JP2006039533A - Resin coated carrier for electrophotographic developer, two-component developer and replenishing developer containing the carrier as constituent - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin-coated carrier for an electrophotographic developer capable of providing an image with excellent image quality, and to provide a two-component developer and a replenishing developer each of which contains the resin-coated carrier as a constituent. <P>SOLUTION: The resin-coated carrier for the electrophotographic developer, including: a core; and a resin coating layer containing a polyhydroxyalkanoate containing one or more units each represented by chemical formula (1) in a molecule, the resin coating layer being placed on the core. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a resin-coated carrier for an electrophotographic developer constituting a two-component developer used for developing an electrostatic latent image such as electrophotography, electrostatic recording, and electrostatic printing, and the resin-coated carrier. The present invention relates to a two-component developer and a replenishment developer as constituent components.

  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 following chemical formula (14) and a β type represented by the following chemical formula (15) are known depending on the polymer form.

  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 the following 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 a 6-membered ring represented by Chemical formula (17). A polymer obtained by copolymerizing a diester monomer, 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 a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a t-butyl group, or a benzyl group.)

  In addition, as polyhydroxyalkanoate having a carboxyl group in the side chain, Non-Patent Document 1 produces a polymer having an ester group in the side chain by ring-opening polymerization of 7-oxo-4-oxepanecarboxylic acid ester. Furthermore, it is disclosed that a polymer having a carboxylic acid in the side chain was produced by hydrogenolysis.

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.

  There has been a report on a polymer having a new function by introducing a structure imparting functionality to a polyhydroxyalkanoate into which a functional group that can be chemically modified is introduced as described above. In Non-Patent Document 6, an α-type malic acid-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 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.

  Further, a polyhydroxyalkanoate represented by the following chemical formula (6) is used as a starting material, and the side chain carbon-carbon double bond is oxidatively cleaved with an oxidizing agent to represent a polyhydroxyalkano represented by the following chemical formula (21). As for the method for obtaining ate, for example, the method using permanganate is in Non-Patent Document 7, the method using dichromate is in Non-Patent Document 8, and the method using periodate is in Non-Patent Document 9. A method using nitric acid is disclosed in Patent Document 4 and a method using ozone is disclosed in Non-Patent Document 10. Non-Patent Document 11 discloses that a carbon-carbon double bond at the end of a side chain of a polyhydroxyalkanoate produced by a microorganism is used by using potassium permanganate as an oxidant and carrying out the reaction under acidic conditions. Methods for obtaining acids have been reported.

  On the other hand, an electrophotographic method in which an electrostatic latent image is formed on the surface of a photoconductive material by electrostatic means, and the latent image is developed to form an image is well known in the art, and many methods are known. That is, in electrophotography, generally, a photoconductive material is used to form an electrical latent image on a photoreceptor by various means, and then the latent image is carried and transported by a developer carrier. A toner image corresponding to an electrostatic latent image is formed by adhering a very finely pulverized electrophotographic material called toner, and the toner image is transferred onto the surface of an image support such as paper as necessary. Thereafter, the toner image is fixed by heating, pressing or solvent vapor to obtain a copy.

  As development methods for visualizing an electric latent image using toner, a powder cloud method, a cascade development method, a magnetic brush method, a method using a conductive magnetic toner, and the like are known. In addition to the above, a so-called J / B development method is known in which development is performed by applying a bias electric field composed of an alternating current component and a direct current component between a developer carrier (developing sleeve) and a photoconductive layer. . A typical method of the developing method is a magnetic brush method. In the magnetic brush method, a two-component developer composed of toner and a magnetic carrier is used. By using magnetic particles such as steel and ferrite as a carrier, a developer carrier having a magnet built in is used. The developer containing the magnetic carrier is held, and the developer is arranged in a brush shape on the developer carrier by the magnetic field of the magnet. When the magnetic brush comes into contact with the electrostatic latent image surface on the photoconductive layer, only the toner in the developer is attracted from the brush to the electrostatic latent image, and the electrostatic latent image is developed.

  Carriers constituting the two-component developer applied to the above developing method are roughly classified into conductive carriers and insulating carriers, and usually oxidized or unoxidized iron powder is used as the conductive carrier. Yes. However, the developer containing the iron powder carrier as a constituent component has an unstable triboelectric chargeability with respect to the toner. On the other hand, a typical example of the insulating carrier is a resin-coated carrier in which the surface of a carrier core made of a ferromagnetic material such as iron, nickel, or ferrite is uniformly coated with an insulating resin. Developers using such an insulating resin-coated carrier are extremely less likely to cause toner particles to fuse to the carrier surface as compared to the conductive carrier described above, and frictional charging between the toner and the carrier. It is easy to control the properties, has excellent durability and has a long service life, and is particularly suitable for high-speed electronic copying machines.

  Here, there are various properties required for the insulating carrier, but particularly important properties include appropriate charging properties, impact resistance, wear resistance, good adhesion between the core material and the coating material, Examples include uniformity of charge distribution. In order to prevent the spent of the carrier such as toner welding, a proposal has been made to improve the durability of the developer by using a resin having a low surface energy as the coating layer material. That is, it is said that a carrier coated with a silicone resin, a fluororesin or the like hardly causes a spent and has a long life as a developer. As described in Patent Document 3, the resin coating layer was improved by adding various silane coupling agents to the condensation reaction type silicone resin.

  Further, another problem in the electrophotographic carrier is related to durability stability and environmental stability. In terms of durability stability, in general, the initial charge amount rises slowly, fogging occurs in the initial image, and the image density tends to increase. Further, in the long-term copying durability, the charge amount is lowered, and the image tends to be fogged or the image density tends to be high. In terms of environmental stability, in general, the charge amount tends to decrease in a high humidity environment, fogging occurs in the image, the image density increases, and toner scattering tends to occur. In a low humidity environment, the charge amount is likely to increase, and the image density tends to decrease.

U.S. Pat. No. 4,265,247 Japanese Patent Laid-Open No. 2-3415 Japanese Patent Laid-Open No. 62-121462 JP 59-190945 A “Macromolecules, Vol. 33, No. 13, p. 4619, 2000. “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 “Journal of Chemical Society, Parkin Transactions” (J. Chem. Soc., Perkin. Trans.), 1973, Vol. 1, p. 806 “Organic Synthesis”, 1963, Vol. 4, p. 698 “Journal of Organic Chemistry” (J. Org. Chem.), 1981, Vol. 46, p. 19 “Journal of American Chemical Society (J. Am. Chem. Soc.)”, 1959, vol. 81, p. 4273 “Macromolecular chemistry”, 2001, vol. 4, p. 289-293

  The present invention provides a resin-coated carrier for an electrophotographic developer, a two-component developer containing the resin-coated carrier as a constituent, and a replenishment developer. Specifically, the present invention is a resin-coated carrier in which the resin coating layer is stably attached to the surface of the core material, and in addition to sufficient charge imparting properties, it is excellent in environmental stability and further has sufficient durability. A resin-coated carrier for electrophotography capable of providing an image with excellent image quality that is difficult to cause image flow and the like, and a two-component developer and a replenishing developer containing the resin-coated carrier as constituents are provided. Is.

  The resin-coated carrier for electrophotographic development according to the present invention that has achieved the above-mentioned object is a resin coating layer containing a polyhydroxyalkanoate containing at least one unit represented by the following chemical formula (1) in a molecule on a core material A resin-coated carrier for an electrophotographic developer.

(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 resin-coated carrier for electrophotographic development according to the present invention has a resin coating layer containing a polyhydroxyalkanoate containing one or more units represented by the following chemical formula (5) in the molecule on the core material. A resin-coated carrier for an electrophotographic developer.

(Wherein R5 represents hydrogen, a group that forms a salt (as a group that forms a salt, Na, K, etc.) or R5a, and R5a is a straight chain having 1 to 12 carbon atoms. Alternatively, it represents a branched alkyl group 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. )

Further, the two-component developer according to the present invention is a two-component developer comprising a resin-coated carrier and a toner containing at least a binder resin and a colorant as the constituent components. A two-component developer characterized by being a coat carrier.
The replenishment developer according to the present invention is a replenishment developer containing 2 to 50 parts by mass of toner with respect to 1 part by mass of the carrier, and the carrier is the resin-coated carrier.

  According to the present invention, a resin-coated carrier for an electrophotographic developer having a characteristic in which a resin coating layer is stably attached to a carrier core material and has excellent environmental stability in addition to sufficient chargeability to toner, Provided are a two-component developer comprising the resin-coated carrier and a toner containing at least a binder resin and a colorant as a constituent, and a replenishment developer containing a predetermined amount of toner with respect to the resin-coated carrier. .

  Hereinafter, the present invention will be described in detail with reference to preferred embodiments. As a result of intensive studies on the above-described problems of the prior art, the present inventors have found a unit represented by the following chemical formula (1) on the core material,

(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. )

  Or a unit represented by the following chemical formula (5)

(Wherein R5 represents hydrogen, a group that forms a salt (the group that forms a salt represents Na or K) or R5a, and R5a is a linear or branched group having 1 to 12 carbon atoms. Represents an alkyl group 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. )

A resin-coated carrier for an electrophotographic developer having a resin coating layer containing a polyhydroxyalkanoate containing one or more of any of the above in a molecule is excellent in durability and sufficiently charged without being influenced by the environment. Furthermore, the present invention has been completed by knowing that it is possible to obtain an excellent image quality without any image flow even for an image flow that tends to occur remarkably under high humidity. It came to do.

  Here, the polyhydroxyalkanoate used in the present invention has a basic skeleton as a biodegradable resin, and therefore can be used for production of various products by melt processing or the like, as in the case of conventional plastics. At the same time, unlike petroleum-derived synthetic polymers, it has the outstanding characteristic of being decomposed by living organisms and taken into the natural material circulation. Therefore, it is not necessary to perform a combustion treatment, and is an effective material from the viewpoint of preventing air pollution and global warming, and can be used as a plastic that enables environmental conservation.

  The polyhydroxyalkanoate 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 at least one aminosulfonic acid compound represented by the chemical formula (13). It is manufactured by the reaction of

(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, 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.

(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 represents 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 a C1-C8 linear or branched substituted or unsubstituted alkylene group, a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthalene group, a 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, a compound represented by the following chemical formula (18) is exemplified.

(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 C 1 -C 8 linear or branched substituted or unsubstituted alkylene group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group, etc. may be substituted.

  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.

  In the case where 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 R3a, R3b, R3c, R3d and R3e is SO2R3f (wherein R3f represents OH, a halogen atom, ONa, OK or OR3f1, and R3f1 represents a linear or branched carbon The other is independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkyl group having 1 to 20 carbon atoms. Alkoxy group, OH group, NH2 group, NO2 group, COOR3g (wherein R3g represents an H atom, Na atom or K atom), an acetamide group, an OPh group (Ph represents a phenyl group), an NHPh group, CF3 group, C2 F5 group or C3 F7 group, and when there are a plurality of units, R3a, R3b, R3c, R3d, R3e, R3f, R3f1, R3g are as defined above independently for each unit. Represents.)

  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, 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, 4-nitroaniline-2-sulfonic acid, 1,5-dinitroaniline-4-sulfonic acid, 2-aminophenol-4-hydroxy-5-nitrobenzenesulfonic acid, 2, 4-dimethylaniline-5-sulfonic acid, 2,4-dimethylaniline-6-sulfonic acid, 3,4-dimethyla Phosphorus-5-sulfonic acid, 4-isopropylaniline-6-sulfonic acid, 4-trifluoromethylaniline-6-sulfonic acid, 3-carboxy-4-hydroxyaniline-5-sulfonic acid, 4-carboxyaniline-6 Examples thereof include 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 SO2 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 phenyl group. And the others are each independently a hydrogen atom, halogen atom, alkyl group having 1 to 20 carbon atoms, alkoxy group having 1 to 20 carbon atoms, OH group, NH2 group, NO2 group, COOR4p ( R4p represents an H atom, Na atom or K atom), an acetamide group, an OPh group (Ph represents a phenyl group), an NHPh group, a CF3 group, a C2 F5 group or a C3 F7 group. .Also When there are multiple units, R4a, R4b, R4c, R4d, R4e, R4f, R4g, R4h, R4i, R4j, R4k, R4l, R4m, R4n, R4o, R4o1, and R4p are independent for each unit. Represents the above meaning.)

  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 include 2-aminopyridine-6-sulfonic acid, 2-aminopiperazine-6-sulfonic acid, sulfonic acid, or alkali metal salts and esterified products thereof.

  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. Those having groups such as OCH3, OC2H5, OC6H5, OC3H7, OC4H9, OCH (CH3) 2, OCH2C (CH3) 3, OC (CH3) 3 and the like from the viewpoint of ease of esterification preferable.

(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 in 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. Although reaction temperature is not specifically limited, Usually, it is the temperature of the range of -20 degreeC-the boiling point of a solvent. However, it is desirable to carry out the reaction at an optimum temperature according to the condensing agent used. 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 polyhydroxyalkanoate represented by the chemical formula (1) thus produced can be isolated and purified from a reaction solution containing the polyhydroxyalkanoate by a conventional method such as distillation. 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 in the present invention, when the R moiety in the chemical formula (1) is —A1 —SO ₃ CH ₃ , a methyl esterifying agent is used after the condensation reaction with the amine to form the R moiety in the chemical formula (1). Can be methyl esterified to -A1 -SO ₃ CH ₃ . As the methyl esterifying agent, a method of methyl esterification of fatty acid in gas chromatography analysis can be used.

  Examples include acid catalyst methods such as hydrochloric acid-methanol method, boron trifluoride-methanol method, sulfuric acid-methanol method, 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 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 not selected or is a linear alkylene chain having 1 to 4 carbon atoms. When R _Gc is a linear alkylene chain having 1 to 4 carbon atoms, the linear alkylene chain is May be optionally 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 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 no _RGc is selected, _RGb 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, examples of the linear or branched alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group (2-methylpropyl group), a butyl group, a 1-methylpropyl group, a pentyl group, and an 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 R _Hc 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 not selected or has 1 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 has a phenyl structure or a thienyl structure at the terminal. In addition, an alkyl group containing a residue having any one of the cyclohexyl structures may be optionally substituted, and R _Hb may be a hydrogen atom, a linear or branched alkyl group, or an aryl group. An aryl group An aralkyl group which may be substituted.
When no R _Hc is selected, R _Hb 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 _H , R _H1 , R _Ha , R _Hb , R _Hc , and A _H represent 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 no R _Hc is selected or a linear alkylene chain is unsubstituted and R _Hb is a hydrogen atom is Using a polyhydroxyalkanoate having a unit represented by the chemical formula (A) as a starting material, 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) Can be manufactured.

(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 in the present invention 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, hexane, cyclohexane, heptane, ligroin or petroleum ether is used. Aliphatic 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- Amides such as dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylpyrrolidinone or hexamethylphosphorotriamide, preferably tetrahydrofuran.

  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.

In the present invention, the reaction temperature is usually −78 ° C. to 40 ° C., preferably −78 ° C. to 30 ° C.
In the present invention, 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) in 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.

(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.

In addition, when there are a plurality of units, R21, 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.
When there are a plurality of units, 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); Non-patent document 7), a method using dichromate (Org. Synth., 4,698 (1963); non-patent document 8), a method using periodate (J. Org). Chem., 46, 19 (1981); Non-Patent Document 9), a method using nitric acid (Japanese Patent Laid-Open No. 59-190945; Patent Document 4), a method using ozone (J. Am. Chem. Soc., 81, 4273 (1959); Non-Patent Document 10) and the like are known, and Macromolecular chemistry, 4, 289-293 (2001); 11) A method for obtaining a carboxylic acid by carrying out a reaction under acidic conditions using a carbon-carbon double bond at the end of a side chain of a polyhydroxyalkanoate produced by a microorganism, using potassium permanganate as an oxidizing agent. Has 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). When the amount is less than 0.2 molar equivalent, the yield is low, and when the amount exceeds 2000 molar equivalent, an acid decomposition product is by-produced. In addition, crown-ether can be used for the purpose of promoting the reaction. In this case, the crown-ether and the permanganate form a complex, and the effect of increasing the reaction activity is obtained. As the crown-ether, dibenzo-18-crown-6-ether, dicyclo-18-crown-6-ether, or 18-crown-6-ether is generally used. The amount of the crown-ether used is usually 0.005 to 2.0 molar equivalents, preferably 0.01 to 1.5 molar equivalents per mole of permanganate.

  In addition, the solvent in the oxidation reaction 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 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. )

(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. )

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. An aralkyl group that may be used. 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, water or a water-soluble organic solvent such as methanol, ethanol, tetrahydrofuran, dioxane, dimethylformamide, dimethylsulfoxide as a solvent. Alternatively, use an aqueous solution of inorganic acids such as phosphoric acid or organic acids such as trifluoroacetic acid, trichloroacetic acid, p-toluenesulfonic acid, methanesulfonic acid, or aqueous caustic alkalis such as sodium hydroxide and potassium hydroxide, carbonic acid It can be carried out using an aqueous solution of an alkali carbonate such as sodium 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 the catalytic reduction method is used, the ester bond in 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 not selected or is a linear alkylene chain having 1 to 4 carbon atoms. When R _Gc is a linear alkylene chain having 1 to 4 carbon atoms, the linear alkylene chain is May be optionally 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 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 no _RGc is selected, _RGb 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. )

(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 anything selected. Or a linear alkylene chain having 1 to 4 carbon atoms, and when R _Jc is a linear alkylene chain having 1 to 4 carbon atoms, the linear alkylene chain is a linear or branched alkyl group, Alternatively, the terminal may be optionally substituted with an alkyl group containing a residue having any one of a phenyl structure, a thienyl structure, and a cyclohexyl structure, and R _Jb is a hydrogen atom, A branched alkyl group, an aryl group, and an aralkyl group optionally substituted with an aryl group.
When no R _Jc is selected, R _Jb 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 _J , R _Jb , R _Jc and m have the above meanings independently 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 which may be 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 an 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 bromate, 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 of the present invention is not particularly limited as long as it is an inert solvent for the reaction and can dissolve the starting material to some extent. For example, hexane, cyclohexane, heptane, ligroin or petroleum ether is used. Aliphatic 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- Amides such as dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylpyrrolidinone or hexamethylphosphorotriamide, preferably tetrahydrofuran.

  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.

In the present invention, the reaction temperature is usually −78 ° C. to 40 ° C., preferably −78 ° C. to 30 ° C.
In the present invention, 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-A 2001-288256, JP-A 2003-319792, 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 prepared as a derivative of the substituted α-hydroxy acid, and then the cyclic dimer lactide is subjected to ring-opening polymerization to thereby obtain a polyester. 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. The polyhydroxyalkanoate composed of a substituted α-hydroxy acid unit used in the present invention is preferably 1,000 to 1,000,000 in terms of polystyrene in consideration of the reaction in the next step.

  A polyhydroxyalkanoate containing a unit represented by the chemical formula (6) is produced by subjecting an intramolecular cyclized compound of ω-hydroxycarboxylic acid represented by the chemical formula (8) to ring-opening polymerization 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.
Moreover, 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 a polyhydroxyalkanoate containing a unit represented by chemical formula (6) using a compound represented by chemical formula (8) which is an intramolecular ring-closing compound of ω-hydroxycarboxylic acid, there is no particular limitation on the polymerization method. For example, a solution polymerization method, a slurry polymerization method, a bulk polymerization method and 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-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, 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 the polymerization can be obtained with various number average molecular weights by changing conditions such as the type and amount of the polymerization catalyst, the polymerization temperature and the polymerization time. 1,000,000 are preferred.

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

(In the formula, R9 represents a linear or branched alkyl group or aralkyl group having 1 to 12 carbon atoms.
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. )

(Wherein R10 represents a linear or branched alkyl group or aralkyl group having 1 to 12 carbon atoms.
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, and n represent 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-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. In the present invention, 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 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.

  In the present invention, the molecular weight of the polyhydroxyalkanoate can be measured as a relative molecular weight or an absolute molecular weight. It can be easily measured by, for example, GPC (gel permeation chromatography). As a specific GPC measurement method, the polyhydroxyalkanoate is dissolved in a soluble solvent in advance, and measurement is performed with the same mobile phase. As 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, and 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.

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

  In the polyhydroxyalkanoate used in the present invention, the monomer unit represented by the chemical formula (1) or (5) is contained in a ratio of 0.2% to 40% with respect to all monomer units constituting the polyhydroxyalkanoate. The number average molecular weight is preferably 1,000 to 200,000. When the proportion of the unit represented by the chemical formula (1) or (5) is 0.2% or more, the ability to induce a positive charge on the toner tends to be improved. On the other hand, when the proportion of the unit represented by the chemical formula (1) or (5) is 40% or less, environmental stability such as moisture resistance and film properties are preferably improved. Further, when the number average molecular weight of the polyhydroxyalkanoate to be used is 1,000 or more, the low molecular weight component is reduced, the toner is difficult to adhere or adhere to the resin coating layer, and the charge imparting property of the resin coating layer is improved. There is a trend. On the other hand, when the number average molecular weight is 200,000 or less, the compatibility with other resins forming the resin coating layer is improved, and it becomes easy to obtain stable chargeability due to environmental fluctuations and aging. In addition, when dissolved in a solvent, the viscosity of the resin solution becomes appropriate and coating is easy, the composition of the resin coating layer becomes uniform, and the toner charge is stabilized. Furthermore, the surface roughness of the resin coating layer is stabilized and the wear resistance is increased.

  In general, since the glass transition point of the binder resin for toner is often about 50 ° C. to 70 ° C., when the polyhydroxyalkanoate is used, the surface of the resin coating layer covering the core material is used. In order to avoid adhesion of the toner, it is preferable to appropriately select polyhydroxyalkanoate so that a resin coating layer having a glass transition point higher than that of the toner is formed.

  The resin-coated carrier for an electrophotographic developer of the present invention has a resin coating layer containing the polyhydroxyalkanoate as described above on a core material. Known magnetic materials may be used, and examples thereof include ferromagnetic metals such as iron, cobalt, and nickel; alloys and compounds such as magnetite, hematite, and ferrite, and particles in which these magnetic materials are dispersed in a binder resin. Also, resin core particles in which a magnetic material is dispersed in a binder resin can be used.

  As the core material used in the present invention, those having an average particle diameter of 20 to 100 μm are preferably used, and those having an average particle diameter of 30 to 65 μm are particularly preferable. That is, when the average particle diameter of the core material is 20 μm or more, the fine particle system is reduced in the particle distribution of the resin-coated carrier, the magnetization per particle is increased, and the resin-coated carrier is less likely to be scattered. On the other hand, when the average particle of the core material is 100 μm or less, the specific surface area is increased and the toner is hardly scattered. Further, in a full color image having many solid portions, the reproduction of the solid portions tends to be improved, which is preferable.

  Further, as a method of coating the core material with a resin coating layer, a method of forming a resin coating layer by coating the surface of the core material as described above with a resin layer containing at least the polyhydroxyalkanoate. Can be mentioned.

  Examples of the solvent that can be used in this method include toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, and cellosol butyl acetate.

  The resin coating amount of the resin coating layer constituting the resin-coated carrier for the electrophotographic developer of the present invention is about 0. 0 with respect to the total amount of the resin-coated carrier when the polyhydroxyalkanoate is used alone in the coating resin layer. When the range is from 1 to 5.0% by mass and other resins are also used, the range is 0.1 to 25 with respect to the total amount of the resin-coated carrier, depending on the mixing ratio of the polyhydroxyalkanoate and the other resins. It is preferable to set it as the range of the mass%.

  The baking apparatus for forming the resin coating layer may be either an external heating method or an internal heating method, for example, a fixed or fluid electric furnace, a rotary electric furnace, a burner furnace, or by a microwave. Baking may be used. The baking temperature is preferably about 130 to 300 ° C.

  The resin coating layer may be a polyhydroxyalkanoate obtained by crosslinking melamine aldehyde resin or isocyanate, and further known other resins, for example, polyolefin resins such as polyethylene and polypropylene; polystyrene, acrylic resin, polyacrylonitrile, Polyvinyl acetate and polyvinylidene resins such as polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, polyvinyl chloride, polyvinyl carbazole, polyvinyl ether and polyvinyl ketone; vinyl chloride-vinyl acetate copolymer; styrene-acrylic acid copolymer; organo Straight silicone resin consisting of siloxane bonds or modified products thereof; polytetrafluoroethylene, polyvinyl fluoride, polyvinylidene fluoride, polychlorotrifluoro Silicone resin; fluorine-based resins such as styrene polyesters, polyurethanes, polycarbonates, phenol resins; -; and epoxy resins may be used in combination urea-formaldehyde resins, melamine resins, benzoguanamine resins, urea resins, amino resins such as polyamide resins. Among these resins, it is also preferable to use a fluororesin and / or a silicone resin. Use of a fluorine-based resin and / or a silicone resin as the resin is advantageous in that it has a high effect of preventing carrier contamination (impact) due to toner and external additives.

  In addition, in order to exhibit the toner used particularly in positive friction, as a resin constituting the resin coating layer of the above resin-coated carrier, in addition to polyhydroxyalkanoate, a fluorine-containing polymer such as polyvinyl fluoride, polyvinylidene fluoride, Polytrifluoroethylene, polytetrafluoroethylene, polyperfluoropropylene, copolymer of vinylidene fluoride and vinyl fluoride, copolymer of tetrafluoroethylene and hexafluoropropylene, vinylidene fluoride and trifluorochloroethylene 30% to 70% by mass of the above copolymer, a copolymer of vinylidene fluoride and hexafluoropropylene, or the like may be contained.

  As described above, a silicone resin may be used as the resin constituting the resin coating layer. Any straight silicone resin composed of an organosiloxane bond can be used. Specifically, for example, KR-271, KR-255 (trade name) manufactured by Shin-Etsu Chemical Co., Ltd., SR-2410, SR-2406, SR-2411 (trade name) manufactured by Toray Dow Corning Silicone, Toshiba Examples include commercially available products such as TSR-127B and TSR-144 (trade name) manufactured by Silicone. You may add a catalyst etc. to these straight silicone resins as needed. Further, as the modified silicone resin, modified silicone resins such as alkyd resins, polyester resins, epoxy resins, polyurethane resins, acrylic resins and the like can be used. Examples of commercially available products include KR-206 (alkyd resin modified product; trade name), KR-9706 (acrylic resin modified product; trade name), ES-1001N (epoxy resin modified product; trade name) manufactured by Shin-Etsu Chemical Co., Ltd. SR-2101 (modified alkyd resin; trade name) manufactured by Toray Dow Corning Silicone Co., Ltd., and the like.

  The resin-coated carrier for an electrophotographic developer of the present invention is mixed with a toner and used as a two-component developer when forming an image. The toner used at this time contains at least a binder resin and a colorant, and may contain various additives such as a charge control agent, if necessary.

  The binder resin used in the toner is not particularly limited, but is polyester, polystyrene; a polymer compound obtained from a styrene derivative such as poly-p-chlorostyrene or polyvinyltoluene; and styrene-p-chlorostyrene. Polymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-acrylic acid ester copolymer, styrene-methacrylic acid ester copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene -Styrene copolymers such as acrylonitrile copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer; polyvinyl chloride, phenol resin , Modified phenolic tree , Maleic resins, acrylic resins, methacrylic resins, polyvinyl acetate resins, silicone resins; monomers selected from aliphatic polyhydric alcohols, aliphatic dicarboxylic acids, aromatic dicarboxylic acids, aromatic dialcohols and diphenols Polyester resins having as structural units: polyurethane resins, polyamide resins, polyvinyl butyral, terpene resins, coumarone indene resins, petroleum resins and the like. These may be used alone or in combination.

  A toner having a core / shell structure and a core formed of a low softening point material is also preferably used. Since the toner uses a low softening point substance, it is advantageous for low-temperature fixing.

  As a method of encapsulating the low softening point substance in the toner particles, the polarity of the material in the aqueous medium is set smaller than that of the main monomer, and the low softening point substance is further reduced, and a small amount of a large polar resin or single substance is used. By adding the monomer, toner particles having a so-called core / shell structure in which a low softening point substance is coated with an outer shell resin can be obtained.

  Toner particle size distribution control and particle size control can be achieved by a method of changing the kind and amount of a slightly water-soluble inorganic salt or a dispersant that acts as a protective colloid, or mechanical device conditions such as the peripheral speed of a roller, It can be performed by controlling the number of passes, the stirring conditions such as the shape of the stirring blade, the shape of the container, or the solid content concentration in the aqueous medium.

  Examples of the outer shell resin of the toner include a styrene- (meth) acryl copolymer, a polyester resin, an epoxy resin, and a styrene-butadiene copolymer.

  In the method of directly obtaining toner particles by a polymerization method, those monomers are preferably used. Specifically, styrene; styrene monomer such as o (m-, p-)-methylstyrene, m (p-)-ethylstyrene; methyl (meth) acrylate, ethyl (meth) acrylate, (meth ) Propyl acrylate, butyl (meth) acrylate, octyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, behenyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, ( (Meth) acrylic acid ester monomers such as dimethylaminoethyl acrylate and diethylaminoethyl (meth) acrylate; ene monomers such as butadiene, isoprene, cyclohexene, (meth) acrylonitrile and acrylamide are preferably used. It is done.

  In these toners, it is preferable to use at least silica fine particles and / or titanium oxide fine particles as an external additive because fluidity can be favorably imparted to the developer and the life of the developer is improved. Further, by using these fine powders, a developer with less environmental fluctuation can be obtained.

  Other external additives include metal oxide fine powder (aluminum oxide, strontium titanate, cerium oxide, magnesium oxide, chromium oxide, tin oxide, zinc oxide, etc.), nitride fine powder (silicon nitride, etc.), carbide fine powder Body (silicon carbide, etc.), metal salt fine powder (calcium sulfate, barium sulfate, calcium carbonate, etc.), fatty acid metal salt fine powder (zinc stearate, calcium stearate, etc.), carbon black, resin fine powder (polytetrafluoroethylene, Polyvinylidene fluoride, polymethyl methacrylate, polystyrene, silicone resin, etc.) are preferred. These external additives may be used alone or in combination. It is more preferable that the external additives including the silica fine powder have been subjected to a hydrophobic treatment.

The above-mentioned external additive preferably has a number average particle size of 0.2 μm or less. When the number average particle size is 0.2 μm or less, the fluidity is improved and the image quality is improved during development and transfer.
The external additive is preferably used in an amount of 0.01 to 10 parts by mass, and more preferably 0.05 to 5 parts by mass with respect to 100 parts by mass of the toner particles.

The external additive preferably has a specific surface area by nitrogen adsorption by the BET method of preferably 30 m ² / g or more, more preferably in the range of 50 to 400 m ² / g.
The mixing of the toner particles and the external additive can be performed using a mixer such as a Henschel mixer.

In the present invention, examples of the colorant used in the toner include the following.
As the yellow colorant, compounds typified by condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds are used. Specifically, C.I. I. Pigment Yellow 12, 13, 14, 15, 17, 62, 74, 83, 93, 94, 95, 109, 110, 111, 128, 129, 147, 168 can be suitably used.

  As the magenta colorant, condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, and perylene compounds are used. Specifically, C.I. I. Pigment Red 2, 3, 5, 6, 7, 23, 48: 2, 48: 3, 48: 4, 57: 1, 81: 1, 144, 146, 166, 169, 177, 184, 185, 202, 206, 220, 221, and 254 can be suitably used.

  Examples of cyan colorants include copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds, and basic dye lake compounds. Specifically, C.I. I. Pigment Blue 1, 7, 15, 15: 1, 15: 2, 15: 3, 15: 4, 60, 62, 66 can be preferably used.

  These colorants can be used alone or in combination and further in the form of a solid solution.

  Examples of the black colorant include carbon black and those prepared by using the yellow / magenta / cyan colorant described above toned to black. Further, as a full color application, magnetic monocomponent development may be applied using magnetic toner only for black toner.

  In the case of a color toner, the colorant is selected in consideration of hue angle, saturation, brightness, weather resistance, OHP transparency, and dispersibility in the toner. The content of the colorant is preferably 1 to 20 parts by mass with respect to 100 parts by mass of the binder resin for toner.

  Known charge control agents can be used for the toner. In the case of a color toner, in particular, a charge control agent that is colorless or light in color, has a high toner charging speed, and can stably maintain a constant charge amount is preferable. Furthermore, in the present invention, when a toner is produced using a polymerization method, a charge control agent having no solubilized product in an aqueous medium having no polymerization inhibition property is particularly preferable.

  Examples of the negative charge control agent include salicylic acid, dialkylsalicylic acid, naphthoic acid, dicarboxylic acid, or a metal compound thereof. Polymer type compound having sulfonic acid or carboxylic acid in the side chain; boron compound; urea compound; Silicon compounds; and calixarene are preferably used. As the positive charge control agent, for example, a quaternary ammonium salt; a polymer compound having the quaternary ammonium salt in the side chain; a guanidine compound; and an imidazole compound are preferably used. The content of the charge control agent is preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the binder resin. However, the addition of a charge control agent to the toner particles is not essential.

  As a method for producing the toner, for example, the binder resin, the colorant, and an additive such as a charge control agent, which are used when desired, are sufficiently mixed with a mixer such as a Henschel mixer, and then a twin screw extruder. After kneading, cooling and roughly pulverizing the mixture with a pulverizer such as a feather mill, etc., then using a jet pulverizer, a classifier, etc., to obtain particles of a desired particle diameter, and if necessary, external addition such as silica fine powder A method of adding an agent and mixing with a mixer, a method of directly producing toner particles using a suspension polymerization method, or a method using a water-based organic solvent that is soluble in monomers and insoluble in a polymer. Examples include a method of producing toner particles using an emulsion polymerization method typified by a dispersion polymerization method for producing toner particles, or a soap-free polymerization method for producing toner particles by direct polymerization in the presence of a water-soluble polar polymerization initiator. Can do.

  In producing the toner used in the present invention, in order to produce toner particles by a polymerization method, 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobis is used as a polymerization initiator. Azo series such as isobutyronitrile, 1,1′-azobis- (cyclohexane-1-carbonitrile), 2,2′-azobis-4-methoxy-2,4-dimethylvaleronitrile, azobisisobutyronitrile Polymerization initiators: Peroxide-based polymerization initiators such as benzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl peroxycarbonate, cumene hydroperoxide, 2,4-dichlorobenzoyl peroxide, lauroyl peroxide are used.

  Although the addition amount of a polymerization initiator changes with the target degree of polymerization, generally 0.5 to 20 mass% is added and used with respect to a monomer. The kind of the polymerization initiator varies slightly depending on the polymerization method, but can be used alone or in combination with reference to the 10-hour half-life temperature. In order to control the degree of polymerization, a known crosslinking agent, chain transfer agent, polymerization inhibitor and the like can be further added and used.

  When suspension polymerization is used as a toner production method, the inorganic oxide used as the dispersant is tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, calcium carbonate, magnesium carbonate, water. Examples include calcium oxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate, bentonite, silica, and alumina. Examples of the organic compound include polyvinyl alcohol, gelatin, methyl cellulose, methyl hydroxypropyl cellulose, ethyl cellulose, sodium salt of carboxymethyl cellulose, starch and the like. These are used by being dispersed in an aqueous phase. These dispersants are preferably used in an amount of 0.2 to 10.0 parts by mass with respect to 100 parts by mass of the polymerizable monomer.

  As these dispersants, commercially available ones may be used as they are, but in order to obtain dispersed particles having a fine uniform particle size, the inorganic compound can be produced in a dispersion medium under high-speed stirring. For example, in the case of tricalcium phosphate, a preferred dispersant for the suspension polymerization method can be obtained by mixing an aqueous sodium phosphate solution and an aqueous calcium chloride solution under high-speed stirring. Moreover, you may use together 0.001 to 0.1 mass part surfactant for refinement | miniaturization of these dispersing agents. Specifically, commercially available nonionic, anionic or cationic surfactants can be used, for example, sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium pendadecyl sulfate, sodium octyl sulfate, sodium oleate, sodium laurate, potassium stearate. Calcium oleate is preferably used.

  When the direct polymerization method is used as the toner production method, specifically, the toner can be produced by the following production method. Monomer composition in which a release agent, a colorant, a charge control agent, a polymerization initiator and other additives composed of a low softening substance are added to the monomer and dissolved or dispersed uniformly by a homogenizer, ultrasonic disperser, etc. The product is dispersed in an aqueous phase containing a dispersion stabilizer by a usual stirrer, homomixer, homogenizer or the like. Preferably, the droplets made of the monomer composition are granulated by adjusting the stirring speed and time so as to have a desired toner particle size. Thereafter, stirring may be performed to such an extent that the particle state is maintained and the sedimentation of the particles is prevented by the action of the dispersion stabilizer. Polymerization is carried out at a polymerization temperature of 40 ° C. or higher, generally 50 to 90 ° C. The temperature may be raised in the latter half of the polymerization reaction, and for the purpose of improving the durability, a part of the aqueous medium is retained after the latter half of the reaction or after the completion of the reaction in order to remove unreacted polymerizable monomers and byproducts. You may leave. After completion of the reaction, the produced toner particles are recovered by washing and filtration and dried. In the suspension polymerization method, it is usually preferable to use 300 to 3000 parts by weight of water as a dispersion medium with respect to 100 parts by weight of the monomer system.

  The toner may be classified to control the particle size distribution. As the method, a multi-division classifying device using inertial force is preferably used. By using this apparatus, a toner having a preferable particle size distribution in the present invention can be efficiently produced.

  In the present invention, when a two-component developer is prepared by mixing a toner and a resin-coated carrier, the mixing ratio is usually 2 to 15% by mass, preferably 4 to 13% by mass, as the toner concentration in the developer. Good results can be obtained. When the toner concentration is 2% by mass or more, the image density is high, and when the toner concentration is 15% by mass or less, fogging and scattering in the apparatus are not caused, and the useful life of the developer is preferably increased.

  Further, in the development method in which development is performed while replenishing the replenishment developer, when the replenishment developer is prepared by mixing the toner and the resin coat carrier, the mixing ratio is 1 part by weight of the resin coat carrier in the developer. When the ratio of the toner is 2 to 50 parts by mass, good results can be obtained. When the amount of toner is 2 parts by mass or more, the ratio of the amount of toner to the resin-coated carrier is appropriate, the charge amount of the developer is suitable, and the image density is stabilized. Moreover, when it is 50 parts by mass or less, the deterioration of the resin-coated carrier is prevented, and the charge amount of the developer becomes suitable, which is preferable.

  Next, the average particle size and particle size distribution of the toner used in the present invention can be measured as follows.

  0.1 to 5 ml of a surfactant (alkylbenzene sulfonate) is added to 100 to 150 ml of the electrolyte solution, and 2 to 20 mg of toner as a measurement sample is added thereto. The electrolytic solution in which the sample is suspended is dispersed with an ultrasonic disperser for 1 to 3 minutes, and the aperture is adjusted to a suitable toner size such as 17 μm or 100 μm by a Coulter Counter Multisizer (trade name, manufactured by Coulter Inc.). A particle size distribution of 0.3 to 40 μm, etc. is measured based on the volume. The number average particle diameter and weight average particle diameter measured under these conditions are determined by computer processing.

Next, a method for measuring the triboelectric charge amount used in the present invention will be described. The toner and the resin-coated carrier of the present invention are mixed so that the toner is 5% on a mass basis, and mixed for 60 seconds with a turbula mixer. This developer is put in a metal container with a 500 mesh conductive screen at the bottom, and sucked with a suction machine, and the triboelectric charge is calculated from the weight difference before and after suction and the potential accumulated in the capacitor connected to the container. Ask. At this time, the suction pressure is 250 mmHg. By this method, the triboelectric charge amount is calculated using the following equation.
Q (μC / g) = (C × V) / (W1−W2)
(W1 is the weight before suction, W2 is the weight after suction, C is the capacity of the condenser, and V is the potential accumulated in the condenser.)

  Hereinafter, the present invention will be described in detail by way of examples. “Parts” shown in the examples are all “parts by mass”. First, the toner and polyhydroxyalkanoate used in the examples were manufactured by the following method.

(Toner Production Example 1)
-Styrene-acrylic acid-2-ethylhexyl dimethylaminoethyl methacrylate copolymer (copolymerization ratio = 80: 15: 5) 100 parts by mass-Copper phthalocyanine pigment 5 parts by mass-Low molecular weight polypropylene 4 parts by mass After sufficient preliminary mixing, the mixture was melt-kneaded, and after cooling, coarsely pulverized to an average particle size of about 1 to 2 mm using a hammer mill. Subsequently, it was finely pulverized by an air jet type fine pulverizer. Further, the obtained finely pulverized product was classified using an elbow jet classifier to obtain a positively charged cyan fine powder. 100 parts by weight of the above cyan fine powder and 0.8 parts by weight of positively charged hydrophobic colloidal silica treated with amino-modified silicone oil were mixed with a Henschel mixer to obtain a cyan toner No. having a weight average particle diameter of 8.2 μm. . 1 was prepared.

(Toner Production Example 2)
To 710 parts of ion-exchanged water, 450 parts of a 0.1M Na ₃ PO ₄ aqueous solution was added, heated to 60 ° C., and then adjusted to 12000 rpm using a TK homomixer (made by Tokushu Kika Kogyo; trade name). And stirred. To this, 68 parts of 1.0 M CaCl ₂ aqueous solution was gradually added to obtain an aqueous medium containing Ca ₃ (PO ₄ ) ₂ .
Next, the following materials were prepared.
Styrene 165 parts n-butyl acrylate 35 parts C.I. I. Pigment Blue 15: 3 (colorant) 12 parts, charge control agent 3 parts, saturated polyester (polar resin) 10 parts, ester wax (melting point 70 ° C) 20 parts The above materials are heated to 60 ° C, and TK homo Using a mixer (made by Tokushu Kika Kogyo; trade name), it was uniformly dissolved and dispersed at 11000 rpm. In this, 10 parts of a polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) was dissolved to prepare a polymerizable monomer composition.
The polymerizable monomer composition is charged into an aqueous medium, and stirred at 11000 rpm for 10 minutes with a TK homomixer (trade name, manufactured by Tokushu Kika Kogyo Co., Ltd.) at 60 ° C. and N ₂ atmosphere. The monomer composition was granulated. Then, while stirring with a paddle stirring blade, the temperature was raised to 80 ° C. and reacted for 10 hours. After completion of the polymerization reaction, the residual monomer is distilled off under reduced pressure, and after cooling, hydrochloric acid is added to dissolve Ca ₃ (PO ₄ ) _{2 and the} like, followed by filtration, washing with water, and drying to obtain a positively charged cyan toner. Particles were obtained.
For 100 parts of the cyan toner particles obtained, 0.5 parts of positively charged hydrophobic colloidal silica (number average particle size of primary particles: 0.03 μm) treated with amino-modified silicone oil, amino-modified silicone oil 0.5 part of positively charged hydrophobic titania powder (number average particle size of primary particles: 0.03 μm) treated with a toner, and a cyan toner No. having a weight average particle size of 6.8 μm. 2 was obtained.

  Next, preparation examples of the polyhydroxyalkanoate used in the present invention are shown below (Preparation Examples A to 2P).

(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 (trade name)
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; It was evaluated by chloroform and 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.

Further, the average molecular weight of the obtained polyhydroxyalkanoate was evaluated by gel permeation chromatography in the same manner 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 AVATAR360FT-IR). In the FT-IR spectrum, a peak at 1695 cm ⁻¹ derived from carboxylic acid decreased, and a new peak derived from an 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; 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 = 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 in the same manner as in Preparation Example A-3. ^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 gel permeation chromatography in the same manner 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 obtain PHA (A).

(Preparation Example B-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, dried under reduced pressure for 1 hour and purged with nitrogen, then sealed under reduced pressure and heated to 150 ° C. to perform ring-opening polymerization. went. 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 1.05 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 (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.

  Further, the average molecular weight of the obtained polyhydroxyalkanoate was evaluated by gel permeation chromatography in the same manner 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 B-2)
Oxidation reaction of polyhydroxyalkanoate composed of unit represented by chemical formula (52) synthesized in Preparation Example B-1

0.50 g of a polyhydroxyalkanoate copolymer (A: 8 mol%, B: 92 mol%) consisting of the unit represented by the chemical formula (52) 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 0.40 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, 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 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 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 (53) as a monomer unit. Was confirmed.

Further, the average molecular weight of the obtained polyhydroxyalkanoate was evaluated by gel permeation chromatography in the same manner 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.
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. By drying under reduced pressure, 28 mg of polyhydroxyalkanoate was obtained.
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 (53) was a copolymer of 8 mol% for the C unit and 92 mol% for the D unit.

(Preparation Example B-3)
Condensation reaction of polyhydroxyalkanoate composed of the unit represented by chemical formula (53) synthesized in Preparation Example B-2 and 2-amino-2-methylpropanesulfonic 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 (53) obtained in Preparation Example B-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, it was recovered by reprecipitation in 150 ml of ethanol. The obtained polymer was washed with 1N hydrochloric acid for 1 day, 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 analyzed by ¹ H-NMR and Fourier transform-infrared absorption (FT-IR) spectrum in the same manner as in Preparation Example A-3. In the FT-IR spectrum, a peak at 1695 cm ⁻¹ derived from carboxylic acid decreased, and a new peak derived from an 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 gel permeation chromatography in the same manner 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 to obtain a large amount of polyhydroxyalkanoate represented by the chemical formula (54) to obtain PHA (B).

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

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 a polymerization ampule, dried under reduced pressure for 1 hour, and purged with nitrogen. Sealed under reduced pressure and heated to 150 ° C. to perform ring-opening polymerization. The reaction was terminated after 12 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 7.08 g of polymer.
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.

  Further, the average molecular weight of the obtained polyhydroxyalkanoate was evaluated by gel permeation chromatography in the same manner 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 C-2)
5.00 g of the polyhydroxyalkanoate copolymer represented by the chemical formula (90) obtained in Preparation Example C-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 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 polymer obtained was collected and dried under reduced pressure to obtain 3.70 g of polymer.
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%.

  Further, the average molecular weight of the obtained polyhydroxyalkanoate was evaluated by gel permeation chromatography in the same manner as in Preparation Example A-1. As a result, the number average molecular weight was Mn = 9500, and the weight average molecular weight was Mw = 1900.

(Preparation Example C-3)
Condensation reaction of polyhydroxyalkanoate composed of the unit represented by chemical formula (91) synthesized in Preparation Example C-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 C-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, and then 1.06 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 0.33 g of polymer.
The structure of the obtained polymer was analyzed by ¹ H-NMR and Fourier transform-infrared absorption (FT-IR) spectrum in the same manner as in Preparation Example A-3. In the FT-IR spectrum, a peak at 1695 cm ⁻¹ derived from carboxylic acid decreased, and a new peak derived from an 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 gel permeation chromatography in the same manner as in Preparation Example A-3. As a result, the number average molecular weight M _n = 8200 and the weight average molecular weight M _w = 12400.

(Preparation Example C-4)
Esterification reaction of polyhydroxyalkanoate composed of unit represented by chemical formula (92) 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 (92) 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, 1.34 ml of a 2 mol / L trimethylsilyldiazomethane-hexane solution (manufactured by Aldrich) was added and stirred for 4 hours. After completion of the reaction, 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 in the same manner as in Preparation Example A-3. ^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, 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 gel permeation chromatography in the same manner as in Preparation Example A-3. 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 obtain PHA (C).

(Preparation Example D-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 solution in toluene and 4.8 ml of 0.01M p-tert-butylbenzyl alcohol in toluene were charged into the polymerization ampule, dried under reduced pressure for 1 hour, and purged with nitrogen, then under reduced pressure. And heated to 150 ° C. to perform ring-opening polymerization. The reaction was terminated after 12 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 0.75 g of polymer.
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 D-2)
Oxidation reaction of polyhydroxyalkanoate comprising unit represented by chemical formula (66) synthesized in Preparation Example D-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 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 0.21 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, 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 (67) as a monomer unit. Was confirmed.

Further, the average molecular weight of the obtained polyhydroxyalkanoate was evaluated by gel permeation chromatography in the same manner 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, 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. 29 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 (67) was a copolymer of 4 mol% for the C unit and 96 mol% for the D unit.
A series of preparation methods were scaled up, and a large amount of polyhydroxyalkanoate represented by the chemical formula (67) was obtained to obtain PHA (D).

(Preparation Example E-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) 4.8 ml of toluene solution and 4.8 ml of 0.01M p-tert-butylbenzyl alcohol in toluene were placed in a polymerization ampule, dried under reduced pressure for 1 hour, and purged with nitrogen, and then dissolved under reduced pressure. Sealed and heated to 150 ° 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 2.06 g of polymer.
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.

  Further, the average molecular weight of the obtained polyhydroxyalkanoate was evaluated by gel permeation chromatography in the same manner 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 E-2)
Oxidation reaction of polyhydroxyalkanoate composed of unit represented by chemical formula (73) synthesized in Preparation Example E-1

0.50 g of a polyhydroxyalkanoate copolymer (A: 12 mol%, B: 88 mol%) consisting of the unit represented by the chemical formula (73) 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 0.35 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, 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 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.

Further, the average molecular weight of the obtained polyhydroxyalkanoate was evaluated by gel permeation chromatography in the same manner 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.
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. By drying under reduced pressure, 28 mg of polyhydroxyalkanoate was obtained.
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 (74) 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, and a large amount of polyhydroxyalkanoate represented by the chemical formula (74) was obtained to obtain PHA (E).

(Preparation Example F-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 solution in toluene and 4.8 ml of 0.01M p-tert-butylbenzyl alcohol in toluene were charged into the polymerization ampule, dried under reduced pressure for 1 hour, and purged with nitrogen, then under reduced pressure. And heated to 150 ° 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 1.32 g of polymer.
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.

  Further, the average molecular weight of the obtained polyhydroxyalkanoate was evaluated by gel permeation chromatography in the same manner 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 F-2)
Oxidation reaction of polyhydroxyalkanoate composed of unit represented by chemical formula (77) synthesized in Preparation Example F-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 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 0.45 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, 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 (78) as a monomer unit. Was confirmed.

Further, the average molecular weight of the obtained polyhydroxyalkanoate was evaluated by gel permeation chromatography in the same manner 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.
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. By drying under reduced pressure, 28 mg of polyhydroxyalkanoate was obtained.
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 (78) was a copolymer of 9 mol% for the C unit and 91 mol% for the D unit.
A series of preparation methods were scaled up, and a large amount of polyhydroxyalkanoate represented by the chemical formula (78) was obtained to obtain PHA (F).

(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 specify 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, polystyrene conversion). . 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 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, 2-aminobenzene 0.27 g of sulfonic acid was put in a 100 ml three-necked flask, 15.0 ml of pyridine was added and stirred, 0.82 ml of triphenyl phosphite was added, and the mixture was 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) Analysis was performed by 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 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 as follows: 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 the exemplified compound PHA (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 was Mn = 32000, and the weight average molecular weight was 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 was Mn = 30100, and the weight average molecular weight was 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]

0.40 g of 4-hydroxyaniline, 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, under a nitrogen atmosphere After putting 0.33 g of 2-sulfonic acid in 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, and a large amount of polyhydroxyalkanoate represented by the chemical formula (107) was obtained to give Exemplified Compound PHA (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, polystyrene conversion). . 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 was dissolved in 60 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 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, polystyrene conversion). . 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, polystyrene conversion). . 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 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 = 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 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 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, and a large amount of polyhydroxyalkanoate represented by the chemical formula (112) was obtained to give the exemplified compound PHA (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 was Mn = 28500, and the weight average molecular weight was Mw = 39600.
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. 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 (2.0 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, and a large amount of polyhydroxyalkanoate represented by the chemical formula (115) was obtained to give the exemplified compound PHA (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 was Mn = 42800, and the weight average molecular weight was Mw = 59100.

(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 was Mn = 30100 and the weight average molecular weight was 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 a 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, and a large amount of polyhydroxyalkanoate represented by the chemical formula (120) was obtained to give the exemplified compound PHA (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.

(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, and a large amount of polyhydroxyalkanoate represented by the chemical formula (123) was obtained to give the exemplified compound PHA (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). 11 mol% and B unit 89 mol% were confirmed.

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 was Mn = 26500, and the weight average molecular weight was Mw = 41100.
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 the exemplified compound PHA (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).

  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 = 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, and as a result, the number average molecular weight Mn = 23000 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.

  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 = 19800 and the weight average molecular weight Mw = 30900 were obtained.

(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 into a 100 ml three-necked flask, add 15.0 ml of pyridine and stir, then add 0.70 ml (2.6 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 the exemplified compound PHA (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 was dissolved in 12 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 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-3, and 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 PHA (2I).

(Preparation Example 2J-1)
In this preparation example, polyhydroxyalkanoate is produced using microorganisms. The microorganism used in this preparation example is Ralstonia eutropha TB64 strain (Ralstonia eutropha TB64, disclosed in JP 2000-166687 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) used in this preparation example has the following composition.
M9 medium composition (in 1 liter):
Na ₂ HPO ₄ 6.2 g
KH ₂ PO ₄ 3.0 g
NaCl 0.5 g
NH ₄ Cl 1.0 g
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, polystyrene conversion). . 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 was dissolved in 60 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 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, polystyrene conversion). . 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, polystyrene conversion). . 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 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 (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 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 = 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, and a large amount of polyhydroxyalkanoate represented by the chemical formula (138) was obtained to give the exemplified compound PHA (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 was Mn = 300300 and the weight average molecular weight was 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%.

  Further, 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 was Mn = 286000 and the weight average molecular weight was 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 the exemplified compound PHA (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 was Mn = 298100, and the weight average molecular weight was Mw = 715400.

(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, and a large amount of polyhydroxyalkanoate represented by the chemical formula (146) was obtained to give the exemplified compound PHA (2L).

(Preparation Example 2M-1)
In this preparation example, polyhydroxyalkanoate is produced using microorganisms. The microorganism used in this preparation example is Pseudomonas chicoryi strain YN2 (Pseudomonas chicory 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 Pseudomonas chicory eye strain YN2 cultured in an M9 medium containing 0.5% polypeptone in advance at 30 ° C. for 8 hours was added, and cultured 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 was Mn = 91000 and the weight average molecular weight was Mw = 172900.
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-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 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 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 was Mn = 72500 and the weight average molecular weight was Mw = 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 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 0.83 ml of diazomethane-hexane solution (manufactured by Aldrich), 0.29 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 (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 the exemplified compound PHA (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). 8 mol% and B unit 92 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 was Mn = 71000 and the weight average molecular weight was 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 was Mn = 68500 and the weight average molecular weight was Mw = 133600.

(Preparation Example 2N-2)
0.40 g of polyhydroxyalkanoate copolymer (C: 8 mol%, D: 92 mol%) composed of the unit represented by 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 into 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.

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 = 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, the polymer 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.

The average molecular weight of the obtained polymer, the results measured at the same conditions as in Preparation Example 2J-4, a number average molecular weight M _n = 52500, a weight average molecular weight M _w = 110300. A series of preparation methods were scaled up, and a large amount of polyhydroxyalkanoate represented by the chemical formula (155) was obtained to give the exemplified compound PHA (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. 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, poly-3-hydroxy-5-phenoxyvaleric acid represented by the general chemical formula (156) as a monomer unit was obtained. 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 was Mn = 201000 and the weight average molecular weight was Mw = 422100.
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, 10.00 g of a polyhydroxyalkanoate composed of a unit represented by the chemical formula (156) obtained in Preparation Example 2O-1 instead of the polyhydroxyalkanoate composed of a unit represented by the chemical formula (134) And 2M lithium diisopropylamide in THF (26.01 ml, 52.0 mmol) and benzyl chloroformate (8.88 g, 104.1 mmol) were used. .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 was Mn = 131500 and the weight average molecular weight was Mw = 282700.
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 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, the polymer 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, and a large amount of polyhydroxyalkanoate represented by the chemical formula (160) was obtained to give the exemplified compound PHA (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 was Mn = 70500, and the weight average molecular weight was Mw = 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) And 2M lithium diisopropylamide in THF (29.72 ml, 59.4 mmol) and benzyl chloroformate (10.14 g, 118.9 mmol) were used in the same manner as in Preparation Example 2J-2, .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 was Mn = 54400, and the weight average molecular weight was Mw = 17,000.
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. 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 polymer was obtained. The obtained polymer was a polyhydroxyalkanoate containing a unit represented by the following chemical formula (164) 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 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 instead 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, the polymer 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 the polyhydroxyalkanoate represented by the chemical formula (165) to give the exemplified compound PHA (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]

(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 (3-butenyl) -1,4-dioxane-2. , 5-dione 1.06 g (41% yield) 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)
The 7- (3-butenyl) -2-oxepanone used in Preparation Example B-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-3)
[Synthesis of 3- (9-decenyl) -2-oxetanone described in Preparation Example D-1]
3- (9-decenyl) -2-oxetanone is a dihydro-3- (2-propenyl) furan-2 (3H) -one described in Journal of American Chemical Society 1995,117,3705-3716 In the synthesis of the compound (6a)), β-propiolactone can be used instead of γ-butyrolactone, and 10-bromo-1-decene can be used instead of allyl bromide.
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, 26.30 g (110.0 mmol) of 10-bromo-1-decene dissolved in 38 ml of hexamethylphosphoramide (HMPA) was added, followed by stirring 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- (9-decenyl) -2-oxetanone. Next, the product was purified by silica gel column chromatography and distilled under reduced pressure to obtain 15.14 g of the intended 3- (9-decenyl) -2-oxetanone. 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- (9-decenyl) -2-oxetanone.

(Preparation Example 2Z-4)
[Synthesis of Tetrahydro-3- (2-propenyl) -2H-pyran-2-one described in Preparation Examples E-1 and 2B-1]
10.01 g (100.0 mmol) of δ-valerolactone instead of β-propiolactone described in Preparation Example 2Z-3, 14.52 g (110.0 mmol) of allyl bromide instead of 10-bromo-1-decene ) 9.81 g of the desired tetrahydro-3- (2-propenyl) -2H-pyran-2-one was obtained in the same manner as in Preparation Example 2Z-3 except that it was used.

(Preparation Example 2Z-5)
[Synthesis of 3- (2-propenyl) -2-oxepanone described in Preparation Example F-1]
11.41 g (100.0 mmol) of ε-caprolactone instead of β-propiolactone described in Preparation Example 2Z-3, 14.52 g (110.0 mmol) of allyl bromide instead of 10-bromo-1-decene 10.02 g of the desired 3- (2-propenyl) -2-oxepanone was obtained in the same manner as in Preparation Example 2Z-3 except that it was used.

Example 1
A core material (sometimes referred to as a carrier core) was produced as follows.
First, they were weighed so that the molar ratio was Fe2O3 = 55 mol%, CuO = 25 mol%, and ZnO = 20 mol%, and mixed using a ball mill. Next, after calcining this, it was pulverized by a ball mill and further granulated by a spray dryer. This was sintered and further classified to obtain a core material (carrier core).
The surface of the obtained core material was coated with a resin coating layer as follows.
A styrene-methyl methacrylate-acrylic acid-2-ethylhexyl copolymer (copolymerization ratio = 40: 50: 10) was made into a 10 mass% solution using toluene as a solvent, and PHA (A) was further added to the above-mentioned copolymer solid content. After adding 5% by mass, the mixture was sufficiently stirred to prepare a resin coating solution.
This resin coating solution is provided with a rotating bottom plate disk and a stirring blade in a fluidized bed, and a coating apparatus that coats while forming a swirling flow is used. It applied so that it might become 2 mass% with respect to it. The above resin coating solution was sprayed from a direction perpendicular to the moving direction in the fluidized bed apparatus, and the spray pressure of the resin coating solution was 4 kg / cm 2. The obtained resin-coated carrier was dried in a fluidized bed at a temperature of 80 ° C. for 1 hour to remove the solvent, thereby obtaining a resin-coated carrier.
The average particle size of the obtained resin-coated carrier was 41 μm. As a result of measuring the coverage of the resin-coated carrier by the resin coating layer with an electron microscope, formation of a uniform resin coating layer was confirmed.
The obtained resin-coated carrier and toner No. 1 was mixed to a toner concentration of 5.5% by mass to obtain a developer.
For this evaluation, this developer was used to output an image in an N / N environment (23 ° C./60% RH) using a blue developer of a modified analog copying machine NP4835 (trade name) manufactured by Canon. . At that time, for the evaluation, fluctuations in image density, fogging on images after 50,000 sheets, environmental fluctuations in charge amount, and image flow on the photosensitive drum were used as indices. The obtained results are shown in Table 1.

(Example 2)
The same core material as in Example 1 was coated with a resin coating layer as follows.
Styrene-methyl methacrylate-methacrylic acid-2-ethylhexyl copolymer (copolymerization ratio = 50: 45: 5) was made into a 10 mass% solution using toluene as a solvent, and PHA (B) was further added to the copolymer solid content. After adding 5% by mass to the mixture, sufficient stirring was performed to prepare a carrier coating solution. Using this resin coating solution, the core material was coated in the same manner as in Example 1 to obtain a resin-coated carrier.
The average particle size of the obtained resin-coated carrier was 40 μm. As a result of measuring the coverage of the resin-coated carrier by the resin coating layer with an electron microscope, formation of a uniform resin coating layer was confirmed.
A developer was prepared in the same manner as in Example 1 using the obtained resin-coated carrier. This developer was evaluated in the same manner as in Example 1, and the results are shown in Table 1.

(Examples 3 and 4)
The surface of the core material used in Example 1 was coated with a resin coating layer as follows.
Styrene-methyl methacrylate-methacrylic acid-2-hydroxyethyl copolymer (copolymerization ratio = 35: 57: 8, hydroxyl number (KOHmg / g) = 35) and vinylidene fluoride-tetrafluoroethylene copolymer ( Copolymerization ratio = 75: 25) was used in the same amount, and a mixed solvent of acetone and methyl ethyl ketone (mixing mass ratio = 1: 1) was used as a 10% by mass solution. Further, in Example 3, PHA (B), Example In No. 4, 5% by mass of PHA (C) was added to the resin solid content, and then sufficiently stirred to prepare a resin coating solution. Using this resin coating solution, coating was performed in the same manner as in Example 1 to obtain a resin-coated carrier.
The average particle size of the obtained resin-coated carriers was 41 μm. As a result of measuring the coverage of the resin-coated carrier particles by the resin coating layer with an electron microscope, formation of a uniform resin coating layer was confirmed.
A developer was produced in the same manner as in Example 1 using the obtained carrier. Further, evaluation was performed in the same manner as in Example 1, and the results are shown in Table 1.

(Examples 5 and 6)
The core material was produced as follows.
They were weighed so that the molar ratio was Fe2O3 = 53 mol%, CuO = 25 mol%, ZnO = 22 mol%, and mixed using a ball mill. After calcining this, it was pulverized with a ball mill and further granulated with a spray dryer. This was sintered and further classified to obtain a core material having an average particle diameter of 65 μm.
In Example 5, a resin coating solution was prepared in the same manner as in Example 1, except that PHA (B) was used instead of PHA (A) in Example 6, except that PHA (B) was used. Using this resin coating solution, the core material was coated in the same manner as in Example 1 to obtain a resin-coated carrier. The average particle size of the obtained resin-coated carriers was 66 μm for both.
Using the obtained resin-coated carrier, a developer was produced in the same manner as in Example 1, and evaluated in the same manner as in Example 1. The obtained results are shown in Table 1.

(Comparative Example 1)
A resin-coated carrier was obtained in the same manner as in Example 1 except that PHA (A) was not used. A developer was prepared and evaluated in the same manner as in Example 1 using the obtained resin-coated carrier. The results are shown in Table 1.

(Comparative Example 2)
A resin-coated carrier was obtained in the same manner as in Examples 5 and 6 except that PHA (A) or PHA (B) was not used. A developer was prepared and evaluated for the obtained resin-coated carrier in the same manner as in Example 1. The results are shown in Table 1.

<Evaluation>
The evaluation was performed for 50,000 images, and the following changes were observed in the image density fluctuation, fogging on the image, environmental change in charge amount, and image flow on the photosensitive drum. The method was evaluated according to the following criteria. Except for the evaluation of the image flow on the photosensitive drum, the evaluation was performed using a Canon analog copying machine NP-4835 (trade name) modified machine.

1. Image Density Copies were performed under appropriate exposure conditions, and the image density (ID) was evaluated by measuring the solid image density with a Macbeth densitometer and performing rank evaluation according to the following criteria.
○: The original density is reproduced very well without density unevenness. Δ: The original density is reproduced. (Practical problem level)
: Uneven and uneven density. (Practical problem level)
×: Large change compared to the original density (impractical level)

2. Fog on the image Toner fog on the white background image was measured using REFECTOMETER MODELTC-6DS (trade name) manufactured by Tokyo Denshoku Co., Ltd., and the rank was evaluated according to the following criteria.
○: Less than 0.5% Δ: 0.5 or more and less than 1.5% ▲: 1.5 or more and less than 2.5% ×: 2.5% or more

3. Change in charge amount environment Charge amount Q (LL) after leaving the developer at 15 ° C and humidity 10% for one day and charge amount Q (HH) after leaving the developer at 30 ° C and humidity 80% for one day Were calculated using a method for measuring the charge amount described later, and then the difference ΔQ (= Q (LL) −Q (HH)) was obtained and rank evaluation was performed according to the following criteria.
◯: ΔQ = less than 10 μC Δ: ΔQ = 10 μC or more and less than 15 μC ▲: ΔQ = 15 μC or more and less than 20 μC ×: ΔQ = 20 μC or more

4). Image Flow on Photosensitive Drum Using a color copier CLC700 (manufactured by Canon) under an environment of 30 ° C. and 80% humidity, a halftone image was formed and the image quality was evaluated according to the following criteria.
○: No image flow at all △: Slightly seen but no problem for practical use ▲: Level for practical use ×: Image flow is observed on the entire surface, impractical level

(Examples 7 to 12)
Toner No. Toner no. A developer was prepared and evaluated in the same manner as in Examples 1 to 6 except that 2. The results are shown in Table 2.

(Comparative Examples 3-4)
Toner No. Toner no. A developer was prepared and evaluated in the same manner as in Comparative Examples 1 and 2 except that No. 2 was used. The results are shown in Table 2.

(Example 13)
These ferrite raw material oxides are wet-mixed in a ball mill so that the molar ratios of Fe ₂ O ₃ : 56.3 mol%, MgO: 23.0 mol%, and SrO: 20.7 mol% are dried and dried. After pulverization, the mixture was calcined at 750 ° C. for 2 hours, and pulverized to about 0.1 to 1.0 mm with a crusher. Furthermore, it is wet pulverized with a ball mill to form a slurry, and 1.0% of polyvinyl alcohol is added as a binder, 3% of CaCO3 is added as a pore adjusting agent, granulated into spherical particles by a spray dryer method, and an oxygen gas concentration of 0.5%. Sintered at 950 ° C. in a nitrogen gas atmosphere, sieved with a sieve having an opening of 250 μm to remove coarse particles, and then an air classifier (Elbow Jet Lab EJ-L3, manufactured by Nippon Steel & Mining Co., Ltd .; trade name) And then the particle size was adjusted to obtain a core material.
Next, a mixture having the following composition was prepared.
-Toluene and methyl ethyl ketone (4: 1) mixed solvent 1000 parts-Styrene methyl methacrylate copolymer 50 parts (Styrene: methyl methacrylate = 4: 6, Mw = 50,000)
-PHA (A) 50 parts A resin coating solution was prepared using the above mixture. Next, the composition of the solution is adjusted with respect to the core material so that the resin solid content is 10.0% by mass, the solvent is removed by drying under reduced pressure while stirring and mixing with a vacuum kneader, and baking is performed at 140 ° C. for 2 hours. And sieved with a sieve having an aperture of 74 μm to obtain a resin-coated carrier having an average particle size (volume average 50% particle size) of 35.3 μm and a BET specific surface area of 0.182 m ² / g.
A developer was prepared in the same manner as in Example 1 except that the obtained carrier was used. This developer was evaluated in the same manner as in Example 1, and the results are shown in Table 3.

(Examples 14 to 16)
80 parts of the above styrene / methyl methacrylate copolymer (styrene: methyl methacrylate = 4: 6, Mw = 50,000) and 20 parts of PHA (A), the resin solids being 15.0% and 20.0%, respectively. A resin-coated carrier was obtained in the same manner as in Example 13 except that the content was 25.0%.
Using the obtained resin-coated carrier, a developer was produced in the same manner as in Example 1, and evaluated in the same manner as in Example 1. The results are shown in Table 3.

(Examples 17 to 20)
Toner No. Toner no. A developer was prepared and evaluated in the same manner as in Examples 13 to 16 except that 2. The results are shown in Table 3.

(Example 21)
A resin-coated carrier was obtained in the same manner as in Example 1 except that PHA (D) was used instead of PHA (A). A developer was prepared and evaluated in the same manner as in Example 1 using the obtained resin-coated carrier. The results are shown in Table 4.

(Example 22)
A resin-coated carrier was obtained in the same manner as in Example 2 except that PHA (E) was used instead of PHA (B). A developer was prepared and evaluated in the same manner as in Example 1 using the obtained resin-coated carrier. The results are shown in Table 4.

(Examples 23 and 24)
Resin-coated carriers were obtained in the same manner as in Examples 3 and 4 except that PHA (E) and PHA (F) were used instead of PHA (B) and PHA (C). A developer was prepared and evaluated in the same manner as in Example 1 using the obtained resin-coated carrier. The results are shown in Table 4.

(Examples 25 and 26)
Resin-coated carriers were obtained in the same manner as in Examples 5 and 6 except that PHA (D) and PHA (E) were used instead of PHA (A) and PHA (B). A developer was prepared and evaluated in the same manner as in Example 1 using the obtained resin-coated carrier. The results are shown in Table 4.

(Examples 27 to 32)
Toner No. Toner no. A developer was prepared and evaluated in the same manner as in Examples 21 to 26 except that No. 2 was used. The results are shown in Table 5.

(Example 33)
A resin-coated carrier was obtained in the same manner as in Example 13 except that PHA (D) was used instead of PHA (A), and a developer was prepared in the same manner as in Example 1 using the obtained resin-coated carrier. evaluated. The results are shown in Table 6.

(Examples 34 to 36)
80 parts of styrene-methyl methacrylate copolymer (4: 6, Mw = 50,000) and 20 parts of PHA (E), and the resin solids were 15.0%, 20.0% and 25.0%, respectively. Except that, resin-coated carriers were obtained in the same manner as in Example 13.
A developer was prepared in the same manner as in Example 1 using the obtained resin-coated carrier. This developer was evaluated in the same manner as in Example 1, and the results are shown in Table 6.

(Examples 37 to 40)
Toner No. Toner no. A developer was prepared and evaluated in the same manner as in Examples 33 to 36 except that No. 2 was used. The results are shown in Table 6.

(Examples 41 to 48)
Other than using PHA (2A), PHA (2B), PHA (2C), PHA (2D), PHA (2E), PHA (2F), PHA (2G), PHA (2H) instead of PHA (A) Obtained a resin-coated carrier in the same manner as in Example 1. A developer was prepared and evaluated in the same manner as in Example 1 using the obtained resin-coated carrier. The results are shown in Table 7.

(Examples 49 to 56)
Other than using PHA (2I), PHA (2J), PHA (2K), PHA (2L), PHA (2M), PHA (2N), PHA (2O), PHA (2P) instead of PHA (B) Obtained a resin-coated carrier in the same manner as in Example 2. A developer was prepared and evaluated in the same manner as in Example 1 using the obtained resin-coated carrier. The results are shown in Table 8.

  As described above, the resin-coated carrier for an electrophotographic developer of the present invention is excellent in environmental stability in addition to sufficient charge imparting properties. Furthermore, it is suitable for use as a component of a two-component developer and a replenishment developer because it has sufficient durability and can provide an image with excellent image quality that hardly causes image flow.

Claims (9)

A resin-coated carrier for an electrophotographic developer, having a resin coating layer containing a polyhydroxyalkanoate containing in the molecule one or more units represented by the following chemical formula (1) on a core material.

(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 resin-coated carrier 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.
Also, for 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 resin-coated carrier 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 an H atom, Na atom or K atom), an acetamide group, an OPh group (Ph represents a phenyl group). , NHPh group, CF ₃ group, C ₂ F ₅ group or 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, R3a, R3b, R3c, R3d, R3e, R3f, R3f1, R3g, Z3a, Z3b, l, and m have the above meanings independently for each unit. ) The resin-coated carrier according to claim 1, wherein the unit represented by the chemical formula (1) is represented by the following chemical formula (4A) or (4B).

(Wherein, R4a, R4b, R4c, R4d, R4e, at least one of R4f and R4g is SO ₂ R4o (here, R4o represents OH, a halogen atom, ONa, OK or OR4o1, R4o1 is 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 (Ph is phenyl Represents an NHPh group, a CF ₃ group, a C ₂ F ₅ group or a C ₃ F ₇ group.
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. )

(Wherein, R4h, R4i, R4j, R4k , R4l, at least one of R4m and R4n is SO ₂ R4o (here, R4o is OH, a halogen atom, ONa, R4o1 represents OK or OR4o1 is linear 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, 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 (Ph is a phenyl group) the represented.) represents an NHPh group, CF3 group, 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.
When there are multiple units, R4h, R4i, R4j, R4k, R4l, R4m, R4n, R4o, OR4o1, R4p, Z4c, Z4d, l, m have the above meanings independently for each unit. To express. ) A resin-coated carrier for an electrophotographic developer, having a resin coating layer containing a polyhydroxyalkanoate containing in the molecule one or more units represented by the following chemical formula (5) on a core material.

(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 resin-coated carrier according to any one of claims 1 to 5, wherein the polyhydroxyalkanoate further contains a unit represented by the following chemical formula (7).

(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 an optionally substituted aryl group. 1 to 5 alkylidene groups are represented.
Further, when a plurality of units are present, R7 represents the above meaning independently for each unit. )   The resin-coated carrier according to any one of claims 1 to 6, wherein the polyhydroxyalkanoate has a number average molecular weight of 1,000 to 1,000,000.   A two-component developer comprising a resin-coated carrier and a toner containing at least a binder resin and a colorant, wherein the resin-coated carrier is the resin-coated carrier according to any one of claims 1 to 7. A two-component developer characterized by being.   A replenishment developer containing 2 to 50 parts by mass of toner with respect to 1 part by mass of the carrier, wherein the carrier is the resin-coated carrier according to any one of claims 1 to 7.