JP4999525B2 - toner - Google Patents

Description

  The present invention relates to a toner used in a recording method using an electrophotographic method, an electrostatic recording method, a toner jet method recording method, and the like, and a manufacturing method thereof. 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. , Relating to toner used in fax machines.

  In recent years, energy saving has been considered as a major technical issue in electrophotographic apparatuses, and the amount of heat applied to the fixing apparatus has been significantly reduced. The need for “fixability” is increasing.

  Conventionally, in order to enable fixing at a lower temperature, the technique of making the binder resin sharper melt is known as one of the 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 that can use a sharp melt polyester resin, a spherical toner is formed by dissolving a resin component in an organic solvent immiscible with water and dispersing the solution in an aqueous phase to form oil droplets. A “dissolution suspension” method for producing particles has been proposed (for example, 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.

  For example, in Patent Document 2, 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 layer, and a droplet is prepared in water. A method for preparing capsule toner particles having polyurethane or polyurea as the outermost shell by interfacial polymerization of a group-containing compound has been proposed.

  In Patent Documents 3 and 4, toner base particles are prepared by a dissolution suspension method in the presence of resin fine particles of vinyl resin, polyurethane resin, epoxy resin, polyester resin, or a combination thereof. A technique for adjusting toner particles coated on the toner surface has been proposed.

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 polyurethane resin (a).
There has been proposed a core-shell type toner particle composed of one or more film-like shell layers (P) made of a resin and one core layer (Q) made of a resin (b).
This capsule-type toner particle has a configuration in which the core portion has a low viscosity and the inferior heat-resistant storage property is compensated by the heat-resistant storage property of the shell portion. 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 low-temperature fixability tends to be hindered.

  However, even when the shell part is not sufficiently formed even when the shell part is made up of the heat softness and inferior heat-resistant storage property of the core part as the capsule toner, the characteristics of the core part are insufficient. As a result, the heat-resistant storage stability deteriorates. Further, even when a sufficient shell is formed, the heat-resistant storage stability is deteriorated when the shell is broken due to thermal and mechanical loads. For this reason, it was difficult to simply soften the core portion even though there was shell formation.

On the other hand, a technique for improving the fixing property by incorporating a crystalline polyester in the core has been introduced.
For example, Patent Document 7 discloses a technique using a dispersion liquid in which crystalline polyester is dispersed in an organic solvent, and a method for producing toner using the dispersion liquid.
However, even when the crystalline polyester is dispersed in the toner by such a method, the effect of the sharp melt property of the crystalline polyester cannot be sufficiently exhibited, and the low-temperature fixability has not been greatly improved.
Patent Document 8 discloses a technique for improving storage stability and offset resistance by causing resin fine particles containing a crystalline polyester resin to be present on the toner surface. In this case, although the meltability of the surface layer portion at a low temperature can be improved, the improvement of the binder resin is insufficient, and the problem of the core / shell structure has not been solved.
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-A-2005-015589 Japanese Patent Laying-Open No. 2005-024784

  The present invention has been made in view of the above problems, and an object of the present invention is to provide a toner having high offset resistance and excellent chargeability while being a capsule toner excellent in low-temperature fixability. Another object of the present invention is to provide a spherical toner having a small particle size and a sharp particle size distribution.

As a result of intensive studies to solve the above problems, the present inventors,
Capsule type having a surface layer (B) containing at least resin (b) on the surface of toner base particles (A) containing at least binder resin (a), crystalline polyester (a2), colorant and wax a toner having a toner particle, the binder resin (a) is a resin mainly composed of polyester resin (a1), the crystalline polyester (a2) is in the toner base particles (a), 3 are contained mass% to 30 mass%, the amount of the surface layer (B), said the toner base particles (a), and 15.0 wt% or less than 1.0 wt%,
In the measurement of the viscoelasticity of the toner, the common logarithm Log (G ′ (T) / (dN / m ² )) of the storage elastic modulus G ′ (T) (dN / m ² ) with respect to the temperature (T) is expressed as F (T). If the, at 0.99 ° C. or less of the range of temperature of 50 ° C., present in a range rate of change dF (T) / dT temperature _{T 0} of the temperature 60 ° C. or higher 100 ° C. below the minimum value of the relative temperature, said minimum value but rather smaller than -0.20 (℃ ^-1),
The toner particles include at least the binder resin (a), the colorant, and the wax in an aqueous medium in which the fine particles mainly containing the resin (b) and the crystalline polyester (a2) are dispersed. These problems are solved by a toner obtained by dispersing a solution or dispersion obtained by dissolving or dispersing in an organic medium, removing the solvent from the obtained dispersion and drying. The present invention was discovered.

In the present invention, the toner has a capsule-type structure. In the present invention, the toner base particles (A) are provided with functions such as low viscosity, releasability, and coloring, and the surface layer (B) is provided with functions such as heat resistance and chargeability related to developability. Therefore, it is possible to provide a toner that can be used stably. Further, by suppressing the influence of the low-viscosity internal shell, it is possible to provide a toner that can satisfy the characteristics required for electrophotographic characteristics such as charging property, developing property, transfer property, and cleaning property. Further, in the measurement of the viscoelasticity of the toner, there exists a temperature T ₀ that takes a minimum value of the rate of change dF (T) / dT with respect to the temperature in the range of 60 to 100 ° C., and the storage elastic modulus (G ′) decreases rapidly. This makes it possible to provide a toner that can satisfy sharp melt at low temperatures while maintaining heat-resistant storage stability.

The present invention has a capsule structure having a surface layer (B) on the surface of toner base particles (A) containing a binder resin (a), a colorant and a wax. When the capsule structure is not employed, for example, in the case of a wax-containing toner, the toner is likely to aggregate due to the precipitation of the wax on the toner surface, which may cause a stirring failure in the developing region and clogging with a cleaner. In addition, since the amount of charge varies depending on each pigment due to the pigment appearing on the toner surface, the behavior of each color is likely to change when used as a full-color color toner. In addition, when carbon black was used as the pigment 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.

  In order to eliminate these influences, the surface layer (B) is 1.0% by mass or more and 15.0% by mass or less with respect to the toner base particles (A). When it is less than 1.0% by mass, the encapsulation is insufficient and the above-mentioned problems are likely to occur. On the other hand, when the content is larger than 15.0% by mass, the properties of the surface layer (B) are strongly reflected even at the time of fixing, and it becomes difficult to exhibit the characteristics of the core that is a sharp melt. Therefore, Preferably it is 2.0 mass% or more and 12.0 mass% or less, More preferably, it is 2.5 mass% or more and 10.0 mass% or less.

However, the capsule-type toner has improved heat-resistant storage stability, but the toner base particles have a surface layer having a relatively high viscosity, so that fixing inhibition tends to occur and it is difficult to obtain sufficient low-temperature fixability. Therefore, the surface layer (B) needs to have a low viscosity as much as possible while satisfying the heat resistant storage stability. On the other hand, however, the toner base particles (A) cannot be set to have a low viscosity at low temperatures.

  On the other hand, as described above, a method has also been proposed in which a crystalline polyester is contained in a toner to achieve sharp melt properties. However, when the crystalline system of the crystalline polyester in the toner collapses, the original sharp melt characteristics cannot be reflected. Even when the crystal system could be maintained, the properties at low temperature could not be improved if there was no compatibility with the binder resin (a).

The present inventors have improved these points and arrived at the present invention. That is, (1) finely disperse the crystalline polyester in the toner, (2) maintain the crystal system of the finely dispersed crystalline polyester, and (3) the crystalline polyester melted at the time of fixing is the binder resin (a It was found necessary to reduce the softening temperature. As a result, in measuring the viscoelasticity of the toner, the common logarithm Log (G ′ (T) / dN / m ² ) of the storage elastic modulus G ′ (T) (dN / m ² ) with respect to the temperature (T) is expressed as F ( T), it is necessary to have a point where F (T) changes greatly at an arbitrary temperature, that is, the rate of change dF (T) / dT with respect to temperature must have a minimum value at an arbitrary temperature. I understood. By achieving the above items, the effect of the crystalline polyester can be sufficiently exhibited.

In the present invention, in the measurement of the viscoelasticity of the toner, when the common logarithm Log (G ′ (T)) of the storage elastic modulus G ′ (T) (dN / m ² ) with respect to the temperature (T) is F (T), In the temperature range of 50 ° C. or more and 150 ° C. or less, the temperature T ₀ that takes the minimum value of the rate of change dF (T) / dT with respect to the temperature exists in the temperature range of 60 ° C. or more and 100 ° C. or less. When T ₀ is smaller than 60 ° C., if the low viscosity surface layer (B) is used, the heat resistant storage stability becomes difficult to satisfy, and if T ₀ exceeds 100 ° C., the effect of low temperature fixability cannot be exhibited. Preferably, it is the range of 60 degreeC or more and 80 degrees C or less.

Furthermore, in the present invention, in order to realize the sharp melt property, the minimum value of the change rate dF (T) / dT is smaller than −0.15 (° C. ⁻¹ ), and preferably the minimum value is −0.20. Smaller than (° C. ⁻¹ ).
Further, from the dissolution properties of the crystalline polyester, the minimum value is -0.70 (° C. ^-1), even using a larger than -0.50 (℃ ^-1).

Further, the storage elastic modulus ratio G ′ (T ₀ −2.5) / G (T ₀ +2.5) at 2.5 ° C. before and after the minimum value is larger than 3.0 and smaller than 50.0. It is preferable. More preferably, it is larger than 5.0 and smaller than 30.0. When this ratio is small, the viscosity cannot be lowered sufficiently, and it becomes difficult to obtain sufficient fixability. When this ratio is large, elasticity at high temperatures becomes insufficient, and inconveniences such as hot offset are likely to occur.

Further, the toner has a storage modulus G 150 ℃ '(150) (dN / m 2), greater than ^{1 × 10 3 dN / m 2} , preferably less than ^{1 × 10 5 dN / m 2} . When the storage elastic modulus G ′ at 150 ° C. is 1 × 10 ³ dN / m ² or less, high-temperature offset of the toner tends to occur during fixing at high temperature. In the case of 1 × 10 ⁵ dN / m ² or more, gloss control becomes difficult and color mixture with other colors tends to be insufficient. More preferably, it is larger than 2 × 10 ³ dN / m ^{2 and} smaller than 5 × 10 ⁴ .

In order to satisfy the above characteristics, the toner of the present invention preferably contains the crystalline polyester (a2) in the toner base particles (A). The crystalline polyester (a2) preferably has a melting point (Tm) of 60 ° C. or more and 100 ° C. or less, more preferably a melting point (Tm) of 60 ° C. or more and 80 ° C. or less.
Further, the condition that the melting point (Tm) of (a2) exists at 60 ° C. or more and 100 ° C. or less can be satisfied by selecting the monomer type of crystalline PES.

  The crystalline polyester (a2) is preferably contained in an amount of 5% by mass to 30% by mass with respect to the toner base particles (A). More preferably, it is 7 mass% or more and 25 mass% or less.

Further, the type of binder resin (a) used for toner base particles (A), crystalline polyester (a2
) Improves the dispersion state of the crystalline polyester (a2) and the compatibility with the binder resin (a) after the crystalline polyester is melted. As a result, the viscoelastic characteristics of the toner can be satisfied.

  Hereinafter, the toner base particles (A) of the present invention will be described in detail. The toner base particles (A) of the present invention contain at least a binder resin (a), a colorant and a wax. Further, the crystalline polyester (a2) and other additives may be included.

The binder resin (a) used in the present invention uses a polyester resin (a1) as a main component. Here, the main component means that the polyester resin (a1) is contained in the binder resin by 50% by mass or more. The alcohol component forming the polyester resin is preferably a resin using an aliphatic dialcohol as a main component. The aliphatic dialcohol is preferably a dialcohol having 2 to 8 carbon atoms, more preferably 2 to 6 carbon atoms. Examples of the aliphatic dialcohol 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. Diols such as neopentyl glycol, 1,4-butenediol, 1,7-heptanediol, and 1,8-octanediol, and trihydric or higher polyhydric alcohols such as glycerin, pentaerythritol, and trimethylolpropane. Among these, α, ω-linear alkanediol is preferable, and 1,4-butanediol and 1,6-hexanediol are more preferable. Furthermore, from the viewpoint of durability, the content of the aliphatic alcohol is preferably 30 to 100 mol%, more preferably 50 to 100 mol% in the alcohol component.

Although the following alcohol may be contained in addition to the aliphatic alcohol, the content of the following alcohol is preferably 50 mol% or less, more preferably 30 mol% or less in the alcohol component. Examples of the alcohol include polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, and the like. Can be mentioned.

  Examples of the acid component forming the polyester resin include: phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid and other aromatic polyvalent carboxylic acids, fumaric acid, maleic acid, adipic acid, Aliphatic polycarboxylic acids such as succinic acid substituted with alkyl groups having 1 to 20 carbon atoms or alkenyl groups having 2 to 20 carbon atoms such as succinic acid, dodecenyl succinic acid, octenyl succinic acid, anhydrides of these acids, and the like Alkyl (carbon number 1 to 8) ester of acid.

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%, and 50 to 100 mol% in the carboxylic acid component. Is more preferable.
From the viewpoint of fixability, 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.

  The production of the polyester resin is not particularly limited, and a known method may be followed. For example, it can be produced by subjecting an alcohol component and a carboxylic acid component to condensation polymerization at a temperature of 180 to 250 ° C. in an inert gas atmosphere using an esterification catalyst as necessary.

  The binder resin preferably contains as a main component a polyester resin using the aliphatic alcohol as an alcohol component. On the other hand, even when the binder resin contains a polyester resin using a bisphenol monomer as an alcohol component, there is no significant difference in the melting characteristics of the binder resin. However, toner base particles using the binder resin have poor granulation properties, and it is difficult to obtain spherical toner base particles.

  The binder resin is a resin other than a polyester resin using a specific amount of an aliphatic alcohol as an alcohol component, for example, a polyester resin, a styrene-acrylic resin, a polyester and a styrene acrylic in which the amount of the aliphatic alcohol used is outside the above range. A mixed resin, an epoxy resin, or the like may be contained. In that case, the content of the polyester resin using a specific amount of aliphatic alcohol 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 binder resin.

Furthermore, in the present invention, the molecular weight of the binder resin is one of the more preferable modes that the peak molecular weight is 8000 or less, preferably less than 5500. Furthermore, the ratio of molecular weight of 100,000 or more is 5
. It is also a preferred embodiment that it is 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 molecular weight of 1000 or less to 10.0% or less.

  In order to reduce the ratio of the molecular weight of 1000 or less, the present inventors effectively reduce the ratio of the molecular weight of 1000 or less by dissolving the binder resin in a solvent and leaving the solution in contact with water. I found that I can do it. That is, it is considered that 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 binder resin solution.

  From the above, in the present invention, the above-described dissolution suspension method is preferably used as the toner production method. A low molecular weight component is efficiently removed by using a method in which a solution in which a binder resin, a colorant, and a wax are dissolved or dispersed is left in contact with an aqueous medium before being suspended in the aqueous medium. be able to.

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

The crystalline polyester (a2) used in the present invention is preferably a resin obtained by polycondensing an alcohol component containing an aliphatic diol as a main component and a carboxylic acid component containing an aliphatic dicarboxylic acid compound as a main component. It is obtained by using a monomer containing an alcohol component composed of a dihydric or higher polyhydric alcohol and a carboxylic acid component composed of a divalent or higher polyvalent carboxylic acid compound. Among them, an alcohol component containing 60 mol% or more of an aliphatic diol having 2 to 6 carbon atoms, preferably 4 to 6 carbon atoms, and an aliphatic dicarboxylic acid having 2 to 8 carbon atoms, preferably 4 to 6 carbon atoms, 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 include: 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 may contain a polyhydric alcohol component other than the aliphatic diol. The polyhydric alcohol component includes the following: polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene (2.2) -2,2-bis Bivalent aromatic alcohols such as alkylene (carbon number 2 to 3) oxide (average number of added moles 1 to 10) adducts of bisphenol A such as (4-hydroxyphenyl) propane, glycerin, pentaerythritol, trimethylolpropane, etc. Trihydric or higher alcohol.

  C2-C8 aliphatic dicarboxylic acid compounds and the following: oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, adipic acid, and these acids Anhydrides, alkyl (C1-3) esters and the like. Among these, fumaric acid and adipic acid are preferable, and fumaric acid is more preferable.

  The carboxylic acid component 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. And alicyclic dicarboxylic acids; trivalent or higher polyvalent carboxylic acids such as trimellitic acid and pyromellitic acid; and anhydrides and alkyl (C1 to C3) esters of these acids.

  Monomers having a sulfonic acid group in the side chain are also effective in improving the dispersibility in the aqueous phase and increasing the solvent resistance in the oil phase. Examples of the diol compound having a sulfonic acid group in the side chain include sulfoisophthalic acid, N, N-bis (2-hydroxyethyl) -2-aminoethanesulfonic acid, and metal salts thereof.

  The alcohol component and the carboxylic acid component can be 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.

The crystalline polyester used in the present invention is preferably finely dispersed while leaving the crystal structure in the toner. For this reason, the crystalline polyester is preferably formed in the state of an aqueous dispersion latex. Therefore, it is preferable that the crystalline polyester contains a sulfone group or a carboxy group to thereby provide self-emulsifying properties.

Preparation of resin fine particles of the crystalline polyester (a2) is not particularly limited, but it is liquefied by using an emulsion polymerization method or by dissolving or melting the resin in a solvent, and this is suspended in an aqueous medium. It can be granulated by becoming cloudy.

  Examples of the release agent (wax) used in the present invention include aliphatic hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, low molecular weight olefin copolymers, microcrystalline wax, paraffin wax, and Fischer-Tropsch wax; Oxides of aliphatic hydrocarbon waxes such as polyethylene wax; waxes based on fatty acid esters such as aliphatic hydrocarbon ester waxes; and fatty acid esters such as deoxidized carnauba wax have been partially or fully deoxidized Things. Furthermore, a partially esterified product of a fatty acid such as behenic acid monoglyceride and a polyhydric alcohol; a methyl ester compound having a hydroxyl group obtained by hydrogenating vegetable oils and the like. The wax particularly preferably used in the present invention is, from the viewpoint of ease of preparation of the WAX dispersion, ease of incorporation into the prepared toner, exudation from the toner at the time of fixing, releasability, in dissolution suspension. Ester wax is good.

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

  Examples of the synthetic ester wax include a monoester wax synthesized from a long-chain fatty acid and a long-chain alcohol. The long-chain linear saturated fatty acid is represented by the general formula Cn H2n + 1COOH, and those with n = about 5 to 28 are preferably used. The long-chain linear saturated alcohol is preferably represented by Cn H2n + 1OH and n = about 5-28.

  Specific examples of the long-chain linear saturated fatty acids 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, myristyl alcohol. , Pentadecyl alcohol, cetyl alcohol, heptadecyl alcohol, stearyl alcohol, nonadecyl alcohol, eicosyl alcohol, seryl alcohol and heptadecanool.

  Examples of ester wax having two or more ester bonds per molecule include trimethylolpropane tribehenate, pentaerythritol tetrabehenate, pentaerythritol diacetate dibehenate, glycerin tribehenate, and 1,18- Octadecanediol-bis-stearate, etc.); polyalkanol esters (tristearyl trimellitic acid, distearyl maleate, etc.).

  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 amides (ethylenediamine dibehenyl amide); polyalkylamides (trimellitic acid tristearyl amide); and dialkyl ketones (distearyl ketone).

  The wax may be partially saponified.

  Among the above, more preferable waxes are synthetic ester waxes composed of linear fatty acid acids and linear 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 high polarity substance such as polyester as a binder resin or a reaction product of diol and diisocyanate on the surface layer during fixing. However, it seems that it is advantageous that the wax has a linear structure as much as possible 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 the above-mentioned wax include synthetic hydrocarbons such as 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, etc.). And natural waxes such as ozokerite and ceresin.

In the present invention, the content of the wax in the toner is 5.0 to 20.0% by mass, more preferably 5.0 to 15.0% by 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 DSC. When the maximum peak is lower than 60 ° C., the wax is likely to be exposed on the toner surface, and the heat resistant storage stability may be lowered. 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.

  As the colorant used in the color toner in the present invention, the following are used.

  As a colorant suitable for the yellow color, a pigment or a dye can be used. Specifically, the following are mentioned as a pigment. C. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 17, 23, 62, 65, 73, 74, 81, 83, 93, 94, 95, 97, 98, 109, 110, 111, 117, 120, 127, 128, 129, 137, 138, 139, 147, 151, 154, 155, 167, 168, 173, 174, 176, 180, 181, 183, 191, C.I. I. Bat yellow 1,3,20. Examples of the dye include the following. C. I. Solvent yellow 19, 44, 77, 79, 81, 82, 93, 98, 103, 104, 112, 162. These are used alone or in combination of two or more.

  As a colorant suitable for magenta, a pigment or a dye can be used. Specific examples include the following. C. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 39, 40, 41, 48, 48; 2, 48; 3, 48; 4, 49, 50, 51, 52, 53, 54, 55, 57, 57; 1, 58, 60, 63, 64, 68, 81, 81; 1, 83, 87, 88, 89, 90, 112, 114, 122, 123, 144, 146, 150, 163, 166, 169, 177, 184, 185, 202, 206, 207, 209, 220, 221, 238, 254; I. Pigment violet 19; C.I. I. Vat Red 1, 2, 10, 13, 15, 23, 29, 35.

  Examples of the magenta dye include the following. C. I. Solvent Red 1, 3, 8, 23, 24, 25, 27, 30, 49, 52, 58, 63, 81, 82, 83, 84, 100, 109, 111, 121, 122, etc. I. Disper thread 9, C.I. I. Solvent Violet 8, 13, 14, 21, 27; C.I. I. Oil-soluble dyes such as Disperse Violet 1; I. B. Basic Red 1, 2, 9, 12, 13, 14, 15, 17, 18, 22, 23, 24, 27, 29, 32, 34, 35, 36, 37, 38, 39, 40; I. Basic dyes such as basic violet 1,3,7,10,14,15,21,25,26,27,28. These are used alone or in combination of two or more.

As a colorant suitable for cyan, a pigment or a dye can be used. Specific examples include the following. C. I. CI pigment blue 1, 7, 15, 15; 1, 15; 2, 15; 3, 15; 4, 16, 17, 60, 62, 66; I. Bat Blue 6, C
. I. Acid Blue 45. Examples of the dye include the following. C. I. Solvent Blue 25, 36, 60, 70, 93, 95. These are used alone or in combination of two or more.

  The following are mentioned as a black pigment. Carbon black such as furnace black, channel black, acetylene black, thermal black, lamp black. Further, metal oxides such as magnetite and ferrite are also used.

  In the present invention, it is not preferable to use a dye or pigment having extremely high solubility in water as the colorant. When the above-mentioned dyes / pigments are used, they may dissolve in water during the production process, and granulation may be disturbed or desired coloration may not be obtained.

  In the present invention, a charge control agent can be used as necessary. The charge control agent may be contained in the core portion of the toner including at least the binder resin and the colorant, or may be contained in the surface layer that is a reaction product of the diol component and the diisocyanate component.

  Examples of the charge control agent include the following. Nigrosine dye, triphenylmethane dye, metal-containing azo complex dye, molybdate chelate pigment, rhodamine dye, alkoxy amine, quaternary ammonium salt (including fluorine-modified quaternary ammonium salt), alkylamide, phosphorus simple substance Or a compound, a simple substance or compound of tungsten, a fluorine-based activator, a metal salt of salicylic acid, and a metal salt of a salicylic acid derivative.

Specific examples include the following. Bontron N-03 of nigrosine dye, Bontron P-51 of quaternary ammonium salt, Bontron S-34 of metal-containing azo dye, E-82 of oxynaphthoic acid metal complex, E-84 of salicylic acid metal complex, Phenolic condensate E-89 (above, manufactured by Orient Chemical Co., Ltd.), quaternary ammonium salt molybdenum complex TP-302, TP-415 (above, manufactured by Hodogaya Chemical Co., Ltd.), quaternary ammonium salt Copy charge PSY VP2038, copy blue PR of triphenylmethane derivative, copy charge of quaternary ammonium salt NEG VP2036, copy charge NX
VP434 (above, manufactured by Hoechst), LRA-901, LR-147 (manufactured by Nippon Carlit Co., Ltd.), copper phthalocyanine, perylene, quinacridone, azo pigment, other sulfonic acid groups, carboxyl groups and quaternary ammonium salts A polymer compound having a functional group such as

Next, the surface layer (B) will be described.
The surface layer (B) preferably contains the 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. It is done. As the resin (b), two or more of the above resins may be used in combination. In the present invention, a resin capable of forming an aqueous dispersion is preferable, and since an aqueous dispersion of fine spherical resin particles is easily obtained, vinyl resins, polyurethane resins, epoxy resins, and polyester resins can be preferably used. 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. In addition, a polyurethane resin, which is a compound formed by urethane bonding, can be particularly preferably used because it exhibits an appropriate affinity for a solvent, water dispersibility, viscosity adjustment, and ease of alignment of particle diameters.

  The polyurethane resin will be described in detail below. The polyurethane resin is a reaction product of a diol and a substance containing a diisocyanate group, and a resin having various functions can be obtained by adjusting the diol and the diisocyanate.

Examples of the substance containing an isocyanate group include the following.
C6-C20 aromatic isocyanate, C2-C18 aliphatic isocyanate, C4-C15 alicyclic isocyanate, C8-C15 aroma Aliphatic isocyanates and modified products of these isocyanates (urethane groups, carbodiimide groups, allophanate groups, urea groups, burette groups, uretdione groups, uretoimine groups, isocyanurate groups, oxazolidone group-containing modified products, etc., hereinafter also referred to as modified isocyanates. And mixtures of two or more thereof.

  The following are mentioned as said aromatic isocyanate. 1,3- and / or 1,4-phenylene diisocyanate, 1,5-naphthylene diisocyanate, 2,4- and / or 2,6-tolylene diisocyanate (TDI), crude TDI, 2,4'- and / or Or 4,4′-diphenylmethane diisocyanate (MDI), crude MDI [crude diaminophenylmethane [condensation product of formaldehyde and an aromatic amine (aniline) or a mixture thereof; diaminodiphenylmethane.

  In addition to the above-mentioned diisocyanate component, the resin (b) can also use a tri- or higher functional isocyanate compound as the polyurethane resin. Examples of the trifunctional or higher functional isocyanate compound include polyallyl polyisocyanate (PAPI)], 4,4 ′, 4 ″ -triphenylmethane triisocyanate, m- and p-isocyanatophenylsulfonyl isocyanate, and the like.

  Examples of the aliphatic isocyanate 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 Aliphatic isocyanates such as proate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate, 2-isocyanatoethyl-2,6-diisocyanatohexanoate;

  Examples of the alicyclic isocyanate 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- and / or 2,6-norbornane diisocyanate.

  Examples of the aromatic aliphatic isocyanate include the following. m- and / or p-xylylene diisocyanate (XDI), α, α, α ′, α′-tetramethylxylylene diisocyanate (TMXDI). Examples of the modified polyisocyanate include urethane group, carbodiimide group, allophanate group, urea group, burette group, uretdione group, uretoimine group, isocyanurate group, and oxazolidone.

  Examples of the modified isocyanate include the following. Modified MDI (urethane-modified MDI, carbodiimide-modified MDI, trihydrocarbyl phosphate-modified MDI, etc.), isocyanate-modified products such as urethane-modified TDI, and mixtures of two or more thereof (for example, modified MDI and urethane-modified TDI (isocyanate-containing prepolymer)) In combination with]. Of these, preferred are 6-15 aromatic isocyanates, C4-C12 aliphatic polyisocyanates, and C4-C15 alicyclic isocyanates, and particularly preferred are TDI, MDI, HDI, Hydrogenated MDI and IPDI.

Moreover, the following are mentioned as a diol component which can be used for the said polyurethane resin. 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, etc.); the alkyl moiety 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.
Alkylene ether glycol (diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc.);
Alicyclic diols (1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.); bisphenols (bisphenol A, bisphenol F, bisphenol S, etc.);
Alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adducts of the above alicyclic diol; alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adducts of the above bisphenols; other polylactone diols (polyε -Caprolactone diol), polybutadiene diol.

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 polyurethane resin, in addition to the diols described above, a polyester oligomer having a terminal hydroxyl group can also be used as a suitable diol.

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

  If the molecular weight of the oligomer is further increased, 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 above-described oligomer is preferably contained in the monomer constituting the reaction product of the diol component and the diisocyanate component in an amount of 1 mol% to 10 mol%, more preferably 3 mol% to 6 mol%.

  When the terminal hydroxyl 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.

If the amount of the polyester oligomer is less than 1 mol%, the reaction product of the diol component and the diisocyanate component becomes too hard and the fixing property is inhibited, or the affinity with the binder resin is lowered to form a surface layer. It may be difficult to be done.

  The polyester skeleton of the above-described polyester oligomer and the polyester skeleton of the binder resin described later are preferably the same in order to form a good core / shell. This is related to the affinity between the reaction product of the diol component and the diisocyanate component on the surface layer and the core.

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

  In the polyurethane resin, in addition to the reaction product of the diol component and the diisocyanate component, a reaction product of an amino compound and an isocyanate compound, so-called a compound having a urea bond, can be used in combination.

The following are mentioned as an amino compound which can be used for the said polyurethane resin. Diamines such as diaminoethane, diaminopropane, diaminobutane, diaminohexane, piperazine, 2,5-dimethylpiperazine, amino-3-aminomethyl-3,5,5-trimethylcyclohexane (isophoronediamine, IPDA), 4,4 ' Diaminodicyclohexylmethane, 1,4-diaminocyclohexane, aminoethylethanolamine, hydrazine, hydrazine hydrate, or triamines such as triethylamine, diethylenetriamine and 1,8-diamino-4-aminomethyloctane.
In the polyurethane resin, in addition to the above-described amino compound, in addition to the reaction product of the diol component and the diisocyanate component, a group having a highly reactive hydrogen such as an isocyanate compound and a carboxylic acid group, a cyano group, or a thiol group. It is also possible to use a reaction product with a compound having

In the polyurethane resin, the reaction product of at least the diisocyanate component and the diol component has a carboxylic acid group, a sulfonic acid group, a carboxylate group or a sulfonic acid group salt structure in the side chain. It is said. The carboxylic acid group, sulfonic acid group, carboxylate group, or salt structure of the sulfonic acid group has a carboxylic acid group, a sulfonic acid group, a carboxylic acid in the side chain of the monomer that forms a reaction product of the diol component and the diisocyanate component. It can be easily introduced by having a salt structure of a salt group or a sulfonic acid group.
Among the monomers, diols having the above-described group in the side chain can be suitably used as versatile monomers.

  Examples of the diol compound having a carboxylic acid group in the side chain include dihydroxylcarboxylic acids such as dimethylolacetic acid, dimethylolpropionic acid, dimethylolbutanoic acid, dimethylolbutyric acid, dimethylolpentanoic acid, and metal salts thereof.

  Monomers having a sulfonic acid group in the side chain can easily form an aqueous dispersion, and are effective for stably forming a capsule structure without dissolving in an oil phase solvent. Examples of the diol compound having a sulfonic acid group in the side chain include sulfoisophthalic acid, N, N-bis (2-hydroxyethyl) -2-aminoethanesulfonic acid, and metal salts thereof.

  The diol having a carboxylic acid group, a sulfonic acid group, a carboxylate group or a sulfonic acid group salt structure in the side chain is 10 moles of monomers forming a reaction product of a diol component and a diisocyanate component. % To 50 mol%, more preferably 20 mol% to 30 mol%.

  When the diol is less than 10 mol%, the dispersibility of the fine particles is deteriorated and the granulation property may be remarkably impaired. When the amount is more than 50 mol%, the reaction product of the diol component and the diisocyanate component may be dissolved in the aqueous medium depending on the case, so that a sufficient function as a dispersant may be achieved.

  Preparation of the resin fine particles used in the resin (b) is not particularly limited, and the emulsion polymerization method or the resin is dissolved in a solvent or melted to be liquefied and suspended in an aqueous medium. It can prepare by the method of granulating by making it.

At this time, known surfactants, dispersants, and the like can be used, and the resin constituting the fine particles can be made self-emulsifying.

  Solvents that can be used for preparing the resin fine particles by dissolving the resin in a solvent are not particularly limited, but hydrocarbon solvents such as ethyl acetate, xylene, and hexane, halogens such as methylene chloride, chloroform, and dichloroethane. Hydrocarbon solvents, ester solvents such as methyl acetate, ethyl acetate, butyl acetate and isopropyl acetate, ether solvents such as diethyl ether, ketone solvents such as acetone, methyl ethyl ketone, diisobutyl ketone, cyclohexanone and methylcyclohexane, methanol, Examples include alcohol solvents such as 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 an isocyanate group is produced, and this is rapidly dispersed in water, followed by addition of a compound having an amino group capable of reacting with an isocyanate group, thereby extending or crosslinking the chain. The method of preparing by this can be used preferably.

  That is, in the case of preparing the resin fine particles, a prepolymer having an isocyanate group and other necessary components as required are dissolved or dispersed in a solvent having high solubility in water such as acetone or alcohol among the above solvents. To do. By introducing this into water, the prepolymer system having the isocyanate group is rapidly dispersed. A method of preparing a reaction product of a diol component and a diisocyanate component having desired physical properties by subsequently introducing an amino group-containing compound can be suitably used.

  The resin fine particles having a number average particle diameter of 30 nm or more and 100 nm or less are preferably used for forming a capsule structure which is a feature of the toner of the present invention.

  That is, when the number average particle size is smaller than 30 nm, as in the case where the coating amount of the resin fine particles is small, when the toner of the present invention is manufactured in an aqueous system, the granulation stability is lowered. Therefore, it becomes difficult to form a capsule structure, and the heat resistant storage stability tends to deteriorate.

  On the other hand, when the particle size is larger than 100 nm, as in the case where the coating amount of the resin fine particles is large, when the toner of the present invention is manufactured in an aqueous system, the dispersibility in the aqueous phase is lowered, and the particles are separated from each other. Unification of particles or irregularly shaped particles.

<Method for producing toner particles>
In the present invention, the following method can be suitably used as a method for easily preparing the capsule-type toner particles.
That is, the preparation method includes dissolving or dispersing at least the binder resin (a), the colorant, and the wax in an organic medium in an aqueous medium in which fine particles mainly composed of the resin (b) are dispersed. An oil phase containing the obtained dissolved or dispersed material is prepared, and the oil phase is dispersed in the aqueous medium to produce a dispersion containing oil droplets. Next, the particles are obtained by removing the solvent from the obtained dispersion and drying. That is, the above system is intended to be a system in which the above-mentioned fine particles function also as a dispersant when suspending the liquid material of the toner composition. By using such a system, the capsule-type toner particles of the present invention can be prepared by a simpler method without requiring an aggregation step on the toner surface.

<Oil phase adjustment>
Solvents that can be used in the oil phase as an organic medium for dissolving the binder resin and the like include hydrocarbon solvents such as ethyl acetate, xylene, and hexane, halogenated hydrocarbon solvents such as methylene chloride, chloroform, dichloroethane, and methyl acetate. And ester solvents such as ethyl acetate, butyl acetate and isopropyl acetate, ether solvents such as diethyl ether, and ketone solvents such as acetone, methyl ethyl ketone, diisobutyl ketone, cyclohexanone and methylcyclohexane.

  The binder resin (a) can be used as a resin dispersion dissolved in the organic medium except for the crystalline polyester (a2). In this case, although it depends on the viscosity and solubility of the resin, the binder resin (a) should be blended in the solvent in the range of 40% to 60% by weight as a resin component in consideration of ease of production in the next step. Is preferred. Heating below the boiling point of the organic medium during dissolution is preferable because the solubility of the resin increases.

  The wax and colorant are also preferably dispersed in an organic solvent. That is, a wax and a colorant that have been previously mechanically pulverized in a wet or dry manner are dispersed in an organic solvent to prepare a wax dispersion and a colorant dispersion, respectively.

  With respect to the wax and the colorant, the dispersibility can also be improved by adding a dispersant, a resin or the like to each of them. Since these differ depending on the wax, colorant, binder resin, and organic solvent used, they can be selected and used as appropriate.

  These resin dispersions, wax dispersions, colorant dispersions, and organic media are blended in desired amounts and dispersed to prepare an oil phase.

<Preparation of aqueous medium>
As an aqueous medium used in the present invention, water alone may be used, but a solvent miscible with water may be used in combination. Examples of miscible solvents include alcohols (methanol, isopropanol, ethylene glycol, etc.), dimethylformamide, tetrahydrofuran, cellosolves (methyl cellosolve, etc.), lower ketones (acetone, methyl ethyl ketone, etc.), and the like. It is also a preferable method to mix an appropriate amount of the organic solvent used as the oil layer 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 that fine particles containing the resin (b) as a main component are dispersed in an aqueous medium. The fine particles are used in a desired amount according to the stability of the oil phase in the next step and the encapsulation as toner particles.

  In the aqueous medium, a known surfactant, water-soluble polymer, viscosity modifier and the like can be added.

  Examples of the surfactant include an anionic surfactant, a cationic surfactant, an amphoteric surfactant, and a nonionic surfactant, and can be arbitrarily selected in accordance with the polarity at the time of toner particle formation. is there.

Examples of amphoteric surfactants include anionic surfactants such as alkylbenzene sulfonates, α-olefin sulfonates and phosphate esters, alkylamine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, amine salt types such as imidazoline, and the like. , Quaternary ammonium salt type cationic surfactants such as alkyltrimethylammonium salt, dialkyldimethylammonium salt, alkyldimethylbenzylammonium salt, pyridinium salt, alkylisoquinolinium salt, benzethonium chloride, fatty acid amide derivative, polyvalent Nonionic surfactants such as alcohol derivatives, for example, amphoteric surfactants such as alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine and N-alkyl-N, N-dimethylammonium betaine That.

  On the other hand, examples of cationic surfactants include aliphatic primary, secondary or secondary amine acids having a fluoroalkyl group, aliphatic quaternary ammonium salts such as perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salts, and benzas. Examples thereof include a ruconium salt, a benzethonium chloride, a pyridinium salt, and an imidazolinium salt.

A polymer dispersant may be used as the dispersant. For example, acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid or maleic anhydride and other (meth) acrylic single monomers containing hydroxyl groups Such as β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate, γ-hydroxypropyl acrylate, γ-hydroxypropyl methacrylate, acrylic acid 3 -Chloro-2-hydroxypropyl, 3-chloro-2-hydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerol monoacrylate, glycerol monomethacrylate, N -Methylol acrylamide, N-methylol methacrylamide, etc., vinyl alcohol, or ethers with vinyl alcohol, such as vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, etc., or esters of compounds containing vinyl alcohol and carboxyl groups Such as vinyl acetate, vinyl propionate, vinyl butyrate, acrylamide, methacrylamide, diacetone acrylamide or their methylol compounds, acid chlorides such as acrylic acid chloride, methacrylic acid chloride, pinylviridine, vinylpyrrolidone, vinylimidazole, ethylene Homopolymers or copolymers such as those having a nitrogen atom such as imine or its heterocyclic ring, polyoxyethylene, polyoxypropylene, polyoxyethylene alcohol Luamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonyl phenyl ether, polyoxyethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ester, polyoxyethylene nonyl phenyl ester, etc. Celluloses such as polyoxyethylene, methylcellulose, hydroxyethylcellulose, hydroxypropylcellulose and the like can be used.
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, the dispersion stabilizer is used for the following reason. That is, the organic medium in which the binder resin that is the main component of the toner is dissolved has a high viscosity, and the dispersion stabilizer surrounds the oil droplets formed by finely dispersing the organic medium with high shearing force. This is to prevent 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, calcium triphosphate and the like can be used.

<Addition of crystalline polyester (a2)>
In the present invention, the fixing property can be improved by adding the crystalline polyester (a2) while maintaining the crystallinity, but the dispersion state can be changed by the addition method of the crystalline polyester.

In the present invention, the crystalline polyester (a2) is preferably used in the state of a dispersion liquid emulsified so as to be resin fine particles having a number average particle diameter of 30 nm to 300 nm dispersed in an aqueous medium. In this case, if necessary, a surfactant may be added and dispersed.
When the number average particle diameter is smaller than 30 nm, the crystalline polyester incorporated in the oil phase is easily dissolved in a resin or an organic solvent, and it is difficult to maintain crystallinity. Therefore, it becomes difficult to obtain the viscoelasticity of the present invention. Further, when the number average particle diameter is larger than 300 nm, poor dispersion of the crystalline polyester is likely to occur. More preferably, the number average particle diameter is 50 nm or more and 200 nm or less.
In order to make the crystalline polyester have the above particle diameter, it can be achieved by the molecular weight of the crystalline polyester and the addition amount of a functional group such as sulfonic acid.

  The dispersion may be added to either the oil phase or the aqueous medium, but it is preferable to disperse the dispersion in the aqueous medium in order to take in while maintaining the crystals.

  When adding the above dispersion to the oil phase, the dispersion of fine particles dispersed in advance in water is mixed with the oil phase in which the binder resin (a), the colorant and the wax are dissolved or dispersed, by changing the solvent to an organic solvent. A coconut oil phase is prepared. In this case, it is preferable that the crystalline polyester does not dissolve and coalesce, and does not dissolve in other binder resins. As the organic medium for dispersing the crystalline polyester, the organic medium used in the preparation of the oil phase can be used. However, alcohols with low solubility, such as methyl alcohol, ethyl alcohol, n-propyl alcohol, iso-propyl, are used. Alcohol and monoalcohol having 4 or more carbon atoms can be used.

When the dispersion is added to an aqueous medium, it is necessary to mix the polyester (a2) with the resin (b) forming the surface layer (B) to incorporate the crystalline polyester (a2) into the toner base particles (A). For this purpose, (1) by adding the aqueous dispersion containing the resin (b) forming the surface layer (B) after adding the dispersion to the aqueous dispersion of the crystalline polyester (a2) by two-stage addition. Incorporating crystalline polyester into the internal phase. (2) By changing the hydrophilicity of the fine particles mainly composed of the resin (b), the target toner particles can be obtained by a method of localizing the resin (b) on the surface side.

  Next, the dispersion method will be described. The dispersion method 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. A shearing type is preferred.

If it is a stirrer 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 Tarrax (manufactured by IKA), Polytron (manufactured by Kinematica), TK Auto Homo Mixer (manufactured by Special Machine Industries 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 include continuous type emulsifiers (manufactured by Taiheiyo Kiko Co., Ltd.), batch types such as CLEARMIX (manufactured by M Technique Co., Ltd.), fill mix (manufactured by Tokushu Kika Kogyo Co., Ltd.), and continuous two-way emulsifiers. .

  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 a 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 dispersion obtained in this way, a method can be employed in which the temperature of the entire system is gradually raised and the organic solvent in the droplets is completely removed by evaporation.

  Alternatively, the dispersion can be sprayed into a dry atmosphere to completely remove the water-insoluble organic solvent in the droplets to form toner fine particles, and the water in the dispersion 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 dispersion obtained by the above dispersion method has a wide particle size distribution, and washing and drying processes 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.

  The toner particles after drying obtained by removing the organic solvent from the dispersion are mixed with different particles such as release agent fine particles, charge control fine particles, fluidizing agent fine particles, and colorant fine particles. By applying mechanical impact force to the mixed powder, the foreign particles are fixed and fused on the surface of the mixed powder to prevent the dissociation of the foreign particles from the surface of the resulting composite particles. I can do it.

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

  In the toner having capsule-type toner particles of the present invention, it is more preferable that the toner base particles are completely covered with the surface layer.

  The inventors consider that the following is important in order to develop good fixing characteristics after completely covering the toner base particles with the surface layer.

In the present invention, when resin fine particles are used for forming the toner particle surface layer, the resin fine particles are 1.0% by mass or more and 15.0% by mass or less with respect to the toner base particles (A) in the toner surface layer.
It is preferably included.

  In the classification operation, fine particles can be removed in the liquid by a cyclone, a decanter, a centrifugal separator or the like. Of course, the classification operation may be performed after obtaining the powder after drying, but it is preferable in the liquid to perform the classification operation.

  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 present invention, if the binder resin is melt-kneaded or excessive stress is applied in the solution, the molecular chain may be broken and the low molecular weight component may be increased. That is not very desirable.

  In the present invention, the weight average particle diameter (D4) of the toner particles is preferably 2.0 or more and 10.0 μm or less.

If the weight average particle diameter of the toner particles is smaller than this, the toner is likely to be charged up after a long period of use or the like, and the concentration tends to decrease. Further, when the weight average particle diameter of the toner particles is larger than 10.0 μm, the output of a line image or the like is likely to cause scattering and blurring, and the fine line reproducibility may be inferior.
Further, the weight average particle diameter (D4) of the toner particles can be adjusted to the above range by controlling the addition amount of the resin (b) and the blending amount of the oil phase and the dispersion liquid.

  In the present invention, the spheroidization degree SF-1 of the toner particles is preferably in the range of 100 to 140, more preferably in the range of 100 to 130.

  When the SF-1 value is larger than 140, the transfer characteristics tend to be deteriorated and the image may be deteriorated. That is, if the SF-1 value is 100, a shape close to a true sphere is shown, and therefore a toner shape closer to 100 is preferable.

  As an external additive for assisting the fluidity, developability and chargeability of the toner particles obtained by the above production method, inorganic fine particles can be preferably used.

The primary particle diameter of the inorganic fine particles is preferably 5 nm to 2 μm, and particularly preferably 5 nm to 500 nm. Moreover, it is preferable that the specific surface area by BET method is 20-500 m < ² > / g.

  The use ratio of the inorganic fine particles is preferably 0.01 to 5% by mass of the toner particles, and particularly preferably 0.01 to 2.0% by mass.

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

  Specific examples of the inorganic fine particles include silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, tin oxide, quartz sand, clay, mica, wollastonite. And diatomaceous earth, chromium oxide, cerium oxide, bengara, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride.

  Other specific examples of inorganic fine particles include the following polymer fine particles, soap-free emulsion polymerization, suspension polymerization, polystyrene obtained by dispersion polymerization, methacrylic acid ester or acrylic acid ester copolymer, silicone, benzoguanamine, Examples thereof include polymer particles such as nylon.

  Such inorganic fine particles can be surface treated with a surface treating agent to increase hydrophobicity, thereby preventing deterioration of toner flow characteristics and charging characteristics even under high humidity.

  For example, preferable surface treatment agents include silane coupling agents, silylating agents, silane coupling agents having an alkyl fluoride group, organic titanate coupling agents, aluminum coupling agents, silicone oils, modified silicone oils, and the like. It can be illustrated.

Examples of the cleaning property improver for removing the toner after transfer remaining on the photoreceptor or the primary transfer medium include, for example, fatty acid metal salts such as zinc stearate, calcium stearate, and stearic acid, such as polymethyl methacrylate fine particles, polystyrene fine particles, etc. Examples thereof include polymer fine particles produced by soap-free emulsion polymerization.

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

  When the toner of the present invention is used for a two-component developer, it may be used by mixing with a magnetic carrier. The carrier to toner content ratio in the developer is 1 to 10 mass of toner with respect to 100 mass parts of the carrier. Part is preferred.

  As the magnetic carrier, conventionally known ones such as iron powder, ferrite powder, magnetite powder, and magnetic resin carrier having an average particle diameter of 20 to 200 μm can be used.

<Method for measuring storage elastic modulus (G ′)>
The storage elastic modulus (G ′) (dynamic viscoelasticity) of the toner was measured using a viscoelasticity measuring device (rheometer) RDA-II type (manufactured by Rheometrics) under the following conditions.
・ Measurement jig: Uses a 7.9 mm diameter, serrated parallel plate. ・ Measurement sample: A cylindrical sample (pellet) having a diameter of about 8 mm and a height of 2 mm is prepared using a pressure molding machine (15 kN, Pressurized at room temperature for 1 minute). Adjust the temperature of the serrated parallel plate to 80 ° C, heat and melt the cylindrical sample to bite the sawtooth, and fix it to the serrated parallel plate, then take the measurement start temperature of 30.00 ° C over 1 hour Then, the serrated parallel plate and the cylindrical sample are slowly cooled.
Measurement frequency: 6.28 radians / second Measurement strain setting: Using the viscoelasticity measuring device, the initial value is set to 0.1%, and measurement is performed in automatic measurement mode.
-Sample elongation correction: Adjustment is performed in the automatic measurement mode using the viscoelasticity measuring apparatus.
Measurement temperature: The temperature is raised from 30 ° C. to 200 ° C. at a rate of 2 ° C. per minute.
Measurement interval: Viscoelasticity data is measured every 30 seconds, that is, every 1 ° C.

A storage elastic modulus (G ′) curve is obtained by the above measurement. In addition, the loss elastic modulus (G ″) and loss tangent (tan δ = G ″ / G ′) with respect to temperature are obtained.
Based on the obtained G ′ curve, the common logarithm Log (G ′ (T) / (dN / m ² )) of the storage elastic modulus G ′ (T) (dN / m ² ) at temperature T is expressed as F (T ), The rate of change dF (T) / dT with respect to temperature can be determined as follows.

First, let T be the temperature at the center of two adjacent measurement temperatures. A slope Δ1 between the measurement data at two adjacent measurement temperatures (T−0.5, T + 0.5) is obtained.
Δ1 = {log G ′ (T + 0.5) −log G ′ (T−0.5)} / {(T + 0.5) − (T−0.5)}
= LogG '(T + 0.5) -logG' (T-0.5)
Let Δ1 be data of the change rate dF (T) / dT at the temperature (T) between the two points. Further, the condition that the temperature T ₀ that takes the minimum value of dF (T) / dT exists in the temperature range of 60 ° C. or more and 100 ° C. or less is satisfied by adding a specific crystalline polyester and adjusting the addition method and the like. It is possible.

Further, in order to eliminate measurement errors, a plurality of toners having the same prescription are measured, the temperature deviation at which the change rate dF (T) / dT data becomes the minimum value is within 1 ° C., and the minimum value deviation is 0 .01 (° C. ⁻¹ ) was confirmed.

Then, the temperature at which the minimum value of the first derivative data _{(T 0),} before and after the 2.5 ° temperature _{(T 0}
From the value of the storage elastic modulus G ′ at −2.5, T ₀ +2.5), the storage elastic modulus ratio G ′ (T ₀ −2.5) / G ′ (T ₀ +2.5) is obtained.
In order to make the storage elastic modulus ratio G ′ (T ₀ −2.5) / G ′ (T ₀ +2.5) larger than 3.0 at 2.5 ° C. before and after the temperature T ₀ It is possible by adjusting the kind of crystalline polyester, the amount added, the introduction method, and the like.

<Measurement method of softening point of resin>
The softening point of the resin refers to that measured by a constant load extrusion capillary rheometer, a so-called flow tester.
As a flow tester, an elevated flow tester CFT500C manufactured by Shimadzu Corporation is used. The flow tester curve based on the data from the flow tester is in a state as shown in FIGS. 3A and 3B, from which each temperature can be read.
In FIG. 3, Ts is the softening temperature, Tfb is the outflow start temperature, and the melting temperature in the 1/2 method is the 1/2 melting temperature.
(Measurement condition)
Load: 10 kgf / cm ² (9.807 × 10 ⁵ Pa)
Temperature increase rate: 4.0 ° C./min
Die diameter: 1.0mm
Die length: 1.0mm

<Measurement of melting point of wax and content of wax>
The method for measuring the melting point of the wax and the wax content in the toner in the present invention is DSC.
The measurement was carried out under the following conditions using Q1000 (manufactured by TA Instruments).
(Measurement condition)
・ Modulation mode ・ Temperature increase rate: 0.5 ℃ / min
Modulation temperature amplitude: ± 1.0 ° C / min
・ Measurement start temperature: 25 ℃
・ Measurement end temperature: 130 ℃

[Calculation method of wax melting point]
The wax alone or toner was measured under the above conditions, and the peak value of the endothermic peak of the wax was defined as the melting point of the wax in the present invention. When two or more peaks exist, the peak with the higher endotherm was taken as the melting point.
From the above measured values, the wax content in the toner was calculated by the following formula.
(Formula): Wax content (%) in toner = (Cp_toner / Cp_wax) × 100 (%)
Moreover, in this invention, when using 2 or more types of wax, content was calculated separately about each wax, and the sum was made into content of wax.

<Measurement of Tg>
In the present invention, the Tg measurement of the toner and the binder resin is also performed by DSC measurement under the same conditions as the measurement of the melting point and the wax content of the wax.
The DSC curve was obtained by taking “Flow” on the vertical axis, and the onset value shown in FIG. 2 was defined as Tg of the present invention.

<Measurement of molecular weight of toner>
In the present invention, the molecular weight distribution of the chromatogram by GPC (gel permeation chromatography) using THF as the solvent for the tetrahydrofuran (THF) soluble part of the toner is measured under the following conditions.
The measurement sample is prepared as follows.
The sample and THF are mixed at a concentration of about 0.5 to 5 mg / ml (for example, about 5 mg / ml) and left at room temperature for several hours (for example, 5 to 6 hours). Are mixed well (until the sample is no longer united), and then allowed to stand at room temperature for 12 hours or longer (for example, 24 hours). At this time, the time from the start of mixing the sample and THF to the end of standing is set to 24 hours or longer.
Then, GPC was passed through a sample processing filter (pore size 0.45-0.5 μm, for example, Mysori Disc H-25-2 manufactured by Tosoh Corp., Excro Disc 25CR manufactured by Gelman Science Japan Co., Ltd., etc.). This sample. The sample concentration is adjusted so that the resin component is 0.5 to 5 mg / ml.

The column was stabilized in a 40 ° C. heat chamber, and THF as a solvent was passed through the column at this temperature at a flow rate of 1 ml / min, and the sample concentration was adjusted to 0.05 to 0.6% by mass. Measurement is performed by injecting 50 to 200 μl of a THF sample solution.
In measuring the molecular weight of the sample, the molecular weight distribution of the sample was calculated from the relationship between the logarithmic value of the calibration curve prepared from several monodisperse polystyrene standard samples and the number of counts. As a standard polystyrene sample for preparing a calibration curve, for example, Pressure Chemical Co. Manufactured by Toyo Soda Kogyo Co., Ltd. and having molecular weights of 6 × 10 ² , 2.1 × 10 ³ , 4 × 10 ³ , 1.75 × 10 ⁴ , 5.1 × 10 ⁴ , 1.1 × 10 ⁵ , 3. 9 × 10 ⁵ , 8.6 × 10 ⁵
2 × 10 ⁶ , 4.48 × 10 ⁶ , and it is appropriate to use at least about 10 standard polystyrene samples. An RI (refractive index) detector is used as the detector.
In order to accurately measure the molecular weight region of 1 × 10 ³ to 2 × 10 ⁶ as the column, it is preferable to combine a plurality of commercially available polystyrene gel columns. Measured in

[GPC measurement conditions]
Equipment LC-GPC 150C (Waters)
Column KF801, 802, 803, 804, 805, 806, 807 (manufactured by Shodex) Column temperature 40 ° C
solv. THF (tetrahydrofuran)

  In general, in the measurement of the GPC chromatogram, the high molecular weight side starts measurement from the starting point of the rise of the chromatogram from the baseline, and the low molecular weight side measures up to about 400 molecular weight.

<Measurement Method of Number Average Particle Size (Dn) and Weight Average Particle Size (D4) of Toner>
A Coulter counter Multisizer II (manufactured by Coulter, Inc.) is used as a measuring device. As the electrolyte, first grade sodium chloride is used to prepare an approximately 1% NaCl aqueous solution. For example, ISTON R-II (manufactured by Coulter Scientific Japan) can be used.
As a measuring method, 0.1 ml of a surfactant (preferably alkylbenzene sulfonate) is added as a dispersant to 100 ml of the electrolytic aqueous solution, and 5 mg of a measurement sample is further added. The electrolyte in which the sample is suspended is subjected to a dispersion treatment for about 3 minutes with an ultrasonic disperser, and the volume and number of toner particles having a particle diameter of 2.00 to 40.30 μm are measured using the 100 μm aperture as the aperture. Is measured for each channel, and the weight average particle diameter D4 and the number average particle diameter Dn are calculated from the volume distribution and number distribution of the toner, respectively. As channels, 2.00 to 2.52 μm; 2.52 to 3.17 μm; 3.17 to 4.00 μm; 4.00 to 5.04 μm; 5.04 to 6.35 μm; 6.35 to 8. 00 μm; 8.00 to 10.08 μm; 10.08 to 12.70 μm; 12.70 to 16.00 μm; 16.00 to 2
13 channels of 0.20 μm; 20.20-25.40 μm; 25.40-32.00 μm; 32.00-40.30 μm are used.

<Measuring method of particle diameter of wax particles in resin fine particles and wax dispersion>
Using a Microtrac particle size distribution measuring device HRA (X-100) (manufactured by Nikkiso Co., Ltd.), measurement is performed with a range setting of 0.001 μm to 10 μm, and the number average particle size (μm) is determined by the resin fine particles and wax particles of the present invention. Particle diameter. As dilution solvents, water was selected for the resin fine particles, and ethyl acetate was selected for the wax particles.

<Method for evaluating 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.

<Low temperature fixability>
Using a color laser copier CLC5000 (manufactured by Canon Inc.), the development contrast is adjusted so that the toner loading on paper is 1.2 mg / cm ² in a single color mode in a normal temperature and humidity environment (23 ° C./60%). A solid unfixed image having a front end margin of 5 mm, a width of 100 mm, and a length of 280 mm was prepared. As the paper, cardboard A4 paper (“Prober Bond paper”: 105 g / m ² , manufactured by Fox River) was used.
The fixing device of CLC5000 (manufactured by Canon Inc.) was remodeled, and the fixing unit was set at a fixing temperature manually, and it was 80 ° C to 200 ° C in a normal temperature and humidity environment (23 ° C / 60%). The fixing test was performed by increasing the temperature by 10 ° C in order.
The image area of the obtained fixed image was rubbed back and forth 5 times while applying a load of 4.9 kPa from a soft thin paper (for example, trade name “Dasper”, manufactured by Ozu Sangyo Co., Ltd.). Each subsequent image density was measured, and an image density reduction rate ΔD (%) was calculated by the following equation. The temperature at which ΔD (%) was less than 10% was defined as a fixing start temperature, and was used as a reference for low-temperature fixability.
The image density was measured with an X-Rite color reflection densitometer (Color reflection densitometer X-Rite 404A).
(Formula): ΔD (%) = (Image density before rubbing−Image density after rubbing) × 100 / Image density before rubbing

This fixing start temperature was evaluated according to the following evaluation criteria.
A: Fixing start temperature is 120 ° C. or less B: 120 ° C. <fixing start temperature ≦ 140 ° C.
C: 140 ° C. <fixing start temperature ≦ 160 ° C.
D: 160 ° C. <fixing start temperature Note that in the present invention, up to rank B was judged to be good low-temperature fixability.

<High temperature offset>
A fixing test similar to the evaluation of the low-temperature fixing property was performed. The obtained fixed image was evaluated as follows and used as an index of high temperature offset.
A: At 180 ° C., there is no gloss reduction of the fixed image and no problem on the image.
B: At 180 ° C., the gloss of the fixed image is reduced, but there is no problem on the image.
C: At 180 ° C., the gloss of the fixed image is reduced and the uniformity of the image is low.
D: The toner on the image is transferred to the fixing roller at 180 ° C., and the image on the front periphery appears on the white background portion after one rotation of the fixing roller.

<Image preservation>
The image used in the low-temperature fixing property is 25 ± 1% at 75 ° gloss using a modified fixing device in which only the fixing device of the CLC5000 (manufactured by Canon Inc.) is removed and the temperature can be arbitrarily changed. Ten fixed images were prepared under temperature conditions. This image is overlaid, a white paper is placed on the top, and a weight of 1 kg with a bottom surface of 100 cm ^{2 on} which pressure is evenly applied is placed on the image portion of the second and subsequent fixed images from above. It was left at 3 ° C. for 3 days.
(Evaluation criteria)
A: The image in contact was not transferred on the opposing paper, and the image could be stored well.
B: Although there is a slight image shift on the opposing paper, there is no problem in actual use.
C: The image is clearly seen on the opposing paper.
D: The image is clearly seen on the opposing paper, and the original image is missing.

<Low-temperature fixability of long-term storage samples>
About 30 g of toner was put in a 100 ml polycup and allowed to stand at 50 ° C. for 3 days, and then mixed with a magnetic carrier for two-component development to prepare a two-component developer. Thereafter, the fixing was evaluated by the method measured by the low-temperature fixability. The evaluation criteria are in accordance with the evaluation criteria for the low-temperature fixability.

<Evaluation of electrification>
Hereinafter, a method for measuring the triboelectric charge amount of the toner in the present invention will be described. First, a predetermined carrier and toner particles are put into a plastic bottle with a lid, and shaken with a shaker (YS-LD, manufactured by Yayoi Co., Ltd.) at a speed of 4 reciprocations per second for 1 minute. The developer consisting of is charged. Next, the triboelectric charge amount is measured by the apparatus for measuring the triboelectric charge amount shown in FIG. In FIG. 4, about 0.5 to 1.5 g of the two-component 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, the toner particles are sucked and removed by suction for 2 minutes. 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 (μC / g) = C × V / (W1−W2)
(Evaluation criteria)
A: The charge amount is -40.0 mc / kg or more and -20.0 mc / kg or less. Those that do not cause problems in the development and transfer processes.
B: Charge amount is -50.0 mc / kg or more and -10.0 mc / kg or less. In image formation, minor image unevenness tends to occur during development and transfer.
C: Charge amount is less than -50.0 mc / kg or greater than -10.0 mc / kg. In many cases, low density and scattering occur.

  Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto.

[Preparation of resin fine particle dispersion 1]
A polyester diol having a number average molecular weight of about 2000, obtained from a 40:50:10 molar mixture of propylene glycol, ethylene glycol and butanediol and an equimolar mixture of terephthalic acid and isophthalic acid.
100 parts by mass, 16 parts by mass of propylene glycol, 94 parts by mass of dimethylolpropanoic acid, sodium N, N-bis (2-hydroxyethyl) -2-aminoethanesulfonate
8 parts by mass-30 parts by mass of tolylene diisocyanate

The raw material was dissolved in 60 parts by mass of acetone and reacted at 67 ° C. for 1 hour.
Next, 271 parts by mass (1.2 mol) of isophorone diisocyanate was added, and the mixture was further reacted at 67 ° C. for 30 minutes and cooled.
After adding 100 parts by mass of acetone to the reaction product, 80 parts by mass (0.8 mol) of triethylamine was added and stirred.
The acetone solution was added dropwise to 1000 parts by mass of ion-exchanged water with stirring at 500 rpm to prepare a fine particle dispersion.
Then, an elongation solution was carried out by adding an aqueous solution in which 50 parts by mass of triethylamine was dissolved in 100 parts by mass of 10% aqueous ammonia and reacting at 50 ° C. for 8 hours. Furthermore, ion-exchange water was added until the solid content became 20% by mass to obtain a resin fine particle dispersion-1. Table 1 shows the Tg and Tm of the resin obtained by drying the resin fine particle dispersion and the number average particle diameter in the dispersion.

[Preparation of resin fine particle dispersion 2]
In an autoclave equipped with a thermometer and a stirrer,
116 parts by weight of dimethyl terephthalate,
66 parts by weight of dimethyl isophthalate,
3 parts by weight of 5-sodium sulfoisophthalate methyl ester,
5 parts by weight trimellitic anhydride,
150 parts by weight of propylene glycol,
Tetrabutoxy titanate 0.1 parts by weight,
Was transesterified by heating at 200 ° C. for 120 minutes. Next, the temperature of the reaction system was raised to 220 ° C., and the reaction was continued for 60 minutes at a system pressure of 1 to 10 mmHg to obtain a polyester resin. After dissolving 40 parts by mass of the polyester resin, 15 parts by mass of methyl ethyl ketone, and 10 parts by mass of tetrahydrofuran at 80 ° C., 60 parts by mass of 80 ° C. water was added with stirring, the solvent was removed under reduced pressure, and ion-exchanged water was added. Was added to obtain a resin fine particle dispersion-2 having a solid content of 20% by mass. The characteristics are shown in Table 1.

[Preparation of resin fine particle dispersion 3]
The following was put into a reaction vessel equipped with a cooling tube, a nitrogen introducing tube and a stirrer.
Styrene 330 parts by mass n-butyl acrylate 110 parts by mass acrylic acid 10 parts by mass 2-butanone (solvent) 50 parts by mass 2,2′-azobis (2,4-dimethylvaleronitrile) 8% as a polymerization initiator Part was dissolved to prepare a polymerizable monomer composition. Polymerization was performed at 60 ° C. for 8 hours, the temperature was raised to 150 ° C., the solvent was removed under reduced pressure, and the product was taken out from the reaction vessel. After cooling to room temperature, it was pulverized and granulated to obtain a binder resin that was a linear vinyl resin. 100 parts by mass of the taken out resin was mixed with 400 parts by mass of toluene and heated to 80 ° C. to dissolve the resin.
Next, 360 parts by mass of ion-exchanged water, 40 parts by mass of a 48.5% aqueous solution of sodium dodecyl diphenyl ether disulfonate (“Eleminol MON-7”, manufactured by Sanyo Kasei Kogyo Co., Ltd.) was added, and the resin solution was added and mixed and stirred to give a milky white color. A liquid was obtained. Toluene was removed under reduced pressure, and ion-exchanged water was added to obtain Resin Fine Particle Dispersion-3 having a solid content of 20% by mass. The characteristics are shown in Table 1.

[Preparation of resin fine particle dispersion 4]
• 1,6-hexanediol 100 parts by mass • fumaric acid 75 parts by mass • adipic acid 30 parts by mass • dibutyltin oxide 0.2 parts by mass • hydroquinone 0.1 parts by mass • 5-sodium sulfoisophthalate methyl ester 3 .0 parts by weight

Was put in a glass 4-liter four-necked flask and reacted at 160 ° C. for 5 hours in a nitrogen atmosphere, and then heated to 200 ° C. and reacted for 1 hour. Furthermore, the reaction proceeded at 8 kPa. 100 parts by mass of the cooled and taken out resin was mixed with 400 parts by mass of toluene and heated to 80 ° C. to dissolve the resin. 3 parts by mass of triethylamine was added to the cooled resin solution.
Next, 360 parts by mass of ion-exchanged water, 40 parts by mass of a 48.5% aqueous solution of sodium dodecyl diphenyl ether disulfonate (“Eleminol MON-7”, manufactured by Sanyo Kasei Kogyo Co., Ltd.) was added, and the resin solution was added and mixed and stirred to give a milky white color. A liquid was obtained. Toluene was removed under reduced pressure, and ion-exchanged water was added to obtain resin fine particle dispersion liquid-4 having a solid content of 20% by mass. The characteristics are shown in Table 1.

[Preparation of resin fine particle dispersion 5]
120 parts by mass of a polyester diol having a number average molecular weight of about 2000 obtained from an equimolar mixture of propylene glycol, ethylene glycol, and butanediol with a 40:50:10 molar mixture of terephthalic acid and isophthalic acid 94 masses of dimethylolpropanoic acid Part 3- (2,3-dihydroxypropoxy) -1-propanesulfonic acid
8 parts by mass, 30 parts by mass of tolylene diisocyanate

The raw material was dissolved in 60 parts by mass of acetone and reacted at 67 ° C. for 1 hour.
Next, 271 parts by mass of isophorone diisocyanate was added, and the mixture was further reacted at 67 ° C. for 30 minutes and cooled.
After adding 100 parts by mass of acetone to the reaction product, 80 parts by mass of triethylamine was added and stirred.
The acetone solution was added dropwise to 1000 parts by mass of ion-exchanged water with stirring at 500 rpm to prepare a fine particle dispersion.
Then, an elongation solution was carried out by adding an aqueous solution in which 50 parts by mass of triethylamine was dissolved in 100 parts by mass of 10% aqueous ammonia and reacting at 50 ° C. for 8 hours. Further, ion-exchanged water was added until the solid content became 20% by mass to obtain a resin fine particle dispersion-5. The characteristics are shown in Table 1.

[Preparation of resin fine particle dispersion 6]
120 parts by mass of a polyester diol having a number average molecular weight of about 2000, obtained from an equimolar mixture of propylene glycol, ethylene glycol and butanediol in a 40:50:10 molar mixture with terephthalic acid and isophthalic acid. 8 parts by mass of propylene glycol -94 parts by mass of dimethylolpropanoic acid-3- (2,3-dihydroxypropoxy) -1-propanesulfonic acid
8 parts by mass-39 parts by mass of isophorone diisocyanate

The raw material was dissolved in 60 parts by mass of acetone and reacted at 67 ° C. for 1 hour.
Next, 271 parts by mass of isophorone diisocyanate was added, and the mixture was further reacted at 67 ° C. for 30 minutes and cooled.
The acetone solution was added dropwise to 1000 parts by mass of ion-exchanged water with stirring at 500 rpm to prepare a fine particle dispersion.
After adding 100 parts by mass of acetone to the reaction product, 80 parts by mass of triethylamine was added and stirred.
Then, an elongation solution was carried out by adding an aqueous solution in which 50 parts by mass of triethylamine was dissolved in 100 parts by mass of 10% aqueous ammonia and reacting at 50 ° C. for 8 hours. Further, ion exchange water was added until the solid content became 20% by mass to obtain a resin fine particle dispersion-6. The characteristics are shown in Table 1.

<Preparation of polyester resin solution-1>
The following was put into a reaction vessel equipped with a cooling tube, a nitrogen introducing tube and a stirrer.
・ 928 parts by mass of 1,4-butanediol, 776 parts by mass of dimethyl terephthalate, 292 parts by mass of 1,6-hexanedioic acid, 3 parts by mass of tetrabutoxy titanate (condensation catalyst), and methanol produced at 160 ° C. under a nitrogen stream. Was allowed to react for 8 hours while distilling off. Next, while gradually raising the temperature to 210 ° 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. Next, the mixture was cooled to 160 ° C., 173 parts by weight of trimellitic anhydride and 125 parts by weight of 1,3-propanedioic acid were added, reacted for 2 hours under normal pressure sealing, and then reacted at 200 ° C. and normal pressure, and the softening point was 170 ° C. When it became, it took out. The taken-out resin was cooled to room temperature and then pulverized and granulated to obtain polyester-1, which is a non-linear polyester resin. Polyester-1 had a Tg of 53 ° C. and an acid value of 25 mgKOH / g.

<Preparation of polyester resin solution-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 mass of terephthalic acid, 1 part by mass of trimellitic anhydride, 3 parts by mass of fumaric acid, 12 parts by mass of dodecenyl succinic acid, 0.1 part by mass 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 215 ° C. for 5 hours to obtain polyester-2 (Tg 62 ° C., acid value 6 mgKOH / g).

<Preparation of polyester resin solution-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 Methanol produced under nitrogen flow at 180 ° C Was allowed to react for 8 hours while distilling off. 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. Next, the mixture was cooled to 180 ° C., 173 parts by mass of trimellitic anhydride was added, reacted for 2 hours under sealed at normal pressure, reacted at 220 ° C. normal pressure, and taken out when the softening point reached 180 ° C. 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 62 ° C. and an acid value of 2 mgKOH / g.

<Preparation of polyester resin solution-4>
The following was put into a reaction vessel equipped with a cooling tube, a nitrogen introducing tube and a stirrer.
-1,3-butanediol 1036 parts by mass-terephthalic acid dimethyl ester 892 parts by mass-1,6-hexanedioic acid 205 parts by mass-tetrabutoxy titanate (condensation catalyst) 3 parts by mass Methanol produced in a nitrogen stream at 180 ° C Was allowed to react for 8 hours while distilling off. Next, while gradually raising the temperature to 230 ° C., the reaction was performed for 4 hours while distilling off the produced propylene glycol and water in a nitrogen stream, and further the reaction was performed under a reduced pressure of 20 mmHg, and the softening point was 150 ° C. Removed at the time. The resin taken out is cooled to room temperature, then pulverized and granulated,
Polyester-4 which is a linear polyester resin was obtained. Polyester-4 had a Tg of 38 ° C. and an acid value of 15 mgKOH / g.

<Preparation of polyester resin solution-5>
The following was put into a reaction vessel equipped with a cooling tube, a nitrogen introducing tube and a stirrer.
-1,2 propanediol 858 parts by mass-terephthalic acid dimethyl ester 873 parts by mass-1,6-hexanedioic acid 219 parts by mass-tetrabutoxy titanate (condensation catalyst) 3 parts by mass Methanol produced at 180 ° C under a nitrogen stream The reaction was allowed to proceed for 8 hours while distilling off. Next, while gradually raising the temperature to 230 ° C., the reaction was performed for 4 hours while distilling off the produced propylene glycol and water in a nitrogen stream, and further the reaction was performed under a reduced pressure of 20 mmHg, and the softening point was 150 ° C. Removed at the time. The resin taken out was cooled to room temperature and then pulverized and granulated to obtain polyester-5, which is a linear polyester resin. Polyester-5 had a Tg of 44 ° C. and an acid value of 13 mgKOH / g.

<Preparation of binder resin solution>
A polyester resin solution was prepared by putting ethyl acetate into an airtight container with stirring wings and stirring the resin powder at a rate of 100 rpm for 3 days at room temperature.
Table 2 shows the blending amounts of ethyl acetate and resin.

<Preparation of crystalline polyester dispersion-1>
・ 100 parts by mass of 1,6-hexanediol, 75 parts by mass of fumaric acid, 30 parts by mass of adipic acid, 0.1 part by mass of dibutyltin oxide, 0.05 part by mass of hydroquinone were placed in a 4-liter glass four-necked flask. The reaction was conducted at 160 ° C. for 5 hours in a nitrogen atmosphere, and then the temperature was raised to 200 ° C. for 1 hour. Furthermore, the reaction proceeded at 8 kPa. To 100 parts by mass of the cooled and taken out resin, 400 parts by mass of toluene was mixed and heated to 80 ° C. to dissolve the resin. 3 parts by mass of triethylamine was added to the cooled resin solution.
Next, 40 parts by mass of 48.5% aqueous solution of sodium dodecyl diphenyl ether disulfonate (“Eleminol MON-7”, manufactured by Sanyo Chemical Industries) is mixed with 360 parts by mass of ion-exchanged water, and the above resin solution is added and mixed and stirred. A milky white liquid was obtained. Toluene was removed under reduced pressure to obtain crystalline polyester dispersion-1 (a2-1). Table 3 shows the characteristics of the resin obtained by drying the crystalline polyester dispersion-1.

<Preparation of crystalline polyester dispersion-2>
Crystalline polyester dispersion-2 (a2-2) was prepared by preparing crystalline polyester dispersion-1 and reacting at 155 ° C. for 4 hours using the same raw materials. Table 3 shows the characteristics of the resin obtained by drying the crystalline polyester dispersion-2.

<Preparation of crystalline polyester dispersion-3>
A crystalline polyester dispersion-2 (a2-3) was prepared in the same manner as in the preparation of the crystalline polyester dispersion-1, except that the raw materials were blended as follows.
-100 parts by weight of 1,6-hexanediol-90 parts by weight of fumaric acid-25 parts by weight of adipic acid-0.1 part by weight of dibutyltin oxide-0.05 part by weight of hydroquinone This crystalline polyester dispersion-3 can be dried The properties of the resin obtained are shown in Table 3.

<Preparation of crystalline polyester dispersions-4 and 5>
Crystalline polyester dispersions-4 and 5 (a2-4, a2-5) were prepared from crystalline polyester dispersion-1 by adding a solvent from ion-exchanged water to ethyl acetate and ethanol. Table 3 shows the properties of the resins obtained by drying the polyester dispersions-4 and 5.

<Preparation of crystalline polyester dispersions-6 and 7>
Crystalline polyester dispersions-1 and 7 (a2-6, a2-7) were prepared using the same raw materials and reacted at 155 ° C for 5 hours and 165 ° C for 7 hours, respectively. ) Was prepared. Table 3 shows the properties of the resins obtained by drying the crystalline polyester dispersions-6 and 7.

<Preparation of crystalline polyester dispersion-8>
Crystalline polyester dispersion-8 (a2-8) was prepared in the same manner from the preparation of crystalline polyester dispersion-1, except that the raw materials were blended as follows.
-69 parts by weight of 1,4-butanediol-10 parts by weight of 1,6-hexanediol-75 parts by weight of fumaric acid-30 parts by weight of adipic acid-0.1 part by weight of dibutyltin oxide-0.05 part by weight of hydroquinone Table 3 shows the properties of the resin obtained by drying the conductive polyester dispersion-8.

<Preparation of wax dispersion-1>
・ Carnauba wax (melting point: 81 ° C.) 20 parts by mass ・ Ethyl acetate: 80 parts by mass Dissolved in.
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 a 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. The characteristics are shown in Table 4.

<Preparation of Wax Dispersion-2>
-Stearyl stearate (melting point 67 ° C) 16 parts by mass-Nitrile group-containing styrene acrylic resin (styrene 65 parts by mass, n-butyl acrylate 35 parts by mass, acrylonitrile 10 parts by mass, peak molecular weight 8500) 8 parts by mass-Ethyl acetate 76 parts by mass Part

The above was put into a glass beaker (made by IWAKI glass) having a stirring blade, and the inside of the system was heated to 65 ° C. to dissolve stearyl stearate in ethyl acetate.
Subsequently, the same operation as wax dispersion-1 was performed to obtain wax dispersion 2. 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 0.12 μm. The characteristics are shown in Table 4.

<Preparation of wax dispersion-3>
Trimethylolpropane tribehenate (melting point: 58 ° C.) 16 parts by mass Nitrile group-containing styrene acrylic resin (styrene 65 parts by mass, n-butyl acrylate 35 parts by mass, acrylonitrile 10 parts by mass, peak molecular weight 8500) 8 parts by mass 76 parts by mass of ethyl acetate

The above was put into a glass beaker (made by IWAKI glass) with a stirring blade, and the inside of the system was heated to 60 ° C. to dissolve trimethylolpropane tribehenate in ethyl acetate.
Subsequently, the same operation as wax dispersion-1 was performed to obtain wax dispersion 3. 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 0.18 μm. The characteristics are shown in Table 4.

<Preparation of Wax Dispersion-4>
Paraffin wax (melting point 74 ° C.) 16 parts by mass Nitrile group-containing styrene acrylic resin (styrene 65 parts by mass, n-butyl acrylate 35 parts by mass, acrylonitrile 10 parts by mass, peak molecular weight 8500) 8 parts by mass Ethyl acetate 76 parts by mass

The above was put into a glass beaker (made by IWAKI glass) with a stirring blade, and the inside of the system was heated to 70 ° C. to dissolve the paraffin wax in ethyl acetate.
Subsequently, the same operation as wax dispersion-1 was performed to obtain wax dispersion-4. 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. The characteristics are shown in Table 4.

<Preparation of Colorant Dispersion-1>
Copper phthalocyanine pigment C.I. I. Pigment Blue 15: 3 100 parts by mass, ethyl acetate 400 parts by mass, glass beads (1 mm) 500 parts by mass

The above substance was put into a heat-resistant glass container, dispersed for 5 hours with a paint shaker (manufactured by Toyo Seiki), glass beads were removed with a nylon mesh, and a colorant dispersion-1 was obtained.

<Preparation of Colorant Dispersion-2>
・ C. I. Pigment Red 122 100 parts by mass, ethyl acetate 400 parts by mass, glass beads (1 mm) 500 parts by mass

The above substance was put into a heat-resistant glass container, dispersed for 5 hours with a paint shaker (manufactured by Toyo Seiki), glass beads were removed with a nylon mesh, and a colorant dispersion-2 was obtained.

<Preparation of Colorant Dispersion-3>
・ C. I. Pigment Yellow 155 100 parts by mass, ethyl acetate 400 parts by mass, glass beads (1 mm) 500 parts by mass

The above substance was put into a heat-resistant glass container, dispersed for 5 hours with a paint shaker (manufactured by Toyo Seiki), and the glass beads were removed with a nylon mesh to obtain Colorant Dispersion-3.

<Preparation of Colorant Dispersion-4>
・ Carbon black (particle size 65 nm) 100 parts by mass ・ Ethyl acetate 400 parts by mass ・ Glass beads (1 mm) 500 parts by mass

The above substance was put into a heat-resistant glass container, dispersed for 5 hours with a paint shaker (manufactured by Toyo Seiki), glass beads were removed with a nylon mesh, and a colorant dispersion-4 was 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 a temperature of 60 ° C. to obtain spherical magnetic resin particles in which a magnetic material was dispersed.

As a coating material, a copolymer of methyl methacrylate having a methyl methacrylate and a perfluoroalkyl group (m = 7) (copolymerization ratio 8: 1 weight average molecular weight 45,000) was further 290 nm with respect to 100 parts by mass of the coating resin. 10 parts by mass of melamine particles, 6 parts by mass of carbon particles having a specific resistance of 1 × 10 ⁻² Ω · cm and 30 nm were added, and the mixture was dispersed with an ultrasonic disperser for 30 minutes. 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, crushed, classified by a 200-mesh sieve, a number average particle diameter of 33 μm, and 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 oil phase)
Wax dispersion-1 50 parts by weight Colorant dispersion-1 25 parts by weight Polyester resin solution-1 150 parts by weight Triethylamine 0.5 parts by weight Ethyl acetate 24.5 parts by weight

The above solution was put into a container, and oil phase 1 was prepared by stirring and dispersing at 1500 rpm for 10 minutes with a homodisper (manufactured by Tokushu Kika Kogyo Co., Ltd.).

(Preparation of aqueous phase)
The following was put into a container, and stirred at 5000 rpm for 1 minute with a TK homomixer (manufactured by Tokushu Kika Co., Ltd.) to prepare an aqueous phase.
・ Ion-exchanged water 255 parts by mass ・ Resin fine particle dispersion 1 25 parts by mass (preparing 5 parts by mass of resin fine particles with respect to 100 parts by mass of toner particles)
-50% aqueous solution of sodium dodecyl diphenyl ether disulfonate (Eleminol MON-7, manufactured by Sanyo Chemical Industries) 25 parts by mass-30 parts by mass of ethyl acetate

(Emulsification and solvent removal process)
Prepare 50 parts by mass of crystalline polyester dispersion-1 (a2-1: solid content 20%), mix with oil phase 1 above, and rotate for 1 minute at 8000 rpm with TK homomixer (manufactured by Tokushu Kika). did.
Next, the mixture was put into the aqueous phase, and stirring was continued for 3 minutes with a TK homomixer at a rotational speed of up to 8000 rpm, whereby the oil phase 1 was suspended.
Next, a stirring blade was set in the container, and 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 to drying process)
Next, the toner particle aqueous dispersion was filtered and reslurried in 500 parts by mass of ion-exchanged water, and the system was stirred until hydrochloric acid was added to 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.
Next, 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 mesh to obtain toner particles 1.

(Toner preparation)
Next, 0.7 parts by mass of hydrophobic silica having an average diameter of 20 nm and 0.8 parts by mass of monodispersed silica having an average diameter of 120 nm are added to Henschel mixer (Mitsui Miike Chemical Co., Ltd.) with respect to 100 parts by mass of the toner particles 1. The toner 1 was obtained by mixing with FM-10B.
Table 5 shows the component composition ratio of the toner, Table 6 shows the toner characteristics, and Table 7 shows the electrophotographic characteristics.

<Examples 2 and 3>
As shown in Table 5, toners 2 and 3 were obtained in the same manner as in Example 1 except that the resin fine particle dispersions 2 and 3 (b-2 and b-3) were changed. Table 6 shows the toner characteristics and Table 7 shows the electrophotographic characteristics.
Shown in

<Comparative Example 1>
As shown in Table 5, a toner 4 was obtained in the same manner as in Example 1 except that the oil phase 2 in which the resin was changed to polyester-2 was used. The toner characteristics are shown in Table 6, and the electrophotographic characteristics are shown in Table 7.

<Comparative example 2>
As shown in Table 5, a toner was prepared without adding crystalline polyester.

(Preparation of oil phase)
Wax dispersion-1 50 parts by weight Colorant dispersion-1 25 parts by weight Polyester resin solution-1 170 parts by weight Triethylamine 0.52 parts by weight Ethyl acetate 24.5 parts by weight

The above solution was put into a container, and oil phase 3 was prepared by stirring and dispersing at 1500 rpm for 10 minutes using a homodisper (manufactured by Tokushu Kika Kogyo Co., Ltd.).

(Preparation of aqueous phase)
The following was put into a container, and stirred at 5000 rpm for 1 minute with a TK homomixer (manufactured by Tokushu Kika Co., Ltd.) to prepare an aqueous phase.
・ Ion-exchanged water 255 parts by mass-Resin fine particle dispersion-1 25 parts by mass (preparing 5 parts by mass of resin fine particles with respect to 100 parts by mass of toner particles)
-50% aqueous solution of sodium dodecyl diphenyl ether disulfonate (Eleminol MON-7, manufactured by Sanyo Chemical Industries) 25 parts by mass-30 parts by mass of ethyl acetate

(Emulsification and solvent removal process)
The oil phase 3 was charged into the aqueous phase, and stirring was continued for 3 minutes with a Tk homomixer (manufactured by Tokushu Kika Co., Ltd.) at a rotational speed of up to 8000 rpm to suspend the oil phase.
Subsequent steps were carried out in the same manner as in Example 1 to obtain toner 5. The toner characteristics are shown in Table 6, and the electrophotographic characteristics are shown in Table 7.

<Comparative Examples 3 and 4>
As shown in Table 5, toners 6 and 7 were obtained in the same manner as in Example 1 except that the formulation in the aqueous phase was changed and the amount of the resin b was adjusted. The formulation of the aqueous phase is shown below.

(Preparation of aqueous phase of Comparative Example 3)
The following was put into a container, and stirred at 5000 rpm for 1 minute with a TK homomixer (manufactured by Tokushu Kika Co., Ltd.) to prepare an aqueous phase.
・ Ion-exchanged water 272.5 parts by mass ・ Resin fine particle dispersion 1 7.5 parts by mass (preparing 1.5 parts by mass of resin fine particles to 100 parts by mass of toner particles)
-50% aqueous solution of sodium dodecyl diphenyl ether disulfonate (Eleminol MON-7, manufactured by Sanyo Chemical Industries) 25 parts by mass-30 parts by mass of ethyl acetate

(Preparation of aqueous phase of Comparative Example 4)
The following was put into a container, and stirred at 5000 rpm for 1 minute with a TK homomixer (manufactured by Tokushu Kika Co., Ltd.) to prepare an aqueous phase.
-195 parts by weight of ion-exchanged water-85 parts by weight of resin fine particle dispersion 1 (preparing 17 parts by weight of resin fine particles with respect to 100 parts by weight of toner particles)
-50% aqueous solution of sodium dodecyl diphenyl ether disulfonate (Eleminol MON-7, manufactured by Sanyo Chemical Industries) 25 parts by mass-30 parts by mass of ethyl acetate

The toner characteristics are shown in Table 6, and the electrophotographic characteristics are shown in Table 7.

<Comparative Examples 5 and 6>
As shown in Table 5, toners 8 and 9 were prepared in the same manner as in Example 1 except that crystalline polyester dispersion-2 (a2-2) and crystalline polyester dispersion-3 (a2-3) were used. Got. The toner characteristics are shown in Table 6, and the electrophotographic characteristics are shown in Table 7.

< Reference Example 1 >
(Preparation of oil phase)
Wax dispersion-1 50 parts by weight Colorant dispersion-1 25 parts by weight Polyester resin solution-1 140 parts by weight Triethylamine 0.5 parts by weight Ethyl acetate 24.5 parts by weight

The above solution was put into a container, and the oil phase 4 was prepared by stirring and dispersing at 1500 rpm for 10 minutes with a homodisper (manufactured by Tokushu Kika Kogyo Co., Ltd.).
65 parts by mass of crystalline polyester dispersion-4 (a2-4: solid content 20%) was prepared, mixed with the oil phase 1 used in Example 1, and TK homomixer (manufactured by Tokushu Kika Co., Ltd.). Rotated at 8000 rpm for 1 minute.
Next, the mixture was put into the aqueous phase used in Example 1, and stirring was continued for 3 minutes with a Tk homomixer at a rotational speed of up to 8000 rpm to suspend the oil phase.
Next, a stirring blade was set in the container, and 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. .
The steps after washing were performed in the same manner as in Example 1 to obtain toner 10. The toner characteristics are shown in Table 6, and the electrophotographic characteristics are shown in Table 7.

< Reference Example 2 >
Prepare 65 parts by mass of crystalline polyester dispersion-5 (a2-5: solid content 20%), mix with oil phase 1 used in Example 1, and use TK homomixer (manufactured by Koki Co., Ltd.). It rotated for 1 minute at 8000 rpm.
Next, the mixture was put into the aqueous phase used in Example 1, and stirring was continued for 3 minutes with a Tk homomixer at a rotational speed of up to 8000 rpm to suspend the oil phase.
Next, a stirring blade was set in the container, and 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. .
The steps after washing were performed in the same manner as in Example 1 to obtain toner 11. The toner characteristics are shown in Table 6, and the electrophotographic characteristics are shown in Table 7.

<Example 6>
As shown in Table 5, a toner 12 was obtained in the same manner as in Example 1 except that the resin fine particle dispersion was changed to b-4 and the addition amount of each raw material was adjusted. The toner characteristics are shown in Table 6, and the electrophotographic characteristics are shown in Table 7.

<Examples 7 and 8>
As shown in Table 5, toners 13 and 14 were obtained in the same manner as in Example 1 except that the formulation in the aqueous phase was changed and the amount of the resin b was adjusted. The formulation of the aqueous phase is shown below.

(Preparation of aqueous phase of Example 7)
The following was put into a container, and stirred at 5000 rpm for 1 minute with a TK homomixer (manufactured by Tokushu Kika Co., Ltd.) to prepare an aqueous phase.
-Ion-exchanged water 268.5 parts by mass-Resin fine particle dispersion-1 11.5 parts by mass (preparing 2.3 parts by mass of resin fine particles with respect to 100 parts by mass of toner particles)
-50% aqueous solution of sodium dodecyl diphenyl ether disulfonate (Eleminol MON-7, manufactured by Sanyo Chemical Industries) 25 parts by mass-30 parts by mass of ethyl acetate

(Preparation of aqueous phase of Example 8)
The following was put into a container, and stirred at 5000 rpm for 1 minute with a TK homomixer (manufactured by Tokushu Kika Co., Ltd.) to prepare an aqueous phase.
-215 parts by mass of ion-exchanged water-65 parts by mass of resin fine particle dispersion 1 (preparing 13.0 parts by mass of resin fine particles with respect to 100 parts by mass of toner particles)
-50% aqueous solution of sodium dodecyl diphenyl ether disulfonate (Eleminol MON-7, manufactured by Sanyo Chemical Industries) 25 parts by mass-30 parts by mass of ethyl acetate

The toner characteristics are shown in Table 6, and the electrophotographic characteristics are shown in Table 7.

<Example 9>
Prepare 65 parts by mass of crystalline polyester dispersion-1 (a2-1: solid content 20%) and use 335 parts by mass of the aqueous phase and TK homomixer (manufactured by Special Machine Industries) used in Example 1 at 8000 rpm. And rotated for 1 minute.
Next, the oil phase 1 used in Example 1 was put into the mixed aqueous phase, and stirring was continued for 3 minutes with a Tk homomixer at a rotational speed of up to 8000 rpm to suspend the oil phase.
Next, a stirring blade was set in the container, and 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. .
The steps after washing were performed in the same manner as in Example 1 to obtain toner 15. Table 6 shows the characteristics of the toner.
Table 7 shows the electrophotographic characteristics.

<Examples 10, 11, and 12>
As shown in Table 5, the combination of wax and crystalline polyester (a2) was mixed with wax dispersion-2 (ester 1), crystalline polyester dispersion-6 (a2-6), and wax dispersion-3 (ester). -2) and crystalline polyester dispersion-7 (a2-7), wax dispersion-
Example 1 except that each was changed to a combination of 4 (paraffin-1) and crystalline polyester dispersion-8 (a2-8), 5 parts by weight of a wax dispersant was added, and the addition amount of each raw material was adjusted. In the same manner, toners 16, 17, and 18 were obtained. The toner characteristics are shown in Table 6, and the electrophotographic characteristics are shown in Table 7.

<Example 13>
As shown in Table 5, a toner 19 was obtained in the same manner as in Example 1 except that the addition amount of the crystalline polyester dispersion-1 (a2-1) was changed and the addition amount of each raw material was adjusted. . The toner characteristics are shown in Table 6, and the electrophotographic characteristics are shown in Table 7.

<Examples 14, 15, and 16>
As shown in Table 5, toners 20, 21, and 22 were obtained in the same manner as in Example 1 except that the colorant dispersions were changed to 2, 3, and 4 and the addition amount of each raw material was adjusted. The toner characteristics are shown in Table 6, and the electrophotographic characteristics are shown in Table 7.

FIG. 6 is a diagram illustrating viscoelastic characteristics of the toner of the present invention. It is a figure of the calculation method of Tg by a DSC curve. It is a flow curve figure based on the data from a flow tester. It is the schematic of the charge amount measuring apparatus in this invention.

Explanation of symbols

1 Suction machine (at least the part in contact with the measurement container 2 is an insulator)
2 Metal measuring container 3 500 mesh screen 4 Metal lid 5 Vacuum gauge 6 Air flow control valve 7 Suction port 8 Condenser 9 Electrometer

Claims (9)

Capsule type having a surface layer (B) containing at least resin (b) on the surface of toner base particles (A) containing at least binder resin (a), crystalline polyester (a2), colorant and wax A toner having toner particles,
The binder resin (a) is a resin mainly composed of a polyester resin (a1),
The crystalline polyester (a2) is contained in the toner base particles (A) in an amount of 3% by mass to 30% by mass,
The amount of the surface layer (B) is 1.0% by mass or more and 15.0% by mass or less based on the toner base particles (A).
In the measurement of the viscoelasticity of the toner, the common logarithm Log (G ′ (T) / (dN / m ² )) of the storage elastic modulus G ′ (T) (dN / m ² ) with respect to the temperature (T) is expressed as F (T). When the temperature is 50 ° C. or more and 150 ° C. or less, the temperature T ₀ that takes the minimum value of the rate of change dF (T) / dT with respect to the temperature exists in the temperature range of 60 ° C. or more and 100 ° C. or less, and the minimum value but rather smaller than -0.20 (℃ ^-1),
The toner particles include at least the binder resin (a), the colorant, and the wax in an aqueous medium in which the fine particles mainly containing the resin (b) and the crystalline polyester (a2) are dispersed. A toner obtained by dispersing a solution or dispersion obtained by dissolving or dispersing in an organic medium, removing the solvent from the obtained dispersion and drying . The storage elastic modulus ratio G ′ (T ₀ −2.5) / G ′ (T ₀ +2.5) at 2.5 ° C. before and after the temperature T ₀ is greater than 3.0. Item 2. The toner according to Item 1. The toner according to claim 1, wherein the toner has a storage elastic modulus G ′ (150) (dN / m ² ) at 150 ° C. of greater than 1 × 10 ³ dN / m ² . The toner according to any one of claims 1 to 3, wherein the polyester resin (a1) is a resin using an aliphatic dialcohol as a main component as an alcohol component . The toner according to claim 1, wherein the crystalline polyester (a2) has a melting point (Tm) of 60 ° C. or more and 100 ° C. or less. The toner according to any one of claims 1 to 5, wherein the crystalline polyester (a2) is contained in an amount of 5% by mass to 30% by mass with respect to the toner base particles (A). The toner according to any one of claims 1 to 6 before Bark fat (b) is characterized in that it is a compound formed by a urethane bond. It said surface layer containing the resin (b) (B), the toner according to any one of claims 1 to 7, characterized in that the number-average particle diameter is formed from 100nm or less of the resin fine particles over 30 nm. The toner according to any one of claims 1 to 8, wherein the crystalline polyester (a2) is formed of resin fine particles having a number average particle diameter of 30 nm to 300 nm dispersed in an aqueous medium.

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