JP2009203251A - Biodegradable polyester resin and its manufacturing method, electrostatic image developing toner, electrostatic image developer, image-forming method, and image-forming apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a manufacturing method of an aliphatic polyester, which has attracted attention as a biodegradable resin, that permits enhancement of its biodegradability while retaining its strengths and, an electrostatic image developing toner, an electrostatic image developer, an image-forming method, and an image-forming apparatus. <P>SOLUTION: The biodegradable polyester resin is an aliphatic polyester resin that comprises a compound represented by formula (II) and/or formula (III) and has a weight-average molecular weight of at least 30,000 and at most 5,000,000. In formula (II), R<SP>1</SP>has preferably a Hammet value for a sulfo group of at least 0.2 and R<SP>1</SP>'s can be the same or different; l is an integer of 0-4; and L is ≥8C alkyl or alkenyl. In formula (III), M is ≥8C alkyl or alkenyl. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a biodegradable polyester resin and a method for producing the same, an electrostatic charge image developing toner, an electrostatic charge image developer, an image forming method, and an image forming apparatus.

Plastics have many advantages over other materials in terms of lightness, processability, strength, cost, etc., and are currently used in products in all fields. However, since it is hardly decomposed in the natural environment at the time of disposal, the harmfulness of plastics and the need for low environmental impact plastics are attracting attention in efforts to reduce environmental impacts that have become important in recent years.
Therefore, it is desired to introduce a biodegradable plastic that can be decomposed and detoxified by many microorganisms present in the environment. For example, an aliphatic polyester that is composed of oxygen, hydrogen, and carbon and generates only water and carbon dioxide when decomposed is a typical biodegradable resin. Biodegradable plastics have already been adopted and commercialized in several fields, but it is necessary to further promote the expansion to general-purpose materials.
The development of aliphatic polyester with sufficient biodegradability that maintains all the properties of conventional general-purpose materials such as cost, productivity, mechanical / physical performance, and chemical performance is still under investigation. Yes.

  Aliphatic polyester has been studied and put to practical use because of its biodegradability and ease of synthesis, but it has been difficult to achieve both high biodegradability and mechanical and physical strength. The invention has been made. For example, Patent Document 1 discloses a method of copolymerizing a polyester containing an aromatic ring and a linear polyester in an oligomer state, and Patent Document 2 further discloses polylactic acid and a trifunctional or higher functional polyisocyanate. Resins obtained by crosslinking natto and the like are disclosed.

On the other hand, with the exception, the normal polyester polycondensation method requires a long reaction under high-power agitation at a high temperature exceeding 200 ° C. and under a high reduced pressure, resulting in a large amount of energy consumption. The same applies to the case where a biodegradable resin is synthesized. As a result, enormous capital investment is often required to obtain durability of the reaction equipment.
However, in recent years, low temperature and desolvation of various reactions including polyester have been reported. For example, Patent Document 3 discloses a method for producing a polyester under a substantially solvent-free condition using a hydrolase as a catalyst, and Patent Document 4 reports a polyester synthesis at 80 to 180 ° C. using a scandium triflate catalyst.

  Many studies on polymerization catalysts have been conducted for the purpose of reducing the environmental burden during the production of biodegradable resins and improving the polymerization rate. Patent Document 5 discloses a method for producing a biodegradable aliphatic polyester in which polycondensation is performed in the presence of an acid catalyst having a logarithmic value of the reciprocal of the tin catalyst and the acid dissociation constant of 3.66 or less, Patent Document 6 discloses a method for producing a polyester composite material using a specific Al compound as a ring-opening polymerization catalyst. Patent Document 7 discloses an aliphatic and / or aromatic compound having an organic phosphonic acid, sulfonic acid or sulfuric acid ester group as a co-catalyst for transesterification catalyst at the time of polyester production with aliphatic dicarboxylic acid or aliphatic diol, In addition, a method using at least one proton acid selected from the group consisting of sulfuric acid is disclosed.

  Furthermore, regarding biodegradability, it is necessary to consider not only the structure of the resin itself but also the environmental impact of the catalyst. For example, in Europe and the United States, there are regions where some heavy metals that can also be used as polymerization catalysts are regulated. In addition, a polyester resin having a structure in which biodegradation in soil is further accelerated is desirable.

  On the other hand, several inventions using surfactants as soil improvers and soil treatment agents are recognized. For example, Patent Document 8 discloses a soil purification composition comprising at least one carbon source selected from a specific carbon number fatty acid and alcohol, and an anionic and / or nonionic surfactant. Discloses a surfactant for soil improvement materials containing a specific fatty acid polyoxyalkylene alkyl ether.

JP 2001-342244 A JP-A-9-281746 Japanese Patent Laid-Open No. 11-313692 JP 2003-306535 A JP 2001-89558 A JP 2005-97361 A JP 2001-19752 A JP 2005-66425 A JP-A-8-1557819

  As described above, there has been a need for an aliphatic biodegradable polyester resin capable of withstanding the biodegradability and practical useability, and further reducing the environmental burden during production.

  The present invention solves the above-mentioned problems, and aims to maintain the strength and improve the biodegradability of aliphatic polyesters that are attracting attention as biodegradable resins.

The above-described problems of the present invention have been solved by means described in the following <1> and <4> to <9>. It is described below together with <2> and <3> which are preferred embodiments.
<1> The monomer unit represented by the formula (I) is contained in an amount of 50% by weight or more of the whole polyester resin, the compound represented by the formula (II) and / or the formula (III) is contained, and the weight average molecular weight is 30. A biodegradable polyester resin characterized by being from 5,000 to 5,000,000,

式（Ｉ）中、Ａは単結合、直鎖又は分岐型アルキレン基、又は、シクロアルキレン基を表し、Ｂは炭素数２以上の直鎖又は分岐型アルキレン基、又は、シクロアルキレン基を表し、Ａ及びＢの炭素数の合計は、２以上１４以下である。

In formula (I), A represents a single bond, a linear or branched alkylene group, or a cycloalkylene group, B represents a linear or branched alkylene group having 2 or more carbon atoms, or a cycloalkylene group, The total number of carbon atoms of A and B is 2 or more and 14 or less.

式（II）中、Ｒ¹は、ハロゲン原子、アルコキシカルボニル基、アシルオキシ基、アシル基、カルバモイル基、一置換若しくは二置換カルバモイル基、シアノ基、パーハロゲノアルキル基、チオシアナト基、スルファモイル基、アルキルスルフィニル基、アリールスルフィニル基、アルキルスルホニル基、アリールスルホニル基、ニトロ基又はアルキニル基を表し、ｌ個のＲ¹はそれぞれ同一でも異なっていてもよい。ｌは０〜４の整数を表す。Ｌは炭素数８以上の直鎖又は分岐型のアルキル基又はアルケニル基を表す。

In the formula (II), R ¹ represents a halogen atom, an alkoxycarbonyl group, an acyloxy group, an acyl group, a carbamoyl group, a mono- or disubstituted carbamoyl group, a cyano group, a perhalogenoalkyl group, a thiocyanato group, a sulfamoyl group, an alkylsulfinyl group. Represents a group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a nitro group or an alkynyl group, and one R ¹ may be the same or different. l represents an integer of 0 to 4. L represents a linear or branched alkyl group or alkenyl group having 8 or more carbon atoms.

式（III）中、Ｍは炭素数８以上の直鎖又は分岐型のアルキル基又はアルケニル基を表す。

In formula (III), M represents a linear or branched alkyl group or alkenyl group having 8 or more carbon atoms.

<2> The biodegradable polyester resin according to <1> above, which contains a metal component derived from a catalyst of 0 ppm to 10 ppm,
<3> The biodegradable polyester resin according to <1> or <2>, wherein the melting point is 50 ° C. or higher.
<4> a step of polycondensing a dicarboxylic acid component represented by the formula (IV) and a diol component represented by the formula (V) in the presence of a polycondensation catalyst, wherein the polycondensation catalyst is represented by the formula (II) And / or the method for producing a biodegradable polyester resin according to any one of <1> to <3> above, which is a compound represented by the formula (III),

式（IV）中、Ｒ⁵は、水素原子、低級アルキル基、又は、アリール基を表し、Ａは単結合、直鎖又は分岐型アルキレン基、又は、シクロアルキレン基を表す。式（Ｖ）中、Ｂは炭素数２以上の直鎖又は分岐型アルキレン基、又は、シクロアルキレン基を表す。Ａ及びＢの炭素数の合計は、２以上１４以下である。

In the formula (IV), R ⁵ represents a hydrogen atom, a lower alkyl group, or an aryl group, and A represents a single bond, a linear or branched alkylene group, or a cycloalkylene group. In formula (V), B represents a linear or branched alkylene group having 2 or more carbon atoms or a cycloalkylene group. The total number of carbon atoms of A and B is 2 or more and 14 or less.

<5> Binder resin for electrostatic charge image developing toner, containing 5% by weight to 80% by weight of biodegradable polyester resin according to any one of <1> to <3> above. ,
<6> An electrostatic charge image developing toner comprising the binder resin for electrostatic charge image development toner according to <5>,
<7> An electrostatic charge image developer comprising the electrostatic charge image developing toner and the carrier according to <6> above,
<8> A latent image forming step for forming an electrostatic latent image on the surface of the latent image holding member, and a toner image is formed by developing the electrostatic latent image formed on the surface of the latent image holding member with a developer containing toner. A developing step, a transfer step of transferring the toner image formed on the surface of the latent image holding member to the surface of the transfer target, and a fixing step of thermally fixing the toner image transferred to the surface of the transfer target, An image forming method comprising using the electrostatic image developing toner according to <6> as the toner, or the electrostatic image developer according to <7> as the developer,
<9> A latent image holding member, a charging unit that charges the latent image holding member, an exposure unit that exposes the charged latent image holding member to form an electrostatic latent image on the latent image holding member, Developing means for developing the electrostatic latent image with a developer containing toner to form a toner image; and transfer means for transferring the toner image from the latent image holding member to a transfer target. An image forming apparatus using the electrostatic charge image developing toner according to <6> or the electrostatic charge image developer according to <7> as the developer.

According to the invention described in the above <1>, it was possible to obtain good biodegradability while maintaining the strength of the aliphatic polyester as a main component.
According to the invention described in the above <2>, the metal component derived from the catalyst existing in the biodegradable polyester resin is small, and the environmental influence derived from the metal catalyst can be reduced.
According to the invention described in <3> above, a biodegradable polyester resin having higher strength can be obtained.
According to the invention described in <4> above, physical properties such as strength can be more easily controlled, and the environmental influence during polymerization can be reduced as compared with the case of using a halogenated material or the like. .
According to the invention described in <5>, it is possible to provide a binder resin for an electrostatic charge image developing toner having the strength required for a toner binder for electrostatic charge developing toner and further having biodegradability. It was.
According to the invention described in <6>, an electrostatic charge image developing toner having biodegradability while having sufficient performance as an electrostatic charge image developing toner can be provided.
According to the invention described in <7>, an electrostatic charge image developing toner having biodegradability while having sufficient performance as an electrostatic charge image developer can be provided.
According to the invention described in <8> above, the image forming ability is excellent, and since the electrostatic charge image developing toner uses a biodegradable polyester resin as a binder resin, the load on the environment is less. An image forming method could be provided.
According to the invention described in <9>, since the image forming ability is excellent and the electrostatic charge image developing toner uses a biodegradable polyester resin as a binder resin, the load on the environment is less. An image forming apparatus could be provided.

(Biodegradable polyester resin)
The biodegradable polyester resin of the present invention contains 50% by weight or more of the monomer unit represented by the above formula (I) and represented by the above formula (II) and / or the above formula (III). It contains a compound and has a weight average molecular weight of 30,000 or more and 5,000,000 or less.
In the present invention, the biodegradability of the polyester is improved by adopting the above configuration. This is predicted to be based on the surface activity ability of the compounds represented by the formulas (II) and (III). That is, the compound represented by the formula (II) and / or the formula (III) present in the biodegradable polyester resin retains moisture in the soil in the vicinity of the polyester resin by the hydrophilic group, and as a result, the resin It is presumed to work to promote the decomposition of
Details will be described below.

<Polyester resin, polycondensable monomer>
The biodegradable polyester resin of the present invention contains a monomer unit (repeating unit) represented by the following formula (I) in an amount of 50% by weight or more based on the whole polyester resin.

In formula (I), A represents a single bond or an aliphatic hydrocarbon group, B represents an aliphatic hydrocarbon group having 2 or more carbon atoms, and the total number of carbon atoms of A and B is 2 or more and 14 or less. .
In this invention, when A and B satisfy | fill said carbon number, high polycondensation property and high biodegradability can be made compatible. Further, since it is excellent in polycondensation property, it is possible to obtain a high-melting-point, high-melting-point biodegradable polyester resin. Such a biodegradable polyester resin is also suitable as a binder resin for electrostatic charge image developing toner. Can be used.

In formula (I), A represents a single bond or a divalent aliphatic hydrocarbon group. The aliphatic hydrocarbon group may be either a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group, such as a linear or branched alkylene group, a cycloalkylene group, a linear or branched alkenylene group, or a cycloalkenylene group. Etc. can be illustrated. The aliphatic hydrocarbon group is preferably a linear or branched alkylene group or a cycloalkylene group.
Among these, A is preferably a single bond, a linear or branched alkylene group, or a cycloalkylene group.
A has 0 to 12 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 2 to 10 carbon atoms. In addition, the number of carbon atoms of A means that A represents a single bond.

B represents a divalent aliphatic hydrocarbon group having 2 or more carbon atoms, and the aliphatic hydrocarbon group may be either a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group, for example, linear or branched Examples include a type alkylene group, a cycloalkylene group, a linear or branched alkenylene group, and a cycloalkenylene group. The aliphatic hydrocarbon group is preferably a linear or branched alkylene group.
B has 2 to 14 carbon atoms, preferably 2 to 11 carbon atoms, and more preferably 2 to 10 carbon atoms.

In the present invention, the total number of carbon atoms of A and B is 2 or more and 14 or less. When the number of carbon atoms exceeds 14, biodegradability cannot be exhibited. Further, when the number of carbon atoms is less than 2, it is difficult to stably obtain such a polyester resin.
The total number of carbon atoms of A and B is preferably 4 or more and 14 or less, more preferably 4 or more and 10 or less, and further preferably 4 or more and 8 or less.

In A and B of the formula (I), the aliphatic hydrocarbon group may have an arbitrary substituent.
When A and B represent a linear or branched alkylene group, the alkylene group may have a cycloalkyl group as a substituent. In this case, the total number of carbon atoms including the substituent is A or B. A preferred range for the number of carbon atoms is set.
In A and B, in the branched alkylene group, the branched chain may form a ring with the main chain.
Here, it is preferable that A and B consist only of carbon and hydrogen from the point of being decomposed into carbon dioxide and water by biodegradation.

The biodegradable polyester resin of the present invention contains the monomer unit represented by the above formula (I) in an amount of 50% by weight or more based on the whole polyester resin. “Containing 50% by weight or more of the whole polyester resin” means that the monomer unit represented by the formula (I) is 50% by weight or more of the whole polyester resin, and other monomer units are: It may be inserted between the monomer units represented by the formula (I) in a proportion of less than 50% by weight of the whole.
The monomer unit represented by the formula (I) is preferably contained in an amount of 55% by weight or more based on the whole polyester resin, and more preferably 60 to 100% by weight.

The biodegradable polyester resin of the present invention uses the dicarboxylic acid component represented by the following formula (IV) and the diol component represented by the following formula (V) as a polycondensable monomer. It is obtained by polycondensation reaction or transesterification reaction of a monomer.
In addition, the said dicarboxylic acid component is not limited to dicarboxylic acid, It is the meaning also including carboxylic acid derivatives, such as the anhydride and acid esterified substance.

In formula (IV), R ⁵ represents a hydrogen atom, a lower alkyl group, or an aryl group, and A represents a single bond or a divalent aliphatic hydrocarbon group. In formula (V), B represents a divalent aliphatic hydrocarbon group having 2 or more carbon atoms. The total number of carbon atoms of A and B is 2 or more and 14 or less.
In the formulas (IV) and (V), preferred ranges of A and B are the same as those in the formula (I).
In formula (IV), the lower alkyl group is an alkyl group having 1 to 4 carbon atoms, which may be linear or branched, and examples thereof include a methyl group, an ethyl group, a propyl group, and a butyl group.
In addition, the aryl group preferably has 6 to 12 carbon atoms, and more preferably has 6 to 10 carbon atoms. The aryl group may have a substituent, and examples of the substituent include a halogen atom and an alkyl group having 1 to 4 carbon atoms.

Examples of the dicarboxylic acid corresponding to the formula (IV) include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid. , Tridecanedicarboxylic acid, β-methyladipic acid, fumaric acid, maleic acid, citraconic acid (cis-HOOC—CH═CMe—COOH).
In Formula (IV), A may be an alicyclic alkylene group, specifically, a group obtained by removing two hydrogen atoms from cyclopropane, cyclobutane, cyclopentane, cyclohexane, cyclooctane, or cyclododecane. Can be mentioned. A particularly preferred compound having an alicyclic alkylene group is cyclohexanedicarboxylic acid.
In addition, 1,1-cyclopentene dicarboxylic acid, 1,2-cyclohexene dicarboxylic acid and the like can also be exemplified.
In addition, as above-mentioned, these acid anhydrides, acid esterified products, etc. can also be used.

  Examples of the diol corresponding to the formula (V) include ethylene glycol, propanediol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol, decanediol, undecanediol, dodecanediol, and tridecanediol. It is done. Examples of the diol having a cyclic structure include cyclohexanediol and cyclohexanedimethanol.

  As the dicarboxylic acid component and diol component represented by formula (IV) and formula (V), particularly preferred are succinic acid, succinic acid, adipic acid, sebacic acid, dodecanedioic acid, ethylene glycol, butanediol, hexanediol, octanediol, Nonanediol and decanediol are exemplified, and combinations satisfying the above-mentioned range of carbon number are exemplified.

  If the combination satisfies this carbon number range, three or more polycondensable monomers can be used. In that case, the dicarboxylic acid component and / or the diol component are each in accordance with the addition amount (% by weight). The average value of the carbon number is calculated, and it can be judged whether or not the carbon number is within a specified range based on the average value.

In the present invention, other monomer units other than the monomer unit represented by the above formula (I) may be contained, with the upper limit being less than 50% by weight of the biodegradable polyester resin.
That is, other polycondensable monomers can be used in combination with the dicarboxylic acid component represented by the above formula (IV) and the diol component represented by the above formula (V).
Examples of the polycondensable monomer that can be used in combination include a polycarboxylic acid component, a polyol component, and a hydroxycarboxylic acid component. Among these, it is preferable to use a dicarboxylic acid component, a diol component, or a monohydroxymonocarboxylic acid component in combination.
The biodegradable polyester resin of the present invention preferably has no cross-linked structure from the viewpoint of achieving high biodegradability. Therefore, it is preferable not to use a trivalent or higher polycarboxylic acid component, a trivalent or higher polyol component, and a trivalent or higher hydroxycarboxylic acid component as the polycondensable monomer.
Here, as described above, the carboxylic acid component means not only carboxylic acid but also carboxylic acid derivatives such as acid anhydrides and acid esterified products thereof.

In the present invention, the other polycarboxylic acid component that can be used in combination with the dicarboxylic acid component represented by the formula (IV) is preferably a dicarboxylic acid component, and specific examples thereof include the following dicarboxylic acids.
Dicarboxylic acids that can be used together as a polycondensable monomer are compounds containing two carboxyl groups in one molecule. For example, phthalic acid, isophthalic acid, terephthalic acid, tetrachlorophthalic acid, chlorophthalic acid, nitrophthalate Acid, p-carboxyphenylacetic acid, p-phenylenediacetic acid, m-phenylenediacetic acid, p-phenylenedipropionic acid, m-phenylenedipropionic acid, m-phenylenediglycolic acid, p-phenylenediglycolic acid, o -Phenylene diglycolic acid, diphenylacetic acid, diphenyl-p, p'-dicarboxylic acid, naphthalene-1,4-dicarboxylic acid, naphthalene-1,5-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, anthracene dicarboxylic acid, etc. Can be mentioned.
Examples of the polyvalent carboxylic acid other than dicarboxylic acid include trimellitic acid, pyromellitic acid, naphthalenetricarboxylic acid, naphthalenetetracarboxylic acid, pyrenetricarboxylic acid, and pyrenetetracarboxylic acid. It is preferable not to use a tricarboxylic or higher polycarboxylic acid.
The carboxylic acid may have a functional group other than a carboxyl group, and carboxylic acid derivatives such as acid anhydrides and acid esters can also be used.

A polyhydric alcohol is a compound containing two or more hydroxyl groups in one molecule. Although it does not specifically limit as a polyhydric alcohol, The following monomer can be mentioned.
Diol is a compound containing two hydroxyl groups in one molecule, and examples thereof include octadecanediol.
Examples of polyvalent ols other than diols include glycol, pentaerythritol, hexamethylol melamine, hexaethylol melamine, tetramethylol benzoguanamine, tetraethylol benzoguanamine, etc. In the present invention, trivalent or more. The polyol (polyhydric alcohol) is preferably not used.
Moreover, the following monomer can be mentioned as a polyhydric alcohol which has a cyclic structure. For example, bisphenol A, bisphenol C, bisphenol E, bisphenol F, bisphenol P, bisphenol S, bisphenol Z, hydrogenated bisphenol, biphenol, naphthalenediol, hydroxyphenylcyclohexane, and the like can be mentioned. Absent. In the present invention, the bisphenols preferably have at least one alkylene oxide group. Examples of the alkylene oxide group include, but are not limited to, an ethylene oxide group, a propylene oxide group, and butylene oxide. Preferably, they are ethylene oxide and propylene oxide, and the added mole number is preferably 1 to 3. When it is within this range, the viscoelasticity and glass transition temperature of the produced polyester can be appropriately controlled for use as a toner.

Further, polycondensation can also be carried out by using a hydroxycarboxylic acid compound containing a carboxylic acid and a hydroxyl group in one molecule as a polycondensable monomer. For example, the monohydroxymonocarboxylic acid includes hydroxyoctanoic acid, hydroxynonanoic acid, hydroxydecanoic acid, hydroxyundecanoic acid, hydroxydodecanoic acid, hydroxytetradecanoic acid, hydroxytridecanoic acid, hydroxyhexadecanoic acid, hydroxypentadecanoic acid, hydroxystearic acid However, it is not limited to this.
Examples of the trivalent or higher valent hydroxycarboxylic acid include malic acid, tartaric acid, mucous acid, dibutyrolbutanoic acid, dibutyrolpropionic acid and the like.

<Compound represented by formula (II) and / or formula (III)>
The biodegradable polyester resin of the present invention contains a compound represented by the following formula (II) and / or the following formula (III). The compound represented by the formula (II) and the formula (III) is a linear or branched type having a sulfo group (—SO ₃ H) which is a hydrophilic group and a long chain (8 or more carbon atoms) which is a hydrophobic group. Therefore, it has surface activity.
Although its mechanism of action is not sufficiently clear, the biodegradable polyester resin of the present invention contains a compound represented by the following formula (II) and / or a compound represented by the following formula (III). Based on the surface activity, biodegradability and dispersal life in soil are expected to improve.

  In the present invention, the compounds represented by formula (II) and / or formula (III) can be used alone or in combination of two or more. That is, the compound represented by the formula (II) and the compound represented by the formula (III) can be used in combination, or two or more compounds represented by the formula (II) or the formula (III) can be used. It can also be used.

In the formula (II), R ¹ represents a halogen atom, an alkoxycarbonyl group, an acyloxy group, an acyl group, a carbamoyl group, a mono- or disubstituted carbamoyl group, a cyano group, a perhalogenoalkyl group, a thiocyanato group, a sulfamoyl group, an alkylsulfinyl group. Represents a group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a nitro group, or an alkynyl group, and one R ¹ may be the same or different. l represents an integer of 0 to 4. L represents a linear or branched alkyl group having 8 or more carbon atoms.

In formula (II), R ¹ is preferably a substituent having a Hammett value based on a sulfo group (—SO ₃ H) of 0.2 or more. Since it improves, it is preferable.
Specific examples of the substituent having a Hammett value of 0.2 or more include, for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a methoxycarbonyl group, an ethoxycarbonyl group, an acetoxy group, a propionyloxy group, an acetyl group, and a benzoyl group. , Formyl group, trifluoroacetyl group, carbamoyl group, cyano group, trifluoromethyl group, thiocyanato group, nitro group and the like. Among these, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are preferable in consideration of the substituent effect, suitability for a polycondensation catalyst, and suitability for a binder resin for toner.
There is no limitation on the number of these substituents, and a plurality of substituents may be included. In that case, it is preferable that the sum of Hammett values based on all sulfo groups of R ¹ is a positive value, that is, R ^{1 as a} whole is electron withdrawing with respect to the sulfo group.
In addition, the number of the substituents of R < ¹ > is 0-4, Preferably it is 0-3, More preferably, it is 0-2.

In formula (II), L is a linear or branched alkyl group or alkenyl group having 8 or more carbon atoms, preferably 8 to 20 carbon atoms, and more preferably 8 to 18 carbon atoms.
L may be any linear or branched alkyl group or alkenyl, but is preferably a linear or branched alkyl group, and more preferably a linear alkyl group.

In the compound represented by formula (II), the sulfo group (—SO ₃ H) is preferably substituted at the para-position of the linear or branched alkyl group or alkenyl group (L).

Among the compounds represented by the formula (II), examples of the compound in which L has a linear alkyl group include 4-n-octylbenzenesulfonic acid, 4-n-nonylbenzenesulfonic acid, 4-n-decyl. Benzenesulfonic acid, 4-n-undecylbenzenesulfonic acid, 4-n-dodecylbenzenesulfonic acid, 4-n-tridecylbenzenesulfonic acid, 4-n-tetradecylbenzenesulfonic acid, 4-n-pentadecylbenzene Sulfonic acid, 4-n-hexadecylbenzenesulfonic acid, 4-n-heptadecylbenzenesulfonic acid, 4-n-octadecylbenzenesulfonic acid, 4-n-nonadecylbenzenesulfonic acid, 4-n-eicosabenzenesulfone Preferred examples include acids such as 4-n-dodecylbenzenesulfonic acid and 4-n-pentadecylbenzene. Sulfonic acid, and more preferably a 4-n-octadecyl benzene sulphonic acid.
Among the compounds represented by the formula (II), examples of the compound having a branched alkyl group as L include, for example, Taca Power B120, B121, B124, B150 manufactured by Teika Co., Ltd., and Rypon LH-9000 manufactured by Lion Co., Ltd. Etc.
Among the catalysts having the structure of the formula (II), the compound having a branched alkyl group as L preferably includes a catalyst having the structure of the following formula (II-2). Of the compounds represented, p is more preferably 3-5.

（式（II−２）中、ｐは２〜５の整数を表す。）

(In formula (II-2), p represents an integer of 2 to 5)

  Among these, as the compound represented by the formula (II), 3-fluoro-4-dodecylbenzenesulfonic acid having a linear alkyl structure, 3-fluoro-4-pentadecylbenzenesulfonic acid, 3-fluoro- 4-octadecylbenzenesulfonic acid, 3-nitro-4-dodecylbenzenesulfonic acid, 3-nitro-4-pentadecylbenzenesulfonic acid, 3-nitro-4-octadecylbenzenesulfonic acid, 4-n-dodecylbenzenesulfonic acid, 4-n-pentadecylbenzenesulfonic acid and 4-n-octadecylbenzenesulfonic acid are preferred.

式（III）中、Ｍは炭素数８以上の直鎖又は分岐型のアルキル基又はアルケニル基を表す。

In formula (III), M represents a linear or branched alkyl group or alkenyl group having 8 or more carbon atoms.

In formula (III), M is a linear or branched alkyl group or alkenyl group having 8 or more carbon atoms, preferably 8 to 20 carbon atoms, and more preferably 8 to 18 carbon atoms.
M may be any linear or branched alkyl group or alkenyl group, but is preferably a linear or branched alkyl group, and more preferably a linear alkyl group.

Examples of the compound represented by the formula (III) include 1-octanesulfonic acid, 1-nonanesulfonic acid, 1-decanesulfonic acid, 1-undecanesulfonic acid, 1-dodecanesulfonic acid, and 1-tridecanesulfonic acid. 1-tetradecanesulfonic acid, 1-pentadecanesulfonic acid, 1-hexadecanesulfonic acid, 1-heptadecanesulfonic acid, 1-octadecanesulfonic acid, 1-nonadecanesulfonic acid, 1-eicosanesulfonic acid, etc. More preferred examples include 1-dodecanesulfonic acid, 1-pentadecanesulfonic acid, and 1-octadecanesulfonic acid.
Moreover, when M is a branched alkyl group, the compound represented by the following formula | equation (III-2) can be illustrated. Of the compounds represented by formula (III-2), q is more preferably 3-5.

（式（III−２）中、ｑは２〜５の整数を表す。）

(In formula (III-2), q represents an integer of 2 to 5.)

  Among these, in this invention, it is preferable to contain the compound represented by Formula (II) among the compounds represented by Formula (II) and / or Formula (III).

In formula (II) or formula (III), when L or M is a linear or branched alkyl group or alkenyl group having less than 8 carbon atoms, sufficient hydrophobicity based on the alkyl group or alkenyl group cannot be obtained. As a result of the decrease in the surface activity of the compounds represented by the formulas (II) and (III), sufficient biodegradability and dispersibility in soil cannot be obtained. In addition, when the compound represented by the formula (II) and / or the formula (III) is used as a polycondensation catalyst, a high catalytic ability cannot be exhibited, and a biodegradable polyester resin having a desired molecular weight can be obtained. It becomes difficult to manufacture with low environmental load.
In particular, when used as a polycondensation catalyst, it is considered that the hydrophobic portion increases the compatibility with the polycondensable monomer and has activity at a low temperature as a Bronsted catalyst. Further, when used as a polycondensation catalyst of the polycondensable monomer represented by the above formulas (IV) and (V), particularly excellent catalytic ability can be exhibited.

The compounds represented by formula (II) and formula (III) have a sulfo group. The sulfo group is a hydrophilic group, and particularly when the compound represented by the formula (II) and / or the formula (III) is used as a polycondensation catalyst, the sulfo group has a high catalytic ability and has a high polymerization rate. It is effective for improving, increasing the molecular weight of the polyester, and lowering the polycondensation temperature, and can produce a high molecular weight polyester resin with a low environmental load.
On the other hand, in the degradation of the biodegradable polyester resin in the soil, the compound represented by the formula (II) and / or the formula (III) is oriented with the sulfo group being a hydrophilic group in the soil on the polyester surface. As a result, the moisture in the soil can be retained on the polyester surface side, so that the degradability is expected to be improved.

The total content of the compound represented by the formula (II) and the compound represented by the formula (III) is 0.03% by weight or more and 10% by weight or less based on the total amount of the biodegradable polyester resin. It is preferable that it is 0.05 wt% or more and 7 wt% or less.
The presence of the compound represented by formula (II) and / or formula (III) can be identified by fluorescent X-ray, mass spectrometry, and liquid chromatography analysis, and the content thereof is fluorescent X-ray and It can be measured by liquid chromatography. For example, it is detailed in “Surfactant Analysis” (Surfactant Analysis Study Group).

  In the present invention, as will be described later, it is preferable to use the compound represented by the formula (II) and / or the compound represented by the formula (III) as a polycondensation catalyst. It is preferable to carry out a polycondensation reaction by adding 0.01 mol% to 5 mol% with respect to the total of the polymerizable monomers, more preferably 0.05 to 2 mol%, still more preferably 0.05 to 1 mol%. This range is preferable because polycondensation proceeds appropriately without causing degradation of the polyester resin, and sufficient biodegradability can be imparted.

[Method for producing compound represented by formula (II) and compound represented by formula (III)]
The compounds represented by formula (II) and formula (III) are not particularly limited and may be produced using known methods or commercially available products. Examples of the production method include alkanes and alkylbenzenes. Can be produced by sulfating the metal or replacing the metal part of the alkylbenzenesulfonic acid metal salt with hydrogen. Examples of the sulfation method include a method of substituting hydrogen with fuming sulfuric acid or anhydrous sulfuric acid gas, and the replacement of the metal salt includes a solution in which a metal salt of alkylbenzene sulfonic acid is dissolved in a solvent. And a method of reacting by adding sulfuric acid.

<Weight average molecular weight>
The biodegradable polyester resin of the present invention has a weight average molecular weight of 30,000 to 5,000,000. If the weight average molecular weight is less than 30,000, sufficient strength cannot be obtained. Moreover, when it exceeds 5,000,000, biodegradability will fall.
When the weight average molecular weight is in the above range, the physical and mechanical properties of the aliphatic polyester are suitable for use as a film, a molded product, a binder resin for electrostatic charge developing toner, and the like.
It is preferable that a weight average molecular weight is 30,000-3,000,000, More preferably, it is 30,000-2,000,000, More preferably, it is 30,000-1,000,000.

<Melting point>
The melting point of the polyester resin of the present invention is preferably 50 ° C. or higher. The temperature is more preferably 50 ° C to 120 ° C, further preferably 60 ° C to 110 ° C, and particularly preferably 70 ° C to 100 ° C.
A melting point of 50 ° C. or higher is preferred because the mechanical strength of the polyester resin is increased and the polyester resin can be suitably used as a binder resin for a film, a molded product, or an electrostatic charge image developing toner.
In the present invention, the melting point of the polyester resin is a value measured by a differential scanning calorimeter.

<Catalyst-derived metal content>
In the present invention, the biodegradable polyester resin preferably has a low content of the metal component derived from the catalyst, more preferably 0 ppm or more and 10 ppm or less, further preferably 0 ppm or more and 7.5 ppm or less, and 0 ppm. It is particularly preferably 5 ppm or less and most preferably 0 ppm.
By setting the content of the metal component derived from the catalyst within the above range, the environmental burden due to the catalyst metal can be reduced, and the biodegradable polyester resin of the present invention can be used as a binder resin for an electrostatic charge image developing toner. When used, it is preferable because a toner having good charging characteristics can be obtained without causing poor charging due to the metal component.

(Method for producing biodegradable polyester resin)
Although the manufacturing method of the biodegradable polyester resin of this invention is not specifically limited, It is preferable to manufacture with the following method.
That is, the method includes a step of polycondensing a dicarboxylic acid component represented by the formula (IV) and a diol component represented by the formula (V) in the presence of a polycondensation catalyst, and the polycondensation catalyst is represented by the formula (II) And / or a method for producing a biodegradable polyester resin, which is a compound represented by the formula (III).

By using the compound represented by the above formula (II) and / or the above formula (III) as a polycondensation catalyst, reactivity at a particularly low temperature can be improved. The reaction at a low temperature has advantages such as suppression of by-products, suppression of coloring, and uniformity of molecular weight distribution resulting from mild reaction conditions.
Since many common polycondensation catalysts and esterification catalysts are catalysts that can be used only at high temperatures, when used in combination, a reaction at high temperatures is required, and the above advantages are impaired. Therefore, the compound represented by the formula (II) and / or the formula (III) can be used alone or in combination with a Bronsted acid compound and / or a general-purpose polycondensation catalyst. At this time, it is preferable to use together with a very small amount of a general-purpose polycondensation catalyst in which the content of metal contained in the general-purpose polycondensation catalyst is 0 to 10 ppm in the resin.

<Combined polycondensation catalyst>
In the present invention, another polycondensation catalyst that can be used in combination with the polycondensation catalyst represented by the above formula (II) and / or formula (III) will be described.
In addition to the compound represented by the formula (II) and / or the formula (III), a commonly used polycondensation catalyst such as a metal catalyst or a hydrolase can be used in combination.
Examples of the metal catalyst include, but are not limited to, the following. For example, organic tin compounds, inorganic tin compounds, organic titanium compounds, organic tin halide compounds, and rare earth metal catalysts can be used.
As the organic tin compound, inorganic tin compound, organic titanium compound, and organic halogenated tin compound, those known as polycondensation catalysts can be used.
As the rare earth-containing catalyst, scandium (Sc), yttrium (Y), as the lanthanoid element, lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu), and the like are effective, especially alkylbenzenesulfone Acid salts, alkyl sulfate esters, or those having a triflate structure are effective.
As the rare earth-containing catalyst, those having a triflate structure such as scandium triflate, yttrium triflate, and lanthanoid triflate are preferable. The lanthanoid triflate is described in detail in Journal of Synthetic Organic Chemistry, Vol. 53, No. 5, p44-54). An example of the triflate is X (OSO ₂ CF ₃ ) _{3 in} the structural formula. Here, X is a rare earth element, and among these, X is more preferably scandium (Sc), yttrium (Y), ytterbium (Yb), samarium (Sm), or the like.

  When a metal catalyst is used as the catalyst, as described above, the metal content derived from the catalyst in the obtained resin is preferably 10 ppm or less, more preferably 7.5 ppm or less, and 5 ppm or less. More preferably.

  The hydrolase that can be used in combination is not particularly limited as long as it catalyzes an ester synthesis reaction. Examples of the hydrolase include EC (enzyme number) 3.1 group (Maruo, Lipoprotein lipase, etc.) such as carboxyesterase, lipase, phospholipase, acetylesterase, pectinesterase, cholesterol esterase, tannase, monoacylglycerol lipase, lactonase and lipoprotein lipase. Hydrolase, epoxide hydrase, etc. classified into EC 3.2 group that acts on glycosyl compounds such as esterase, glucosidase, galactosidase, glucuronidase, xylosidase, etc. classified in “Enzyme Handbook” supervised by Tamiya (1982). It is classified into EC3.4 group that acts on peptide bonds such as hydrolase, aminopeptidase, chymotrypsin, trypsin, plasmin, subtilisin etc. Hydrolase, mention may be made of hydrolytic enzymes such as classified into EC3.7 group such as furo retinoic hydrolase.

  Among these esterases, the enzyme that hydrolyzes glycerol esters and liberates fatty acids is called lipase, but lipase has high stability in organic solvents, catalyzes ester synthesis reaction with good yield, and can be obtained at low cost. There are advantages such as. Therefore, also in the manufacturing method of polyester of this invention, it is preferable to use a lipase from the surface of a yield or cost.

  Lipases of various origins can be used, but preferable examples include Pseudomonas genus, Alcaligenes genus, Achromobacter genus, Candida genus, Aspergillus genus, Rhizopus Examples include lipases obtained from microorganisms such as (Rhizopus) genus and Mucor genus, lipases obtained from plant seeds, lipases obtained from animal tissues, pancreatin, and steapsin. Among these, it is preferable to use lipases derived from microorganisms of the genus Pseudomonas, Candida, and Aspergillus.

Examples of the basic catalyst include, but are not limited to, general organic basic compounds, nitrogen-containing basic compounds, and tetraalkyl or arylphosphonium hydroxides such as tetrabutylphosphonium hydroxide.
Examples of the organic base compound include ammonium hydroxides such as tetramethylammonium hydroxide and tetraethylammonium hydroxide, and examples of the nitrogen-containing basic compound include amines such as triethylamine and dibenzylmethylamine, pyridine, methylpyridine, methoxypyridine, Quinolin, imidazole, alkali metals such as sodium, potassium, lithium, cesium, and alkaline earth metals such as calcium, magnesium, barium, hydroxides, hydrides, amides, alkalis, alkaline earth metals and acids Examples of such salts include carbonates, phosphates, borates, carboxylates, and salts with phenolic hydroxyl groups.
Moreover, a compound with an alcoholic hydroxyl group, a chelate compound with acetylacetone, and the like can be mentioned, but it is not limited to these.

  The polycondensation reaction in the polycondensation step of the present invention can be carried out by general polycondensation methods such as underwater polymerization such as bulk polymerization, emulsion polymerization and suspension polymerization, solution polymerization and interfacial polymerization. Although the reaction is possible under atmospheric pressure, general conditions such as reduced pressure and nitrogen flow can be widely used for the purpose of increasing the molecular weight of the polyester.

<Bulk polymerization>
A polycondensation reaction can be advanced by stirring the polycondensable monomer and polycondensation catalyst while heating under reduced pressure.
The heating temperature is preferably 70 ° C to 180 ° C, more preferably 70 ° C to 170 ° C, and further preferably 90 ° C to 160 ° C. In the present invention, the compound represented by the formula (II) and / or the formula (III) has high reactivity as a polycondensation catalyst, and is polycondensed at a lower temperature than a conventionally used metal catalyst. The reaction can proceed. A heating temperature of 70 ° C. or higher is preferable because the solubility of the polycondensable monomer, the decrease in reactivity based on the decrease in catalytic activity, and the suppression of the molecular weight elongation do not occur. Moreover, since it can manufacture with low energy as it is 180 degrees C or less, it is preferable.
Moreover, it is preferable for the heating temperature to be within the above-mentioned range since the polycondensation reaction proceeds sufficiently and the polymerization reaction can be performed with a low environmental load.
The polymerization time is within a range where a desired weight average molecular weight can be obtained, and can be appropriately selected depending on the reaction temperature and the like, but is preferably 0.5 to 72 hours, more preferably 1 to 48 hours, More preferably, it is 2 to 36 hours.
A reaction time within the above range is preferred because control for obtaining a desired weight average molecular weight and molecular weight distribution is easy.

<Aqueous medium>
The polycondensation reaction in the polycondensation step of the present invention may be performed in an aqueous medium.
Examples of the aqueous medium that can be used in the present invention include water such as distilled water and ion exchange water, and alcohols such as ethanol and methanol. Among these, ethanol and water are preferable, and water such as distilled water and ion-exchanged water is particularly preferable. These may be used individually by 1 type and may use 2 or more types together.
The aqueous medium may contain a water-miscible organic solvent. Examples of water miscible organic solvents include acetone and acetic acid.

<Organic solvent>
The polycondensation reaction in the polycondensation step of the present invention may be performed using an organic solvent.
Specific examples of the organic solvent that can be used in the present invention include, for example, hydrocarbon solvents such as toluene, xylene, mesitylene, chlorobenzene, bromobenzene, iodobenzene, dichlorobenzene, 1,1,2,2-tetrachloroethane. Halogen solvents such as p-chlorotoluene, ketone solvents such as 3-hexanone, acetophenone and benzophenone, dibutyl ether, anisole, phenetole, o-dimethoxybenzene, p-dimethoxybenzene, 3-methoxytoluene, dibenzyl ether, Ether solvents such as benzyl phenyl ether, methoxynaphthalene and tetrahydrofuran, thioether solvents such as phenyl sulfide and thioanisole, ethyl acetate, butyl acetate, pentyl acetate, methyl benzoate, methyl phthalate, phthalic acid Ester solvents such as chill and cellosolve acetate, diphenyl ether, or alkyl-substituted diphenyl ethers such as 4-methylphenyl ether, 3-methylphenyl ether, and 3-phenoxytoluene, or 4-bromophenyl ether, 4-chlorophenyl ether, 4 -Halogen-substituted diphenyl ethers such as bromodiphenyl ether and 4-methyl-4'-bromodiphenyl ether, or alkoxy such as 4-methoxydiphenyl ether, 4-methoxyphenyl ether, 3-methoxyphenyl ether, 4-methyl-4'-methoxydiphenyl ether Diphenyl ether solvents such as substituted diphenyl ethers or cyclic diphenyl ethers such as dibenzofuran and xanthene may be mentioned, and these may be used as a mixture. A solvent that can be easily separated from water is preferable, and an ester solvent, an ether solvent, and a diphenyl ether solvent are more preferable to obtain a polyester having a high average molecular weight, and an alkyl-aryl ether solvent and an ester are preferable. System solvents are particularly preferred.

  Furthermore, in the present invention, in order to obtain a binder resin having a high average molecular weight, dehydration and demonomers may be added to the organic solvent. Specific examples of the dehydration and demonomer include, for example, molecular sieves such as molecular sieve 3A, molecular sieve 4A, molecular sieve 5A, molecular sieve 13X, alumina, silica gel, calcium chloride, calcium sulfate, diphosphorus pentoxide, concentrated Examples include sulfuric acid, magnesium perchlorate, barium oxide, calcium oxide, potassium hydroxide, sodium hydroxide, or metal hydrides such as calcium hydride, sodium hydride, lithium aluminum hydride, or alkali metals such as sodium. It is done. Among these, molecular sieves are preferable because of easy handling and regeneration.

  The biodegradable polyester resin of the present invention can be polycondensed with a polycondensable monomer (monomer) other than those described above as long as the properties are not impaired. For example, a monovalent carboxylic acid, a monohydric alcohol, and a radical polymerizable monomer having an unsaturated bond. Since such a monofunctional monomer caps the polyester terminal, it is possible to effectively modify the terminal and control the properties of the polyester. The monofunctional monomer may be used from the initial stage of polymerization or may be added during the polymerization.

In the present invention, the polycondensation step may include a polymerization reaction between the aforementioned monomers and a prepolymer prepared in advance. The prepolymer is not limited as long as it is a polymer that can be melted or uniformly mixed with the monomer.
Furthermore, the biodegradable polyester resin of the present invention is a homopolymer using one of each of the above-described dicarboxylic acid component and diol component, a copolymer obtained by combining two or more monomers including the above-mentioned monomers, or They may have a mixture, graft polymer, partially branched or cross-linked structure.

  In the present invention, the “biodegradable polyester resin” means a polyester resin that is decomposed by microorganisms or the like. Whether it has biodegradability can be evaluated by the method described in JIS K 6950, JIS K 6951, JIS K 6953, JIS K 6955, ISO 14855-2, OECD 301C and the like.

The biodegradable polyester resin of the present invention can be used for various purposes and is not particularly limited. Specific examples include films, molded articles, toner binder resins, and the like. Among these, the biodegradable polyester resin of the present invention is particularly preferably used as a binder resin for electrostatic image developing toners. Can do.
Hereinafter, the case where the biodegradable polyester resin of the present invention is used as a binder resin for an electrostatic charge image developing toner will be described in detail.

(Binding resin for electrostatic image developing toner)
The biodegradable polyester resin of the present invention can be suitably used as a binder resin for an electrostatic charge image developing toner.
When used as a binder resin for an electrostatic charge image developing toner (hereinafter also simply referred to as a binder resin), the biodegradable polyester resin of the present invention is preferably contained in an amount of 5% by weight of the total binder resin. More preferably, it is contained in an amount of 5 wt% to 80 wt%, more preferably 15 wt% to 70 wt%, and particularly preferably 25 wt% to 70 wt%.
When the content of the biodegradable polyester resin is within the above range, it is preferable because biodegradability as a toner can be imparted and characteristics as a toner can be maintained.

Moreover, as other binder resin used together with the biodegradable polyester resin of this invention, it can select from a conventionally well-known binder resin suitably, and can be used.
The resin to be used in combination is not particularly limited, but is preferably a polyester resin, and more preferably a linear polyester resin. The binder resin used in combination is preferably a polyester resin because biodegradability as a whole binder resin can be obtained.

  The biodegradable polyester resin of the present invention is a so-called chemical method in which a resin particle dispersion is produced using a mechanical production method such as a kneading pulverization method or the biodegradable polyester resin, and a toner is produced from the resin particle dispersion. A toner can be manufactured by a manufacturing method.

(Electrostatic image developing toner)
In the present invention, the electrostatic charge image developing toner can be produced by a known method, specifically, it can be produced by a kneading pulverization method or the like, and a chemical production method (so-called agglomeration coalescence method, Polyester elongation method, suspension polymerization method, emulsion polymerization method, dispersion polymerization method, dissolution suspension method and the like).
The electrostatic image developing toner may be produced by any of these methods. In the present invention, the biodegradable polyester resin of the present invention is contained as the binder resin for the electrostatic image developing toner.
Hereinafter, the electrostatic image developing toner (electrostatic image developing pulverized toner) produced by the kneading and pulverizing method and the electrostatic image developing toner produced by the aggregation and coalescence method will be described.

<Kneading and grinding method>
In the present invention, the electrostatic image developing toner is a pulverized toner including at least a binder resin, and the binder resin may include the biodegradable polyester resin of the present invention.

The above pulverized toner can be produced by a known method, for example, a kneading pulverization method or the like.
When the pulverized toner is produced by the kneading and pulverization method, the biodegradable polyester resin is preferably mixed with other toner raw materials in advance with a Henschel mixer, a supermixer or the like before melt-kneading. At this time, a combination of the agitator capacity, the rotation speed of the agitator, the agitation time, and the like must be selected.
Next, the agitated product of the binder resin and the other toner raw materials is kneaded in a molten state by a known method. Kneading with a single-screw or multi-screw extruder is preferable because dispersibility is improved. At this time, the number of kneading screw zones of the kneading apparatus, the cylinder temperature, the kneading speed, etc. must all be set to appropriate values and controlled. Among the control factors at the time of kneading, the number of rotations of the kneader, the number of kneading screw zones, and the cylinder temperature have a particularly great influence on the kneading state. In general, the number of rotations is preferably 300 to 1,000 rpm, and the number of kneading screw zones is kneaded better by using a multi-stage zone such as a two-stage screw rather than a single stage. For example, when the main component of the binder resin is a crystalline polyester resin, the cylinder set temperature is determined from the melting point of the crystalline polyester resin and is preferably about −50 to + 100 ° C. than the normal melting point temperature. The above range is preferable because sufficient kneading and dispersion can be obtained, aggregation hardly occurs, kneading share is applied, and sufficient dispersion and cooling after kneading can be easily performed.
The melt-kneaded kneaded product is sufficiently cooled and then pulverized by a known method such as a mechanical pulverization method such as a ball mill, a sand mill, or a hammer mill, or an airflow pulverization method. If cooling by a conventional method is not sufficient, a cooling or freeze pulverization method can also be selected.

  For the purpose of controlling the particle size distribution of the toner, the pulverized toner may be classified. By eliminating particles having an inappropriate diameter by classification, there is an effect of improving toner fixing property and image quality.

<Aggregating coalescence method>
On the other hand, in response to the recent demand for high image quality, many toner chemical manufacturing methods have been adopted as a technology for reducing the diameter of toner and supporting low energy manufacturing methods. As a chemical production method of the toner using the biodegradable polyester resin of the present invention, a general production method can be used, but an agglomeration and coalescence method is preferable. The aggregation coalescence method is a known aggregation method in which a latex in which a binder resin is dispersed in an aqueous medium is produced and agglomerated (aggregated) together with other toner raw materials.
In the present invention, when an electrostatic charge image developing toner (also simply referred to as “toner”) is produced by chemical production, the production method comprises at least the resin particles in a dispersion containing a resin particle dispersion. An electrostatic charge image developing toner including a step of aggregating to obtain aggregated particles (hereinafter also referred to as “aggregation step”) and a step of heating and aggregating the aggregated particles (hereinafter also referred to as “fusion step”). It is preferable that the resin particle dispersion contains the biodegradable polyester resin of the present invention.
The “electrostatic image developing toner” and the “toner” are not limited to the toner manufactured by a chemical manufacturing method, but may include the pulverized toner described above.
The toner obtained by the kneading and pulverizing method (hereinafter also referred to as “pulverized toner”) and the toner produced by the chemical manufacturing method include the biodegradable polyester resin of the present invention as a binder resin. Excellent decomposability, hot offset at fixing, and cold offset. Further, a toner produced by a chemical production method is preferable because of excellent particle distribution.

[Resin particle dispersion for electrostatic image developing toner]
In the present invention, an electrostatic charge image developing toner resin particle dispersion (hereinafter also simply referred to as “resin particle dispersion”) is obtained by dispersing resin particles containing at least the biodegradable polyester resin of the present invention in a dispersion medium. The resin particle dispersion.

-Aqueous medium-
In the present invention, the dispersion medium of the resin particle dispersion is preferably an aqueous medium.
Examples of the aqueous medium that can be used in the present invention include water such as distilled water and ion exchange water, and alcohols such as ethanol and methanol. Among these, ethanol and water are preferable, and water such as distilled water and ion-exchanged water is particularly preferable. These may be used individually by 1 type and may use 2 or more types together.
The aqueous medium may contain a water-miscible organic solvent. Examples of water miscible organic solvents include acetone and acetic acid.

In the present invention, the median diameter (center diameter) of the resin particle dispersion is preferably 0.05 μm or more and 2.0 μm or less, more preferably 0.1 μm or more and 1.5 μm or less, and further preferably 0.1 μm or more and 1 or less. 0.0 μm or less. This median diameter within the above range is preferable because the dispersion state of the resin particles in the aqueous medium is stabilized as described above. Further, when used for toner preparation, it is preferable because the particle size can be easily controlled and the releasability and the offset property during fixing are excellent.
The median diameter of the resin particles can be measured, for example, with a laser diffraction particle size distribution measuring device (LA-920, manufactured by Horiba, Ltd.).

The resin particle dispersion can be produced by a known method using the biodegradable polyester resin of the present invention.
Examples thereof include a method including a dispersion step of dispersing the biodegradable polyester resin-containing material in an aqueous medium to obtain a resin particle dispersion.
In the dispersion step, it is preferable to perform dispersion by adding a surfactant or the like in order to increase the dispersion efficiency or improve the stability of the resin particle dispersion.
As a method of dispersing and granulating the biodegradable polyester resin of the present invention in an aqueous medium, for example, when producing a biodegradable polyester resin, a suspension polymerization method, a dissolution suspension method in an aqueous medium, Examples include a miniemulsion method, a microemulsion method, a multistage swelling method, and an emulsion polymerization method including seed polymerization.
Further, when emulsification polycondensation is carried out in an aqueous medium, the preferable emulsification temperature is preferably lower in consideration of energy saving, polymer production rate and thermal decomposition rate of the produced polymer, preferably 40 to 150 ° C. Yes, more preferably 60-130 ° C. It is preferable that the emulsification temperature is 150 ° C. or lower because the required energy does not become excessive and the molecular weight is not lowered due to decomposition of the resin due to high heat. Moreover, it is preferable for the temperature to be 40 ° C. or higher because the resin viscosity is moderate and the formation of fine particles is easy.

The method for dispersing and granulating the biodegradable polyester resin of the present invention in an aqueous medium can be selected from known methods such as forced emulsification, self-emulsification, and phase inversion emulsification. . Of these, the self-emulsification method and the phase inversion emulsification method are preferably applied in consideration of the energy required for emulsification, the particle size controllability of the obtained emulsion, stability, and the like.
The self-emulsification method and the phase inversion emulsification method are described in “Application Technology of Ultrafine Particle Polymer (CMC Publishing)”. As the polar group used for self-emulsification, a carboxyl group, a sulfone group, and the like can be used. When applied to the biodegradable polyester resin of the present invention, a carboxyl group is preferably used.

When an organic solvent is used in the dispersion step, the method for producing a resin particle dispersion may include a step of removing at least part of the organic solvent and a step of forming resin particles.
For example, after emulsifying the biodegradable polyester resin-containing material of the present invention, it is preferable to solidify as particles by removing a part of the organic solvent. As a specific method of solidification, after emulsifying and dispersing the biodegradable polyester resin-containing material of the present invention in an aqueous medium, air or an inert gas such as nitrogen is fed into the gas-liquid interface while stirring the solution. A method of drying an organic solvent in the method (waste wind drying method), a method of drying while maintaining a reduced pressure and bubbling an inert gas as necessary (a reduced pressure topping method), An emulsified dispersion obtained by emulsifying and dispersing the biodegradable polyester resin-containing material in an aqueous medium or the emulsified liquid of the biodegradable polyester resin-containing material of the present invention is discharged from the pores in a shower shape and dropped into, for example, a dish-shaped receiver. There is a method of drying while repeating (shower-type solvent removal method). It is preferable to remove the solvent by selecting or combining these methods as appropriate based on the evaporation rate of the organic solvent to be used, solubility in water, and the like.

  Using the resin particle dispersion prepared as described above, so-called latex, it is possible to produce a toner whose toner particle diameter and distribution are controlled using an aggregation (association) method. Specifically, the latex prepared as described above is mixed with a colorant particle dispersion and a release agent particle dispersion, and an aggregating agent is added to form heteroaggregation to form aggregated particles having a toner diameter. Then, it is obtained by heating to a temperature above the glass transition point or above the melting point of the resin particles to fuse and coalesce the aggregated particles, and wash and dry. In this manufacturing method, the toner shape can be controlled from an indeterminate shape to a spherical shape by selecting a heating temperature condition.

In the present invention, in the aggregation step, it is also possible to carry out the steps after aggregation by mixing with a resin particle dispersion other than the dispersion of the biodegradable polyester resin of the present invention. At that time, after the biodegradable polyester resin particle dispersion of the present invention is aggregated in advance and the first aggregated particles are formed, the biodegradable polyester resin particle dispersion of the present invention or another resin particle dispersion is further added. It is also possible to make particles multi-layered, for example, by forming a second shell layer on the particle surface. Of course, it is also possible to produce multilayer particles in the reverse order of the above example.
Further, for example, in the aggregation step, the resin particle dispersion containing the biodegradable polyester resin of the present invention and the colorant particle dispersion are aggregated in advance, and after the formation of the first aggregated particles, the biodegradable polyester resin of the present invention is further formed. It is also possible to add a resin particle dispersion containing or another resin particle dispersion to form a second shell layer on the surface of the first particles. In this illustration, the colorant dispersion is separately prepared, but naturally the colorant may be blended in advance with the resin particles.

  After completing the coalescence and coalescence process of the aggregated particles, the desired toner particles are obtained through an optional washing process, solid-liquid separation process, and drying process. Replacement cleaning is desirable. Moreover, although there is no restriction | limiting in particular in a solid-liquid separation process, From the point of productivity, suction filtration, pressure filtration, etc. are suitable. Further, the drying process is not particularly limited, but freeze drying, flash jet drying, fluidized drying, vibration fluidized drying and the like are preferably used from the viewpoint of productivity.

  As a flocculant, besides a surfactant, an inorganic salt or a divalent or higher metal salt can be suitably used. In particular, when a metal salt is used, it is preferable in characteristics such as cohesion control and toner chargeability. The metal salt compound used for aggregation is obtained by dissolving a general inorganic metal compound or a polymer thereof in a resin fine particle dispersion, but the metal elements constituting the inorganic metal salt are a periodic table (long-period table). 2A, 3A, 4A, 5A, 6A, 7A, 8, 1B, 2B, and 3B, and those having a valence of 2 or more and soluble in the form of ions in the agglomeration system of resin fine particles. Good. Specific examples of preferred inorganic metal salts include metal salts such as calcium chloride, calcium nitrate, barium chloride, magnesium chloride, zinc chloride, aluminum chloride, and aluminum sulfate, and polyaluminum chloride, polyaluminum hydroxide, calcium sulfide. And inorganic metal salt polymers. Among these, an aluminum salt and a polymer thereof are particularly preferable. In general, in order to obtain a sharper particle size distribution, even if the valence of the inorganic metal salt is divalent to monovalent, bivalent to trivalent or higher, and even to the same valence, the polymerization type inorganic metal salt weight Combined is more suitable.

  In the present invention, if necessary, known additives can be blended in combination of one or more kinds within a range that does not affect the results of the present invention. For example, flame retardants, flame retardant aids, brighteners, waterproofing agents, water repellents, inorganic fillers (surface modifiers), mold release agents, antioxidants, plasticizers, surfactants, dispersants, lubricants, Fillers, extenders, binders, charge control agents and the like. These additives can be blended in any process for producing an electrostatic image developing toner.

  Examples of internal additives include various commonly used charge control agents such as quaternary ammonium salt compounds and nigrosine compounds as charge control agents. However, stability during production and reduction of wastewater contamination can be used. Therefore, materials that are difficult to dissolve in water are suitable.

Examples of mold release agents include low molecular weight polyolefins such as polyethylene, polypropylene, polybutene, silicones having a softening point upon heating, fatty acid amides such as oleic acid amide, erucic acid amide, ricinoleic acid amide, stearic acid amide, etc. And waxes such as plant waxes such as ester wax, carnauba wax, rice wax, candelilla wax, tree wax and jojoba oil, animal waxes such as beeswax, montan wax, ozokerite, ceresin, paraffin wax, microcrystalline wax Minerals such as microcrystalline wax and Fischer-Tropsch wax, petroleum waxes, and modified products thereof can be used.
These waxes are dispersed in water together with ionic surfactants, polymer electrolytes such as polymer acids and polymer bases, and heated with a homogenizer or pressure discharge type disperser that can be heated to the melting point or higher and subjected to strong shearing. And a dispersion of particles less than 1 micron can be made.

  Examples of flame retardants and flame retardant aids include, but are not limited to, bromine flame retardants that have already been widely used, antimony trioxide, magnesium hydroxide, aluminum hydroxide, and ammonium polyphosphate.

  Examples of coloring components include carbon black such as furnace black, channel black, acetylene black, and thermal black, inorganic pigments such as bengara, bitumen, and titanium oxide, fast yellow, disazo yellow, pyrazolone red, chelate red, brilliant carmine, and paraffin. Examples thereof include azo pigments such as brown, phthalocyanine pigments such as copper phthalocyanine and metal-free phthalocyanine, and condensed polycyclic pigments such as flavantron yellow, dibromoanthrone orange, perylene red, quinacridone red, and dioxazine violet. Chrome Yellow, Hansa Yellow, Benzidine Yellow, Slen Yellow, Quinoline Yellow, Permanent Orange GTR, Pyrarozone Orange, Vulcan Orange, Watch Young Red, Permanent Red, Dupont Oil Red, Resol Red, Rhodamine B Lake, Lake Red C, Rose Bengal, aniline blue, ultramarine blue, calco oil blue, methylene blue chloride, phthalocyanine blue, phthalocyanine green, malachite green oxalate, C.I. I. Pigment red 48: 1, C.I. I. Pigment red 122, C.I. I. Pigment red 57: 1, C.I. I. Pigment yellow 12, C.I. I. Pigment yellow 97, C.I. I. Pigment yellow 17, C.I. I. Pigment blue 15: 1, C.I. I. Examples thereof include various pigments such as CI Pigment Blue 15: 3, and these can be used alone or in combination of two or more.

  In addition, after drying in the same way as normal toner, inorganic particles such as silica, alumina, titania and calcium carbonate, and resin particles such as vinyl resin, polyester and silicone are added to the surface by applying shear to the surface in a dry state to make it flowable. It can also be used as an auxiliary agent or a cleaning auxiliary agent.

  Examples of surfactants that can be used in the present invention include sulfate ester-based, sulfonate-based, phosphate-based, soap-based anionic surfactants, amine salt types, quaternary ammonium salt types, and the like. It is also effective to use a cationic surfactant, or a non-ionic surfactant such as polyethylene glycol, alkylphenol ethylene oxide adduct, polyhydric alcohol, etc. as a means for dispersion. Common ones such as a ball mill, sand mill, and dyno mill having a homogenizer and a medium can be used.

In the present invention, the electrostatic charge image developing toner preferably has an average volume particle diameter (D ₅₀ ) of 3.0 to 20.0 μm. More preferably, the average volume particle diameter is 3.0 to 9.0 μm. It is preferable that D ₅₀ is 3.0 μm or more because the adhesive force is appropriate and the developability is excellent. Moreover, since it is excellent in the resolution of an image as it is 20.0 micrometers or less, it is preferable. The average volume particle diameter (D ₅₀ ) can be measured using a laser diffraction particle size distribution measuring apparatus or the like.

In the present invention, the electrostatic charge image developing toner preferably has an average volume particle distribution GSDv of 1.4 or less. In particular, in the case of chemically produced toner, it is more preferable that GSDv is 1.3 or less. As the particle distribution, the following average volume particle distribution GSD or number GSD can be simply used by using the cumulative distributions D ₁₆ and D ₈₄ .
Volume GSDv = (Volume D ₈₄ / Volume D ₁₆ ) ^0.5
When the GSDv is 1.4 or less, the particle size is uniform, the fixing property is excellent, the apparatus failure due to the fixing failure is unlikely to occur, and the contamination inside the apparatus due to the scattering of the toner and the deterioration of the developer are unlikely to occur. Therefore, it is preferable. The average volume particle distribution GSD can be measured using a laser diffraction particle size distribution measuring apparatus or the like.

  Similarly, when the toner of the present invention is produced by a chemical production method, the shape factor SF1 is preferably 100 to 140, and more preferably 110 to 135 from the viewpoint of image forming properties. At this time, SF1 is calculated as follows.

ここでＭＬ：粒子の絶対最大長、Ａ：粒子の投影面積
これらは、主に顕微鏡画像又は走査電子顕微鏡画像をルーゼックス画像解析装置によって取り込み、解析することによって数値化される。

Here, ML: absolute maximum length of particle, A: projected area of particle These are quantified mainly by capturing and analyzing a microscope image or a scanning electron microscope image by a Luzex image analyzer.

(Static charge image developer)
In the present invention, the electrostatic image developing toner can be used as an electrostatic image developer. The developer is not particularly limited except that it contains the electrostatic image developing toner, and can have an appropriate component composition depending on the purpose. When the electrostatic image developing toner is used alone, it is prepared as a one-component electrostatic image developer, and when used in combination with a carrier, it is prepared as a two-component electrostatic image developer.
As a one-component developer, a method in which a charged toner is formed by frictional charging with a developing sleeve or a charging member, and development according to an electrostatic latent image can be applied.
The carrier is not particularly limited, but usually, magnetic particles such as iron powder, ferrite, iron oxide powder, nickel, etc .; the magnetic particles as a core material and the surface thereof as a styrene resin, vinyl resin, ethylene resin, rosin Resin-coated carrier formed by coating a resin such as a resin based on polyester, polyester or melamine, or a wax such as stearic acid, and forming a resin coating layer; a magnetic material obtained by dispersing magnetic particles in a binder resin Examples include a distributed carrier. Among them, the resin-coated carrier is particularly preferable because the chargeability of the toner and the resistance of the entire carrier can be controlled by the configuration of the resin coating layer.
The mixing ratio of the toner of the present invention and the carrier in the two-component electrostatic image developer is usually 2 to 10 parts by weight of the toner with respect to 100 parts by weight of the carrier. Moreover, the preparation method of a developing agent is not specifically limited, For example, the method of mixing with a V blender etc. is mentioned.

(Image forming method and image forming apparatus)
Further, the electrostatic image developing toner and the electrostatic image developer of the present invention can be used in an image forming method of a normal electrostatic image developing system (electrophotographic system).
An image forming method that can be suitably used in the present invention includes a latent image forming step of forming an electrostatic latent image on the surface of the latent image holding member, and a development including toner on the electrostatic latent image formed on the surface of the latent image holding member. A developing step for forming a toner image by developing with an agent, a transferring step for transferring the toner image formed on the surface of the latent image holding member to the surface of the transfer target, and a toner image transferred on the surface of the transfer target A fixing step for heat fixing, and the toner includes an electrostatic charge image developing toner containing the biodegradable polyester resin of the present invention as a binder resin, or the electrostatic charge image developing toner and a carrier as the developer. An electrostatic charge image developer is used.
In addition, an image forming apparatus that can be suitably used in the present invention includes a latent image holding member, a charging unit that charges the latent image holding member, and exposing the charged latent image holding member to the latent image holding member. An exposure unit for forming an electrostatic latent image; a developing unit for developing the electrostatic latent image with a developer containing toner to form a toner image; and transferring the toner image from the latent image holding member to a transfer target. An electrostatic image developing toner comprising the biodegradable polyester resin of the present invention as a binder resin, or the electrostatic image comprising the electrostatic image developing toner and a carrier as the developer. It is characterized by using a developer.
As each of the above steps, a known step can be used in the image forming method, which is described in, for example, JP-A-56-40868 and JP-A-49-91231.
Further, the image forming method of the present invention may include steps other than the above-described steps. For example, a cleaning step for removing the electrostatic charge image developer remaining on the electrostatic latent image carrier is preferable. Can be mentioned. In the image forming method of the present invention, an embodiment that further includes a recycling step is preferable. The recycling step is a step of transferring the electrostatic charge image developing toner collected in the cleaning step to a developer layer. The image forming method including the recycling step can be carried out using an image forming apparatus such as a toner recycling system type copying machine or facsimile machine. Further, the present invention can be applied to a recycling system in which the cleaning step is omitted and toner is collected simultaneously with development.

As the latent image holding member, for example, an electrophotographic photosensitive member and a dielectric recording member can be used.
In the case of an electrophotographic photosensitive member, the surface of the electrophotographic photosensitive member is uniformly charged by a corotron charger, a contact charger or the like and then exposed to form an electrostatic latent image (latent image forming step). Next, the toner particles are attached to the electrostatic latent image by contacting or approaching a developing roll having a developer layer formed on the surface, thereby forming a toner image on the electrophotographic photosensitive member (developing step). The formed toner image is transferred onto the surface of a transfer medium such as paper using a corotron charger or the like (transfer process). Further, the toner image transferred to the surface of the transfer medium is thermally fixed by a fixing device (fixing step), and a final toner image is formed.
In the heat fixing by the fixing device, a release agent is usually supplied to a fixing member in the fixing device in order to prevent offset and the like.

EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated concretely, this invention is not limited only to the Example shown below.
In the examples, “parts” and “%” mean “parts by weight” and “% by weight” unless otherwise specified.

(catalyst)
In the examples, the following catalysts were used.
(1) Octadecylbenzenesulfonic acid Purchased product was used (manufactured by Teika).
(2) Dodecanesulfonic acid (manufactured by Teika)
Purchased product was used (manufactured by Teika).
(3) 3-Fluoro-4-dodecylbenzenesulfonic acid (synthesis)
2-Fluorophenol and bromooctadecane were reacted to perform etherification, and then sulfonation was performed. 99.5% of the compound was obtained with HPLC purity, and its structure was confirmed by NMR.
(4) 3-Fluoro-4-octadecyloxybenzenesulfonic acid (synthesis)
Octadecylbenzene and potassium fluorophosphate were reacted to introduce fluorine atoms onto the benzene ring, and then sulfonated with fuming sulfuric acid.
(5) Sulfuric acid (reagent purchase)
(6) Sodium dodecylbenzenesulfonate (reagent purchase)

Example 1
Succinic acid 56 parts by weight 1,4-butanediol 45 parts by weight octadecylbenzenesulfonic acid 0.2 mol%
The above components were put into a Magneo Seal Mixer manufactured by Magneo Giken Co., Ltd. and subjected to polycondensation at 140 ° C. under reduced pressure. When the physical properties after 8 hours were measured, the molecular weight was 65,000 and the melting point was 89 ° C.
In addition, the addition amount of the said octylbenzenesulfonic acid is the addition amount with respect to the total number of moles of a polymerizable monomer (succinic acid and 1, 4- butanediol) (hereinafter the same).

(Example 2)
Adipic acid 73 parts by weight 1,4-butanediol 45 parts by weight Dodecanesulfonic acid 0.2 mol%
The above components were put into a Magneo Seal Mixer manufactured by Magneo Giken Co., Ltd. and subjected to polycondensation at 130 ° C. under reduced pressure. When the physical properties after 8 hours were measured, the molecular weight was Mw 58,000 and the melting point was 58 ° C.

(Example 3)
Succinic acid 45 parts by weight 1,6-hexanediol 59 parts by weight 3-fluoro-4-dodecylbenzenesulfonic acid 0.2 mol%
The above components were put into a Magneo Seal Mixer manufactured by Magneo Giken Co., Ltd. and subjected to polycondensation at 140 ° C. under reduced pressure. When the physical properties after 10 hours were measured, the molecular weight was 87,000 and the melting point was 71 ° C.

Example 4
Succinic acid 56 parts by weight 1,4-butanediol 45 parts by weight 3-fluoro-4-octadecylbenzenesulfonic acid 0.2 mol%
The above components were put into a Magneo Seal Mixer manufactured by Magneo Giken Co., Ltd. and subjected to polycondensation at 140 ° C. under reduced pressure. When the physical properties after 7 hours were measured, the molecular weight was 85,000 and the melting point was 89 ° C.

(Example 5)
Succinic acid 17 parts by weight Tetradecanedioic acid 51 parts by weight 1,4-butanediol 45 parts by weight Octadecylbenzenesulfonic acid 0.2 mol%
The above components were put into a Magneo Seal mixer manufactured by Magneo Giken Co., Ltd. and subjected to polycondensation at 120 ° C. under reduced pressure. When the physical properties after 15 hours were measured, the molecular weight was Mw 41,000 and the melting point was 86 ° C.

(Comparative Example 1)
Succinic acid 56 parts by weight 1,4-butanediol 45 parts by weight octadecylbenzenesulfonic acid 0.2 mol%
The above components were put into a Magneo Seal Mixer manufactured by Magneo Giken Co., Ltd. and subjected to polycondensation at 140 ° C. under reduced pressure. When the physical properties after 2 hours were measured, the molecular weight was Mw 18,000 and the melting point was 46 ° C.

(Comparative Example 2)
Decanedicarboxylic acid 115 parts by weight 1,6-hexanediol 59 parts by weight Octylbenzenesulfonic acid 0.2 mol%
The above components were put into a Magneo Seal Mixer manufactured by Magneo Giken Co., Ltd. and subjected to polycondensation at 140 ° C. under reduced pressure. When the physical properties after 7 hours were measured, the molecular weight was 39,000 and the melting point was 59 ° C.

(Comparative Example 3)
Succinic acid 56 parts by weight 1,4-butanediol 45 parts by weight Sulfuric acid 0.2 mol%
The above components were put into a Magneo Seal Mixer manufactured by Magneo Giken Co., Ltd. and subjected to polycondensation at 140 ° C. under reduced pressure. When the physical properties after 8 hours were measured, the molecular weight was Mw 26,000 and the melting point was 80 ° C.

(Comparative Example 4)
Succinic acid 56 parts by weight 1,4-butanediol 45 parts by weight Dodecylbenzenesulfonic acid Na 0.2 mol%
The above components were put into a Magneo Seal Mixer manufactured by Magneo Giken Co., Ltd. and subjected to polycondensation at 140 ° C. under reduced pressure. When the physical properties after 8 hours were measured, the molecular weight was Mw 11,000 and the melting point was 59 ° C.

(Comparative Example 5)
Succinic acid 56 parts by weight 1,4-butanediol 45 parts by weight Dibutyltin oxide 0.2 mol%
The above components were put into a Magneo Seal Mixer manufactured by Magneo Giken Co., Ltd. and subjected to polycondensation at 140 ° C. under reduced pressure. When the physical properties after 8 hours were measured, the molecular weight was 10,000 and the melting point was 59 ° C.

A plate (thickness 3 mm) was produced at a temperature 15 ° C. higher than the melting point of each resin using the above resins, and biodegradability and the following physical properties were evaluated.
(Biodegradability test)
For biodegradability, the above film was cut into a 10 cm square and embedded in relatively humid (slightly lit) soil (15 cm from the surface) where the moisture content in the soil could be maintained at 50% or more. Moreover, the test piece was similarly embedded also in the soil with comparatively good sunlight and low humidity (7 cm from the ground surface), and visual evaluation was performed twice for 6 months and 12 months.
<Evaluation>
○: Most of the plate shape disappeared.
Δ: The plate shape disappeared almost half.
X: The plate shape remains almost as it is.

(Evaluation of the physical properties)
<Scratch strength test>
Using a surface tester (HEIDON Type 14DR: manufactured by Shinto Kagaku Co., Ltd.), 5 points were scratched with a needle having a needle tip diameter of 0.2 mm at a load of 50 g, and the influence on each film was visually observed.
[Evaluation]
○: The surface is scratched.
Δ: A slight scratch is formed on the film.
X: A clear scratch mark is formed on the film.

<Heat-bonding (blocking) test>
Two films were placed in a thermostatic bath at 50 ° C. and allowed to stand, and left for 30 minutes with a 250 g weight placed on the top. The heat-fusibility of the film at that time was evaluated.
[Evaluation]
○: Blocking of the film is not recognized.
Δ: The two films have slight adhesion.
X: Two films are adhered and are not separated or difficult to separate.

  The results are shown in Table 1 below.

<Production of linear polyester (production of linear polyester obtained from terephthalic acid / bisphenol A / ethylene oxide adduct / cyclohexanedimethanol)>
A heat-dried three-necked flask was charged with 50 mol% of dimethyl terephthalate, 35 mol% of bisphenol A / ethylene oxide adduct, 15 mol% of cyclohexanedimethanol, and 0.3 mol% of octadecylbenzenesulfonic acid as a catalyst. The air in the container was depressurized, and the atmosphere was made inert with nitrogen gas, followed by heating at 180 ° C. for 6 hours with mechanical stirring. Thereafter, the pressure was reduced, the molecular weight was confirmed by GPC, and when the weight average molecular weight reached 15,000, the pressure reduction was stopped and air cooling was performed to obtain an amorphous polyester resin 1. The Tg of this resin was 61 ° C.

(Production of toner-1)
76 parts of linear polyester resin (terephthalic acid / bisphenol A / ethylene oxide adduct / linear polyester obtained from cyclohexanedimethanol)
4 parts of cyan pigment (manufactured by Dainichi Seika Kogyo Co., Ltd., copper phthalocyanine CI Pigment Blue 15: 3)
Resin 1 (Example 1) 20 parts The above mixture was kneaded with an extruder (TEM48, manufactured by Toshiba Machine Co., Ltd.). The obtained kneaded product was cooled, crushed with a hammer mill, and then pulverized with a jet mill. Thereafter, the toner particles were classified by an air classifier to obtain toner particles having an average volume particle diameter of 7.5 μm and an average volume particle distribution GSDv 1.29.

(Production of toner-2)
An electrophotographic toner was produced by an aggregation coalescence method.
(Preparation of resin dispersion)
Resin particle dispersion 1 and resin particle dispersion 2 were prepared using a solvent emulsification method for the linear polyester resin and the resin of Example 1, respectively.
That is, 50 parts of each resin was dissolved in 33 parts of ethyl acetate, then placed in 280 parts of distilled water containing 3 parts of sodium dodecylbenzenesulfonate, and a dispersion obtained by remodeling Eurotech Emulsifier Cavitron CD1010 into a high temperature and high pressure type After dispersion and emulsification using a machine, ethyl acetate was distilled off under reduced pressure to obtain a dispersion having a solid content concentration of 20%.
The volume average particle diameter of particles made of the resin 1 in the obtained resin particle dispersion 1 was 180 nm.
Moreover, the volume average particle diameter of the particle | grains which consist of resin of Example 1 in the obtained resin particle dispersion liquid 2 was 130 nm.

(Preparation of colorant dispersion)
Here, an adhesive dispersion in which a cyan colorant was dispersed was prepared. That is, cyan pigment (copper phthalocyanine CI Pigment Blue 15: 3 manufactured by Dainichi Seika Kogyo Co., Ltd.) 20 parts, anionic surfactant (Neogen RK, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), ion 77 parts of exchanged water was mixed and dissolved, and dispersed by a homogenizer (manufactured by IKA, Ultra Tarrax) to obtain a colorant dispersion in which colorant particles having a volume average particle diameter of 168 nm were dispersed.

(Preparation of release agent dispersion)
120 parts of paraffin wax HNP-9 (Nippon Seiki Co., Ltd.), 3 parts of an anionic surfactant (Neogen RK, Daiichi Kogyo Seiyaku Co., Ltd.) and 77 parts of ion-exchanged water are mixed. The mixture was heated to ° C. and dispersed with a pressure discharge type gorin homogenizer to obtain a 20 wt% release agent dispersion having a volume average particle size of 170 nm.

[Example 6: Production of toner 1]
Resin particle dispersion 1 380 parts Resin particle dispersion 2 100 parts Colorant particle dispersion 50 parts Release agent particle dispersion 90 parts Ion exchange water 540 parts The above is put into a round stainless steel flask and homogenizer (manufactured by IKA). And Ultra-Turrax T50) were mixed at room temperature to obtain a mixed dispersion. While mixing, 1.5 parts of dodecyldimethylbenzylammonium chloride salt (Sanisol B50: manufactured by Kao Corporation) was gradually added and mixed well. This was set in a heating apparatus capable of controlling the temperature, the internal temperature was raised to 45 ° C., and the temperature was maintained as it was to grow aggregated particles. The dispersion was sampled and the particle size was measured. The volume average particle size was 5.4 μm.
Subsequently, 280 parts of the resin particle dispersion 1 is gradually added to the mixed dispersion in which the aggregated particles are formed, and the resin particles are adhered to the surface of the aggregated particles, thereby agglomerating with a volume average particle diameter of 6.1 μm. Particles were obtained. After adding a 20% aqueous solution of sodium dodecylbenzenesulfonate (Neogen RK: manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), the internal temperature was raised to 90 ° C. and held for 3 hours to fuse and coalesce the aggregated particles. I made one. Subsequently, the mixture was cooled to room temperature to obtain a dispersion containing toner particles. This dispersion was subjected to solid-liquid separation by suction filtration, sufficiently washed with ion-exchanged water, and vacuum dried to obtain toner 1.

To the toner particles, 0.5% by weight of silica TS720 (manufactured by Cabot) was added and mixed with a Henschel mixer to prepare an externally added toner.
Further, a carrier in which 50% ferrite core was coated with 1% by weight of polymethyl methacrylate (manufactured by Soken Chemical Co., Ltd.) was produced.
This externally added toner and carrier were mixed to prepare a developer.

Using the developer produced as described above, a full-color copy paper was used as the image forming medium, and a solid image having an area of 10 cm ² with an image area ratio of 100% was formed on the image forming medium. At that time, the loss or unevenness of the image was visually determined. The results are shown in Table 2 below.
<Evaluation>
○: Defects and unevenness are not observed in the image.
Δ: Slight image defects and unevenness are observed.
X: A clear image defect is recognized.

[Examples 7 to 10 and Comparative Examples 6 to 10]
Further, except that the resin prepared in Example 1 was changed to the resin prepared in Examples 2 to 5 and Comparative Examples 1 to 5, kneaded toner and agglomerated toner, and Each developer was prepared and evaluated.

Claims (9)

Containing at least 50% by weight of the whole polyester resin of the monomer unit represented by the formula (I),
Containing a compound represented by formula (II) and / or formula (III),
A biodegradable polyester resin having a weight average molecular weight of 30,000 or more and 5,000,000 or less.

In formula (I), A represents a single bond or a divalent aliphatic hydrocarbon group, B represents a divalent aliphatic hydrocarbon group having 2 or more carbon atoms, and the total number of carbon atoms of A and B is: 2 or more and 14 or less.

In the formula (II), R ¹ represents a halogen atom, an alkoxycarbonyl group, an acyloxy group, an acyl group, a carbamoyl group, a mono- or disubstituted carbamoyl group, a cyano group, a perhalogenoalkyl group, a thiocyanato group, a sulfamoyl group, an alkylsulfinyl group. Represents a group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a nitro group or an alkynyl group, and one R ¹ may be the same or different. l represents an integer of 0 to 4. L represents a linear or branched alkyl group or alkenyl group having 8 or more carbon atoms.

In formula (III), M represents a linear or branched alkyl group or alkenyl group having 8 or more carbon atoms.   The biodegradable polyester resin according to claim 1, comprising a metal component derived from a catalyst of 0 ppm to 10 ppm.   The biodegradable polyester resin according to claim 1 or 2, which has a melting point of 50 ° C or higher. A step of polycondensing a dicarboxylic acid component represented by the formula (IV) and a diol component represented by the formula (V) in the presence of a polycondensation catalyst,
The polycondensation catalyst is a compound represented by the above formula (II) and / or the above formula (III),
The manufacturing method of the biodegradable polyester resin as described in any one of Claims 1-3.

In formula (IV), R ⁵ represents a hydrogen atom, a lower alkyl group, or an aryl group, and A represents a single bond or an aliphatic hydrocarbon group. In the formula (V), B represents an aliphatic hydrocarbon group having 2 or more carbon atoms. The total number of carbon atoms of A and B is 2 or more and 14 or less.   A binder resin for an electrostatic charge image developing toner, comprising the biodegradable polyester resin according to any one of claims 1 to 3 in an amount of 5% by weight to 80% by weight.   An electrostatic image developing toner comprising the binder resin for an electrostatic image developing toner according to claim 5.   An electrostatic charge image developer comprising the electrostatic charge image developing toner according to claim 6 and a carrier. A latent image forming step of forming an electrostatic latent image on the surface of the latent image holding member;
A developing step of developing the electrostatic latent image formed on the surface of the latent image holding body with a developer containing toner to form a toner image;
A transfer step of transferring the toner image formed on the surface of the latent image carrier to the surface of the transfer target;
A fixing step of thermally fixing the toner image transferred to the surface of the transfer target,
An image forming method using the electrostatic image developing toner according to claim 6 as the toner, or the electrostatic image developer according to claim 7 as the developer. A latent image carrier,
Charging means for charging the latent image carrier;
Exposure means for exposing the charged latent image carrier to form an electrostatic latent image on the latent image carrier;
Developing means for developing the electrostatic latent image with a developer containing toner to form a toner image;
Transfer means for transferring the toner image from the latent image holding member to a transfer target;
An image forming apparatus using the electrostatic charge image developing toner according to claim 6 as the toner or the electrostatic charge image developer according to claim 7 as the developer.