JP2012048014A - Toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner capable of suppressing inhibition in low-temperature fixing and decrease in chargeability in a high temperature and high humidity environment although the toner has a large nitrogen content, and capable of giving a high-quality image.SOLUTION: The toner comprises toner particles containing a resin essentially comprising polyester, a colorant and wax, and has a surface nitrogen amount ranging from 1.0 to 10.0 atomic% measured by X-ray photoelectron spectroscopy on the surface of the toner particles. The toner particles have a specific surface area St ranging from 0.60 to 2.00 m/g; and when the toner particles are dispersed in water to measure an acidic value, denoted as Ut (mgKOH/g), of the toner particles, an acidic value per surface area Ut/St of the toner particles ranges from 0.2 to 1.5 mgKOH/m. The toner particles have a work function W0 ranging from 5.65 to 6.00 eV.

Description

  The present invention relates to a toner used in a recording method using an electrophotographic method, an electrostatic recording method, a toner jet recording method or the like. More specifically, the present invention relates to a copying machine and printer in which a toner image is formed on an electrostatic latent image carrier and then transferred onto a transfer material to form a toner image and fixed under thermal pressure to obtain a fixed image. The present invention relates to cyan toner used for fax.

  In recent years, energy saving has been considered as a major technical problem in electrophotographic apparatuses, and a great reduction in the amount of heat applied to a fixing apparatus has been cited. Accordingly, there is a growing need for so-called “low-temperature fixability” that can fix toner with lower energy.

  Conventionally, in order to enable fixing at a lower temperature, a technique of making the binder resin sharper melt is known as one of effective methods. In this respect, the polyester resin exhibits excellent characteristics.

  On the other hand, as another aspect of improving the image quality, for the purpose of high resolution and high definition, the toner particle size is reduced and the particle size distribution is sharpened, while the spherical shape is improved for the purpose of improving transfer efficiency and fluidity. Toner is now being used favorably. As a method for efficiently preparing spherical toner particles having a small particle size, a wet method has been used.

  As a wet method in which a sharp melt polyester resin can be used, a resin component is dissolved in an organic solvent immiscible with water, and this solution is dispersed in an aqueous phase to form oil droplets. A “dissolution suspension” method for producing toner particles has been proposed (Patent Document 1). According to this method, a spherical toner having a small particle diameter using polyester having excellent low-temperature fixability as a binder resin can be easily obtained.

  Further, capsule-type toner particles have been proposed for the purpose of further low-temperature fixability in the toner particles produced by the above-described dissolution suspension method using polyester as a binder resin.

  Patent Document 2 proposes the following method.

  A polyester resin, a low-molecular compound having an isocyanate group, and other components are dissolved and dispersed in ethyl acetate to prepare an oil phase, and droplets are prepared in water. As a result, a compound having an isocyanate group at the droplet interface is subjected to interfacial polymerization to prepare capsule toner particles having polyurethane or polyurea as the outermost shell.

  In Patent Documents 3 and 4, toner base particles are prepared by a dissolution suspension method in the presence of resin fine particles that are any of vinyl resins, polyurethane resins, epoxy resins, polyester resins, or a combination thereof. There has been proposed a method for preparing toner particles in which the surface of toner base particles is coated with resin fine particles.

  Patent Document 5 proposes toner particles by a dissolution suspension method using urethane-modified polyester resin fine particles as a dispersant.

  Patent Document 6 discloses a core-shell type composed of one or more film-like shell layers (P) made of polyurethane resin (a) and one core layer (Q) made of resin (b). Toner particles have been proposed.

  The core-shell type toner particles have a structure in which the core portion has a low viscosity and the heat resistance storage stability of the shell portion compensates for the inferior heat resistance storage stability. In this case, since the shell portion is somewhat thermally hard, it is necessary to devise such as highly cross-linking or high molecular weight, so that the low-temperature fixability tends to be hindered.

  When a core / shell type toner is manufactured by a wet method, it is possible to dispose a polar material on the toner surface. In the process of using resin fine particles as a dispersant, the resin fine particles have polarity, so that they easily become compatible with the aqueous phase and have a capsule structure (Patent Document 7). However, when the surface layer material has a polar group such as a sulfonic acid group or a carboxyl group, it is easy to cause an adverse effect due to water absorption on the toner surface. When the water absorption amount of the toner particles is large, the charge amount of the toner particles after being left in a high humidity environment tends to be insufficient. Further, the toner may be plasticized and aggregated by water absorption. When the glass transition temperature of the toner in the water absorption state is lower than the storage temperature, this aggregation is likely to occur.

Japanese Patent Laid-Open No. 08-248680 JP 05-297622 A JP 2004-226572 A JP 2004-271919 A Japanese Patent No. 3455523 WO2005 / 073287 JP 2006-206848 A

  The present invention has been made in view of the above problems, and provides a toner having a high offset resistance and an excellent charging property while being a capsule-type toner excellent in low-temperature fixability. is there. In particular, the object is to stabilize the chargeability while satisfying the preservation in the environment, and to obtain a high-quality image with fine characters, lines and dots. Further, it is possible to suppress the water absorption amount of the toner even under high temperature and high humidity, and to solve problems such as a decrease in the charge amount due to plasticization of the toner, scattering fog during development, and transfer defects. Another object is to provide a spherical toner having a small particle size and a sharp particle size distribution.

The present invention is a toner having toner particles containing at least a resin (a) based on polyester, a colorant and a wax,
The amount of surface nitrogen by X-ray photoelectron spectroscopy (ESCA) of the toner particle surface is 1.0 atomic% or more and 10.0 atomic% or less,
When the acid value of the resulting toner particles the toner particles were measured were dispersed in water and Ut (mgKOH / g), specific surface area St of the toner particles is 0.60 m ² / g or more 2.0 m ² The acid value per surface area of the toner particles (Ut / St) satisfies 0.2 mgKOH / m ² or more and 1.5 mgKOH / m ² or less,
The present invention relates to a toner having a work function W0 of 5.65 eV or more and 6.00 eV or less when measured after the toner particles are left for 3 days in an environment of 23.0 ° C. and 25% RH.

  According to the present invention, since the toner base particles (A) have functions such as low viscosity, releasability, and coloring, excellent low temperature fixability is realized.

  Even though the toner has a large amount of nitrogen, it is possible to suppress the inhibition of low-temperature fixing and a decrease in charging ability in a high-temperature and high-humidity environment and obtain a high-quality image. In addition, it can solve problems such as toner scattering and fogging, and further satisfies the characteristics required for electrophotographic characteristics such as chargeability, developability, transferability, and cleaning properties by suppressing the influence of the low viscosity internal shell. It has become possible to provide a toner that can be used.

The calculation method of Tg by a DSC curve is shown. A mass change curve for measuring water absorption at a temperature of 40 ° C. and a relative humidity of 95%. It is the schematic of the apparatus which measures a triboelectric charge amount.

  According to the present invention, by using a resin mainly composed of polyester as the resin (a), it is easy to control the melting characteristics related to sharp melt properties such as softening point, glass transition temperature, and molecular weight distribution. As a result, the fixing temperature can be lowered, a high gloss can be imparted at a low temperature, and it is possible to provide a toner that is easily melted at the time of fixing and has a high image density.

  In the toner of the present invention, the amount of nitrogen in the vicinity of 399 to 401 eV by X-ray photoelectron spectroscopy (ESCA) on the surface of the toner particles is preferably 1.0 atomic% or more and 10.0 atomic% or less. When the surface nitrogen amount is less than 1.0 atomic%, the surface nitrogen amount is derived from the pigment (near 398 eV), and the wax or pigment is exposed on the toner surface, so that storage stability cannot be obtained. On the other hand, when the amount of surface nitrogen is more than 10.0 atomic%, the amount of nitrogen becomes too large and the charge becomes positive. In addition, storage stability in the environment is also deteriorated by an increase in water absorption.

The toner of the present invention is characterized in that the water absorption amount of the shell is adjusted to suppress the water absorption on the surface of the toner particles. That is, when the acid value of the toner particles obtained by measuring the particles in water is Ut (mgKOH / g) and the specific surface area of the toner particles is St, (Ut / St) is 0.2 mgKOH / g. m ² or more and 1.5 mgKOH / m ² or less are preferable. When (Ut / St) is smaller than 0.2 mgKOH / m ² , although the change in toner surface strength due to water absorption is small, charging problems such as insufficient charge retention at low humidity and charging up are likely to occur. . Further, when (Ut / St) is larger than 1.5 mgKOH / m ² , the change in the toner surface viscosity due to water absorption becomes remarkable, and both the heat resistant storage stability and the fixability become severe.

Ut is preferably at most 0.2 mgKOH / g or more 1.0 mgKOH / g, the specific surface area St of the toner particles is preferably from 0.60 m ² / g or more 2.00 m ² / g or less.

  In order to reduce the water absorption amount on the toner surface, it is necessary to reduce the water absorption amount of the material used for the surface layer. When a core / shell type toner is produced by a wet method, a polar material is arranged on the toner surface. However, when there are many polar groups such as carboxylic acid and sulfonic acid, the amount of water absorption tends to increase. However, if polar groups such as carboxylic acid and sulfonic acid are simply reduced, water absorption is suppressed, but toner granulation becomes difficult and the level of capsules is lowered. In addition, the charge amount of the toner decreases and a problem occurs in developability.

  Therefore, the present invention focuses on the work function of the toner particles. The work function is quantified as energy (eV) for extracting electrons from the substance, and the chargeability by contact between various substances can be evaluated. The smaller the work function, the easier it is to emit electrons, and the larger the work function, the harder it is to emit electrons. The work function of the toner particles is strongly influenced by the functional group on the toner surface, and the work function of toner particles having a high acid value is generally high. Carboxylic acid and sulfonic acid necessary for encapsulation are electron-withdrawing functional groups, and have a high work function but high water absorption. In the present invention, the amount of carboxylic acid necessary for encapsulation is introduced, and non-water-absorbing electron-withdrawing functional groups are introduced to increase the work function, so that both water absorption resistance and chargeability can be individually controlled. I found out.

  The work function of the toner particles of the present invention is preferably 5.65 eV or more and 6.00 eV or less. If it is less than 5.65 eV, charging becomes insufficient, causing problems in developability such as fogging and scattering. If it is larger than 6.00 eV, the image density is likely to be lowered due to charge up. The work function is within the above range even in a temperature of 23.0 ° C and humidity of 25.0% RH where charging is likely to occur during charging, and in a temperature of 40.0 ° C and humidity of 95.0% RH where charging is likely to decrease due to water absorption. Preferably there is.

  Further, since it is required that the performance of the toner does not change in any environment, the charge amount of the toner after being left for 3 days in a temperature 23.0 ° C. humidity 25.0% RH environment, and a temperature 40.0 ° C. humidity 95 The difference from the charge amount of the toner after standing for 3 days in a 0.0% RH environment is preferably 10.0 mC / kg or less.

  In order to satisfy the low-temperature fixing, it is effective to use a toner design having a low glass transition temperature, but it is preferable to design the toner at an appropriate temperature in order to achieve both heat-resistant storage stability. In addition, it is desirable to design the glass transition temperature appropriate for the storage stability of the image.

The toner of the present invention is characterized in that the glass transition temperature Tg (0.5) at a temperature rising rate of 0.5 ° C./min satisfies the following relationship.
35.0 ≦ Tg (0.5) ≦ 60.0 (1)

  That is, it is 35.0 degreeC or more and 60.0 degreeC or less, Preferably it is 40.0 degreeC or more and 58.0 degreeC or less. When the glass transition temperature Tg (0.5) is smaller than 35.0 ° C., the fixing property at low temperature is excellent, but the problem of winding and offset at high temperature is likely to occur, and the fixing temperature range is likely to be narrowed. . Further, the stability during storage of the toner is impaired, and the stability during image storage after fixing is likely to be insufficient. When the glass transition temperature Tg (0.5) exceeds 60.0 ° C., it is difficult to realize low-temperature fixability.

  Furthermore, the toner of the present invention is characterized by a glass transition temperature in DSC measurement.

In DSC measurement, it is observed as an endothermic peak of the glass transition temperature of the toner. However, if the rate of temperature rise is changed at the time of temperature rise in measuring the glass transition point of the toner, the change in glass transition temperature satisfies the following relationship: It is characterized by doing.
2.0 ≦ Tg (4.0) −Tg (0.5) ≦ 10.0 (2)
(Here, Tg (0.5) is obtained at a glass transition temperature (° C.) obtained at a heating rate of 0.5 ° C./min, and Tg (4.0) is obtained at a heating rate of 4.0 ° C./min. Glass transition temperature (° C.).)

  That is, Tg (4.0) -Tg (0.5) is 2.0 ° C. or higher and 10.0 ° C. or lower, preferably 2.5 ° C. or higher and 8.0 ° C. or lower. When Tg (4.0) -Tg (0.5) is smaller than 2.0 ° C., the heat-resistant storage stability becomes insufficient, and the influence of wax and colorant is easily picked up. Also, when Tg (4.0) -Tg (0.5) is higher than 10.0 ° C., a sufficient capsule structure is obtained, but low-temperature fixability cannot be exhibited, or the wax does not bleed out sufficiently. , Winding around the fixing member is likely to occur.

  It is necessary to control the water absorption of the toner surface. The toner of the present invention preferably has a water absorption of 0.5% by mass or more and 2.0% by mass or less at a temperature of 40 ° C. and a humidity of 95% RH. More preferably, it is 1.5 mass% or less.

  The toner of the present invention preferably has a capsule structure, and a shell layer having a relatively high viscosity is provided on the surface layer. In the present invention, a capsule-type toner is achieved by using a resin dispersant. By using a capsule-type toner, it is difficult to pick up the characteristics of the core portion, and the characteristics of the colorant and the wax can be confined in the core. However, in the case of a complete capsule-type toner, it is necessary to satisfy both the water absorption resistance and the charging characteristics of the shell portion, and it is necessary to design a shell material that controls them.

  When the capsule structure is not adopted, for example, in a toner containing wax, the wax is likely to aggregate due to precipitation of the wax on the surface of the toner, which may cause poor stirring in the developing region and clogging with a cleaner. In addition, since the amount of charge varies depending on each colorant due to the colorant appearing on the toner surface, the development and transfer behavior of each color tends to change when used as a full-color color toner. In addition, when carbon black was used as the colorant for black toner, the toner resistance was changed, and the behavior during transfer was easily changed in addition to the change in charge amount. Further, when the low-viscosity toner base particles (A) are used, it is difficult to satisfy the heat resistant storage stability.

  Since the main component of the toner surface layer (B) is the resin (b), the work function of the resin (b) directly affects the work function of the toner. Therefore, the work function of the resin (b) used in the present invention is It is preferably 5.65 eV or more and 6.00 eV or less. When the work function is less than 5.65 eV, the toner is not sufficiently charged, and developability such as fogging and scattering occurs. On the other hand, when the work function is larger than 6.00 eV, the toner is charged up, so that the image density is likely to be lowered.

  In the present invention, it is preferable that the water absorption amount of the resin (b) at a temperature of 40 ° C. and a humidity of 95% RH is 2.5% by mass or less.

  When the water absorption amount of the resin (b) in a temperature of 40 ° C. and humidity of 95% RH exceeds 2.5 mass%, the water absorption amount of the toner particles tends to be larger than 2.0 mass%. Further, the Tg of the surface is lowered, and it becomes difficult to obtain stability in a harsh environment (temperature 40 ° C., humidity 95% RH). In high-temperature and high-humidity environments, the toner tends to aggregate and storage stability tends to decrease. Furthermore, it is easy to generate a jump in the development process, and it is difficult to obtain a clear image.

  When the acid value of the urethane resin (b) measured by dissolving the urethane resin (b) in tetrahydrofuran is Ub (mgKOH / g), the Ub is 10.0 to 50.0 mgKOH / g. Is preferred.

  When the Ub is smaller than 10.0 mgKOH / g, the heat resistant storage stability of the toner tends to be lowered. Furthermore, the surface layer (B) is easily peeled off and durability stability may be lowered. On the other hand, when the Ub exceeds 50.0 mgKOH / g, it tends to be difficult to satisfy a desired toner acid value. The Ub is preferably adjusted by the blending ratio of the carboxyl group-containing monomer.

  It is possible to reduce the water absorption by reducing the functional groups such as carboxylic acid and sulfonic acid that the urethane resin (b) has. However, when a toner is prepared by a wet method, the toner preparation becomes difficult or the capsule property is lost. Or insufficient charging performance. However, if functional groups such as carboxylic acid and sulfonic acid are reduced and electron-withdrawing functional groups such as nitrile and methyl carboxylate that are not involved in water absorption are introduced, the water absorption is small and the work function is high, and even under high-temperature and high-humidity environments. It becomes possible to maintain stable charging performance.

  The toner base particles (A) used in the present invention are described in detail below.

  The toner base particles (A) used in the present invention contain at least a resin (a) mainly composed of polyester, a colorant, and a wax. Therefore, in addition to the above, other additives may be included as necessary.

  The resin (a) used in the present invention contains polyester as a main component. Here, “main component” means that polyester accounts for 50% by mass or more based on the total amount of the resin (a). As the polyester, it is preferable to use a polyester using an aliphatic diol as a main component as an alcohol component and / or a polyester using an aromatic diol as a main component as an alcohol component.

  The aliphatic diol preferably has 2 to 8 carbon atoms, more preferably 2 to 6 carbon atoms.

  Examples of the aliphatic diol having 2 to 8 carbon atoms include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol. , Neopentyl glycol, 1,4-butenediol, 1,7-heptanediol, 1,8-octanediol diol, glycerin, pentaerythritol, and trimethylolpropane trihydric or higher polyhydric alcohol. Among these, α, ω-linear alkanediol is preferable, and 1,4-butanediol and 1,6-hexanediol are more preferable. Further, from the viewpoint of durability, the content of the aliphatic diol is preferably 30 to 100 mol%, more preferably 50 to 100 mol% in the alcohol component constituting the polyester.

  Examples of the aromatic diol include polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane and polyoxyethylene (2.2) -2,2-bis (4-hydroxyphenyl) propane. Is mentioned.

  The following are mentioned as a carboxylic acid component which comprises the said polyester.

  Aromatic polyvalent carboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid and pyromellitic acid, fumaric acid, maleic acid, adipic acid, succinic acid, dodecenyl succinic acid, octenyl succinic acid, etc. Aliphatic polycarboxylic acids such as succinic acid substituted with an alkyl group or an alkenyl group having 2 to 20 carbon atoms, anhydrides of these acids, and alkyl (1 to 8 carbon atoms) esters of these acids.

  From the viewpoint of chargeability, the carboxylic acid preferably contains an aromatic polyvalent carboxylic acid compound, and the content thereof is preferably 30 to 100 mol% in the carboxylic acid component constituting the polyester, 50 to 100 mol% is more preferable.

  In addition, the raw material monomer may contain a trivalent or higher polyvalent monomer, that is, a trivalent or higher polyhydric alcohol and / or a trivalent or higher polyvalent carboxylic acid compound from the viewpoint of fixability.

  The manufacturing method of the said polyester is not specifically limited, What is necessary is just to follow a well-known method. For example, a production method in which an alcohol component and a carboxylic acid component are subjected to polycondensation in an inert gas atmosphere at a temperature of 180 to 250 ° C. using an esterification catalyst as necessary.

  The resin (a) preferably contains as a main component a polyester using the aliphatic diol as an alcohol component. On the other hand, even when the resin (a) contains a polyester using a bisphenol monomer as an alcohol component, there is no significant difference in the melting characteristics of the resin (a). However, in order to affect the granulation property in relation to the urethane resin (b), it is effective to select an appropriate polyester as appropriate.

  The resin (a) is a polyester other than a polyester using an aliphatic diol or an aromatic diol as an alcohol component, for example, a polyester resin, a styrene-acrylic resin, a polyester and a styrene in which the amount of the aliphatic diol is outside the above range. An acrylic mixed resin, an epoxy resin, or the like may be contained. In that case, the content of the polyester using the specific amount of aliphatic diol as an alcohol component is preferably 50% by mass or more, and more preferably 70% by mass or more based on the total amount of the resin (a).

  Furthermore, in the present invention, the molecular weight of the resin (a) is one of the more preferable modes that the peak molecular weight is 8000 or less, preferably less than 5500. Furthermore, it is one of the preferred embodiments that the ratio of the molecular weight of 100,000 or more is 5.0% or less, more preferably 1.0% or less.

  If the peak molecular weight exceeds 8000 or the ratio of molecular weight 100,000 or more exceeds 5.0%, the fixability may be significantly impaired depending on the type and amount of the surface layer resin.

  In the present invention, the ratio of the binder resin having a molecular weight of 1000 or less is preferably 10.0% or less, more preferably less than 7.0%. When the ratio of the molecular weight of 1000 or less is more than 10.0%, a low molecular weight component that is relatively thermally unstable may contaminate the member.

  In the present invention, in particular, the following preparation method can be suitably used in order to make the ratio of the above-described molecular weight of 1000 or less 10.0% or less.

  In order to reduce the ratio of the molecular weight of 1000 or less, the ratio of the molecular weight of 1000 or less can be effectively reduced by dissolving the binder resin in a solvent and leaving the solution in contact with water. That is, by such an operation, the low molecular weight component having a molecular weight of 1000 or less is eluted in water and can be effectively removed from the resin solution.

  For the above reasons, for example, the above-described dissolution suspension method is preferably used as a toner production method. The low molecular weight component is efficiently removed by using a method in which a solution in which the resin (a), the colorant and the wax are dissolved or dispersed is left in contact with the aqueous medium before being suspended in the aqueous medium. can do.

  In the present invention, when the molecular weight of the toner is adjusted, a resin having two or more kinds of molecular weights may be mixed and used.

  In the present invention, a crystalline polyester may be contained in the resin (a). As the crystalline polyester, a resin obtained by polycondensation of an alcohol component mainly containing an aliphatic diol and a carboxylic acid component mainly containing an aliphatic dicarboxylic acid compound is preferable.

  The crystalline polyester can be obtained using a monomer containing an alcohol component composed of a polyhydric alcohol having a valence of 2 or more and a carboxylic acid component composed of a polycarboxylic acid compound having a valence of 2 or more. Among them, an alcohol component containing 60 mol% or more of an aliphatic diol having 2 to 6, preferably 4 to 6 carbon atoms, and an aliphatic dicarboxylic acid having 2 to 8, preferably 4 to 6, more preferably 4 carbon atoms. A resin obtained by condensation polymerization of a carboxylic acid component containing 60 mol% or more of an acid compound is preferred.

  Examples of the aliphatic diol having 2 to 6 carbon atoms constituting the crystalline polyester include the following.

  Ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 1,4-butenediol. Among these, 1,4-butanediol and 1,6-hexanediol are preferable.

  The alcohol component constituting the crystalline polyester may contain a polyhydric alcohol component other than the aliphatic diol. Examples of the polyhydric alcohol component include the following. Bisphenol A alkylene such as polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene (2.2) -2,2-bis (4-hydroxyphenyl) propane ( Carbon number 2 to 3) Divalent aromatic alcohols such as oxides (average added mole number 1 to 10) adducts, and trivalent or higher alcohols such as glycerin, pentaerythritol, and trimethylolpropane.

  Examples thereof include aliphatic dicarboxylic acid compounds having 2 to 8 carbon atoms constituting the crystalline polyester and the following. Oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, adipic acid, and anhydrides and alkyl (carbon number 1 to 3) esters of these acids. Among these, fumaric acid and adipic acid are preferable, and fumaric acid is more preferable.

  The carboxylic acid component constituting the crystalline polyester may contain a polyvalent carboxylic acid component other than the aliphatic dicarboxylic acid compound. Examples of the polyvalent carboxylic acid component include aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid; aliphatic dicarboxylic acids such as sebacic acid, azelaic acid, n-dodecyl succinic acid and n-dodecenyl succinic acid; cyclohexane dicarboxylic acid, etc. Alicyclic dicarboxylic acids of the above; trivalent or higher polyvalent carboxylic acids such as trimellitic acid and pyromellitic acid; and anhydrides and alkyl (C 1 to C 3) esters of these acids.

  The alcohol component and the carboxylic acid component constituting the crystalline polyester are subjected to polycondensation by reacting at a temperature of 150 to 250 ° C. in an inert gas atmosphere, if necessary, using an esterification catalyst or the like. Can do.

  The resin (a) based on polyester used in the present invention preferably has a water absorption of 2.0% by mass or less at a temperature of 40 ° C. and a humidity of 95% RH, more preferably 1.5% by mass or less. is there. The resin (b) preferably has a water absorption of 2.5% by mass or less, more preferably 2.0% by mass or less, at a temperature of 40 ° C. and a humidity of 95% RH.

  Examples of the wax used in the present invention include the following.

  Low molecular weight polyethylene, low molecular weight polypropylene, low molecular weight olefin copolymer, aliphatic hydrocarbon wax such as microcrystalline wax, paraffin wax, Fischer-Tropsch wax; oxide of aliphatic hydrocarbon wax such as oxidized polyethylene wax; fat A wax mainly composed of a fatty acid ester such as an aromatic hydrocarbon ester wax; and a partially or completely deoxidized fatty acid ester such as a deoxidized carnauba wax; a partial ester of a fatty acid and a polyhydric alcohol such as behenic acid monoglyceride A methyl ester compound having a hydroxyl group obtained by hydrogenating vegetable oils and fats.

  The wax particularly preferably used in the present invention is, in the dissolution suspension method, easy preparation of the wax dispersion, easy incorporation into the prepared toner, seepage from the toner during fixing, releasability Therefore, ester wax is preferable.

  In the present invention, the ester wax only needs to have at least one ester bond in one molecule, and either natural ester wax or synthetic ester wax may be used.

Examples of the synthetic ester wax include a monoester wax synthesized from a long-chain linear saturated fatty acid and a long-chain linear saturated alcohol. The long-chain linear saturated fatty acid is represented by the general formula C _n H _{2n + 1} COOH, and those having n = 5 to 28 are preferably used. The long-chain linear saturated alcohol is preferably represented by C _n H _{2n + 1} OH, where n = about 5 to 28.

  Specific examples of the long-chain linear saturated fatty acid include capric acid, undecyl acid, lauric acid, tridecyl acid, myristic acid, palmitic acid, pentadecylic acid, heptadecanoic acid, tetradecanoic acid, stearic acid, nonadecanoic acid, aramonic acid, Examples include behenic acid, lignoceric acid, serotic acid, heptacosanoic acid, montanic acid, and melicic acid.

  On the other hand, specific examples of the long-chain linear saturated alcohol include amyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, capryl alcohol, nonyl alcohol, decyl alcohol, undecyl alcohol, lauryl alcohol, tridecyl alcohol, and myristyl alcohol. Pentadecyl alcohol, cetyl alcohol, heptadecyl alcohol, stearyl alcohol, nonadecyl alcohol, eicosyl alcohol, seryl alcohol and heptadecanool.

  Examples of the ester wax having two or more ester bonds per molecule include, for example, trimethylolpropane tribehenate, pentaerythritol tetrabehenate, pentaerythritol diacetate dibehenate, glycerin tribehenate, 18-octadecanediol-bis-stearate, polyalkanol esters (tristearyl trimellitic acid, distearyl maleate are mentioned.

  Examples of natural ester waxes include candelilla wax, carnauba wax, rice wax, wax, jojoba oil, beeswax, lanolin, castor wax, montan wax and derivatives thereof.

  Other modified waxes include polyalkanoic acid amide (ethylenediamine dibehenyl amide); polyalkylamide (trimellitic acid tristearyl amide); and dialkyl ketone (distearyl ketone).

  The wax may be partially saponified.

  Among the above, more preferable waxes are synthetic ester waxes composed of long-chain linear saturated fatty acids and long-chain linear saturated aliphatic alcohols, or natural waxes based on the above esters.

  The reason for this is not clear, but it is thought that the mobility in the molten state is increased due to the wax having a linear structure. In other words, it is necessary for the wax to permeate into the toner surface layer through a relatively polar substance such as polyester as a binder resin or a reaction product of diol and diisocyanate on the surface layer at the time of fixing. Therefore, it seems that it is advantageous that the wax has a linear structure as much as possible in order to pass between such highly polar substances.

  Further, in the present invention, it is more preferable that the ester is a monoester in addition to the linear structure described above. For the same reason as described above, in a bulky structure in which esters are bonded to the branched chains, it penetrates through a highly polar substance such as polyester or the surface layer of the present invention and oozes out to the surface. The authors speculate that it may be difficult.

  In the present invention, it is also one of preferred modes to use a hydrocarbon wax other than the ester wax as needed.

  Examples of hydrocarbon waxes other than the ester wax include petroleum-based natural waxes such as paraffin wax, microcrystalline wax, petrolatum, and derivatives thereof, Fischer-Tropsch wax, polyolefin wax, and derivatives thereof (polyethylene wax, polypropylene wax). And natural waxes such as synthetic hydrocarbons such as ozokerite and ceresin.

  In the present invention, the wax content in the toner is preferably 5.0 to 20.0 mass%, more preferably 5.0 to 15.0 mass%. When the amount is less than 5.0% by mass, the releasability of the toner cannot be maintained. When the amount is more than 20.0% by mass, the wax is likely to be exposed on the toner surface, which may cause a decrease in heat resistant storage stability.

  In the present invention, the wax preferably has a maximum endothermic peak at 60 ° C. or higher and 90 ° C. or lower in differential scanning calorimetry (DSC). If the maximum endothermic peak is lower than 60 ° C., the wax is likely to be exposed on the toner surface, which may cause a decrease in heat resistant storage stability. On the other hand, if the maximum endothermic peak is higher than 90 ° C., the wax does not melt properly at the time of fixing, and the low-temperature fixability and offset resistance may be poor.

  The following are mentioned as a coloring agent used for this invention.

  Examples of the colorant for yellow include compounds typified by condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds.

  Specific examples include the following.

  C. I. Pigment Yellow 12, 13, 14, 15, 17, 62, 74, 83, 93, 94, 95, 97, 109, 110, 111, 120, 128, 129, 138, 147, 150, 151, 154, 155, 168, 180, 185, 213, 214. These can be used alone or in combination of two or more.

  Examples of the colorant for magenta include condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, and perylene compounds.

  Specific examples include the following.

  C. I. Pigment Red 2, 3, 5, 6, 7, 23, 48: 2, 48: 3, 48: 4, 57: 1, 81: 1, 122, 146, 150, 166, 169, 177, 184, 185, 202, 206, 220, 221, 238, 254, 269, C.I. I. Pigment Bio Red 19. These can be used alone or in combination of two or more.

  Examples of the colorant for cyan include copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds, and basic dye lake compounds.

  Specific examples include the following.

  C. I. Pigment blue 1, 7, 15, 15: 1, 15: 2, 15: 3, 15: 4, 60, 62, 66. These can be used alone or in combination of two or more.

  Examples of black colorants include the following. Furnace black, channel black, acetylene black, thermal black, lamp black carbon black. Further, metal oxides such as magnetite and ferrite are also used.

  In the present invention, when a dye or pigment having extremely high solubility in water is used as a colorant, it may be dissolved in water during the production process, and granulation may be disturbed or a desired color may not be obtained. .

  In the present invention, when used as a colorant for a normal color toner, the content of the colorant is preferably 2.0% by mass or more and 15.0% by mass or less based on the toner. When it is less than 2.0% by mass, the coloring power is lowered. On the other hand, when it is more than 15.0% by mass, the color space tends to be small. More preferably, it is 2.5 mass% or more and 12.0 mass% or less. Further, a light color toner having a reduced density can be preferably used in combination with a normal color toner. In this case, the content of the colorant is preferably 0.5% by mass or more and 5.0% by mass or less with respect to the toner. More preferably, it is 0.7 mass% or more and 3.0 mass% or less.

  The colorant preferably has a number average particle diameter of 200 nm or less in an image of the toner particles obtained by taking an enlarged photograph of the cross section of the toner particles. More preferably, it is 150 nm or less. On the other hand, the number average particle diameter is preferably 50 nm or more. When it exceeds 200 nm, the particle size is large and the shell of the colorant is difficult to form. Therefore, it tends to cause a reduction in coloring power and a color gamut.

  In the present invention, a charge control agent can be used as necessary. The charge control agent may be contained in the toner base particles (A) containing at least the resin (a), the colorant and the wax, or may be contained in the surface layer (B).

  As the charge control agent that can be used in the present invention, known ones can be used, and examples thereof include the following.

  Negative charge control agents include metal compounds of aromatic carboxylic acids such as salicylic acid, alkyl salicylic acid, dialkyl salicylic acid, naphthoic acid, dicarboxylic acid, metal salts or metal complexes of azo dyes or azo pigments, sulfonic acid or carboxylic acid groups. Examples thereof include a polymer compound having a chain, a boron compound, a urea compound, a silicon compound, and a calixarene. The positive charge control agent includes a quaternary ammonium salt, a polymer compound having the quaternary ammonium salt in the side chain, a guanidine compound, a nigrosine compound, and an imidazole compound.

  Next, the surface layer (B) used in the present invention will be described.

  The surface layer (B) preferably contains a resin (b). Examples of the resin (b) include vinyl resins, polyurethane resins, epoxy resins, polyester resins, polyamide resins, polyimide resins, silicon resins, phenol resins, melamine resins, urea resins, aniline resins, ionomer resins, and polycarbonate resins. .

  As the resin (b), two or more of the above resins may be used in combination.

  The resin (b) used in the present invention is preferably a resin that can form an aqueous dispersion. Accordingly, vinyl resins, polyurethane resins, epoxy resins, and polyester resins are preferable because an aqueous dispersion of fine spherical resin particles can be easily obtained.

  In order to lower the viscosity of the surface layer (B), a polyurethane resin or polyester resin having polyester as a constituent element is preferable. Furthermore, it is preferable that the resin (b) contains a resin that is a reaction product of a diol component and a diisocyanate component because it exhibits a moderate affinity for a solvent and is water dispersible, viscosity-adjusted, and particle size is easily aligned. Polyurethane resin is particularly preferable. It is also possible to give the surface layer (B) various functions. In particular, since the surface affects the chargeability of the toner, a resin having charge controllability can be used for the surface layer.

  Hereinafter, the polyurethane resin will be described in detail.

  The urethane resin is a reaction product of a diol component that is a prepolymer and a diisocyanate component. Resins having various functionalities can be obtained by adjusting the diol component and the diisocyanate component.

  The urethane resin (b) preferably contains diisocyanate at 2.5 mmol / g or more and 3.5 mmol / g or less. When it is lower than 2.5 mmol / g, when the functional groups such as carboxylic acid and sulfonic acid are reduced and the water absorption is lowered, it is difficult to produce toner, the capsule property is lost, and sufficient toner performance is hardly obtained. When the amount is more than 3.5 mmol / g, the toner can be easily produced, but it becomes difficult to measure the viscoelasticity of the urethane resin (b).

  Examples of the diisocyanate component include the following.

  C6-C20 aromatic diisocyanate, C2-C18 aliphatic diisocyanate, C4-C15 alicyclic diisocyanate, C8-C15 aromatic Group hydrocarbon diisocyanates and modified products of these diisocyanates (urethane group, carbodiimide group, allophanate group, urea group, burette group, uretdione group, uretoimine group, isocyanurate group, oxazolidone group-containing modified product, hereinafter also referred to as modified diisocyanate) As well as a mixture of two or more of these.

  Although the following are mentioned as said aromatic diisocyanate, It does not specifically limit.

  1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 1,5-naphthylene diisocyanate.

  Examples of the aliphatic diisocyanate include the following.

  Ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 1,6,11-undecane triisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanatomethyl carbonate Proate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate, 2-isocyanatoethyl-2,6-diisocyanatohexanoate.

  Examples of the alicyclic diisocyanate include the following.

  Isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4′-diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), bis (2-isocyanatoethyl) -4-cyclohexene-1, 2-dicarboxylate, 2,5-norbornane diisocyanate, 2,6-norbornane diisocyanate.

  Of these, preferred are aromatic diisocyanates having 6 to 15 carbon atoms, aliphatic diisocyanates having 4 to 12 carbon atoms, and alicyclic diisocyanates having 4 to 15 carbon atoms, and particularly preferred are HDI and IPDI.

  Moreover, in addition to the above-mentioned diisocyanate component, the said urethane resin (b) can also use a trifunctional or more than trifunctional isocyanate compound. Examples of the trifunctional or higher functional isocyanate compound include polyallyl polyisocyanate (PAPI)], 4,4 ′, 4 ″ -triphenylmethane triisocyanate, m-isocyanatophenylsulfonyl isocyanate and p-isocyanatophenylsulfonyl. Isocyanates.

  Moreover, the following are mentioned as a diol component which can be used for the said urethane resin (b).

Alkylene glycol (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, octanediol, decanediol, dodecanediol, tetradecanediol, neopentyl glycol, 2,2-diethyl-1,3-propanediol);
Alkylene ether glycol (diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol);
Alicyclic diols (such as 1,4-cyclohexanedimethanol, hydrogenated bisphenol A);
Bisphenols (bisphenol A, bisphenol F, bisphenol S, etc.);
Alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adduct of the above alicyclic diol;
Alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adducts of the above bisphenols;
In addition, polylactone diol (such as poly ε-caprolactone diol), polybutadiene diol.

  The alkyl part of the above-described alkylene ether glycol may be linear or branched. In the present invention, an alkylene glycol having a branched structure can also be preferably used.

  Among these, an alkyl structure is preferable in view of solubility (affinity) in ethyl acetate, and an alkylene glycol having 2 to 12 carbon atoms is preferably used.

  In the urethane resin, in addition to the diol component described above, a polyester oligomer having a terminal hydroxyl group (terminal diol polyester oligomer) can also be used as a suitable diol component.

  At this time, the molecular weight (number average molecular weight) of the terminal diol polyester oligomer is preferably 3000 or less, more preferably 800 or more and 2000 or less.

  When the molecular weight of the terminal diol polyester oligomer is larger than the above, the reactivity with the isocyanate-terminated compound is lowered, and the properties of the polyester become too strong and become soluble in ethyl acetate.

  Further, the content of the terminal diol polyester oligomer described above is preferably 1 mol% or more and 10 mol% or less, more preferably 3 mol% or more and 6 mol%, in the monomer constituting the reaction product of the diol component and the diisocyanate component. It is as follows.

  When the terminal diol polyester oligomer is contained in an amount exceeding 10 mol%, the reaction product of the diol component and the diisocyanate component may be soluble in ethyl acetate.

  On the other hand, when the amount of terminal diol polyester oligomer is less than 1 mol%, the reaction product of the diol component and the diisocyanate component becomes too hard to inhibit the fixing property, or the affinity with the resin (a) decreases. It may be difficult to form a surface layer.

  The polyester skeleton of the terminal diol polyester oligomer and the polyester skeleton of the resin (a) are preferably the same in order to form good capsule-type toner particles. This is related to the affinity between the reaction product of the diol component and diisocyanate component in the surface layer and the toner base particles (core).

  Moreover, the terminal diol polyester oligomer mentioned above may have an ether bond modified with ethylene oxide, propylene oxide or the like.

  Moreover, in the said urethane resin, in addition to the reaction material of a diol component and a diisocyanate component, the compound in which the reaction product of the amino compound and the isocyanate compound was urea-bonded can also be contained together.

  The following are mentioned as said amino compound.

  Diaminoethane, diaminopropane, diaminobutane, diaminohexane, piperazine, 2,5-dimethylpiperazine, amino-3-aminomethyl-3,5,5-trimethylcyclohexane (isophoronediamine, IPDA), 4,4'-diaminodicyclohexyl Diamines such as methane, 1,4-diaminocyclohexane, aminoethylethanolamine, hydrazine, hydrazine hydrate.

  Triamines such as triethylamine, diethylenetriamine and 1,8-diamino-4-aminomethyloctane.

  In the urethane resin, in addition to the above, a reaction product of an isocyanate compound and a compound having a highly reactive hydrogen group such as a carboxylic acid group, a cyano group, or a thiol group can be used in combination. It is.

  The urethane resin preferably has a carboxylic acid group, a sulfonic acid group, a carboxylate or a sulfonate in the side chain. Thereby, it is easy to form an aqueous dispersion, and it is effective for stably forming a capsule structure without dissolving in an oil phase solvent. These can be easily produced by introducing a carboxylic acid group, a sulfonic acid group, a carboxylate or a sulfonate into the side chain of the diol component or diisocyanate component.

  For example, diol components in which a carboxylic acid group or a carboxylate salt is introduced into the side chain include dimethylolacetic acid, dimethylolpropionic acid, dimethylolbutanoic acid, dimethylolbutyric acid, dimethylolpentanoic acid, and the like, and their hydroxyl groups Mention may be made of metal salts.

  On the other hand, examples of the diol compound having a sulfonic acid group in the side chain include sodium 3- (2,3-dihydroxypropoxy) -1-propanesulfonate, N, N-bis (2-hydroxyethyl) -2-aminoethane. Examples thereof include sulfonic acid, 1,4-dihydroxy-2-sulfonic acid benzene, 1,3-dihydroxymethyl-5-sulfonic acid benzene, 2-sulfo-1,4-butanediol, and metal salts thereof.

  The content of the diol component in which a carboxylic acid group, a sulfonic acid group, a carboxylate salt or a sulfonate salt is introduced into the side chain as described above is based on all monomers forming a reaction product of the diol component and the diisocyanate component. Preferably they are 10 mol% or more and 50 mol% or less, More preferably, they are 20 mol% or more and 30 mol% or less.

  When the diol component is less than 10 mol%, the dispersibility of resin fine particles, which will be described later, tends to deteriorate and the granulation property may be impaired. On the other hand, when it is more than 50 mol%, the reaction product of the diol component and the diisocyanate component may be dissolved in the aqueous medium, and the function as a dispersant may not be achieved.

  The urethane resin preferably has a non-water-absorbing electron-withdrawing group such as a nitrile group or a carboxylic acid methyl group. As a result, only the amount of carboxylic acid and sulfonic acid required to form the capsule structure can suppress the water absorption amount of the toner, and the work function of the urethane resin present on the toner surface layer is high, so it is stable even in high temperature and high humidity The toner having the charging performance can be provided.

For example, when introducing an electron-withdrawing group into the urethane resin, for example,
1) A diol component having an electron-withdrawing functional group introduced in the side chain is used.
2) The NCO end of the urethane prepolymer is end-capped with an electron-withdrawing group-containing amine.
Can be easily introduced.

  Examples of the diol component having an electron-withdrawing functional group introduced in the side chain include methyl dimethylolpropanoate, methyl dimethylolsulfonate, methyl dimethylolbutanoate, and methyldimethylolpentanoate.

  End compounds that block the NCO end of the urethane prepolymer include 6-aminohexanitrile, 5-aminopentanitrile, 4-aminobutanenitrile, 2-aminobenzonitrile, 3-aminobenzonitrile, 2-aminobenzene acid sulfone. Mention may be made of methyl phenyl and 2-aminobenzenesulfonate.

  The surface layer (B) is preferably formed of resin fine particles containing the resin (b). The method for preparing the resin fine particles is not particularly limited, and is an emulsion polymerization method or a method in which the resin is dissolved or melted in a solvent to be liquefied and granulated by suspending it in an aqueous medium. Can be used.

  For the preparation of the resin fine particles, a known surfactant or dispersant can be used, or the resin constituting the resin fine particles can be made self-emulsifying.

  The solvent that can be used in preparing the resin fine particles by dissolving the resin in a solvent is not particularly limited, but includes the following.

  Hydrocarbon solvents such as ethyl acetate, xylene and hexane, halogenated hydrocarbon solvents such as methylene chloride, chloroform and dichloroethane, ester solvents such as methyl acetate, ethyl acetate, butyl acetate and isopropyl acetate, ethers such as diethyl ether Solvents, ketone solvents such as acetone, methyl ethyl ketone, diisobutyl ketone, cyclohexanone and methylcyclohexane, alcohol solvents such as methanol, ethanol and butanol.

  Moreover, when preparing the said resin fine particle, the manufacturing method using the resin fine particle containing the reaction material of a diol component and a diisocyanate component as a dispersing agent is one of the preferable forms. In this production method, a prepolymer having a diisocyanate component is produced, which is rapidly dispersed in water, followed by the addition of a diol component, thereby extending or crosslinking the chain.

  That is, a prepolymer having a diisocyanate component and other necessary components as necessary are dissolved or dispersed in a solvent having high solubility in water such as acetone or alcohol among the above solvents. By throwing this into water, the prepolymer having a diisocyanate component is rapidly dispersed. And it is the method of adding the said diol component continuously and preparing the reaction material of the diol component and diisocyanate component with a desired physical property.

  The resin fine particles containing the resin (b) preferably have a number average particle diameter of 100 nm or more and 300 nm or less so that the toner particles form a capsule structure.

  That is, when the number average particle diameter is smaller than 100 nm, when an appropriate amount of the resin (b) is added, defective granulation tends to occur. The granulation stability and the like tend to decrease. As a result, it becomes difficult to form the capsule structure, and the shielding effect inside the core is difficult to appear.

  On the other hand, when the number average particle diameter is larger than 300 nm, the coating amount of the resin fine particles increases, and the resin (b) characteristic is easily received.

  More preferably, it is 120 nm or more and 250 nm or less. By using resin fine particles in this range, the coatability of the resin (b) is improved and the stability during storage and development is excellent.

  In the present invention, it is preferable that the weight average particle diameter (D4) of the toner is 4.0 μm or more and 9.0 μm or less. More preferably, it is 4.5 μm or more and 7.0 μm or less.

  If the weight average particle diameter of the toner is smaller than 4.0 μm, the toner is likely to be charged up after a long period of use or the like, and the density tends to decrease. Further, when the weight average particle diameter of the toner is larger than 9.0 μm, when a line image or the like is output, the toner tends to be scattered or dropped, and the fine line reproducibility may be inferior.

  Further, the weight average particle diameter (D4) of the toner can be adjusted to the above range by controlling the addition amount of the urethane resin (b) and the blending amount of the oil phase and the dispersion liquid.

  In the toner of the present invention, it is preferable that the number of particles (hereinafter also referred to as toner fine powder amount) of 0.6 μm or more and 2.0 μm or less of the toner is 2.0% by number or less. When there are many fine powders of 2.0 micrometers or less, it will become a factor of agent contamination and a charge amount fluctuation | variation, and it will be easy to cause the problem of a density | concentration fall and a scattering fog after a long-term image output. More preferably, it is 1.5 number% or less.

  The ratio D4 / D1 of the weight average particle diameter (D4) and the number average particle diameter (D1) of the toner of the present invention is preferably 1.25 or less. More preferably, it is 1.20 or less. On the other hand, D4 / D1 is preferably 1.00 or more.

  Hereinafter, a simple method for preparing the toner particles used in the present invention will be described, but the present invention is not limited thereto.

  The toner particles include at least a resin (a) mainly composed of polyester, a colorant and a wax in an organic medium in an aqueous medium (hereinafter also referred to as an aqueous phase) in which resin fine particles containing the resin (b) are dispersed. It is preferably obtained by dispersing a solution or dispersion (hereinafter, also referred to as an oil phase) obtained by dissolving or dispersing therein, removing the solvent from the obtained dispersion, and drying.

  In the above system, the resin fine particles function as a dispersant when suspending the dissolved or dispersed material (oil phase) in the aqueous phase. By preparing toner particles by the above method, capsule-type toner particles can be easily prepared without requiring an aggregation step on the toner surface.

  In the above oil phase preparation method, the following can be exemplified as the organic medium for dissolving the resin (a) and the like.

  Hydrocarbon solvents such as ethyl acetate, xylene and hexane, halogenated hydrocarbon solvents such as methylene chloride, chloroform and dichloroethane, ester solvents such as methyl acetate, ethyl acetate, butyl acetate and isopropyl acetate, ethers such as diethyl ether Ketone solvents such as solvent, acetone, methyl ethyl ketone, diisobutyl ketone, cyclohexanone, methylcyclohexane.

  The resin (a) is preferably used in the form of a resin dispersion dissolved in the organic medium. In this case, although depending on the viscosity and solubility of the resin, the resin (a) is blended in the range of 40% by mass to 60% by mass as a resin component in the organic solvent in consideration of ease of production in the next step. Is preferred. In addition, heating at the melting point or lower of the organic medium at the time of dissolution is preferable because the solubility of the resin increases.

  The wax and the colorant are also preferably dispersed in the organic medium. That is, it is preferable to disperse a wax and a colorant, which are previously wet or dry mechanically pulverized, in an organic medium to prepare a wax dispersion and a colorant dispersion, respectively.

  The dispersibility of the wax and the colorant can also be improved by adding a dispersant and a resin that match each of them. Since these differ depending on the wax, colorant, resin, and organic solvent used, they can be selected and used as appropriate. In particular, the colorant is preferably used after being previously dispersed in an organic medium together with the resin (a).

  The oil phase can be prepared by blending a desired amount of these resin dispersion, wax dispersion, colorant dispersion, and organic medium, and dispersing each of the above components in the organic medium.

  The colorant dispersion will be described in more detail.

  Hereinafter, the preparation method of the colorant dispersion will be further described with reference to examples.

  In the present invention, the following method was used in order to increase the dispersibility of the colorant more than usual.

(1) Wet dispersion (media dispersion)
In this method, a colorant is dispersed in a solvent in the presence of a dispersing medium.

  For example, a colorant, a resin, other additives and the organic solvent are mixed, and the mixture is dispersed using a disperser in the presence of a dispersing medium. The used dispersion medium is collected to obtain a colorant dispersion. As the dispersing machine, for example, an attritor (Mitsui Miike Koki Co., Ltd.) is used. Examples of the dispersing medium include alumina, zirconia, glass, and iron beads, but zirconia beads with very little media contamination are preferable. In this case, the bead diameter is preferably 2 to 5 mm because of excellent dispersibility.

(2) Dry kneading Resin, colorant, and other additives are melt kneaded with a kneader and roll type disperser (dry type), and the resulting melt kneaded product of resin and colorant is pulverized and dissolved in the organic solvent. To obtain a colorant dispersion.

(3) Wet dispersion of dry melt-kneaded product The colorant dispersion prepared by using the melt-kneaded product of the resin and the colorant obtained by the above dry method is further wet-dispersed using the above-mentioned dispersion media and disperser. .

(4) Solvent addition at the time of preparation of the dry melt kneaded product A solvent is added at the time of preparation of the dry melt kneaded product. The temperature during melt-kneading is preferably from the glass transition point (Tg) of the resin to the boiling point of the solvent. The solvent to be used is preferably a solvent capable of dissolving the resin, and a solvent used in the oil phase is preferable.

(5) Addition of wax during preparation of dry melt-kneaded product A wax is added during preparation of the dry melt-kneaded product. The temperature during melt-kneading is preferably from the glass transition point (Tg) of the resin to the boiling point of the solvent. As the wax to be used, a wax that dissolves in the oil phase may be used, but another wax having a relatively high melting point may be used.

  (6) A resin having a high affinity with the colorant is used as the resin.

  A resin having a high affinity with the colorant is used as the resin used for the production of the dry melt kneaded product. In particular, the resin in which the colorant is dispersed is preferably a polyester resin in which the dialcohol component is mainly composed of bisphenol A. The acid value of the resin (a) is preferably 15 mgKOH / g or more and 30 mgKOH / g or less, and the weight average molecular weight Mw is preferably 30,000 or less.

  Furthermore, after mixing each dispersion liquid, a fine dispersion process using ultrasonic waves is effective. In this case, the aggregates of the colorant in the dispersion after the oil phase adjustment are easily loosened, and further fine dispersion is possible.

  The ultrasonic oscillation device preferably used in the present invention is of an ultrasonic oscillation element type having a vibrator for irradiating ultrasonic waves having a cylindrical structure, has an ultrasonic cleaning tank, and has ultrasonic waves on the tank bottom surface. What attaches a vibrator | oscillator and performs ultrasonic irradiation in water can be used.

  The mechanism of high dispersion of the pigment by ultrasonic irradiation is not exactly known, but is presumably due to the following reasons.

  The vibration of the solution itself by ultrasonic irradiation is proportional to the frequency. Since the acceleration is as large as about 1000 to 5000 times the gravitational acceleration, it is considered that the pigment can be highly dispersed more efficiently than the shearing force action by the conventional stirring blade.

  The aqueous medium may be water alone or a solvent miscible with water may be used in combination. Examples of miscible solvents include alcohols (methanol, isopropanol, ethylene glycol), dimethylformamide, tetrahydrofuran, cellosolves (methylcellosolve), and lower ketones (acetone, methylethylketone). It is also a preferred method to mix an appropriate amount of the organic medium used as the oil phase in the aqueous medium used in the present invention. This seems to have the effect of enhancing droplet stability during granulation and making the aqueous medium and the oil phase more easily suspended.

  In the present invention, it is preferable to disperse and use the resin fine particles containing the urethane resin (b) in an aqueous medium. The resin fine particles containing the urethane resin (b) are used in a desired amount according to the stability of the oil phase in the next step and the encapsulation of the toner base particles. In the present invention, when resin fine particles are used for forming the surface layer (B), the amount of the resin fine particles used is 5.0% by mass or more and 15.0% by mass or less based on the toner base particles (A). It is preferable that

  In the aqueous medium, a known surfactant, dispersant, dispersion stabilizer, water-soluble polymer, or viscosity modifier can be added.

  Examples of the surfactant include an anionic surfactant, a cationic surfactant, an amphoteric surfactant, and a nonionic surfactant. These can be arbitrarily selected according to the polarity at the time of toner particle formation.

  Specifically, anionic surfactants such as alkylbenzene sulfonates, α-olefin sulfonates, phosphate esters; amine salt types such as alkylamine salts, aminoalcohol fatty acid derivatives, polyamine fatty acid derivatives, imidazolines, and alkyltrimethyls. Ammonium salt, dialkyldimethylammonium salt, alkyldimethylbenzylammonium salt, pyridinium salt, alkylisoquinolinium salt, quaternary ammonium salt type cationic surfactants such as benzethonium chloride; fatty acid amide derivatives, polyhydric alcohol derivatives, etc. Nonionic surfactants; amphoteric surfactants such as alanine, dodecyl di (aminoethyl) glycine, di (octylaminoethyl) glycine and N-alkyl-N, N-dimethylammonium betaine.

  The following are mentioned as said dispersing agent.

Acids such as acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid or maleic anhydride;
Β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate, γ-hydroxypropyl acrylate, γ-hydroxypropyl methacrylate, 3-chloro-2-acrylate Hydroxypropyl, 3-chloro-2-hydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerol monoacrylate, glycerol monomethacrylate, N-methylolacrylamide, N-methylolmethacrylamide, etc. (Meth) acrylic monomers containing the hydroxyl groups of
Vinyl alcohol or ethers with vinyl alcohol such as vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether;
Esters of vinyl alcohol and vinyl-containing compounds such as vinyl acetate, vinyl propionate and vinyl butyrate;
Acrylamide, methacrylamide, diacetone acrylamide or their methylol compounds; acid chlorides such as acrylic acid chloride and methacrylic acid chloride; those having nitrogen atoms such as vinylpyridine, vinylpyrrolidone, vinylimidazole, ethyleneimine, or heterocyclic rings thereof Homopolymers or copolymers such as;
Polyoxyethylene, polyoxypropylene, polyoxyethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonylphenyl ether, polyoxyethylene lauryl phenyl ether, polyoxyethylene stearyl Polyoxyethylenes such as phenyl ester and polyoxyethylene nonylphenyl ester;
Celluloses such as methyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose.

  When a dispersant is used, the dispersant can remain on the surface of the toner particles, but it is preferable to dissolve and remove it from the charged surface of the toner.

  In the present invention, a solid dispersion stabilizer may be used to maintain a more preferable dispersion state.

  In the present invention, it is preferable to use a dispersion stabilizer. The reason is as follows. The organic medium in which the resin (a) as the main component of the toner is dissolved has a high viscosity. Therefore, the dispersion stabilizer surrounds the oil droplets formed by finely dispersing the organic medium with a high shearing force, preventing the oil droplets from reaggregating and stabilizing.

  As the dispersion stabilizer, inorganic dispersion stabilizers and organic dispersion stabilizers can be used. In the case of inorganic dispersion stabilizers, toner particles are granulated in a state of being adhered on the particle surface after dispersion, and thus have an affinity for a solvent. Those which can be removed by non-acidic acids such as hydrochloric acid are preferred. For example, calcium carbonate, calcium chloride, sodium hydrocarbon, potassium hydrocarbon, sodium hydroxide, potassium hydroxide, hydroxyapatite, and calcium triphosphate can be used.

  The dispersion method used at the time of preparing the toner particles is not particularly limited, and general-purpose devices such as a low-speed shear method, a high-speed shear method, a friction method, a high-pressure jet method, and an ultrasonic wave can be used, but the dispersion particle size is 2 to 20 μm. In order to achieve the degree, a high speed shearing type is preferable.

  If it is an agitator which has a rotary blade, there will be no restriction | limiting in particular, If it is a general thing as an emulsifier and a disperser, it can be used for the said dispersion | distribution method.

  For example, Ultra Turrax (manufactured by IKA), Polytron (manufactured by Kinematica), TK Auto Homo Mixer (manufactured by Special Mechanized Industry Co., Ltd.), Ebara Milder (manufactured by Ebara Corporation), TK Homomic Line Flow (Made by Special Machine Industries Co., Ltd.), colloid mill (made by Shinko Pantech Co., Ltd.), thrasher, trigonal wet pulverizer (made by Mitsui Miike Chemical Co., Ltd.), Cavitron (made by Eurotech), fine flow mill Examples thereof include a continuous emulsifier such as (manufactured by Taiheiyo Kiko Co., Ltd.), a batch type of CLEARMIX (manufactured by M Technique Co., Ltd.), a fill mix (manufactured by Tokushu Kika Kogyo Co., Ltd.), or a continuous-use emulsifier.

  When a high-speed shearing disperser is used for the dispersion method, the rotation speed is not particularly limited, but is usually 1000 to 30000 rpm, preferably 3000 to 20000 rpm.

  In the case of the batch method, the dispersion time in the dispersion method is usually 0.1 to 5 minutes. The temperature during dispersion is usually 10 to 150 ° C. (under pressure), preferably 10 to 100 ° C.

  In order to remove the organic solvent from the obtained dispersion, a method of gradually elevating the temperature of the entire system and completely removing the organic solvent in the droplets can be employed.

  Alternatively, the dispersion liquid can be sprayed into a dry atmosphere to completely remove the water-insoluble organic solvent in the droplets to form toner particles, and the water in the dispersion liquid can be removed by evaporation. .

  In that case, as the dry atmosphere in which the dispersion is sprayed, a gas heated with air, nitrogen, carbon dioxide gas, combustion gas, etc., especially various air streams heated to a temperature higher than the boiling point of the highest boiling solvent used are generally used. It is done. Sufficient quality can be obtained even in a short time such as spray dryer, belt dryer or rotary kiln.

  When the particle size distribution of the dispersion obtained by the above dispersion method is wide and washing and drying are performed while maintaining the particle size distribution, the particle size distribution can be adjusted by classification into a desired particle size distribution.

  The dispersant used in the above dispersion method is preferably removed from the obtained dispersion as much as possible, but more preferably it is performed simultaneously with the classification operation.

  In the production method, it is also possible to provide a heating step after removing the organic solvent. By providing the heating step, the toner particle surface can be smoothed or the sphericity of the toner particle surface can be adjusted.

  In the classification operation, the fine particle portion can be removed in the liquid by a cyclone, a decanter, centrifugation, or the like. Of course, the classification operation may be performed after obtaining the powder after drying, but it is preferably performed in a liquid in view of efficiency.

  Unnecessary fine particles or coarse particles obtained by the classification operation can be returned to the dissolving step and used for forming particles. At that time, fine particles or coarse particles may be wet.

  In the cyan toner of the present invention, inorganic fine particles can be used as an external additive for assisting the fluidity, developability and chargeability of the toner.

The primary particle diameter of the inorganic fine particles is preferably 5 nm or more and 2 μm or less, and more preferably 5 nm or more and 500 nm or less. Further, the specific surface area of the inorganic fine particles by BET method is preferably 20 m ² / g or more and 500 m ² / g or less.

  The proportion of the inorganic fine particles used is preferably 0.01 parts by mass or more and 5 parts by mass or less, and more preferably 0.01 parts by mass or more and 2.0 parts by mass or less with respect to 100 parts by mass of the toner particles. .

  These inorganic fine particles may be used alone or in combination of plural kinds.

  Specific examples of the inorganic fine particles include the following.

  Silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, tin oxide, silica sand, clay, mica, wollastonite, diatomaceous earth, chromium oxide, cerium oxide, bengara , Antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, silicon nitride.

  The inorganic fine particles are preferably increased in hydrophobicity using a surface treatment agent in order to prevent deterioration of the flow characteristics and charging characteristics of toner under high humidity.

  Examples of preferable surface treatment agents include silane coupling agents, silylating agents, silane coupling agents having alkyl fluoride groups, organic titanate coupling agents, aluminum coupling agents, silicone oils, and modified silicone oils. it can.

  In addition, as external additives (cleaning improvers) for removing the toner after transfer remaining on the photosensitive member and the primary transfer medium, fatty acid metal salts such as zinc stearate, calcium stearate, stearic acid, and polymethyl methacrylate fine particles Examples thereof include polymer fine particles produced by soap-free emulsion polymerization such as polystyrene fine particles.

  The polymer fine particles preferably have a relatively narrow particle size distribution and a volume average particle size of 0.01 to 1 μm.

  A method for measuring various physical properties of the toner of the present invention will be described below.

<Method for measuring acid value of resin>
The acid value is the number of mg of potassium hydroxide necessary for neutralizing the acid contained in 1 g of the sample. The acid value of the binder resin is measured according to JIS K 0070-1966. Specifically, it is measured according to the following procedure.

(1) Preparation of Reagent 1.0 g of phenolphthalein is dissolved in 90 ml of ethyl alcohol (95 vol%), and ion exchange water is added to make 100 ml to obtain a “phenolphthalein solution”.

  7 g of special grade potassium hydroxide is dissolved in 5 ml of water, and ethyl alcohol (95 vol%) is added to make 1 l. Place in an alkali-resistant container so as not to touch carbon dioxide gas, leave it for 3 days, and filter to obtain a “potassium hydroxide solution”. The obtained potassium hydroxide solution is stored in an alkali-resistant container. The orientation is performed according to JIS K 0070-1996.

(2) Operation (A) Main test 2.0 g of the pulverized binder resin sample is precisely weighed into a 200 ml Erlenmeyer flask, and 100 ml of a mixed solution of toluene / ethanol (2: 1) is added and dissolved over 5 hours. . Subsequently, several drops of the phenolphthalein solution is added as an indicator, and titration is performed using the potassium hydroxide solution. The end point of titration is when the light red color of the indicator lasts for about 30 seconds.

(B) Blank test Titration is performed in the same manner as above except that no sample is used (that is, only a mixed solution of toluene / ethanol (2: 1) is used).

(3) The acid value is calculated by substituting the obtained result into the following formula.
A = [(BC) × f × 5.61] / S

Here, A: acid value (mgKOH / g), B: addition amount (ml) of a potassium hydroxide solution in a blank test, C: addition amount (ml) of a potassium hydroxide solution in this test, f: potassium hydroxide Solution factor, S: sample (g).
D: Acid value (mgKOH / g) of the sample.

<Measurement Method of X-ray Photoelectron Spectroscopy (ESCA)>
The content of the nitrogen element present on the toner particle surface in the present invention is calculated by performing a surface composition analysis by ESCA (X-ray photoelectron spectroscopy). The ESCA apparatus and measurement conditions may be as follows.
Device used: Quantum 2000 Scanning ESCA Microprobe manufactured by PHI (Physical Electronics Industries, Inc.)

・ Narrow analysis measurement conditions: X-ray source Al K ・ (25W, 15KV)
Photoelectron Angle: 45 °
Pass Energy: 58.70eV
Measurement range: φ100μm
Number of sweeps: 30 times

<Method for measuring work function of toner particles and resin>
The work function is measured using a photoelectron spectrometer (AC-2 manufactured by Riken Keiki Co., Ltd.). The sample is uniformly spread and placed on the apparatus measurement holder, a deuterium lamp is used as a UV light source for exciting the sample, and the irradiation light quantity is set to 500 mW. Further, monochromatic light is selected by a spectroscope, and the sample is irradiated with a spot size of 4 mm square, an energy scanning range of 3.4 to 6.2 eV, and a measurement time of 10 sec / 1 point. The photoelectrons emitted from the surface of the sample are detected and can be calculated using work function meter software. The work function is measured with a repeatability (standard deviation) of 0.02 eV.

<Measurement method of Tg>
The measuring method of Tg in the present invention was measured using DSC Q1000 (manufactured by TA Instruments) under the following conditions.

"Measurement condition"
・ Modulation mode ・ Temperature increase rate: 0.5 ° C./min or 4.0 ° C./min ・ Modulation temperature amplitude: ± 1.0 ° C./min ・ Measurement start temperature: 25 ° C.
-Measurement end temperature: 130 ° C

  When changing the heating rate, a new measurement sample was prepared. The temperature was raised only once and the DSC curve was obtained by taking “Reversing Heat Flow” on the vertical axis, and the onset value shown in FIG. 1 was defined as Tg of the present invention.

  The glass transition temperature at a heating rate of 0.5 ° C./min was measured as Tg (0.5), and the glass transition temperature at a heating rate of 4.0 ° C./min was measured as Tg (4.0). 4.0) -Tg (0.5) is calculated as the difference between the two.

<Measuring method of weight average particle diameter (D4) and number average particle diameter (D1)>
The weight average particle diameter (D4) and number average particle diameter (D1) of the toner are calculated as follows. As a measuring device, a precise particle size distribution measuring device “Coulter Counter Multisizer 3” (registered trademark, manufactured by Beckman Coulter, Inc.) using a pore electrical resistance method equipped with a 100 μm aperture tube is used. For setting the measurement conditions and analyzing the measurement data, the attached dedicated software “Beckman Coulter Multisizer 3 Version 3.51” (manufactured by Beckman Coulter, Inc.) is used. Note that the measurement is performed with 25,000 effective measurement channels.

  As the electrolytic aqueous solution used for the measurement, special grade sodium chloride is dissolved in ion-exchanged water so as to have a concentration of about 1% by mass, for example, “ISOTON II” (manufactured by Beckman Coulter, Inc.) can be used.

  Prior to measurement and analysis, the dedicated software was set as follows.

  On the “Change Standard Measurement Method (SOM)” screen of the dedicated software, set the total count in the control mode to 50,000 particles, set the number of measurements once, and set the Kd value to “standard particles 10.0 μm” (Beckman Coulter Set the value obtained using By pressing the “Threshold / Noise Level Measurement Button”, the threshold and noise level are automatically set. In addition, the current is set to 1600 μA, the gain is set to 2, the electrolyte is set to ISOTON II, and the “aperture tube flush after measurement” is checked.

  In the “Pulse to particle size conversion setting” screen of the dedicated software, the bin interval is set to logarithmic particle size, the particle size bin is set to 256 particle size bin, and the particle size range is set to 2 μm to 60 μm.

  The specific measurement method is as follows.

(1) About 200 ml of the electrolytic aqueous solution is put in a glass 250 ml round bottom beaker exclusively for Multisizer 3, set on a sample stand, and the stirrer rod is stirred counterclockwise at 24 rotations / second. Then, the dirt and bubbles in the aperture tube are removed by the “aperture flush” function of the dedicated software.
(2) About 30 ml of the electrolytic aqueous solution is put into a glass 100 ml flat bottom beaker. In this, "Contaminone N" (nonionic surfactant, anionic surfactant, 10% by weight aqueous solution of neutral detergent for pH7 precision measuring instrument cleaning, made by organic builder, manufactured by Wako Pure Chemical Industries, Ltd. About 0.3 ml of a diluted solution obtained by diluting 3) with ion-exchanged water is added.
(3) Two oscillators with an oscillation frequency of 50 kHz are incorporated with the phase shifted by 180 degrees, and an ultrasonic disperser “Ultrasonic Dissipation System Tetora 150” (manufactured by Nikki Bios Co., Ltd.) having an electrical output of 120 W is prepared. About 3.3 l of ion-exchanged water is placed in the water tank of the ultrasonic disperser, and about 2 ml of Contaminone N is added to the water tank.
(4) The beaker of (2) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. And the height position of a beaker is adjusted so that the resonance state of the liquid level of the electrolyte solution in a beaker may become the maximum.
(5) In a state where the electrolytic aqueous solution in the beaker of (4) is irradiated with ultrasonic waves, about 10 mg of toner is added to the electrolytic aqueous solution little by little and dispersed. Then, the ultrasonic dispersion process is continued for another 60 seconds. In the ultrasonic dispersion, the temperature of the water tank is appropriately adjusted so as to be 10 ° C. or higher and 40 ° C. or lower.
(6) To the round bottom beaker of (1) installed in the sample stand, the electrolyte solution of (5) in which the toner is dispersed is dropped using a pipette, and the measurement concentration is adjusted to about 5%. . The measurement is performed until the number of measured particles reaches 50,000.
(7) The measurement data is analyzed with the dedicated software attached to the apparatus, and the weight average particle diameter (D4) and the number average particle diameter (D1) are calculated. The “average diameter” on the “analysis / volume statistic (arithmetic average)” screen when the graph / volume% is set in the dedicated software is the weight average particle size (D4). When the number% is set, the “average diameter” on the “analysis / number statistics (arithmetic average)” screen is the number average particle diameter (D1).

<Method for measuring particle diameter of resin fine particles>
The particle diameter of the resin fine particles is measured using a Microtrac particle size distribution analyzer HRA (X-100) (manufactured by Nikkiso Co., Ltd.) with a range setting of 0.001 μm to 10 μm, and the number average particle diameter (μm or nm) is obtained. It was measured. In addition, water was selected as a dilution solvent.

<Measurement method of melting point of wax>
The melting point of the wax was measured using a differential scanning calorimeter (DSC) “Q1000” (manufactured by TA Instruments) according to ASTM D3418-82.

  For the temperature correction of the device detector, the melting points of indium and zinc were used, and for the correction of heat quantity, the heat of fusion of indium was used.

  Specifically, about 10 mg of a sample is accurately weighed and placed in an aluminum pan, and an empty aluminum pan is used as a reference. Measurement was performed in min. In the measurement, the temperature is once raised to 200 ° C., subsequently lowered to 30 ° C., and then the temperature is raised again. In this second temperature raising process, the temperature showing the maximum endothermic peak of the DSC curve in the temperature range of 30 to 200 ° C. was defined as the melting point of the wax. The maximum endothermic peak means a peak having the largest endothermic amount when there are a plurality of peaks.

<Measurement method of water absorption in a temperature of 40 ° C. and a humidity of 95% RH>
(Sample preparation)
The toner particles used are dried. Resin (a) and resin (b) are crushed to a center diameter of 10 μm and dried. Although a well-known thing can be used as a grinding | pulverization means, Nippon Analytical Industrial Co., Ltd. freezing grinding machine JFC-300 can be used.

(Measurement of water absorption)
The amount of water absorption of the sample at a temperature of 40 ° C. and a humidity of 95% RH is measured using an adsorption analyzer Q5000SA manufactured by TA Instruments. The outline of the measurement is described in the operation manual “Q Series Startup Guide” (Revised B, issued in February 2006) issued by TA company, and is as follows.

  Empty pans are set in the Q5000SA reference chamber and sample chamber, respectively, and zero adjustment is performed. Next, the sample is put into the sample side pan and measurement is started.

"Measurement condition"
・ Apparatus: Q5000SA manufactured by TA Instruments
・ Pan: Quartz deposition pan 957210.903 for Q5000SA
-Gas: Dry air-Sample amount: 1 to 2 mg
・ Temperature and humidity program:
Step 1) Temperature 40 ° C. and humidity 0% RH for 30 minutes step 2) Temperature 40 ° C. and humidity 95% RH for 60 minutes step 3) Temperature 40 ° C. and humidity 0% RH for 30 minutes

(analysis)
The chart shown in FIG. 2 is obtained and analyzed as follows. The value obtained by subtracting the weight (%) (W1) at the end of step 1 (30 minutes from the start of measurement) from the weight (%) (W2) at the end of step 2 (90 minutes from the start of measurement) under a 40 ° C. and 95% RH environment. It is obtained as the amount of water absorption (%).

<Method for Measuring Surface Acid Value (Ut) of Toner Particles>
(1) Preparation of Reagent 1.0 g of phenolphthalein is dissolved in 90 mL of ethyl alcohol (95 vol%), and ion exchange water is added to make 100 mL to obtain a “phenolphthalein solution”.
7 g of special grade potassium hydroxide is dissolved in 5 mL of water, and ethyl alcohol (95 vol%) is added to make 1 L. In order to avoid contact with carbon dioxide, etc., it is placed in an alkali-resistant container and allowed to stand for 3 days, followed by filtration to obtain a “potassium hydroxide solution”. The obtained potassium hydroxide solution is stored in an alkali-resistant container. The orientation is performed according to JIS K 0070-1996.
(2) Titration (A) Main test 0.5 g of toner particles are precisely weighed into a 100 ml Erlenmeyer flask, and 25 ml of ion exchange water and about 3% by weight aqueous solution of surfactant “Contaminone N” manufactured by Wako Pure Chemical Industries, Ltd. Add 0.3 ml. Disperse with an ultrasonic disperser (Sharp UT-305HS) for 1 minute. Next, 5 drops of the phenolphthalein solution is added as an indicator and titrated with the potassium hydroxide solution. Note that the end point of the titration is when the light red color of the indicator lasts for about 10 seconds.
(B) Blank test Titration similar to the above operation is performed except that no sample is used.
(3) Substituting the obtained result into the following formula, Ut is calculated.
Ut = [(BC) × f × 56.1] / W
Ut: Acid value of toner particle aqueous dispersion (mgKOH / g)
B: Addition amount (mL) of potassium hydroxide solution for blank test
C: Amount of potassium hydroxide solution added in this test (mL)
f: Factor of potassium hydroxide solution W: Sample (g)

  In the case of measuring magenta toner, thymol blue is used in place of phenolphthalein because it is difficult to observe the color change at the end point.

<Method for Measuring BET Specific Surface Area (St) of Toner and Toner Particle>
Next, the specific surface area of the toner is measured. The specific surface area of the toner is measured according to the BET method in ASTM D3037-78. According to the flow shown in FIG. 3, a mixed gas of N ₂ and He is allowed to flow through the toner, N ₂ is adsorbed and the amount thereof is detected by a thermal conductivity cell, and the specific surface area of the sample is obtained by calculation from the N ₂ adsorption amount.
(1) The sample is dried at 105 ° C. for 1 hour and then precisely weighed 0.1 to 1.0 g, put in a U-shaped tube 514 and attached to the flow path.
(2) The N ₂ / He mixing ratio is changed by the flow controllers 510 and 511 and set to a predetermined P / P0.
(3) After opening the cock and introducing the adsorption gas into the sample layer, the U-shaped tube is immersed in the liquid N ₂ 513 to adsorb N ₂ .
(4) After the adsorption equilibrium, the liquid N ₂ is removed and exposed to air for about 30 seconds, and then the U-tube is immersed in room temperature water to desorb N ₂ .
(5) Draw a desorption curve on the recorder and measure the area.
(6) Using a calibration curve prepared by introducing a known amount of N ₂ prior to these operations, the N ₂ adsorption amount at a predetermined P / P0 is determined from the area obtained for the above sample.

Hereinafter, the specific surface area is obtained by applying the following equation.
P / ν (P0−P) = 1 / νm / C + (C−1) / νm / C · (P / P0)
P0: Saturated vapor pressure of adsorbate at measurement temperature P: Pressure in adsorption equilibrium ν: Adsorption amount in adsorption equilibrium C: Constant

The relationship between P / P0 and P / ν (P0−P) is a straight line, and νm is obtained from the gradient and intercept. If νm is obtained, the specific surface area S is calculated by the following equation.
S = A × νm × N / W where S: specific surface area A: cross-sectional area of adsorbed molecule N: Avogadro number W: sample amount

  Hereinafter, the present invention will be described specifically by way of examples.

<Preparation of resin fine particle dispersion 1>
The following was charged into a reactor equipped with a stirrer and a thermometer while introducing nitrogen gas.
・ Polyester resin (number average molecular weight 2000) obtained from isophthalic acid and bisphenol A propylene oxide 2 mol adduct 32 parts by mass ・ Neopentyl glycol 19 parts by mass ・ 2,2-dimethylol propanoic acid 4 parts by mass ・ Isophorone diisocyanate 15 parts by mass / hexane diisocyanate 30 parts by mass / triethylamine (catalyst for urethanization reaction) 0.5 part by mass / acetone (solvent) from which water has been removed 100 parts by mass

  The mixture was heated to 50 ° C. and subjected to urethanization reaction for 15 hours to obtain a urethane prepolymer. To this prepolymer, 2.8 parts by mass of 6-aminohexanitrile was added and reacted. After cooling to 40 ° C., in order to neutralize the carboxyl group of 2,2-dimethylolpropanoic acid, 4 parts by mass was added to and mixed with triethylamine, and a reaction mixture was obtained. A part of the reaction mixture was dried to obtain urethane resin (b) -1. Table 1 shows the physical properties of the urethane resin (b) -1.

  This reaction mixture was poured and emulsified in 600 parts by mass of water under stirring at 10,000 rpm with a TK homomixer manufactured by Tokushu Kika Kogyo Co., Ltd. It diluted with water so that solid content ratio might be 20 mass%, and the resin fine particle dispersion 1 which is an emulsion of a polyester containing urethane was obtained.

<Preparation of resin fine particle dispersion 2>
The following was charged while introducing nitrogen into a reactor equipped with a stirrer and a thermometer.
・ Polyester resin (number average molecular weight 4000) obtained from isophthalic acid and bisphenol A propylene oxide 2 mol adduct 86 parts by mass. 2,2-dimethylolpropanoic acid 4 parts by mass. Hexane diisocyanate 10 parts by mass. Acetone 250 parts by mass. Part

  The mixture was heated to 50 ° C. and subjected to urethanization reaction for 15 hours to obtain a urethane prepolymer. To this prepolymer, 2.8 parts by mass of 6-aminohexanitrile was added and reacted. After cooling to 40 ° C., in order to neutralize the carboxyl group of 2,2-dimethylolpropanoic acid, 1.7 parts by mass were further added and mixed in addition to the amount of triethylamine already added, to obtain a reaction mixture. A part of the reaction mixture was dried to obtain urethane resin (b) -2. Table 1 shows the physical properties of the urethane resin (b) -2.

  This reaction mixture was poured and emulsified in 600 parts by mass of water under stirring at 10,000 rpm with a TK homomixer manufactured by Tokushu Kika Kogyo Co., Ltd. It diluted with water so that solid content ratio might be 20 mass%, and obtained resin fine particle dispersion 2 which is an emulsion of polyester containing urethane.

<Preparation of resin fine particle dispersion 3>
The following was charged while introducing nitrogen into a reactor equipped with a stirrer and a thermometer.
・ Polyester resin (number average molecular weight 2000) obtained from isophthalic acid and bisphenol A propylene oxide 2 mol adduct 7 parts by mass ・ Neopentyl glycol 29 parts by mass ・ 2,2-dimethylolpropanoic acid 4 parts by mass ・ Isophorone diisocyanate 20 parts by mass, hexane diisocyanate 40 parts by mass, acetone 250 parts by mass

  The mixture was heated to 50 ° C. and subjected to urethanization reaction for 15 hours to obtain a urethane prepolymer. To this prepolymer, 2.8 parts by mass of 6-aminohexanitrile was added and reacted. After cooling to 40 ° C., in order to neutralize the carboxyl group of 2,2-dimethylolpropanoic acid, 1.7 parts by mass were further added and mixed in addition to the amount of triethylamine already added, to obtain a reaction mixture. A part of the reaction mixture was dried to obtain urethane resin (b) -3. Table 1 shows the physical properties of the urethane resin (b) -3.

  This reaction mixture was poured and emulsified in 600 parts by mass of water under stirring at 10,000 rpm with a TK homomixer manufactured by Tokushu Kika Kogyo Co., Ltd. It diluted with water so that solid content ratio might be 20 mass%, and the resin fine particle dispersion 3 which is an emulsion of a polyester containing urethane was obtained.

<Preparation of resin fine particle dispersion 4>
The following was charged into a reactor equipped with a stirrer and a thermometer while introducing nitrogen gas.
・ Polyester resin (number average molecular weight 2000) obtained from isophthalic acid and bisphenol A propylene oxide 2 mol adduct 32 parts by mass ・ Neopentyl glycol 20 parts by mass ・ 2,2-dimethylol propionic acid 3 parts by mass ・ Isophorone diisocyanate 15 parts by mass / hexane diisocyanate 30 parts by mass / triethylamine (catalyst for urethanization reaction) 0.5 part by mass / acetone (solvent) from which water has been removed 100 parts by mass

  The mixture was heated to 50 ° C. and subjected to urethanization reaction for 15 hours to obtain a urethane prepolymer. To this prepolymer, 2.8 parts by mass of 6-aminohexanitrile was added and reacted. After cooling to 40 ° C., in order to neutralize the carboxyl group of 2,2-dimethylolpropanoic acid, 1.7 parts by mass were further added and mixed in addition to the amount of triethylamine already added, to obtain a reaction mixture. A part of the reaction mixture was dried to obtain urethane resin (b) -4. Table 1 shows the physical properties of the urethane resin (b) -4.

  This reaction mixture was poured and emulsified in 600 parts by mass of water under stirring at 10,000 rpm with a TK homomixer manufactured by Tokushu Kika Kogyo Co., Ltd. It diluted with water so that solid content ratio might be 20 mass%, and obtained resin fine particle dispersion 4 which is an emulsion of polyester containing urethane.

<Preparation of resin fine particle dispersion 5>
The following was charged into a reactor equipped with a stirrer and a thermometer while introducing nitrogen gas.
・ Polyester resin (number average molecular weight 2000) obtained from isophthalic acid and bisphenol A propylene oxide 2 mol adduct 30 parts by mass ・ Neopentyl glycol 14 parts by mass ・ 11 parts by mass of 2,2-dimethylolpropanoic acid ・ Isophorone diisocyanate 15 parts by mass / hexane diisocyanate 30 parts by mass / triethylamine (catalyst for urethanization reaction) 0.5 part by mass / acetone (solvent) from which water has been removed 100 parts by mass

  The mixture was heated to 50 ° C. and subjected to urethanization reaction for 15 hours to obtain a urethane prepolymer. To this prepolymer, 2.8 parts by mass of 6-aminohexanitrile was added and reacted. After cooling to 40 ° C., in order to neutralize the carboxyl group of 2,2-dimethylolpropanoic acid, 1.7 parts by mass were further added and mixed in addition to the amount of triethylamine already added, to obtain a reaction mixture. A part of the reaction mixture was dried to obtain urethane resin (b) -5. Table 1 shows the physical properties of the urethane resin (b) -5.

  This reaction mixture was poured and emulsified in 600 parts by mass of water under stirring at 10,000 rpm with a TK homomixer manufactured by Tokushu Kika Kogyo Co., Ltd. It diluted with water so that solid content ratio might be 20 mass%, and the resin fine particle dispersion 5 which is an emulsion of a polyester containing urethane was obtained.

<Preparation of resin fine particle dispersion 6>
The following was charged into a reactor equipped with a stirrer and a thermometer while introducing nitrogen gas.
-Polyester resin (number average molecular weight 2000) obtained from isophthalic acid and bisphenol A propylene oxide 2 mol adduct 29 parts by mass-Neopentyl glycol 12 parts by mass-2,2-dimethylolpropanoic acid 4 parts by mass-2, 2-methylolpropanoic acid methyl 10 parts by mass, isophorone diisocyanate 15 parts by mass, hexane diisocyanate 30 parts by mass, triethylamine (catalyst for urethanization reaction) 0.5 part by mass, acetone (solvent) from which water has been removed 100 parts by mass

  The mixture was heated to 50 ° C. and subjected to urethanization reaction for 15 hours to obtain a urethane prepolymer. After cooling to 40 ° C., in order to neutralize the carboxyl group of 2,2-dimethylolpropanoic acid, 4 parts by mass was added to and mixed with triethylamine, and a reaction mixture was obtained. A part of the reaction mixture was dried to obtain urethane resin (b) -6. Table 1 shows the physical properties of the urethane resin (b) -6.

  This reaction mixture was poured and emulsified in 600 parts by mass of water under stirring at 10,000 rpm with a TK homomixer manufactured by Tokushu Kika Kogyo Co., Ltd. It diluted with water so that solid content ratio might be 20 mass%, and obtained resin fine particle dispersion 6 which is an emulsion of polyester containing urethane.

<Preparation of resin fine particle dispersion 7>
The following was charged into a reactor equipped with a stirrer and a thermometer while introducing nitrogen gas.
・ Polyester resin (number average molecular weight 2000) 29 parts by mass obtained from isophthalic acid and bisphenol A propylene oxide 2-mole adduct 29 parts by mass neopentyl glycol 17 parts by mass 2,4-dimethylolpropanoic acid 4 parts by mass (2,3-dihydroxypropoxy) -1-propanesulfonic acid methyl 5 parts by mass, isophorone diisocyanate 15 parts by mass, hexane diisocyanate 30 parts by mass, triethylamine (catalyst for urethanization reaction) 0.5 part by mass, acetone from which water has been removed (Solvent) 100 parts by mass

  The mixture was heated to 50 ° C. and subjected to urethanization reaction for 15 hours to obtain a urethane prepolymer. To this prepolymer, 2.8 parts by mass of 6-aminohexanitrile was added and reacted. After cooling to 40 ° C., in order to neutralize the carboxyl group of 2,2-ethylolmethylolpropionic acid, 4 parts by mass was added to and mixed with triethylamine, and a reaction mixture was obtained. A part of the reaction mixture was dried to obtain urethane resin (b) -7. Table 1 shows the physical properties of the urethane resin (b) -7.

  This reaction mixture was poured and emulsified in 600 parts by mass of water under stirring at 10,000 rpm with a TK homomixer manufactured by Tokushu Kika Kogyo Co., Ltd. It diluted with water so that solid content ratio might be 20 mass%, and the resin fine particle dispersion 7 which is an emulsion of a polyester containing urethane was obtained.

<Preparation of resin fine particle dispersion 8>
The following was charged while introducing nitrogen into a reactor equipped with a stirrer and a thermometer.
・ Polyester resin (number average molecular weight 2000) obtained from isophthalic acid and bisphenol A propylene oxide 2 mol adduct 135 parts by mass ・ 2,2-dimethylol propanoic acid 3 parts by mass ・ hexane diisocyanate 8 parts by mass ・ acetone 250 parts by mass Part

  The mixture was heated to 50 ° C. and subjected to urethanization reaction for 15 hours to obtain a urethane prepolymer. To this prepolymer, 2.8 parts by mass of 6-aminohexanitrile was added and reacted. After cooling to 40 ° C., in order to neutralize the carboxyl group of 2,2-dimethylolpropanoic acid, 4 parts by mass was added to and mixed with triethylamine, and a reaction mixture was obtained. A part of the reaction mixture was dried to obtain urethane resin (b) -8. Table 1 shows the physical properties of the urethane resin (b) -8.

  This reaction mixture was poured and emulsified in 600 parts by mass of water under stirring at 10,000 rpm with a TK homomixer manufactured by Tokushu Kika Kogyo Co., Ltd. It diluted with water so that solid content ratio might be 20 mass%, and the resin fine particle dispersion 8 which is an emulsion of polyester containing urethane was obtained.

<Preparation of resin fine particle dispersion 9>
The following was charged while introducing nitrogen into a reactor equipped with a stirrer and a thermometer.
-Neopentyl glycol 31 parts by mass-2,2-dimethylolpropanoic acid 4 parts by mass-Isophorone diisocyanate 25 parts by mass-Hexane diisocyanate 40 parts by mass-Acetone 250 parts by mass

  The mixture was heated to 50 ° C. and subjected to urethanization reaction for 15 hours to obtain a urethane prepolymer. To this prepolymer, 2.8 parts by mass of 6-aminohexanitrile was added and reacted. After cooling to 40 ° C., in order to neutralize the carboxyl group of 2,2-dimethylolpropanoic acid, 4 parts by mass was added to and mixed with triethylamine, and a reaction mixture was obtained. A part of the reaction mixture was dried to obtain urethane resin (b) -9. Table 1 shows the physical properties of Urethane resin (b) -9.

  This reaction mixture was poured and emulsified in 600 parts by mass of water under stirring at 10,000 rpm with a TK homomixer manufactured by Tokushu Kika Kogyo Co., Ltd. It diluted with water so that solid content ratio might be 20 mass%, and the resin fine particle dispersion 9 which is an emulsion of polyester containing urethane was obtained.

<Preparation of resin fine particle dispersion 10>
The following was charged into a reactor equipped with a stirrer and a thermometer while introducing nitrogen gas.
・ Polyester resin (number average molecular weight 2000) obtained from isophthalic acid and 2 mol adduct of bisphenol A 30 parts by mass ・ 21 parts by mass of neopentyl glycol ・ 2 parts by mass of 2,2-dimethylolpropanoic acid ・ Isophorone diisocyanate 15 parts by mass / hexane diisocyanate 30 parts by mass / triethylamine (catalyst for urethanization reaction) 0.5 part by mass / acetone (solvent) from which water has been removed 100 parts by mass

  The mixture was heated to 50 ° C. and subjected to urethanization reaction for 15 hours to obtain a urethane prepolymer. To this prepolymer, 2.8 parts by mass of 6-aminohexanitrile was added and reacted. After cooling to 40 ° C., in order to neutralize the carboxyl group of 2,2-dimethylolpropanoic acid, 4 parts by mass was added to and mixed with triethylamine, and a reaction mixture was obtained. A part of the reaction mixture was dried to obtain urethane resin (b) -10. Table 1 shows the physical properties of Urethane resin (b) -10.

  This reaction mixture was poured and emulsified in 600 parts by mass of water under stirring at 10,000 rpm with a TK homomixer manufactured by Tokushu Kika Kogyo Co., Ltd. It diluted with water so that solid content ratio might be 20 mass%, and the resin fine particle dispersion 10 which is an emulsion of a polyester containing urethane was obtained.

<Preparation of resin fine particle dispersion 11>
The following was charged into a reactor equipped with a stirrer and a thermometer while introducing nitrogen gas.
・ Polyester resin (number average molecular weight 2000) 30 parts by mass obtained from isophthalic acid and bisphenol A propylene oxide 2 mol adduct ・ 12 parts by mass of neopentyl glycol ・ 13 parts by mass of 2,2-dimethylolpropanoic acid ・ Isophorone diisocyanate 15 parts by mass / hexane diisocyanate 30 parts by mass / triethylamine (catalyst for urethanization reaction) 0.5 part by mass / acetone (solvent) from which water has been removed 100 parts by mass

  The mixture was heated to 50 ° C. and subjected to urethanization reaction for 15 hours to obtain a urethane prepolymer. To this prepolymer, 2.8 parts by mass of 6-aminohexanitrile was added and reacted. After cooling to 40 ° C., in order to neutralize the carboxyl group of 2,2-dimethylolpropanoic acid, 1.7 parts by mass were further added and mixed in addition to the amount of triethylamine already added, to obtain a reaction mixture. A part of the reaction mixture was dried to obtain urethane resin (b) -11. Table 1 shows the physical properties of the urethane resin (b) -11.

  This reaction mixture was poured and emulsified in 600 parts by mass of water under stirring at 10,000 rpm with a TK homomixer manufactured by Tokushu Kika Kogyo Co., Ltd. It diluted with water so that solid content ratio might be 20 mass%, and the resin fine particle dispersion 11 which is an emulsion of a polyester containing urethane was obtained.

<Preparation of resin fine particle dispersion 12>
The following was charged into a reactor equipped with a stirrer and a thermometer while introducing nitrogen gas.
・ Polyester resin (number average molecular weight 2000) obtained from isophthalic acid and bisphenol A propylene oxide 2 mol adduct 32 parts by mass ・ Neopentyl glycol 19 parts by mass ・ 2,2-dimethylol propanoic acid 4 parts by mass ・ Isophorone diisocyanate 15 parts by mass / hexane diisocyanate 30 parts by mass / triethylamine (catalyst for urethanization reaction) 0.5 part by mass / acetone (solvent) from which water has been removed 100 parts by mass

  The mixture was heated to 50 ° C. and subjected to urethanization reaction for 15 hours to obtain a urethane prepolymer. After cooling to 40 ° C., in order to neutralize the carboxyl group of 2,2-dimethylolpropanoic acid, 4 parts by mass was added to and mixed with triethylamine, and a reaction mixture was obtained. A part of the reaction mixture was dried to obtain urethane resin (b) -12. Table 1 shows the physical properties of the urethane resin (b) -12.

  This reaction mixture was poured and emulsified in 600 parts by mass of water under stirring at 10,000 rpm with a TK homomixer manufactured by Tokushu Kika Kogyo Co., Ltd. It diluted with water so that solid content ratio might be 20 mass%, and the resin fine particle dispersion 12 which is an emulsion of polyester containing urethane was obtained.

<Preparation of resin fine particle dispersion 13>
The following was charged into a reactor equipped with a stirrer and a thermometer while introducing nitrogen gas.
・ Polyester resin (number average molecular weight 2000) obtained from isophthalic acid and bisphenol A propylene oxide 2 mol adduct 35 parts by mass ・ Neopentyl glycol 10 parts by mass ・ 2,2-dimethylolpropanoic acid 11 parts by mass ・ Isophorone diisocyanate 15 parts by mass / hexane diisocyanate 30 parts by mass / triethylamine (catalyst for urethanization reaction) 0.5 part by mass / acetone (solvent) from which water has been removed 100 parts by mass

  The mixture was heated to 50 ° C. and subjected to urethanization reaction for 15 hours to obtain a urethane prepolymer. To this prepolymer, 5.6 parts by mass of 6-aminohexanitrile was added and reacted. After cooling to 40 ° C., in order to neutralize the carboxyl group of 2,2-dimethylolpropanoic acid, 4 parts by mass was added to and mixed with triethylamine, and a reaction mixture was obtained. A part of the reaction mixture was dried to obtain urethane resin (b) -13. Table 1 shows the physical properties of Urethane resin (b) -13.

  This reaction mixture was poured and emulsified in 600 parts by mass of water under stirring at 10,000 rpm with a TK homomixer manufactured by Tokushu Kika Kogyo Co., Ltd. It diluted with water so that solid content ratio might be 20 mass%, and the resin fine particle dispersion 13 which is an emulsion of a polyester containing urethane was obtained.

<Preparation of polyester-1>
・ Polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane
30 parts by mass-polyoxyethylene (2.2) -2,2-bis (4-hydroxyphenyl) propane
33 parts by mass, 21 parts by weight of terephthalic acid, 1 part by weight of trimellitic anhydride, 3 parts by weight of fumaric acid, 12 parts by weight of dodecenyl succinic acid, 0.1 part by weight of dibutyltin oxide are placed in a 4-liter 4-neck flask made of glass. Then, a thermometer, a stirring bar, a condenser and a nitrogen introduction tube were attached and placed in a mantle heater. Under a nitrogen atmosphere, reaction was performed at 210 ° C. for 2.5 hours to obtain polyester-1. Polyester-1 had a Tg of 45 ° C., an acid value of 18 mgKOH / g, and a hydroxyl value of 26 mgKOH / g.

<Preparation of polyester-2>
・ Polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane
30 parts by mass-polyoxyethylene (2.2) -2,2-bis (4-hydroxyphenyl) propane
33 parts by mass, 21 parts by weight of terephthalic acid, 1 part by weight of trimellitic anhydride, 3 parts by weight of fumaric acid, 12 parts by weight of dodecenyl succinic acid, 0.1 part by weight of dibutyltin oxide are placed in a 4-liter 4-neck flask made of glass. Then, a thermometer, a stirring bar, a condenser and a nitrogen introduction tube were attached and placed in a mantle heater. Under a nitrogen atmosphere, the mixture was reacted at 200 ° C. for 3.5 hours to obtain polyester-2. Polyester-2 had a Tg of 36 ° C., an acid value of 21 mgKOH / g, and a hydroxyl value of 28 mgKOH / g.

<Preparation of polyester-3>
The following was put into a reaction vessel equipped with a cooling tube, a nitrogen introducing tube and a stirrer.
-1,2-propanediol 799 parts by mass-terephthalic acid dimethyl ester 815 parts by mass-1,5-pentanedioic acid 238 parts by mass-tetrabutoxy titanate (condensation catalyst) 3 parts by mass

  The reaction was carried out for 8 hours at 180 ° C. while distilling off the methanol produced under a nitrogen stream. Then, while gradually raising the temperature to 230 ° C., the reaction was carried out for 4 hours while distilling off the produced propylene glycol and water under a nitrogen stream, and the reaction was further carried out for 1 hour under a reduced pressure of 20 mmHg. Subsequently, it cooled to 180 degreeC, 173 mass parts of trimellitic anhydride was added, it was made to react at 220 degreeC normal pressure after reacting under normal pressure sealing for 2 hours, and it took out when the softening point became 170 degreeC. The resin taken out was cooled to room temperature and then pulverized and granulated to obtain polyester-3, which is a nonlinear polyester resin. Polyester-3 had a Tg of 58 ° C., an acid value of 4 mgKOH / g, and a hydroxyl value of 20 mgKOH / g.

<Preparation of polyester resin solution>
Polyester resin solutions 1 to 9 were prepared by putting ethyl acetate into a hermetic container with stirring blades and stirring the polyester at 1 to 3 at room temperature for 3 days. The resin content was adjusted to 50% by mass.

<Preparation of Wax Dispersion-1>
・ Carnauba wax (melting point: 81 ° C.) 20 parts by mass ・ Ethyl acetate: 80 parts by mass The above is put into a glass beaker with a stirring blade (IWAKI glass) and heated to 70 ° C. to convert the carnauba wax to ethyl acetate. Dissolved.

  Next, the system was gradually cooled while gently stirring at 50 rpm, and cooled to 25 ° C. over 3 hours to obtain a milky white liquid.

  This solution was put into a heat-resistant container together with 20 parts by mass of 1 mm glass beads, and dispersed for 3 hours with a paint shaker (manufactured by Toyo Seiki) to obtain wax dispersion-1.

  When the wax particle size in the wax dispersion-1 was measured with a Microtrac particle size distribution analyzer HRA (X-100) (manufactured by Nikkiso Co., Ltd.), the number average particle size was 0.15 μm. Table 3 shows the properties of the wax dispersion-1.

<Preparation of Colorant Dispersion-1>
Copper phthalocyanine pigment C.I. I. Pigment Blue 15: 3 100 parts by mass, 100 parts by weight of the above polyester-1 300 parts by weight of ethyl acetate, 400 parts by weight of glass beads (1 mm) 400 parts by weight The above materials are put into a heat-resistant glass container and dispersed for 5 hours in a paint shaker. And the glass beads were removed with a nylon mesh to obtain Colorant Dispersion-1.

<Preparation of Colorant Dispersions-2 and 3>
In the production of the colorant dispersion, the resin used was changed to polyester 2 or 3, and colorant dispersion-2 and colorant dispersion-3 were obtained.

(Example of carrier production)
4.0% by mass of a silane coupling agent (3- (2-aminoethylaminopropyl) trimethyl) with respect to a magnetite powder having a number average particle diameter of 0.25 μm and a hematite powder having a number average particle diameter of 0.60 μm. Methoxysilane) was added, and the mixture was stirred and mixed at a high speed at 100 ° C. or higher to make each fine particle lipophilic.

-Phenol 10 parts by mass-Formaldehyde solution (formaldehyde 40%, methanol 10%, water 50%)
6 parts by mass-lipophilic magnetite 63 parts by mass-lipophilic hematite 21 parts by mass The above materials, 5 parts by mass of 28% ammonia water, and 10 parts by mass of water are placed in a flask and stirred and mixed with 30 parts. The temperature was raised and maintained at 85 ° C. for 3 minutes, and the polymerization reaction was carried out for 3 hours to cure. Then, after cooling to 30 degreeC and adding water, the supernatant liquid was removed, the precipitate was washed with water, and then air-dried. Subsequently, this was dried under reduced pressure (5 mmHg or less) at 60 ° C. to obtain spherical magnetic resin particles in which a magnetic material was dispersed.

As the coating resin, a copolymer of methyl methacrylate and methyl methacrylate having a perfluoroalkyl group (m = 7) (copolymerization ratio 8: 1 weight average molecular weight 45,000) was used. To 100 parts by weight of the coating resin, 10 parts by weight of melamine particles having a particle size of 290 nm, 6 parts by weight of carbon particles having a specific resistance of 1 × 10 ⁻² Ω · cm and a particle size of 30 nm are added, and dispersed for 30 minutes with an ultrasonic disperser. I let you. Further, a mixed solvent coating solution of methyl ethyl ketone and toluene was prepared so that the coating resin content was 2.5 parts by mass with respect to the carrier core (solution concentration: 10% by mass).

The coating solution was applied to the surface of the magnetic resin particles by volatilizing the solvent at 70 ° C. while continuously applying shear stress. The resin-coated magnetic carrier particles were heat-treated with stirring at 100 ° C. for 2 hours, cooled and pulverized, and then classified by a 200-mesh sieve to obtain a number average particle diameter of 33 μm, a true specific gravity of 3.53 g / cm ³ , A carrier having an apparent specific gravity of 1.84 g / cm ³ and a magnetization strength of 42 Am ² / kg was obtained.

<Example 1>
(Preparation of Liquid Toner Composition 1)
・ Wax dispersion-1 50 parts by mass (carnauba wax solid content: 20%)
Colorant dispersion-1 25 parts by mass (pigment solid content: 20%, resin solid content: 20%)
-Polyester resin solution-1 160 parts by mass (resin solid content: 50%)
-Triethylamine 0.5 mass part-Ethyl acetate 14.5 mass part The said solution was thrown in in a container, and it stirred and disperse | distributed for 10 minutes at 1500 rpm with the homodisper (made by Tokushu Kika Kogyo Co., Ltd.). Furthermore, the oil phase 1 was prepared by dispersing the above solution at room temperature with an ultrasonic disperser for 30 minutes.

(Preparation of aqueous phase)
The following was put into a container, and the mixture was stirred for 1 minute at 5000 rpm with a TK homomixer (manufactured by Tokushu Kika Co., Ltd.) to prepare an aqueous phase.
-215.5 parts by mass of ion-exchanged water-35.0 parts by mass of resin fine particle dispersion-1 (7.0 parts by mass of resin fine particles with respect to 100 parts by mass of toner base particles)
-50% aqueous solution of sodium dodecyl diphenyl ether disulfonate (Eleminol MON-7, manufactured by Sanyo Chemical Industries) 25.0 parts by mass-30.0 parts by mass of ethyl acetate

(Emulsification and solvent removal process)
The oil phase was charged into the aqueous phase, and stirring was continued for 1 minute under the condition of a rotational speed of 8000 rpm with a TK homomixer to suspend the oil phase 1.

  Next, a stirring blade was set in the container, the system was heated to 50 ° C. while stirring at 200 rpm, and the solvent was removed over 5 hours in a state where the pressure was reduced to 500 mmHg to obtain an aqueous dispersion of toner particles. .

(Washing or drying process)
Next, the aqueous dispersion of toner particles was filtered and reslurried to 500 parts by mass of ion-exchanged water. Then, while stirring the system, hydrochloric acid was added until the system reached pH 4 and stirred for 5 minutes. The slurry was filtered again, and the operation of adding 200 parts by mass of ion-exchanged water and stirring for 5 minutes was repeated three times to remove triethylamine remaining in the system and obtain a filter cake of toner particles.

  The above filter cake was dried with a hot air dryer at 45 ° C. for 3 days, and sieved with an opening of 75 μm to obtain toner particles 1.

(Preparation of toner and two-component developer)
Next, anatase-type titanium oxide fine powder (BET specific surface area 80 m ² / g, number average particle diameter (D1): 15 nm, treated with 12% by mass of isobutyltrimethoxysilane) with respect to 100 parts by mass of the toner particles 1. First, 9 parts by mass are externally added by a Henschel mixer, and further, oil-treated silica fine particles (BET specific surface area 95 m ² / g, silicone oil 15% by mass treatment) 1.2 parts by mass, the above-mentioned inorganic fine particles (sol-gel silica fine particles: BET specific surface area) 24 m ² / g, number average particle diameter (D1): 110 nm) Toner 1 was obtained by mixing 1.5 parts by mass with a Henschel mixer (manufactured by Mitsui Miike Chemical Co., Ltd.) FM-10B.

  In the present invention, a two-component developer 1 prepared by mixing 8 parts by mass of the toner 1 and 92 parts by mass of the carrier was prepared.

  Table 3 shows the component composition ratio of the toner, and Tables 4 and 5 show the characteristics of the toner.

[Image evaluation]
A method for evaluating the obtained toner will be described. For image evaluation, a commercially available Canon color copier (trade name: CLC5000) was used.

<Evaluation of low-temperature fixability>
For the evaluation, the above-described two-component developer 1 and a color laser copying machine CLC5000 (manufactured by Canon Inc.) were used. The development contrast of the copying machine is adjusted so that the amount of toner on the paper is 1.2 mg / cm ² , and a “solid” unfixed image having a front margin of 5 mm, a width of 100 mm, and a length of 280 mm is obtained in the single color mode. It was created in a normal temperature and humidity environment (23 ° C./60% RH). As the paper, thick paper A4 paper ("Prober bond paper": 105 g / m ² , manufactured by Fox River) was used.

  Next, the fixing device of LBP5900 (manufactured by Canon Inc.) was modified so that the fixing temperature can be manually set. Set the fixing member to be 245 mm / s, and use the modified fixing device with NN (23 ° C./60%) in a normal temperature and normal humidity environment and NL (23 ° C./5%) in a normal temperature and low humidity environment, While increasing the fixing temperature by 10 ° C. in the range of 80 ° C. to 200 ° C., a fixed image was obtained at each temperature of the “solid” unfixed image.

  Cover the image area of the obtained fixed image with a soft thin paper (for example, trade name “Dasper”, manufactured by Ozu Sangyo Co., Ltd.), and apply the load of 4.9 KPa on the thin paper for 5 reciprocations. Rubbed. The image density before and after rubbing was measured, respectively, and the reduction rate ΔD (%) of the image density was calculated by the following formula. The temperature at which ΔD (%) was less than 10% was defined as the fixing start temperature, and the low temperature fixability was evaluated according to the following evaluation criteria.

The image density was measured with a color reflection densitometer (Color reflection densitometer X-Rite 404A: manufacturer X-Rite).
(Expression): ΔD (%) = (Image density before rubbing−Image density after rubbing) / Image density before rubbing × 100

<Evaluation of electrification (tribo)>
Preparation of sample Toner and predetermined carrier (spherical carrier N-01 with a surface treatment of ferrite imager standard carrier of Japan Imaging Society) 1.0 g and 19.0 g, respectively, are put in a plastic bottle with a lid and left in the environment for 1 day. The environment is N / L (temperature 23.0 ° C./humidity 5%), H / H (temperature 30.0 ° C./humidity 80%), and severe (temperature 40.0 ° C./humidity 95%).

  The chargeability (tribo) was evaluated using the triboelectric charge amount of the toner.

  A method for measuring the triboelectric charge amount of the toner will be described below.

First, a predetermined carrier (spherical carrier N-01 with a surface treatment of the Japan Imaging Society standard carrier ferrite core) and toner are put in a plastic bottle with a lid, and a shaker (YS-LD, manufactured by Yayoi Co., Ltd.) Shake for 1 minute at a speed of 4 reciprocations per second to charge the developer composed of toner and carrier. Next, the triboelectric charge amount is measured in the apparatus for measuring the triboelectric charge amount shown in FIG. In FIG. 3, about 0.5 to 1.5 g of the developer described above is placed in a metal measuring container 2 having a 500 mesh screen 3 at the bottom, and a metal lid 4 is formed. The total mass of the measurement container 2 at this time is weighed and is defined as W1 (g). Next, in the suction machine 1 (at least the part in contact with the measurement container 2) is suctioned from the suction port 7 and the air volume control valve 6 is adjusted so that the pressure of the vacuum gauge 5 is 250 mmAq. In this state, suction is performed for 2 minutes to remove the toner by suction. The potential of the electrometer 9 at this time is set to V (volt). Here, 8 is a capacitor, and the capacity is C (mF). Moreover, the mass of the whole measurement container after suction is weighed and is defined as W2 (g). The triboelectric charge amount (mC / kg) of this sample is calculated as follows.
Sample triboelectric charge (mC / kg) = C × V / (W1-W2)

<Heat resistant storage stability>
About 10 g of toner was put in a 100 ml polycup and allowed to stand at 50 ° C. for 3 days, and then visually evaluated.
(Evaluation criteria)
A: Aggregates are not seen.
B: Although aggregates are seen, they break apart easily.
C: Aggregates can be grasped and do not collapse easily.

<Severe preservation>
About 10 g of toner is put in a 100 ml polycup, and further sealed in a bag Unipack J-4 (Production Japan) with a chuck. The sample is placed in an environment of 40 ° C. and 95% relative humidity, and after adjusting the temperature to the environment for 1 hour, the sample is taken out from the bag with a chuck and left for 3 days. Remove from the environment of temperature 40 ° C. and relative humidity 95% and leave in a normal environment (temperature 23 ° C., relative humidity 60%) for 1 day. The left toner was visually evaluated.
(Evaluation criteria)
A: Aggregates are not seen.
B: Although aggregates are seen, they break apart easily.
C: Aggregates can be grasped and do not collapse easily.

[Evaluation of actual machine]
A method for evaluating the obtained toner will be described. For image evaluation, a commercially available Canon color copier (trade name: CLC5000) was used.

The test machine for the above image evaluation is left overnight in an environment of 23 ° C and 5% RH, and the machine is temporarily stopped between jobs with a horizontal line pattern of 3% print rate per job. Then, in the mode set so that the next job starts, an image endurance test of 10,000 sheets was performed using A4 plain paper (75 g / m ² ).

<Transfer efficiency>
The test machine for image evaluation was evaluated using A4 plain paper (75 g / m ² ) under the conditions of a temperature of 23 ° C. and a relative humidity of 60%. The potential contrast of the photoconductor is adjusted so that the applied amount on the photoconductor of the evaluation machine is 0.60 mg / cm ² , and the image density transferred onto the transfer paper and the residual image density on the photoconductor are expressed as X -Measured using a reflection densitometer (500 Series Spectrodensitometer) manufactured by Rite. From the image density, the applied amount was converted to obtain the transfer efficiency onto the transfer paper.
(Evaluation criteria)
A: The toner transfer efficiency is 95% or more.
B: The transfer efficiency of the toner is 93% or more.
C: The toner transfer efficiency is 90% or more.
D: The transfer efficiency of the toner is less than 90%.

<Comparative Example 1>
A toner 14 was obtained by the same production method as in Example 1 except that an aqueous phase produced under the following conditions was used. Table 3 shows the component composition ratio of the toner, and Tables 4 and 5 show the characteristics of the toner.

(Preparation of aqueous phase)
The following was put into a container, and the mixture was stirred for 1 minute at 5000 rpm with a TK homomixer (manufactured by Tokushu Kika Co., Ltd.) to prepare an aqueous phase.
-Ion exchange water 215.5 parts by mass-Resin fine particle dispersion-8 35.0 parts by mass (7.0 parts by mass of resin fine particles with respect to 100 parts by mass of toner base particles)
-50% aqueous solution of sodium dodecyl diphenyl ether disulfonate (Eleminol MON-7, manufactured by Sanyo Chemical Industries) 25.0 parts by mass-30.0 parts by mass of ethyl acetate

<Comparative example 2>
A toner 15 was obtained by the same production method as in Example 1 except that an aqueous phase produced under the following conditions was used. Table 3 shows the component composition ratio of the toner, and Tables 4 and 5 show the characteristics of the toner.

(Preparation of aqueous phase)
The following was put into a container, and the mixture was stirred for 1 minute at 5000 rpm with a TK homomixer (manufactured by Tokushu Kika Co., Ltd.) to prepare an aqueous phase.
・ Ion-exchanged water 215.5 parts by mass ・ Resin fine particle dispersion-9 35.0 parts by mass (7.0 parts by mass of resin fine particles with respect to 100 parts by mass of toner base particles)
-50% aqueous solution of sodium dodecyl diphenyl ether disulfonate (Eleminol MON-7, manufactured by Sanyo Chemical Industries) 25.0 parts by mass-30.0 parts by mass of ethyl acetate

<Comparative Example 3>
A toner 16 was obtained by the same production method as in Example 1 except that an aqueous phase produced under the following conditions was used. Table 3 shows the component composition ratio of the toner, and Tables 4 and 5 show the characteristics of the toner.

(Preparation of aqueous phase)
The following was put into a container, and the mixture was stirred for 1 minute at 5000 rpm with a TK homomixer (manufactured by Tokushu Kika Co., Ltd.) to prepare an aqueous phase.
-215.5 parts by mass of ion-exchanged water-35.0 parts by mass of resin fine particle dispersion-10 (7.0 parts by mass of resin fine particles with respect to 100 parts by mass of toner base particles)
-50% aqueous solution of sodium dodecyl diphenyl ether disulfonate (Eleminol MON-7, manufactured by Sanyo Chemical Industries) 25.0 parts by mass-30.0 parts by mass of ethyl acetate

<Comparative example 4>
A toner 17 was obtained by the same production method as in Example 1 except that an aqueous phase produced under the following conditions was used. Table 3 shows the component composition ratio of the toner, and Tables 4 and 5 show the characteristics of the toner.

(Preparation of aqueous phase)
The following was put into a container, and the mixture was stirred for 1 minute at 5000 rpm with a TK homomixer (manufactured by Tokushu Kika Co., Ltd.) to prepare an aqueous phase.
-215.5 parts by mass of ion-exchanged water-35.0 parts by mass of resin fine particle dispersion-11 (7.0 parts by mass of resin fine particles with respect to 100 parts by mass of toner base particles)
-50% aqueous solution of sodium dodecyl diphenyl ether disulfonate (Eleminol MON-7, manufactured by Sanyo Chemical Industries) 25.0 parts by mass-30.0 parts by mass of ethyl acetate

<Comparative Example 5>
A toner 18 was obtained by the same production method as in Example 1 except that an aqueous phase produced under the following conditions was used. Table 3 shows the component composition ratio of the toner, and Tables 4 and 5 show the characteristics of the toner.

(Preparation of aqueous phase)
The following was put into a container, and the mixture was stirred for 1 minute at 5000 rpm with a TK homomixer (manufactured by Tokushu Kika Co., Ltd.) to prepare an aqueous phase.
-215.5 parts by mass of ion-exchanged water-35.0 parts by mass of resin fine particle dispersion-12 (7.0 parts by mass of resin fine particles with respect to 100 parts by mass of toner base particles)
-50% aqueous solution of sodium dodecyl diphenyl ether disulfonate (Eleminol MON-7, manufactured by Sanyo Chemical Industries) 25.0 parts by mass-30.0 parts by mass of ethyl acetate

<Comparative Example 6>
A toner 19 was obtained by the same production method as in Example 1 except that an aqueous phase produced under the following conditions was used. Table 3 shows the component composition ratio of the toner, and Tables 4 and 5 show the characteristics of the toner.

(Preparation of aqueous phase)
The following was put into a container, and the mixture was stirred for 1 minute at 5000 rpm with a TK homomixer (manufactured by Tokushu Kika Co., Ltd.) to prepare an aqueous phase.
・ Ion-exchanged water 215.5 parts by mass ・ Resin fine particle dispersion-13 35.0 parts by mass (7.0 parts by mass of resin fine particles with respect to 100 parts by mass of toner base particles)
-50% aqueous solution of sodium dodecyl diphenyl ether disulfonate (Eleminol MON-7, manufactured by Sanyo Chemical Industries) 25.0 parts by mass-30.0 parts by mass of ethyl acetate

<Example 2>
An aqueous phase was prepared using the resin fine particle dispersion-2 instead of the resin fine particle dispersion-1 used in Example 1. Except for this, toner 2 was obtained by the same production method as in Example 1. Table 3 shows the component composition ratio of the toner, and Tables 4 and 5 show the characteristics of the toner.

<Example 3>
An aqueous phase was prepared using resin fine particle dispersion-3 instead of resin fine particle dispersion-1 used in Example 1. Except for this, toner 3 was obtained by the same production method as in Example 1. Table 3 shows the component composition ratio of the toner, and Tables 4 and 5 show the characteristics of the toner.

<Example 4>
An aqueous phase was prepared using resin fine particle dispersion-4 instead of resin fine particle dispersion-1 used in Example 1. Except for this, toner 4 was obtained by the same production method as in Example 1. Table 3 shows the component composition ratio of the toner, and Tables 4 and 5 show the characteristics of the toner.

<Example 5>
An aqueous phase was prepared using resin fine particle dispersion-5 instead of resin fine particle dispersion-1 used in Example 1. Except for this, toner 5 was obtained by the same production method as in Example 1. Table 3 shows the component composition ratio of the toner, and Tables 4 and 5 show the characteristics of the toner.

<Example 6>
An aqueous phase was prepared using resin fine particle dispersion-6 instead of resin fine particle dispersion-1 used in Example 1. Except for this, toner 6 was obtained by the same production method as in Example 1. Table 3 shows the component composition ratio of the toner, and Tables 4 and 5 show the characteristics of the toner.

<Example 7>
An aqueous phase was prepared using resin fine particle dispersion-7 instead of resin fine particle dispersion-1 used in Example 1. Except for this, toner 7 was obtained by the same production method as in Example 1. Table 3 shows the component composition ratio of the toner, and Tables 4 and 5 show the characteristics of the toner.

<Example 8>
Toner 8 was obtained by the same production method as in Example 1 except that the following oil phase was used instead of the oil phase used in Example 1. Table 3 shows the component composition ratio of the toner, and Tables 4 and 5 show the characteristics of the toner.

(Preparation of Liquid Toner Composition 1)
・ Wax dispersion-1 50 parts by mass (carnauba wax solid content: 20%)
Colorant dispersion-1 25 parts by mass (pigment solid content: 20%, resin solid content: 20%)
-Polyester resin solution-1 160 parts by mass (resin solid content: 50%)
-Triethylamine 0.9 mass part-Ethyl acetate 14.4 mass part The said solution was thrown in in a container, and it stirred and disperse | distributed for 10 minutes at 1500 rpm with the homodisper (made by Tokushu Kika Kogyo Co., Ltd.). Further, the above solution was dispersed at room temperature for 30 minutes with an ultrasonic disperser.

<Example 9>
Toner 9 was obtained by the same production method as in Example 1 except that the following oil phase was used instead of the oil phase used in Example 1. Table 3 shows the component composition ratio of the toner, and Tables 4 and 5 show the characteristics of the toner.

・ Wax dispersion-1 50 parts by mass (carnauba wax solid content: 20%)
Colorant dispersion-1 25 parts by mass (pigment solid content: 20%, resin solid content: 20%)
-Polyester resin solution-1 160 parts by mass (resin solid content: 50%)
-Triethylamine 0.2 mass part-Ethyl acetate 14.4 mass part The said solution was thrown in in a container, and it stirred and disperse | distributed for 10 minutes at 1500 rpm with the homodisper (made by Tokushu Kika Kogyo Co., Ltd.). Further, the above solution was dispersed at room temperature for 30 minutes with an ultrasonic disperser.

<Example 10>
A toner 10 was obtained by the same production method as in Example 1 except that the oil phase shown below was used instead of the oil phase used in Example 1. Table 3 shows the component composition ratio of the toner, and Tables 4 and 5 show the characteristics of the toner.

・ Wax dispersion-1 50 parts by mass (carnauba wax solid content: 20%)
Colorant dispersion-2 25 parts by mass (pigment solid content: 20%, resin solid content: 20%)
Polyester resin solution-2 160 parts by mass (resin solid content: 50%)
-Triethylamine 0.5 mass part-Ethyl acetate 14.4 mass part The said solution was thrown in in a container, and it stirred and disperse | distributed for 10 minutes at 1500 rpm with the homodisper (made by Tokushu Kika Kogyo Co., Ltd.). Further, the above solution was dispersed at room temperature for 30 minutes with an ultrasonic disperser.

<Example 11>
Toner 11 was obtained by the same production method as in Example 1 except that the oil phase shown below was used in place of the oil phase used in Example 1. Table 3 shows the component composition ratio of the toner, and Tables 4 and 5 show the characteristics of the toner.

・ Wax dispersion-1 50 parts by mass (carnauba wax solid content: 20%)
Colorant dispersion-3 25 parts by mass (pigment solid content: 20%, resin solid content: 20%)
-Polyester resin solution-3 160 parts by mass (resin solid content: 50%)
-Triethylamine 0.5 mass part-Ethyl acetate 14.4 mass part The said solution was thrown in in a container, and it stirred and disperse | distributed for 10 minutes at 1500 rpm with the homodisper (made by Tokushu Kika Kogyo Co., Ltd.). Further, the above solution was dispersed at room temperature for 30 minutes with an ultrasonic disperser.

<Example 12>
A toner 12 was obtained by the same production method as in Example 1 except that an aqueous phase produced under the following conditions was used. Table 3 shows the component composition ratio of the toner, and Tables 4 and 5 show the characteristics of the toner.

(Preparation of aqueous phase)
The following was put into a container, and the mixture was stirred for 1 minute at 5000 rpm with a TK homomixer (manufactured by Tokushu Kika Co., Ltd.) to prepare an aqueous phase.
-Ion exchange water 235.5 parts by mass-Resin fine particle dispersion-1 15.0 parts by mass (7.0 parts by mass of resin fine particles with respect to 100 parts by mass of toner base particles)
-50% aqueous solution of sodium dodecyl diphenyl ether disulfonate (Eleminol MON-7, manufactured by Sanyo Chemical Industries) 25.0 parts by mass-30.0 parts by mass of ethyl acetate

<Example 13>
A toner 13 was obtained by the same production method as in Example 1 except that an aqueous phase produced under the following conditions was used. Table 3 shows the component composition ratio of the toner, and Tables 4 and 5 show the characteristics of the toner.

(Preparation of aqueous phase)
The following was put into a container, and the mixture was stirred for 1 minute at 5000 rpm with a TK homomixer (manufactured by Tokushu Kika Co., Ltd.) to prepare an aqueous phase.
-200.5 parts by mass of ion-exchanged water-50.0 parts by mass of resin fine particle dispersion-1 (7.0 parts by mass of resin fine particles with respect to 100 parts by mass of toner base particles)
-50% aqueous solution of sodium dodecyl diphenyl ether disulfonate (Eleminol MON-7, manufactured by Sanyo Chemical Industries) 25.0 parts by mass-30.0 parts by mass of ethyl acetate

1 Suction machine (at least the part in contact with the measurement container 2 is an insulator), 2 metal measurement container, 3 500 mesh screen, 4 metal lid, 5 vacuum gauge, 6 air volume control valve, 7 suction port, 8 condenser , 9 Electrometer, 11 Lower electrode, 12 Upper electrode, 13 Insulator, 14 Ammeter, 15 Voltmeter, 16 Constant voltage device, 17 Carrier, 18 Guide ring, d Sample thickness, E Resistance measurement cell

Claims (7)

A toner having toner particles containing at least a resin (a) based on polyester, a colorant and a wax,
The amount of surface nitrogen by X-ray photoelectron spectroscopy (ESCA) of the toner particle surface is 1.0 atomic% or more and 10.0 atomic% or less,
The When the toner particles have an acid value of the obtained toner particles was measured by dispersing in water and Ut (mgKOH / g), the specific surface area St of the toner particles is 0.60 m ² / g or more 2.00 m ² The acid value per surface area of the toner particles (Ut / St) satisfies 0.2 mgKOH / m ² or more and 1.5 mgKOH / m ² or less,
A toner having a work function W0 of 5.65 eV or more and 6.00 eV or less when measured after the toner particles are left for 3 days in an environment of 23.0 ° C. and 25% RH.   In the measurement of the toner with a differential scanning calorimeter (DSC), the glass transition temperature measured at a heating rate of 0.5 ° C./min was Tg (0.5) (° C.), and the heating rate was 4.0. When the measured glass transition temperature at ° C./min is Tg (4.0) (° C.), the Tg (0.5) is 35.0 ° C. or more and 60.0 ° C. or less, and the Tg (4.0) The difference (Tg (4.0) -Tg (0.5)) (° C.) between the Tg and the Tg (0.5) is 2.0 ° C. or higher and 10.0 ° C. or lower. The toner described in 1.   The toner according to claim 1, wherein the toner has a water absorption amount of 0.5% by mass or more and 2.0% by mass or less in a temperature of 40 ° C. and a humidity of 95% RH.   Capsule type toner particles having a surface layer (B) containing resin (b) as a main component on the surface of toner base particles (A) containing at least a resin (a) containing polyester as a main component, a colorant and a wax. The toner according to claim 1, wherein the toner has a toner.   The toner according to claim 1, wherein a work function of the resin (b) is 5.65 eV or more and 6.00 eV or less.   The resin (b) is a urethane resin, the water absorption of the urethane resin (b) is 2.5% by mass or less, and the urethane obtained by measuring the urethane resin (b) dispersed in water. The Ub is 10.0 to 50.0 mgKOH / g, where the acid value of the resin (b) is Ub (mgKOH / g). toner.   The toner according to claim 1, wherein the resin (b) is a urethane resin and has a nitrile (cyano) group.

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