w / v), M9 medium 200 mL, in advance M9 medium containing polypeptone 0.5% at 30 ° C. 1 mL of a culture solution of Pseudomonas chicory eye strain YN2 cultured with shaking for 8 hours was added and cultured in a 500 mL shaking flask at 30 ° C. for 45 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 24 hours. Chloroform from which the polymer was extracted was filtered and concentrated by an evaporator, and then the portion precipitated and solidified with cold methanol was collected and dried under reduced pressure to obtain 0.36 g of polymer per liter of production medium. In order to specify the structure of the obtained polymer, NMR analysis was performed under the same conditions as in Example 1. As a result, as a monomer unit, a homopolymer of poly-3-hydroxy-5-phenoxyvaleric acid represented by the chemical formula (156) was obtained. It was a polymer. The average molecular weight of the obtained polyhydroxyalkanoate was measured under the same conditions as in Preparation Example 2J-1. As a result, the number average molecular weight Mn = 201000 and the weight average molecular weight Mw = 422100 were obtained.
By the above method, 44.8 g of polyhydroxyalkanoate used in the following preparation examples was prepared from 125 L of the production medium.

(Preparation Example 2O-2)
In Preparation Example 2J-2, instead of the polyhydroxyalkanoate comprising the unit represented by the chemical formula (134), 10.00 g polyhydroxyalkanoate comprising the unit represented by the chemical formula (156) obtained in Preparation Example 2O-1 And 2M lithium diisopropylamide in THF (26.01 ml, 52.0 mmol) and benzyl chloroformate (8.88 g, 104.1 mmol). .29 g was obtained. The obtained polymer was subjected to NMR analysis under the same conditions as in Preparation Example 2J-1, and as a result, was a polyhydroxyalkanoate containing a unit represented by the following chemical formula (157). 11 mol% and B unit 89 mol% were confirmed.

Moreover, the average molecular weight of the obtained polyhydroxyalkanoate was measured under the same conditions as in Preparation Example 2J-1. As a result, the number average molecular weight Mn = 131500 and the weight average molecular weight Mw = 282700 were obtained.
The polymer was hydrocracked in the same manner as in Preparation Example 2J-2 to obtain 3.75 g of a polymer. As a result of conducting NMR analysis under the same conditions as in Preparation Example 2J-1, the obtained polymer was confirmed to be a polyhydroxyalkanoate copolymer containing a unit represented by the following chemical formula (158) as a monomer unit. It was done. Moreover, it was confirmed that the ratio of the monomer unit is C unit 11 mol% and D unit 89 mol%.

  Moreover, the average molecular weight of the obtained polyhydroxyalkanoate was measured under the same conditions as in Preparation Example 2J-1. As a result, the number average molecular weight Mn = 121000 and the weight average molecular weight Mw = 260200.

(Preparation Example 2O-3)
0.40 g of a polyhydroxyalkanoate copolymer (C: 11 mol%, D: 89 mol%) composed of the unit represented by the chemical formula (158) obtained in Preparation Example 2O-2 under a nitrogen atmosphere, 2-aminobenzene After adding 0.19 g (1.1 mmol) of sulfonic acid to a 100 ml three-necked flask, adding 15.0 ml of pyridine and stirring, 0.58 ml (2.2 mmol) of triphenyl phosphite was added, and Preparation Example 2J-3 and 0.33g of polymer was obtained by the same method. The obtained polymer was a polyhydroxyalkanoate containing a unit represented by the following chemical formula (159) as a result of NMR analysis and Fourier transform-infrared absorption spectrum analysis under the same conditions as in Preparation Example 2J-3. It was confirmed to be a copolymer containing 10 mol% of E units.

Moreover, the average molecular weight of the obtained polymer was measured under the same conditions as in Preparation Example 2J-3. As a result, the number average molecular weight M _n = 100500 and the weight average molecular weight M _w = 221100 were obtained.

(Preparation Example 2O-4)
The polyhydroxyalkanoate represented by the chemical formula (159) obtained in Preparation Example 2O-3 was used in place of the polyhydroxyalkanoate represented by the chemical formula (137) in Preparation Example 2J-4, and 2 mol / L of trimethylsilyl was used. Except for using 0.71 ml of diazomethane-hexane solution (manufactured by Aldrich), 0.30 g of polymer was obtained by the same method as in Preparation Example 2J-4. The obtained polymer was subjected to NMR analysis under the same conditions as in Preparation Example 2J-4. As a result, it was a polyhydroxyalkanoate containing a unit represented by the following chemical formula (160) and a copolymer containing 10 mol% of G unit. It was confirmed that.
Further, the acid value titration similar to that of Preparation Example 2J-4 revealed that no sulfonic acid-derived peak was observed, and that sulfonic acid was methyl sulfonate.

Moreover, the average molecular weight of the obtained polymer was measured under the same conditions as in Preparation Example 2J-4. As a result, the number average molecular weight M _n = 101000 and the weight average molecular weight M _w = 227300 were obtained. A series of preparation methods were scaled up to obtain a large amount of the polyhydroxyalkanoate represented by the chemical formula (160) to obtain Exemplified Compound 2O.

(Preparation Example 2P-1)
(Synthesis of poly-3-hydroxy-4-cyclohexylbutyric acid represented by the chemical formula (161))

Poly-3-hydroxy-4-cyclohexylbutyric acid represented by the chemical formula (161) was synthesized by the method disclosed in Example 9 of JP-A-2003-319792.
As a production medium, polypeptone 0.5% (w / v), 4-cyclohexylbutyric acid 0.1% (w / v), M9 medium 200 mL, in advance M9 medium containing polypeptone 0.5% at 30 ° C., 1 mL of a culture solution of Pseudomonas chicory eye strain YN2 cultured with shaking for 8 hours was added, and cultured in a 500 mL shaking flask at 30 ° C. for 48 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 24 hours. Chloroform from which the polymer was extracted was filtered and concentrated by an evaporator, and then the portion precipitated and solidified with cold methanol was collected and dried under reduced pressure to obtain 0.48 g of polymer per liter of production medium. As a result of conducting NMR analysis under the same conditions as in Preparation Example 2J-1, in order to specify the structure of the obtained polymer, the monomer unit was obtained from poly-3-hydroxy-4-cyclohexylbutyric acid represented by the chemical formula (161). It was a homopolymer. The average molecular weight of the obtained polyhydroxyalkanoate was measured under the same conditions as in Preparation Example 2J-1. As a result, the number average molecular weight Mn was 70500 and the weight average molecular weight Mw was 155100.
By the above method, 47.9 g of polyhydroxyalkanoate used in the following preparation examples was prepared from 100 L of the production medium.

(Preparation Example 2P-2)
In Preparation Example 2J-2, 10.00 g of a polyhydroxyalkanoate composed of a unit represented by the chemical formula (161) obtained in Preparation Example 2P-1 instead of the polyhydroxyalkanoate composed of a unit represented by the chemical formula (134) The polymer was prepared in the same manner as in Preparation Example 2J-2 except that 29.72 ml (59.4 mmol) of 2M lithium diisopropylamide in THF and 10.14 g (118.9 mmol) of benzyl chloroformate were used. .66 g was obtained. The obtained polymer was subjected to NMR analysis under the same conditions as in Preparation Example 2J-1, and as a result, was a polyhydroxyalkanoate containing a unit represented by the following chemical formula (162). 10 mol% and B unit 90 mol% were confirmed.

Moreover, the average molecular weight of the obtained polyhydroxyalkanoate was measured under the same conditions as in Preparation Example 2J-1. As a result, the number average molecular weight Mn was 54400 and the weight average molecular weight Mw was 11700.
Further, the above polymer was subjected to hydrogenolysis in the same manner as in Preparation Example 2J-2 to obtain 3.85 g of a polymer. As a result of conducting NMR analysis under the same conditions as in Preparation Example 2J-1, the obtained polymer was confirmed to be a polyhydroxyalkanoate copolymer containing a unit represented by the following chemical formula (163) as a monomer unit. It was done. Moreover, it was confirmed that the ratio of the monomer unit is 10 mol% for C unit and 90 mol% for D unit.

  Moreover, the average molecular weight of the obtained polyhydroxyalkanoate was measured under the same conditions as in Preparation Example 2J-1. As a result, the number average molecular weight Mn = 47500 and the weight average molecular weight Mw = 103600.

(Preparation Example 2P-3)
Under a nitrogen atmosphere, 0.40 g of a polyhydroxyalkanoate copolymer (C: 10 mol%, D: 90 mol%) composed of the unit represented by the chemical formula (163) obtained in Preparation Example 2P-2, 2-amino- 1-Naphthalenesulfonic acid 0.26 g (1.2 mmol) was placed in a 100 ml three-necked flask, 15.0 ml of pyridine was added and stirred, then 0.60 ml (2.3 mmol) of triphenyl phosphite was added, and Preparation Example 2J In the same manner as in -3, 0.36 g of a polymer was obtained. The obtained polymer was a polyhydroxyalkanoate containing a unit represented by the following chemical formula (164) as a result of performing NMR analysis and Fourier transform-infrared absorption spectrum analysis under the same conditions as in Preparation Example 2J-3. It was confirmed to be a copolymer containing 9 mol% of E units.

Moreover, the average molecular weight of the obtained polymer was measured under the same conditions as in Preparation Example 2J-3. As a result, the number average molecular weight M _n = 30500 and the weight average molecular weight M _w = 65600 were obtained.

(Preparation Example 2P-4)
The polyhydroxyalkanoate represented by the chemical formula (164) obtained in Preparation Example 2P-3 was used in place of the polyhydroxyalkanoate represented by the chemical formula (137) in Preparation Example 2J-4, and 2 mol / L of trimethylsilyl was used. Except for using 0.71 ml of diazomethane-hexane solution (manufactured by Aldrich), 0.28 g of polymer was obtained in the same manner as in Preparation Example 2J-4. The obtained polymer was subjected to NMR analysis under the same conditions as in Preparation Example 2J-4. As a result, it was a polyhydroxyalkanoate containing a unit represented by the following chemical formula (165) and a copolymer containing 9 mol% of G unit. It was confirmed that.
Further, the acid value titration similar to that of Preparation Example 2J-4 revealed that no sulfonic acid-derived peak was observed, and that sulfonic acid was methyl sulfonate.

Further, the average molecular weight of the obtained polymer was measured under the same conditions as in Preparation Example 2J-4. As a result, the number average molecular weight M _n = 31000 and the weight average molecular weight M _w = 68200 were obtained. A series of preparation methods were scaled up to obtain a large amount of polyhydroxyalkanoate represented by the chemical formula (165) to give Exemplified Compound 2P.

(Preparation Example 2Z-1)
[Synthesis of 3,6-di (3-butenyl) -1,4-dioxane-2,5-dione represented by chemical formula (166) with m = 2 from 2-hydroxy-5-hexenoic acid]

(In the formula, m is an integer selected from 2 to 8.)

The synthesis of 3,6-di (3-butenyl) -1,4-dioxane-2,5-dione used in Preparation Example A-1 is as follows.
In a 1 L flask equipped with a reflux condenser and a Dean-Stark trap, 3.0 g of 2-hydroxy-5-hexenoic acid, 400 ml of toluene and 30 mg of p-toluenesulfonic acid were added and refluxed in a nitrogen atmosphere. Water collected in the trap was removed from time to time. The mixture was refluxed for 72 hours and then cooled. After washing twice with 10 ml saturated aqueous sodium hydrogen carbonate solution, the obtained crude product was distilled under reduced pressure in the presence of zinc oxide to give the desired 3,6-di (ω'-butenyl) -1,4-dioxane- 1.06 g (yield 41%) of 2,5-dione was obtained.
In order to specify the structure of the obtained compound, 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 used: DMSO-d ₆
Measurement temperature: room temperature As a result, it was confirmed that the obtained compound was the desired 3,6-di (3-butenyl) -1,4-dioxane-2,5-dione.

(Preparation Example 2Z-2)
[Synthesis of 3,6-di (6-heptenyl) -1,4-dioxane-2,5-dione represented by chemical formula (166) with m = 4 from 2-hydroxy-8-nonenoic acid]

(In the formula, m is an integer selected from 2 to 8.)

The synthesis of 3,6-di (6-heptenyl) -1,4-dioxane-2,5-dione used in Preparation Example B-1 is as follows.
The same procedure was followed except that 2-hydroxy-8-nonenoic acid was used instead of 2-hydroxy-5-hexenoic acid in Preparation Example 2Z-1, and 3,6-di (6-heptenyl) -1 Thus, 1.07 g (yield 40%) of 1,4-dioxane-2,5-dione was obtained. In order to specify the structure of the obtained compound, NMR analysis was performed under the same conditions as in Preparation Example 2Z-1. As a result, the desired 3,6-di (6-heptenyl) -1,4-dioxane-2 was obtained. , 5-dione.

(Preparation Example 2Z-3)
[Synthesis of 3,6-di (2-propenyl) -1,4-dioxane-2,5-dione represented by chemical formula (166) with m = 1 from 2-hydroxy-4-pentenoic acid]

(In the formula, m is an integer selected from 2 to 8.)

The synthesis of 3,6-di (2-propenyl) -1,4-dioxane-2,5-dione used in Preparation Example C-1 is as follows.
The same procedure as in Preparation Example 2Z-1, except that 2-hydroxy-4-pentenoic acid was used instead of 2-hydroxy-5-hexenoic acid, 3,6-di (2-propenyl) -1, 1.09 g (43% yield) of 4-dioxane-2,5-dione was obtained. In order to specify the structure of the obtained compound, NMR analysis was performed under the same conditions as in Preparation Example 2Z-1, and as a result, the desired 3,6-di (2-propenyl) -1,4-dioxane-2, It was confirmed to be 5-dione.

(Preparation Example 2Z-4)
7- (3-Butenyl) -2-oxepanone used in Preparation Example H-1 was prepared with reference to the method described in JP-A-5-310721. Specifically, 7- (3-butenyl) -2-oxeppanone was prepared by using 2- (3-butenyl) cyclohexanone instead of the raw material 2-allylcyclohexanone described in Example 43 of the patent document.

(Preparation Example 2Z-5)
[Synthesis of 3- (2-propenyl) -2-oxetanone described in Preparation Examples I-1, J-1, and K-1]
3- (2-propenyl) -2-oxetanone is dihydro-3- (2-propenyl) furan-2 (3H) -one described in Journal of American Chemical Society 1995,117,3705-3716 (in non-patent literature) In the synthesis of the compound (6a)), β-propiolactone can be used instead of γ-butyrolactone.
Specifically, 7.20 g (100.0 mmol) of β-propiolactone was added to an eggplant flask, and 55 ml of THF was added and dissolved. This was placed under a nitrogen atmosphere and stirred at -78 ° C. Next, 55 ml of 2M lithium diisopropylamide in THF was slowly added and stirred at −78 ° C. for 20 minutes. Next, after adding 14.52 g (110.0 mmol) of allyl bromide dissolved in 38 ml of hexamethylphosphoramide (HMPA), the mixture was stirred at −30 ° C. for 3 hours. After completion of the reaction, the reaction solution was poured into an aqueous ammonium chloride solution, and dichloromethane was added to extract the organic layer. After washing 3 times with water, the organic layer was recovered. The collected organic layer was dried over anhydrous sodium sulfate. After removing sodium sulfate, the solution was evaporated to recover crude 3- (2-propenyl) -2-oxetanone. Next, 9.42g of the target 3- (2-propenyl) -2-oxetanone was obtained by refine | purifying by silica gel column chromatography and performing distillation under reduced pressure. In order to specify the structure of the obtained compound, 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 used: CDCl ₃
Measurement temperature: room temperature As a result, it was confirmed that the obtained compound was the target 3- (2-propenyl) -2-oxetanone.

(Preparation Example 2Z-6)
[Synthesis of 3- (9-decenyl) -2-oxetanone described in Preparation Example L-1]
The target 3- (9) was prepared in the same manner as in Preparation Example 2Z-5 except that 26.30 g (110.0 mmol) of 10-bromo-1-decene was used instead of allyl bromide described in Preparation Example 2Z-5. 15.14 g of (decenyl) -2-oxetanone was obtained.

(Preparation Example 2Z-7)
[Synthesis of 3- (2-propenyl) dihydro-2 (3H) -furanone described in Preparation Example M-1]
The target 3- (2-) was prepared in the same manner as in Preparation Example 2Z-5, except that 8.61 g (100.0 mmol) of γ-butyrolactone was used instead of β-propiolactone described in Preparation Example 2Z-5. 10.72 g of propenyl) dihydro-2 (3H) -furanone was obtained.

(Preparation Example 2Z-8)
[Synthesis of Tetrahydro-3- (2-propenyl) -2H-pyran-2-one described in Preparation Example N-1]
The target tetrahydro-3-like compound was prepared in the same manner as in Preparation Example 2Z-5, except that 10.01 g (100.0 mmol) of δ-valerolactone was used instead of β-propiolactone described in Preparation Example 2Z-5. 9.81 g of (2-propenyl) -2H-pyran-2-one was obtained.

(Preparation Example 2Z-9)
[Synthesis of 3- (2-propenyl) -2-oxepanone described in Preparation Example O-1]
The target 3- (2-propenyl) was prepared in the same manner as in Preparation Example 2Z-5 except that 11.41 g (100.0 mmol) of ε-caprolactone was used instead of β-propiolactone described in Preparation Example 2Z-5. ) -2-Oxepanone 10.02g was obtained.

(Preparation Example 2Z-10)
[Synthesis of 7-oxo-3-oxepanecarboxylic acid phenylmethyl ester described in Preparation Example R-1]
The 7-oxo-3-oxepanecarboxylic acid phenylmethyl ester described in Preparation Example R-1 can be obtained by using the method described in Macromolecules, 2000, 33, 4622 (compound (12) in the literature). it can.
In an acetone solution containing 12.0 g (84.4 mmol) of 3-ketocyclohexanecarboxylic acid and 4.7 g (33.8 mmol) of potassium carbonate, 17.3 g (101.3 mmol) of benzyl bromide was added at room temperature. Next, this was stirred at 60 ° C. for 3 hours. After completion of the reaction, potassium carbonate was removed by filtration, and acetone was distilled off to obtain a crude product. The crude product was purified by silica gel column chromatography to obtain 16.5 g of 3-ketocyclohexanecarboxylic acid phenylmethyl ester.
A chloroform solution containing metachloroperbenzoic acid was added at room temperature to a chloroform solution containing 16.5 g (71.0 mmol) of 3-ketocyclohexanecarboxylic acid phenylmethyl ester. This was stirred at 65 ° C. for 2 hours. After completion of the reaction, the mixture was filtered using celite, and then an aqueous sodium hydrogen carbonate solution was added to separate the layers. After collecting the organic layer, it was dried over sodium sulfate. After distilling off the solvent, purification was carried out by silica gel column chromatography, followed by distillation under reduced pressure, thereby obtaining 6.0 g of 7-oxo-3-oxepanecarboxylic acid phenylmethyl ester which was the target product. In order to specify the structure of the obtained compound, 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 used: CDCl ₃
Measurement temperature: room temperature As a result, it was confirmed that the obtained compound was the intended 7-oxo-3-oxepanecarboxylic acid phenylmethyl ester.

(Preparation Example 2Z-11)
[Synthesis of tetrahydro-6-oxo-2H-pyran-3-carboxylic acid phenylmethyl ester described in Preparation Example T-1]
Tetrahydro-6-oxo-2H-pyran-3-carboxylic acid phenylmethyl ester described in Preparation Example T-1 can be produced using the method described in Preparation Example 2Z-10. Specifically, the target product can be obtained by carrying out in the same manner using 3-ketocyclopentanecarboxylic acid instead of 3-ketocyclohexanecarboxylic acid in Preparation Example 2Z-10.
The purpose is to carry out the same method as in Preparation Example 2Z-10 except that 10.8 g (84.4 mmol) of 3-ketocyclopentanecarboxylic acid is used instead of 3-ketocyclohexanecarboxylic acid in Preparation Example 2Z-10. Thus, 4.5 g of tetrahydro-6-oxo-2H-pyran-3-carboxylic acid phenylmethyl ester was obtained.

  Next, various toners were produced using a charge control agent produced by a method selected from the methods of the present invention and evaluated (Examples 1 to 60).

Example 1
First, a Na ₃ PO ₄ aqueous solution was added to a 2 liter four-necked flask equipped with a high-speed stirring device 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 the following composition was dispersed for 3 hours using a ball mill, 10 parts by mass of a release agent (ester wax) and 10 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator. A polymerizable monomer composition was prepared by adding parts.
-Styrene monomer 82 parts by mass-Ethylhexyl acrylate monomer 18 parts by mass-Divinylbenzene monomer 0.1 part by mass-Cyan colorant (CI Pigment Blue 15) 6 parts by mass-Polyethylene oxide resin (molecular weight) 3200, acid value 8) 5 parts by mass-Exemplified Compound A 2 parts by mass Next, the polymerizable monomer composition obtained above was charged into the aqueous dispersion medium prepared above, and the rotational speed was 10,000 rpm. Granulation while maintaining Thereafter, the mixture was reacted at 65 ° C. for 3 hours while stirring with a paddle stirring blade, 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 resulting blue polymer particles (1) were measured using a Coulter Counter Multisizer (manufactured by Coulter Co., Ltd.) with a weight-average particle size of 6.5 μm and the presence of fine particles (particles of 3.17 μm or less in the number distribution). Ratio) was 5.0% by number.
1.3 parts by mass of hydrophobic silica fine powder (BET: 270 m ^{2 /} g) treated with hexamethyldisilazane as a flow improver is added to 100 parts by mass of the blue polymer particles (1) prepared above with a Henschel mixer. The blue toner (1) of this example was obtained by dry mixing and external addition. 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 2 to 4)
Blue toners (2) to (4) of Examples 2 to 4 were obtained in the same manner as in Example 1 except that Exemplified Compound A was changed to Exemplified Compounds B, C-8, and C-4, respectively. The characteristics of this toner were measured in the same manner as in Example 1. The results are shown in Table 1. In addition, using this, in the same manner as in Example 1, the two-component blue developers (2) to (4) of Examples 2 to 4 were obtained.

(Comparative Example 1)
A blue toner (5) of Comparative Example 1 was obtained in the same manner as in Example 1 except that the exemplified compound was not used. The characteristics of this toner were measured in the same manner as in Example 1. The results are shown in Table 1. Further, using this, the two-component blue developer (5) of Comparative Example 1 was obtained in the same manner as in Example 1.

<Evaluation>
About the two-component blue developers (1) to (4) obtained in Examples 1 to 4 and the two-component blue developer (5) 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.
[Chargeability]
A: Very good (−20 μC / g or less)
○: Good (−19.9 to −10.0 μC / g)
Δ: Practical use possible (−9.9 to −5.0 μC / g)
×: Not practical (-4.9 μC / g or more)

(Examples 5 to 8)
Example Compound C-5, C-9, C-10 and E were used in the same manner as in Example 1 except that 2.0 parts by mass of each of Exemplified Compounds C-5, C-10 and E were used, and a yellow colorant (Hansa Yellow G) was used instead of the cyan colorant. Thus, yellow (yellow) toners (1) to (4) of Examples 5 to 8 were obtained. The characteristics of these toners were measured in the same manner as in Example 1, and the results are shown in Table 1. Further, using this, in the same manner as in Example 1, two-component yellow (yellow) developers (1) to (4) were obtained.

(Comparative Example 2)
A yellow (yellow) toner (5) of Comparative Example 2 was obtained in the same manner as in Example 1 except that the exemplified compound was not used and a yellow colorant (Hansa Yellow G) was used instead of the cyan colorant. It was. The characteristics of this toner were measured in the same manner as in Example 1. The results are shown in Table 1. In addition, using this, the two-component yellow (yellow) developer (5) of Comparative Example 2 was obtained in the same manner as in Example 1.

<Evaluation>
About the two-component yellow (yellow) developers (1) to (4) obtained in Examples 5 to 8 and the two-component yellow (yellow) developer (5) obtained in Comparative Example 2, Stir for 10 seconds and 300 seconds under the normal humidity (25 ° C., 60% RH) and high temperature and high humidity (30 ° C., 80% RH) using the above-mentioned method for measuring the charge amount. The charge amount of the subsequent toner 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.
[Chargeability]
A: Very good (−20 μC / g or less)
○: Good (−19.9 to −10.0 μC / g)
Δ: Practical use possible (−9.9 to −5.0 μC / g)
×: Not practical (-4.9 μC / g or more)

(Examples 9 to 12)
Except for using 2.0 parts by mass of each of Exemplified Compounds G, H, I, and J, and using carbon black (DBP oil absorption 110 mL / 100 g) instead of the cyan colorant, Black toners (1) to (4) of Examples 9 to 12 were obtained. The characteristics of these toners were measured in the same manner as in Example 1, and the results are shown in Table 1. Moreover, using this, it carried out similarly to Example 1, and obtained two-component system black developer (1)-(4).

(Comparative Example 3)
A black toner (5) of Comparative Example 3 was obtained in the same manner as in Example 1 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 characteristics of this toner were measured in the same manner as in Example 1. The results are shown in Table 1. In addition, using this, the two-component black developer (5) of Comparative Example 3 was obtained in the same manner as in Example 1.

<Evaluation>
For the two-component black developers (1) to (4) obtained in Examples 9 to 12 and the two-component black developer (5) 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, the charge amount of toner after stirring for 10 seconds and 300 seconds using the method for measuring charge amount 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 1.
[Chargeability]
A: Very good (−20 μC / g or less)
○: Good (−19.9 to −10.0 μC / g)
Δ: Practical use possible (−9.9 to −5.0 μC / g)
×: Not practical (-4.9 μC / g or more)

(Example 13)
-Styrene-butyl acrylate copolymer resin (glass transition temperature 70 ° C) 100 parts by mass-Magenta pigment (CI Pigment Red 114) 5 parts by mass-Exemplified compound F 2 parts by mass The above composition is mixed and a biaxial extruder The mixture was melt kneaded at (L / D = 30). The kneaded product was cooled, coarsely pulverized with a hammer mill, finely pulverized with a jet mill, and then classified to obtain magenta colored particles (1) by a pulverization method. The magenta colored particles (1) had a weight average particle size of 7.0 μm and a fine powder amount of 5.6% 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 is dry-mixed with a Henschel mixer. Thus, the magenta (red) toner (1) of this example was obtained. Further, 7 parts by mass of the obtained magenta (red) toner (1) and 93 parts by mass of a resin-coated magnetic ferrite carrier (average particle size: 45 μm) are mixed to produce a two-component magenta (red) for magnetic brush development. Developer (1) was prepared.

(Examples 14 to 16)
Magenta (red) toners (2) to (4) of Examples 14 to 16 were obtained in the same manner as in Example 13, except that Exemplified Compound F was changed to Exemplified Compounds K, L, and M, respectively. The characteristics of this toner were measured in the same manner as in Example 1. The results are shown in Table 1. Using this, in the same manner as in Example 13, the two-component magenta (red) developers (2) to (4) of Examples 14 to 16 were obtained.

(Comparative Example 4)
A magenta (red) toner (5) of Comparative Example 4 was obtained in the same manner as in Example 13 except that the exemplified compound was not used. The characteristics of this toner were measured in the same manner as in Example 1. The results are shown in Table 1. In addition, using this, the two-component magenta (red) developer (5) of Comparative Example 4 was obtained in the same manner as in Example 13.

<Evaluation>
Regarding the two-component magenta (red) developers (1) to (4) obtained in Examples 13 to 16 and the two-component magenta (red) developer (5) obtained in Comparative Example 4, Stir for 10 seconds and 300 seconds under the normal humidity (25 ° C., 60% RH) and high temperature and high humidity (30 ° C., 80% RH) using the above-mentioned method for measuring the charge amount. The charge amount of the subsequent toner 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.
[Chargeability]
A: Very good (−20 μC / g or less)
○: Good (−19.9 to −10.0 μC / g)
Δ: Practical use possible (−9.9 to −5.0 μC / g)
×: Not practical (-4.9 μC / g or more)

(Examples 17 to 20)
Except that 2.0 parts by mass of each of Exemplified Compounds D, N, O, and P were used, and carbon black (DBP oil absorption 110 mL / 100 g) was used instead of the magenta pigment, the same procedure as in Example 13 was performed. Black toners (6) to (9) of Examples 17 to 20 were obtained. The characteristics of these toners were measured in the same manner as in Example 1, and the results are shown in Table 1. In addition, using this, in the same manner as in Example 13, two-component black developers (6) to (9) were obtained.

(Comparative Example 5)
A black toner (10) of Comparative Example 5 was obtained in the same manner as in Example 13, 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 1. The results are shown in Table 1. Further, using this, the two-component black developer (10) of Comparative Example 5 was obtained in the same manner as in Example 13.

<Evaluation>
About the two-component black developers (6) to (9) obtained in Examples 17 to 20 and the two-component black developer (10) 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, the charge amount of toner after stirring for 10 seconds and 300 seconds using the method for measuring charge amount 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 1.
[Chargeability]
A: Very good (−20 μC / g or less)
○: Good (−19.9 to −10.0 μC / g)
Δ: Practical use possible (−9.9 to −5.0 μC / g)
×: Not practical (-4.9 μC / g or more)

(Example 21)
・ Polyester resin 100 parts by mass Carbon black 5 parts by mass (DBP oil absorption 110 mL / 100 g)
-Exemplified Compound Q 2 parts by mass The polyester resin was synthesized as follows. Bisphenol A propylene oxide 2-mole adduct 751 parts, terephthalic acid 104 parts and trimellitic anhydride 167 parts were polycondensed using 2 parts of dibutyltin oxide as a catalyst 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 (11) by a pulverization method. The black colored particles (11) had a weight average particle size of 7.0 μm and a fine powder amount of 4.9% by number.
To 100 parts by mass of the black colored particles (11), 1.5 parts by mass of a hydrophobic silica fine powder (BET: 250 m ^{2 /} g) treated with hexamethyldisilazane as a flow improver is dry-mixed with a Henschel mixer. As a result, a black toner (11) of this example was obtained. Further, 7 parts by mass of the obtained black toner (11) and 93 parts by mass of a resin-coated magnetic ferrite carrier (average particle diameter: 45 μm) are mixed to prepare a two-component black developer (11) for magnetic brush development. Prepared.

(Examples 22 to 24)
Black toners (11) to (14) of Examples 22 to 24 were obtained in the same manner as in Example 21, except that the exemplified compound Q was changed to the exemplified compounds R, S, and T, respectively. The characteristics of this toner were measured in the same manner as in Example 1. The results are shown in Table 1. In addition, using this, in the same manner as in Example 21, two-component black developers (11) to (14) of Examples 22 to 24 were obtained.

(Comparative Example 6)
A black toner (15) of Comparative Example 6 was obtained in the same manner as in Example 21 except that the exemplified compound was not used. The characteristics of this toner were measured in the same manner as in Example 1. The results are shown in Table 1. In addition, using this, the two-component black developer (15) of Comparative Example 6 was obtained in the same manner as in Example 21.

<Evaluation>
About the two-component black developers (11) to (14) obtained in Examples 21 to 24 and the two-component black developer (15) obtained in Comparative Example 6, normal temperature and normal humidity (25 ° C., 60% RH) and high-temperature and high-humidity (30 ° C., 80% RH) environments, the charge amount of toner after stirring for 10 seconds and 300 seconds using the method for measuring charge amount 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 1.
[Chargeability]
A: Very good (−20 μC / g or less)
○: Good (−19.9 to −10.0 μC / g)
Δ: Practical use possible (−9.9 to −5.0 μC / g)
×: Not practical (-4.9 μC / g or more)

(Example 25 to Example 30 and Comparative Example 7 to Comparative Example 12)
First, image forming apparatuses used in the image forming methods of Examples 25 to 30 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 is opposed to 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 core metal 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 photosensitive member according to digital image information by the polygon mirror. An electrostatic charge image having a dark portion 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, and 4-4. A toner image is formed. At that time, as the developer, the two-component developers obtained in Examples 2, 6, 9, 16, 20, 24 and Comparative Examples 1 to 6 were used, respectively, with yellow toner, magenta toner, cyan toner or black toner. A toner image was formed. 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 includes 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 5a 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 5a measured in accordance with “JISK-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 a sufficiently large amount of carbon in a foam of ethylene-propylene-diene three-dimensional copolymer (EPDM) on a cored bar 7b having an outer diameter of 10 mm and carbon as a conductivity-imparting material. Thus, an elastic layer 7a coated with a material dispersed in such a state is formed. The volume specific resistance value was 10 ⁶ Ω · cm, and the hardness measured in accordance with “JIS K-6301” showed 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. 5 and 6 is used as the heat fixing apparatus H. 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 conditions, Example 2 at a printout speed of 8 sheets (A4 size) / min under normal temperature and normal humidity (25 ° C, 60% RH) and high temperature and high humidity (30 ° C, 80% RH) environment, A two-component developer produced using the toners 6, 9, 16, 20, and 24 and a two-component developer produced using the toners of Comparative Examples 1 to 6, respectively, were replenished sequentially. However, a printout test was performed in a single color intermittent mode (that is, a mode in which the developing device is paused for 10 seconds each time one printout is performed, and toner deterioration is promoted by a preliminary operation upon restarting). Printout images were evaluated for the following items: The evaluation results are summarized in Table 2.

[Printout image evaluation]
1. Image Density A predetermined number of printouts were made on ordinary copier 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 Co.) was used, and the relative density with respect to a printout image of a white background portion having an original density of 0.00 was measured and used for evaluation.
A: Excellent (image density at the end is 1.40 or higher)
○: Good (the image density at the end is 1.35 or more and less than 1.40)
Δ: Acceptable (image density at 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 type densitometer (Reflectometric Meter ODEL TC-6DS manufactured by TOKYODENSHOKU CO., LTD) is Ds, and the average reflection density value of the paper before printing is Dr. (Ds-Dr) was determined from the value of the value, 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 is 1.5% or more and less than 3.0%)
Δ: Practical use possible (fogging amount of 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 / m2), 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 ×: Practical use not possible

  Also, in Example 25 to Example 30 and Comparative Example 7 to Comparative Example 12, when the image output of 5000 sheets was performed, the occurrence of scratches on the surface of the photosensitive drum and the intermediate transfer member and the sticking of residual toner, and the printout image When the two-component developer in Examples 25 to 30 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. Furthermore, in the system using the two-component developer of Comparative Examples 7 to 12, the toner can be confirmed to adhere to the surface of the intermediate transfer member and the surface can be confirmed. There was a problem in matching with the forming device.

(Example 31 to Example 33, Comparative Example 13 to Comparative Example 15)
In carrying out the image forming methods of Examples 31 to 33 and Comparative Examples 13 to 15, the toners obtained in Examples 2, 6, and 9 and Comparative Examples 1 to 3 were used as developers, respectively. 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 A system that feeds the toner into the cleaner 21, passes through the cleaner reuse 23, returns to the developing device 26 through a hopper 25 by a supply pipe 24 provided with a conveying screw, and again uses a collected toner is attached. .
In the image forming apparatus shown in FIG. 3, the surface of the photosensitive drum 20 is charged by the primary charging roller 27. As the primary charging roller 27, a rubber roller (diameter 12 mm, contact pressure 50 gf / cm) coated with nylon resin and dispersed with conductive carbon is used, and an electrostatic latent image carrier (photosensitive drum 20). On the top, an electrostatic latent image having a dark part potential VD = −700 V and a bright part 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 a one-component developer used in Examples 31 to 33 and Comparative Examples 13 to 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 surface of the opposing photosensitive drum 20, and the photosensitive drum 20 is further developed. And the developing sleeve 28 is set to a distance α (between S and D) of 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 humidity (25 ° C., 60% RH) environment, at a printout speed of 8 sheets (A4 size) / min. In a mode in which the toner consumption is promoted without printing), up to 30,000 sheets were printed out, the image density of the obtained printout image was measured, and the durability was evaluated according to the criteria shown below. 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 3.

[Image density transition during durability]
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 Co.) was used, and the relative density with respect to a printout image of a white background portion having an original density of 0.00 was measured and used for evaluation.
A: Excellent (image density at the end is 1.40 or higher)
○: Good (the image density at the end is 1.35 or more and less than 1.40)
Δ: Acceptable (image density at 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 type densitometer (Reflectometric Meter ODEL TC-6DS manufactured by TOKYODENSHOKU CO., LTD) is Ds, and the average reflection density value of the paper before printing is Dr. (Ds-Dr) was determined from the value of the value, 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 is 1.5% or more and less than 3.0%)
Δ: Practical use possible (fogging amount of 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 residual toner adhering to the surface of the developing sleeve and the effect on the printout image were visually evaluated.
A: Very good (not generated)
○: Good (almost no occurrence)
Δ: Practical use possible (there is sticking, but there is little influence on the image)
×: Impractical (non-sticking, causing image unevenness)
2. Matching with the photoconductive drum The surface of the photoconductive drum was scratched, the residual toner was fixed, and the printout image was visually evaluated.
A: Very good (not generated)
○: Good (slight scratches are observed, but there is no effect on the image)
Δ: Practical (possibly fixed or scratched, but has little effect on the image)
×: Impractical use (Many sticking, causing vertical streak-like image defects)
3. Matching with fixing device The state of the surface of the fixing film was observed, and the results of the surface property and the fixing state of the residual toner 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.
A: Very good (not generated)
○: Good (almost no occurrence)
Δ: Practical use ×: Practical use (2) Residual toner fixing situation The residual toner fixing condition on the surface of the fixing film after the printout test was visually observed and evaluated.
A: Very good (not generated)
○: Good (almost no occurrence)
Δ: Practical use ×: Practical use not possible

(Example 34)
While removing the toner reuse mechanism of the image forming apparatus in FIG. 3 and changing the printout speed to 16 sheets (A4 size) / min, the same as in Example 31, while sequentially supplying the yellow toner (2) of Example 6 The printout test was performed in a continuous mode (ie, a mode that promotes toner consumption without pausing the developer). The same items as in Examples 31 to 33 and Comparative Examples 13 to 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 35-38)
Blue toners (6) to (9) of Examples 35 to 38 were obtained in the same manner as in Example 1 except that the exemplified compound A was changed to the exemplified compounds 2A, 2B, 2C, and 2D, respectively. The toner characteristics were measured in the same manner as in Example 1. The results are shown in Table 4. In addition, using this, in the same manner as in Example 1, the two-component blue developers (6) to (9) of Examples 35 to 38 were obtained.

<Evaluation>
For the two-component blue developers (6) to (9) obtained in Examples 35 to 38, normal temperature and normal humidity (25 ° C., 60% RH) and high temperature and high humidity (30 ° C., 80% RH) Under each environment, the charge amount of the toner after stirring for 10 seconds and 300 seconds was measured using the method for measuring the charge amount described above. 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 4.
[Chargeability]
A: Very good (−20 μC / g or less)
○: Good (−19.9 to −10.0 μC / g)
Δ: Practical use possible (−9.9 to −5.0 μC / g)
×: Not practical (-4.9 μC / g or more)

(Examples 39 to 42)
Except that 2.0 parts by mass of Exemplified Compounds 2E, 2F, 2G, and 2H are used, and a yellow colorant (Hansa Yellow G) is used in place of the cyan colorant, Example 1 is used. 39 to 42 yellow (yellow) toners (6) to (9) were obtained. The characteristics of these toners were measured in the same manner as in Example 1, and the results are shown in Table 4. In addition, using this, in the same manner as in Example 1, two-component yellow (yellow) developers (6) to (9) were obtained.

<Evaluation>
About the two-component yellow (yellow) developers (6) to (9) obtained in Examples 39 to 42, 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 was measured using the charge amount measurement method described above. 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 4.
[Chargeability]
A: Very good (−20 μC / g or less)
○: Good (−19.9 to −10.0 μC / g)
Δ: Practical use possible (−9.9 to −5.0 μC / g)
×: Not practical (-4.9 μC / g or more)

(Examples 43 to 46)
Except for using 2.0 parts by mass of each of Exemplified Compounds 2I, 2J, 2K, and 2L, and using carbon black (DBP oil absorption 110 mL / 100 g) instead of the cyan colorant, Black toners (16) to (19) of Examples 43 to 46 were obtained. The characteristics of these toners were measured in the same manner as in Example 1, and the results are shown in Table 4. In addition, using this, in the same manner as in Example 1, two-component black developers (16) to (19) were obtained.

<Evaluation>
About the two-component black developers (16) to (19) obtained in Examples 43 to 46, normal temperature and normal humidity (25 ° C., 60% RH), and high temperature and high humidity (30 ° C., 80% RH). Under each environment, the charge amount of the toner after stirring for 10 seconds and 300 seconds was measured using the method for measuring the charge amount described above. 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 4.
[Chargeability]
A: Very good (−20 μC / g or less)
○: Good (−19.9 to −10.0 μC / g)
Δ: Practical use possible (−9.9 to −5.0 μC / g)
×: Not practical (-4.9 μC / g or more)

(Examples 47 to 50)
Magenta (red) toners (6) to (9) of Examples 47 to 50 were obtained in the same manner as in Example 13, except that Exemplified Compound F was changed to Exemplified Compounds 2M, 2N, 2O and 2P, respectively. The toner characteristics were measured in the same manner as in Example 1. The results are shown in Table 4. Using this, in the same manner as in Example 13, the two-component magenta (red) developers (6) to (9) of Examples 47 to 50 were obtained.

<Evaluation>
For the two-component magenta (red) developers (6) to (9) obtained in Examples 47 to 50, 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 was measured using the charge amount measurement method described above. 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 4.
[Chargeability]
A: Very good (−20 μC / g or less)
○: Good (−19.9 to −10.0 μC / g)
Δ: Practical use possible (−9.9 to −5.0 μC / g)
×: Not practical (-4.9 μC / g or more)

(Example 51 to Example 54)
Image formation was performed in the same manner as in Example 25. As the developer, the two-component developers obtained in Examples 36, 41, 44, and 50 were used, and toner images were formed with blue toner, yellow toner, black toner, or red toner.

<Evaluation>
Under the same conditions as in Example 25, at a normal temperature and humidity (25 ° C., 60% RH) and a high temperature and high humidity (30 ° C., 80% RH) environment, a printout speed of 8 sheets (A4 size) / min. A two-component developer prepared using the toners of Examples 36, 41, 44 and 50 was used, respectively, and replenished sequentially while developing in a single color intermittent mode (ie, developing for 10 seconds each time one sheet was printed out). The printer was paused, and a printout test was conducted in a mode in which toner deterioration was promoted by a preliminary operation upon restarting, and the obtained printout images were evaluated for the following items. The evaluation results are summarized in Table 5.

[Printout image evaluation]
1. Image Density A predetermined number of printouts were made on ordinary copier 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 Co.) was used, and the relative density with respect to a printout image of a white background portion having an original density of 0.00 was measured and used for evaluation.
A: Excellent (image density at the end is 1.40 or higher)
○: Good (the image density at the end is 1.35 or more and less than 1.40)
Δ: Acceptable (image density at 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 type densitometer (Reflectometric Meter ODEL TC-6DS manufactured by TOKYODENSHOKU CO., LTD) is Ds, and the average reflection density value of the paper before printing is Dr. (Ds-Dr) was determined from the value of the value, 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 is 1.5% or more and less than 3.0%)
Δ: Practical use possible (fogging amount of 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 / m2), 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 ×: Practical use not possible

  Further, in Example 51 to Example 54, the occurrence of scratches on the surface of the photosensitive drum and the intermediate transfer member and the sticking of the residual toner and the influence on the printout image when outputting 5000 images (with the image forming apparatus) As a result of visual evaluation of the matching), in the system using the two-component developer of Example 51 to Example 54, the scratches on the surface of the photosensitive drum and the intermediate transfer member and the fixing of the residual toner could not be confirmed at all. Matching with the forming apparatus was very good.

(Example 55 to Example 58)
Image formation was performed in the same manner as in Example 31. The toners obtained in Examples 36, 41, 44 and 50 were used as developers, and toner images were formed with blue toner, yellow toner, black toner or red toner.

<Evaluation>
In the same manner as in Example 31, continuous mode (i.e., the developer is used) while supplying toner sequentially at a printout speed of 8 sheets (A4 size) / min in an environment of normal temperature and normal humidity (25 ° C., 60% RH). In a mode in which toner consumption is promoted without pausing), up to 30,000 sheets were printed out, the image density of the obtained printout image was measured, and the durability was evaluated according to the criteria shown below. 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 6.

[Image density transition during durability]
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 Co.) was used, and the relative density with respect to a printout image of a white background portion having an original density of 0.00 was measured and used for evaluation.
A: Excellent (image density at the end is 1.40 or higher)
○: Good (the image density at the end is 1.35 or more and less than 1.40)
Δ: Acceptable (image density at 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 type densitometer (Reflectometric Meter ODEL TC-6DS manufactured by TOKYODENSHOKU CO., LTD) is Ds, and the average reflection density value of the paper before printing is Dr. (Ds-Dr) was determined from the value of the value, 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 is 1.5% or more and less than 3.0%)
Δ: Practical use possible (fogging amount of 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 residual toner adhering to the surface of the developing sleeve and the effect on the printout image were visually evaluated.
A: Very good (not generated)
○: Good (almost no occurrence)
Δ: Practical use possible (there is sticking, but there is little influence on the image)
×: Impractical (non-sticking, causing image unevenness)
2. Matching with the photoconductive drum The surface of the photoconductive drum was scratched, the residual toner was fixed, and the printout image was visually evaluated.
A: Very good (not generated)
○: Good (slight scratches are observed, but there is no effect on the image)
Δ: Practical (possibly fixed or scratched, but has little effect on the image)
×: Impractical use (Many sticking, causing vertical streak-like image defects)
3. Matching with fixing device The state of the surface of the fixing film was observed, and the results of the surface property and the fixing state of the residual toner 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.
A: Very good (not generated)
○: Good (almost no occurrence)
Δ: Practical use ×: Practical use (2) Residual toner fixing situation The residual toner fixing condition on the surface of the fixing film after the printout test was visually observed and evaluated.
A: Very good (not generated)
○: Good (almost no occurrence)
Δ: Practical use ×: Practical use not possible

(Examples 59 and 60)
In the same manner as in Example 34, the toner consumption is promoted while the blue toner (7) in Example 36 or the red toner (9) in Example 50 is replenished in succession (ie, without stopping the developing device). The printout test was performed in the mode for The same items as in Example 55 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.

  The present invention can be used as a constituent of toner for developing an electrostatic image.

6 is a schematic explanatory diagram of an image forming apparatus used in Examples 25 to 30 and Comparative Examples 7 to 12. FIG. It is sectional drawing of the principal part of the developing apparatus for two-component developers used for Example 25-Example 30 and Comparative Example 7-Comparative Example 12. FIG. 6 is a schematic explanatory diagram of an image forming apparatus having a toner reuse mechanism used in Examples 31 to 34 and Comparative Examples 13 to 15. FIG. FIG. 6 is a cross-sectional view of a main part of a developing device for a one-component developer used in Examples 31 to 34 and Comparative Examples 13 to 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 Photosensitive drum (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 body 6 Transfer material 7 Transfer roller 13 Photosensitive drum 11, 28 Developer carrier (developing sleeve)
30 stays 31 heating element 31a heater substrate 31b heating element 31c surface protection layer 31d temperature detecting element 32 fixing film 33 heating roller 34 coil spring 35 film edge regulating flange 36 power supply connector 37 insulating member 38 inlet guide 39 outlet guide (separation guide)
43 Screen 45 Vacuum gauge 47 Suction port 49 Electrometer

Claims (10)

A charge control agent for controlling a charged state of a granular material, wherein the unit contains at least one unit represented by the following chemical formula (1) in a molecule.

(Wherein, R represents -A1-SO ₂ R1,
R1 represents OH, a halogen atom, ONa, OK or OR1a;
R1a and A1 each independently represents a group having a substituted or unsubstituted aliphatic hydrocarbon structure, a substituted or unsubstituted aromatic ring structure, or a substituted or unsubstituted heterocyclic structure.
In addition, about l, m, Z1a, Z1b in the formula,
When l is an integer selected from 2 to 4, Z1a is not selected or is a linear alkylene chain having 1 to 4 carbon atoms, Z1b is a hydrogen atom, and m is selected from 0 to 8 An integer,
When l is 1 and Z1a is a linear alkylene chain having 1 to 4 carbon atoms, Z1b is a hydrogen atom, m is an integer selected from 0 to 8,
When l is 1 and Z1a is not selected, Z1b is a hydrogen atom, m is 0,
When l is 0 and Z1a is a linear alkylene chain having 1 to 4 carbon atoms, the linear alkylene chain has a linear or branched alkyl group or a phenyl structure, thienyl structure, or cyclohexyl structure at the terminal. Among them, it may be substituted with an alkyl group containing a residue having any structure, and Z1b is substituted with a hydrogen atom, or a linear or branched alkyl group, aryl group, aryl group. An aralkyl group, m is an integer selected from 0 to 8;
When l is 0 and Z1a is not selected, Z1b is a hydrogen atom or a linear or branched alkyl group, aryl group, aryl group optionally substituted with an aryl group, and m is It is an integer selected from 0-8.
When there are a plurality of units, R, R 1, R 1a, A 1, Z 1a, Z 1b, l, m have the above meanings independently for each unit. ) The charge control agent according to claim 1, wherein the unit represented by the chemical formula (1) is represented by the following chemical formula (2).

(Wherein R2 represents OH, a halogen atom, ONa, OK or OR2a;
R2a represents a linear or branched alkyl group having 1 to 8 carbon atoms or a substituted or unsubstituted phenyl group, and A2 represents a linear or branched alkylene group having 1 to 8 carbon atoms.
In addition, about l, m, Z2a, Z2b in the formula,
When l is an integer selected from 2 to 4, Z2a is not selected or is a linear alkylene chain having 1 to 4 carbon atoms, Z2b is a hydrogen atom, and m is selected from 0 to 8 An integer,
When l is 1 and Z2a is a linear alkylene chain having 1 to 4 carbon atoms, Z2b is a hydrogen atom, m is an integer selected from 0 to 8,
When l is 1 and Z2a is not selected, Z2b is a hydrogen atom, m is 0,
When l is 0 and Z2a is a linear alkylene chain having 1 to 4 carbon atoms, the linear alkylene chain has a linear or branched alkyl group, or a phenyl structure, a thienyl structure, or a cyclohexyl structure at the terminal. Of these, Z2b may be substituted with an alkyl group containing a residue having any structure, and Z2b is substituted with a hydrogen atom, or a linear or branched alkyl group, aryl group, or aryl group. An aralkyl group, m is an integer selected from 0 to 8;
When l is 0 and Z2a is not selected, Z2b is a hydrogen atom or an aralkyl group which may be substituted with a linear or branched alkyl group, aryl group or aryl group, and m is It is an integer selected from 0-8.
When there are a plurality of units, R 2, R 2a, A 2, Z 2a, Z 2b, l, m have the above meanings independently for each unit. ) The charge control agent according to claim 1, wherein the unit represented by the chemical formula (1) is represented by the following chemical formula (3).

(In the formula, at least one of R 3a, R 3b, R 3c, R 3d and R 3e is SO ₂ R 3f (where R 3f represents OH, halogen atom, ONa, OK or OR 3f 1, R 3f 1 is linear or branched) Represents an alkyl group having 1 to 8 carbon atoms or a substituted or unsubstituted phenyl group.) Others are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, or 1 to 20 carbon atoms. Alkoxy group, OH group, NH ₂ group, NO ₂ group, COOR 3g (where R 3g represents H atom, Na atom or K atom), acetamide group, OPh group, NHPh group, CF ₃ group, C ₂ It represents an F ₅ group or a C ₃ F ₇ group.
In addition, about l, m, Z3a, Z3b in the formula,
When l is an integer selected from 2 to 4, Z3a is not selected or is a linear alkylene chain having 1 to 4 carbon atoms, Z3b is a hydrogen atom, and m is selected from 0 to 8 An integer,
When l is 1 and Z3a is a linear alkylene chain having 1 to 4 carbon atoms, Z3b is a hydrogen atom, m is an integer selected from 0 to 8,
When l is 1 and no Z3a is selected, Z3b is a hydrogen atom, m is 0,
When l is 0 and Z3a is a linear alkylene chain having 1 to 4 carbon atoms, the linear alkylene chain has a linear or branched alkyl group, or a phenyl structure, thienyl structure, or cyclohexyl structure at the terminal. Of these, Z3b may be substituted with an alkyl group containing a residue having any structure, and Z3b is substituted with a hydrogen atom, or a linear or branched alkyl group, aryl group, or aryl group. An aralkyl group, m is an integer selected from 0 to 8;
When l is 0 and Z3a is not selected, Z3b is a hydrogen atom, or an aralkyl group that may be substituted with a linear or branched alkyl group, aryl group, or aryl group, and m is It is an integer selected from 0-8.
When there are a plurality of units, R 3a, R 3b, R 3c, R 3d, R 3e, R 3f, R 3f 1, R 3g, Z 3a, Z 3b, l and m independently represent the above meaning for each unit. ) The charge control agent according to claim 1, wherein the unit represented by the chemical formula (1) is represented by the following chemical formula (4A) or (4B).

(In the formula, at least one of R4a, R4b, R4c, R4d, R4e, R4f and R4g is SO ₂ R4o (where R4o represents OH, halogen atom, ONa, OK or OR4o1, and R4o1 represents a straight chain) And represents a branched or branched alkyl group having 1 to 8 carbon atoms or a substituted or unsubstituted phenyl group, and the others are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, C1-C20 alkoxy group, OH group, NH ₂ group, NO ₂ group, COOR 4p (where R 4p represents an H atom, Na atom or K atom), acetamide group, OPh group, NHPh group, CF ₃ groups, C ₂ F ₅ groups or C ₃ F ₇ groups are represented.
In addition, about l, m, Z4a, Z4b in the formula,
When l is an integer selected from 2 to 4, Z4a is not selected or is a linear alkylene chain having 1 to 4 carbon atoms, Z4b is a hydrogen atom, and m is selected from 0 to 8 An integer,
When l is 1 and Z4a is a linear alkylene chain having 1 to 4 carbon atoms, Z4b is a hydrogen atom, m is an integer selected from 0 to 8,
When l is 1 and no Z4a is selected, Z4b is a hydrogen atom, m is 0,
When l is 0 and Z4a is a linear alkylene chain having 1 to 4 carbon atoms, the linear alkylene chain is a linear or branched alkyl group, or has a phenyl structure, thienyl structure, or cyclohexyl structure at the terminal. Among them, Z4b may be substituted with an alkyl group containing a residue having any structure, and Z4b is substituted with a hydrogen atom, or a linear or branched alkyl group, aryl group, or aryl group. An aralkyl group, m is an integer selected from 0 to 8;
When l is 0 and Z4a is not selected, Z4b is a hydrogen atom or a linear or branched alkyl group, aryl group, aryl group optionally substituted with an aryl group, and m is It is an integer selected from 0-8.
In addition, when there are a plurality of units, R4a, R4b, R4c, R4d, R4e, R4f, R4g, R4o, OR4o1, R4p, Z4a, Z4b, l and m have the above meanings independently for each unit. To express. )

(In the formula, at least one of R4h, R4i, R4j, R4k, R4l, R4m and R4n is SO ₂ R4o (where R4o represents OH, a halogen atom, ONa, OK or OR4o1 and R4o1 is a straight chain) Or a branched alkyl group having 1 to 8 carbon atoms or a substituted or unsubstituted phenyl group.) And the others are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, carbon An alkoxy group of 1 to 20 groups, OH group, NH ₂ group, NO ₂ group, COOR 4p (where R 4p represents an H atom, Na atom or K atom), an acetamide group, an OPh group, an NHPh group, CF ₃ Represents a group, a C ₂ F ₅ group or a C ₃ F ₇ group.
In addition, about l, m, Z4c, Z4d in the formula,
When l is an integer selected from 2 to 4, Z4c is not selected or is a linear alkylene chain having 1 to 4 carbon atoms, Z4d is a hydrogen atom, and m is selected from 0 to 8 An integer,
When l is 1 and Z4c is a linear alkylene chain having 1 to 4 carbon atoms, Z4d is a hydrogen atom, m is an integer selected from 0 to 8,
When l is 1 and no Z4c is selected, Z4d is a hydrogen atom, m is 0,
When l is 0 and Z4c is a linear alkylene chain having 1 to 4 carbon atoms, the linear alkylene chain has a linear or branched alkyl group, or a phenyl structure, thienyl structure, or cyclohexyl structure at the terminal. Of these, Z4d may be substituted with an alkyl group containing a residue having any structure, and Z4d is substituted with a hydrogen atom, or a linear or branched alkyl group, aryl group, or aryl group. An aralkyl group, m is an integer selected from 0 to 8;
When l is 0 and Z4c is not selected, Z4d is a hydrogen atom or an aralkyl group which may be substituted with a linear or branched alkyl group, aryl group or aryl group, and m is It is an integer selected from 0-8.
If there are multiple units, R4h, R4i, R4j, R4k, R4l, R4m, R4n, R4o, OR4o1, R4p, Z4c, Z4d, l and m have the above meanings independently for each unit. To express. ) The charge control agent which controls the charge state of a granular material, The charge control agent characterized by including 1 unit or more of units represented by following Chemical formula (5) in a molecule | numerator.

(Wherein R5 represents hydrogen, a salt-forming group or R5a, and R5a represents a linear or branched alkyl group having 1 to 12 carbon atoms or an aralkyl group.
Also, for l, m, Z5a, Z5b in the formula,
When l is an integer selected from 2 to 4, Z5a is not selected or is a linear alkylene chain having 1 to 4 carbon atoms, Z5b is a hydrogen atom, and m is selected from 0 to 8 An integer,
When l is 1 and Z5a is a linear alkylene chain having 1 to 4 carbon atoms, Z5b is a hydrogen atom, m is an integer selected from 0 to 8,
When l is 1 and no Z5a is selected, Z5b is a hydrogen atom, m is 0,
When l is 0 and Z5a is a linear alkylene chain having 1 to 4 carbon atoms, the linear alkylene chain has a linear or branched alkyl group or a phenyl structure, a thienyl structure, or a cyclohexyl structure at the terminal. Of these, Z5b may be substituted with an alkyl group including a residue having any structure, and Z5b is substituted with a hydrogen atom, or a linear or branched alkyl group, aryl group, or aryl group. An aralkyl group, m is an integer selected from 0 to 8;
When l is 0 and Z5a is not selected, Z5b is a hydrogen atom or an aralkyl group which may be substituted with a linear or branched alkyl group, aryl group or aryl group, and m is It is an integer selected from 0-8.
Further, when there are a plurality of units, R5, R5a, Z5a, Z5b, l, and m have the above meanings independently for each unit. ) 6. The charge control agent according to claim 1, further comprising a unit represented by the following chemical formula (7) in the molecule.

(In the formula, R7 represents a linear or branched alkylene group having 1 to 11 carbon atoms, an alkyleneoxyalkylene group having 1 to 2 carbon atoms in each alkylene, or a carbon optionally substituted with an aryl group. The alkylidene group of number 1-5 is represented.
Further, when a plurality of units are present, R7 represents the above meaning independently for each unit. )   The charge control agent according to claim 1, wherein the granular material is an electrostatic image developing toner.   An electrostatic charge image developing toner, comprising at least a binder resin, a colorant, and the charge control agent according to any one of claims 1 to 6.   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 image on the charged electrostatic latent image carrier, and the electrostatic image as an electrostatic 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, wherein the electrostatic image developing toner according to claim 8 is used.   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 for fixing an image by heating, wherein the electrostatic image developing toner according to claim 8 is used.

Images