JP2008170569A - Resin particle-dispersed liquid and its production method, electrostatic charge image development toner and its production method, electrostatic charge image developer, and image forming method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin particle-dispersed liquid having initial image quality and long term image quality maintainability under high temperature and high humidity environment when being used for an electrostatic charge image development toner, and further having excellent toner fixing image preservation properties. <P>SOLUTION: The resin particle-dispersed liquid is characterized in that resin particles containing polyester obtained by polycondensing polycondensable monomers having a composition comprising: (a) polycarboxylic acid monomer and/or the derivative thereof by 10 to 80 mol% in all the polycondensable monomers; and (b) a polyhydric alcohol monomer by 10 to 80 mol% in all the polycondensable monomers; and comprising (c) at least one monomer selected from a group composed of compounds expressed by formulae (1) to (3) by 0.5 to 40 mol% in all the polycondensable monomers, and sulfur acid into a water base medium. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an electrostatic charge image developing toner used for developing an electrostatic latent image formed by an electrophotographic method or an electrostatic recording method with a developer, a manufacturing method thereof, and a resin that can be used as a raw material thereof The present invention relates to a particle dispersion and a method for producing the same. The present invention also relates to an electrostatic image developer using the electrostatic image developer and an image forming method using the electrostatic image developer or the electrostatic image developer.

  A method of visualizing image information through an electrostatic charge image such as electrophotography is currently used in various fields. In electrophotography, an electrostatic charge image is formed on a photoreceptor by charging and exposure processes, the electrostatic latent image is developed with a developer containing toner, and visualized through a transfer and fixing process. The developer used here includes a two-component developer composed of a toner and a carrier and a one-component developer using a magnetic toner or a non-magnetic toner alone. The toner is usually produced by using a thermoplastic resin as a pigment. In addition, a kneading and pulverizing method is used in which melt-kneading is performed together with a release agent such as a charge control agent and wax, and the mixture is cooled, finely pulverized, and further classified. In these toners, if necessary, inorganic and organic particles for improving fluidity and cleaning properties may be added to the toner particle surfaces.

  In recent years, in order to meet various demands on toner, studies on wet-process toner are proceeding. In this production method produced in an aqueous medium, the toner resin also needs to be an aqueous dispersion. There are various methods for preparing an aqueous dispersion of resin, but mainly a copolymer containing acrylic acid and methacrylic acid, which are vinyl monomers, is neutralized with an amine to obtain a water-soluble acrylic copolymer. And a method in which a water-insoluble resin such as various copolymers, cyclized rubber, and polyamide is dissolved in an organic solvent and dispersed together with a surfactant, and then the solvent is removed. In order to obtain an aqueous dispersion of polyester suitable for fixing properties and color images, a method of dissolving in an organic solvent, dispersing in an aqueous medium, and then removing the organic solvent from the particles has been used.

  On the other hand, an aqueous dispersion of a resin by a solvent-free emulsification method has many advantages that are more suitable for current than a solvent solution of a resin, in terms of not only convenience of handling but also safety of workers and working environment. However, it is very difficult to disperse polyester in an aqueous medium by solvent-free emulsification. A method in which a high acid value polyester produced by bulk polymerization is dissolved and emulsified in a vinyl monomer, etc., and then a vinyl monomer is polymerized (miniemulsion polymerization method), and a method in which a polycondensable monomer is dispersed in water and polymerized in water ( Water polycondensation method).

  Patent Document 1 describes an example of a solvent-free emulsification method in which a polyester is melted and then neutralized with an amine. Patent Document 2 discloses an example of a solvent-free emulsification method of a polyester having biodegradable crystallinity, but the monomer used is not a general-purpose material as a resin for toner.

  In Patent Document 3, there is an example of an aqueous polyurethane dispersion using a hydroxy acid having a specific chemical structure as a chain extension component, however, there is no technical suggestion for recalling the present invention. The fact is that nothing is described about the aqueous dispersion of polyester.

  As a conventional technique using a polyvalent hydroxy acid as a polyester monomer, Patent Document 4 discloses a method in which a trivalent or higher hydroxy acid is used in a polyester composition and heat is applied together with a monomer capable of reacting with a carboxyl group to perform extension polymerization. Is described.

  Patent Document 5 describes a method of adding a hydroxy acid to an isocyanate-reactive emulsion, which is a nonionic system having a suspended polyoxyethylene chain and a free acid group or a free tertiary amino group. There is an example of a dispersion of a hydrophilic polyurethane, and there is an example of a polyvalent hydroxy acid.

  However, when a hydroxy acid, particularly a trivalent or higher polyhydric hydroxy acid is used as such a polyester composition, it is difficult to control the polymerization and, for example, gelation may occur during the polymerization. In a polyester using a trivalent or higher polyvalent hydroxy acid as a monomer, the hydroxy acid portion serves as a crosslinking point, and the resulting polymer has a crosslinked or branched structure. If an aqueous dispersion is prepared on the basis of such a cross-linked polyester, the viscosity becomes severe and gelation occurs, which makes emulsification difficult. Furthermore, when such an excessively crosslinked polyester is used for a toner resin, the color developability of the image is poor, and it has been difficult to use it for a resin for a color toner that particularly requires a high-quality image.

JP 2006-18227 A Japanese Patent Laid-Open No. 2002-3607 JP-A-1-104613 JP-A-9-227668 JP 59-113053 A

One of the problems to be solved by the present invention is that it is excellent in hydrolysis resistance, and when used as an electrostatic charge image developing toner, the initial image quality and the long-term image quality maintenance property under high temperature and high humidity, and also the toner fixed image storage It is to provide a resin particle dispersion excellent in properties.
In addition, another problem to be solved by the present invention is an electrostatic charge image developing toner excellent in long-term image quality maintenance under high temperature and high humidity, and also excellent in image storage, a method for producing the same, an electrostatic charge image developer, The present invention also provides an image forming method and an image forming apparatus using them.
Furthermore, another problem to be solved by the present invention is that, when emulsifying polyester, it is possible to form particles up to a particle size suitable for a toner raw material in an aqueous medium, and in combination with low-temperature polymerizability of polyester, It is an object of the present invention to provide a novel method for producing a resin particle dispersion that can fundamentally improve the production energy of a resin for charge image developing toner.

The above problems have been solved by means <1> to <11> shown below.
<1> (a) a polyhydric carboxylic acid monomer and / or a derivative thereof is included in the total polycondensable monomer in an amount of 10 to 80 mol%, and (b) a polyhydric alcohol monomer is a total polycondensable monomer. 0.5 to 40 mol in the total polycondensable monomer containing 10 to 80 mol% in the mixture and (c) at least one monomer selected from the group consisting of compounds represented by formulas (1) to (3) %, A resin particle dispersion characterized by dispersing polyester particles obtained by polycondensation of a polycondensable monomer composed of a composition and resin particles containing sulfur acid in an aqueous medium,

（Ｒ¹〜Ｒ⁴はそれぞれ独立に水素原子又はアルキル基を示す。）
なお、（ａ）成分、（ｂ）成分及び（ｃ）成分の合計は１００ｍｏｌ％である。

(R ^{1 to} R ⁴ each independently represents a hydrogen atom or an alkyl group.)
In addition, the sum total of (a) component, (b) component, and (c) component is 100 mol%.

<2> The resin particle dispersion according to <1>, wherein the resin particles do not contain a metal element, or the metal element content of the resin particles is 100 ppm or less.
<3> The resin particle dispersion according to <1> or <2>, wherein the polyester has an acid value of 5 to 50 mg · KOH / g,
<4> The resin particle dispersion according to any one of <1> to <3>, wherein a median diameter of the resin particles is 0.1 μm or more and 0.6 μm or less,
<5> (a) The polyhydric carboxylic acid monomer and / or derivative thereof is contained in the total polycondensable monomer in an amount of 10 to 80 mol%, and (b) the polyhydric alcohol monomer is the total polycondensable monomer. 0.5 to 40 mol in the total polycondensable monomer containing 10 to 80 mol% in the mixture and (c) at least one monomer selected from the group consisting of compounds represented by formulas (1) to (3) A step of obtaining a polyester by polycondensation of a polycondensable monomer comprising a composition in the presence of sulfur acid, and a step of neutralizing the polyester with a basic substance and dispersing the polyester in an aqueous medium, A method for producing a resin particle dispersion according to any one of <1> to <4>,

（Ｒ¹〜Ｒ⁴はそれぞれ独立に水素原子又はアルキル基を示す。）
なお、（ａ）成分、（ｂ）成分及び（ｃ）成分の合計は１００ｍｏｌ％である。

(R ^{1 to} R ⁴ each independently represents a hydrogen atom or an alkyl group.)
In addition, the sum total of (a) component, (b) component, and (c) component is 100 mol%.

<6> The method for producing a resin particle dispersion according to <5>, wherein the polycondensable monomer is polycondensed at a temperature of 150 ° C. or lower.
<7> A method for producing an electrostatic charge image developing toner comprising: a step of aggregating the resin particles in a dispersion containing at least a resin particle dispersion to obtain aggregated particles; and a step of heating and coalescing the aggregated particles. A method for producing an electrostatic charge image developing toner, wherein the resin particle dispersion is the resin particle dispersion according to any one of <1> to <4>.
<8> An electrostatic image developing toner produced by the production method according to <7>,
<9> An electrostatic charge image developer comprising the electrostatic charge image developing toner according to <8> and a carrier,
<10> A latent image forming step for forming an electrostatic latent image on the surface of the latent image holding member, and developing the electrostatic latent image formed on the surface of the latent image holding member with a developer containing toner to form a toner image. An image forming method comprising: a developing step, a transfer step of transferring a toner image formed on the surface of the latent image holding member to the surface of the transfer member, and a fixing step of fixing the toner image transferred to the surface of the transfer member An image forming method using the electrostatic charge image developing toner according to <8> as the toner, or the electrostatic charge image developer according to <9> as the developer,
<11> The formed electrostatic latent image is formed by at least a latent image forming unit that forms an electrostatic latent image on the surface of the electrostatic latent image holding member and an electrostatic charge image developer contained in the developing device. An image forming apparatus comprising: a developing unit that visualizes and forms a toner image on the surface of the electrostatic latent image holding member; and a transfer unit that transfers the formed toner image onto the surface of a transfer target. An image forming apparatus in which the electrostatic charge image developer is the electrostatic charge image developer according to <9>.

According to the present invention, it has excellent hydrolysis resistance and, when used in an electrostatic image developing toner, has low temperature fixability, initial image quality, long-term image quality maintenance under high temperature and high humidity, and toner fixed image storage. An excellent resin particle dispersion can be provided.
In addition, according to the present invention, an electrostatic charge image developing toner excellent in long-term image quality maintenance under high temperature and high humidity, and also excellent in image storability, a production method thereof, an electrostatic charge image developer, an image forming method and an image A forming apparatus can be provided.
Furthermore, according to the present invention, when emulsifying polyester, it is possible to form particles up to a particle size suitable for a toner raw material with an aqueous medium, and in combination with low-temperature polymerizability of polyester, the production energy of toner resin is fundamentally reduced. It is possible to provide a new manufacturing method that can be improved.

  The resin particle dispersion of the present invention contains (a) a polyvalent carboxylic acid monomer and / or a derivative thereof in a total polycondensable monomer in an amount of 10 to 80 mol%, and (b) a polyhydric alcohol monomer. Total polycondensable monomer containing at least one monomer selected from the group consisting of (c) compounds represented by formulas (1) to (3), containing 10 to 80 mol% in the polycondensable monomer A resin particle containing polyester obtained by polycondensation of a polycondensable monomer having a composition containing 0.5 to 40 mol% is dispersed in an aqueous medium.

（Ｒ¹〜Ｒ⁴はそれぞれ独立に水素原子又はアルキル基を示す。）

(R ^{1 to} R ⁴ each independently represents a hydrogen atom or an alkyl group.)

  Here, the alkyl group is preferably a lower alkyl group (having 1 to 6 carbon atoms). Detailed description of the equations (1) to (3) will be described later.

The “total polycondensable monomer” means the total amount of the polycondensable monomers (a) to (c). “10 to 80 mol%” or the like means a value where the total polycondensable monomer is 100 mol%. In the present invention, the polycondensable monomer, polyhydric alcohol monomer, and hydroxy acid monomer, which are polycondensable monomers for obtaining polyester, are collectively referred to as a polycondensable monomer. It is also referred to as a body or polyester-forming polycondensable monomer.
Hereinafter, the present invention will be described in detail.

<Polyester>
In order to improve the water dispersibility of the polyester, a polycondensable monomer having an alkali metal salt or the like obtained by neutralizing a polycondensable monomer having a sulfo group or a carboxy group with a base is copolymerized. There is a method for producing a polyester having a sulfo group or a carboxy group, such as a method for introducing a hydrophilic group into a polyester chain. However, in order to impart sufficient emulsifiability to the polyester obtained by the method of introducing a hydrophilic group into such a chain, it is necessary to introduce a large number of hydrophilic groups. The problem will come out.

  In this invention, the water dispersibility of polyester can be improved by using the compound represented by Formula (1)-(3) as a polyester production | generation polycondensable monomer. When a polyester having a neutralizable hydrophilic group such as formulas (1) to (3) is introduced into the polyester main chain to effectively modify the polyester, the monomer having a hydrophilic group is Compared with the case of copolymerization only at the terminal, water dispersion and particle formation of the polyester are facilitated. Furthermore, it is possible to minimize the amount of neutralizing agent required for dispersion in an aqueous medium. Moreover, this makes it possible to avoid a decrease in chargeability under high temperature and high humidity.

<Polyester-forming polycondensable monomer>
In the present invention, the polycondensable monomer contains the monomers shown in the above (a) to (c), and further, these ester compounds (oligomers and / or prepolymers), and a direct ester reaction, or The thing which can obtain polyester through transesterification is preferable.
In this case, the polycondensed polyester may take any form such as amorphous (amorphous) polyester (non-crystalline polyester), crystalline polyester, or a mixed form thereof. In the present invention, an amorphous polyester or a mixed form of a crystalline polyester and an amorphous polyester is preferable.

<(A) Polycarboxylic acid monomer and / or derivative thereof>
In the present invention, it goes without saying that the polyvalent carboxylic acid monomer and / or derivative thereof excludes the compounds (2) and (3). The derivative of a polyvalent acid monomer represents an anhydride of a polyvalent acid or a lower alkyl ester of a polyvalent acid. Moreover, in this invention, the said lower alkyl ester represents the alkyl ester whose carbon number of the alkoxy part of ester is 1-8.

  The dicarboxylic acid that can be used in the present invention is a compound containing two carboxy groups in one molecule. For example, oxalic acid, succinic acid, n-dodecyl succinic acid, n-dodecenyl succinic acid, isododecyl succinic acid, isodode. Decenyl succinic acid, n-octyl succinic acid, n-octenyl succinic acid, maleic acid, adipic acid, β-methyl adipic acid, azelaic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid , Fumaric acid, citraconic acid, diglycolic acid, cyclohexane-3,5-diene-1,2-dicarboxylic acid, hexahydroterephthalic acid, malonic acid, pimelic acid, glutaric acid, peric acid, itaconic acid, glutaconic acid, phthalate Acid, isophthalic acid, terephthalic acid, tetrachlorophthalic acid, Lolophthalic acid, nitrophthalic acid, p-carboxyphenylacetic acid, p-phenylenediacetic acid, m-phenylenediacetic acid, o-phenylenediacetic acid, diphenyldiacetic acid, diphenyl-p, p'-dicarboxylic acid, naphthalene-1,4- Examples include dicarboxylic acid, naphthalene-1,5-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, anthracene dicarboxylic acid, and the like, and examples thereof include acid anhydrides and lower alkyl esters thereof.

  Moreover, as polyvalent carboxylic acid other than dicarboxylic acid, for example, benzenetricarboxylic acid such as 1,2,4-benzenetricarboxylic acid, 1,3,5-benzenetricarboxylic acid, benzenetetracarboxylic acid such as pyromellitic acid, Examples include naphthalene tricarboxylic acid such as 1,2,4-naphthalene tricarboxylic acid, naphthalene tetracarboxylic acid, pyrene tricarboxylic acid, pyrene tetracarboxylic acid, and the like, and lower esters thereof. Furthermore, the acid chloride is not limited to this. These may be used alone or in combination of two or more. In addition, a lower ester shows that the carbon number of the alkoxy part of ester is 1-8. Specific examples include methyl ester, ethyl ester, n-propyl ester, isopropyl ester, n-butyl ester and isobutyl ester, and examples thereof include acid anhydrides and lower alkyl esters thereof.

  Examples of the polyvalent carboxylic acid used to obtain the crystalline polyester include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, peric acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, Citraconic acid, itaconic acid, glutaconic acid, n-dodecyl succinic acid, n-dodecenyl succinic acid, isododecyl succinic acid, isododecenyl succinic acid, n-octyl succinic acid, n-octenyl succinic acid, dodecanedioic acid, etc. , These acid anhydrides or lower alkyl esters thereof. Furthermore, the acid chloride is not limited to this. In the present invention, dodecanedioic acid can be preferably used.

  The polyvalent carboxylic acid used to obtain the amorphous polyester includes phthalic acid, isophthalic acid, terephthalic acid, naphthalene-2,6-dicarboxylic acid, 1,4-phenylenediacetic acid, 1,4-cyclohexane. Examples thereof include aromatic dicarboxylic acids such as dicarboxylic acids and dicarboxylic acids having an alicyclic hydrocarbon group, and examples thereof include, but are not limited to, acid anhydrides and lower alkyl esters thereof. Examples of the trivalent or higher carboxylic acid include 1,2,4-benzenetricarboxylic acid, 1,3,5-benzenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, and anhydrides thereof, 2-sulfo Examples include, but are not limited to, sodium terephthalate, sodium 5-sulfoisophthalate, sodium sulfosuccinate and lower esters thereof. In the present invention, 1,4-phenylenediacetic acid or 1,4-cyclohexanedicarboxylic acid can be preferably used.

  The component (a) is used in an amount of 10 to 80 mol%, preferably 15 to 65 mol%, more preferably 20 to 50 mol%, based on all monomers. When the amount of the component (a) used is less than 10 mol% in all the monomers, the reactivity at low temperature polycondensation becomes insufficient, resulting in a polyester having a low degree of polymerization. Further, if the amount of component (a) used exceeds 80 mol% in the total monomer, the mixture of residual polycondensation components increases in the polyester, so that the resin becomes sticky at room temperature, or this may result in the formation of an electrostatic image developing toner. When used as a resin, the fluidity of the toner powder deteriorates.

<(B) Polyhydric alcohol monomer>
The polyhydric alcohol monomer (polyol) used in the present invention is a compound containing two or more hydroxyl groups in one molecule, and it goes without saying that the compounds (1) and (2) are excluded.
Of the polyhydric alcohol monomers used in the present invention, the diol is a compound having two hydroxyl groups in one molecule. For example, ethylene glycol, propylene glycol, butanediol, diethylene glycol, hexanediol, cyclohexanediol, octanediol, Examples include decanediol and dodecanediol.

  Also, a diol containing a bisphenol skeleton group can be used as the polyhydric alcohol monomer. The bisphenol skeleton is not particularly limited as long as it is composed of two phenol groups. Specifically, bisphenol A, bisphenol C, bisphenol E, bisphenol F, bisphenol M, bisphenol P, bisphenol S, bisphenol Z, etc. It can be mentioned, but is not limited to these.

  The polyhydric alcohol containing the bisphenol skeleton group preferably has at least one alkylene oxide group. Examples of the alkylene oxide group include an ethylene oxide group, a propylene oxide group, and butylene oxide, and ethylene oxide and propylene oxide are preferable.

  Specific examples of the polyhydric alcohol monomer containing a bisphenol skeleton group that can be used in the present invention include bisphenol A ethylene oxide adduct, bisphenol A propylene oxide adduct, ethylene oxide propylene oxide adduct, and bisphenol Z. Ethylene oxide adduct, bisphenol Z propylene oxide adduct, bisphenol S ethylene oxide adduct, bisphenol S propylene oxide adduct, bisphenol F ethylene oxide adduct, bisphenol F propylene oxide adduct, bisphenol E ethylene oxide adduct, bisphenol E propylene Oxide adduct, bisphenol C ethylene oxide adduct, bisphenol C propylene oxide adduct, bisphenol Le M ethylene oxide adduct (bisphenol M propylene oxide adduct, bisphenol P ethylene oxide adduct, do not can be mentioned bisphenol P propylene oxide adduct being limited thereto.

  In the present invention, bisphenol A ethylene oxide 2 mol adduct, bisphenol A ethylene oxide 4 mol adduct, bisphenol A propylene oxide 2 mol adduct, bisphenol A propylene oxide 4 mol adduct, bisphenol A ethylene oxide 2 mol propylene oxide 2 Mole adduct, bisphenol Z ethylene oxide 2 mol adduct, bisphenol Z ethylene oxide 4 mol adduct, bisphenol Z propylene oxide 2 mol adduct, bisphenol Z propylene oxide 4 mol adduct, bisphenol Z ethylene oxide 2 mol propylene oxide 2 Mole adduct, bisphenol S ethylene oxide 2 mol adduct, bisphenol S ethylene oxide 4 mol adduct, bisphenol S Pyrene oxide (2 mol) adduct, bisphenol S propylene oxide 4 mol adduct, can be used bisphenol S ethylene key side 2 moles of propylene oxide 2 mol adduct.

  Examples of polyols other than diols include glycerin, pentaerythritol, hexamethylol melamine, hexaethylol melamine, tetramethylol benzoguanamine, and tetraethylol benzoguanamine, and these may be used alone. Two or more types may be used in combination. In addition, an amorphous resin or a crystalline resin can be easily obtained by combining these polycondensable monomers.

  Polyols used to obtain crystalline polyester include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,4-butenediol. , Neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, etc., and 1,6-hexane Diols and 1,9-nonanediol can be preferably used.

  Examples of the polyhydric alcohol used for obtaining the non-crystalline polyester include aliphatic, alicyclic, and aromatic polyhydric alcohols. Specific examples include 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, alkylene oxide adduct of bisphenol A, alkylene oxide adduct of bisphenol Z, and alkylene oxide adduct of hydrogenated bisphenol A. An alkylene oxide adduct of bisphenol A can be preferably used, and a bisphenol A ethylene oxide 2 mol adduct and a bisphenol A propylene oxide 2 mol adduct can be more preferably used.

  The component (b) is used in an amount of 10 to 80 mol%, preferably 15 to 65 mol%, more preferably 20 to 50 mol% in all monomers. When the amount of component (b) used is less than 10 mol% in all monomers, the reactivity in low-temperature polycondensation becomes insufficient, resulting in a polyester having a low degree of polymerization. Further, if the amount of component (b) exceeds 80 mol% in the total monomer, the mixture of residual polycondensation components increases in the polyester, so that the resin becomes sticky at room temperature, or this is a result for the electrostatic image developing toner. When used as a resin, the fluidity of the toner powder deteriorates.

<(C) Compounds represented by formulas (1) to (3)>
The present invention uses at least one monomer selected from the group consisting of compounds represented by formulas (1) to (3).

In the formula (1), R ¹ is a hydrogen atom or an alkyl group, preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, methyl And more preferably an ethyl group.
Specifically, the compound represented by the formula (1) is 2,2-dimethylolacetic acid, 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, 2,2-dimethylolpentanoic acid, 2,2 -Dimethylolhexanoic acid, 2,2-dimethylolheptanoic acid, 2,2-dimethyloloctanoic acid, etc. can be mentioned, and it should be 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid Is preferred.

In Formula (2), R ² and R ³ are each a hydrogen atom or an alkyl group, preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ² and R ³ are both hydrogen atoms. Is more preferable.
Specifically, the compound represented by the formula (2) is preferably 2,3-dihydroxybutanedioic acid (tartaric acid).

In the formula (3), R ⁴ is a hydrogen atom or an alkyl group, preferably an alkyl group having 1 to 6 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, More preferably.
Specifically, the compound represented by the formula (3) is 2-hydroxybutanedioic acid (malic acid), 2-methyl-2-hydroxybutanedioic acid, 2-ethyl-2-hydroxybutanedioic acid, 2-propyl- Examples include 2-hydroxybutanedioic acid, 2-butyl-2-hydroxybutanedioic acid, 2-pentyl-2-hydroxybutanedioic acid, 2-hexyl-2-hydroxybutanedioic acid, and the like. 2-hydroxybutanedioic acid (Malic acid) is preferred.

In the present invention, the component (c) is preferably a compound represented by the formula (1), more preferably 2,2-dimethylolpropionic acid or 2,2-dimethylolbutanoic acid.
When the component (c) is a compound represented by the formula (1), the component (c) can be easily polycondensed not into the terminal of the polyester but inside, and the components (a) to (c) are mixed together. Even if it is polycondensed, it is preferable in that a polyester having an addition-polymerizable unsaturated group can be easily obtained.

As the component (c) that can be used in the present invention, only one of the monomers represented by the formulas (1) to (3), the oligomer, and the prepolymer is used. Or two or more of them may be used in combination.
The oligomer is a polycondensate of two or more monomers having a molecular weight of 2,500 or less, preferably a molecular weight of 500 to 2,500. A polymer of two or more of the above monomers having a molecular weight of 2,500 to 10,000. The polymer refers to a polymer and a polycondensate having a molecular weight of 10,000 or more. In the present invention, the oligomer and prepolymer can be used as the component (c) in the same manner as the monomer.

  The component (c) is used at 0.5 to 40 mol% in all monomers, preferably 0.5 to 20 mol%, and more preferably 1.0 to 10 mol%. When the amount of the component (c) used is less than 0.5 mol%, the polyester is not sufficiently made hydrophilic, and the particles cannot be reduced to a particle size suitable as a resin particle dispersion. When the amount of the component (c) used exceeds 40 mol%, the hydrophilicity of the polyester becomes too strong, and the chargeability at high temperature and high humidity is lowered when the toner is used.

  In the present invention, the polycondensable monomer contains (a) a polyvalent carboxylic acid monomer and / or a derivative thereof in an amount of 10 to 80 mol% in the total polycondensable monomer, and (b) a polyhydric alcohol monomer. In the total polycondensable monomer, and (c) at least one monomer selected from the group consisting of compounds represented by formulas (1) to (3) It is characterized by containing 0.5 to 40 mol% in the monomer. In addition, the sum total of (a) component, (b) component, and (c) component is 100 mol%.

<Blending ratio of component (a) and component (b)>
What is important in this case is the ratio of (a) the polyvalent carboxylic acid monomer and / or derivative thereof to (b) the polyhydric alcohol monomer. ) Divided by the amount (mol) of (b) polyhydric alcohol monomer used, (a) / (b) = 0.4 to 2.5 is preferable, and 0.6 to 1.9 is more preferable. Preferably, 0.7 to 1.6 is most preferable.

<Combination ratio of (a) component to (c) component>
In the present invention, the polycondensation ratio of the polycondensable monomers (a) to (c) can be set as follows. For example, when 2,2-dimethylolpropionic acid or 2,2-dimethylolbutanoic acid is used as component (c), that is, when a compound of formula (1) having one carboxyl group in one molecule is used, The molar ratio between the sum of the hydroxy groups in the component (b) and the hydroxy groups contributing to the reaction of the component (c) and the number of carboxyl groups in the component (a) is more than 1.0 and not more than 2.0. It is preferably 1.05 or more and 1.8 or less, and more preferably 1.05 or more and 1.5 or less. Within the above range, the component (c) can be sufficiently introduced into the polyester, which is preferable. The carboxyl group in component (a) includes a carboxyl group, an acid anhydride group, and a lower alkyl ester group, the acid anhydride group is two carboxyl groups, and the lower alkyl ester group is one carboxyl group. Convert as

<Polycondensable catalyst>
Conventionally, in order to impart water dispersibility to a polyurethane resin, a method of copolymerizing a hydroxy acid has been proposed. However, when a hydroxy acid is used in a polyester, gelation or polyester viscosity increase resulting from insufficient polymerization control. Therefore, it is difficult to produce a resin particle dispersion suitable for an electrostatic image developing toner. Furthermore, when polycondensation is performed at a temperature exceeding 150 ° C., the hydroxy acid causes crosslinking and branching, so that the polyester has an excessively high molecular weight. As a result, the melt viscosity of the toner increases, which leads to image defects that impair the fixability and the quality of the color image. In the present invention, a polyester having a crosslinked or branched structure that causes such inconvenience is not used.

  In addition, it is extremely important to use polyester polycondensed at 150 ° C. or lower in order to reduce the total toner production energy. The significance of realizing low-temperature fixing as an electrostatic charge image developing toner using the crystalline or non-crystalline polyester obtained as described above is extremely significant from the viewpoint of reducing the environmental load that has been attracting attention in recent years.

  In the polycondensation reaction in the present invention, it is preferable to use a polycondensation catalyst in order to increase the reaction rate at a low temperature of 150 ° C. or lower, preferably 100 ° C. or lower. Among them, as the polycondensation catalyst having catalytic activity at a low temperature, an acid catalyst, a rare earth-containing catalyst, a hydrolase, or the like can be used, preferably an acid catalyst, and most preferably a sulfur acid catalyst.

  In the present invention, by adding a sulfur acid catalyst during the polycondensation reaction and performing polycondensation at 150 ° C. or lower, it is possible to avoid gelation due to crosslinkability of the hydroxy acid and increase in the viscosity of the polyester. It becomes. As a result, a resin particle dispersion having a particle size suitable for toner can be produced without causing problems in production such as gelation.

  The sulfur acid catalyst that is an acid catalyst that can be used in the present invention is preferably a Bronsted acid-like acid, and specifically, toluenesulfonic acid, benzenesulfonic acid, camphor sulfonic acid. And sulfonic acids such as Na salts thereof. Furthermore, an acid having a surface active effect may be used. The acid having a surface-active effect has a chemical structure composed of a hydrophobic group and a hydrophilic group, and has an acid structure in which at least a part of the hydrophilic group is composed of protons.

  Examples of the sulfur acid having a surfactant effect that can be used in the present invention include alkylbenzene sulfonic acids such as dodecylbenzene sulfonic acid, isopropyl benzene sulfonic acid, and camphor sulfonic acid, alkyl sulfonic acid, alkyl disulfonic acid, and alkyl phenol sulfone. Acid, alkyl naphthalene sulfonic acid, alkyl tetralin sulfonic acid, alkyl allyl sulfonic acid, petroleum sulfonic acid, alkyl benzimidazole sulfonic acid, higher alcohol ether sulfonic acid, alkyl diphenyl sulfonic acid, monobutyl phenyl phenol sulfate, dibutyl phenyl phenol sulfate dodecyl sulfate Higher fatty acid sulfate, higher alcohol sulfate, higher alcohol ether sulfate, higher fatty acid amide alkylol sulfate , Higher fatty acid amide alkylated sulfate, naphthenyl alcohol sulfate, sulfated fat, sulfosuccinate, various fatty acids, sulfonated higher fatty acid, higher alkyl phosphate, resin acid, resin acid alcohol sulfate, naphthenic acid, para Examples thereof include toluenesulfonic acid and all salt compounds thereof, and a plurality thereof may be combined as necessary.

In the present invention, by adding a sulfur acid catalyst, a polyester can be obtained even if a polycondensation reaction is performed at 150 ° C. or lower, which is lower than the conventional reaction temperature. The reaction temperature is preferably 70 ° C or higher and 150 ° C or lower. More preferably, it is 80 degreeC or more and 140 degrees C or less.
It is preferable that the reaction temperature is 70 ° C. or higher because the reactivity of the polycondensation component is not decreased due to the decrease in the catalytic activity and the molecular weight is not increased. Moreover, since it can manufacture with low energy as reaction temperature is 150 degrees C or less, it is preferable. Moreover, since coloring of polyester, decomposition | disassembly of produced | generated polyester, etc. do not arise, it is preferable. Conventionally, the polycondensation reaction has been performed at a high temperature exceeding 200 ° C., but in order to perform polymerization at a low temperature of 150 ° C. or lower, which is several tens of degrees Celsius to several tens of degrees Celsius below, a sulfur acid catalyst is used. Is preferred. This is because conventional metal catalysts such as Sn-based and Ti-based materials exhibit high catalytic activity particularly at 200 ° C. or higher, and very low activity at low temperatures of 150 ° C. or lower. Sulfuric acid has a catalytic activity that decreases as the temperature rises at a high temperature of 160 ° C. or higher. However, since the reaction proceeds due to the nucleophilic addition of the catalytic acid, the polymerization temperature is about 70 ° C. or higher. The catalytic activity is high in a low temperature range of 150 ° C. or lower, and it can be suitably used for a polycondensation reaction at 150 ° C. or lower.

  The amount of sulfur acid that can be used in the present invention is preferably 0.01 to 5% by weight, preferably 0.03 to 3% by weight, based on the total weight of the polycondensable monomer. More preferably, the content is 0.05 to 2% by weight.

  As the rare earth-containing catalyst, scandium (Sc), yttrium (Y), as the lanthanoid element, lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu), etc. are effective. In particular, alkylbenzene sulfonates, 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 the 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.

However, among the above metal catalysts, when using a metal catalyst such as Sn-based or Ti-based as the catalyst, the metal content derived from the catalyst in the obtained polyester is preferably 100 ppm or less, and 75 ppm or less. More preferably, it is more preferably 50 ppm or less. Therefore, it is preferable not to use a metal catalyst or to use a very small amount even when a metal catalyst is used.
When an electrostatic charge image developing toner is obtained by producing a polyester using a metal catalyst that exceeds the above range, when it is stored for a long time under high temperature and high humidity, moisture in the atmosphere is caused by the presence of residual metal. If the toner adheres to the toner, the electrical resistance value of the toner particles decreases, the charge amount decreases, and fogging of the non-image area may occur.
The amount of metal in the polyester can be measured by various analysis methods such as analysis by fluorescent X-rays and ICP (Inductively Coupled Plasma) emission analysis. Here, the metal content derived from the catalyst means the total amount of titanium, tin and rare earth metal elements.

  The hydrolase 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 and Lipoprotein lipase) such as carboxyesterase, lipase, phospholipase, acetylesterase, pectinesterase, cholesterol esterase, tannase, monoacylglycerol lipase, lactonase and lipoprotein lipase. Such as hydrolase epoxide hydrase classified in 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 which acts on peptide bonds such as hydrolase, aminopeptidase, chymotrypsin, trypsin, plasmin, subtilisin etc. classified into EC3.3 group Water degrading enzymes, hydrolases such classified into EC3.7 group such as furo retinoic hydrolase can be exemplified.

  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 in high yield, and can be obtained at a low price. There are advantages such as.

Lipases of various origins can be used, but preferred are 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, steapsin and the like. Among these, it is desirable to use lipases derived from microorganisms of the genus Pseudomonas, Candida, and Aspergillus.
These polycondensation catalysts may be used alone or in combination. Further, these catalysts can be recovered and regenerated if necessary.

  In the above-described polyester polycondensation, it is preferable to carry out a polycondensation catalyst polycondensation reaction. If necessary, a known polycondensation catalyst can be blended in the polycondensable monomer in advance.

  In the present invention, when the polyester is polycondensed, the hydroxy chain acid monomer having a carboxyl group and / or its derivative, and the components (a) and (b) are reacted at a low temperature of 150 ° C. or less, which is preferable for environmental load. The hydroxy acid monomer having a carboxyl group or a derivative thereof can be finally incorporated into the polyester composition by neutralization.

<Other ingredients>
In the present invention, in addition to the components (a) to (c), a hydroxy acid other than (1) to (3) may be used in combination. Examples of the hydroxy acid other than (1) to (3) include dimethylolbutanoic acid, dimethylolpropionic acid, hydroxyheptanoic acid, hydroxyoctanoic acid, hydroxydecanoic acid, and hydroxyundecanoic acid. Among them, dimethylolbutane is exemplified. Acid and dimethylolpropionic acid are preferred.

  In the present invention, in addition to the above polycondensable monomers (a) to (c), an addition polymerizable monomer, preferably a radical polymerizable monomer, may be added as necessary. In this case, the polycondensation reaction and the addition polymerization reaction may be combined simultaneously or separately. Examples of the addition polymerizable monomer include a cationic polymerizable monomer and a radical polymerizable monomer, and a radical polymerizable monomer is preferable.

  Examples of the radical polymerizable monomer that can be used in the present invention include α-substituted styrene such as styrene, α-methylstyrene, α-ethylstyrene, m-methylstyrene, p-methylstyrene, and 2,5-dimethyl. Nuclear aromatic styrene such as styrene, vinyl aromatics such as nuclear substituted halogenated styrene such as p-chlorostyrene, p-bromostyrene and dibromostyrene, (meth) acrylic acid (in addition, “(meth) acryl” Acrylic and methacrylic are meant, the same shall apply hereinafter.), Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) ) Acrylate, 2-ethylhexyl (meth) acrylate, glycidyl (meth) (Meth) acrylic acid esters such as acrylate, benzyl (meth) acrylate, unsaturated carboxylic acid derivatives such as (meth) acrylaldehyde, (meth) acrylonitrile, (meth) acrylamide, N-vinylpyridine, N-vinylpyrrolidone N-vinyl compounds such as vinyl esters such as vinyl formate, vinyl acetate and vinyl propionate, vinyl halide compounds such as vinyl chloride, vinyl bromide and vinylidene chloride, N-methylol acrylamide and N-ethylol acrylamide N-substituted amides such as N-propanol acrylamide, N-methylol maleamic acid, N-methylol maleamic acid ester, N-methylol maleimide and N-ethylol maleimide, conjugated dienes such as butadiene and isoprene, Gibini Polyfunctional vinyl compounds such as benzene, divinylnaphthalene and divinylcyclohexane, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, neopentyl glycol Di (meth) acrylate, hexamethylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerol di (meth) acrylate, glycerol tri (meth) acrylate, pentaerythritol di (Meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipenta Lithritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, sorbitol tri (meth) acrylate, sorbitol Examples thereof include polyfunctional acrylates such as tetra (meth) acrylate, sorbitol penta (meth) acrylate, and sorbitol hexa (meth) acrylate. Among these, N-substituted unsaturated amides, conjugated dienes, polyfunctional vinyl compounds, polyfunctional acrylates, and the like can also cause a crosslinking reaction in the produced polymer. These can be used alone or in combination.

<Addition polymerization initiator>
These addition polymerizable monomers may be polymerized by a radical polymerization initiator, a method using a cationic polymerization initiator or an anionic polymerization initiator, a self-polymerization by heat, a method using ultraviolet irradiation, or a known polymerization method. it can.
As the radical polymerization initiator, the cationic polymerization initiator, or the anionic polymerization initiator, a known initiator can be used, and it may be used alone or in combination of two or more initiators.

  There are oil-soluble and water-soluble radical initiators, but either initiator may be used. Specific examples of radical initiators include 2,2′-azobis (2-methylpropionitrile), 2,2′-azobis (2-methylbutyronitrile), and 2,2′-azobisisobutyronitrile. 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethyl-4-methoxyvaleronitrile), 1,1′-azobis (cyclohexanecarbonitrile), 2 Azobisnitriles such as 2,2'-azobis (2-aminopropane) hydrochloride, acetyl peroxide, octanoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, decanoyl peroxide, lauroyl peroxide, Diacyl peroxide such as benzoyl peroxide, di-t-butyl peroxide, t-butyl Dialkyl peroxides such as α-cumyl peroxide and dicumyl peroxide, t-butyl peroxyacetate, α-cumyl peroxypivalate, t-butyl peroxyoctoate, t-butylperoxyneodecanoate, t -Peroxyesters such as butyl peroxylaurate, t-butyl peroxybenzoate, di-t-butyl peroxyphthalate, di-t-butyl peroxyisophthalate, t-butyl hydroperoxide, 2,5-dimethyl Organic peroxides such as hexane-2,5-dihydroperoxide, cumene hydroperoxide, hydroperoxide such as di-isopropylbenzene hydroperoxide, peroxycarbonate such as t-butylperoxyisopropyl carbonate, peroxide hydrogen Inorganic peroxides, potassium persulfate, sodium persulfate, radical polymerization initiators such as persulfates such as ammonium persulfate. In addition, a well-known redox polymerization initiator can also be used together.

<Acid value>
The acid value of the polyester that can be used in the present invention is preferably 5 to 50 mg · KOH / g, more preferably 8 to 40 mg · KOH / g, and most preferably 10 to 25 mg · KOH / g. It is. When the acid value is less than 5 mg · KOH / g, the polyester is not sufficiently made hydrophilic, and it becomes impossible to form particles to a particle size suitable as a resin particle dispersion. When the acid value exceeds 50 mg · KOH / g, the hydrophilicity becomes too strong when the toner is used, and the chargeability under high temperature and high humidity decreases.

In the present invention, the method for measuring the acid value of the polyester is as follows.
The acid value refers to the number of mg of ethanolic potassium hydroxide required to neutralize the resin acid or free fatty acid contained in 1.0 g of polyester. The acid value was measured by collecting 1.0 g of polyester, dissolving it in 50 mL of toluene, preparing a solution to which 1% phenolphthalein indicator solution was added, stirring with a stirrer for 2 hours or more, and then using a burette. Titrate with 1 mol / L ethanolic potassium hydroxide solution.
The acid value at this time is: acid value (mgKOH / g) = A × 5.611 × f ÷ sampled weight (g)
It is represented by
Here, A is the amount (mL) of a 0.1 mol / L ethanolic potassium hydroxide solution required for titration, and f is a factor of the ethanolic potassium hydroxide solution used.

<Weight average molecular weight>
The weight average molecular weight of the polyester obtained by polycondensation of the polycondensable monomer is preferably 1,500 to 40,000, more preferably 3,000 to 30,000. When the weight average molecular weight is 1,500 or more, the cohesive force of the binder resin is good and the hot offset property is excellent, and when it is 40,000 or less, the hot offset property is excellent and the minimum fixing temperature is excellent. Value is preferred.

<Resin particle dispersion>
The resin particle dispersion of the present invention is obtained by polycondensing a polycondensable monomer (a) and (b) with a hydroxy acid monomer and / or its derivative (c) in the presence of a polycondensation catalyst. After being obtained, it is preferable to obtain the polyester by dispersing and granulating it in an aqueous medium.
The resin particle dispersion of the present invention is preferably produced by the production method described later.

<Median diameter>
The median diameter (center diameter) of the resin particles in the resin particle dispersion of the present invention is preferably from 0.10 μm to 0.60 μm, more preferably from 0.15 μm to 0.45 μm, and still more preferably 0.15 μm. It is above 0.30 μm.
When the median diameter is within the above numerical range, the dispersion state of the resin particles in the aqueous medium is stabilized. Accordingly, when the toner is produced, if the median diameter is 0.10 μm or more, the agglomeration property at the time of particle formation is good, free resin particles are hardly generated, and the viscosity of the system is not easily increased. The control of the particle size is easy and preferable. On the other hand, when the median diameter is 0.60 μm or less, coarse powder is hardly generated and the particle size distribution is good, and a release agent such as wax is difficult to be released. The median diameter of the polycondensation resin particles can be measured, for example, with a laser diffraction particle size distribution analyzer (LA-920, manufactured by Horiba, Ltd.).

  The resin particle dispersion of the present invention is suitable not only for its median diameter, but also for generation of ultrafine powder of 0.03 μm or less and supercoarse powder of 5.0 μm or more, and the median diameter is 0.03 μm. The ratio of the polycondensed resin particles of 5.0 μm or more is preferably 10% or less, more preferably 5% or less. This ratio can be obtained, for example, by plotting the relationship between the particle diameter and the frequency integration in the measurement result in LA-920 and obtaining from the frequency integration amount of 0.03 μm or less or 5.0 μm or more.

<Crystal melting point / glass transition point>
The crystalline melting point Tm of the crystalline polyester contained in the resin particle dispersion of the present invention is preferably 50 to 120 ° C, more preferably 55 to 90 ° C, still more preferably 60 to 80 ° C. When Tm is 50 ° C. or higher, the cohesive force in a high temperature range is good, so that it is excellent in releasability and hot offset during fixing, and when it is 120 ° C. or lower, sufficient melting is obtained. The minimum fixing temperature is unlikely to rise.
On the other hand, the glass transition point Tg of the amorphous polyester contained in the resin particle dispersion of the present invention is preferably 40 to 80 ° C., more preferably 50 to 65 ° C. When Tg is 40 ° C. or higher, the cohesive strength of the binder resin itself in a high temperature range is good, so that it is excellent in hot offset at the time of fixing, and when it is 80 ° C. or lower, sufficient melting can be obtained. Therefore, it is preferable that the minimum fixing temperature does not easily rise.
Here, the melting point of the crystalline polyester resin contained in the resin particle dispersion is measured using a differential scanning calorimeter (DSC) from room temperature to 150 ° C. at a heating rate of 10 ° C. per minute. The melting peak temperature of the input compensation differential scanning calorimetry shown in JIS K-7121 can be obtained. A crystalline resin may show a plurality of melting peaks, but in the present invention, the maximum peak is regarded as the melting point.
Further, the glass transition point of the amorphous resin contained in the resin particle dispersion refers to a value measured by a method (DSC method) defined in ASTM D3418-82.

<Method for producing resin particle dispersion>
The method for producing a resin particle dispersion of the present invention comprises a step of obtaining a polyester by polycondensation of a polycondensable monomer comprising the compositions (a) to (c) in the presence of a polycondensation catalyst (hereinafter referred to as “polymerization”). And a step of dispersing the polyester in an aqueous medium (hereinafter also referred to as “dispersing step”).

<Polycondensation process>
The first step in the method for producing a resin particle dispersion of the present invention is to obtain a polyester using a polycondensable monomer and a polycondensation catalyst. At this time, the hydroxy acid monomer having a carboxyl group and / or a derivative thereof may be used from the beginning together with the polycondensable monomer, or may be added during the polycondensation.

  The polycondensation step in the present invention is a step of obtaining a polyester by polycondensation of a polycondensable monomer having the composition (a) to (c) in the presence of a polycondensation catalyst.

  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. Underwater polymerization is used. 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.

In the method for producing the resin particle dispersion of the present invention, the reaction is preferably performed at 150 ° C. or lower, which is lower than the conventional reaction temperature, more preferably 70 to 150 ° C., and 70 to 140 ° C. or lower. More preferably, it is most preferable that it is 80 to 140 degreeC.
When the temperature is lower than the above temperature range, the solubility of the monomer, the decrease in the reactivity due to the decrease in the catalyst activity, the suppression of the elongation of the molecular weight and the like may occur. It will deviate from the original purpose of manufacturing. Furthermore, coloring of the resin due to high temperature, decomposition of the produced polyester, and the like may occur.
Moreover, although the reaction time at the time of polycondensation is dependent also on reaction temperature, 0.5 to 72 hours are preferable and 1 to 48 hours are more preferable.

<Dispersing process>
The step in the method for producing the resin particle dispersion of the present invention preferably includes a step of dispersing the polyester in an aqueous medium, and more preferably neutralizing the carboxy group of the polyester with an alkali. The amount of alkali used for neutralization is adjusted based on the acid value, and is preferably in the range of 50% to 200% of the acid value. The polyester made hydrophilic by neutralization is made into particles by ordinary emulsification and / or shearing by a disperser.

The neutralizing agent that can be used in the present invention is not particularly limited as long as it is a basic substance capable of causing a neutralization reaction with the carboxyl group contained in the polyester, and M (OH) _n (M is an alkali metal, Alternatively, alkaline earth metals, metal hydroxides having a chemical formula of n = 1 to 2), amine compounds, ammonium compounds, and the like can be given.
As the alkali hydroxide compound, NaOH, KOH, LiOH or the like can be preferably used. Amine compounds and ammonium compounds are dimethylethanolamine, diethylethanolamine, triethanolamine, tripropanolamine, tributanolamine, triethylamine, propylamine, butylamine, isopropylamine, monomethanolamine, morpholine, methoxypropylamine, pyridine, Vinyl pyridine, aqueous ammonia and the like can be used, and materials having high solubility in water such as triethanolamine and aqueous ammonia can be preferably used.

The basic substance contained in the resin dispersion in the present invention may contain a polycondensed basic catalyst. In the case of using a basic catalyst, for example, after obtaining a polyester by performing polycondensation using an amount of acid catalyst larger than the amount of base catalyst, the basic catalyst is added in an amount equal to or more than the amount of acid catalyst after polycondensation, It is also possible to use it by the method of emulsifying later.
Further, in the present invention, as described above, the method for deactivating the acid catalyst is to add a basic substance at the end of the polycondensation reaction to stop the polycondensation, and then to add the basic substance again during emulsification of the resin. It is also possible to take additional methods. At this time, the basic substance added at the end of the polycondensation reaction and the basic substance added at the time of emulsification may be the same or different.

  Examples of a method for dispersing and granulating the polyester in an aqueous medium include, for example, a mechanical existing resin pulverization method, and a suspension polymerization method in an aqueous medium when the polyester is produced as described above. Examples thereof include a dissolution suspension method, a miniemulsion method, a microemulsion method, a multistage swelling method, and an emulsion polymerization method including seed polymerization.

Further, the method for dispersing and granulating the polyester 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 hydrophilicity used for self-emulsification, a carboxyl group, a sulfone group, and the like can be used. When applied to polyester that can be used in the present invention, a carboxyl group is preferably used.
In the dispersion step in the present invention, a surfactant or the like can be added for dispersion in order to increase the dispersion efficiency or improve the stability of the resin particle dispersion.

In the present invention, the aqueous medium means water or a mixed solvent containing 50% by weight or more of water, and water may be mixed with a water-miscible organic solvent. The mixing ratio of water in the mixed solvent is preferably 60 to 100% by weight, more preferably 70 to 100% by weight.
As an aqueous medium which can be used for this invention, water, such as distilled water and ion-exchange water, ethanol, methanol, etc. are mentioned, for example. 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. Examples of the water miscible organic solvent include acetone and acetic acid. When an organic solvent is used for emulsification and granulation of polyester, not only is a large investment required for the recovery equipment, but it is also not preferable from the viewpoint of environmental safety. Furthermore, since it is difficult to completely remove the solvent used from the toner, there are quality problems such as toner storage stability.

When an organic solvent is used in the dispersion step, the method for producing a resin particle dispersion of the present invention may include a step of removing at least a part of the organic solvent and a step of forming resin particles.
For example, after emulsifying the polyester-containing material, it is preferable to solidify as particles by removing a part of the organic solvent. As a specific method of solidification, after the polycondensation resin-containing material is emulsified and dispersed in an aqueous medium, while stirring the solution, an inert gas such as air or nitrogen is fed into the organic solvent at the gas-liquid interface. A method of drying (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), and further a polycondensation resin-containing material in an aqueous medium There is a method in which an emulsified dispersion liquid emulsified and dispersed or an emulsion liquid containing a polycondensation resin is discharged from the pores in a shower-like manner and dropped into a dish-shaped receiver and dried while repeating this (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, the solubility in water, and the like.

Further, in the method for producing a resin particle dispersion of the present invention, when emulsification polycondensation is performed in an aqueous medium, a preferable emulsification temperature is determined in consideration of energy saving property, polymer production rate, and thermal decomposition rate of the produced polymer. Although the lower one is preferable, More preferably, it is 40-150 degreeC, More preferably, it is 80-130 degreeC.
When the emulsification temperature is within the above numerical range, the required energy does not become excessive, the molecular weight is not reduced due to decomposition of the resin due to high heat, the resin viscosity is moderate, and particle formation is easy. .

  In the polymerization in the aqueous medium, it is possible to previously mix a colorant, wax and the like in addition to the monomer components before polymerization. By doing so, polymerizable composite particles can be obtained in a form incorporating a colorant and wax.

  The solid content concentration of the resin particle dispersion of the present invention is preferably 5 to 40% by weight, more preferably 10 to 30% by weight, and most preferably 15 to 25% by weight. When the solid content concentration of the resin particle dispersion is 5% by weight or more, the viscosity of the polymer composition is not too low and the stability of the particles is good, and the proportion of the dispersion in the total composition does not increase. Therefore, the composition can be easily adjusted and the transportation cost is excellent. When the solid content is 40 parts by weight or less, the viscosity is appropriate and stirring can be performed uniformly, and the polymerization proceeds sufficiently. Moreover, the fluidity | liquidity of latex is favorable and it does not change to cream mousse shape with storage conditions, and is preferable.

<Surfactant>
When dispersing and emulsifying in an aqueous medium, the above materials are emulsified or dispersed in the aqueous medium using, for example, mechanical shear or ultrasonic waves. It is also possible to add a molecular dispersant, an inorganic dispersant and the like to the aqueous medium. Further, an aqueous medium is added to a mixture (oil phase) containing a polyester and a monomer having a carboxyl group and an addition-polymerizable unsaturated group, and finally the polyester, carboxyl group and addition-polymerizability are added to the aqueous medium. A monomer having an unsaturated group may be emulsified and dispersed.

  Examples of the surfactant that can be used in the present invention include anionic surfactants such as sulfate ester, sulfonate, and phosphate ester; cationic surfactants such as amine salt type and quaternary ammonium salt type. Agents: Nonionic surfactants such as polyethylene glycol, alkylphenol ethylene oxide adducts, polyhydric alcohols, and the like. Among these, anionic surfactants and cationic surfactants are preferable. The nonionic surfactant is preferably used in combination with the anionic surfactant or the cationic surfactant. The said surfactant may be used individually by 1 type, and may use 2 or more types together.

  Anionic surfactants include sodium dodecylbenzenesulfonate, sodium alkylnaphthalenesulfonate, sodium arylalkylpolyethersulfonate, 3,3′-disulfonediphenylurea-4,4′-diazo-bis-amino-8-naphthol Sodium 6-sulfonate, ortho-carboxybenzene-azo-dimethylaniline, 2,2 ′, 5,5′-tetramethyl-triphenylmethane-4,4′-diazo-bis-β-naphthol-6-sulfone Sodium sulfate, sodium dialkylsulfosuccinate, sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, sodium laurate, sodium caprate, sodium caprylate, Sodium prong, potassium stearate, and the like calcium oleate.

  Examples of the cationic surfactant include alkylbenzene dimethyl ammonium chloride, alkyl trimethyl ammonium chloride, distearyl ammonium chloride and the like.

  Nonionic surfactants include polyethylene oxide, polypropylene oxide, combinations of polypropylene oxide and polyethylene oxide, esters of polyethylene glycol and higher fatty acids, alkylphenol polyethylene oxide, esters of higher fatty acids and polyethylene glycol, higher fatty acids and polypropylene oxide. Examples thereof include esters and sorbitan esters.

  Examples of the polymer dispersant include sodium polycarboxylate and polyvinyl alcohol, and examples of the inorganic dispersant include calcium carbonate. However, these do not limit the present invention.

  Furthermore, in order to prevent the Ostwald Ripping phenomenon of emulsion particles in a normal aqueous medium, higher alcohols typified by heptanol and octanol and / or higher aliphatic hydrocarbons typified by hexadecane are blended as a stabilizing aid. It is also possible.

<Co-surfactant>
In the present invention, a co-surfactant can be used in combination in order to keep the average particle size of the oil phase containing the monomer in a specific range. As the co-surfactant, a co-surfactant which is water-insoluble or hardly soluble and monomer-soluble and which is used in the conventionally known “miniemulsion polymerization” can be used.
Examples of suitable co-surfactants include alkanes having 8 to 30 carbon atoms such as dodecane, hexadecane and octadecane, alkyl alcohols having 8 to 30 carbon atoms such as lauryl alcohol, cetyl alcohol and stearyl alcohol, lauryl (meta C8-C30 alkyl (meth) acrylates such as acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, dodecanethiol, lauryl mercaptan, cetyl mercaptan, stearyl mercaptan and other alkanethiols having 8 to 30 carbon atoms And other polymers such as polystyrene and polymethyl methacrylate, polyadducts, carboxylic acids, ketones, amines and the like.

Here, in order to produce an emulsion, for example, a monomer solution to which a co-surfactant is added and an aqueous solution of a surfactant are mixed with a piston homogenizer, a microfluidizer (for example, “Microfluid,” manufactured by Dix Corporation). The mixture is uniformly mixed and emulsified by a shear mixing device such as a microfluidizer ") or an ultrasonic disperser.
At that time, the amount of the monomer charged with respect to water is preferably about 0.1 to 50% by weight with respect to the total amount with water. The amount of surfactant used is preferably less than the critical micelle concentration (CMC) in the presence of the emulsion to be formed. The amount of the co-surfactant used is preferably 0.1 to 40 parts by weight, more preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the monomer.

<Addition polymerization process>
In the present invention, after the polyester is dissolved in the monomer having an addition-polymerizable unsaturated group, a step of dispersing in water to form particles and then making particles by radical polymerization may be provided (hereinafter referred to as addition). Also called a polymerization step).

  The addition polymerization method of the present invention is not particularly limited, but a polymerization method in which addition polymerization is performed by dispersing in an aqueous medium is preferable. Polymerization methods in aqueous media include suspension polymerization methods, dissolution suspension methods, miniemulsion methods, microemulsion methods, multistage swelling methods, emulsion polymerization methods including seed polymerization, and other conventional polymerization methods in aqueous media. Can be used.

  In this case, the rate of addition polymerization depends on the molecular weight and particle diameter of the polyester. The most preferable polyester particle diameter is 1 μm or less. The most preferable method is a polymerization method capable of obtaining submicron particles such as a mini-emulsion method and a micro-emulsion method as a method that enables efficient production with a particle size of 1 μm or less.

  In the present invention, the polymerization of the monomer in the presence of the polymerization initiator of the monomer emulsion by the combined use of the surfactant amount less than the critical micelle concentration (CMC) and the co-surfactant is, for example, P . L. Tang, E .; D. Sudol, C.I. A. Silebi, and M.M. S. El-Asser, J.A. Appl. Polym. Sci. 43, page 1059 (1991), etc., and is known as so-called “miniemulsion polymerization”. In conventional emulsion polymerization, an aqueous emulsion of monomer particles having a particle size of several μm is polymerized using a water-soluble polymerization initiator in the presence of a surfactant having a critical micelle concentration (CMC) or higher. Polymerization is initiated in the activator micelles, and polymer particles grow and form upon receipt of monomer diffusion from the monomer particles. In “miniemulsion polymerization”, monomers are polymerized in the monomer particles, so that uniform polymer particles are formed. In the “mini-emulsion polymerization” of the polyester / addition polymerization type resin composite polymer as in the present invention, since the diffusion of the monomer is unnecessary in the polymerization process, the polyester has an advantage that it can exist in the polymer particles as it is. .

  Also, for example, J. Org. S. Guo, M .; S. El-Asser, and J.M. W. Vanderhoff, J. et al. Polym. Sci. : Polym. Chem. Ed. 27, page 691 (1989), etc., so-called “microemulsion polymerization” can obtain particles having a particle diameter of 5 to 50 nm, and has the same dispersion structure as “miniemulsion polymerization” in the present invention. And having a polymerization mechanism. However, "microemulsion polymerization" uses a large amount of surfactant with a critical micelle concentration (CMC) or higher, and a large amount of surfactant is mixed in the resulting polymer particles. Alternatively, there is a problem that a long time is required for a process such as alkali cleaning.

<Electrostatic image developing toner and production method thereof>
The resin particle dispersion of the present invention can be suitably used as a resin particle dispersion for an electrostatic charge image developing toner.
The method for producing an electrostatic charge image developing toner (hereinafter also simply referred to as “toner”) of the present invention comprises a step of aggregating the resin particles in a dispersion containing at least a resin particle dispersion to obtain aggregated particles, and A method for producing an electrostatic charge image developing toner including a step of heating and aggregating the aggregated particles, wherein the resin particle dispersion is the above-described resin particle dispersion of the present invention.

  The method for producing an electrostatic charge image developing toner of the present invention comprises a composite resin particle of a polyester and an addition-polymerizable resin by polymerizing an addition-polymerizable monomer emulsion containing polyester in the presence of a polymerization initiator. It is possible to adjust the toner particle size and distribution by forming a certain polyester / addition polymerization type resin polymer particle, and then using a particle aggregation fusion method such as a known aggregation method in which the formed polymer particles are aggregated (aggregated). It is.

  The toner particles in the emulsion polymerization aggregation method shown here are, for example, the polyester / addition polymerization type resin composite resin particle dispersion prepared in the present invention is mixed with the colorant particle dispersion and the release agent particle dispersion, and further aggregated. Aggregated particles having a toner diameter are formed by adding an agent to cause heteroaggregation, and then heated to a temperature above the glass transition point or the melting point of the resin particles to fuse and coalesce the aggregated particles, wash, and dry Can be obtained.

  The toner shape is preferably from an indeterminate shape to a spherical shape. In addition to surfactants, inorganic salts and divalent or higher metal salts can be suitably used as the flocculant. In particular, when a metal salt is used, it is desirable in terms of cohesion control and toner charging characteristics.

  In addition, the resin particle dispersion containing the polyester of the present invention and the colorant particle dispersion are aggregated in advance in the above-described aggregation step, and after the formation of the first aggregated particles, the resin particle dispersion containing the polyester of the present invention or another polymer is further formed. It is also possible to add a particle dispersion to form a second shell layer on the first particle surface. In this illustration, the colorant dispersion is prepared separately, but naturally the colorant may be blended in advance with the resin particles in the resin particle dispersion of the present invention.

  In the present invention, the agglomeration method of the colorant-containing resin particles obtained by the above-described polymerization is not particularly limited, and conventionally known agglomeration methods used in the emulsion polymerization aggregation method of electrostatic charge image developing toners. For example, a method of reducing the stability of the emulsion by elevating temperature, changing pH, adding salt, etc., and stirring with a disperser or the like is used.

  Further, after the agglomeration treatment, the particle surface may be cross-linked by heat treatment or the like for the purpose of suppressing leaching of the colorant from the particle surface. In addition, you may remove the used surfactant etc. by water washing | cleaning, acid washing | cleaning, or alkali washing | cleaning as needed.

  In the method for producing an electrostatic charge image developing toner of the present invention, a charge control agent used for this type of toner may be used as necessary. In that case, the charge control agent may be added as an aqueous dispersion or the like at the start of production of the monomer particle emulsion, at the start of polymerization, or at the start of aggregation of the resin particles. The addition amount of the charge control agent is preferably 1 to 25 parts by weight, more preferably 5 to 15 parts by weight with respect to 100 parts by weight of the monomer or polymer.

  Examples of the charge control agent include positive charge control agents such as nigrosine dyes, quaternary ammonium salt compounds, triphenylmethane compounds, imidazole compounds, and polyamine resins, or chromium, cobalt, aluminum, and iron. Metal-containing azo dyes such as, salicylic acid or metal salts and metal complexes of hydroxycarboxylic acids such as acrylic acid, benzylic acid such as chromium, zinc, and aluminum, amide compounds, phenol compounds, naphthol compounds, phenolamide compounds, etc. Known charge control agents can be used.

  In the method for producing an electrostatic charge image developing toner of the present invention, waxes as a release agent used for this type of toner may be used as necessary. Examples of the release agent include polyolefin waxes such as low molecular weight polyethylene, low molecular weight polypropylene, and ethylene-propylene copolymers, plant waxes such as paraffin wax, hydrogenated castor oil, carnauba wax, rice wax, and stearic acid. Higher fatty acid ester waxes such as esters, behenic acid esters and montanic acid esters, higher alcohols such as alkyl-modified silicones and higher fatty acid stearyl alcohols such as stearic acid, higher fatty acid amides such as oleic acid amide and stearic acid amide, distearyl ketone Well-known things, such as a ketone which has long-chain alkyl groups, such as, can be used.

  The release agent can be added as an aqueous dispersion or the like at the start of production of the monomer emulsion, at the start of polymerization, or at the start of aggregation of the polymer particles. The amount of the release agent used is preferably 1 to 25 parts by weight, more preferably 5 to 15 parts by weight with respect to 100 parts by weight of the monomer or polymer.

  In the method for producing an electrostatic charge image developing toner of the present invention, various known internal additives such as antioxidants and ultraviolet absorbers used in this type of toner may be used as necessary.

  The toner obtained by the method for producing an electrostatic charge image developing toner of the present invention preferably has an average particle diameter of 1 to 10 μm.

<Colorant>
Examples of the colorant that can be used in the toner of the present invention include carbon black, chrome yellow, hansa yellow, benzidine yellow, sren yellow, quinoline yellow, permanent orange GTR, pyrazolone orange, vulcan orange, watch young red, and permanent red. , Brilliantamine 3B, brilliantamine 6B, dapon oil red, pyrazolone red, risor red, rhodamine B rake, lake red C rose bengal, aniline blue, ultramarine blue, calco oil blue, methylene blue chloride, phthalocyanine blue, phthalocyanine green, Various pigments such as malachite green oxalate, titanium black, acridine, xanthene, azo, benzox , Azine, anthraquinone, thioindico, dioxazine, thiazine, azomethine, indico, thioindico, phthalocyanine, aniline black, polymethine, triphenylmethane, diphenylmethane, thiazine, thiazole And various dyes such as xanthene series.

  Specific examples of the colorant include carbon black, nigrosine dye (C.I. No. 50415B), aniline blue (C.I.No. 50405), and calco oil blue (C.I.No. azoic). Blue 3), chrome yellow (C.I. No. 14090), ultramarine blue (C.I.No. 77103), DuPont oil red (C.I.No. 26105), quinoline yellow (C.I.No. 47005), methylene blue chloride (C.I.No. 52015), phthalocyanine blue (C.I.No. 74160), malachite green oxalate (C.I.No. 42000), lamp black (C.I.No. 77266), Rose Bengal (C.I. No. 45435), mixtures thereof, etc. Preferably it can be used.

  The amount of the colorant used is usually 0.1 to 20 parts by weight, particularly preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the toner. Moreover, as a coloring agent, these pigments, dyes, etc. can be used individually by 1 type, or 2 or more types can be used together.

  As these dispersion methods, any method such as a general dispersion method such as a rotary shear type homogenizer, a ball mill having media, a sand mill, or a dyno mill can be used, and is not limited at all. These colorant fine particles may be added together with other fine particle components in the mixed solvent at once, or may be divided and added in multiple stages.

The electrostatic charge image developing toner of the present invention may contain a magnetic material and a property improving agent as necessary.
As the magnetic material, ferrite, magnetite and other iron, cobalt, nickel and other metals or alloys exhibiting ferromagnetism, compounds containing these elements, or containing no ferromagnetic elements, but subjected to appropriate heat treatment Examples thereof include alloys that exhibit ferromagnetism, such as manganese-copper-aluminum, manganese-copper-tin, and other types of alloys called Heusler alloys containing manganese and copper, or chromium dioxide.
For example, in the case of obtaining a black toner, it is particularly preferable to use magnetite that is black in itself and also functions as a colorant. In the case of obtaining a color toner, a toner having a small blackness such as metallic iron is preferable. Some of these magnetic materials also function as a colorant, and in that case, they may also be used as a colorant. When the magnetic toner is used, the content of these magnetic materials is preferably 20 to 70 parts by weight, more preferably 40 to 70 parts by weight per 100 parts by weight of the toner.

Examples of the property improver include a fixability improver, a charge control agent, and the like.
Examples of fixability improvers include polyolefins, fatty acid metal salts, fatty acid esters and fatty acid ester waxes, partially saponified fatty acid esters, higher fatty acids, higher alcohols, fluid or solid paraffin waxes, polyamide waxes, polyhydric alcohol esters, Silicon varnish, aliphatic fluorocarbon, and the like can be used. In particular, a wax having a softening point (ring and ball method: JIS K2207: 96) of 60 to 150 ° C. is preferable.
As the charge control agent, those conventionally known can be used, and examples thereof include nigrosine dyes and metal-containing dyes.

Furthermore, the toner of the present invention is preferably used by mixing inorganic particles such as a fluidity improver.
The inorganic particles used in the present invention are particles having a primary particle diameter of 5 nm to 2 μm, preferably 5 nm to 500 nm. Moreover, it is preferable that the specific surface area by BET method is 20-500 m < ² > / g. The proportion mixed with the toner is 0.01 to 5% by weight, preferably 0.01 to 2.0% by weight. Examples of such inorganic particles include silica powder, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, silica sand, clay, mica, wollastonite, diatomaceous earth, Examples thereof include chromium oxide, cerium oxide, bengara, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride, and silica powder is particularly preferable.

The silica powder here is a powder having a Si—O—Si bond, and includes both those produced by a dry method and a wet method. In addition to anhydrous silicon dioxide, any of aluminum silicate, sodium silicate, potassium silicate, magnesium silicate, zinc silicate and the like may be used, but those containing SiO _{2 in an amount} of 85% by weight or more are preferable.

  Specific examples of these silica powders include various commercially available silicas, but those having a hydrophobic group on the surface are preferable. For example, AEROSIL R-972, R-974, R-805, R-812 (manufactured by Aerosil Co., Ltd.) ), Thalax 500 (manufactured by Tarco) and the like. In addition, silica powder treated with a silane coupling agent, a titanium coupling agent, silicon oil, silicon oil having an amine in the side chain, or the like can be used.

The cumulative volume average particle diameter D ₅₀ of the toner obtained by the method for producing an electrostatic charge image developing toner of the present invention is preferably in the range of 3.0 to 9.0 μm, more preferably 3.0 to 5.0 μm. Range. When D ₅₀ is within the above numerical range, the adhesive force is appropriate, the developability is good, and the image resolution is excellent.

  Further, the volume average particle size distribution index GSDv of the obtained toner is preferably 1.30 or less. When GSDv is 1.30 or less, the resolution is excellent, and image defects such as toner scattering and fogging do not occur.

Here, the cumulative volume-average particle diameter D ₅₀ and an average particle size distribution index, for example a Coulter Counter TAII (Beckman - Coulter Inc.), Coulter Multisizer II - particle size distribution measured by (Beckman Coulter), such as instrument In the particle size range (channel) divided on the basis of volume, the cumulative distribution of volume and number from the small diameter side is drawn, and the particle size that becomes 16% cumulative is the volume D16v, the number D16P, the particle size that becomes 50% cumulative Is defined as a volume D50v, a number D50P, and a particle size of 84% cumulative is defined as a volume D84v, a number D84P. Using these, the volume average particle size distribution index (GSDv) is calculated as (D84v / D16v) ^1/2 and the number average particle size distribution index (GSDp) is calculated as (D84P / D16P) ^1/2 .

  The shape factor SF1 is quantified mainly by analyzing a microscope image or a scanning electron microscope image with an image analyzer, and is obtained as follows, for example. For the measurement of the shape factor SF1, first, an optical microscope image of toner spread on a slide glass is taken into a Luzex image analyzer through a video camera, and SF1 of the following formula is calculated for 50 or more toners to obtain an average value. Can be obtained.

ここでＭＬはトナー粒子の絶対最大長、Ａはトナー粒子の投影面積である。
得られたトナーの形状係数ＳＦ１は、画像形成性の点より１００〜１４０であることが好ましく、より好ましくは１１０〜１４０の範囲である。

Here, ML is the absolute maximum length of the toner particles, and A is the projected area of the toner particles.
The shape factor SF1 of the obtained toner is preferably from 100 to 140, more preferably from 110 to 140, from the viewpoint of image formability.

  The obtained toner is dried in the same manner as a normal toner for the purpose of imparting fluidity and improving cleaning properties, and then inorganic particles such as silica, alumina, titania and calcium carbonate, and resins such as vinyl resins, polyesters and silicones. The particles can be added to the surface of the toner particles while being sheared in a dry state.

  In addition, when adhering to the toner surface in an aqueous medium, examples of inorganic particles include silica, alumina, titania, calcium carbonate, magnesium carbonate, tricalcium phosphate, etc. Can be used by dispersing with an ionic surfactant, polymer acid, or polymer base.

<Electrostatic image developer>
The toner obtained by the method for producing an electrostatic charge image developing toner of the present invention can be used as an electrostatic charge 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.

The carrier that can be used in the present invention is not particularly limited. Usually, magnetic particles such as iron powder, ferrite, iron oxide powder, and nickel; magnetic particles are used as a core material, and the surface thereof is a styrene resin or vinyl resin. A resin-coated carrier formed by coating a resin, an ethylene-based resin, a rosin-based resin, a polyester-based resin, a melamine-based resin or the like, or a wax such as stearic acid, and forming a resin-coated layer; magnetic particles in the binder resin And a magnetic material-dispersed carrier in which is dispersed. 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>
The image forming method of 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 development with a developer containing electrostatic latent image toner formed on the surface of the latent image holding member. A developing step for forming a toner image, a transfer 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 fixing step for thermally fixing the toner image transferred on the surface of the transfer target. The electrostatic charge image developing toner of the present invention is used as the toner, or the electrostatic charge image developer of the present invention is used as the developer.

  In the image forming method of the present invention, a developer is prepared using the specific toner as described above, and an electrostatic image is formed and developed by a conventional electrophotographic copying machine using the developer. The image is electrostatically transferred onto the transfer paper, and is fixed by a heating roller fixing device in which the temperature of the upper heating roller is set to a constant temperature to form a copy image.

The image forming method of the present invention is particularly preferably used when performing high-speed fixing such that the contact time between the toner on the transfer paper and the heating roller is within 1 second, particularly within 0.5 seconds.
The electrostatic image developer (electrostatic image developing toner) of the present invention can be used in an image forming method of a normal electrostatic image developing system (electrophotographic system). Specifically, the image forming method of the present invention includes, for example, an electrostatic latent image forming step, a toner image forming step, a transfer step, and a cleaning step. Each of the above steps is a general step per se, and is described in, for example, JP-A-56-40868 and JP-A-49-91231. The image forming method of the present invention can be carried out using an image forming apparatus such as a copier or a facsimile machine known per se.

  The electrostatic latent image forming step is a step of forming an electrostatic latent image on the electrostatic latent image carrier. The toner image forming step is a step of developing the electrostatic latent image with a developer layer on a developer carrier to form a toner image. The developer layer is not particularly limited as long as it contains the electrostatic image developer of the present invention containing the electrostatic image developing toner of the present invention. The transfer step is a step of transferring the toner image onto a transfer body. The cleaning step is a step of removing the electrostatic charge image developer remaining on the electrostatic latent image carrier. 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 performed using an image forming apparatus such as a toner recycling system type copying machine or facsimile machine. The present invention can also be applied to a recycling system in which the cleaning process is omitted and toner is collected simultaneously with development.

Examples of the present invention will be described in detail below, but the present invention is not limited to these examples.
The toner of this example was prepared by preparing the following resin particle dispersion, colorant particle dispersion, and release agent particle dispersion, respectively, and mixing and stirring them at a predetermined ratio while polymerizing a metal salt. Were added and ionically neutralized to form aggregated particles.
Next, inorganic hydroxide was added to adjust the pH of the system from weakly acidic to neutral, and then the mixture was heated to a temperature above the glass transition point or above the melting point of the resin particles for fusing and coalescence.
After completion of the reaction, a desired toner was obtained through sufficient washing, solid-liquid separation, and drying processes. Hereinafter, each preparation method and the measuring method of each characteristic value are demonstrated.

<Measurement of melting point and glass transition point>
According to the differential scanning calorimetry (DSC), using “DSC-20” (manufactured by Seiko Denshi Kogyo Co., Ltd.), 10 mg of the sample is heated at a constant rate of temperature increase (10 ° C./min), and from the baseline and endothermic peak The melting point was determined.

<Measurement of weight average molecular weight Mw and number average molecular weight Mn>
The weight average molecular weight Mw and the number average molecular weight Mn were measured by gel permeation chromatography (GPC) under the conditions described below. At a temperature of 40 ° C., a solvent (tetrahydrofuran) was flowed at a flow rate of 1.2 ml / min, and 3 mg of a tetrahydrofuran sample solution having a concentration of 0.2 g / 20 ml was injected as a sample weight for measurement. In addition, when measuring the molecular weight of a sample, the measurement conditions included in the range in which the logarithm of the molecular weight of the prepared calibration curve and the count number are in a straight line by using several types of monodisperse polystyrene standard samples. Shall be selected.
In addition, the reliability of the measurement results is that the NBS706 polystyrene standard sample performed under the above measurement conditions is
Weight average molecular weight Mw = 28.8 × 10 ⁴
Number average molecular weight Mn = 13.7 × 10 ⁴
Can be confirmed.
Moreover, TSK-GEL and GMH (made by Tosoh Corporation) were used as a GPC column.
The solvent and measurement temperature were changed to appropriate conditions according to the measurement sample.
When an aliphatic polyester is used as the polyester and a resin particle dispersion using an aromatic monomer as the addition polymerizable resin is prepared, UV and RI are separated as a detector when analyzing the molecular weight of both by GPC. It is also possible to analyze the molecular weight of each device after retrofitting.

<Hydrolysis rate>
The hydrolysis rate is defined below.
Hydrolysis rate = weight average molecular weight of resin in dispersion / weight average molecular weight of resin used for emulsification
0.9 or more and 1.0 or less ○ 0.7 or more and less than 0.9 △
0.7 or less ×
○ is accepted.

(Example 1)
<Preparation of Amorphous Resin Particle Dispersion (A1)>
1,4-cyclohexanedicarboxylic acid 199 parts by weight Bisphenol A ethylene oxide 2-mole adduct 210 parts by weight Bisphenol A propylene oxide 2-mole adduct 115 parts by weight 2,2-dimethylolbutanoic acid 50 parts by weight Dodecylbenzenesulfonic acid 0.35 Part by weight The above materials were mixed, put into a reactor equipped with a stirring function, and subjected to polycondensation at 120 ° C. for 7 hours under a nitrogen atmosphere. After 7 hours of polymerization time, the temperature was raised to 135 ° C., and polycondensation was further performed for 5 hours. As a result, a uniform transparent amorphous polyester was obtained. The weight average molecular weight by GPC was 27,000, the glass transition temperature (onset) was 63 ° C., and the resin acid value was 22 mg · KOH / g.

  To 100 parts by weight of this resin, 3 parts by weight of linear sodium dodecylbenzenesulfonate as a surfactant is added, and then 300 parts by weight of ion-exchanged water is added, heated to 80 ° C. and heated to a round glass flask. An ultrasonic wave was applied with an ultrasonic disperser (Branson 500, Branson 500). Then, after further adjusting the pH in the system to 7.5 with a 1.3 mol / liter aqueous ammonia solution, if the ultrasonic emulsification is continued, the emulsification gradually proceeds and eventually emulsifies completely. An amorphous resin particle dispersion (A1) having a center diameter of 210 nm and a solid content concentration of 20% by weight was obtained. When this dispersion was dried and analyzed, the weight average molecular weight by GPC was 26,000. The hydrolysis rate was 0.96.

(Example 2)
<Preparation of Amorphous Resin Particle Dispersion (A2)>
1,4-phenylenediacetic acid 240 parts by weight Bisphenol A propylene oxide 2-mole adduct 190 parts by weight Bisphenol A ethylene oxide 2-mole adduct 100 parts by weight 2,2-dimethylolpropionic acid 28 parts by weight p-toluenesulfonic acid 0. 7 parts by weight The above materials were mixed, put into a reactor equipped with a stirrer, and subjected to polycondensation at 120 ° C. for 7 hours in a nitrogen atmosphere. After further 7 hours, 3 parts by weight of trimellitic anhydride was added, and then the temperature was raised to 138 ° C. and polycondensation was carried out for 3 hours to obtain a uniform transparent amorphous polyester. The weight average molecular weight by GPC was 31,800, the glass transition temperature (onset) was 55 ° C., and the resin acid value was 20 mg · KOH / g.

  To 100 parts by weight of this resin, 4 parts by weight of linear soft sodium dodecylbenzenesulfonate was added as a surfactant and heated to 100 ° C. to melt the resin. Furthermore, while gradually adding 300 parts by weight of ion-exchanged water, the mixture was sufficiently mixed and dispersed in a round glass flask with a homogenizer (manufactured by IKA, Ultra Turrax T50). Thereafter, the pH of the system is further adjusted to 7.5 with 0.5 mol / liter of triethanolamine, and then emulsification is continued while stirring with a homogenizer. When the emulsification is continued, the center diameter is 300 nm and the solid content concentration is 20 wt. % Amorphous resin particle dispersion (A2). When this dispersion was dried and analyzed, the weight average molecular weight determined by GPC was 31,000. The hydrolysis rate was 0.97.

(Example 3)
<Preparation of crystalline resin particle dispersion (C1)>
Dodecylbenzenesulfonic acid 0.36 parts by weight 1,9-nonanediol 66 parts by weight Dodecanedioic acid 120 parts by weight Malic acid (2-hydroxybutanedioic acid) 19 parts by weight Mix in a 500 ml flask and use a mantle heater at 130 ° C. After the mixture was melted, the mixture was melted and kept at 80 ° C. for 4 hours while stirring and degassing with a three-one motor to obtain a uniform transparent crystalline polyester with a viscous melt. The weight average molecular weight by GPC was 29,000, the melting point was 70 ° C., and the resin acid value was 16 mg · KOH / g.

  15 parts by weight of styrene was added to 100 parts by weight of this polyester and melted at 100 ° C. An aqueous solution for neutralization, in which 2.0 parts by weight of 1N NaOH solution is dissolved in 650 parts by weight of ion-exchanged water heated to 80 ° C., is added to the resin in the flask and emulsified with a three-one motor for 1 minute. 0.5 parts by weight of potassium sulfate was added, and the reaction was further continued at 90 ° C. for 5 hours to obtain a resin particle dispersion of copolymer resin. The flask was cooled with room temperature water. As a result, a resin particle dispersion (C1) of crystalline polyester having a resin particle center diameter of 180 nm and a solid content concentration of 20% by weight was obtained. When this dispersion was dried and analyzed, the weight average molecular weight of only the polyester portion by GPC was 28,500, and the melting point was 71 ° C. The hydrolysis rate was 0.98.

Example 4
<Preparation of crystalline resin particle dispersion (C2)>
Pentadecylbenzenesulfonic acid 0.9 parts by weight 1,6-hexanediol 71 parts by weight Dodecanedioic acid 120 parts by weight Tartaric acid (2,3-dihydroxybutanedioic acid) 25 parts by weight Mix in a flask and 130 with a mantle heater After the mixture was melted by heating to 150C and stirred with a three-one motor and kept at 115 ° C for 4 hours while degassing, the content was a viscous melt and a uniform transparent crystalline polyester was obtained. The weight average molecular weight by GPC was 28,000, the melting point was 72 ° C., and the resin acid value was 18 mg · KOH / g.

Take 100 parts by weight of this resin and add 550 parts by weight of ion-exchanged water heated to 80 ° C. to a neutralizing aqueous solution in which 2.0 parts by weight of 1N NaOH solution is dissolved in the resin in the flask and emulsify for 1 minute with a three-one motor. Then, the mixture was further emulsified in an ultrasonic bath for 5 minutes, and then the emulsion was maintained at 68 ° C. in the flask while being stirred and held for 1 minute. A resin particle dispersion (C2) was obtained.
As a result, a resin particle dispersion (C2) having a resin particle center diameter of 300 nm, a melting point of 70 ° C., a weight average molecular weight of 26,000, and a solid content concentration of 20 wt% was obtained. The hydrolysis rate was 0.91.

(Comparative Example 1)
<Preparation of Amorphous Resin Particle Dispersion (A3)>
1,4-cyclohexanedicarboxylic acid 200 parts by weight Bisphenol A ethylene oxide 1 mol adduct 210 parts by weight Bisphenol A propylene oxide 1 mol adduct 100 parts by weight Toluenesulfonic acid 0.35 parts by weight The above materials are mixed and provided with a stirring function The reactor was charged and subjected to polycondensation under nitrogen atmosphere at 120 ° C. for 7 hours. From the middle of the polymerization, the viscosity of the resin increased. After 7 hours of polymerization, a viscous resin component having low transparency was obtained. Further, the temperature was raised to 140 ° C. and polymerization was continued for 3 hours to obtain a uniform transparent amorphous polyester. The weight average molecular weight by GPC was 14,000, the glass transition temperature (onset) was 59 ° C., and the resin acid value was 18 mg · KOH / g.

  To 100 parts by weight of this resin, 3 parts by weight of linear sodium dodecylbenzenesulfonate as a surfactant is added, and then 300 parts by weight of ion-exchanged water is added, heated to 80 ° C. and heated to a round glass flask. An ultrasonic wave was applied with an ultrasonic disperser (Branson 500, Branson 500). Then, after further adjusting the pH in the system to 7.5 with an aqueous 1.3 mol / liter ammonia solution, if the ultrasonic emulsification is continued, the emulsification gradually proceeds. A poorly emulsified product remained at the bottom of the bottom flask. When the emulsified liquid portion was taken and analyzed, an amorphous resin particle dispersion (A3) having a center diameter of 500 nm was obtained. When this dispersion was dried and analyzed, the weight average molecular weight determined by GPC was 8,000, and the glass transition temperature (onset) was 58 ° C. The hydrolysis rate was 0.57.

(Comparative Example 2)
<Preparation of Amorphous Resin Particle Dispersion (A4)>
Dimethyl terephthalate 130 parts by weight Bisphenol A ethylene oxide 2-mole adduct 210 parts by weight Bisphenol A propylene oxide 2-mole adduct 100 parts by weight Tartaric acid 12 parts by weight Dibutyltin oxide 0.35 parts by weight The above materials were mixed and provided with a stirring function The reactor was charged and polycondensation was carried out at 180 ° C. for 7 hours under a nitrogen atmosphere. From the middle of the polymerization, the viscosity of the resin increased. After 7 hours of polymerization, a viscous resin component having low transparency was obtained. After further 7 hours, the temperature was raised to 220 ° C. and polycondensation was carried out for 3 hours. As a result, an opaque polyester was obtained. Although an insoluble substance was observed in THF, the THF-dissolved substance had a weight average molecular weight by GPC of 120,000, and a glass transition temperature (onset) having a broad peak at 63 ° C. The resin acid value was 21 mg · KOH / g.

  To 100 parts by weight of this resin, 5 parts by weight of linear sodium dodecylbenzenesulfonate as a surfactant is added, and then 300 parts by weight of ion-exchanged water is added, heated to 90 ° C., and heated to a round glass flask. The mixture was thoroughly mixed and dispersed with a homogenizer (manufactured by IKA, Ultra Tarrax T50). Thereafter, the pH of the system was further adjusted to 7.5 with a 0.5 mol / liter sodium hydroxide aqueous solution, and then heated to 95 ° C. while stirring with a homogenizer was continued. The resulting emulsion was gradually gel-like, and the resulting emulsion was not uniform. The resin particle dispersion had a center diameter of 3,400 nm and precipitates were observed in the emulsion. When this dispersion was dried and analyzed, the weight average molecular weight by GPC was 20,000. The hydrolysis rate was 0.17. The solid content was adjusted to 20% to obtain an amorphous resin particle dispersion (A4).

(Comparative Example 3)
<Preparation of crystalline resin particle dispersion (C3)>
Benzenesulfonic acid 0.6 parts by weight 1,6-hexanediol 100 parts by weight Dodecanedioic acid 120 parts by weight SDS (sodium isophthalic acid-5-sulfonate) 20 parts by weight The above materials were mixed in a reactor equipped with a stirrer. Then, polycondensation was carried out for 7 hours at 120 ° C. in a nitrogen atmosphere, whereby a uniform transparent crystalline polyester was obtained. The weight average molecular weight by GPC was 23,000, the melting point was 68 ° C., and the resin acid value was 55 mg · KOH / g.

  To 100 parts by weight of this resin, 0.5 parts by weight of linear sodium dodecylbenzenesulfonate as a surfactant is added, and 300 parts by weight of ion-exchanged water is further added. The mixture was thoroughly mixed and dispersed in a flask made with a homogenizer (IKA, Ultra Turrax T50). Thereafter, the pH of the system was further adjusted to 7.5 with a 0.5 mol / liter sodium hydroxide aqueous solution, and then heated to 95 ° C. while stirring with a homogenizer was continued. An amorphous resin particle dispersion (C3) having a resin particle central diameter of 110 nm and a solid content of 20% was obtained. When this dispersion was dried and analyzed, the weight average molecular weight by GPC was 11,000. The hydrolysis rate was 0.49. The solid content concentration was adjusted to 20% by weight to obtain a crystalline resin particle dispersion (C3).

(Comparative Example 4)
<Preparation of crystalline resin particle dispersion (C4)>
10-camphorsulfonic acid 0.9 parts by weight 1,6-hexanediol 100 parts by weight Sebacic acid 120 parts by weight Cyclohexanedimethanol 20 parts by weight The above materials were mixed and charged into a reactor equipped with a stirrer. When polycondensation was carried out at 7 ° C. for 7 hours, a uniform transparent crystalline polyester was obtained. The weight average molecular weight by GPC was 19,000, the melting point was 70 ° C., and the resin acid value was 51 mg · KOH / g.
To 100 parts by weight of this resin, 0.5 parts by weight of linear sodium dodecylbenzenesulfonate as a surfactant is added, and 300 parts by weight of ion-exchanged water is further added. The mixture was thoroughly mixed and dispersed in a flask made with a homogenizer (IKA, Ultra Turrax T50). Thereafter, the pH of the system was further adjusted to 7.5 with a 0.5 mol / liter sodium hydroxide aqueous solution, and then heated to 95 ° C. while stirring with a homogenizer was continued. A crystalline resin particle dispersion (C4) having a resin particle central diameter of 90 nm and a solid content of 20% was obtained. When this dispersion was dried and analyzed, the weight average molecular weight by GPC was 11000. The hydrolysis rate was 0.58. The solid content concentration was adjusted to 20% by weight to obtain a crystalline resin particle dispersion (C4).

  The physical property values of the obtained resin particle dispersions are shown in Table 1 below.

<Preparation of release agent particle dispersion (W1)>
30 parts by weight of dodecyl sulfate, 852 parts by weight of ion-exchanged water, 188 parts by weight of palmitic acid, 25 parts by weight of pentaerythritol, mixed with palmitic acid and pentaerythritol as mold release agents at 250 ° C. and melted, And then emulsified for 5 minutes with a homogenizer (IKA Corporation, Ultra Tarrax), and further emulsified in an ultrasonic bath for 5 minutes. After stirring, the emulsion was maintained at 70 ° C. in a flask and held for 15 hours. . As a result, a release agent particle dispersion (W1) having a resin particle central diameter of 310 nm, a melting point of 72 ° C., and a solid content concentration of 20 wt% was obtained.

<Preparation of release agent particle dispersion (W2)>
Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd., Neogen R) 2 parts by weight Ion-exchanged water 800 parts by weight Carnauba wax 200 parts by weight were mixed, heated to 100 ° C and melted, and then homogenizer (manufactured by IKA) Then, emulsification was carried out at 100 ° C. using a gorin homogenizer. As a result, a release agent particle dispersion (W2) having a resin particle central diameter of 250 nm, a melting point of 83 ° C., and a solid content concentration of 20 wt% was obtained.

<Preparation of Colorant Particle Dispersion (P1)>
Cyan pigment (Daiichi Seika Kogyo Co., Ltd., CI Pigment Blue 15: 3)
50 parts by weight Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd., Neogen R) 5 parts by weight Ion-exchanged water 200 parts by weight The above components are mixed and dissolved, and a homogenizer (manufactured by IKA, Ultra Turrax) for 5 minutes. Dispersion was carried out with an ultrasonic bath for 10 minutes to obtain a cyan colorant particle dispersion (P1) having a center diameter of 190 nm and a solid content concentration of 21.5% by weight.

(Toner Example 1)
<Preparation of toner particles>
Amorphous resin particle dispersion (A1) 210 parts by weight (42 parts by weight of resin)
Colorant particle dispersion (P1) 40 parts by weight (8.6 parts by weight of pigment)
Release agent particle dispersion (W1) 40 parts by weight (release agent 8.6 parts by weight)
Polyaluminum chloride 0.15 parts by weight Deionized water 300 parts by weight The above components were thoroughly mixed and dispersed in a round stainless steel flask with a homogenizer (IKA, Ultra Tarrax T50), and then heated in an oil bath for heating. The mixture was heated to 42 ° C. with stirring and maintained at 42 ° C. for 60 minutes, and then 50 parts by weight (21 parts by weight of the resin) of the amorphous resin particle dispersion (A1) was added and gently stirred.
Thereafter, the pH in the system was adjusted to 6.0 with a 0.5 mol / liter aqueous sodium hydroxide solution, and then heated to 80 ° C. while continuing stirring.
During the temperature rise to 80 ° C., the pH in the system usually drops to 5.0 or less, but here, an aqueous sodium hydroxide solution is added dropwise to keep the pH from dropping to 5.5 or less. did. After completion of the reaction, the reaction mixture was cooled to 55 ° C., kept at this temperature for 3 hours, and then cooled again to room temperature. Further, after filtration and sufficient washing with ion exchange water, solid-liquid separation was performed by Nutsche suction filtration. And it re-dispersed in 3 liters of ion-exchanged water at 40 ° C., and stirred and washed at 300 rpm for 15 minutes. This washing operation was repeated 5 times, followed by solid-liquid separation by Nutsche suction filtration and then vacuum drying for 12 hours to obtain toner particles (toner 1).
When the particle size of the toner particles was measured with a Coulter counter, the cumulative volume average particle size D50 was 5.0 μm, and the volume average particle size distribution index GSDv was 1.19. The shape factor SF1 of the toner particles obtained from the shape observation with Luzex was a potato shape of 139.

<Preparation of external toner>
Silica (SiO 2) particles having an average particle diameter of 40 nm and surface hydrophobized with hexamethyldisilazane (hereinafter sometimes abbreviated as “HMDS”), a primary product that is a reaction product of metatitanic acid and isobutyltrimethoxysilane 1 wt% of metatitanic acid compound particles having an average particle diameter of 20 nm were added and mixed with a Henschel mixer to prepare a cyan externally added toner.

<Creation of carrier>
A methanol solution containing 0.1 part by weight of γ-aminopropyltriethoxysilane was added to 100 parts by weight of Cu—Zn ferrite particles having a volume average particle diameter of 40 μm and coated with a kneader. The silane compound was completely cured by heating at 0 ° C. for 2 hours. To this particle, a perfluorooctylethyl methacrylate-methyl methacrylate copolymer (copolymerization ratio 40:60) dissolved in toluene was added, and perfluorooctylethyl methacrylate-methyl was added using a vacuum reduced pressure kneader. A resin-coated carrier was produced so that the coating amount of the methacrylate copolymer was 0.5% by weight.

<Production of developer>
5 parts by weight of each toner prepared as described above was mixed with 100 parts by weight of the obtained resin-coated carrier for 20 minutes in a V blender to prepare an electrostatic charge image developer. This was used as a developer in the following evaluation.

(Toner Example 2)
Similarly to the toner used in Example 1, toner 2 was prepared using the resin particle dispersion (A2) shown in Table 2, and a developer was prepared in the same manner as in Example 1.

(Toner Example 3)
Similarly to the toner used in Example 1, toner 3 was prepared using the resin particle dispersions (A1) and (C1) shown in Table 2, and a developer was prepared in the same manner as in Example 1. The mixing ratio of the resin particle dispersion (A1) and (C1) is shown below.
Amorphous resin particle dispersion (A1) 210 parts by weight (42 parts by weight of resin)
Crystalline resin particle dispersion (C1) 50 parts by weight (21 parts by weight of resin)
Colorant particle dispersion (P1) 40 parts by weight (8.6 parts by weight of pigment)
Release agent particle dispersion (W1) 40 parts by weight (release agent 8.6 parts by weight)
Polyaluminum chloride 0.15 parts by weight Deionized water 300 parts by weight The production method was carried out in the same manner as in Example 1, and the results shown in Table 2 below were obtained.

(Toner Example 4)
Similarly to the toner used in Example 3, toner 4 was prepared using the resin particle dispersions (A1) and (C2) shown in Table 2, and a developer was prepared in the same manner as in Example 1. The mixing ratio of the resin particle dispersions (A1) and (C2) was the same as in Example 3, and the production method was also the same.

(Toner Comparative Example 1)
A toner 5 was prepared in the same manner as in Example 1 except that the resin particle dispersion (A1) was replaced with (A3), and a developer was further prepared in the same manner as in Example 1.

(Toner Comparative Example 2)
A toner 6 was prepared in the same manner as in Example 1 except that the resin particle dispersion (A1) was replaced with (A4), and a developer was further prepared in the same manner as in Example 1.

(Toner Comparative Example 3)
A toner 7 was prepared in the same manner as in Example 1 except that the resin particle dispersion (A1) was replaced with (C3), and a developer was further prepared in the same manner as in Example 1.

(Toner Comparative Example 4)
A toner 8 was produced in the same manner as in Example 1 except that the resin particle dispersion (A1) was replaced with (C4), and a developer was produced in the same manner as in Example 1.

<Evaluation criteria for electrification under high temperature and high humidity>
The charge amount of the developer under high temperature and high humidity was measured by the following method.
The prepared developer was allowed to stand for 20 hours in a high-temperature and high-humidity environment at 30 ° C. and 80%, and the amount of reverse polarity toner was measured with a toner charge distribution measuring device (Espert Analyzer: manufactured by Hosokawa Micron).
The evaluation criteria are as follows.
A: The amount of reverse polarity toner is less than 5%.
Δ: The amount of the reverse polarity toner is 5% or more and less than 10%.
X: The amount of reverse polarity toner is 10% or less.
○ was accepted.

<Image storability>
Image storability was evaluated by the following method.
In a modified machine of DocuCenterColor500 manufactured by Fuji Xerox Co., Ltd., J-coated paper manufactured by Fuji Xerox Co., Ltd. was used as transfer paper, the process speed was adjusted to 180 mm / sec, the fixing roll temperature was set to 135 ° C., and a fixed image was created. Next, the two fixed images were bonded to each other between the image portions, a load of 50 g / cm ² was applied, the sample was left in an environment of 28 ° C. and 90% RH for 5 days, and the image after peeling was evaluated. The evaluation of the fixed image storage property of the toner is as follows.
A: There are almost no defects in the image.
Δ: Some image defects are observed.
X: Significant image defects are observed.
○ was accepted.

<Initial image quality evaluation>
In a modified machine of DocuCenterColor500 manufactured by Fuji Xerox Co., Ltd., J-coated paper manufactured by Fuji Xerox Co., Ltd. was used as transfer paper, the process speed was adjusted to 180 mm / sec, the fixing roll temperature was set to 135 ° C., and a fixed image was created.
Images were formed under the above conditions, and the initial image quality was evaluated according to the following criteria.
○: Image density, background stain, and fine line reproducibility are extremely good (no image defects)
Δ: Slightly inferior in image density, background stain, fine line reproducibility, but no problem in use (slight image defects)
×: Inferior in image density, background stain, or fine line reproducibility (with image defects)
○ was accepted.

<Image quality evaluation criteria under high temperature and high humidity (Long-term image quality maintenance evaluation under high temperature and high humidity)>
In the modified machine, a continuous print test of 50,000 sheets was performed under the conditions of 30 ° C. and 80% high temperature and high humidity.
Images were formed under the above conditions, and the image quality was evaluated according to the following criteria.
○: Good image quality maintenance and no filming on the photoreceptor.
Δ: Image quality maintenance is good in the range of continuous printing of 50,000 sheets. However, slight filming on the photoreceptor is observed.
×: Image quality deterioration is observed. In addition, filming on the photoconductor is also observed.

<Evaluation of toner>
Using the developer described above, Fuji Xerox J Co-coated paper was used as a transfer sheet in a modified DocuCenterColor 500 manufactured by Fuji Xerox Co., and the process speed was adjusted to 180 mm / sec.
The oil-less fixability by the PFA tube fixing roll was good, the fixing temperature (this temperature was determined by image rubbing by image rubbing and rubbing of the image) was 120 ° C. or more, and the image showed sufficient fixability. Both developability and transferability were good, and there was no image defect and high quality and good initial image quality (◯) were exhibited.

  In the above modified machine, a continuous print test of 50,000 sheets was performed under conditions of 30 ° C. and 80% high temperature and high humidity, but the initial good image quality was maintained until the end, and filming on the photoconductor occurred. (Image quality evaluation under high temperature and high humidity: ○).

  For the toner examples 2 to 4 and the toner comparative examples 1 to 4, the toner was evaluated in the same manner as the toner example 1. The evaluation results are shown in Table 2 below.

Claims (10)

(A) containing 10 to 80 mol% of a polyvalent carboxylic acid monomer and / or a derivative thereof in the total polycondensable monomer,
(B) 10-80 mol% of polyhydric alcohol monomer in the total polycondensable monomer,
(C) containing at least one monomer selected from the group consisting of compounds represented by formulas (1) to (3) in an amount of 0.5 to 40 mol% in the total polycondensable monomer,
A resin particle dispersion, wherein resin particles containing polyester and sulfur acid obtained by polycondensation of a polycondensable monomer having a composition are dispersed in an aqueous medium.

(R ^{1 to} R ⁴ each independently represents a hydrogen atom or an alkyl group.)   The resin particle dispersion according to claim 1, wherein the resin particles do not contain a metal element, or the content of the metal element in the resin particles is 100 ppm or less.   The resin particle dispersion according to claim 1, wherein the polyester has an acid value of 5 to 50 mg · KOH / g. (A) containing 10 to 80 mol% of a polyvalent carboxylic acid monomer and / or a derivative thereof in the total polycondensable monomer,
(B) 10-80 mol% of polyhydric alcohol monomer in the total polycondensable monomer,
(C) containing at least one monomer selected from the group consisting of compounds represented by formulas (1) to (3) in an amount of 0.5 to 40 mol% in the total polycondensable monomer,
A step of polycondensing a polycondensable monomer comprising a composition in the presence of a sulfur acid to obtain a polyester, and
The method for producing a resin particle dispersion according to any one of claims 1 to 3, comprising a step of neutralizing the polyester with a basic substance and dispersing the polyester in an aqueous medium.

(R ^{1 to} R ⁴ each independently represents a hydrogen atom or an alkyl group.)   The method for producing a resin particle dispersion according to claim 4, wherein the polycondensable monomer is polycondensed at a temperature of 150 ° C. or lower. A step of aggregating the resin particles in a dispersion containing at least a resin particle dispersion to obtain aggregated particles; and
A method for producing an electrostatic image developing toner comprising a step of heating and coalescing the aggregated particles,
The method for producing an electrostatic charge image developing toner, wherein the resin particle dispersion is the resin particle dispersion according to claim 1. An electrostatic image developing toner produced by the production method according to claim 6.   An electrostatic charge image developer comprising the electrostatic charge image developing toner according to claim 7 and a carrier. A latent image forming step for 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 member 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 holding member to the surface of the transfer target; and
An image forming method comprising a fixing step of fixing the toner image transferred to the surface of the transfer material,
An image forming method using the electrostatic image developing toner according to claim 7 as the toner, or the electrostatic image developer according to claim 8 as the developer. At least latent image forming means for forming an electrostatic latent image on the surface of the electrostatic latent image holding member;
Developing means for visualizing the formed electrostatic latent image with an electrostatic charge image developer accommodated in a developing device to form a toner image on the surface of the electrostatic latent image holding body; and
Transfer means for transferring the formed toner image to the surface of the transfer target;
An image forming apparatus having
The image forming apparatus according to claim 8, wherein the electrostatic image developer is the electrostatic image developer according to claim 8.