JP4591332B2 - Binder resin production method, resin particle dispersion and production method thereof, electrostatic image developing toner and production method thereof, electrostatic charge image developer, and image forming method - Google Patents

Description

  The present invention relates to a binder resin suitably used when developing an electrostatic latent image formed by an electrophotographic method or an electrostatic recording method with a developer. Furthermore, the present invention relates to a resin particle dispersion produced from the binder resin, and an electrostatic charge image developing toner produced using the resin particle dispersion. The present invention also relates to an electrostatic charge image developer using the electrostatic charge image developing toner and an image forming method.

  In recent years, due to the rapid spread of digitization technology, high image quality is required for output such as printing and copying for users in general households, offices, and publishing areas. There is a growing demand for low energy and energy savings for corporate activities and products resulting from these activities. Therefore, in the image forming method such as the electrophotographic method or the electrostatic recording method, the energy saving of the fixing process that consumes a lot of energy and the low environmental load activity of the process of manufacturing the product using the material are performed. It is necessary. Measures corresponding to the former include measures such as lowering the toner fixing temperature. By lowering the toner fixing temperature, in addition to saving power, it is possible to shorten the waiting time until the fixing temperature on the surface of the fixing member when power is input, the so-called warm-up time, and the life of the fixing member. is there.

  Conventionally, vinyl polymers have been widely used as binder resins for toners, but high molecular weight vinyl polymers have a high softening point, so that a fixed image having excellent glossiness can be obtained. It is necessary to set the temperature of the heat roller high, which goes against energy saving.

  On the other hand, when the polyester resin has a rigid aromatic ring in the chain, it has flexibility as compared with the vinyl polymer, and the molecular weight when the mechanical strength is the same can be set low. Furthermore, polyester is often used as a binder resin for energy-saving toner because it has the advantage of being easier to design as a low-temperature fixing resin than a vinyl binder resin in terms of molecular chain entanglement, limiting molecular weight, and the like.

  In general, the polycondensation method of polyester requires a reaction that takes 10 hours or more under stirring at high temperature exceeding 200 ° C. under high power and under high vacuum, resulting in a large amount of energy consumption. For this reason, enormous capital investment is often required to obtain durability of the reaction equipment.

  Recently, however, studies on methods for producing polyester resins at low temperatures have been reported. For example, Patent Document 1 reports a method for producing a polyester using an enzyme as a catalyst, and Patent Document 2 reports a polyester synthesis at 160 to 200 ° C. using a scandium triflate catalyst.

  The polycondensation catalyst generally has an effect of promoting an ester synthesis reaction by forming an intermediate between the catalyst and the monomer during the reaction and lowering the activation energy. The Bronsted acid type catalyst is determined by a balance between a catalytic acid and a lipophilic hydrophobic group. In other words, the acidity controls the direct catalytic ability, and the hydrophobic group controls the compatibility with the monomer, the oligomer to be formed, and the polymer and affects the progress of the reaction.

  Conventionally, as in the example shown below, a Bronsted acid catalyst has been used for polycondensation, but the structure of the catalyst and the invention of using a Bronsted acid catalyst having a plurality of specific structures It was not reported.

  For example, Patent Documents 3 and 4 describe an underwater dehydration reaction method and a polycondensation method characterized by performing a dehydration reaction in water in the presence of a surfactant-type catalyst. However, it does not mention the structure or combination of substances that can be used as a catalyst.

Patent Document 5 discloses R—COOH (C1-4 linear hydrocarbyl group) and R′—OH (C2-5 alkali group) as R ″ —C ₆ H ₅ —SO ₃ H alkylbenzenesulfone. An ester production process is described in which an esterification catalyst having an acid structure (R ″: C8-20) is reacted in an anhydrous reaction medium. However, although the structure of R ″ is linear or branched, no mechanism for use or use thereof is mentioned, and no application to polycondensation is described.

  Also, the Bronsted acid catalyst tended to reduce the reactivity when present in a large amount. This property was particularly remarkable in Bronsted acid having a long-chain linear fatty acid called a soft type. That is, when an amount of catalyst exceeding an appropriate amount of catalyst is used, a phenomenon occurs in which the reactivity rapidly decreases and the molecular weight does not increase. When such an appropriate amount of use is limited and a slight change in the catalyst amount affects the progress of the reaction, assuming large-scale continuous production, the difference in physical properties between batches, Precise process design and management are required, which can cause productivity to drop.

Japanese Patent Laid-Open No. 11-313692 JP 2003-306535 A JP 2002-55302 A JP 2003-26162 A Japanese Patent Laid-Open No. 5-194318

An object of the present invention is to provide a binder resin composed of a polycondensation resin stably, a resin particle dispersion using the same, and a method for producing the same, by reducing the variation in reactivity caused by the amount of catalyst.
Another object of the present invention is to provide an electrostatic image developing toner sufficiently satisfying the toner characteristics, a method for producing the same, an electrostatic image developer, and an image forming method using them. That is.

The above problems have been solved by means <1> to <5> shown below.
<1> A method for producing a binder resin comprising a step of polycondensing a polycondensable monomer using a polycondensation catalyst, wherein the polycondensation catalyst is represented by the following formula (I) or (II): And at least one of the compounds represented by the following formula (III) or (IV), the total amount of the compound represented by the following formula (I) or (II) and A method for producing a binder resin, wherein the weight ratio of the compound represented by formula (III) or (IV) to the total amount used is 5:95 to 95: 5;

（式（I）中、Ｒ¹は炭素数８〜２０の直鎖アルキル基を表し、Ｒ²は一価の有機基を表し、また、Ｒ²の置換基数ｎは０〜４の整数を表す。）

(In formula (I), R ¹ represents a linear alkyl group having 8 to 20 carbon atoms, R ² represents a monovalent organic group, and the number n of substituents of R ² represents an integer of 0 to 4. .)

（式（II）中、Ｒ³は炭素数８〜２０の直鎖アルキル基を表す。）

(In the formula (II), R ³ represents a linear alkyl group having 8 to 20 carbon atoms.)

（式（III）中、Ｒ⁴は炭素数８〜２０の分岐型アルキル基を表し、Ｒ⁵は一価の有機基を表し、また、Ｒ⁵の置換基数ｍは０〜４の整数を表す。）

(In the formula (III), R ⁴ represents a branched alkyl group having 8 to 20 carbon atoms, R ⁵ represents a monovalent organic group, and the number m of substituents in R ⁵ represents an integer of 0 to 4. .)

（式（IV）中、Ｒ⁶は炭素数８〜２０の分岐型アルキル基を表す。）
＜２＞ 少なくとも結着樹脂を含む樹脂粒子が分散媒に分散している樹脂粒子分散液であって、前記結着樹脂が、上記＜１＞に記載の製造方法により製造された結着樹脂を含む樹脂粒子分散液、
＜３＞ 少なくとも重縮合性単量体を含む油相が水系媒体中に乳化分散された乳化分散液を調製する工程、及び、重縮合性単量体を前記重縮合触媒を用いて水系媒体中で重縮合する工程を含む上記＜２＞に記載の樹脂粒子分散液の製造方法、
＜４＞ 少なくとも樹脂粒子分散液を含む分散液中で該樹脂粒子を凝集して凝集粒子を得る工程、及び、該凝集粒子を加熱して融合させる工程を含む静電荷像現像トナーの製造方法であって、前記樹脂粒子分散液が、上記＜２＞に記載の樹脂粒子分散液、又は、上記＜３＞に記載の製造方法により製造された樹脂粒子分散液である静電荷像現像トナーの製造方法、
＜５＞ 上記＜４＞に記載の製造方法により製造された静電荷像現像トナー、
＜６＞ 上記＜５＞に記載の静電荷像現像トナーとキャリアとを含む静電荷像現像剤、
＜７＞ 潜像保持体表面に静電潜像を形成する潜像形成工程、前記潜像保持体表面に形成された静電潜像をトナーを含む現像剤により現像してトナー像を形成する現像工程、前記潜像保持体表面に形成されたトナー像を被転写体表面に転写する転写工程、及び、前記被転写体表面に転写されたトナー像を熱定着する定着工程を含む画像形成方法であって、前記トナーとして上記＜５＞に記載の静電荷像現像トナー、又は、前記現像剤として上記＜６＞に記載の静電荷像現像剤を用いる画像形成方法。

(In formula (IV), R ⁶ represents a branched alkyl group having 8 to 20 carbon atoms.)
<2> A resin particle dispersion in which resin particles containing at least a binder resin are dispersed in a dispersion medium, wherein the binder resin is a binder resin produced by the production method according to the above <1>. Containing resin particle dispersion,
<3> a step of preparing an emulsified dispersion in which an oil phase containing at least a polycondensable monomer is emulsified and dispersed in an aqueous medium; and the polycondensable monomer in the aqueous medium using the polycondensation catalyst. A process for producing a resin particle dispersion according to the above <2>, comprising a step of polycondensation with
<4> 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 aggregating the aggregated particles Production of an electrostatic charge image developing toner, wherein the resin particle dispersion is the resin particle dispersion according to <2> or the resin particle dispersion produced by the production method according to <3>. Method,
<5> An electrostatic image developing toner produced by the production method according to <4> above,
<6> An electrostatic charge image developer comprising the electrostatic charge image developing toner according to <5> and a carrier,
<7> A latent image forming step of 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 transferring step for transferring the toner image formed on the surface of the latent image holding member to the surface of the transfer target, and a fixing step for thermally fixing the toner image transferred to the surface of the transfer target An image forming method using the electrostatic image developing toner according to <5> as the toner or the electrostatic image developer according to <6> as the developer.

  According to the present invention, it is possible to produce a binder resin made of a polycondensation resin in a stable manner by reducing the variation in reactivity due to the amount of catalyst. Further, according to the present invention, the resin particle dispersion produced from the binder resin can achieve both good dispersibility and molecular weight. Furthermore, according to the present invention, the toner produced from this resin particle dispersion has high fluidity, hardly causes soft blocking, and can improve heat storage properties.

The method for producing a binder resin of the present invention is a method for producing a binder resin including a step of polycondensing a polycondensable monomer using a polycondensation catalyst (hereinafter also referred to as “polycondensation step”). As the polycondensation catalyst, at least one of the compounds represented by the formula (I) or (II) (hereinafter also referred to as “linear polycondensation catalyst”), and the formula (III) or Using at least one of the compounds represented by (IV) (hereinafter also referred to as “branched polycondensation catalyst”), the total amount of the compound represented by the formula (I) or (II) and the formula The weight ratio with respect to the total amount of the compound represented by (III) or (IV) is 5:95 to 95: 5.
Hereinafter, the present invention will be described in detail.

(Binder resin production method)
[Polycondensation step]
The method for producing the binder resin of the present invention includes a step of polycondensing a polycondensable monomer using the following polycondensation catalyst.
Further, the binder resin produced by the method for producing a binder resin of the present invention can be suitably used as a binder resin for an electrostatic charge image developing toner.

<Polycondensation catalyst>
In the method for producing a binder resin for an electrostatic charge image developing toner of the present invention, in the polycondensation step, as the polycondensation catalyst, at least one of the compounds represented by formula (I) or (II) and formula (III) ) Or (IV) is used.

（式（I）中、Ｒ¹は炭素数８〜２０の直鎖アルキル基を表し、Ｒ²は一価の有機基を表し、また、Ｒ²の置換基数ｎは０〜４の整数を表す。）

(In formula (I), R ¹ represents a linear alkyl group having 8 to 20 carbon atoms, R ² represents a monovalent organic group, and the number n of substituents of R ² represents an integer of 0 to 4. .)

（式（II）中、Ｒ³は炭素数８〜２０の直鎖アルキル基を表す。）

(In the formula (II), R ³ represents a linear alkyl group having 8 to 20 carbon atoms.)

（式（III）中、Ｒ⁴は炭素数８〜２０の分岐型アルキル基を表し、Ｒ⁵は一価の有機基を表し、また、Ｒ⁵の置換基数ｍは０〜４の整数を表す。）

(In the formula (III), R ⁴ represents a branched alkyl group having 8 to 20 carbon atoms, R ⁵ represents a monovalent organic group, and the number m of substituents in R ⁵ represents an integer of 0 to 4. .)

（式（IV）中、Ｒ⁶は炭素数８〜２０の分岐型アルキル基を表す。）

(In formula (IV), R ⁶ represents a branched alkyl group having 8 to 20 carbon atoms.)

The amount of the polymerizable catalyst used in the polycondensation step is the total amount Wa of the compound represented by the formula (I) or (II) and the total amount of the compound represented by the following formula (III) or (IV). The weight ratio with the use amount Wb is Wa: Wb = 5: 95 to 95: 5, preferably Wa: Wb = 15: 85 to 85:15, and Wa: Wb = 40: 60 to 85:15. It is more preferable that The above range is preferable because both the reactivity of the linear catalyst and the characteristics of the branched catalyst can be sufficiently exhibited, and fluctuations in the reactivity with respect to the amount of the catalyst can be suppressed.
Two or more compounds represented by formula (I) or (II) may be used, and two or more compounds represented by formula (III) or (IV) may also be used.

The method for producing a binder resin according to the present invention uses two types of acid catalysts, that is, a combination of a linear polycondensation catalyst and a branched polycondensation catalyst, to reduce reactivity associated with variations in the amount of catalyst. Can be suppressed. This is because, for example, a large amount of catalyst was present because the catalyst having a branched fatty chain structure used together with an acid catalyst having a linear fatty chain having a high catalytic ability is entangled and compatible with the polycondensate. In some cases, the reverse reaction is suppressed to promote polycondensation and promote dehydration. On the other hand, when a large amount of a catalyst having a linear fatty chain is present, the degree of polymerization and the viscosity increase at a stretch. However, because of the linear chain, it tends to be in a state of little entanglement, and it is considered that the reactivity is lowered. By combining the characteristics of the branched acid catalyst and the high reactivity of the linear acid catalyst, fluctuations in the reactivity with respect to the catalyst amount can be suppressed. This property can be preferably applied to, for example, increasing the amount of Bronsted acid catalyst having a surface activity as shown in the above formulas (I) to (IV) for the purpose of enhancing emulsifying properties, or in water polycondensation. Moreover, since the manufacturing method of the binder resin of this invention suppresses the fall of the reactivity accompanying the fluctuation | variation of a catalyst amount, it can apply preferably also to manufacture of a binder resin by a continuous production system.
A toner prepared using a binder resin prepared by balancing such a linear polycondensation catalyst and a branched polycondensation catalyst has a good dispersion of the catalyst in the resin, so that the latex particles are uniform. Sexuality can be increased. Such a toner can achieve uneven distribution of the composition and homogenization of the toner at the time of emulsification / toner production, and in particular, thermal aggregation and blocking due to a low molecular weight component and a low polymerization degree component can be suppressed.

R ¹ in Formula (I) and R ³ in Formula (II) are linear alkyl groups having 8 to 20 carbon atoms, preferably 10 to 20 carbon atoms, more preferably 12 to 20 carbon atoms, You may have a substituent chosen from a substituent group mentioned below.
R ⁴ in formula (III) and R ⁶ in formula (IV) are alkyl groups having 8 to 20 carbon atoms, preferably 10 to 20 carbon atoms, more preferably 12 to 20 carbon atoms. Preferably, it may have a substituent selected from the substituent group described later. The “linear alkyl group” in the present invention is an n-alkyl group having no branch, and the “alkyl group having a branch” is an alkyl group having one or more branches. It is. The branch of the branched alkyl group may be any structure such as a comb structure generally called a hard structure, a normal bifurcated structure, or a ring structure in which two or more branched structures are combined.

In the structures of the formulas (I) to (IV), when the carbon number of R ¹ , R ³ , R ⁴ or R ⁶ is smaller than the stated value, the polycondensation does not progress so much and the molecular weight does not increase. An influence such as broadening of the molecular weight distribution may appear due to the residual molecular weight component. Expansion of molecular weight distribution due to low molecular weight component due to low molecular weight or large amount of low molecular weight component is likely to cause offset when it is made into toner, and deteriorates powder fluidity of toner, heat storage property, grindability, etc. May occur.
On the other hand, when the carbon number of R ¹ , R ³ , R ⁴ or R ⁶ is larger than the stated value, stable production of the catalyst is industrially difficult, and at the same time, the solubility is low, so the catalyst capacity May not be fully utilized.

Further, the carbon number of R ¹ , R ³ , R ⁴ or R ⁶ in the catalyst of the present invention may have a distribution. For example, in the catalyst having the structure of the formula (I), 70 weight of the catalyst It is sufficient that the carbon number of R ^{1 as} a main component occupying at least ¹⁵ % is 13 to 20, and a catalyst having a carbon number of R ¹ of 12 or less may be included in the distribution of catalyst components. It is a known fact in industrial products to have such a distribution, and as an industrially acceptable purity, the main component is 70% by weight or more, preferably 80% by weight or more, more preferably 90% by weight or more. Used properly. These separation and quantification can be performed by, for example, high performance liquid chromatography.

R ¹ , R ³ , R ⁴ and R ⁶ may have a substituent selected from the following substituent group, and the substituent may have two or more. In addition, if possible, the substituent may be further substituted with a substituent selected from the following substituent group. Two or more substituents may be bonded to form a ring. The substituent includes a branched structure of an alkyl group as described above. R ¹ , R ³ , R ⁴ and R ⁶ preferably have no substituent other than an alkyl group.
(Substituent group)
Halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), hydrocarbon group (alkyl group, alkenyl group, alkynyl group, aryl group, hydrocarbon ring group), heterocyclic group, alkoxy group, aryloxy group, alkoxycarbonyl Group, acyloxy group, acyl group, carbamoyl group, mono- or disubstituted carbamoyl group, cyano group, perhalogenoalkyl group, thiocyanato group, sulfamoyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, nitro Group, acylamino group, N-substituted acylamino group, sulfonylamino group, N-substituted sulfonylamino group, amide group, N-monosubstituted or disubstituted amide group, sulfonamido group, N-monosubstituted or disubstituted sulfonamido group, Alkylsulfinyl group An arylsulfinyl group, an alkylsulfonyl group, an aryl sulfonyl group.

The sulfo group (—SO ₃ H) in the formula (I) or the formula (III) may be any position on the benzene ring other than the position to which R ¹ or R ⁴ is bonded (R ¹ or R on the benzene ring). ^When the bonding position of ⁴ is the 1st position, the bonding is performed at any of positions 2-6.

R ² and R ⁵ are monovalent organic groups such as halogen atoms (fluorine atoms, chlorine atoms, bromine atoms, iodine atoms), hydrocarbon groups (alkyl groups, alkenyl groups, alkynyl groups, aryl groups, carbonized groups). Hydrogen ring group), heterocyclic group, alkoxy group, aryloxy group, alkoxycarbonyl group, acyloxy group, acyl group, carbamoyl group, mono- or disubstituted carbamoyl group, cyano group, thiocyanato group, sulfamoyl group, alkylsulfinyl group, aryl Sulfinyl group, alkylsulfonyl group, arylsulfonyl group, nitro group, acylamino group, N-substituted acylamino group, sulfonylamino group, N-substituted sulfonylamino group, amide group, N-monosubstituted or disubstituted amide group, sulfonamide group N-monosubstituted or disubstituted sulfonamido groups, etc. I can get lost. Further, these monovalent organic groups may be further substituted with a monovalent organic group selected from the above, if possible. When it has a substituent, the substituent is preferably electron withdrawing. (If necessary), for example, halogen atom, alkoxycarbonyl group, acyloxy group, acyl group, carbamoyl group, mono- or disubstituted carbamoyl group, cyano group, perhalogenoalkyl group, thiocyanato group, sulfamoyl group, alkylsulfinyl group, Arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, nitro group, alkynyl group, aryloxy group (m-position only) and the like can be mentioned.
The number n of substituents of R ² represents an integer of 0 to 4. When n is 0, it represents that there is no R ² , and when n is 1 to 4, it represents that there are 1 to 4 R ^2. . When there are two or more R ^{2 s} , a monovalent organic group can be independently selected. The number of substituents n of R ² is preferably 0.
The number m of substituents of R ⁵ represents an integer of 0 to 4. When m is 0, it represents that there is no R ⁵ , and when m is 1 to 4, it represents that there are 1 to 4 R ^2. . When two or more R ^{5 s} are present, a monovalent organic group can be independently selected. The number of substituents m of R ⁵ is preferably 0.

Examples of the catalyst having the structure of the formula (I) include 4-n-octylbenzenesulfonic acid, 4-n-nonylbenzenesulfonic acid, 4-n-decylbenzenesulfonic acid, 4-n-undecylbenzenesulfonic acid. 4-n-dodecylbenzenesulfonic acid, 4-n-tridecylbenzenesulfonic acid, 4-n-tetradecylbenzenesulfonic acid, 4-n-pentadecylbenzenesulfonic acid, 4-n-hexadecylbenzenesulfonic acid, Preferred examples include 4-n-heptadecylbenzenesulfonic acid, 4-n-octadecylbenzenesulfonic acid, 4-n-nonadecylbenzenesulfonic acid, 4-n-eicosabenzenesulfonic acid, and the like. Dodecylbenzenesulfonic acid, 4-n-pentadecylbenzenesulfonic acid, 4-n-octadecylbenzenes More preferable examples include sulfonic acid.
Examples of the catalyst having the structure of the formula (II) include 1-octanesulfonic acid, 1-nonanesulfonic acid, 1-decanesulfonic acid, 1-undecanesulfonic acid, 1-dodecanesulfonic acid, 1-tridecanesulfonic acid. 1-tetradecanesulfonic acid, 1-pentadecanesulfonic acid, 1-hexadecanesulfonic acid, 1-heptadecanesulfonic acid, 1-octadecanesulfonic acid, 1-nonadecanesulfonic acid, 1-eicosanesulfonic acid, etc. More preferred examples include 1-dodecanesulfonic acid, 1-pentadecanesulfonic acid, and 1-octadecanesulfonic acid.

Examples of the catalyst having the structure of the formula (III) include Taker Power B120, B121, B124, B150 manufactured by Teika Co., Ltd., and Rypon LH-9000 manufactured by Lion Corporation.
Moreover, as a catalyst which has a structure of Formula (III), the catalyst which has the structure of following formula (V) is mentioned preferably, and it is more preferable that p is 3-5 among the compounds represented by Formula (V). preferable.

（式（V）中、ｐは２〜５の整数を表す。）

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

  Preferred examples of the catalyst having the structure of the formula (IV) include a catalyst having the structure of the following formula (VI). Among the compounds represented by the formula (VI), q is more preferably 3 to 5. preferable.

（式（VI）中、ｑは２〜５の整数を表す。）

(In formula (VI), q represents an integer of 2 to 5)

  Further, as the polycondensation catalyst, the compound represented by the following formula (I) or (II) is preferably a compound represented by the formula (I), and represented by the following formula (III) or (IV). Preferably, the compound represented by the formula (III) is a compound represented by the formula (I) and the compound represented by the formula (I) is more preferably used in combination with the compound represented by the formula (III). .

  The total amount of the polycondensation catalyst of the present invention (compounds represented by formulas (I) to (IV)) is preferably 0.01 to 30 mol% based on the total amount of the polycondensable monomer. 0.05 to 20 mol% is more preferable.

  These polycondensation catalysts are not particularly limited and may be produced using a known method or may be a commercially available product. Examples of the production method include sulfation of alkane and alkylbenzene, or alkylbenzenesulfonic acid. It can be produced by replacing the metal part of the metal salt with hydrogen. Examples of the sulfation method include a method of substituting hydrogen with fuming sulfuric acid or anhydrous sulfuric acid gas, and the replacement of the metal salt includes a solution in which a metal salt of alkylbenzene sulfonic acid is dissolved in a solvent. And a method of reacting by adding sulfuric acid.

<Polycondensable monomer>
The polycondensable monomer that can be used in the present invention is not particularly limited, and any polycondensable monomer may be used as long as it is used in various polymerization methods described later. Details are described below.

The polycondensable monomer that can be used in the present invention is not particularly limited, and a monomer that forms either a crystalline multimer or an amorphous multimer can be used. It is preferably a monomer that forms any of the body.
Examples of the polycondensable monomer include aliphatic, alicyclic and aromatic polycarboxylic acids and alkyl esters thereof, polyhydric alcohols and ester compounds thereof, and hydroxycarboxylic acid compounds. The polycondensation resin is obtained by polymerizing them by direct esterification reaction, transesterification reaction or the like.
A polyhydric alcohol is a compound containing two or more hydroxyl groups in one molecule. Although it does not specifically limit as a polyhydric alcohol, The following monomer can be mentioned.
Diol is a compound containing two hydroxyl groups in one molecule, such as propanediol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol, decanediol, dodecanediol, tetradecanediol, octadecanediol, etc. Can be mentioned.
Examples of polyvalent ols other than diols include glycol, pentaerythritol, hexamethylol melamine, hexaethylol melamine, tetramethylol benzoguanamine, and tetraethylol benzoguanamine.
Moreover, the following monomer can be mentioned as a polyhydric alcohol which has a cyclic structure. For example, cyclohexanediol, cyclohexanedimethanol, bisphenol A, bisphenol C, bisphenol E, bisphenol F, bisphenol P, bisphenol S, bisphenol Z, hydrogenated bisphenol, biphenol, naphthalenediol, 1,3-adamantanediol, 1,3- Examples thereof include, but are not limited to, adamantanedimethanol, 1,3-adamantanediethanol, and hydroxyphenylcyclohexane. In the present invention, the bisphenols preferably have at least one alkylene oxide group. Examples of the alkylene oxide group include, but are not limited to, an ethylene oxide group, a propylene oxide group, and butylene oxide. Preferably, they are ethylene oxide and propylene oxide, and the added mole number is preferably 1 to 3. When it is within this range, the viscoelasticity and glass transition temperature of the produced polyester can be appropriately controlled for use as a toner.
Among the above-mentioned monomers, hexanediol, cyclohexanediol, octanediol, decanediol, dodecanediol, bisphenol A, bisphenol C, bisphenol E, bisphenol S, bisphenol Z are preferably used. Is an alkylene oxide adduct.

The polyvalent carboxylic acid that can be used as a monomer used for polycondensation is a compound containing two or more carboxyl groups in one molecule. Among these, dicarboxylic acid is a compound containing two carboxyl groups in one molecule. For example, oxalic acid, succinic acid, fumaric acid, maleic acid, adipic acid, β-methyladipic acid, malic acid, malonic acid, Pimelic acid, tartaric acid, azelaic acid, pimelic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, citraconic acid, cyclohexane-3,5-diene-1,2-carboxylic acid, citric acid , Hexahydroterephthalic acid, mucous acid, phthalic acid, isophthalic acid, terephthalic acid, tetrachlorophthalic acid, chlorophthalic acid, nitrophthalic acid, p-carboxyphenylacetic acid, p-phenylenediacetic acid, m-phenylenediacetic acid, p-phenylene Dipropionic acid, m-phenylene dipropionic acid, -Phenylene diglycolic acid, p-phenylene diglycolic acid, o-phenylene diglycolic acid, diphenylacetic acid, diphenyl-p, p'-dicarboxylic acid, 1,1-cyclopentenedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1 , 3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,2-cyclohexenedicarboxylic acid, norbornene-2,3-dicarboxylic acid, 1,3-adamantanedicarboxylic acid, 1,3-adamantanediacetic acid, naphthalene- Examples thereof include 1,4-dicarboxylic acid, naphthalene-1,5-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, anthracene dicarboxylic acid and the like.
Examples of the polyvalent carboxylic acid other than dicarboxylic acid include trimellitic acid, pyromellitic acid, naphthalenetricarboxylic acid, naphthalenetetracarboxylic acid, pyrenetricarboxylic acid, and pyrenetetracarboxylic acid.
The carboxylic acid may have a functional group other than a carboxyl group, and carboxylic acid derivatives such as acid anhydrides and acid esters can also be used.
Among these polyvalent carboxylic acids, the monomers preferably used are sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, p-phenylenediacetic acid, m-phenylenediacetic acid, p-phenylenediprote. Pionic acid, m-phenylene dipropionic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, naphthalene-1,4-dicarboxylic acid, naphthalene-1,5-dicarboxylic acid, naphthalene-2, 6-dicarboxylic acid, trimellitic acid, pyromellitic acid.

  Further, polycondensation can be carried out using a hydroxycarboxylic acid compound containing a carboxylic acid and a hydroxyl group in one molecule. Examples include hydroxyoctanoic acid, hydroxynonanoic acid, hydroxydecanoic acid, hydroxyundecanoic acid, hydroxydodecanoic acid, hydroxytetradecanoic acid, hydroxytridecanoic acid, hydroxyhexadecanoic acid, hydroxypentadecanoic acid, hydroxystearic acid, and the like. It is not meant to be limited to this.

In the present invention, any of the above-described monomers can be used without limitation, but it is preferable that the produced polyester is non-crystalline. Amorphous polyester has a high hardness at normal temperature, and thus has high fluidity, and has properties that are very suitable for toners in terms of offset suppression, low-temperature fixability, image quality, and the like. Crystalline polyester mainly composed of linear monomers has sharp melt properties due to crystallinity and has great merit for low-temperature fixability, but has the disadvantage of being inferior in powder flowability and image strength, Non-crystalline properties are more appropriate as the main component of the binder resin. The confirmation of non-crystallinity can be determined by the presence or absence of glass transition temperature and melting point by differential thermal analysis (DSC) of the produced polyester.
Here, the glass transition point of an amorphous resin means the value measured by the method (DSC method) prescribed | regulated to ASTMD3418-82.
“Crystallinity” as shown in the above “crystalline polyester resin” means that, in differential scanning calorimetry (DSC), it has a clear endothermic peak rather than a stepwise endothermic change. Means that the half-value width of the endothermic peak when measured at a heating rate of 10 ° C./min is within 6 ° C.
On the other hand, a resin having an endothermic peak with a half-value width exceeding 6 ° C. or a resin having no clear endothermic peak means non-crystalline (amorphous).

  Examples of the monomer constituting the non-crystalline polyester include, among the above monomers, polyhydric alcohols that include alkylene oxide adducts of bisphenol A, bisphenol C, bisphenol E, bisphenol S, and bisphenol Z. The polyvalent carboxylic acids include p-phenylene diacetic acid, m-phenylene diacetic acid, p-phenylene dipropionic acid, m-phenylene dipropionic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexane. Examples thereof include dicarboxylic acid, naphthalene-1,4-dicarboxylic acid, naphthalene-1,5-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, trimellitic acid, pyromellitic acid and the like.

  The structure of the binder resin obtained by the method for producing the binder resin of the present invention is not particularly limited, but is preferably polyester, and 90% or more of the repeating units in the polyester contain the following Unit-A, Unit. More preferably, the resin has a structure of -B and / or Unit-C, and more preferably 90% or more of the repeating units in the polyester are resins having a structure of Unit-A or Unit-B. In addition, for example, in the case of Unit-A, these structures may include only one type of structure represented by Unit-A in the resin or a mixture of two or more types. The same applies to the structure. The binder resin is preferably an amorphous resin.

In Unit-A, A ¹ represents a polyvalent hydrocarbon group which may contain a linking group, and the number n of carboxy binding sites represents an integer of 0 or more.
In Unit-B, B ¹ represents a polyvalent hydrocarbon group which may contain a linking group, or a group in which one or more alkylene oxide groups are bonded to the hydrocarbon group, and the number of alkoxy bonding sites. m represents an integer of 0 or more.
In UnitC, it represents a polyvalent hydrocarbon group which may contain a linking group, or a group in which one or more alkylene oxide groups are bonded to the hydrocarbon group, and the number p of carboxy bonding sites is an integer of 0 or more. In addition, the number q of the alkoxy bonding sites represents an integer of 0 or more.
The double wavy line part and the double dotted line part in the Unit-A to C represent a connecting part with another structure, and the double wavy line part is a double dotted line part or Unit-A in Unit-B or the like. ~ C and structures other than Unit-D and E, which will be described later, may be combined, and the double dotted line part may be combined with structures other than double wavy lines, Unit-A to C and Unit-D and E, which will be described later. In addition, the double wavy line portions and the double dotted line portions are not coupled to each other.
The A ¹ preferably has 3 or more carbon atoms, and the B ¹ preferably has 5 or more carbon atoms.
The alkylene oxide group in B ¹ and C ¹ may be one in which two or more alkylene oxide groups are bonded, and in that case, one in which two or more alkylene oxide groups are bonded may be used. Moreover, it is preferable that an alkylene oxide group couple | bonds directly with an alkoxy part, and the number is the same number in the alkoxy part of both ends.
The polyvalent hydrocarbon group which may contain the linking group is an alkane, alkene, alkyne, aromatic hydrocarbon or a group obtained by removing two or more hydrogen atoms from a hydrocarbon ring, or a group in which two or more of these groups are bonded. In addition, a group in which two or more of these groups are bonded and at least a part of the bond is a linking group can be exemplified.
The alkane, alkene and alkyne may be linear or branched, and preferably have 1 to 20 carbon atoms.
The aromatic hydrocarbon and hydrocarbon ring may further have an alkyl group, an alkenyl group and / or an alkynyl group in the cyclic structure, or may have a structure in which two or more rings are bonded. Moreover, it is preferable that carbon number of aromatic hydrocarbon is 6-30. The hydrocarbon ring preferably has 3 to 20 carbon atoms, more preferably 5 to 12 carbon atoms, and still more preferably 6 to 8 carbon atoms.
The linking group, -O -, - S -, - SO -, - SO 2 - can be preferably exemplified, among which -O -, - SO ₂ - is more preferable.
B ¹ represents bisphenol A skeleton (—C ₆ H ₄ —C (CH ₃ ) ₂ —C ₆ H ₄ —), bisphenol E skeleton (—C ₆ H ₄ —C (CH ₂ ) —C ₆ H ₄ — ), Bisphenol F skeleton (—C ₆ H ₄ —CH ₂ —C ₆ H ₄ —), bisphenol P skeleton (—C (CH ₃ ) ₂ -1,4-C ₆ H ₄ —C (CH ₃ ) ₂ — ), Bisphenol M skeleton (—C (CH ₃ ) ₂ -1,3-C ₆ H ₄ —C (CH ₃ ) ₂ —), bisphenol S skeleton (—C ₆ H ₄ —SO ₂ —C ₆ H ₄ — ), A bisphenol Z skeleton (—C ₆ H ₄ —C ₆ H ₁₀ —C ₆ H ₄ —), or a group in which one or more alkylene oxide groups are bonded to these groups, —C ₆ H _{4 -C (CH 3) 2 -C} 6 H 4 -, - C 6 H 4 -SO 2 -C 6 H 4 -, - C 6 H 4 -C 6 H 10 -C 6 H 4 -, or they of A group in which one or more alkylene oxide groups are bonded to the group is more preferable.

The number n of carboxy binding sites in Unit-A is preferably 0 to 5, and more preferably 0 to 2.
The number m of alkoxy bond sites in Unit-B is preferably 0 to 5, and more preferably 0 to 2.
The number p of carboxy binding sites in Unit-C is preferably 0 to 5, and more preferably 0.
The number q of alkoxy bonding sites in Unit-C is preferably 0 to 5, and more preferably 0.
When n, m, p and q are 0, it means that there is no carboxy bond site or alkoxy bond site in parentheses, and when n, m, p and q are integers of 1 or more, It represents that there are 1 or more integers of carboxy bond sites or alkoxy bond sites in parentheses.

  Moreover, as the binder resin obtained by the method for producing the binder resin of the present invention, among Unit-A to C, a resin in which 90% or more of the repeating units have the following Unit-AB structure is preferable.

In Unit-AB, A ¹ represents a polyvalent hydrocarbon group which may contain a linking group, and B ¹ represents a polyvalent hydrocarbon group which may contain a linking group, or the hydrocarbon group. It represents a group to which one or more alkylene oxide groups are bonded, the number n of carboxy bond sites represents an integer of 0 or more, and the number m of alkoxy bond sites represents an integer of 0 or more. In addition, a double wavy line part and a double dotted line part represent that it is a coupling | bond part with another structure, and the double wavy line part has couple | bonded with other structures other than a double dotted line part and Unit-A-E. The double dotted line part may be combined with a structure other than the double dotted line part or Units A to E, and the double dotted line parts and the double dotted line parts are not connected to each other. To do.

A ^1, B ^1, n and m in the Unit-AB are as defined A ^1, B ^1, n and m in the Unit-A or B, the preferred scopes are also same.

  The Unit-A is preferably the following Unit-D.

In Unit-D, A ² is a group having 2 or more hydrogen atoms removed from an alkane having 1 to 20 carbon atoms, an aromatic hydrocarbon having 6 to 20 carbon atoms or a hydrocarbon ring having 3 to 20 carbon atoms, or this group Represents a group in which two or more are bonded.
The double wavy line part in the Unit-D represents a joint part with another structure, and the double wavy line part is a double dotted line part in the Unit-B or the like other than Unit-A to E. It may be combined with other structures other than the above, and the double wavy line portions shall not be combined.
A ² is preferably a group having 3 or more carbon atoms. As A ² , for example, a straight chain alkylene group having 6 to 18 carbon atoms, a phenylene group, a naphthylene group, a cyclohexylene group, a hydrocarbon ring containing a bridge such as norbornene and adamantane, and two alkylene groups in the phenylene group A group in which two alkylene groups are bonded to a naphthylene group (for example, —CH ₂ —C ₆ H ₄ —CH ₂ — or —CH ₂ CH ₂ —C ₆ H ₄ —CH ₂ CH ₂ —, etc.) And a group in which two alkylene groups are bonded to a cyclohexylene group are more preferred.

  The Unit-B is preferably the following Unit-E.

In UnitE, B ² represents a linear alkylene group, a hydrocarbon ring, or a group obtained by removing two hydroxy groups from a bisphenol compound, and E ¹ and E ² are each independently a single bond or an alkylene oxide group. Or a group in which two or more alkylene oxide groups are bonded.
The double dotted line portion in the Unit-E represents a connecting portion with another structure, and the double dotted line portion is a double wavy line portion in the Unit-A or a structure other than Unit-A to E. It may be bonded, and the double dotted line portions are not bonded to each other.
Preferred examples of the bisphenol compound include bisphenol A, bisphenol E, bisphenol P, bisphenol M, bisphenol S, and bisphenol Z.
When B ² is a linear alkylene group, E ¹ and E ² are preferably hydrocarbons, and when B ² is a group obtained by removing two hydroxy groups from the bisphenol compound, E ¹ and E 2 ² is each independently an alkylene oxide group or a group in which two or more alkylene oxide groups are bonded, and the hydrocarbon ring can be any of the above. Further, the alkylene oxide group is more preferably an ethylene oxide group and / or a propylene oxide group.

  The binder resin of the present invention is particularly preferably a polyester in which 80% or more of the repeating units in the resin are Unit-D or Unit-E.

  Further, the binder resin of the present invention is particularly preferably a polyester in which 80% or more of the repeating units in the resin have the following Unit-DE structure.

In Unit-DE, A ² is a group in which two or more hydrogen atoms have been removed from an alkane having 1 to 20 carbon atoms, an aromatic hydrocarbon having 6 to 20 carbon atoms or a hydrocarbon ring having 3 to 20 carbon atoms, or this group Represents a group in which two or more are bonded, B ² represents a linear alkylene group or a group obtained by removing two hydroxy groups from a bisphenol compound, and E ¹ and E ² are each independently a single bond Represents an alkylene oxide group or a group in which two or more alkylene oxide groups are bonded.

Similarly the A ^2, B ^2, E ¹ and E ² in Unit-DE has the same meaning as A ^2, B ^2, E ¹ and E ² in Unit-D or Unit-E, also preferable range It is.

  The binder resin glass transition temperature for toner produced in the present invention is preferably 30 to 80 ° C. from the viewpoints of fixability and image formability. A glass transition temperature of 30 ° C. or higher is preferable because the fluidity of the toner powder at normal temperature is good, the cohesive force of the binder resin itself is excellent in a high temperature range, and hot offset is difficult during fixing. A glass transition temperature of 80 ° C. or lower is preferable because sufficient melting can be obtained and the minimum fixing temperature does not easily rise. The glass transition temperature is more preferably 35 to 75 ° C, and most preferably 45 to 65 ° C. The glass transition temperature can be controlled by the molecular weight of the binder resin, the monomer composition of the binder resin, the addition of a crosslinking agent, and the like.

  The binder resin of the present invention is preferably reacted at a temperature lower than the conventional reaction temperature. The reaction temperature is preferably 70 to 150 ° C. Preferably it is 70 degreeC or more and 140 degrees C or less, More preferably, it is 80 degreeC or more and less than 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.

  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.

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

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

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

In the present invention, in addition to the polycondensation catalyst represented by the above formulas (I) to (IV), for example, a commonly used polycondensation catalyst such as a metal catalyst or a hydrolase can be used in combination.
Examples of the metal catalyst include, but are not limited to, the following. For example, an organic tin compound, an organic titanium compound, an organic tin halide compound, and a rare earth metal catalyst can be used.
As the organotin compound, the organotitanium compound, and the organotin halide compound, those known as polycondensation catalysts can be used.
As the rare earth-containing catalyst, scandium (Sc), yttrium (Y), as the lanthanoid element, lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu), and the like are effective, especially alkylbenzenesulfone Acid salts, alkyl sulfate esters, or those having a triflate structure are effective.
As the rare earth-containing catalyst, those having a triflate structure such as scandium triflate, yttrium triflate, and lanthanoid triflate are preferable. The lanthanoid triflate is described in detail in 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.

  When a metal catalyst is used as the catalyst, the metal content derived from the catalyst in the obtained resin is preferably 100 ppm or less, more preferably 75 ppm or less, and even more preferably 50 ppm or less.

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

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

  Lipases of various origins can be used, but 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 preferable to use lipases derived from microorganisms of the genus Pseudomonas, Candida, and Aspergillus.

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

In order for the binder resin produced in the present invention to have toner suitability, an appropriate weight average molecular weight is preferably 5,000 to 60,000, more preferably 7,000 to 40,000, and even more preferably 10. , 35,000 to 35,000. When the weight average molecular weight is 5,000 or more, powder flowability at room temperature is excellent, toner blocking is difficult to occur, and cohesion as a binder resin for toner is sufficient, and hot offset property is excellent. preferable. Further, it is preferable that the weight average molecular weight is 50,000 or less because both the hot offset property and the minimum fixing temperature are good, the time required for polycondensation is short, and the temperature during polycondensation is low, resulting in excellent production efficiency. .
A weight average molecular weight can be measured by a well-known method, for example, can be measured by a gel permeation chromatography (GPC) etc.

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

In the present invention, the polycondensation step may include a polymerization reaction between the aforementioned monomers and a prepolymer prepared in advance. The prepolymer is not limited as long as it is a polymer that can be melted or uniformly mixed with the monomer.
Furthermore, the binder resin of the present invention is a homopolymer of the above-mentioned monomers, a copolymer obtained by combining two or more monomers containing the above-mentioned monomers, or a mixture thereof, a graft polymer, a part thereof. It may have a branching or cross-linking structure.

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

(Resin particle dispersion and production method thereof)
The resin particle dispersion of the present invention is a resin particle dispersion in which resin particles containing at least a binder resin are dispersed in a dispersion medium, and the binder resin is produced by the method for producing a binder resin of the present invention. It is characterized by containing the binder resin made.
In the present invention, the dispersion medium of the resin particle dispersion is preferably the above-mentioned aqueous medium.
Further, the resin particle dispersion of the present invention can be suitably used as a resin particle dispersion for developing an electrostatic charge image.

The median diameter (center diameter) of the resin particle dispersion of the present invention is preferably from 0.05 μm to 2.0 μm, more preferably from 0.1 μm to 1.5 μm, still more preferably from 0.1 μm to 1. 0 μm or less. This median diameter within the above range is preferable because the dispersion state of the resin particles in the aqueous medium is stabilized as described above. Further, when used for toner preparation, it is preferable because the particle diameter can be easily controlled and the releasability and offset property during fixing are excellent.
The median diameter of the resin particles can be measured, for example, with a laser diffraction particle size distribution measuring device (LA-920, manufactured by Horiba, Ltd.).

The method for producing the resin particle dispersion of the present invention is not particularly limited as long as the binder resin of the present invention is used, and can be produced by a known method.
Examples of the method for producing the resin particle dispersion of the present invention include a method including a dispersion step in which the binder resin-containing material is dispersed in an aqueous medium to obtain a resin particle dispersion.
In the dispersion step, it is preferable to carry out dispersion by adding a surfactant or the like in order to increase the dispersion efficiency or improve the stability of the resin particle dispersion.
As a method for dispersing and granulating the binder resin of the present invention in an aqueous medium, for example, when the binder resin is produced as described above, a suspension polymerization method, a dissolution suspension method in an aqueous medium, Examples include a miniemulsion method, a microemulsion method, a multistage swelling method, and an emulsion polymerization method including seed polymerization.
Among these methods for producing resin particle dispersions, the method for producing resin particle dispersions of the present invention is a step of preparing an emulsion dispersion in which an oil phase containing at least a polycondensable monomer is emulsified and dispersed in an aqueous medium. And a step of polycondensing a polycondensable monomer in an aqueous medium using the polycondensation catalyst, and producing a resin particle dispersion in which the binder resin produced by the production method of the present invention is dispersed A method is preferred. The above production method is preferable because the resin particle dispersion of the present invention can be produced by a simple operation and is excellent in energy saving.

  Further, in the method for producing a binder resin and 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 energy saving, polymer production rate, and heat of the produced polymer. In consideration of the decomposition rate, a lower value is desirable, but it is preferably 40 to 150 ° C, more preferably 80 to 130 ° C. It is preferable that the emulsification temperature is 150 ° C. or lower because the required energy does not become excessive and the molecular weight is not lowered due to decomposition of the resin due to high heat. Moreover, it is preferable for the temperature to be 40 ° C. or higher because the resin viscosity is moderate and the formation of fine particles is easy.

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

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 binder resin-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.

(Electrostatic image developing toner and method for producing the same)
The method for producing an electrostatic charge image developing toner (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 (hereinafter referred to as “aggregation”). And a process for heating and aggregating the aggregated particles (hereinafter also referred to as “fusion process”), wherein the resin particle dispersion comprises It is a resin particle dispersion of the present invention.
The toner of the present invention is preferable by using the binder resin of the present invention because it has high fluidity, hardly causes soft blocking, and improves heat storage properties.

  As a method for producing the electrostatic image developing toner of the present invention, for example, a toner in which the resin particle dispersion prepared as described above, so-called latex, is used, and the toner particle size and distribution are controlled using an aggregation (association) method. Can be manufactured. Specifically, the latex prepared as described above is mixed with a colorant particle dispersion and a release agent particle dispersion, and an aggregating agent is added to form heteroaggregation to form aggregated particles having a toner diameter. Then, it is obtained by heating to a temperature above the glass transition point or above the melting point of the resin particles to fuse and coalesce the aggregated particles, and wash and dry. In this manufacturing method, the toner shape can be controlled from an indeterminate shape to a spherical shape by selecting a heating temperature condition.

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

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

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

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

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

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

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

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

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

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

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

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

  Similarly, the shape factor SF1 of the toner of the present invention is preferably 100 to 140, and more preferably 110 to 135 from the viewpoint of image forming property. At this time, SF1 is calculated as follows.

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

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

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

(Image forming method)
Further, the electrostatic image developing toner and the electrostatic image developer of the present invention can be used in an ordinary electrostatic image developing system (electrophotographic system) 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 developing the electrostatic latent image formed on the surface of the latent image holding member with a developer containing toner. 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 for thermally fixing the toner image transferred to the surface of the transfer target. An electrostatic image developing and pulverizing toner of the present invention or an electrostatic image developing toner of the present invention as the toner, or the electrostatic image developer of the present invention as the developer. It is characterized by.
For each of the above steps, a known step can be used in the image forming method, and are described in, for example, JP-A-56-40868 and JP-A-49-91231.
Further, the image forming method of the present invention may include steps other than the above-described steps. For example, a cleaning step for removing the electrostatic charge image developer remaining on the electrostatic latent image carrier is preferable. Can be mentioned. In the image forming method of the present invention, an embodiment that further includes a recycling step is preferable. The recycling step is a step of transferring the electrostatic charge image developing toner collected in the cleaning step to a developer layer. The image forming method including the recycling step can be 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.

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

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited at all.

1) Bulk Polymerization Example <Amorphous Resin Particle Dispersion Example 1-1>
17.5 parts by weight of 1,4-cyclohexanedicarboxylic acid 31.0 parts by weight of bisphenol A-ethylene oxide 1 mol adduct 0.6 parts by weight of n-dodecylbenzenesulfonic acid (1 mol% based on the total monomers)
-Branched dodecylbenzene sulfonic acid (Taika Power B120 manufactured by Teika Co., Ltd.) 0.6 parts by weight (1 mol% based on the total monomers)
The above materials were mixed, put into a 200 ml reactor equipped with a stirrer, and subjected to monomer polycondensation to obtain a uniform transparent amorphous polyester resin.
Weight average molecular weight by GPC 12,000
Glass transition temperature (onset) 55 ° C

  This resin was put into a three-necked flask equipped with a stirrer and a condenser, and stirring was continued while gradually adding a 1N NaOH aqueous solution while maintaining the temperature at 95 ° C. When 50 parts by weight of NaOH aqueous solution was added in total, the resin became a slurry. The slurry was put into a flask containing 180 parts by weight of ion-exchanged water adjusted to 85 ° C., emulsified with a homogenizer (IKA, Ultra Tarrax) for 10 minutes, and then an ultra-high pressure homogenizer (Yoshida Kikai Kogyo Co., Ltd.). (Nanomizer) was emulsified for 10 passes, and then the dispersion was ice-cooled to obtain a resin particle dispersion. The median diameter of the resin particles was 380 nm.

<Amorphous resin particle dispersion example 1-2>
17.5 parts by weight of 1,4-cyclohexanedicarboxylic acid 31.0 parts by weight of bisphenol A-ethylene oxide 1 mol adduct 0.06 parts by weight of n-dodecylbenzenesulfonic acid (0.1 mol% based on the total monomers)
-Branched dodecylbenzene sulfonic acid (Taika Power B120 manufactured by Teika Co., Ltd.) 0.06 parts by weight (0.1 mol% based on the total monomers)
The above materials were mixed, put into a 200 ml reactor equipped with a stirrer, and subjected to polycondensation at 120 ° C. for 24 hours. As a result, a uniform transparent amorphous polyester resin was obtained.
Weight average molecular weight by GPC 14,500
Glass transition temperature (onset) 55.5 ° C
A resin particle dispersion having a median diameter of 420 nm was prepared in the same manner as in 1-1.

<Amorphous resin particle dispersion example 1-3>
17.5 parts by weight of 1,4-cyclohexanedicarboxylic acid 31.0 parts by weight of bisphenol A-ethylene oxide 1 mol adduct 0.2 parts by weight of n-dodecylbenzenesulfonic acid (0.35 mol% based on the total monomers)
-Branched dodecylbenzene sulfonic acid (Taika Power B120 manufactured by Teika Co., Ltd.) 0.2 parts by weight (0.35 mol% based on the total monomers)
The above materials were mixed, put into a 200 ml reactor equipped with a stirrer, and subjected to polycondensation at 120 ° C. for 24 hours. As a result, a uniform transparent amorphous polyester resin was obtained.
Weight average molecular weight by GPC 14,000
Glass transition temperature (onset) 55.5 ° C
A resin particle dispersion having a median diameter of 410 nm was prepared in the same manner as in 1-1.

<Crystalline resin particle dispersion example 2-1>
-1,9-nonanediol 16.0 parts by weight-Dodecanedioic acid 23.0 parts by weight-n-pentadecylbenzenesulfonic acid 1.1 parts by weight (1.5 mol% based on the total monomers)
-Branched pentadecylbenzene sulfonic acid (Taika Power B150 manufactured by Teika Co., Ltd.) 0.4 parts by weight (0.5 mol% based on the total monomers)
The above materials were mixed, put into a 200 ml reactor equipped with a stirrer, and subjected to polycondensation at 120 ° C. for 24 hours. As a result, a uniform transparent amorphous polyester resin was obtained.
Weight average molecular weight by GPC 17,000
Melting point 67.0 ° C
A resin particle dispersion having a median diameter of 320 nm was produced in the same manner as in 1-1.

<Crystalline resin particle dispersion example 2-2>
-1,9-nonanediol 16.0 parts by weight-Dodecanedioic acid 23.0 parts by weight-n-pentadecylbenzenesulfonic acid 0.11 parts by weight (0.15 mol% based on the total monomers)
-Branched pentadecylbenzene sulfonic acid (Taika Power B150 manufactured by Teica Co., Ltd.) 0.04 parts by weight (0.05 mol% based on the total monomers)
The above materials were mixed, put into a 200 ml reactor equipped with a stirrer, and subjected to polycondensation at 120 ° C. for 24 hours. As a result, a uniform transparent amorphous polyester resin was obtained.
Weight average molecular weight by GPC 18,500
Melting point 68.5 ° C
A resin particle dispersion having a median diameter of 360 nm was prepared in the same manner as in 1-1.

<Crystalline resin particle dispersion example 2-3>
-1,9-nonanediol 16.0 parts by weight-Dodecanedioic acid 23.0 parts by weight-n-pentadecylbenzenesulfonic acid 0.4 parts by weight (0.53 mol% based on the total monomers)
・ Branched pentadecylbenzenesulfonic acid (Taika Power B150 manufactured by Teika Co., Ltd.) 0.1 parts by weight (0.17 mol% based on the total monomers)
The above materials were mixed, put into a 200 ml reactor equipped with a stirrer, and subjected to polycondensation at 120 ° C. for 24 hours. As a result, a uniform transparent amorphous polyester resin was obtained.
Weight average molecular weight by GPC 18,500
Melting point 68.0 ° C
A resin particle dispersion having a median diameter of 340 nm was prepared in the same manner as in 1-1.

<Crystalline resin particle dispersion example 3-1>
17.5 parts by weight of 1,4-cyclohexanedicarboxylic acid 16.0 parts by weight of 1 mol adduct of bisphenol A-ethylene oxide 17.0 parts by weight of 1 mol adduct of bisphenol S-ethylene oxide 1 n-dodecanesulfonic acid 0 .5 parts by weight (1.0 mol% with respect to the total monomers)
-Branched dodecylbenzene sulfonic acid (Taika Power B120 manufactured by Teika Co., Ltd.) 0.6 parts by weight (1.0 mol% based on the total monomers)
The above materials were mixed, put into a 200 ml reactor equipped with a stirrer, and subjected to polycondensation at 120 ° C. for 24 hours. As a result, a uniform transparent amorphous polyester resin was obtained.
Weight average molecular weight by GPC 8,600
Glass transition temperature (onset) 62.0 ℃
A resin particle dispersion having a median diameter of 390 nm was produced in the same manner as in 1-1.

<Crystalline Resin Particle Dispersion Example 3-2>
17.5 parts by weight of 1,4-cyclohexanedicarboxylic acid 16.0 parts by weight of 1 mol adduct of bisphenol A-ethylene oxide 17.0 parts by weight of 1 mol adduct of bisphenol S-ethylene oxide 1 n-dodecanesulfonic acid 0 .95 parts by weight (0.18 mol% based on total monomers)
・ 0.06 parts by weight of dodecylbenzenesulfonic acid (0.02 mol% based on the total monomers)
The above materials were mixed, put into a 200 ml reactor equipped with a stirrer, and subjected to polycondensation at 120 ° C. for 24 hours. As a result, a uniform transparent amorphous polyester resin was obtained.
Weight average molecular weight by GPC 11,500
Glass transition temperature (onset) 63.0 ° C
A resin particle dispersion having a median diameter of 450 nm was prepared in the same manner as in 1-1.

2) Bulk polymerization comparative example <Amorphous resin particle dispersion comparative example 1-1>
17.5 parts by weight of 1,4-cyclohexanedicarboxylic acid 31.0 parts by weight of bisphenol A-ethylene oxide 1 mol adduct 1.2 parts by weight of n-dodecylbenzenesulfonic acid (2 mol% based on the total monomers)
The above materials were mixed, put into a 200 ml reactor equipped with a stirrer, and subjected to polycondensation at 120 ° C. for 24 hours. As a result, a uniform transparent amorphous polyester resin was obtained.
Weight average molecular weight by GPC 9,200
Glass transition temperature (onset) 51 ℃
A resin particle dispersion having a median diameter of 400 nm was prepared in the same manner as in 1-1.

<Amorphous resin particle dispersion comparative example 1-2>
17.5 parts by weight of 1,4-cyclohexanedicarboxylic acid 31.0 parts by weight of bisphenol A-ethylene oxide 1 mol adduct 0.12 parts by weight of n-dodecylbenzenesulfonic acid (0.2 mol% based on the total monomers)
The above materials were mixed, put into a 200 ml reactor equipped with a stirrer, and subjected to polycondensation at 120 ° C. for 24 hours. As a result, a uniform transparent amorphous polyester resin was obtained.
Weight average molecular weight by GPC 15,000
Glass transition temperature (onset) 55.5 ° C
A resin particle dispersion having a median diameter of 450 nm was prepared in the same manner as in 1-1.

<Amorphous resin particle dispersion comparative example 1-3>
17.5 parts by weight of 1,4-cyclohexanedicarboxylic acid 31.0 parts by weight of bisphenol A-ethylene oxide 1 mol adduct 0.45 parts by weight of n-dodecylbenzenesulfonic acid (0.7 mol% based on the total monomers)
The above materials were mixed, put into a 200 ml reactor equipped with a stirrer, and subjected to polycondensation at 120 ° C. for 24 hours. As a result, a uniform transparent amorphous polyester resin was obtained.
Weight average molecular weight by GPC 11,500
Glass transition temperature (onset) 53.5 ° C
A resin particle dispersion having a median diameter of 420 nm was prepared in the same manner as in 1-1.

<Amorphous resin particle dispersion comparative example 2>
・ 17.5 parts by weight of 1,4-cyclohexanedicarboxylic acid ・ 31.0 parts by weight of 1 mol adduct of bisphenol A-ethylene oxide ・ 0.12 parts by weight of branched dodecylbenzenesulfonic acid (Taika Power B120 manufactured by Teica Co., Ltd.) 0.2 mol% with respect to all monomers)
The above materials were mixed, put into a 200 ml reactor equipped with a stirrer, and subjected to polycondensation at 120 ° C. for 24 hours. As a result, a uniform transparent amorphous polyester resin was obtained.
Weight average molecular weight by GPC 8,800
Glass transition temperature (onset) 50 ° C
A resin particle dispersion having a median diameter of 410 nm was prepared in the same manner as in 1-1.

<Crystalline resin particle dispersion comparative example 3-1>
-1,9-nonanediol 16.0 parts by weight-Dodecanedioic acid 23.0 parts by weight-n-pentadecylbenzenesulfonic acid 1.5 parts by weight (2.0 mol% based on the total monomers)
-Branched pentadecylbenzene sulfonic acid (Taika Power B150 manufactured by Teika Co., Ltd.) 0.015 parts by weight (0.02 mol% based on the total monomers)
The above materials were mixed, put into a 200 ml reactor equipped with a stirrer, and subjected to polycondensation at 120 ° C. for 24 hours. As a result, a uniform transparent amorphous polyester resin was obtained.
Weight average molecular weight by GPC 11,500
Melting point 64.0 ° C
A resin particle dispersion having a median diameter of 340 nm was prepared in the same manner as in 1-1.

<Crystalline resin particle dispersion comparative example 3-2>
-1,9-nonanediol 16.0 parts by weight-Dodecanedioic acid 23.0 parts by weight-n-pentadecylbenzenesulfonic acid 0.5 parts by weight (0.7 mol% based on the total monomers)
・ Branched pentadecylbenzenesulfonic acid (Taika Power B150 manufactured by Teika Co., Ltd.) 0.01 part by weight (0.013 mol% based on the total monomers)
The above materials were mixed, put into a 200 ml reactor equipped with a stirrer, and subjected to polycondensation at 120 ° C. for 24 hours. As a result, a uniform transparent amorphous polyester resin was obtained.
Weight average molecular weight by GPC 16,500
Melting point 67.0 ° C
A resin particle dispersion having a median diameter of 390 nm was produced in the same manner as in 1-1.

<Crystalline resin particle dispersion comparative example 4-1>
-1,9-nonanediol 16.0 parts by weight-Dodecanedioic acid 23.0 parts by weight-n-pentadecylbenzenesulfonic acid 0.015 parts by weight (0.02 mol% based on the total monomers)
・ Branched pentadecylbenzenesulfonic acid (Taika Power B150 manufactured by Teika Co., Ltd.) 1.5 parts by weight (2.0 mol% based on the total monomers)
The above materials were mixed, put into a 200 ml reactor equipped with a stirrer, and subjected to polycondensation at 120 ° C. for 24 hours. As a result, a uniform transparent amorphous polyester resin was obtained.
Weight average molecular weight by GPC 7,500
Melting point 63.0 ° C
A resin particle dispersion having a median diameter of 470 nm was prepared in the same manner as in 1-1.

<Crystalline resin particle dispersion comparative example 4-2>
-1,9-nonanediol 16.0 parts by weight-Dodecanedioic acid 23.0 parts by weight-n-pentadecylbenzenesulfonic acid 0.01 parts by weight (0.013 mol% based on the total monomers)
・ Branched pentadecylbenzenesulfonic acid (Taika Power B150 manufactured by Teika Co., Ltd.) 0.5 part by weight (0.7 mol% based on the total monomers)
The above materials were mixed, put into a 200 ml reactor equipped with a stirrer, and subjected to polycondensation at 120 ° C. for 24 hours. As a result, a uniform transparent amorphous polyester resin was obtained.
Weight average molecular weight by GPC 8,000
Melting point 63.5 ° C
A resin particle dispersion having a median diameter of 490 nm was produced in the same manner as in 1-1.

<Crystalline resin particle dispersion comparative example 5-1>
17.5 parts by weight of 1,4-cyclohexanedicarboxylic acid 16.0 parts by weight of 1 mol adduct of bisphenol A-ethylene oxide 17.0 parts by weight of 1 mol adduct of bisphenol S-ethylene oxide 1 n-dodecanesulfonic acid 1 0.0 part by weight (2.0 mol% based on the total monomers)
The above materials were mixed, put into a 200 ml reactor equipped with a stirrer, and subjected to polycondensation at 120 ° C. for 24 hours. As a result, a uniform transparent amorphous polyester resin was obtained.
Weight average molecular weight by GPC 6,500
Glass transition temperature (onset) 60.0 ℃
A resin particle dispersion having a median diameter of 370 nm was produced in the same manner as in 1-1.

<Crystalline resin particle dispersion comparative example 5-2>
17.5 parts by weight of 1,4-cyclohexanedicarboxylic acid 16.0 parts by weight of 1 mol adduct of bisphenol A-ethylene oxide 17.0 parts by weight of 1 mol adduct of bisphenol S-ethylene oxide 1 n-dodecanesulfonic acid 0 .1 part by weight (0.2 mol% based on the total monomers)
The above materials were mixed, put into a 200 ml reactor equipped with a stirrer, and subjected to polycondensation at 120 ° C. for 24 hours. As a result, a uniform transparent amorphous polyester resin was obtained.
Weight average molecular weight by GPC 8,500
Glass transition temperature (onset) 62.0 ℃
A resin particle dispersion having a median diameter of 400 nm was prepared in the same manner as in 1-1.

  As described above, when the linear and branched catalysts are used in the scope of the present invention, the variation of the polycondensate is small relative to the change in the amount of the catalyst, but when the combination of the present invention is not employed, It was shown that the physical properties of the polycondensate vary greatly with changes in the catalyst amount.

3) In-water polycondensation example 4
<Preparation of oil phase 1>
-1,6-hexanediol 5.9 parts by weight-Sebacic acid 10.0 parts by weight-Styrene 35.0 parts by weight-Dodecanethiol 1.0 parts by weight The above is heated and dissolved at 130 ° C to produce a uniform oil phase 1 did.
<Preparation of aqueous phase 1>
・ 1.2 parts by weight of n-pentadecylbenzenesulfonic acid (3.3 mol% based on the total monomers)
・ Branched pentadecylbenzenesulfonic acid (Taika Power B150 manufactured by Teika Co., Ltd.) 2.4 parts by weight (6.6 mol% based on the total monomers)
Cetyl alcohol 1.5 parts by weight Water 200 parts by weight <Preparation of resin particle dispersion 1>
The aqueous solution was prepared and stirred in a constant temperature bath at 70 ° C. for 1 hour. After the water phase 1 was put in a 1 liter container and the oil phase was added, Ultra Turrax (manufactured by IKA) was stirred at 8000 rpm for 3 minutes, and then the emulsion was charged into a 500 ml reactor equipped with a stirrer. Polycondensation was carried out at 70 ° C. for 24 hours under a nitrogen atmosphere.
To this resin particle dispersion, 1.1 parts by weight of ammonium persulfate dissolved in 10 parts by weight of ion-exchanged water was added, and polymerization was further performed in a nitrogen atmosphere for 6 hours to obtain a stable resin particle dispersion. It was. Similarly, a small amount was taken and the physical properties of the polyester / styrene composite polymer were measured.
Weight average molecular weight of styrene by GPC: 41,000
GPC polyester weight average molecular weight: 6,800
Melting point of polyester: 58 ° C
Median diameter: 350 nm
It was confirmed that the obtained polymer was a composite particle of styrene and polyester.

4) Comparative Example 6
<Preparation of oil phase 2>
-1,6-hexanediol 5.9 parts by weight-Sebacic acid 10.0 parts by weight-Styrene 35.0 parts by weight-Dodecanethiol 1.0 parts by weight The above is heated and dissolved at 130 ° C to produce a uniform oil phase 2. did.
<Preparation of aqueous phase 2>
・ Branched pentadecylbenzenesulfonic acid (Taika Power B150 manufactured by Teika Co., Ltd.) 3.6 parts by weight (9.9 mol% based on the total monomers)
Cetyl alcohol 1.5 parts by weight Water 200 parts by weight <Preparation of resin particle dispersion 2>
The aqueous solution was prepared and stirred in a constant temperature bath at 70 ° C. for 1 hour. Put the aqueous phase 2 in a 1 liter container, add the oil phase, and then stir for 3 minutes at 8000 rpm with Ultra Turrax (manufactured by IKA), then throw the emulsion into a 500 ml reactor equipped with a stirrer In a nitrogen atmosphere, polycondensation was carried out at 70 ° C. for 24 hours.
To this resin particle dispersion, 1.1 parts by weight of ammonium persulfate dissolved in 10 parts by weight of ion-exchanged water was added, and polymerization was further performed in a nitrogen atmosphere for 6 hours to obtain a stable resin particle dispersion. It was. Similarly, a small amount was taken and the physical properties of the polyester / styrene composite polymer were measured.
Weight average molecular weight of styrene by GPC: 43,500
Weight average molecular weight of polyester by GPC: 3,100
Melting point of polyester: 57 ° C
Median diameter: 350 nm
It was confirmed that the obtained polymer was a composite particle of styrene and polyester.

4) Comparative Example 7
<Production of oil phase>
-1,6-hexanediol 5.9 parts by weight-Sebacic acid 10.0 parts by weight-Styrene 35.0 parts by weight-Dodecanethiol 1.0 parts by weight The above is heated and dissolved at 130 ° C to produce a uniform oil phase 2. did.
<Preparation of aqueous phase>
・ 5.5 parts by weight of n-pentadecylbenzenesulfonic acid (15.0 mol% based on the total monomers)
Cetyl alcohol 1.5 parts by weight Water 200 parts by weight <Preparation of resin particle dispersion>
The aqueous solution was prepared and stirred in a constant temperature bath at 70 ° C. for 1 hour. Put the aqueous phase 2 in a 1 liter container, add the oil phase, and then stir for 3 minutes at 8000 rpm with Ultra Turrax (manufactured by IKA), then throw the emulsion into a 500 ml reactor equipped with a stirrer In a nitrogen atmosphere, polycondensation was carried out at 70 ° C. for 24 hours.
To this resin particle dispersion, 1.1 parts by weight of ammonium persulfate dissolved in 10 parts by weight of ion-exchanged water was added, and polymerization was further performed in a nitrogen atmosphere for 6 hours to obtain a stable resin particle dispersion. It was. Similarly, a small amount was taken and the physical properties of the polyester / styrene composite polymer were measured.
Weight average molecular weight of styrene by GPC: 39,000
Weight average molecular weight of polyester by GPC: 4,200
Melting point of polyester: 57 ° C
Median diameter: 290 nm
It was confirmed that the obtained polymer was a composite particle of styrene and polyester.

(Preparation of release agent fine particle dispersion (W1))
・ Polyethylene wax 30 parts by weight (Toyo Petrolite, Polywax 725, melting point 103 ° C.)
3 parts by weight of a cationic surfactant (manufactured by Kao Corporation, Sanizol B50) 67 parts by weight of ion-exchanged water After sufficiently dispersing the above components while heating to 95 ° C. with a homogenizer (manufactured by IKA, Ultra Turrax T50) Then, dispersion treatment was performed with a pressure discharge type homogenizer (manufactured by Gorin, Gorin homogenizer) to prepare a release agent particle dispersion (W1). The number average particle diameter D _50n of the release agent particles in the obtained dispersion was 460 nm. Thereafter, ion exchange water was added to adjust the solid concentration of the dispersion to 30%.

(Adjustment of cyan pigment dispersion (C1))
Cyan pigment 20 parts by weight (Daiichi Seika Kogyo Co., Ltd., CI Pigment Blue 15: 3)
・ Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd., Neogen R) 2 parts by weight ・ Ion exchange water 78 parts by weight The above components were adjusted in the same manner as the magenta pigment dispersion (M1), and a cyan pigment dispersion was prepared. Obtained. The number average particle diameter D _50n of the pigment in the dispersion was 121 nm. Thereafter, ion exchange water was added to adjust the solid content concentration of the dispersion to 20%.

(Preparation of resin particle dispersion A: non-crystalline vinyl resin latex)
Styrene 460 parts by weight n-butyl acrylate 140 parts by weight Acrylic acid 12 parts by weight Dodecanethiol 9 parts by weight The above components were mixed and dissolved to prepare a solution.
On the other hand, 12 parts by weight of an anionic surfactant (manufactured by Dow Chemical Co., Dowfax) was dissolved in 250 parts by weight of ion-exchanged water, and the above solution was added and dispersed and emulsified in a flask. (Monomer emulsion A)
Furthermore, 1 part by weight of an anionic surfactant (manufactured by Dow Chemical Co., Dowfax) was dissolved in 555 parts by weight of ion-exchanged water and charged into a polymerization flask.
The polymerization flask was sealed, a reflux tube was installed, and the polymerization flask was heated to 75 ° C. with a water bath while being slowly stirred while injecting nitrogen.
9 parts by weight of ammonium persulfate was dissolved in 43 parts by weight of ion-exchanged water and dropped into the polymerization flask via a metering pump over 20 minutes, and then the monomer emulsion A was added for 200 minutes through the metering pump. It was dripped over.
Thereafter, the polymerization flask was kept at 75 ° C. for 3 hours while continuing the stirring slowly to complete the polymerization.
As a result, an anionic resin particle dispersion A having a median diameter of the resin particles of 290 nm, a glass transition point of 52.0 ° C., a weight average molecular weight of 30,000, and a solid content of 42% was obtained.

<Toner Example 1-1: Preparation of toner using resin particle dispersion example 1-1>
(Preparation of cyan toner (toner C1))
Resin particle dispersion 1 120 parts by weight Resin particle dispersion A 40 parts by weight Release agent particle dispersion (W1) 33 parts by weight Cyan pigment dispersion (C1) 60 parts by weight Polyaluminum chloride 10% by weight aqueous solution 15 parts by weight (Asada Chemical Co., PAC1000W)
-1% nitric acid aqueous solution 3 parts by weight The above components were dispersed in a round stainless steel flask for 3 minutes at 5000 rpm using a homogenizer (manufactured by LKA, Ultra Turrax T50), and then the flask had a magnetic seal. A lid equipped with a stirrer, a thermometer and a pH meter, set a heating mantle heater, and appropriately adjust to the minimum number of revolutions at which the entire dispersion in the flask is stirred, stirring at 62 ° C. The mixture was heated at 1 ° C./1 min until it was kept at 62 ° C. for 30 minutes, and the particle size of the aggregated particles was confirmed with a Coulter counter (manufactured by Nikka Machine Co., Ltd., TA II). Immediately after the temperature increase was stopped, 50 parts by weight of the resin particle dispersion 1 was added and held for 30 minutes. Then, an aqueous sodium hydroxide solution was added until the pH in the system reached 6.5, and then 97 ° C. at 1 ° C./1 min. Until heated. After the temperature rise, an aqueous nitric acid solution was added to adjust the pH in the system to 5.0, and the aggregated particles were heated and fused by holding for 10 hours. Thereafter, the temperature in the system was lowered to 50 ° C., an aqueous sodium hydroxide solution was added to adjust the pH to 12.0, and the mixture was maintained for 10 minutes. Then, after removing from the flask, sufficiently filtering with ion-exchanged water and washing with water, dispersed in ion-exchanged water so that the solid content becomes 10% by weight, added nitric acid and stirred at pH 3.0 for 10 minutes Then, the slurry obtained by sufficiently filtering and washing with water through ion exchange water again was freeze-dried to obtain a cyan toner (toner C1).

To the cyan toner, silica (SiO ₂ ) fine particles having a primary particle average particle size of 40 nm and surface hydrophobized with hexamethyldisilazane (hereinafter sometimes abbreviated as “HMDS”), metatitanic acid and isobutyltrimethoxysilane Metatitanic acid compound fine particles having an average primary particle diameter of 20 nm as a reaction product were added in an amount of 1% by weight, respectively, and mixed with a Henschel mixer to prepare a silica externally added toner.
The cumulative volume average particle diameter D ₅₀ of the toner before external addition thus prepared was 5.7 μm, the volume average particle size distribution index GSDv was 1.23, and the shape factor of the toner particles was 129.
The volume average cumulative volume-average particle diameter D ₅₀ particle size distribution index GSDv of a laser diffraction type particle size distribution measuring apparatus of the toner (manufactured by Horiba, Ltd., LA-700), also, the shape factor was calculated respectively by the shape observation with LUZEX image analyzer .

  Cyan toners were prepared using the resin dispersions of all Examples and Comparative Examples by the same method and formulation as in Toner Example 1-1.

[Toner Evaluation Method]
<Evaluation of thermal storage stability (heat resistance blocking property) of toner>
5 g of toner was left in a chamber at 40 ° C. and 50% RH for 17 hours. Thereafter, after returning to room temperature, 2 g of toner was put into a mesh having an opening of 45 μm and vibrated under certain conditions. The weight of the toner remaining on the mesh was measured, the weight ratio with respect to the charged amount was calculated, and this value was used as the heat resistant blocking index of the toner.
Heat blocking index
When it is 5% or less, “Grade 3”
“Grade 2” when it exceeds 5% and is below 10%
When it exceeds 10%, "Grade 1"
It was.

<Cold offset evaluation>
An image was formed on the transfer paper by changing the fixing set temperature using an image forming apparatus (a modified DocuCenterColor 500 manufactured by Fuji Xerox Co., Ltd.), and the hot offset generation temperature was evaluated.
Hot offset evaluation criteria are
"Grade 3" over 200 ℃,
“Grade 2” from 190 ° C to less than 200 ° C
"Grade 1" below 190 ° C
It was.

<Image stability evaluation>
Using the modified machine, 100,000 images were printed, and image defects due to photoconductor filming were evaluated for the initial and 100,000-image images.
The evaluation criteria for image quality stability are shown below.
No image defects: “Grade 3”
Slight image defects occur: “Grade 2”
Obvious image defects occur: “Grade 1”

<Comprehensive evaluation of toner performance>
The above evaluation was performed, and the performance of each toner was determined from each evaluation grade as follows.
Average of each evaluation grade is 2.5 or more: ○
Average of each evaluation grade is 2.0 or more: △
Average of each evaluation grade is less than 2.0: ×

<Comprehensive evaluation of toner stability>
Further, the above evaluation was performed, and the stability of each toner with respect to the catalyst amount was evaluated as follows.
1 or less grades with different grades with changes in catalyst concentration:
There are two or more evaluations with different grades according to changes in the catalyst concentration, and there is one evaluation with two or more changes: Δ
There are three types of evaluations with different grades 1 as the catalyst concentration changes, and there are two or more types of evaluations with grades changing by 2 or more: ×

  The evaluation results of Examples 1 to 4 and Comparative Examples 1 to 7 are shown in Table 1 and Table 2 below.

Claims (7)

A method for producing a binder resin comprising a step of polycondensing a polycondensable monomer using a polycondensation catalyst,
As the polycondensation catalyst, at least one compound represented by the following formula (I) or (II) and at least one compound represented by the following formula (III) or (IV) are used,
The weight ratio of the total amount of the compound represented by the following formula (I) or (II) to the total amount of the compound represented by the following formula (III) or (IV) is 5:95 to 95: 5 There is provided a method for producing a binder resin.

(In formula (I), R ¹ represents a linear alkyl group having 8 to 20 carbon atoms, R ² represents a monovalent organic group, and the number n of substituents of R ² represents an integer of 0 to 4. .)

(In the formula (II), R ³ represents a linear alkyl group having 8 to 20 carbon atoms.)

(In the formula (III), R ⁴ represents a branched alkyl group having 8 to 20 carbon atoms, R ⁵ represents a monovalent organic group, and the number m of substituents in R ⁵ represents an integer of 0 to 4. .)

(In formula (IV), R ⁶ represents a branched alkyl group having 8 to 20 carbon atoms.) A resin particle dispersion in which resin particles containing at least a binder resin are dispersed in a dispersion medium,
A resin particle dispersion comprising the binder resin produced by the production method according to claim 1. A step of preparing an emulsified dispersion in which an oil phase containing at least a polycondensable monomer is emulsified and dispersed in an aqueous medium; and
The method for producing a resin particle dispersion according to claim 2, comprising a step of polycondensing a polycondensable monomer in an aqueous medium using the polycondensation catalyst. 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 aggregating 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 2 or the resin particle dispersion produced by the production method according to claim 3.   An electrostatic charge image developing toner produced by the production method according to claim 4.   An electrostatic image developer comprising the electrostatic image developing toner according to claim 5 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 thermally 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 5 as the toner or the electrostatic image developer according to claim 6 as the developer.