JP2009197069A - Aqueous dispersion liquid of resin particle and method for manufacturing the same, toner for electrostatic charge image development and method for manufacturing the same, electrostatic charge image developer, image forming method, and image forming apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an aqueous dispersion liquid of resin particles and a method for manufacturing the aqueous dispersion liquid with a simple manufacturing process and excellent dispersibility of resin particles, and to provide a toner for electrostatic charge image development and a method for manufacturing the toner improved in maintaining property of picture quality when continuously used for a long period of time even under high temperature and high humidity conditions. <P>SOLUTION: The aqueous dispersion liquid of resin particles contains a polymer dispersant by 0.1 to 30 wt.% with respect to a resin solid content, the polymer dispersant having a weight-average molecular weight of not less than 5,000 and comprising a condensate of a monomer having polycondensation property and containing a hydroxycarboxylic acid that has hydroxy groups and carboxy groups in total not less than three. The toner for electrostatic charge image development is produced by using the above aqueous dispersion liquid of resin particles. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an aqueous dispersion of resin particles and a method for producing the same. The present invention also relates to an electrostatic charge image developing toner using the aqueous dispersion of resin particles as a raw material, a method for producing the same, an electrostatic charge image developer, an image forming method and an image forming apparatus using them.

An organic solvent is usually required for preparing an emulsified dispersion of a polycondensation resin such as a polyester resin. Since the organic solvent tends to remain in the electrostatic image developing toner, image defects such as toner fusing (filming) to the photoreceptor are likely to occur.
Various studies have been made on the preparation of emulsion dispersions of polycondensation resins such as polyester resins.
For example, studies have been made on solvent-free emulsification at high temperatures. In Patent Document 1, a toner raw material containing at least a polyester resin is heated and melted to produce a melt of the toner raw material, and then the melt is emulsified in an aqueous medium to form resin particles. Then, a method for producing a toner for developing an electrostatic charge image is disclosed, in which the resin particles are aggregated and further fused to produce an aggregate of the resin particles.

Furthermore, means for obtaining a composite resin particle dispersion by dissolving a polycondensation resin in an addition polymerizable monomer or the like and so-called miniemulsion polymerization has been studied.
Conventionally, a method in which a polyester resin having an acidic group is emulsified and dispersed in water in the presence of a basic neutralizing agent, and the dispersed resin particles are aggregated and fused to form a toner is known.

  Patent Document 2 has a dispersion stabilizer after dissolving a hydrophobic polycondensable compound in a solution obtained by dissolving and dispersing an electrophotographic toner component in a volatile solvent having a boiling point of 100 ° C. or less. A step of mixing and stirring with water to emulsify and removing the volatile solvent from the emulsion, and then adding a hydrophilic compound that reacts with the polycondensable compound, followed by interfacial polycondensation substantially. A method for producing a spherical toner is disclosed.

  Patent Document 3 discloses a synthetic resin that generates an aqueous slurry containing colorant-containing synthetic resin particles by heating or heat-pressing a resin kneaded product containing a synthetic resin that can be granulated in a molten state and a colorant in water. In the toner production method including the particle generation step and the cooling step of cooling the aqueous slurry containing the colorant-containing synthetic resin particles, the resin kneaded product does not contain an organic solvent, and the water-soluble in the synthetic resin particle generation step. Generating colorant-containing synthetic resin particles in the presence of a polymer dispersant and adding an aqueous dispersion containing a poorly water-soluble alkaline earth metal salt to an aqueous slurry containing the colorant-containing synthetic resin particles in the cooling step A method for producing a toner is disclosed.

  Patent Document 4 discloses a method in which a trivalent or higher valent hydroxy acid is used in the composition of a polyester resin and heat is applied together with a monomer capable of reacting with a carboxy group to perform extension polymerization.

  A polyester resin is often used as a toner resin for low-temperature fixing because the strength of the resin is relatively high even at a low molecular weight as compared with a resin such as a styrene acrylic copolymer. Moreover, the method of mixing 2 types of polyester resins from which molecular weight distribution differs is proposed (refer patent documents 5-7).

JP 2002-351140 A Japanese Patent Laid-Open No. 63-030863 JP 2005-345734 A JP-A-9-227668 JP-A-60-214368 JP-A-63-225244 JP-A-4-313760

The problem to be solved by the present invention is to provide an aqueous dispersion of resin particles having a simple production process and excellent resin particle dispersibility, and a method for producing the same.
Another problem to be solved by the present invention is to provide a toner for developing an electrostatic charge image with improved maintainability of image quality during long-term continuous use even under high temperature and high humidity, and a method for producing the same.

The above-described problems of the present invention have been solved by means described in <1> to <15> below.
<1> A polymer dispersant comprising a condensation product of a polycondensable monomer containing a hydroxycarboxylic acid having a weight average molecular weight of 5,000 or more and a total of 3 or more hydroxy groups and carboxy groups is 0 per resin solid content. An aqueous dispersion of resin particles, characterized by containing 1 to 30% by weight,
<2> At least one polymerizable resin selected from the group consisting of the polymer dispersant, a polycondensation resin excluding the polymer dispersant, a polyaddition resin, and an addition polymerizable resin in the resin solid content. An aqueous dispersion of the resin particles according to <1>, containing 50 to 100% by weight,
<3> An aqueous dispersion of resin particles according to <1> or <2>, wherein the content of the polymer dispersant is 5% by weight or more based on the polymerizable resin excluding the polymer dispersant,
<4> The polymer dispersant is a condensate obtained by polycondensation of at least one hydroxycarboxylic acid selected from the group consisting of formulas (1) to (3) <1> to <3> An aqueous dispersion of the resin particles according to any one of the above,

Ｒ¹〜Ｒ⁴はそれぞれ独立に水素原子又はアルキル基を表し、同一でも異なっていてもよい。

R ^{1 to} R ⁴ each independently represent a hydrogen atom or an alkyl group, and may be the same or different.

<5> The aqueous dispersion of resin particles according to any one of <1> to <4>, wherein the polymer dispersant is a self-condensate of hydroxycarboxylic acid having a total of 3 or more hydroxy groups and carboxy groups,
<6> An aqueous dispersion of resin particles according to any one of <1> to <5>, wherein an average particle diameter of the resin particles is 50 to 600 nm,
<7> A mixing step of mixing the polymer dispersant with the melted polycondensation resin and an emulsification step of emulsifying the mixture obtained by the mixing step <1> to <6> A method for producing an aqueous dispersion of resin particles according to any one of the above,
<8> A mixing step of mixing an aqueous phase containing the polymer dispersant and an oil phase containing a polycondensation resin and / or a polyaddition resin and an addition polymerizable monomer, and a mixture obtained by the mixing step The method for producing an aqueous dispersion of resin particles according to any one of <1> to <6>, comprising an emulsification step for emulsification and an addition polymerization step for addition polymerization of the addition polymerizable monomer. Method,
<9> Aggregation step of aggregating the resin particles in a dispersion containing a resin particle dispersion, a colorant dispersion, and a release agent dispersion to obtain aggregated particles, and heating the aggregated particles for fusion A resin obtained by the aqueous dispersion of resin particles according to any one of <1> to <6> or the production method according to <7> or <8> A method for producing a toner for developing an electrostatic image, wherein the toner is an aqueous dispersion of particles,
<10> An electrostatic image developing toner produced by the method for producing an electrostatic image developing toner according to <9>,
<11> An OH value (before thermal fixing) of the electrostatic image developing toner before thermal fixing and an image after thermal fixing, further comprising a compound having two or more groups that react with the hydroxy group in the electrostatic image developing toner. The toner for developing an electrostatic charge image according to <10>, which is for heat fixing having the following relationship with the OH value (after heat fixing):
OH value (before heat fixing)> OH value (after heat fixing)
<12> The electrostatic image developing toner according to <11>, wherein the compound having two or more groups that react with a hydroxy group in the electrostatic image developing toner is a polyisocyanate compound.
<13> An electrostatic charge image developer comprising the electrostatic charge image developing toner according to any one of <10> to <12>,
<14> An electrostatic latent image forming step for forming an electrostatic latent image on the electrostatic latent image holding member, and developing the latent image on the electrostatic latent image holding member with a developer containing an electrostatic charge image developing toner. An image forming step for forming a toner image, a transfer step for transferring the toner image, and a fixing step for fixing the toner image. <10> to <12> An image forming method comprising using the electrostatic charge image developing toner according to any one of the above, or the electrostatic charge image developer according to <13> as the developer,
<15> An electrostatic latent image holding member, a charging unit for charging the electrostatic latent image holding member, and exposing the charged electrostatic latent image holding member to expose the electrostatic latent image on the electrostatic latent image holding member. An exposure unit for forming an image; a developing unit for developing the electrostatic latent image with a developer containing toner for developing an electrostatic image; and a toner image is formed from the electrostatic latent image holding member. <13> as the toner for developing an electrostatic charge image according to any one of <10> to <12> as the toner for developing an electrostatic image, or the developer as a developer. An image forming apparatus using the electrostatic charge image developer described in 1.

According to the present invention, it is possible to provide an aqueous dispersion of resin particles having a simple production process and excellent resin particle dispersibility, and a method for producing the same.
In addition, according to the present invention, it is possible to provide a toner for developing an electrostatic image having improved image quality maintainability during long-term continuous use and a method for producing the same even under high temperature and high humidity.
Furthermore, the present invention can provide an electrostatic charge image developer containing the electrostatic charge image developing toner, an image forming method and an image forming apparatus using the electrostatic charge image developing toner or the electrostatic charge image developer. It was.

I. Aqueous dispersion of resin particles The aqueous dispersion of resin particles of the present invention is a polycondensable monomer containing a hydroxycarboxylic acid having a weight average molecular weight of 5,000 or more and a total of three or more hydroxy groups and carboxy groups. It is characterized by containing 0.1 to 30% by weight of a polymer dispersant made of a condensate (hereinafter also simply referred to as “polymer dispersant”) per resin solid content.
In the present invention, “0.1 to 30% by weight”, which is a description of numerical ranges, is synonymous with “0.1 to 30% by weight”, and hereinafter, other numerical ranges unless otherwise specified. The same applies to the description.
Hereinafter, the aqueous dispersion of resin particles of the present invention will be described in detail.

The aqueous dispersion of resin particles of the present invention refers to a resin particle dispersed in an aqueous medium.
In the present invention, the aqueous medium means a mixed solvent that preferably contains 50% by weight or more of water and may be mixed with a water-miscible organic solvent. The mixing ratio of water in the mixed solvent is more preferably 60 to 100% by weight, still more preferably 70 to 100% by weight. Most preferably, the aqueous medium is 100% by weight of water. The water is preferably soft water or ion exchange water. These may be used individually by 1 type and may use 2 or more types together.
Examples of the water-miscible organic solvent include ethyl alcohol, methyl alcohol, acetone and acetic acid. Among them, ethyl alcohol is preferable.

  The aqueous dispersion of the resin particles of the present invention is obtained by dispersing a polymer resin such as a polycondensation resin, a polyaddition resin and an addition polymerizable resin using a polymer dispersant, and is substantially solvent-free. Dispersed in an aqueous medium. The term “substantially solvent-free” means that the solvent is not dispersed using a volatile substance such as an aromatic group such as toluene, an ester group such as acetate, or a ketone group such as acetone.

  When an electrostatic charge image developing toner (hereinafter, also simply referred to as “toner”) is prepared using an aqueous dispersion of resin particles that does not use a solvent, the toner particles are exposed to high temperature and high humidity due to the influence of the solvent remaining on the toner. Suppresses the softening behavior of the toner, thereby preventing the occurrence of image defects in which black streaks, black spots, etc. appear in the image due to the phenomenon that the electrostatic image developing toner is fused to the photoreceptor (hereinafter also referred to as filming). it can.

1. Polymer Dispersant The aqueous dispersion of resin particles of the present invention includes a polymer dispersant made of a condensate of hydroxycarboxylic acid having a weight average molecular weight of 5,000 or more and a total of three or more hydroxy groups and carboxy groups. .

  When emulsifying and dispersing a resin solid content composed of a polymerizable resin such as a polycondensation resin, a polyaddition resin and an addition polymerizable resin together with the polymer dispersant in an aqueous medium while heating, the polymer dispersant has a viscosity of the aqueous medium. There is an effect to raise. In addition, the surface active effect of the polymer dispersant promotes uniform dispersion of the molten resin solids in the aqueous medium. Due to these effects, an aqueous dispersion of resin particles can be produced by low-temperature, short-time dispersion treatment.

(Weight average molecular weight of polymer dispersant)
The aqueous dispersion of resin particles of the present invention contains a polymer dispersant having a weight average molecular weight of 5,000 or more. The weight average molecular weight is preferably 6,500 or more, and more preferably 7,500 or more.
When the weight average molecular weight is less than 5,000, the effect of increasing the viscosity of the aqueous medium cannot be obtained. In addition, the emulsifying force is decreased and the dispersed particle diameter of the resin is increased, and when the toner is prepared using the aqueous dispersion of the resin particles, the effect of suppressing the occurrence of filming cannot be obtained. Further, a hydrophobic behavior cannot be obtained after toner drying, and a softening behavior due to water adsorption occurs under high humidity, causing image defects due to filming.

  The upper limit of the weight average molecular weight of the polymer dispersant is preferably 500,000 or less, more preferably 300,000 or less, and still more preferably 100,000 in consideration of dispersibility in an aqueous medium. It is as follows.

(Hydroxycarboxylic acid)
A hydroxycarboxylic acid is a compound having one or more hydroxy groups (—OH) and one or more carboxy groups (—COOH).
In the present invention, the polymer dispersant is a condensate obtained by condensing a polycondensable monomer containing at least one hydroxycarboxylic acid (hydroxy acid) having a total of 3 or more hydroxy groups (hydroxyl groups) and carboxy groups.

  In the present invention, the hydroxycarboxylic acid having a total of 3 or more of at least one kind of hydroxy group and carboxy group includes a hydroxycarboxylic acid having a total of 3 or more of a hydroxy group, a carboxy group, and a group protecting these and / or a protected product thereof. included. A hydroxycarboxylic acid in which at least one hydroxy group or carboxy group is protected is also referred to as a protected product of hydroxycarboxylic acid.

The protective group that the hydroxycarboxylic acid may have is a group that can be deprotected under conditions that do not cause a problem in the production of the polymer dispersant, and a known protective group can be used. Protective groups described in, for example, “Protective Groups in Organic Synthesis” (3rd Edition, by Theodora D. Greene and Peter GM Wuts, published by Wiley, John & Sons, 1999), etc., depending on the reaction conditions, etc. You can choose.
In addition, when performing the synthesis reaction of the polymer dispersant, it is preferable to remove the protecting group from the hydroxy group and carboxy group at the site where the reaction is carried out. May be performed.

  In the present invention, the polymer dispersant is a condensate obtained using at least one hydroxycarboxylic acid having a total of 3 or more hydroxy groups and carboxy groups as a structural unit, and the hydroxycarboxylic acid is a structural unit of 50 It is preferable to contain -100 mol%, It is more preferable to contain 80-100 mol%, It is more preferable to contain 100 mol%. Within the above numerical range, the dispersibility of the resin particles in the aqueous medium is excellent, and the toner production process is stabilized.

  Moreover, as a hydroxycarboxylic acid which has 3 or more in total of the hydroxy group and carboxy group which can be used for this invention, it is preferable that it is a C3-C30 thing, and it is more preferable that it is a C4-C20 thing. Preferably, the carbon number is 4-12.

  Specific examples of the hydroxycarboxylic acid that can be used in the present invention include, but are not limited to, hydroxycarboxylic acids having a total of 3 or more hydroxy groups and carboxy groups. It is preferably at least one hydroxycarboxylic acid selected from the group consisting of hydroxycarboxylic acids represented by 1) to formula (3).

In Formula (1), R ¹ is a hydrogen atom or a linear or branched alkyl group, and the alkyl group is preferably an alkyl group having 1 to 8 carbon atoms, such as a methyl group, an ethyl group, a propyl group, A butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group are more preferable.
Specifically, the compound represented by the formula (1) is 2,2-dimethylolacetic acid, 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, 2,2-dimethylolpentanoic acid, 2,2 -Dimethylolhexanoic acid, 2,2-dimethylolheptanoic acid, 2,2-dimethyloloctanoic acid, etc. can be mentioned, and it should be 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid Is preferred.

In Formula (2), R ² and R ³ are each a hydrogen atom or an alkyl group, preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ² and R ³ are both hydrogen atoms. Is more preferable.
Specific examples of the compound represented by the formula (2) include 2,3-dihydroxybutanoic acid (tartaric acid), 3-methyl-2,3-dihydroxybutanoic acid, 3-ethyl-2,3-dihydroxybutanoic acid, 3-propyl-2,3-dihydroxybutanoic acid, 3-butyl-2,3-dihydroxybutanoic acid, 3-pentyl-2,3-dihydroxybutanoic acid, 3-hexyl-2,3-dihydroxybutanoic acid, 2, 3-dimethyl-2,3-dihydroxybutanoic acid, 2-methyl-3-ethyl-2,3-dihydroxybutanoic acid, 2-methyl-3-propyl-2,3-dihydroxybutanoic acid, 2-methyl-3- Butyl-2,3-dihydroxybutanoic acid, 2-methyl-3-pentyl-2,3-dihydroxybutanoic acid, 2-methyl-3-hexyl-2,3-dihydroxybutanoic acid, 2 3-diethyl-2,3-dihydroxybutanoic acid, 2-ethyl-3-propyl-2,3-dihydroxybutanoic acid, 2-ethyl-3-butyl-2,3-dihydroxybutanoic acid, 2-ethyl-3- Pentyl-2,3-dihydroxybutanoic acid, 2-ethyl-3-hexyl-2,3-dihydroxybutanoic acid, 2,3-dipropyl-2,3-dihydroxybutanoic acid, 2-propyl-3-butyl-2, 3-dihydroxybutanoic acid, 2-propyl-3-pentyl-2,3-dihydroxybutanoic acid, 2-propyl-3-hexyl-2,3-dihydroxybutanoic acid, 2,3-dibutyl-2,3-dihydroxybutane Acid, 2-butyl-3-pentyl-2,3-dihydroxybutanoic acid, 2-butyl-3-hexyl-2,3-dihydroxybutanoic acid, 2,3-dipenti -2,3-dihydroxybutanoic acid, 2-pentyl-3-hexyl-2,3-dihydroxybutanoic acid, 2,3-dihexyl-2,3-dihydroxybutanoic acid, etc., among others, 2,3-dihydroxybutane Acid (tartaric acid) is preferred.

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

  The polymer dispersant is preferably a self-condensate of hydroxycarboxylic acid having a total of 3 or more hydroxy groups and carboxy groups, and is a hydroxycarboxylic acid self-condensate represented by formulas (1) to (3). More preferably.

  In the case of using a polycondensable monomer other than hydroxycarboxylic acid having a total of 3 or more hydroxy groups and carboxy groups, mention may be made of hydroxy acids having one hydroxy group and one carboxy group and / or their protectors. It is done.

(Amount of polymer dispersant used)
The aqueous dispersion of resin particles of the present invention contains the polymer dispersant in an amount of 0.1 to 30% by weight, preferably 0.5 to 20% by weight, in the resin solid content.
When the content of the polymer dispersant is less than 0.1% by weight, the resin solid content is not dispersed in the aqueous medium, or the stability of the dispersion diameter is lost. On the other hand, if the content of the polymer dispersant exceeds 30% by weight, the hygroscopicity of the toner becomes high and image defects occur due to filming under high temperature and high humidity. Inferior.

In the aqueous dispersion of resin particles of the present invention, the content of the polymer dispersant is 5 with respect to the total amount of the polymerizable resin such as a polycondensation resin, a polyaddition resin, and an addition polymerizable resin excluding the polymer dispersant. It is preferably at least wt%, more preferably at least 7 wt%. Moreover, it is preferable that it is 20 weight% or less, and it is more preferable that it is 15 weight% or less.
When the content of the polymer dispersant is 5% by weight or more with respect to the polymerizable resin excluding the polymer dispersant, it is preferable because good dispersibility can be obtained, and generation of bulk solids can be suppressed.

(Manufacture of polymer dispersants)
In the present invention, the polymer dispersant can be obtained by a known method and is not limited. For example, the polymer dispersant is synthesized by polycondensing a hydroxycarboxylic acid having a total of 3 or more hydroxy groups and carboxy groups using a polycondensation catalyst. be able to.
Although a well-known thing can be used as a polycondensation catalyst, an acidic catalyst and a metal catalyst are preferable, and an acidic catalyst is more preferable especially.

(Polycondensation catalyst)
In a system using a conventional metal catalyst such as Sn-based or Ti-based, a polycondensation reaction has been performed at a high temperature exceeding 200 ° C. In order to carry out the polymerization at a low temperature of 150 ° C. or lower, which is several tens of degrees Celsius to several tens of degrees Celsius below, an acid catalyst is preferably used, and a sulfur acid catalyst is more preferably used.
This is because conventional metal catalysts such as Sn-based and Ti-based metals exhibit high catalytic activity particularly at 200 ° C. or higher, and very low activity at low temperatures of 150 ° C. or lower. On the other hand, the catalytic activity capacity of sulfuric acid decreases as the temperature rises at a high temperature of 160 ° C. or higher. However, the catalytic activity is high in the low temperature range of 70 to 150 ° C., and the polycondensation reaction at 150 ° C. or lower. Can be suitably used. A reaction mechanism in which the reaction proceeds with the nucleophilic addition of sulfur acid as being within the above numerical range is efficient.

As the sulfur acid catalyst that is an acid catalyst, one that exhibits Bronsted acid-like acidity is preferable. The sulfur acid is a sulfur oxygen acid, and examples thereof include inorganic sulfur acids and organic sulfur acids.
Examples of inorganic sulfur acids include sulfuric acid, sulfurous acid, and salts thereof, and examples of organic sulfur acids include sulfonic acids such as alkylsulfonic acid, arylsulfonic acid, and salts thereof, alkylsulfuric acid, arylsulfuric acid, and salts thereof, and the like. Organic sulfates. The sulfur acid that can be used in the present invention is preferably an organic sulfur acid.
It is more preferable to use an acid having a surface active effect. The acid having a surface-active effect has a chemical structure composed of a hydrophobic group and a hydrophilic group, and has an acid structure in which at least a part of the hydrophilic group is composed of protons. It is a compound having both.

  Examples of the sulfur acid that can be used in the present invention include alkylbenzene sulfonic acid such as dodecylbenzene sulfonic acid, isopropyl benzene sulfonic acid, and camphor sulfonic acid, alkyl sulfonic acid, alkyl disulfonic acid, alkyl phenol sulfonic acid, and alkyl naphthalene sulfone. Higher fatty acid sulfuric acid such as acid, alkyltetralinsulfonic acid, alkylallylsulfonic acid, petroleum sulfonic acid, alkylbenzimidazolesulfonic acid, higher alcohol ether sulfonic acid, alkyldiphenylsulfonic acid, monobutylphenylphenol sulfate, dibutylphenylphenol sulfate dodecyl sulfate Ester, higher alcohol sulfate, higher alcohol ether sulfate, higher fatty acid amide alkylol sulfate, higher fatty acid amide ester Killed sulfate ester, naphthenyl alcohol sulfate, sulfated fat, sulfosuccinate ester, various fatty acids, sulfonated higher fatty acid, higher alkyl phosphate ester, resin acid, resin acid alcohol sulfuric acid, naphthenic acid, paratoluene sulfonic acid and these All the salt compounds etc. are mentioned, These may be used independently and may combine two or more as needed.

In the present invention, by adding a sulfur acid catalyst, a polymer dispersant can be obtained even when a polycondensation reaction is performed at a temperature lower than the conventional reaction temperature.
The reaction temperature is preferably 70 to 150 ° C, more preferably 80 to 140 ° C. When the reaction temperature is 70 ° C. or higher, the reactivity of the polycondensation component is not decreased due to the decrease in the solubility and the catalyst activity, and the molecular weight is not prevented from increasing. Moreover, it can manufacture with low energy as reaction temperature is 150 degrees C or less. Further, coloring of the polymer dispersant, decomposition of the generated polymer dispersant, and the like do not occur.

  The amount of the sulfur acid used is preferably 0.01 to 5% by weight based on the total weight of the polycondensable monomer such as hydroxycarboxylic acid having a total of 3 or more hydroxy groups and carboxy groups, and 0.03 It is more preferably ˜3% by weight, and further preferably 0.05 to 2% by weight.

In the present invention, for the polycondensation of the polymer dispersant, a polycondensation catalyst such as the following metal catalyst or hydrolase may be used in addition to the sulfur acid as necessary.
(Metal catalyst)
Examples of the metal catalyst include, but are not limited to, the following. Examples thereof include organic tin compounds, organic titanium compounds, organic antimony compounds, organic beryllium compounds, organic strontium compounds, organic germanium compounds, organic tin halide compounds, and rare earth-containing catalysts. Among these, an organic tin compound and an organic titanium compound are preferable, and dibutyltin oxide, tetrabutoxy titanium and the like are more preferable.

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

As the rare earth-containing catalyst, those having a triflate structure such as scandium triflate, yttrium triflate and lanthanoid triflate are preferable. The lanthanoid triflate is described in detail in Journal of Synthetic Organic Chemistry, Vol. 53, No. 5, p44-54). An example of the triflate is X (OSO ₂ CF ₃ ) _{3 in} the structural formula. Here, X is a rare earth element, and among these, X is more preferably scandium (Sc), yttrium (Y), ytterbium (Yb), samarium (Sm), or the like.

  However, among the above metal catalysts as the catalyst, when using a metal catalyst such as Sn-based or Ti-based, the metal content derived from the catalyst in the resulting polymer dispersant is preferably 100 ppm or less, More preferably, it is 75 ppm or less, and further preferably 50 ppm or less. Therefore, it is preferable not to use a metal catalyst or to use a very small amount even when a metal catalyst is used.

The amount of the metal catalyst used is preferably 0.01 to 5% by weight, more preferably 0.03 to 3% by weight, based on the total weight of the polycondensable monomer containing hydroxycarboxylic acid. 0.05 to 2% by weight is more preferable. Within the above numerical range, the amount of residual metal can be kept small, and the toner can be stabilized in terms of chargeability and hygroscopicity.
Within the above numerical range, even when the electrostatic charge image developing toner is stored for a long time under high temperature and high humidity, the decrease in the electrical resistance value of the toner particles due to the presence of the residual metal can be suppressed, and the charge amount is decreased. It is possible to suppress the fogging of the non-image part.

  The amount of metal in the polymer dispersant can be measured by various analysis methods such as analysis by fluorescent X-rays and ICP (Inductively Coupled Plasma) emission analysis. Here, the metal content derived from the catalyst means the total amount of titanium, tin and rare earth metal elements.

(Hydrolytic enzyme)
The hydrolase is not particularly limited as long as it catalyzes an ester synthesis reaction. Examples of the hydrolase include EC (enzyme number) 3.1 group (Maruo, Lipoprotein lipase, etc.) such as carboxyesterase, lipase, phospholipase, acetylesterase, pectinesterase, cholesterol esterase, tannase, monoacylglycerol lipase, lactonase and lipoprotein lipase. Such as hydrolase epoxide hydrase 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 which acts on peptide bonds such as hydrolase, aminopeptidase, chymotrypsin, trypsin, plasmin, subtilisin etc. classified into EC3.3 group Water degrading enzymes, hydrolases such classified into EC3.7 group such as furo retinoic hydrolase can be exemplified.

  Among these esterases, the enzyme that hydrolyzes glycerol esters and liberates fatty acids is called lipase, but lipase has high stability in organic solvents, catalyzes ester synthesis reaction in high yield, and can be obtained at a low price. There are advantages such as.

Lipases of various origins can be used, but preferable examples include Pseudomonas genus, Alcaligenes genus, Achromobacter genus, Candida genus, Aspergillus genus, Rhizopus Examples include lipases obtained from microorganisms such as (Rhizopus) genus and Mucor genus, lipases obtained from plant seeds, lipases obtained from animal tissues, pancreatin, and steapsin. Among these, it is desirable to use lipases derived from microorganisms of the genus Pseudomonas, Candida, and Aspergillus.
These polycondensation catalysts may be used alone or in combination. Further, these catalysts can be recovered and regenerated if necessary.

  In the present invention, if necessary, a polycondensation catalyst can be blended in advance in a polycondensable monomer such as hydroxycarboxylic acid.

  This polycondensation reaction can be carried out by a general polycondensation method such as bulk polymerization, emulsion polymerization, suspension polymerization, or other underwater polymerization, solution polymerization, interfacial polymerization, etc., but bulk polymerization and underwater polymerization are preferably used. . Among these, it is preferable to obtain a polymer dispersant by directly polycondensing a polycondensable monomer by bulk polymerization.

2. Resin Solid Content The aqueous dispersion of resin particles of the present invention contains a resin solid content. The resin solid content here is a resin solid content contained in an aqueous dispersion of resin particles, and is mainly obtained by a polymer dispersant that forms resin particles, a polycondensation resin excluding the polymer dispersant, and a polyaddition reaction. And polymerizable resins such as polyaddition resins and addition polymerizable resins. Hereinafter, the polymerizable resin that can be used in the present invention will be described.

(1) Polycondensation resin The aqueous dispersion of the resin particles of the present invention comprises the polymer dispersant in the resin solids, and the polycondensation resin, polyaddition resin and addition polymerizable resin excluding the polymer dispersant. It is preferable to contain 50 to 100% by weight of at least one polymerizable resin selected from the group consisting of

The polycondensation resin that can be used in the present invention is obtained by polycondensation of at least one selected from the group consisting of polycondensable monomers, oligomers thereof, and prepolymers. It is preferable to use the body.
Examples of the polycondensable monomer include polycarboxylic acids, polyols, and polyamines. Preferred examples of polycondensation resins obtained from these polycondensable monomers include polyester resins and polyamide resins.

(1-1) Polyester resin The polyester resin that can be used in the present invention is a polycondensable monomer such as polyol (polyhydric alcohol), polycarboxylic acid (polycarboxylic acid), and hydroxycarboxylic acid (hydroxy acid). And / or obtained by polycondensation of the oligomer or prepolymer of the polycondensable monomer, obtained by polycondensation of a polycondensable monomer containing polycarboxylic acid and polyol. A polyester resin is preferred. In the present invention, it is preferable to use a dicarboxylic acid as the polycarboxylic acid and a diol as the polyol.

Polycarboxylic acids that can be used in the present invention include aliphatic, alicyclic, aromatic polycarboxylic acids, and alkyl esters thereof. Polyols include polyhydric alcohols, ester compounds thereof, hydroxycarboxylic acids, and the like. Including.
The polyester resin can be produced by polycondensation by direct esterification reaction or transesterification reaction using a polycondensable monomer. In this case, the polyester resin to be polymerized may take any form such as an amorphous (amorphous / amorphous / amorphous) polyester resin, a crystalline polyester resin, or a mixed form thereof.

(Polycarboxylic acid)
The polycarboxylic acid that can be used in the present invention is preferably a compound containing two or more carboxy groups in one molecule. Among these, divalent polycarboxylic acid is a compound containing two carboxy groups in one molecule. For example, itaconic acid, mesaconic acid, oxalic acid, succinic acid, maleic acid, adipic acid, glutaric acid, β- Methyl adipic acid, azelaic acid, sebacic acid, suberic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, tetradecanedicarboxylic acid, octadecyldicarboxylic acid, fumaric acid, citraconic acid, diglycolic acid, glutaconic acid, n-dodecyl succinic acid, n-dodecenyl succinic acid, isododecyl succinic acid, isododecenyl succinic acid, n-octyl succinic acid, n-octenyl succinic acid, norbornene dicarboxylic acid, adamantane dicarboxylic acid, adamantane diacetic acid, cyclohexane dicarboxylic acid, Siku Hexene dicarboxylic acid, cyclohexane-3,5-diene-1,2-dicarboxylic acid, malic acid, citric acid, hexahydroterephthalic acid, malonic acid, pimelic acid, tartaric acid, mucoic acid, phthalic acid, isophthalic acid, terephthalic acid, Tetrachlorophthalic acid, chlorophthalic acid, nitrophthalic acid, p-carboxyphenylacetic acid, p-phenylenediacetic acid, p-phenylenedipropionic acid, m-phenylenediglycolic acid, p-phenylenediglycolic acid, o-phenylenediglycolic acid , Diphenylacetic acid, diphenyl-p, p′-dicarboxylic acid, naphthalene-1,4-dicarboxylic acid, naphthalene-1,5-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, anthracene dicarboxylic acid and the like. .
Examples of polycarboxylic acids other than divalent carboxylic acids include trimellitic acid, pyromellitic acid, naphthalenetricarboxylic acid, naphthalenetetracarboxylic acid, pyrenetricarboxylic acid, and pyrenetetracarboxylic acid.
Furthermore, carboxylic acid derivatives such as lower esters, acid chlorides and acid anhydrides of these polycarboxylic acids may be mentioned.
These polycarboxylic acids may be used alone or in combination of two or more. Further, a dicarboxylic acid component having a double bond can be contained in addition to the aliphatic dicarboxylic acid and aromatic dicarboxylic acid described above.

  In the method for producing a polyester resin in the present invention, among the above polycarboxylic acids, 1,4-cyclohexanedicarboxylic acid, azelaic acid, sebacic acid, 1,9-nonanedicarboxylic acid, 1,10-decamethylenedicarboxylic acid, It is preferable to use 1,11-undecanedicarboxylic acid, 1,12-dodecanedicarboxylic acid, terephthalic acid, trimellitic acid, pyromellitic acid and the like. Since these polycarboxylic acids are hardly soluble or insoluble in water, the ester synthesis reaction proceeds in a suspension in which the polycarboxylic acid is dispersed in water, which is preferable.

(Polyol)
The polyol that can be used in the present invention is a compound having two or more hydroxy groups in one molecule.
Examples of the diol include ethylene glycol, propylene glycol, butanediol, butenediol, neopentyl glycol, pentanediol, hexanediol, cyclohexanediol, cyclohexanedimethanol, heptanediol, diethylene glycol, triethylene glycol, dipropylene glycol, and octanediol. , Nonanediol, decanediol, undecanediol, dodecanediol, tridecanediol, tetradecanediol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, octadecanediol, eicosandecanediol, bisphenol A, bisphenol S, bisphenol Z, biphenol, Naphthalenediol, adamantanediol Hydrogenated bisphenol A, and the like.
Examples of polyols other than diols include glycerin, pentaerythritol, hexamethylol melamine, hexaethylol melamine, tetramethylol benzoguanamine, and tetraethylol benzoguanamine.
These may be used alone or in combination of two or more.

In the method for producing a polyester resin of the present invention, among the above-mentioned polyols, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecane. It is preferable to use a divalent polyol such as diol or bisphenol A ethylene oxide adduct.
Since these polyols are hardly soluble or insoluble in water, the ester synthesis reaction proceeds in a suspension in which the polyol is dispersed in water, which is preferable.

  You may use a polycondensable monomer combining 2 or more types by arbitrary ratios. In addition, an amorphous resin or a crystalline resin can be easily obtained by combining these polycondensable monomers.

(Crystalline polyester resin)
As the polycarboxylic acid used to obtain the crystalline polyester resin, among the above carboxylic acids, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, Aliphatic dicarboxylic acids such as 1,9-nonanedicarboxylic acid, 1,10-decanedicarboxylic acid, 1,12-dodecanedicarboxylic acid, 1,14-tetradecanedicarboxylic acid, 1,18-octadecanedicarboxylic acid, maleic acid, fumarate Acid, citraconic acid, itaconic acid, glutaconic acid, n-dodecyl succinic acid, n-dodecenyl succinic acid, isododecyl succinic acid, isododecenyl succinic acid, n-octyl succinic acid, n-octenyl succinic acid, anhydrides thereof , Lower esters or acid chlorides.

Examples of the diol used for obtaining the crystalline polyester resin include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, and 1,4-butene. Diol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1, 11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1,18-octadecanediol, 1,19-eicosandecanediol, dipropylene glycol, polyethylene glycol, Polypropylene Call, polytetramethylene ether glycol, etc. can also be mentioned.
Further, a dihydric or higher polyhydric alcohol can be used in combination. For example, pentaerythritol, hexamethylol melamine, hexaethylol melamine, tetramethylol benzoguanamine, tetraethylol benzoguanamine and the like can be mentioned.

  As such a crystalline polyester resin, a polyester resin obtained by reacting 1,9-nonanediol and 1,10-decanedicarboxylic acid, and obtained by reacting 1,9-nonanediol and sebacic acid. Polyester resin, polyester resin obtained by reacting 1,6-hexanediol and sebacic acid, polyester resin obtained by reacting ethylene glycol and succinic acid, polyester obtained by reacting ethylene glycol and sebacic acid Mention may be made of polyester resins obtained by reacting resins, 1,4-butanediol and succinic acid. Among these, polyester resins obtained by reacting 1,9-nonanediol and 1,10-decanedicarboxylic acid, 1,9-nonanediol and sebacic acid, and 1,6-hexanediol and sebacic acid are more preferable. However, this is not the case.

(Non-crystalline polyester resin)
In addition, as the polycarboxylic acid used for obtaining the non-crystalline polyester resin in the present invention, among the above polycarboxylic acids, the dicarboxylic acids include phthalic acid, isophthalic acid, terephthalic acid, tetrachlorophthalic acid, chlorophthalic acid. Acid, nitrophthalic acid, malonic acid, mesaconic acid, p-carboxyphenylacetic acid, p-phenylene diacetic acid, m-phenylene diglycolic acid, p-phenylene diglycolic acid, o-phenylene diglycolic acid, diphenylacetic acid, diphenyl-p , P′-dicarboxylic acid, naphthalene-1,4-dicarboxylic acid, naphthalene-1,5-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, anthracene dicarboxylic acid, cyclohexanedicarboxylic acid, cyclohexene dicarboxylic acid, norbornene-2, 3-dicarboxylic acid, a Examples thereof include damantane dicarboxylic acid and adamantane diacetic acid.
Examples of the polycarboxylic acid other than dicarboxylic acid include trimellitic acid, pyromellitic acid, naphthalenetricarboxylic acid, naphthalenetetracarboxylic acid, pyrenetricarboxylic acid, and pyrenetetracarboxylic acid. Moreover, you may use what derived the carboxy group of these carboxylic acid into the acid anhydride, acid chloride, ester, etc.
Among these, it is preferable to use terephthalic acid, phenylenediacetic acid, cyclohexanedicarboxylic acid, lower esters of these polycarboxylic acids, and the like. The lower ester means an ester of an aliphatic alcohol having 1 to 8 carbon atoms.

The polyol used for obtaining the non-crystalline polyester resin in the present invention includes, among the above-mentioned polyols, in particular, polytetramethylene glycol, bisphenol A, bisphenol Z, bisphenol S, biphenol, naphthalenediol, adamantanediol, and adamantane. It is preferable to use dimethanol, hydrogenated bisphenol A, cyclohexane dimethanol or the like. The bisphenols are also preferably alkylene oxide adducts, particularly ethylene oxide adducts and propylene oxide adducts.
Among these, the polyol used for obtaining the amorphous polyester resin is preferably an alkylene oxide adduct of bisphenol A, more preferably an ethylene oxide adduct and a propylene oxide adduct of bisphenol A. Further, the alkylene oxide is preferably added in an amount of 2 mol to 4 mol in terms of both ends, and more preferably 2 mol or 4 mol.

  As the non-crystalline polyester resin, polycondensation of bisphenol A propylene oxide 2 mol adduct (2 mol adduct in terms of both ends) or 4 mol adduct (4 mol adduct in terms of both ends) and dimethyl terephthalate , Bisphenol A ethylene oxide 2 mol adduct (2 mol adduct in terms of both ends) or 4 mol adduct (4 mol adduct in terms of both ends) and cyclohexanedicarboxylic acid polycondensate or bisphenol A ethylene oxide Alternatively, a 2-condensation product of propylene oxide (2 mol adduct in terms of both ends) or a polycondensate of 4 mol adduct (4 mol adduct in terms of both ends) and phenylenediacetic acid or phenylenedipropionic acid is particularly preferred.

  The polycarboxylic acid and polyol may be used alone or in combination of two or more, each of which may be used alone or in combination of two or more to produce one type of polycondensation resin. May be used. Moreover, when using hydroxycarboxylic acid in order to produce 1 type of polycondensation resin, 1 type may be used individually, 2 or more types may be used, and polycarboxylic acid and a polyol may be used together.

  In the present invention, the polycondensation step may include a polymerization reaction between the polycarboxylic acid and polyol, which are the aforementioned polycondensable monomers, and an oligomer and / or prepolymer prepared in advance. The oligomer and / or prepolymer is not limited as long as it is an oligomer and / or prepolymer that can be melted or uniformly mixed with the polycondensable monomer.

Furthermore, in the present invention, the polycondensation resin contained in the resin particles includes a polycondensation resin obtained by polycondensation of one of the above-described polycarboxylic acid and polyol, one of the above-described polycarboxylic acid and polyol, or both. The polycondensation resin obtained by polycondensation of a polycondensable monomer containing two or more types of polycondensable monomers or a mixture thereof can be used. The polycondensation resin may be a graft polymer or may have a partially branched or crosslinked structure.
In the present invention, a polycondensation resin obtained by polycondensation of each of a polycarboxylic acid and a polyol can be preferably used.

(Crystal melting point)
In the present invention, when a crystalline polyester resin is used as the polycondensation resin, the crystal melting point Tm is preferably 50 to 120 ° C, and more preferably 55 to 90 ° C. It is preferable that Tm is 50 ° C. or higher because the peelability is improved and the offset can be reduced. Further, it is preferable that Tm is 120 ° C. or lower because fixing can be performed at a lower temperature.

  Here, a differential scanning calorimeter (DSC) can be used for measuring the melting point of the crystalline polyester resin. The melting point of the crystalline polyester resin can be obtained as the melting peak temperature of the input compensated differential scanning calorimetry shown in JIS K-7121: 87 when measured from room temperature to 150 ° C. at a heating rate of 10 ° C. per minute. it can. In the measurement using a differential scanning calorimeter (DSC), the crystalline polyester resin may show a plurality of melting peaks, but in the present invention, the maximum peak is regarded as the melting point.

  In the present invention, the “crystallinity” in the “crystalline polyester resin” means that it has a clear endothermic peak, not a stepwise endothermic change, in differential scanning calorimetry (DSC). Specifically, it means that the half-value width of the endothermic peak when measured at a heating rate of 10 ° C./min is within 15 ° C. On the other hand, a resin having a half-value width of an endothermic peak exceeding 15 ° C. or a resin in which no clear endothermic peak is observed means non-crystalline (amorphous).

(Glass-transition temperature)
On the other hand, when an amorphous polyester resin is used as the polycondensation resin, the glass transition temperature (Tg) of the amorphous polyester resin is preferably 30 ° C. or higher, more preferably 30 to 100 ° C., 50 More preferably, it is -80 degreeC.

Here, the glass transition temperature of the non-crystalline polyester resin refers to a value measured by a method (DSC method) defined in ASTM D3418-82.
The glass transition temperature can be measured by, for example, “DSC-20” (manufactured by Seiko Denshi Kogyo Co., Ltd.) according to differential scanning calorimetry (DSC). Specifically, about 10 mg of a sample is heated at a constant rate of temperature increase (10 ° C./min), and the glass transition temperature can be obtained from the intersection of the baseline and the endothermic peak tilt line.

  The amorphous polyester resin having a Tg of 30 ° C. to 100 ° C. is preferably contained in an amount of 5.0% by weight or more, more preferably 10.0 to 90.0% by weight based on the entire resin particles.

(Weight average molecular weight)
In the present invention, when a crystalline polyester resin is used as the polycondensation resin, the weight average molecular weight is 1,000 to 60, as measured by the molecular weight measurement by gel permeation chromatography (GPC) of the tetrahydrofuran (THF) soluble content. 000, preferably 1,500 to 50,000, and more preferably 2,000 to 40,000.
Moreover, when using an amorphous polyester resin as a polycondensation resin, it is preferable that the weight average molecular weight is 1,000-60,000 by the molecular weight measurement by GPC method of THF soluble part, 3,000- It is more preferably 50,000, and further preferably 5,000 to 40,000.
It is preferable that the weight average molecular weight is within the range of the above numerical values since both image strength and fixability can be achieved.
In the present invention, the weight average molecular weight of the polycondensation resin can be measured using a THF soluble material, such as TSK-GEL, GMH (manufactured by Tosoh Corporation), in a THF solvent, and a monodisperse polystyrene standard sample The molecular weight can be calculated using the molecular weight calibration curve prepared by the above.

(1-2) Polyamide resin A polyamine and the polycarboxylic acid can be used as a polycondensable monomer, and an aqueous dispersion of similar resin particles can be produced using a polyamide resin.
Polyamines used to obtain the polyamide resin include ethylenediamine, diethylenediamine, 1,2-propanediamine, 1,3-propanediamine, 1,4-butanediamine, 1,4-butenediamine, 2,2- Examples thereof include dimethyl-1,3-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,4-cyclohexanediamine, 1,4-cyclohexanebis (methylamine), and the like.

(2) Production of polycondensation resin <Polycondensation catalyst>
In the present invention, the polycondensation resin is obtained by polycondensation of a polycondensable monomer or the like. Particularly preferred is a polycondensation resin obtained by polycondensation in the presence of a catalyst. In the present invention, it is preferable that sulfur acid (Bronsted acid containing a sulfur atom) is included as a polycondensation catalyst.
Furthermore, the polycondensation resin is preferably a polycondensation resin obtained by polycondensation at 150 ° C. or lower using sulfur acid as a catalyst.

It is extremely important to avoid the conventional high energy consumption type production method and to produce the polycondensation resin at a low temperature of 150 ° C. or lower in order to reduce the resin production energy in a total sense. Conventionally, a polycondensation reaction has been performed at a high temperature exceeding 200 ° C., but in order to perform polymerization at a low temperature of 150 ° C. or lower which is several tens of degrees Celsius to several tens of degrees Celsius, a sulfur acid catalyst is used. Is preferred. This is because conventional metal catalysts such as Sn-based and Ti-based metals exhibit high catalytic activity especially at 200 ° C. or higher, and very low activity at low temperatures of 150 ° C. or lower.
Sulfuric acid has a catalytic activity that decreases with increasing temperature at temperatures higher than 160 ° C. However, since the reaction proceeds with the nucleophilic addition of the catalytic acid, the polymerization temperature is about 70 ° C to about 70 ° C. Since the catalyst activity is high in a low temperature range of 150 ° C. and can be suitably used for a polycondensation reaction at 150 ° C. or less, it can be suitably used as a polycondensation catalyst in the present invention.

(Sulfur acid)
The sulfur acid is a Bronsted acid containing a sulfur atom, and examples of the sulfur acid include inorganic sulfur acids and organic sulfur acids. Examples of inorganic sulfur acids include sulfuric acid, sulfurous acid, and salts thereof, and examples of organic sulfur acids include sulfonic acids such as alkylsulfonic acid, arylsulfonic acid, and salts thereof, alkylsulfuric acid, arylsulfuric acid, and the like. Organic sulfates such as salts can be mentioned.
The sulfur acid is preferably an organic sulfur acid, and more preferably an organic sulfur acid having a surface active effect. The acid having a surface-active effect has a chemical structure composed of a hydrophobic group and a hydrophilic group, and at least a part of the hydrophilic group has an acid structure composed of protons, and has both an emulsifying function and a catalytic function. A compound.
Examples of organic sulfur acids having a surface active effect include alkylbenzene sulfonic acid, alkyl sulfonic acid, alkyl disulfonic acid, alkylphenol sulfonic acid, alkyl naphthalene sulfonic acid, alkyl tetralin sulfonic acid, alkyl allyl sulfonic acid, petroleum sulfonic acid, alkyl benzoic acid. Imidazole sulfonic acid, higher alcohol ether sulfonic acid, alkyl diphenyl sulfonic acid, long chain alkyl sulfate, higher alcohol sulfate, higher alcohol ether sulfate, higher fatty acid amide alkylol sulfate, higher fatty acid amide alkylated sulfate, sulfate Fat, sulfosuccinic acid ester, resin acid alcohol sulfuric acid, and all of these salt compounds may be mentioned, and a plurality of them may be combined as necessary. Among these, a sulfonic acid having an alkyl group or an aralkyl group, a sulfate ester having an alkyl group or an aralkyl group, or a salt compound thereof is preferable, and the alkyl group or the aralkyl group has 7 to 20 carbon atoms. Is more preferable. Specifically, dodecylbenzenesulfonic acid, pentadecylbenzenesulfonic acid, isopropylbenzenesulfonic acid, camphor sulfonic acid, p-toluenesulfonic acid, monobutylphenylphenol sulfate, dibutylphenylphenol sulfate, dodecyl sulfate, naphthenyl alcohol Examples include sulfuric acid. These sulfur acids may have some functional group in the structure.

The amount of sulfur acid that can be used in the present invention is preferably 0.05 to 20% by weight, and preferably 0.1 to 10% by weight, based on the total weight of the polycondensable monomer component. Is more preferable. It is preferable for the amount of sulfur acid used to be within the above numerical value range since sufficient catalytic activity can be exhibited.
Particularly, it is preferable to add it to the aqueous medium together with the polycondensable monomer, because the stability of the particles is maintained, the polycondensation reaction is further enhanced, and the polycondensation reaction can proceed at a low temperature.

  Other polycondensation catalysts generally used can be used together with the sulfur acid catalyst or alone. Specifically, an acid having a surface active effect, a metal catalyst, a hydrolase type catalyst, and a basic catalyst can be exemplified. As for the metal catalyst and hydrolase type catalyst, the metal catalyst and hydrolase type catalyst used in the production of the polymer dispersant can be used.

(Acid having surface-active effect)
Examples of the acid having a surface active effect include various fatty acids, higher alkyl phosphate esters, resin acids, and all salt compounds thereof, and a plurality of them may be combined as necessary.

(Metal catalyst)
As the polycondensation catalyst, the same metal catalyst used for the production of the polymer dispersant can be used.
When a metal catalyst is used as the catalyst, the metal content derived from the catalyst in the polycondensation resin obtained is preferably 10 ppm or less, more preferably 7.5 ppm or less, and 5.0 ppm or less. More preferably. Therefore, it is preferable not to use a metal catalyst or to use a very small amount even when a metal catalyst is used.

(Basic catalyst)
Examples of basic catalysts include, but are not limited to, general organic basic compounds, nitrogen-containing basic compounds, and tetraalkyl or arylphosphonium hydroxides such as tetrabutylphosphonium hydroxide.

As organic base compounds, ammonium hydroxides such as tetramethylammonium hydroxide and tetraethylammonium hydroxide, and nitrogen-containing basic compounds as 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 thereof such as 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 mentioned, but it is not limited to these.

(Total amount of catalyst added)
The total amount of the catalyst added is preferably 0.05 to 20% by weight, more preferably 0.1 to 10% by weight, based on the polycondensable monomer component. One or a plurality of them can be added in the above ratio.
It is preferable that the total addition amount of the catalyst is within the range of the above numerical value because the polycondensation reactivity can be sufficiently obtained while the reverse reaction and side reaction can be suppressed.

(Polycondensation reaction)
Next, the polycondensation reaction will be described.
In the present invention, it is preferable to obtain a polycondensation resin by polycondensation reaction at a temperature lower than the conventional reaction temperature, and the reaction temperature is preferably 70 to 150 ° C. More preferably, it is 75-130 degreeC, Most preferably, it is 80-100 degreeC.
When the reaction temperature is 70 ° C. or higher, the polycondensable monomer has high solubility and high catalytic activity, so that the reactivity is excellent and the increase in molecular weight is not suppressed. Moreover, polycondensation resin can be manufactured with low energy as reaction temperature is 150 degrees C or less. Further, coloring of the resulting polycondensation resin, decomposition of the produced polycondensation resin, and the like do not occur.

  This polycondensation reaction can be carried out by a general polycondensation method such as bulk polymerization, emulsion polymerization, suspension polymerization, or other underwater polymerization, solution polymerization, interfacial polymerization, etc., but bulk polymerization and underwater polymerization are preferably used. . Among these, it is preferable to obtain a polycondensation resin by directly polycondensing a polycondensable monomer by bulk polymerization.

(Bulk polymerization)
In the case of bulk polymerization, the reaction is possible under atmospheric pressure, but general conditions such as reduced pressure and nitrogen flow can be used for the purpose of increasing the molecular weight of the resulting polycondensation resin.
As the polycondensable monomer, the polycarboxylic acid and polyol are preferably used, and dicarboxylic acid and diol are particularly preferably used. Moreover, it is preferable to use a sulfuric acid as a catalyst, and it is preferable that polycondensation is performed at 150 degrees C or less as mentioned above.

(3) Method for Producing Aqueous Dispersion of Resin Particles Using Polycondensation Resin The method for producing an aqueous dispersion of resin particles according to the present invention is a mixing step in which a polymer dispersant is mixed with a molten polycondensation resin. And an emulsification step of emulsifying the mixture obtained by the mixing step.
The mixing method can be appropriately selected. Examples of the production method that can be suitably used in the present invention include (I) batch emulsification method and (II) continuous emulsification method. Hereinafter, each manufacturing method will be described.

(I) Batch emulsification method In the batch emulsification method, a dispersion or solution of a polymer dispersant in water is prepared and heated. After emulsification, a method of cooling and producing an aqueous dispersion of resin particles can be exemplified.

For example, a polymer dispersant having a weight average molecular weight of 5,000 or more is prepared by self-condensing a hydroxycarboxylic acid such as dimethylolbutanoic acid in the presence of a sulfur acid catalyst, and a predetermined amount is dispersed in water.
Furthermore, in a high-viscosity stirrer such as a desktop kneader, polycarboxylic acid and polyol are melted and mixed, using sulfur acid as a catalyst, polycondensation is carried out under reduced pressure for about 8 hours at 120 ° C. Make it.
The obtained polycondensation resin is cooled to 100 ° C., and the aqueous dispersion of the above-described polymer dispersant is heated to 95 ° C. while stirring the polycondensation resin at 15 RPM, and stirring and rotating while gradually putting it into a desktop kneader. The number is increased to 30 RPM and melt phase inversion emulsification is performed, followed by cooling to produce an emulsion dispersion of a polycondensation resin.

In the batch emulsification method, the dispersion or solution of the polymer dispersant added to the polycondensation resin preferably contains 2 to 50% by weight of the polymer dispersant, more preferably 5 to 40% by weight. 10 to 30% by weight is particularly preferable.
It is preferable that the content of the polymer dispersant is within the above range because the resin dispersion diameter can be controlled within a suitable range.

(II) Continuous emulsification method As a method for dispersing and emulsifying the polycondensation resin, a batch-type kneader such as the above kneader may be used. It is also preferred to produce a dispersion.
FIG. 1 shows an example of a process schematic diagram of the continuous emulsification method. An example of a continuous emulsification method that can be suitably used in the present invention will be described with reference to FIG. In this example, the polycondensation reaction was carried out in an ordinary reactor to obtain a polycondensation resin, and then the above polymer dispersant dispersion was mixed at 95 ° C. while kneading the polycondensation resin using an extruder. And then injecting into the kneading zone of the extruder, and further diluting water is injected into the subsequent process to dilute and stabilize. In this case, a continuous non-solvent emulsification process can be realized, and efficient production can be realized.

(III) Methods other than the above (I) and (II) A polymer obtained by uniformly polymerizing in advance by a solution polymerization method or a cage polymerization method is added to a solvent in which the polymer does not dissolve together with a stabilizer to mechanically An aqueous dispersion of resin particles in which resin particles are dispersed can be obtained by an arbitrary method such as a method of mixing and dispersing the resin particles.
For example, if the solubility in water is relatively low and the resin is soluble in a solvent, the resin is dissolved in the solvent and dispersed with a polymer electrolyte such as an ionic surfactant or polyacrylic acid, and a homogenizer or the like. An aqueous dispersion of resin particles can be obtained by dispersing as a particle in water with a machine and then evaporating the solvent by heating or decompressing.

  Surfactants used here are anionic surfactants such as sulfate, sulfonate, phosphate, and soap, cationic surfactants such as amine and quaternary ammonium salts, polyethylene Nonionic surfactants such as glycols, alkylphenol ethylene oxide adducts, and polyhydric alcohols, and various graft polymers can be exemplified, and are not particularly limited.

(Average particle diameter of resin particles)
In the present invention, the average particle size of the resin particles contained in the aqueous dispersion of resin particles is preferably 50 to 600 nm, and more preferably 150 to 550 nm. Within the above numerical range, the toner particle size distribution after toner preparation can be narrowed.
Here, the average particle diameter means a volume average particle diameter. The volume average particle diameter can be measured using a laser diffraction particle size distribution measuring apparatus or the like.

(4) Polyaddition Resin Preferred examples of the polyaddition resin that can be used in the present invention include polyurethane resins. Hereinafter, the polyurethane resin that can be used in the present invention will be described in more detail.
The polyurethane resin has a urethane bond. The urethane bond is formed by a reaction between a group having active hydrogen (hereinafter also referred to as an active hydrogen group) and an isocyanate group, and is represented by the following formula.
Formula: -N (H) -C (= O) -O-

Active hydrogen refers to a hydrogen atom constituting an organic compound that is easily dissociated as a proton. Specifically, in addition to hydrogen atoms bonded to atoms with high electronegativity, such as hydroxy groups (hydroxyl groups) and amino groups, it binds to carbon substituted with electron-withdrawing groups such as cyano groups, nitro groups, and carbonyl groups. And hydrogen.
Examples of active hydrogen groups involved in the formation of urethane bonds include hydroxy groups, phenolic hydroxyl groups, acetoacetoxy groups, carboxy groups, amino groups and amide groups contained in primary to tertiary alcohols. Hydroxyl groups, phenolic hydroxyl groups, and acetoacetoxy groups contained in alcohols ranging from primary to tertiary are preferred, with hydroxyl groups contained in primary alcohols being most preferred.
Preferred examples of the compound having a group having active hydrogen include a polyol having a hydroxy group.

(Polyol)
In the present invention, the polyol that can be used in the polyaddition reaction of the polyurethane resin may be a known polyol, and is not limited, but is a polycondensable monomer used for the polymerization of the polyester resin. The thing similar to a polyol can be used.
Among them, a diol is preferable, and a diol having a hydroxyl group at both ends of a linear or branched alkylene group having 1 to 20 carbon atoms is more preferable. 1,6-hexanediol, 1,9-nonanediol More preferred is a diol having 5 to 15 carbon atoms such as 1,10-decanediol.

(Polyisocyanate compound)
The polyurethane resin that can be used in the present invention is obtained by polyaddition polymerization of a polyisocyanate compound and a polyol. In the present invention, the polyisocyanate compound (hereinafter also referred to as polyisocyanate) refers to a compound containing at least two isocyanate groups, and is not limited to any other.

The isocyanate content of the polyisocyanate compound (synonymous with “isocyanurate group content”) is preferably 0.5 to 35% by weight based on the total weight of the polyisocyanate compound. The optimum isocyanate content can be varied depending on the application. When the isocyanate content is as high as 15 to 35% by weight, a hard and rigid polyurethane resin is produced. On the other hand, when the isocyanate content is as low as 0.5 to 15% by weight, a soft and low-rigid polyurethane resin is produced.
In the present invention, the isocyanate compound content is preferably 0.5 to 12% by weight, more preferably 1 to 10% by weight, and even more preferably 4 to 9% by weight. It is preferable that the value is within the above range because the mechanical strength when the toner is used is maintained. Further, it is preferable because there is no problem with the charging property of the toner.
The isocyanurate content can be measured according to JIS K7301.

The polyisocyanate compound that can be used in the present invention can be used alone or in combination of two or more polyisocyanate compounds. When two or more polyisocyanate compounds are used in combination, the polyisocyanate compound is preferably at least 1 on average. .5, more preferably at least 1.8 isocyanate groups / molecule.
Also preferably, on average, up to 8 isocyanate groups / molecule, more preferably up to 6 isocyanate groups / molecule, even more preferably up to 4 isocyanate groups / molecule, particularly preferably up to 3 isocyanate groups / molecule. May contain molecules. In the present invention, a diisocyanate compound having two isocyanate groups / molecule can be preferably used.
It is preferable that the value is within the above range because the mechanical strength when the toner is used is maintained. There is no problem with the charging property of the toner.

Specific examples of polyisocyanate compounds that can be used in the present invention include aliphatic polyisocyanate compounds, alicyclic polyisocyanate compounds, aromatic diisocyanate compounds, araliphatic diisocyanate compounds, isocyanurates, and these polyisocyanate compounds. Examples thereof include those blocked with a phenol derivative, oxime, caprolactam and the like.
Examples of the aliphatic polyisocyanate compound include tetramethylene diisocyanate, hexamethylene diisocyanate, and 2,6-diisocyanatomethyl caproate, and examples of the alicyclic polyisocyanate compound include isophorone diisocyanate and cyclohexylmethane diisocyanate. Examples of the aromatic diisocyanate compound include xylylene diisocyanate, tolylene diisocyanate, and diphenylmethane diisocyanate. Examples of the araliphatic diisocyanate compound include α, α, α ′, α′-tetramethylxylylene diisocyanate, and the like. And those obtained by blocking the polyisocyanate compound with a phenol derivative, oxime, caprolactam and the like.

  Among these, the polyisocyanate compound is preferably an aromatic isocyanate, an alicyclic isocyanate, or an aliphatic isocyanate, more preferably an aromatic isocyanate or an alicyclic isocyanate, isophorone diisocyanate, xylylene diene. Isocyanates are more preferred.

Mixtures of isocyanates such as the commercially available mixtures of 2,4- and 2,6-isomers of toluene diisocyanate may also be used. Crude polyisocyanates such as crude toluene diisocyanate obtained by phosgenation of a mixture of toluenediamine isomers, crude diphenylmethane diisocyanate obtained by phosgenation of crude methylenediphenylamine, and the like may also be used in the practice of the present invention. TDI / MDI blends may also be used. TDI represents tolylene diisocyanate, and MDI represents diphenylmethane diisocyanate.
In addition, these polyisocyanate compounds may be used individually by 1 type, and may use 2 or more types together.

  In the polyaddition polymerization of a polyurethane resin using these polyaddition monomers, a known polyaddition polymerization catalyst can be blended in advance if necessary. Examples of the polyaddition polymerization catalyst include the following.

  Specifically, (a) tertiary amine, (b) tertiary phosphine, (c) various metal chelates, (d) strong acid acidic metal salts, (e) strong base, (f) various metals (G) salts of organic acids with various metals such as alkali metals, alkaline earth metals, Al, Sn, Pb, Mn, Co, Ni and Cu, (h) tetravalent tin, 3 Valent and pentavalent As, Sb and Bi, organometallic derivatives of iron and cobalt metal carbonyls, (i) mixtures of two or more of the foregoing.

Examples of (a) tertiary amines include trimethylamine, triethylamine, N-methylmorpholine, N-ethylmorpholine, N, N-dimethylbenzylamine, N, N-dimethylethanolamine, and (b) third. Examples of the class phosphine include trialkylphosphine and dialkylbenzylphosphine. (C) Examples of various metal chelates include Be, Mg, Zn, Cd, Pd, Ti, Zr, Sn, As, Bi, Examples thereof include those obtained from acetylacetone, benzoylacetone, trifluoroacetylacetone, ethyl acetoacetate and the like together with metals such as Cr, Mo, Mn, Fe, Co and Ni. Ferric, stannic chloride, stannous chloride, antimony trichloride, bis nitrate (E) Strong bases include, for example, alkali metal and alkaline earth metal hydroxides, alkoxides and phenoxides, and (f) various metal alcoholates and phenolates. For example, Ti (OR) ₄ , Sn (OR) ₄ and Al (OR) ₃ (wherein R represents an alkyl group or an aryl group) and the alcoholate and carboxylic acid, β-diketone and 2- (N, N -Dialkylamino) reaction products with alcohols, etc. (g) Salts of organic acids with various metals such as alkali metals, alkaline earth metals, Al, Sn, Pb, Mn, Co, Ni and Cu Examples include sodium acetate, stannous octoate (stannous octoate), stannous oleate, lead octoate, and metallic desiccants such as cobalt naphthenate. And (h) tetravalent tin, trivalent and pentavalent As, Sb and Bi, and organometallic derivatives of metal carbonyl of iron and cobalt, etc. (i) two or more of the foregoing Among them, (g) salts of organic acids with various metals such as alkali metals, alkaline earth metals, Al, Sn, Pb, Mn, Co, Ni and Cu are preferable, and tin octoate is preferable. More preferred.

  The polyaddition polymerization catalyst is preferably contained in an amount of 0.01 to 2.0% by weight, more preferably 0.1 to 1.0% by weight, based on the total amount of the polyaddition monomer. When the value is within the above range, the polymerization rate is appropriate, and there is no influence on toner charging.

Here, when the polyaddition resin is a crystalline resin, the crystalline melting point Tm is preferably 50 to 120 ° C, more preferably 55 to 90 ° C. When the Tm is 50 ° C. or higher, the cohesive force of the binder resin itself in a high temperature range is good, and therefore excellent in releasability and hot offset property during fixing. A Tm of 120 ° C. or lower is preferable because sufficient melting can be obtained and the minimum fixing temperature is hardly increased.
On the other hand, when the polyaddition resin is an amorphous resin, the glass transition temperature Tg is preferably 50 to 80 ° C, more preferably 50 to 65 ° C. When the Tg is 50 ° C. or higher, the cohesive force of the binder resin itself in a high temperature range is good, so that it is excellent in hot offset property at the time of fixing. A Tg of 80 ° C. or lower is preferable because sufficient melting can be obtained and the minimum fixing temperature is hardly increased. The crystal melting point Tm and the glass transition temperature Tg can be measured according to the measuring method of the crystal melting point Tm and the glass transition temperature Tg in the polycondensation resin.

  The weight average molecular weight of the polyurethane resin is preferably 1,500 to 50,000, and more preferably 3,000 to 30,000. When the weight average molecular weight is 1,500 or more, the cohesive force of the binder resin is good and the hot offset property is excellent, and when it is 50,000 or less, the hot offset property is excellent and the minimum fixing temperature is excellent. Value is preferred.

(5) Addition polymerizable resin In the present invention, an addition polymerizable monomer, preferably a radical polymerizable monomer, may be added as necessary. For example, polycondensation, polyaddition and addition polymerization may be performed simultaneously or separately to form a composite. The addition polymerizable monomer is preferably a compound having an ethylenically unsaturated bond, and examples thereof include a cationic polymerizable monomer and a radical polymerizable monomer. Preferably there is.

(Radical polymerizable monomer)
Specific examples of the radical polymerizable monomer include α-substituted styrene such as styrene, α-methylstyrene, α-ethylstyrene, m-methylstyrene, p-methylstyrene, 2,5-dimethylstyrene, and the like. Vinyl aromatics such as nucleus-substituted halogenated styrene such as nucleus-substituted styrene, p-chlorostyrene, p-bromostyrene, dibromostyrene, (meth) acrylic acid ("(meth) acryl" means acrylic and methacrylic) The same shall apply hereinafter.), Unsaturated carboxylic acids such as crotonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth ) Acrylate, butyl (meth) acrylate (n-butyl (meth) acrylate, isobutyl (meth) acrylic Pentyl (meth) acrylate, hexyl (meth) acrylate, dodecyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, glycidyl (meth) acrylate, benzyl (meth) acrylate , 2-chloroethyl (meth) acrylate, phenyl (meth) acrylate, α-chloromethyl (meth) acrylate and other unsaturated carboxylic esters, (meth) acrylaldehyde, (meth) acrylonitrile, (meth) acrylamide and the like Saturated carboxylic acid derivatives, N-vinyl compounds such as N-vinyl pyridine and N-vinyl pyrrolidone, vinyl esters such as vinyl formate, vinyl acetate, vinyl propionate, vinyl benzoate, vinyl butyrate, vinyl fluoride, chloride Vinyl, vinyl bromide Nyl, vinylidene chloride and other halogenated vinyl compounds, vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether and other vinyl ethers, N-vinyl pyrrole, N-vinyl carbazole, N-vinyl indole, N-vinyl pyrrolidone and other N N-substitution such as vinyl compounds, N-methylol acrylamide, N-ethylol acrylamide, N-propanol acrylamide, N-methylol maleamic acid, N-methylol maleamic acid ester, N-methylol maleimide, N-ethylol maleimide, etc. Unsaturated amides, conjugated dienes such as butadiene and isoprene, polyfunctional vinyl compounds such as divinylbenzene, divinylnaphthalene and divinylcyclohexane, ethylene glycol di (meth) acrylate, and ethylene Glycol di (meth) acrylate, propylene glycol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, hexamethylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate , Trimethylolpropane tri (meth) acrylate, glycerol di (meth) acrylate, glycerol tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipenta Erythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate Dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, sorbitol tri (meth) acrylate, sorbitol tetra (meth) acrylate, sorbitol penta (meth) acrylate, sorbitol hexa (meth) acrylate, etc. Examples thereof include functional acrylates. Among these, N-substituted unsaturated amides, conjugated dienes, polyfunctional vinyl compounds, polyfunctional acrylates, and the like can also cause a crosslinking reaction in the produced polymer. These can be used alone or in combination.

  The addition amount of the addition polymerizable monomer is preferably 1.0 to 50.0 parts by weight with respect to 100 parts by weight of the resin excluding the addition polymerizable resin such as polycondensation resin and polyaddition resin. More preferably, it is 0.0-30.0 parts by weight. It is preferable that the addition amount of the addition polymerizable monomer is within the above range since a resin excellent in fixing property and particle forming property can be obtained.

(Radical polymerization initiator)
As the polymerization method of the radical polymerizable monomer, a known polymerization method such as a method using a radical polymerization initiator, a self-polymerization method by heat, a method using ultraviolet irradiation or the like can be employed. In this case, the radical polymerization initiator may be oil-soluble or water-soluble, but either radical polymerization initiator can be used.
As the radical polymerization initiator, a known radical polymerization initiator can be appropriately selected and used.
Specifically, for example, 2,2′-azobis (2-methylpropionitrile), 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobisisobutyronitrile, 2 , 2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethyl-4-methoxyvaleronitrile), 1,1′-azobis (cyclohexanecarbonitrile), 2,2 Azobisnitriles such as' -azobis (2-amidinopropane) hydrochloride, acetyl peroxide, octanoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, decanoyl peroxide, lauroyl peroxide, benzoyl peroxide Diacyl peroxide such as oxide, di-t-butyl peroxide, t-butyl-α-cumyl peroxy And dialkyl peroxides such as dicumyl peroxide, t-butyl peroxyacetate, α-cumyl peroxypivalate, t-butyl peroxyoctoate, t-butylperoxyneodecanoate, t-butylperoxy Peroxyesters such as laurate, t-butylperoxybenzoate, di-t-butylperoxyphthalate, di-t-butylperoxyisophthalate, t-butylhydroperoxide, 2,5-dimethylhexane-2, Hydroperoxides such as 5-dihydroperoxide, cumene hydroperoxide, di-isopropylbenzene hydroperoxide, organic peroxides such as peroxycarbonate such as t-butylperoxyisopropyl carbonate, inorganic such as hydrogen peroxide Peroxides, Examples include radical polymerization initiators such as persulfates such as potassium persulfate, sodium persulfate, and ammonium persulfate. A redox polymerization initiator may be used in combination.
The polymerization initiator can be added to a mixture containing a polycondensable monomer or a polycondensation resin, but can also be added to an aqueous medium. Moreover, it can also add to both. It can also be added before emulsification dispersion and can also be added after emulsification dispersion.

  As a usage-amount of a radical polymerization initiator, it is preferable to add 0.001-5 weight part with respect to 100 weight part of addition polymerizable monomers. When it is within the above numerical range, the polymerization rate becomes appropriate and the toner charging is not affected.

(Chain transfer agent)
Moreover, you may use a chain transfer agent at the time of addition polymerization. There is no restriction | limiting in particular as a chain transfer agent, Specifically, what has the covalent bond of a carbon atom and a sulfur atom is preferable, For example, thiols are mentioned preferably.

(Surfactant)
In the present invention, a co-surfactant can be used in combination in order to keep the average particle size of the oil phase containing the addition polymerizable monomer within a specific range. As the co-surfactant, those which are water-insoluble or hardly soluble and monomer-soluble, and those conventionally used in “miniemulsion polymerization” can be used.
Examples of suitable cosurfactants include alkanes having 8 to 30 carbon atoms such as dodecane, hexadecane and octadecane, alkyl alcohols having 8 to 30 carbon atoms such as lauryl alcohol, cetyl alcohol and stearyl alcohol, lauryl ( C8-C30 alkyl (meth) acrylates such as meth) acrylate, cetyl (meth) acrylate and stearyl (meth) acrylate, C8-C30 alkyl mercaptans such as lauryl mercaptan, cetyl mercaptan and stearyl mercaptan Other examples include polymers such as polystyrene and polymethyl methacrylate, polyadducts, carboxylic acids, ketones, amines, and the like.

(Glass-transition temperature)
The glass transition temperature of the addition polymerizable resin is preferably 18.0 ° C or higher, more preferably 20.0 to 80.0 ° C, and further preferably 22.0 to 70.0 ° C. It is preferable that Tg is in the above range since both image storage properties and fixing properties can be achieved.

(Weight average molecular weight)
Moreover, it is preferable that the weight average molecular weight (Mw) of the addition polymerizable resin obtained is 1,500-50,000, and it is more preferable that it is 2,000-40,000. The number average molecular weight (Mn) is preferably 1,000 to 10,000, more preferably 1,500 to 8,000, and still more preferably 2,000 to 6,000. It is preferable that the weight average molecular weight and the number average molecular weight are within the above ranges since both image storage properties and fixing properties can be achieved.

(6) Aqueous dispersion of resin particles having a core-shell structure The method for producing an aqueous dispersion of resin particles of the present invention includes an aqueous phase containing the polymer dispersant, a polycondensation resin and / or a polyaddition resin, and Including a mixing step of mixing an oil phase containing an addition polymerizable monomer, an emulsifying step of emulsifying the mixture obtained by the mixing step, and an addition polymerization step of addition polymerization of the addition polymerizable monomer. It is characterized by.

For example, an addition polymerizable monomer, particularly an addition polymerizable monomer having an ethylenically unsaturated bond such as styrene or acrylate, is added to the obtained polycondensation resin or polyaddition resin, and this is emulsified and dispersed. It is preferable to polymerize the addition polymerizable monomer using a polymerization initiator, particularly a radical polymerization initiator. In this case, the polymerization initiator can be added to the polycondensation resin or the mixture containing the polyaddition resin and the addition polymerizable monomer before emulsification and dispersion, but is preferably added to the aqueous medium.
Further, an addition polymerizable monomer is added to the polycondensable monomer component, and only the polycondensable monomer is polycondensed in the presence of a polycondensation catalyst, and then emulsified and dispersed in an aqueous medium, to form a polymerization initiator. Can also be added to the addition polymerizable monomer for addition polymerization.
When the resin particles contain an addition polymerizable resin, a polycondensation resin or a hybrid resin with the polyaddition resin (particles thereof) can be obtained.
These addition polymerizable monomers can also be polymerized by adding a new monomer after polymerization of the polycondensable monomer.

In the present invention, as described above, polycondensation reaction, polyaddition reaction and the like can be performed in the presence of an addition polymerizable monomer. It is also possible to mix an addition polymerizable monomer after the polycondensation reaction. Finally, addition polymerization of an addition polymerizable monomer can be performed to give composite particles of a polycondensation resin and an addition polymerizable resin.
In the present invention, the average particle diameter of the resin particles having a core-shell structure contained in the aqueous dispersion of resin particles is preferably 50 to 600 nm, and more preferably 150 to 550 nm. It is preferable that the value is within the above numerical range because the particle size distribution of the toner is narrowed.

(7) Addition-polymerizable resin particle dispersion In addition to the above-mentioned aqueous dispersion of resin particles, an addition-polymerizable resin particle dispersion prepared by using conventionally known emulsion polymerization or the like is also used. Can do.

As an example of the addition polymerizable monomer for preparing these addition polymerization type resin particle dispersions, the aforementioned addition polymerizable monomer can be preferably exemplified.
In the case of a highly water-soluble addition polymerizable monomer, an aqueous dispersion of resin particles can be prepared by carrying out emulsion polymerization using an ionic surfactant or the like. In the case of other resins, if they are oily and can be dissolved in a solvent with relatively low solubility in water, dissolve the resin in those solvents and use a disperser such as a homogenizer together with an ionic surfactant or polymer electrolyte. A resin particle dispersion can be obtained by dispersing in an aqueous medium in the form of particles and then heating or reducing the pressure to evaporate the solvent. Moreover, the above-mentioned polymerization initiator, chain transfer agent, etc. can also be used at the time of superposition | polymerization of an addition polymerization type monomer.

II. Toner for developing electrostatic image (1) Method for producing toner for developing electrostatic image The method for producing toner for developing an electrostatic image of the present invention comprises a dispersion comprising a resin particle dispersion, a colorant dispersion, and a release agent dispersion. An aggregating step of aggregating the resin particles in a liquid to obtain aggregated particles, and a fusing step of fusing the aggregated particles by heating, wherein the aqueous dispersion of resin particles is an aqueous dispersion of resin particles of the present invention or It is a water dispersion of resin particles obtained by the production method of the present invention. In addition, the electrostatic image developing toner of the present invention is manufactured by the method for manufacturing an electrostatic image developing toner of the present invention.

  More specifically, the aqueous dispersion of resin particles (aqueous dispersion of resin particles) used in the production of the toner for developing an electrostatic charge image obtained as described above may be used, if necessary. The mixture is mixed with a mold liquid particle dispersion and the like, and further, an aggregating agent is added to cause heteroaggregation to form toner-aggregated particles, and then heated to a temperature equal to or higher than the glass transition temperature or the melting point of the resin particles. The agglomerated particles are fused and united, and further washed and dried.

(Aggregation process)
An agglomeration step of aggregating the resin particles in a dispersion containing a resin particle dispersion, a colorant dispersion, and a release agent dispersion to obtain aggregated particles will be described.
In the aggregation step, when resin particles containing a polymerizable resin such as a polycondensation resin as a resin solid content are prepared in an aqueous medium, they can be used as an aqueous dispersion of resin particles as they are. This aqueous dispersion of resin particles is mixed with a release agent particle dispersion and, if necessary, a colorant particle dispersion and the like. Further, an aggregating agent is added, and these particles are heteroaggregated to agglomerate toner particles. Can be formed.

  Further, after the formation of the first agglomerated particles, an aqueous dispersion of the resin particles of the present invention or another aqueous dispersion of resin particles may be added to form a second shell layer on the surface of the first particles. Is possible. In this illustration, the colorant dispersion is prepared separately. However, when the colorant is blended in advance with the resin particles, the colorant dispersion is not necessary.

Here, as the flocculant, in addition to the surfactant, inorganic salts and divalent or higher metal salts can be preferably used. In particular, when a metal salt is used, it is preferable in characteristics such as aggregation control and toner chargeability. Further, for example, the above-described surfactants can be used for resin emulsion polymerization, pigment dispersion, resin particle dispersion, release agent dispersion, aggregation, aggregation particle stabilization, and the like.
As the dispersing means, a general means such as a rotary shear type homogenizer, a ball mill having a medium, a sand mill, a dyno mill or the like can be used.

  In the present invention, the aggregating method is not particularly limited, and the aggregating method conventionally used in the emulsion polymerization aggregating method of electrostatic charge image developing toner, for example, temperature increase, pH change, salt addition For example, a method of reducing the stability of the emulsion by a method such as stirring with a disperser or the like is used.

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

In the method for producing the toner for developing an electrostatic image of the present invention, various known internal additives such as a charge control agent, an antioxidant, and an ultraviolet absorber used for this type of toner are used as necessary. May be.
The charge control agent can be added either during preparation of the emulsified dispersion (oil phase), during emulsification dispersion, or during aggregation. The charge control agent is preferably added as an aqueous dispersion or the like. The amount of the charge control agent added is preferably 1 to 25 parts by weight, more preferably 5 to 15 parts per 100 parts by weight of the oil phase. It is preferable to add so that it may become a weight part.
Here, in the case of bulk polymerization, the oil phase is a component that contains at least a polymerizable resin and is emulsified and dispersed in an aqueous medium. In the case of polymerization in water, it is a component that contains at least a polymerization component and is emulsified and dispersed in an aqueous medium.

  Examples of the charge control agent include positive charge control agents such as nigrosine dyes, quaternary ammonium salt compounds, triphenylmethane compounds, imidazole compounds, and polyamine resins, or chromium, cobalt, aluminum, iron, and the like. Negative charge charging of metal-containing azo dyes, metal salts and metal complexes such as chromium, zinc and aluminum of hydroxycarboxylic acids such as salicylic acid or acetylsalicylic acid and benzylic acid, amide compounds, phenolic compounds, naphtholic compounds and phenolamide compounds Known agents such as a control agent can be used.

<Release agent>
In the method for producing a toner for developing an electrostatic charge image of the present invention, a wax may be used as a release agent as necessary. In this case, the addition of the release agent is performed during the preparation of the oil phase. It can be added either during emulsification dispersion or aggregation. The release agent is preferably added as an aqueous dispersion or the like. The amount of the release agent added is preferably 1 to 30 parts by weight, more preferably 5 to 5 parts by weight based on 100 parts by weight of the resin solid content. It is preferable to add so that it may become 20 weight part.

  In the present invention, a known release agent can be used. Specific examples of such release agents include low molecular weight polyethylene, low molecular weight polypropylene, copolymerized polyethylene, grafted polyethylene, grafted polyethylene, and other olefinic waxes, behenyl behenate, montanate, stearyl stearate, and the like. Ester wax having long chain aliphatic group, plant wax such as hydrogenated castor oil, carnauba wax, ketone having long chain alkyl group such as distearyl ketone, silicone wax having alkyl group or phenyl group, stearic acid, etc. Higher fatty acid amides, higher fatty acid amides such as oleic acid amide and stearic acid amide, long chain fatty acid alcohols, long chain fatty acid polyhydric alcohols such as pentaerythritol and partial ester thereof, paraffinic wax, Fischer-Tropsch wax There are exemplified, can be used alone or in combination of two or more of these release agents.

  The release agent particle dispersion liquid preferably has a median diameter of 1 μm or less, more preferably 0.1 to 0.8 μm. By setting the median diameter of the release agent particles within the above range, it becomes easier to control the cohesiveness during particle formation and the particle size distribution as a toner, and the releasability during fixing and the temperature at which offset occurs. Can be maintained appropriately.

  The release agent is preferably in the range of 5 to 30% by weight and more preferably in the range of 5 to 25% by weight with respect to the total weight of the solid component constituting the toner. In order to ensure the peelability of the fixed image in the oilless fixing system, it is preferable to be within the above range.

<Colorant>
The electrostatic image developing toner of the present invention preferably contains a colorant.
Examples of the colorant used in the toner of the present invention include carbon black, chrome yellow (CI No. 14090), Hansa yellow, benzidine yellow, selenium yellow, quinoline yellow (CI No. 47005), and permanent orange GTR. , Pyrazolone Orange, Vulcan Orange, Watch Young Red, Permanent Red, Brilliantamine 3B, Brilliantamine 6B, DuPont Oil Red (CI No. 26105), Pyrazolone Red, Resol Red, Rhodamine B Lake, Lake Red C, Rose Bengal (C.I.No. 45435), aniline blue (C.I.No. 50405), ultramarine blue (C.I.No. 77103), calco oil blue (C.I.No. azoic Blue 3) ), Methylene blue chloride (C.I.No. 52015), phthalocyanine blue (C.I.No. 74160), phthalocyanine green, malachite green oxalelate (C.I.No. 42000), titanium black, lamp black (C Various pigments such as I. No. 77266), acridine, xanthene, azo, benzoquinone, azine, anthraquinone, thioindico, dioxazine, thiazine, azomethine, indico, thioindico, Various dyes such as phthalocyanine series, aniline black series, polymethine series, triphenylmethane series, diphenylmethane series, thiazine series, thiazole series, xanthene series, nigrosine series dyes (CI. No. 50415B) etc. Use two or more types together Rukoto can.

  As a method for dispersing these colorants, any method, for example, a general dispersion method such as a rotary shearing homogenizer, a ball mill having a medium, a sand mill, or a dyno mill can be used, and is not limited at all. . Moreover, these colorant particles may be added together with other particle components in the mixed solvent at once, or may be divided and added in multiple stages.

  The amount of the colorant used is preferably 0.1 to 20 parts by weight and more preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the toner.

The toner for developing an electrostatic charge image of the present invention may contain a magnetic material as necessary.
Examples of the magnetic material include ferrite, magnetite, iron, cobalt, nickel and other metals or alloys exhibiting ferromagnetism, compounds containing these elements, or ferromagnetic elements that do not contain ferromagnetic elements but are subjected to appropriate heat treatment. Examples include alloys that exhibit ferromagnetism, for example, a kind of alloy called Heusler alloy containing manganese and copper, such as manganese-copper-aluminum, manganese-copper-tin, or chromium dioxide. For example, in the case of obtaining a black toner, it is particularly preferable to use magnetite which is black in itself and also functions as a colorant. In the case of obtaining a color toner, a toner with less blackness such as metallic iron is preferable. Some of these magnetic materials also function as a colorant, and in that case, they may also be used as a colorant. When the magnetic toner is used, the content of these magnetic materials is preferably 20 to 70 parts by weight, more preferably 40 to 70 parts by weight per 100 parts by weight of the toner.

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

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

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

(2) Toner for developing electrostatic image The cumulative volume average particle diameter D ₅₀ of the toner obtained by the method for producing a toner for developing an electrostatic image of the present invention is preferably 3.0 to 9.0 μm, more preferably. It is 3.0-7.0 micrometers, More preferably, it is 3.0-5.0 micrometers. It is preferable for D _{50 to} be in the above-mentioned range since adhesion is strong and developability is good. Further, it is preferable because the resolution of the image is good.

  Further, the volume average particle size distribution index GSDv of the obtained toner is preferably 1.30 or less. It is preferable that GSDv is 1.30 or less because resolution is good and image loss such as toner scattering and fogging does not occur.

Here, the cumulative volume average particle diameter D ₅₀ and the volume average particle size distribution index can be measured by a measuring instrument such as Coulter Counter TAII (manufactured by Nikka Kisha Co., Ltd.), Multisizer II (manufactured by Nikka Kisha Co., Ltd.), or the like. A cumulative distribution is drawn from the smaller diameter side for each particle size range (channel) divided based on the particle size distribution, and the particle diameter that becomes 16% cumulative is the volume D _16v , the number D _16P , and the cumulative 50%. The particle diameter is _defined as a volume D _50v and a number D _50P , and the particle diameter at a cumulative 84% is defined as a volume D _84v and a number D _84P . Using these, the volume average particle size distribution index (GSDv) is calculated as (D _84v / D _16V ) ^1/2 and the number average particle size distribution index (GSDp) is calculated as (D _84P / D _16P ) ^1/2 .

  The shape factor SF1 of the obtained toner is preferably from 100 to 140, more preferably from 110 to 135, from the viewpoint of image formability. The shape factor SF1 is obtained as follows. First, an optical microscope image of the toner spread on the slide glass is taken into a Luzex image analyzer through a video camera, SF1 is obtained for 50 or more toners, and an average of these is obtained. SF1 is defined as follows.

ここでＭＬ：トナ−粒子の絶対最大長、Ａ：トナ−粒子の投影面積である。

Here, ML is the absolute maximum length of toner particles, and A is the projected area of toner particles.

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

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

(3) Electrostatic image developing toner whose OH value is reduced after thermal fixing In the present invention, the following electrostatic image developing toner can be suitably used as another embodiment of the electrostatic image developing toner.
That is, the toner further includes a compound having two or more groups that react with hydroxy groups in the toner for developing an electrostatic image, and the OH value (before heat fixing) of the toner for developing an electrostatic image before heat fixing and the image after heat fixing. An electrostatic image developing toner for thermal fixing having the following relationship with OH value (after thermal fixing) (hereinafter also referred to as “electrostatic image developing toner whose OH value is reduced during thermal fixing”).
OH value (before heat fixing)> OH value (after heat fixing)

  The toner binder (binder resin) used for electrophotography, electrostatic recording, electrostatic printing, etc. can fix the toner even when the hot roll temperature is low (low temperature fixability), and the toner is heated even at a high hot roll temperature. It is required to satisfy the conflicting performance of not fusing to a roll (hot offset resistance). In recent years, further low-temperature fixability is required from the viewpoint of energy saving, and further hot offset resistance is required from the viewpoint of miniaturization of apparatuses such as copying machines.

  In addition, those disclosed in Patent Documents 5 to 7 are mixed with polyester resins having different softening points, although the balance between low-temperature fixability and hot offset resistance is improving compared to conventional polyester resins. Therefore, there is a problem in uniformity, and in particular, there is a problem that the offset (hereinafter referred to as document offset) when the image portions are stored in an overlapping manner cannot be improved.

  When a toner image containing this type of binder resin is heated near or above the glass transition temperature, the resin component of the image portion melts and adheres to the back side of the printed matter or other printed matter, A problem that an image is lost, that is, a document offset problem occurs.

  In recent years, double-sided printing has been increasing. However, in double-sided output, image portions are inevitably brought into contact with each other, and thus image loss is more likely to occur than in single-sided output. If the difference between the softening points of the two polyester resins is reduced, the image offset property is improved, but conversely, the problem of insufficient improvement in low-temperature fixability and document offset property arises.

  As a result of intensive studies to develop a technique for emulsifying a toner having excellent low-temperature fixing property, hot offset resistance, and document offset property by an environmentally friendly manufacturing method without using an organic solvent. The present invention has been reached.

In the electrostatic image developing toner in which the OH value is reduced before and after the thermal fixing of the present invention, the compound having two or more groups that react with the hydroxy group in the resin contained in the electrostatic image developing toner is a known one. Although it can be used and is not limited, it is preferably a compound having at least two isocyanate groups (polyisocyanate compound).
Examples of the resin having a hydroxy group contained in the electrostatic image developing toner include the polymer dispersant. It is preferable that the hydroxyl group contained in the polymer dispersant and the isocyanate group contained in the polyisocyanate compound form a urethane bond by heating during heat fixing.

  The toner for developing an electrostatic charge image whose OH value is reduced at the time of heat fixing is a toner in which the OH value in the polymer dispersant contained in the toner is reduced before and after the toner is melted, and the nitrogen atom ratio derived from the urethane bond is increased. is there.

  Due to the pseudo-crosslinking structure formed by urethane bonds formed when the toner is melted, the binder resin is thickened and the offset resistance of the electrostatic image developing toner is improved. In addition, even if the initial melt is low viscosity, thickening due to urethane bond formation occurs in the latter half of the melt, it is possible to improve the low temperature fixability by reducing the molecular weight of the resin while maintaining hot offset resistance Is possible. Furthermore, since the binder resin has a strong urethane bond in the fixed image, it is excellent in storage stability of the fixed image, and in particular, the document offset phenomenon when the fixed image surfaces are bonded together is improved.

Whether or not a urethane bond has been formed can be determined by measuring the OH value before and after thermal fixing. Specifically, the OH value (before heat fixing) caused by the binder resin contained in the toner before fixing and the OH value (after heat fixing) caused by the binder resin of the image after fixing have the following relationship: Can be judged.
OH value (before heat fixing)> OH value (after heat fixing)

  For the OH value, the binder resin before or after heat fixing is allowed to act with an excess of succinic anhydride in a molten state to convert hydroxy groups into COOH groups. Next, the binder resin is dissolved in chloroform or dimethyl sulfoxide. It is then purified by repeated reprecipitation with acetone. The purified binder resin is subjected to non-aqueous titration with an N / 50 caustic soda ethanol solution using phenolphthalein as an indicator to determine the OH value. The OH value is mainly derived from the number of hydroxy groups contained in the chain and at the end of the polymer dispersant obtained by polycondensation of the hydroxycarboxylic acid.

  The OH value of the polymer dispersant that can be used in the present invention is preferably in the range of 300 to 1,000 mgKOH / g. The value of the OH value (before heat fixing) depends on the amount of the polymer dispersant contained in the toner, but is preferably in the range of 30 to 500 mg KOH / g in terms of OH value (before heat fixing).

  Further, the nitrogen atom ratio derived from the urethane bond of the binder resin in the fixed image is preferably 10 atm% or more. Within the above numerical range, a firm fixed image is formed, and it is possible to achieve both low temperature fixability of toner and document offset.

Here, the nitrogen element ratio (urethane exposure amount) derived from urethane bonds on the surface of the resin particles can be quantified by photoelectron spectroscopy (XPS).
In this method, first, each individual spectrum of a material constituting a polymer, that is, a polyurethane resin, a polyester resin, a polymer dispersant, and, if necessary, a colorant and a release agent is measured, and By fitting the spectrum obtained from the measurement with each individual spectrum, the surface exposure rate of polyurethane in the resin particles is determined. Specifically, it is determined as a nitrogen element ratio derived from urethane bonds measured by XPS.

The polyisocyanate compound that can be used in the present invention is not particularly limited as long as it can be a known one and has two or more isocyanate groups in the molecule. And alicyclic polyisocyanate compounds.
Specific examples of the aromatic polyisocyanate compound include 2,4-tolylene diisocyanate (2,4-TDI), 2,6-tolylene diisocyanate (2,6-TDI), 4,4′-diphenylmethane diisocyanate ( 4,4'-MDI), 2,4'-diphenylmethane diisocyanate (2,4'-MDI), 1,4-phenylene diisocyanate, polymethylene polyphenylene polyisocyanate, xylylene diisocyanate (XDI), tetramethylxylylene diisocyanate ( TMXDI), tolidine diisocyanate (TODI), 1,5-naphthalene diisocyanate (NDI), triphenylmethane triisocyanate, and the like. As the aliphatic polyisocyanate compound, hexamethylene diisocyanate (H I), trimethylhexamethylene diisocyanate (TMHDI), lysine diisocyanate, norbornane diisocyanate methyl (NBDI), and the like. Examples of alicyclic polyisocyanate compounds include transcyclohexane-1,4-diisocyanate and isophorone diisocyanate (IPDI). Bis (isocyanatomethyl) cyclohexane (H6XDI), dicyclohexylmethane diisocyanate (H12MDI), and the like. In addition, carbodiimide-modified polyisocyanate of each of the above polyisocyanate compounds and their isocyanurate-modified polyisocyanate compounds. These can be used alone or in combination of two or more.
In the present invention, an aromatic polyisocyanate compound and an alicyclic polyisocyanate compound are preferable, and isophorone diisocyanate (IPDI) and xylylene diisocyanate (XDI) are more preferable because they are easily available.

  The polyisocyanate compound may be blended in any step of the production process of the electrostatic image developing toner. For example, when an aqueous dispersion of resin particles is produced, a resin particle aqueous dispersion is prepared by previously blending with a raw material such as a polycondensable monomer, and a resin particle dispersion containing a polyisocyanate compound is prepared. A preferred example is an embodiment used in the production of toner for developing an electrostatic image.

The polyisocyanate compound is preferably contained in an amount of 1 to 50% by weight, more preferably 2 to 30% by weight, based on 100% by weight of the entire electrostatic charge image developing toner. It is preferable that the value is within the above range because the toner has good fixability and storage property.
The content of the polyisocyanate compound is preferably 10 to 50 parts by weight, more preferably 5 to 20 parts by weight, based on 100 parts by weight of the polymer dispersant contained in the electrostatic image developing toner. preferable.

III. Electrostatic Image Developer The toner obtained by the method for producing an electrostatic image developing toner of the present invention described above is 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.

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.

IV. Image Forming Apparatus and Image Forming Method An image forming apparatus according to the present invention includes an electrostatic latent image holding member (photosensitive member), charging means for charging the electrostatic latent image holding member, and the charged electrostatic latent image holding member. And developing to form a toner image by developing the electrostatic latent image with an exposure means for forming an electrostatic latent image on the electrostatic latent image holding member and a developer containing an electrostatic charge image developing toner. And a transfer means for transferring the toner image from the electrostatic latent image holding member to the recording material, and the electrostatic charge image developing toner of the present invention or the developer as the electrostatic charge image developing toner. The electrostatic image developer of the present invention is used. It is also preferable to have a cleaning means arbitrarily.
Further, the image forming method of the present invention includes an electrostatic latent image forming step for forming an electrostatic latent image on the electrostatic latent image holding member, and a developer containing an electrostatic charge image developing toner. The electrostatic image developing toner includes an image forming step of developing the latent image to form a toner image, a transfer step of transferring the toner image, and a fixing step of fixing the toner image. The electrostatic image developer of the present invention is used as the electrostatic image developing toner of the present invention or the developer.

  In the image forming apparatus of the present invention, each of the means is a general process per se, and is described in, for example, Japanese Patent Laid-Open Nos. 56-40868 and 49-91231. In addition, the image forming apparatus of the present invention can be implemented in a known image forming apparatus such as a copying machine or a facsimile machine using the electrostatic image developing toner or the electrostatic image developer of the present invention.

  An electrostatic latent image is formed on the latent image carrier, and then the electrostatic latent image is developed by a developer layer on the developer carrier to form a toner image. The developer layer is not particularly limited as long as it contains the electrostatic image developer of the present invention containing the electrostatic image developing toner of the present invention. The transfer means is means for transferring the toner image onto a transfer body.

  The transferred toner image is fixed by fixing means. As a fixing unit, it is preferable to fix the transfer body by a heating roller heated to a constant temperature. The contact time between the transfer member and the heating roller is preferably 1 second or shorter, and more preferably 0.5 seconds or shorter. It is preferable to set the contact time within the above range because high-speed fixing can be performed.

  The cleaning means is means for removing the electrostatic charge image developer remaining on the electrostatic latent image holding member. In the image forming apparatus of the present invention, it is preferable to further include a recycling unit. The recycling means is a step of transferring the electrostatic charge image developing toner collected by the cleaning means to the developer layer. Examples of the image forming apparatus including the recycling means include image forming apparatuses such as a toner recycling system type copying machine and facsimile machine. Further, the present invention can be applied to a recycling system in which the cleaning unit is omitted and toner is collected simultaneously with development.

V. Binder resin, polycondensation resin, and polymer dispersant detection method In the present invention, a method for isolating and extracting a binder resin from an electrostatic charge image developer or an electrostatic charge image developing toner, and in the binder resin A method for detecting the weight% of the polycondensation resin and the polymer dispersant of the present invention will be described below.

(Binder resin isolation method)
As a method for isolating and extracting the binder resin from the electrostatic charge image developer, the developer is fixed with a magnet, blown with compressed air, etc., and the electrostatic charge image developing toner is collected, and then the electrostatic charge image is collected. The binder resin can be extracted by dissolving the developing toner in a hydrophobic organic solvent such as toluene and collecting the supernatant from which the pigments and inorganic additives have been removed using a centrifuge. It can also be extracted by filtration.

(Method for measuring weight fraction of polycondensation resin)
As a method for evaluating the weight percent of the polycondensation resin in the binder resin, the isolated binder resin is analyzed by infrared absorption (IR), and the components are clarified. NMR) can determine the weight fraction of the polycondensation resin by quantifying the condensed ester component.

(Method for detecting polymer dispersant)
The polymer dispersant can be extracted by a method of adding ion-exchanged water to a binder resin dissolved in a hydrophobic organic solvent, shaking in a separatory funnel, and drying and separating components separated in water. If necessary, a polymer dispersant having a wide range of compositions can be extracted by dissolving alcohol or the like in water. In addition, the organic solvent solution of the binder resin is added to an alcohol such as methyl alcohol or a mixture of ion exchange water and alcohol with stirring, and the polymer dispersant is extracted into the alcohol or the mixture of ion exchange water and alcohol. You can also
The proportion of hydroxycarboxylic acid in the polymer dispersant is evaluated by infrared absorption (IR) analysis, elucidating the constituent components, and then quantifying the copolymer components by high resolution nuclear magnetic resonance (NMR). be able to.

  EXAMPLES Hereinafter, although this invention is explained in full detail based on an Example, this invention is not limited to this. In the following examples, “part” means “part by weight” unless otherwise specified.

(Preparation of polymer dispersant)
<Preparation of Polymer Dispersant PD1: Examples>
100 parts of dimethylolbutanoic acid 1.6 parts of dodecylbenzenesulfonic acid 1.6 parts or more were stirred and mixed in a polymerization vessel equipped with a reflux tube and a mantle heater, and then stirred at 130 ° C. while blowing nitrogen into the polymerization vessel. Held for hours. Thereafter, the pressure was reduced to 1 KPa using a vacuum pump, and polymerization was continued for another 8 hours while removing water. The obtained polymer was dissolved in 300 parts of THF solvent, and then poured into 500 parts of methyl alcohol, and the precipitate was filtered. The same operation was repeated for purification, and finally the polymer was dried with a hot air dryer. A powdery polymer dispersant PD1 was obtained by pulverization with a sample mill.
When PD1 was analyzed by GPC as a molecular weight measuring means, the weight average molecular weight was 12,500 and the number average molecular weight was 5,200.

Here, the weight average molecular weight and the number average molecular weight of the polymer dispersant were measured as follows. HLC-8220GPC (manufactured by Tosoh Corporation) was used as the GPC apparatus. 5 mg of the obtained PD1 was dissolved in 1 ml of THF, and the soluble content was used as a sample.
As the column, an analytical column TSKgel SuperHM-M manufactured by Tosoh Corporation was used, and the temperature of the column oven and the inlet oven was set to 40 ° C., and the measurement was performed.

<Preparation of Polymer Dispersant PD2: Examples>
Dimethylolpropionic acid 100 parts p-toluenesulfonic acid 1.1 parts The above components were stirred and mixed in a polymerization vessel equipped with a reflux tube and a mantle heater. Held for hours. Thereafter, the pressure was reduced to 1 KPa using a vacuum pump, and polymerization was continued for another 8 hours while removing water.
The obtained polymer was dissolved in 300 parts of THF solvent, and then poured into 500 parts of methyl alcohol, and the precipitate was filtered. The same operation was repeated for purification, and finally the polymer was dried with a hot air dryer. By pulverizing with a sample mill, a powdery polymer dispersant PD2 was obtained.
When PD2 was analyzed by GPC as a molecular weight measuring means in the same manner as PD1, the weight average molecular weight was 8,500 and the number average molecular weight was 3,500.

<Preparation of Polymer Dispersant PD3: Examples>
Tartaric acid 100 parts Dibutyltin oxide 0.7 parts The above was stirred and mixed in a polymerization vessel equipped with a reflux tube and a mantle heater, and then held for 3 hours while stirring at 200 ° C while blowing nitrogen into the polymerization vessel. Thereafter, the pressure was reduced to 1 KPa using a vacuum pump, and polymerization was continued for another 8 hours while removing water.
The obtained polymer was dissolved in 300 parts of THF solvent, and then poured into 500 parts of methyl alcohol, and the precipitate was filtered. The same operation was repeated again for purification, and finally the polymer was dried with a hot air dryer. By pulverizing with a sample mill, a powdery polymer dispersant PD3 was obtained.
When PD3 was analyzed by GPC as a molecular weight measuring means in the same manner as PD1, the weight average molecular weight was 11,000 and the number average molecular weight was 3,900.

<Preparation of Polymer Dispersant PD4: Examples>
Malic acid 100 parts Titanium catalyst (tetrabutoxytitanium) 0.7 parts The above is stirred and mixed in a polymerization vessel equipped with a reflux tube and a mantle heater, and then stirred at 200 ° C while blowing nitrogen into the polymerization vessel. For 3 hours. Thereafter, the pressure was reduced to 1 KPa using a vacuum pump and polymerization was continued for another 8 hours while removing water.
The obtained polymer was dissolved in 300 parts of THF solvent, and then poured into 500 parts of methyl alcohol, and the precipitate was filtered. The same operation was repeated for purification, and finally the polymer was dried with a hot air dryer and pulverized with a sample mill to obtain a powdery polymer dispersant PD4.
When PD4 was analyzed by GPC as a molecular weight measuring means in the same manner as PD1, the weight average molecular weight was 20,000 and the number average molecular weight was 6,800.

<Preparation of Polymer Dispersant PD5: Examples>
Dimethylolbutanoic acid 100 parts dodecylbenzenesulfonic acid 1.1 parts dimethylbenzylamine 0.5 part The above is stirred and mixed in a polymerization vessel equipped with a reflux tube and a mantle heater, and nitrogen is blown into the polymerization vessel. The mixture was held at 131 ° C. with stirring for 3 hours. Thereafter, using a vacuum pump, the pressure was reduced to 1 KPa and the polymerization was continued for another 8 hours while removing water.
The obtained polymer was dissolved in 300 parts of THF solvent, and then poured into 500 parts of methyl alcohol, and the precipitate was filtered. The same operation was repeated for purification, and finally the polymer was dried with a hot air dryer. By pulverizing with a sample mill, a powdery polymer dispersant PD5 was obtained.
When PD5 was analyzed by GPC as a molecular weight measuring means in the same manner as PD1, the weight average molecular weight was 7,500 and the number average molecular weight was 3,200.

<Preparation of Polymer Dispersant PD6: Comparative Example>
Dimethylol butanoic acid 100 parts Tungstosilicic acid 1.1 parts The above components were stirred and mixed in a polymerization vessel equipped with a reflux tube and a mantle heater, and then held for 3 hours while stirring at 131 ° C while blowing nitrogen into the polymerization vessel. did. Thereafter, the pressure was reduced to 1 KPa using a vacuum pump, and polymerization was continued for another 8 hours while removing water.
The obtained polymer was dissolved in 300 parts of THF solvent, and then poured into 500 parts of methyl alcohol, and the precipitate was filtered. The same operation was repeated again for purification, and finally the polymer was dried with a hot air dryer. By pulverizing with a sample mill, a powdery polymer dispersant PD6 was obtained.
When PD6 was analyzed by GPC as a molecular weight measuring means in the same manner as PD1, the weight average molecular weight was 3,600 and the number average molecular weight was 1,200.

<Preparation of Polymer Dispersant PD7: Comparative Example>
Hydroxyoctanoic acid 100 parts Dodecyl benzene sulfonic acid 1.5 parts or more in a polymerization vessel equipped with a reflux tube and a mantle heater, after stirring and mixing, 3 hours with stirring at 131 ° C. while blowing nitrogen into the polymerization vessel Retained. Thereafter, the pressure was reduced to 1 KPa using a vacuum pump, and polymerization was continued for another 8 hours while removing water.
The obtained polymer was dissolved in 300 parts of THF solvent, and then poured into 500 parts of methyl alcohol, and the precipitate was filtered. The same operation was repeated for purification, and finally the polymer was dried with a hot air dryer. A powdery polymer dispersant PD7 was obtained by pulverization with a sample mill.
When PD7 was analyzed by GPC as a molecular weight measuring means in the same manner as PD1, the weight average molecular weight was 7,900 and the number average molecular weight was 2,100.

<Preparation of Polymer Dispersant PD8: Comparative Example>
Styrene 50 parts Acrylic acid 50 parts Dodecanethiol 4 parts The above was mixed in a glass flask container, and then held for 1 hour while blowing nitrogen into the flask. Further, 0.5 part of benzoyl peroxide was added, and the temperature was raised to 70 ° C. with stirring and held for 5 hours.
The obtained polymer was dissolved in 300 parts of a 1: 1 mixed solvent of THF and acetone, and then poured into 500 parts of methyl alcohol, and the precipitate was filtered. The same operation was repeated for purification, and finally the polymer was dried with a hot air dryer. By pulverizing with a sample mill, a powdery polymer dispersant PD8 was obtained.
When PD8 was analyzed by GPC as a molecular weight measuring means in the same manner as PD1, the weight average molecular weight was 9,200 and the number average molecular weight was 2,400.

  The polymer dispersants (PD1 to PD8) are summarized in Table 1 below.

(Preparation of resin particle dispersion)
(Example C1-1)
<Preparation of aqueous dispersion (C1-1) of crystalline resin particles>
p-Toluenesulfonic acid 0.7 parts 1,6-hexanediol 59 parts Sebacic acid 101 parts The above materials are mixed in a kneader and then heated to 120 ° C to melt the mixture and then stirred at 15 RPM. When the pressure was reduced and maintained at 90 ° C. for 8 hours, the contents became a viscous melt.
16 parts of polymer dispersant PD1 powder (10% by weight based on the polycondensation resin component) was dispersed in 64 parts of ion-exchanged water and stirred for 10 minutes. Then, after emulsification with a homogenizer (IKA, Ultra Tarrax) for 1 minute, when heated to 95 ° C. and stirred for 3 minutes in the kneader with stirring at 30 RPM, a white emulsion and became. Further, the stirring speed was increased to 40 RPM, and 160 parts of ion-exchanged water heated to 60 ° C. was added over 5 minutes, then held for 10 minutes and further cooled to room temperature.
As a result, an aqueous dispersion (C1-1) of crystalline resin particles having a volume average particle diameter (center diameter) of 350 nm, a melting point of 69 ° C., a weight average molecular weight of 14,000, and a solid content of 40% by weight is obtained. It was.

The volume average particle diameter (center diameter) of the particles in the aqueous dispersion of resin particles was measured with a laser diffraction / scattering particle size distribution analyzer LA-920 (manufactured by Horiba, Ltd.).
In addition, the melting point of the crystalline polyester resin was measured using a DSC-60 differential scanning calorimeter (DSC) manufactured by Shimadzu Corporation at a heating rate of 10 ° C. per minute from room temperature to 150 ° C. The melting peak temperature of the input compensation differential scanning calorimetry shown in JIS K-7121: 87 was determined as the melting point. The crystalline polyester resin may show a plurality of melting peaks, but the maximum peak was regarded as the melting point. Moreover, the glass transition temperature was measured by the method (DSC method) prescribed | regulated to ASTMD3418-82.
The weight average molecular weight of the resin was measured by GPC in the same manner as the method for measuring the weight average molecular weight of the polymer dispersant PD1.

(Example A1-1)
<Preparation of Amorphous Resin Particle Water Dispersion (A1-1)>
175 parts of 1,4-cyclohexanedicarboxylic acid 380 parts of bisphenol A ethylene oxide 2 mol adduct (2 mol adduct in terms of both ends)
0.5 parts of dodecylbenzenesulfonic acid The above materials were mixed in a kneader and then heated to 120 ° C. to melt the mixture. Thereafter, the pressure was reduced while stirring at 15 RPM, and the content became a viscous melt when kept at 100 ° C. for 8 hours.
44 parts of polymer dispersant PD2 powder (6% by weight based on the polycondensation resin component) was dispersed in 230 parts of ion-exchanged water and stirred for 10 minutes. Then, after emulsifying for 1 minute with a homogenizer (manufactured by IKA, Ultra Tarrax), heating to 95 ° C. and pouring the melt into the kneader for 3 minutes with stirring at 30 RPM, a white emulsion It became. Further, the stirring speed was increased to 40 RPM, 550 parts of ion-exchanged water heated to 95 ° C. was added over 5 minutes, then held for 10 minutes, and further cooled to room temperature.
As a result, an aqueous dispersion (A1-1) of amorphous resin particles having a particle central diameter of 210 nm, a glass transition temperature of 60 ° C., a weight average molecular weight of 19,000, and a solid content of 40% by weight was obtained.

(Example A1-2)
<Preparation of Amorphous Resin Particle Water Dispersion (A1-2)>
175 parts of 1,4-cyclohexanedicarboxylic acid 380 parts of bisphenol A ethylene oxide 2 mol adduct (2 mol adduct in terms of both ends)
Dodecylbenzenesulfonic acid 0.5 part 50 L Mix in a 50 L vacuum reactor, then heat to 120 ° C., melt the mixture, depressurize with stirring and hold at 100 ° C. for 8 hours, the contents are viscous It became a melt.
This polycondensation resin melt was transferred to a hopper of a twin-screw co-directional kneading extruder.
Separately, 44 parts of polymer dispersant PD3 powder (10% by weight based on the polycondensation resin component) was dispersed in 230 parts of ion-exchanged water and stirred for 10 minutes. Then, it emulsified for 1 minute with a homogenizer (manufactured by IKA, Ultra Tarrax) to prepare an aqueous polymer dispersant solution.
A viscous melt is continuously supplied to the kneading extruder from the hopper of a biaxial co-directional kneading extruder (manufactured by Nippon Steel Works, Ltd., Supertex 44α). While maintaining the molecular dispersant aqueous solution at 80 ° C., it is press-fitted and continuously supplied by a plunger pump, and at the downstream side, ion-exchanged water at room temperature is similarly press-fitted and diluted to continuously An aqueous dispersion of resin particles of the polycondensation resin was obtained.
As a result, an aqueous dispersion (A1-2) of amorphous resin particles having a resin particle center diameter of 219 nm, a glass transition temperature of 59 ° C., a weight average molecular weight of 19,000, and a solid content of 40% by weight was obtained.

(Example A1-3)
<Preparation of Aqueous Dispersion of Amorphous Resin Particles (A1-3)>
Except for using PD4 in place of the polymer dispersant PD3, the same operation as in the preparation of the aqueous dispersion of amorphous resin particles (A1-2) was performed, and the aqueous dispersion of amorphous resin particles (A1- 3) was produced.
The center diameter was 190 nm, the glass transition temperature was 56 ° C., the weight average molecular weight was 16,500, and the solid content was 40% by weight.

(Example A1-4)
<Preparation of Amorphous Resin Particle Water Dispersion (A1-4)>
Except for using PD5 in place of the polymer dispersant PD3, the same operation as in the preparation of the aqueous dispersion of amorphous resin particles (A1-2) was performed, and the aqueous dispersion of amorphous resin particles (A1- 4) was produced.
The center diameter was 220 nm, the glass transition temperature was 55 ° C., the weight average molecular weight was 16,200, and the solid content was 40% by weight.

(Comparative Example A1-5)
<Preparation of Aqueous Dispersion of Amorphous Resin Particles (A1-5)>
In preparation of the aqueous dispersion (A1-1) of amorphous resin particles, the conditions of the aqueous dispersion (A1-1) of amorphous resin particles were the same except that PD6 was used instead of the polymer dispersant PD2. In the same manner as in the production, an aqueous dispersion (A1-5) of amorphous resin particles was produced.
The center diameter was 219 nm, the glass transition temperature was 60 ° C., the weight average molecular weight was 14,500, and the solid content was 40% by weight.

(Comparative Example A1-6)
<Preparation of Aqueous Dispersion of Amorphous Resin Particles (A1-6)>
In preparation of the aqueous dispersion (A1-1) of amorphous resin particles, the conditions of the aqueous dispersion (A1-1) of amorphous resin particles were the same except that PD7 was used instead of the polymer dispersant PD2. In the same manner as in the production, an aqueous dispersion (A1-6) of amorphous resin particles was produced.
The center diameter was 190 nm, the glass transition temperature was 55 ° C., the weight average molecular weight was 16,100, and the solid content was 40% by weight.

(Comparative Example A1-7)
<Aqueous dispersion of non-crystalline resin particles (A1-7)>
In preparation of the aqueous dispersion (A1-1) of amorphous resin particles, the conditions of the aqueous dispersion (A1-1) of amorphous resin particles were the same except that PD8 was used instead of the polymer dispersant PD2. In the same manner as in the production, an aqueous dispersion (A1-7) of amorphous resin particles was produced.
The center diameter was 200 nm, the glass transition temperature was 57 ° C., the weight average molecular weight was 13,100, and the solid content was 40% by weight.

(Preparation of release agent particle dispersion (W1))
Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd., Neogen R) 2 parts Ion-exchanged water 800 parts Carnauba wax 200 parts After mixing the above ingredients, heating to 100 ° C and melting, homogenizer (manufactured by IKA) Then, emulsification was carried out at 100 ° C. using a gorin homogenizer.
As a result, a release agent particle dispersion (W1) having a particle central diameter of 259 nm, a melting point of 79 ° C., and a solid content of 20% by weight was obtained.

(Preparation of colorant particle dispersion (P1))
Cyan pigment (Daiichi Seika Kogyo Co., Ltd., copper phthalocyanine B15: 3) 50 parts Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd., Neogen R) 5 parts Ion-exchanged water 200 parts Mixing and dissolving the above components Then, it was dispersed for 5 minutes using a homogenizer (manufactured by IKA, Ultra Tarrax). Further, the dispersion was carried out for 10 minutes by an ultrasonic bath to obtain a Sian colorant particle dispersion (P1) having a center diameter of 165 nm and a solid content of 21.5% by weight.

(Preparation of colorant particle dispersion (P2))
In the preparation of the colorant particle dispersion (P1), it was prepared in the same manner as the colorant particle dispersion (P1), except that a magenta pigment (PR122) manufactured by Dainichi Ink Chemical Co., Ltd. was used instead of the cyan pigment. Thus, a magenta colorant particle dispersion (P2) having a center diameter of 155 nm and a solid content of 21.5% by weight was obtained.

(Preparation of toner for developing electrostatic image)
<Example 1-1>
(Preparation of toner particles)
Aqueous dispersion of crystalline resin particles (C1-1) 25 parts (10 parts of resin)
Amorphous resin particle aqueous dispersion (A1-1) 125 parts (resin 50 parts)
Colorant particle dispersion (P1) 40 parts (8.6 parts pigment)
40 parts of release agent particle dispersion (W1) (8.6 parts of release agent)
Polyaluminum chloride 0.15 parts Ion-exchanged water 400 parts The above components are thoroughly mixed and dispersed in a round stainless steel flask with a homogenizer (IKA, Ultra Turrax T50), and then the flask is stirred with an oil bath for heating. While heating to 40 ° C. and holding at 40 ° C. for 60 minutes, 62.5 parts (25 parts of resin) of an aqueous dispersion (A1-1) of resin particles was added and gently stirred.
Thereafter, the pH in the system was adjusted to 6.5 with a 0.5 mol / liter sodium hydroxide aqueous solution, and then heated to 85 ° C. while stirring was continued.
A sodium hydroxide aqueous solution was further added dropwise, and the pH was maintained so as not to be 5.5 or less. After completion of the reaction, the mixture was cooled, filtered, sufficiently washed with ion exchange water, and then solid-liquid separated by Nutsche suction filtration. And it re-dispersed in 3 liters of ion-exchanged water at 40 ° C., and stirred and washed at 300 rpm for 15 minutes. This washing operation was repeated 5 times, followed by solid-liquid separation by Nutsche suction filtration, and then freeze-drying for 10 hours to obtain toner particles. When the particle diameter of the toner particles was measured with a Coulter counter, the cumulative volume average particle diameter D ₅₀ was 5.9 μm, and the volume average particle size distribution index GSDv was 1.20. In addition, the toner particle shape factor SF1 obtained by shape observation with Luzex was 130.

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

<Creation of carrier>
A methanol solution containing 0.1 part of γ-aminopropyltriethoxysilane was added to 100 parts of Cu—Zn ferrite particles having a volume average particle diameter of 40 μm, and after covering with a kneader, the methanol was distilled off, and further at 120 ° C. The silane compound was completely cured by heating for 2 hours. To this particle, a perfluorooctylethyl methacrylate-methyl methacrylate copolymer (copolymerization ratio 40:60) dissolved in toluene was added, and perfluorooctylethyl methacrylate-methyl was added using a vacuum reduced pressure kneader. A resin-coated carrier was produced so that the coating amount of the methacrylate copolymer was 0.5% by weight.

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

(Evaluation of toner)
Using the developer, an image was formed on a recording material (trade name Green 100, manufactured by Fuji Xerox Co., Ltd.) using a modified DocuCenterColor 500 manufactured by Fuji Xerox Co., Ltd. in a normal laboratory environment.
In the modified machine, seasoning was carried out by leaving it overnight in a laboratory environment under conditions of high temperature and high humidity of 30 ° C. and 80% (summer environmental conditions).
Furthermore, 100,000 continuous printing tests were conducted under this summer environment condition, but the image quality was well maintained and no image defects such as streaks or dots due to filming were observed.
The results of the printing test were evaluated according to the following criteria.
Print test result evaluation criteria:
○: Image quality defects such as streaks and dots are not generated up to 100,000 sheets. △: Slightly visible but acceptable. ×: Image quality defects are observed. XX: Image quality defects are observed in the initial stage from the start of the test.

<Examples 1-2 to 1-4 and Comparative Examples 1-1 to 1-3>
In Example 1-2, a toner for developing an electrostatic charge image was prepared in the same manner as in Example 1-1 except that the aqueous dispersion of amorphous resin particles was changed to A1-2.
In Example 1-3, the electrostatic charge image developing was performed in the same manner as in Example 1-1 except that the aqueous dispersion of the amorphous resin particles was changed to A1-3 and the colorant particle dispersion was changed to P2. A toner was prepared.
In Example 1-4, the electrostatic charge was changed in the same manner as in Example 1-1 except that the aqueous dispersion of amorphous resin particles was changed to A1-7 and the colorant particle dispersion was changed to P2. An image developing toner was prepared.
Comparative Examples 1-1, 1-2, and 1-3 were the same as Example 1-1 except that the aqueous dispersions of the amorphous resin particles were changed to A1-4, A1-5, and A1-6, respectively. Thus, a toner for developing an electrostatic image was prepared.
Using the toners obtained in Examples 1-2 to 1-4 and Comparative Examples 1-1 to 1-3, the cumulative volume average particle diameter D ₅₀ , GSDV, shape factor SF1, and the like as in Example 1-1, and A summer environmental continuous printing test was conducted. The results are shown in Table 3.

(Example C2-1)
(Preparation of aqueous dispersion of resin particles)
<Preparation of Crystalline Resin Particle Water Dispersion (C2-1)>
-Production of oil phase 1-
-1,9-nonanediol 10.01 parts-Isophorone diisocyanate 8.30 parts-Styrene 22.5 parts-Acrylic acid 2.5 parts-Hexadecane 1.66 parts-Dodecanethiol 0.75 parts-Tin octoate catalyst 0 .1 part The above raw materials were heated and dissolved at 80 ° C. to prepare a uniform oil phase.
In addition, isophorone diisocyanate is an isocyanate group-containing monomer and has two isocyanate groups in one molecule.

-Preparation of aqueous phase 1-
-Dodecyl benzene sulfonic acid 1.66 parts-Polymer dispersing agent PD1 powder 5.08 parts-Water 200 parts The said raw material was heat-dissolved at 80 degreeC, and the uniform aqueous phase was produced.

-Preparation of aqueous dispersion C2-1 of resin particles-
The aqueous phase 1 and the oil phase 1 are put in a container, stirred for 3 minutes at 8,000 rpm using an ultra turrax (manufactured by IKA), and then discharged using a nanomizer (manufactured by Yoshida Kikai Kogyo Co., Ltd.). An emulsion was obtained by dispersing 5 passes at a speed of 60 m / s (discharge pressure 504 kgf / cm ² ).
When the volume average particle diameter of the droplets was measured using a laser diffraction / scattering particle size distribution analyzer (Horiba, Ltd. LA-920), the average diameter was 0.35 μm. The emulsion was charged into a 1 liter reactor equipped with a stirrer, and polymerization was carried out at 70 ° C. for 4 hours in a nitrogen atmosphere.
When a small amount of this reaction product was taken out and IR analysis was performed, it was found that the polymer at this point was almost a polyurethane resin, and there was no production of a polymer having urea bonds as a by-product.
Furthermore, the following various analyzes were performed. The physical properties of the produced polyurethane resin are as follows. In addition, the polyaddition reaction which forms a urethane bond continued the polyaddition polymerization reaction until absorption of the 2,260 cm < ^-1 > isocyanate group by IR spectrum was lost.
・ GPC weight average molecular weight 5,800
・ Polymer NMR yield of styrene resin 2%
Furthermore, when the thermal characteristics of the resin were examined with a differential scanning calorimeter of the resin (Shimadzu Corporation, DSC-50), it was found that the resin had a melting point at 65 ° C.

A solution obtained by dissolving 0.8 part of ammonium persulfate in 10 parts of ion exchange water was dropped into the resin particle dispersion obtained above, and radical polymerization was further performed in a nitrogen atmosphere for 6 hours. As a result, an aqueous dispersion of stable resin particles having a volume average particle diameter (center diameter) of 0.4 μm and a ratio of volume average particle diameter to number average particle diameter distribution (volume average particle diameter / number average particle diameter) of 1.3. Got. Similarly, the physical properties of a small amount of polyurethane resin / addition polymerizable vinyl resin composite were measured.
-Weight average molecular weight of addition-polymerizable vinyl resin by GPC 40,000
・ GPC weight average molecular weight of polyurethane resin 8,000
-Polymerization yield of styrene resin by proton NMR 99%
Melting point 68 ° C

After the polymerization, a small sample was taken and water was dried at room temperature. Thereafter, methanol washing filtration and drying were performed in the same manner as the polymerization of the polyurethane resin. Thereafter, the ratio of the polyurethane resin to the vinyl resin in the polymer was determined by proton NMR, and the yield of the vinyl resin was determined. As a result, almost the blended radical polymerizable monomer was subjected to addition polymerization. The rate was 99% or more.
Further, the total amount of the remaining vinyl monomer (radically polymerizable monomer) component obtained from gas chromatographic analysis of the emulsion was 200 ppm or less. Furthermore, when the molecular weight was measured by GPC, two peaks of 40,000 and 8,000 were shown in the weight average molecular weight. A value almost equal to the value of the previously polymerized polyurethane resin and a new high molecular weight peak were exhibited. The melting point of the polyurethane resin was maintained at 68 ° C. The polymer obtained as described above was confirmed to be composite particles of a vinyl resin and a polyurethane resin.

  Further, 10 parts of the prepared resin particles were placed in a watch glass and dried in an oven dryer at 40 ° C. for 4 hours to obtain a solid polymer. The solid polymer was embedded in an epoxy resin, and a test piece cut out with a microtome was stained for 2 hours under ruthenium oxide vapor. When contrast was photographed, it had a core-shell structure with polyurethane resin as the core.

(Example C2-2)
<Preparation of Crystalline Resin Particle Water Dispersion (C2-2)>
-Production of oil phase 2-
・ 1,6-hexanediol 9.95 parts ・ xylylene diisocyanate 8.80 parts ・ styrene 22.5 parts ・ butyl acrylate 2.5 parts ・ acrylic acid 2.5 parts ・ stearyl methacrylate 1.66 parts ・ dodecanethiol 0 .75 parts / tin octoate catalyst 0.1 part The above raw materials were heated and dissolved at 80 ° C. to prepare a uniform oil phase 2.
Xylylene diisocyanate is an isocyanate group-containing monomer and has two isocyanate groups in one molecule.

-Preparation of aqueous phase 2-
-Dodecyl benzene sulfonic acid 1.66 parts-Polymer dispersing agent PD2 5.6 parts-Water 200 parts The said raw material was heat-dissolved at 80 degreeC, and the uniform aqueous phase 2 was produced.

-Production of aqueous dispersion C2-2 of resin particles-
The aqueous phase 2 and the oil phase 2 were put in a container and stirred at 8,000 rpm for 3 minutes using an ultra turrax (manufactured by IKA). Thereafter, using a nanomizer (manufactured by Yoshida Kikai Kogyo Co., Ltd.), an emulsion was obtained by dispersing 4 passes at a discharge speed of 60 m / s (discharge pressure 504 kgf / cm ² ). When the volume average particle diameter of the droplets was measured using a laser diffraction / scattering particle size distribution measuring apparatus (Horiba, Ltd. LA-920), the average diameter was 0.45 μm. The above emulsion was charged into a reactor equipped with a stirrer, and polymerization was carried out at 70 ° C. for 4 hours in a nitrogen atmosphere. When a small amount of this reaction product was taken out and IR analysis was performed, it was found that the polymer at this point was almost a polyurethane resin, and there was no production of a polymer having urea bonds as a by-product. Furthermore, the following various analyzes were performed. The physical properties of the produced polyurethane resin are as follows. The polyaddition polymerization reaction was continued until there was no absorption of 2,260 cm ⁻¹ isocyanate group by IR spectrum.
・ GPC weight average molecular weight 6,900
・ Polymer NMR yield of styrene resin 2%
Further, when the thermal characteristics of the resin were examined using a differential scanning calorimeter (Shimadzu Corporation, DSC-50), it was found that the resin had a melting point at 69 ° C.

A solution obtained by dissolving 0.8 part of potassium persulfate in 10 parts of ion-exchanged water was added dropwise to the aqueous dispersion of resin particles obtained above, and radical polymerization was further performed in a nitrogen atmosphere for 6 hours. As a result, water dispersion of stable resin particles having a volume average particle diameter (center diameter) of 0.55 μm and a ratio of volume average particle diameter to number average particle diameter distribution (volume average particle diameter / number average particle diameter) of 1.2. A liquid was obtained. Similarly, a small sample was taken and the physical properties of the composite of polyurethane resin / addition polymerizable vinyl resin were measured.
・ GPC weight average molecular weight of vinyl resin 38,000
・ GPC weight average molecular weight of polyurethane resin 7,500
-Polymerization yield of styrene resin by proton NMR 99%
Melting point 69 ° C

  After the polymerization, a small sample was taken out, water was dried at room temperature, washed with methanol, filtered and dried in the same manner as in the polymerization of the polyurethane resin, and the ratio of the polyurethane resin and the vinyl resin in the polymer was determined by proton NMR. Further, when the polymerization yield of the vinyl-based resin was determined, the almost polymerizable radical polymerizable monomer was subjected to polymerization, and the polymerization yield was 99% or more. From the gas chromatographic analysis of the emulsion, the total amount of the remaining radically polymerizable monomer was 200 ppm or less. Further, when the molecular weight was measured by GPC, the weight average molecular weight showed two peaks of 38,000 and 7,500, and the same value as that of the previously polymerized polyurethane resin and a new high molecular weight peak. The melting point of the polyurethane resin was maintained at 69 ° C.

  The polymer obtained as described above was confirmed to be composite particles of addition-polymerizable vinyl resin and polyurethane resin. Further, 10 parts of the prepared resin particles were placed in a watch glass and dried in an oven dryer at 40 ° C. for 4 hours to obtain a solid polymer. Further, the solid polymer was embedded in an epoxy resin, and a test piece cut out with a microtome was dyed for 2 hours under ruthenium oxide vapor. When contrast was photographed, it had a core-shell structure with polyurethane resin as the core.

(Example C2-3)
<Preparation of aqueous dispersion C2-3 of resin particles>
-Production of oil phase 3-
-1,10-dodecanediol 10.89 parts-Isophorone diisocyanate 8.30 parts-Styrene 22.5 parts-Butyl acrylate 2.5 parts-Stearyl methacrylate 1.66 parts-Dodecanethiol 0.75 parts-AIBN (2, 2′-Azobis (2-methylpropionitrile)) 0.5 part The above material was heated and dissolved at 80 ° C. to prepare a uniform oil phase 3.

-Preparation of aqueous phase 3-
-Polymer dispersing agent PD3 powder 5.00 parts-Dodecylbenzene sulfonic acid 1.0 part-Water 200 parts The said raw material was heat-dissolved at 80 degreeC, and the uniform aqueous phase 3 was produced.

-Production of aqueous dispersion C2-3 of resin particles-
The water phase 3 and the oil phase 3 are put in a container, stirred for 3 minutes at 8,000 rpm using an ultra turrax (manufactured by IKA), and then discharged using a nanomizer (manufactured by Yoshida Kikai Kogyo Co., Ltd.). The emulsion was obtained by dispersing 4 passes at 60 m / s (discharge pressure 504 kgf / cm ² ). When the volume average particle size of the droplets was measured using a laser diffraction / scattering particle size distribution analyzer (Horiba, Ltd. LA-920), the volume average particle size was 0.5 μm. The above emulsion was charged into a reactor equipped with a stirrer, and polymerization was carried out at 70 ° C. for 8 hours in a nitrogen atmosphere. A small amount of this reaction product was taken out and subjected to IR analysis. As a result, no polymer having a urea bond as a by-product was produced. The reaction continued the polyaddition polymerization reaction and radical polymerization reaction until there was no absorption of 2,260 cm ⁻¹ isocyanate group by IR spectrum. The obtained dispersion was a stable resin having a volume average particle diameter (center diameter) of 0.40 μm and a ratio of volume average particle diameter to number average particle diameter distribution (volume average particle diameter / number average particle diameter) of 1.2. An aqueous dispersion of particles was obtained. Similarly, the physical properties of a small amount of polyurethane resin / addition polymerizable vinyl resin composite were measured.
・ GPC weight average molecular weight of vinyl resin 75,000
・ GPC weight average molecular weight of polyurethane resin 12,000
-Polymerization yield of styrene resin by proton NMR 99%
Melting point 73 ° C

  After the polymerization, a small sample was taken out, water was dried at room temperature, washed with methanol, filtered and dried in the same manner as the polymerization of the polyurethane resin. Thereafter, the ratio of the polyurethane resin and the vinyl resin in the polymer was determined by proton NMR, and the yield of the vinyl resin was determined. Almost blended radical monomer was subjected to polymerization, and the polymerization yield was 99% or more. Further, the total amount of vinyl monomer (radically polymerizable monomer) component remaining from gas chromatographic analysis of the emulsion was 200 ppm or less. Furthermore, when the molecular weight was measured by GPC, two peaks of 75,000 and 12,000 were shown in the weight average molecular weight. The melting point of the polyurethane resin was 73 ° C.

  The polymer obtained as described above was confirmed to be composite particles of a vinyl resin and a polyurethane resin. Further, 10 parts of the prepared resin particles were placed in a watch glass and dried in an oven dryer at 40 ° C. for 4 hours to obtain a solid polymer. Further, the dried polymer was embedded in an epoxy resin, and a test piece cut out with a microtome was dyed for 2 hours under ruthenium oxide vapor. When contrast was photographed, it had a core-shell structure with polyurethane resin as the core.

(Example C2-4)
<Preparation of aqueous dispersion (C2-4) of crystalline resin particles>
-0.7 parts of p-toluenesulfonic acid-59 parts of 1,6-hexanediol-101 parts of sebacic acid-21 parts of isophorone diisocyanate After mixing in a table kneader and then heating to 100 ° C, the mixture was melted, When the pressure was reduced with stirring at 15 RPM and the temperature was maintained at 90 ° C. for 8 hours, the contents became a viscous melt.

16 parts of polymer dispersant PD4 powder (10% by weight with respect to the polycondensation resin component) is dispersed in 64 parts of ion-exchanged water, stirred for 10 minutes, and then emulsified for 1 minute with a homogenizer (Ultra Turrax, manufactured by IKA). Thereafter, the mixture was heated to 95 ° C., and the melt in the table kneader was added to the table kneader for 3 minutes with stirring at 30 RPM, resulting in a white emulsion. Further, the stirring speed was increased to 40 RPM, and 160 parts of ion-exchanged water heated to 60 ° C. was added over 5 minutes, then held for 10 minutes and further cooled to room temperature.
As a result, an aqueous dispersion (C2-4) of crystalline resin particles having a volume average particle diameter (center diameter) of 350 nm, a melting point of 69 ° C., a weight average molecular weight of 14,000, and a solid content of 40% by weight is obtained. It was.
Further, 10 parts of the prepared latex was placed in a watch glass and dried in an oven dryer at 40 ° C. for 4 hours to obtain a solid polymer. The XPS was used to quantify the surface nitrogen atom ratio attributable to the urethane bond, and it was 15.9 atomic%.

(Example C2-5)
<Preparation of aqueous dispersion (C2-5) of crystalline resin particles>
-Octadecylbenzenesulfonic acid 0.7 parts-1,9-nonanediol 46 parts-Sebacic acid 98 parts-Isophorone diisocyanate 21 parts After mixing in a table kneader and then heating to 100 ° C to melt the mixture, 15 RPM When the pressure was reduced with stirring at 90 ° C. for 8 hours, the contents became a viscous melt.
16 parts of polymer dispersant PD4 powder (10% by weight based on the polycondensation resin component) was dispersed in 64 parts of ion-exchanged water and stirred for 10 minutes. Then, after emulsifying for 1 minute with a homogenizer (IKA Corporation, Ultra Tarrax), heating to 95 ° C. and adding the melt in the table kneader for 3 minutes while stirring at 30 RPM, Became an emulsion. Further, the stirring speed was increased to 40 RPM, and 160 parts of ion-exchanged water heated to 60 ° C. was added over 5 minutes, then held for 10 minutes and further cooled to room temperature.
Thus, an aqueous dispersion (C2-5) of crystalline resin particles having a volume average particle diameter (center diameter) of 210 nm, a melting point of 72 ° C., a weight average molecular weight of 15,000, and a solid content of 40% by weight is obtained. It was.
Moreover, 10 g of the produced resin particles were placed in a watch glass and dried in an oven dryer at 40 ° C. for 4 hours to obtain a solid polymer.

(Example A2-1)
<Preparation of Amorphous Resin Particle Water Dispersion (A2-1)>
175 parts of 1,4-cyclohexanedicarboxylic acid 380 parts of bisphenol A ethylene oxide 2 mol adduct (2 mol adduct in terms of both ends)
・ Isophorone diisocyanate 19 parts ・ Dodecylbenzenesulfonic acid 0.5 parts Mix in a table kneader, then heat to 120 ° C., melt the mixture, reduce pressure while stirring at 15 RPM, and hold at 100 ° C. for 8 hours. The contents became a viscous melt.

After dispersing 44 parts (6% by weight with respect to the polycondensation resin component) of the polymer dispersant PD5 powder in 230 parts of ion-exchanged water and stirring for 10 minutes, the mixture is stirred for 1 minute with a homogenizer (manufactured by IKA, Ultra Turrax). After emulsification, the mixture was heated to 95 ° C., and the melt in the table kneader was added to the table kneader with stirring at 30 RPM for 3 minutes, resulting in a white emulsion. Further, the stirring speed was increased to 40 RPM, 550 parts of ion-exchanged water heated to 95 ° C. was added over 5 minutes, then held for 10 minutes, and further cooled to room temperature.
As a result, an aqueous dispersion (A2-1) of amorphous resin particles having a center diameter of 210 nm, a glass transition temperature of 60 ° C., a weight average molecular weight of 19,000, and a solid content of 40% by weight was obtained.
Further, 10 parts of the prepared non-crystalline resin particle aqueous dispersion (A2-1) was placed in a watch glass and dried in an oven dryer at 40 ° C. for 4 hours to obtain a solid polymer. When this polymer was quantified using XPS, the surface nitrogen atom ratio attributable to the urethane bond was 18.1 atomic%.

(Comparative Example A2-2)
<Preparation of Amorphous Resin Particle Water Dispersion (A2-2)>
In preparation of the aqueous dispersion (A2-1) of amorphous resin particles, the conditions were the same as those for the aqueous dispersion (A2-1) of amorphous resin particles, except that PD6 was used instead of the polymer dispersant PD5. Similarly, an aqueous dispersion (A2-2) of amorphous resin particles was produced.
The center diameter was 219 nm, the glass transition temperature was 60 ° C., the weight average molecular weight was 14,500, and the solid content was 40% by weight.
Further, 10 parts of the prepared resin particles were placed in a watch glass and dried in an oven dryer at 40 ° C. for 4 hours to obtain a solid polymer.

(Comparative Example A2-3)
<Preparation of Aqueous Dispersion of Amorphous Resin Particles (A2-3)>
In preparation of the aqueous dispersion (A2-1) of amorphous resin particles, the conditions were the same as those for the aqueous dispersion (A2-1) of amorphous resin particles, except that PD7 was used instead of the polymer dispersant PD5. In the same manner, an aqueous dispersion (A2-3) of amorphous resin particles was produced.
The center diameter was 190 nm, the glass transition temperature was 57 ° C., the weight average molecular weight was 16,100, and the solid content was 40% by weight.
Further, 10 parts of the prepared resin particles were placed in a watch glass and dried in an oven dryer at 40 ° C. for 4 hours to obtain a solid polymer.

(Comparative Example A2-4)
<Aqueous dispersion of non-crystalline resin particles (A2-4)>
In preparation of the aqueous dispersion (A2-1) of amorphous resin particles, the conditions were the same as those for the aqueous dispersion (A2-1) of amorphous resin particles, except that PD8 was used instead of the polymer dispersant PD5. In the same manner, an aqueous dispersion (A2-4) of amorphous resin particles was produced.
The center diameter was 200 nm, the glass transition temperature was 57 ° C., the weight average molecular weight was 13,100, and the solid content was 40% by weight.
Further, 10 parts of the prepared resin particles were placed in a watch glass and dried in an oven dryer at 40 ° C. for 4 hours to obtain a solid polymer.

-Storage stability of aqueous dispersion of resin particles-
150 cc of the prepared aqueous dispersion of resin particles was placed in a 300 cc glass bottle and left in a constant temperature bath at 85 ° C. for 1 week. The storage stability of the aqueous dispersion of resin particles was judged according to the following criteria. The evaluation criteria are as follows. In addition, (circle) was set as the pass.
○ ・ ・ ・ Good dispersibility without sedimentation and separation △ ・ ・ ・ Slight separation is observed × ・ ・ ・ Sedimentation and separation

  From the results of Table 4, the aqueous dispersions of the resin particles of Examples C2-1 to C2-3 were polymerized with polyurethane resin in water, and further composite resin particles with vinyl resin were prepared by radical polymerization. Yes. It can be seen that the nitrogen atom ratio on the surface of the resin particles is moderate (10 atomic% or more), and thus the storage stability is also high.

<Example 2-1>
In Example 1-1, the aqueous dispersion of crystalline resin particles was changed to an aqueous dispersion C2-1 of crystalline resin particles, and the aqueous dispersion of amorphous resin particles was changed to an aqueous dispersion A2 of amorphous resin particles. A toner for developing an electrostatic charge image of Example 2-1 was produced in the same manner as in Example 1-1 except that the toner was changed to -1.
Using the obtained toner of Example 2-1, cumulative volume average particle diameter D ₅₀ (μm), GSDv, shape factor SF1, OH value of toner (before heat fixing), OH value of fixed image (after heat fixing) The summer environment continuous printing test and document offset were evaluated. The results are shown in Table 5.
The measurement methods of the cumulative volume average particle diameter D ₅₀ (μm), GSDv, shape factor SF1, and summer environment continuous printing test are as described above.

(Measurement of OH number of toner and fixed images)
The OH value of the electrostatic image developing toner prepared in Example 2-1 was measured and found to be 35 mgKOH / g. Further, when the resin component was cut out from the fixed image and the OH value was measured, it was 28 mgKOH / g.
The OH value was measured as follows. The binder resin contained in the toner before or after heat fixing is allowed to react with excess succinic anhydride in a molten state to convert hydroxy groups to COOH groups, and the binder resin is dissolved in chloroform or dimethyl sulfoxide. It was. It was then purified by repeated reprecipitation with acetone. The purified binder resin was subjected to non-aqueous titration with an N / 50 caustic soda ethanol solution using phenolphthalein as an indicator to determine the OH value.

(Document offset evaluation method)
The images of the fixed images formed at 120 ° C. are overlapped and left in a 60 ° C. atmosphere under a load of 80 g / cm ² for 7 days, after which they are peeled off, and the presence or absence of document offset is visually confirmed and evaluated. did. The evaluation criteria were ○ that the image was not deteriorated even if the force was applied to peel it, and △ that there was slight image deterioration, and marked image deterioration occurred. The thing was made into x.
The result of measuring the document offset was ○.

<Examples 2-2 to 2-5 and Comparative Examples 2-1 to 2-3>
In Example 2-2, an electrostatic charge image developing toner was produced in the same manner as in Example 2-1, except that the aqueous dispersion of crystalline resin particles was changed to C2-2.
In Example 2-3, the electrostatic charge image developing was performed in the same manner as in Example 2-1, except that the aqueous dispersion of crystalline resin particles was changed to C2-3 and the colorant particle dispersion was changed to P2. A toner was prepared.
In Example 2-4, the electrostatic charge image developing was performed in the same manner as in Example 2-1, except that the aqueous dispersion of crystalline resin particles was changed to C2-4 and the colorant particle dispersion was changed to P2. A toner was prepared.
In Example 2-5, the electrostatic charge image development was performed in the same manner as in Example 2-1, except that the aqueous dispersion of crystalline resin particles was changed to C2-5 and the colorant particle dispersion was changed to P2. A toner was prepared.
In Comparative Example 2-1 to Comparative Example 2-3, the electrostatic charge image development was performed in the same manner as in Example 2-1, except that the aqueous dispersion of amorphous resin particles was changed to A2-2 to A2-4, respectively. A toner was prepared.
For each of the toners obtained in Example 2-2 to Example 2-5 and Comparative Example 2-1 to Comparative Example 2-3, the cumulative volume average particle diameter D ₅₀ (μm) in the same manner as in Example 2-1, GSDv, shape factor SF1, OH value of toner (before heat fixing), OH value of fixed image (after heat fixing), summer environment continuous printing test and document offset were evaluated. The results are shown in Table 5.

It is process schematic of the process of the continuous emulsification method which is an example of the manufacturing method of the aqueous dispersion of the resin particle of this invention.

Claims (15)

A polymer dispersant comprising a condensation product of a polycondensable monomer containing a hydroxycarboxylic acid having a weight average molecular weight of 5,000 or more and a total of 3 or more hydroxy groups and carboxy groups is 0.1 to 0.1 per resin solid content. An aqueous dispersion of resin particles, characterized by containing 30% by weight.   50 to 100 at least one polymerizable resin selected from the group consisting of the polymer dispersant, a polycondensation resin excluding the polymer dispersant, a polyaddition resin, and an addition polymerizable resin in the solid content of the resin. The aqueous dispersion of resin particles according to claim 1, which is contained by weight%.   3. The aqueous dispersion of resin particles according to claim 1, wherein the content of the polymer dispersant is 5% by weight or more based on the polymerizable resin excluding the polymer dispersant. The polymer dispersant is a condensate obtained by polycondensation of at least one hydroxycarboxylic acid selected from the group consisting of formulas (1) to (3). An aqueous dispersion of the resin particles described.

R ^{1 to} R ⁴ each independently represent a hydrogen atom or an alkyl group, and may be the same or different.   The aqueous dispersion of resin particles according to any one of claims 1 to 4, wherein the polymer dispersant is a self-condensate of hydroxycarboxylic acid having a total of 3 or more hydroxy groups and carboxy groups.   The resin particle aqueous dispersion according to any one of claims 1 to 5, wherein the resin particles have an average particle diameter of 50 to 600 nm. A mixing step of mixing the polymer dispersant with the polycondensation resin in a molten state; and
The method for producing an aqueous dispersion of resin particles according to any one of claims 1 to 6, further comprising an emulsification step of emulsifying the mixture obtained by the mixing step. A mixing step of mixing an aqueous phase containing the polymer dispersant and an oil phase containing a polycondensation resin and / or a polyaddition resin and an addition polymerizable monomer;
An emulsification step of emulsifying the mixture obtained by the mixing step; and
The method for producing an aqueous dispersion of resin particles according to any one of claims 1 to 6, further comprising an addition polymerization step of addition polymerization of the addition polymerizable monomer. An aggregation step of aggregating the resin particles in a dispersion containing a resin particle dispersion, a colorant dispersion, and a release agent dispersion to obtain aggregated particles; and
Including a fusing step of heating and fusing the agglomerated particles,
The resin particle dispersion is an aqueous dispersion of resin particles according to any one of claims 1 to 6 or an aqueous dispersion of resin particles obtained by the production method according to claim 7 or 8. A method for producing a toner for developing an electrostatic image. An electrostatic image developing toner produced by the method for producing an electrostatic image developing toner according to claim 9. A compound having two or more groups capable of reacting with a hydroxy group in the toner for developing an electrostatic image,
11. The toner for heat fixing according to claim 10, wherein the OH value (before heat fixing) of the electrostatic image developing toner before heat fixing and the OH value (after heat fixing) of the image after heat fixing have the following relationship. Toner for developing electrostatic images.
OH value (before heat fixing)> OH value (after heat fixing)   The toner for developing an electrostatic charge image according to claim 11, wherein the compound having two or more groups capable of reacting with a hydroxy group in the toner for developing an electrostatic charge image is a polyisocyanate compound.   An electrostatic image developer comprising the electrostatic image developing toner according to claim 10. An electrostatic latent image forming step of forming an electrostatic latent image on the electrostatic latent image holding member;
An image forming step of developing the latent image on the electrostatic latent image holding member with a developer containing toner for developing an electrostatic charge image to form a toner image;
A transfer step of transferring the toner image;
A fixing step of fixing the toner image,
The electrostatic charge image developing toner according to any one of claims 10 to 12 is used as the electrostatic charge image developing toner, or the electrostatic charge image developer according to claim 13 is used as the developer. Image forming method. An electrostatic latent image carrier;
Charging means for charging the electrostatic latent image holding member;
Exposure means for exposing the charged electrostatic latent image holding member to form an electrostatic latent image on the electrostatic latent image holding member;
Developing means for developing the electrostatic latent image with a developer containing an electrostatic charge image developing toner to form a toner image;
Transfer means for transferring the toner image from the electrostatic latent image holding member to a recording material;
The electrostatic charge image developing toner according to any one of claims 10 to 12 is used as the electrostatic charge image developing toner, or the electrostatic charge image developer according to claim 13 is used as the developer. Image forming apparatus.

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