JP2009015212A - Toner - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide toner comprising capsule-shaped toner particles and improved in low temperature fixing characteristics, developing characteristics, and transfer characteristics. <P>SOLUTION: This toner comprises capsule-shaped toner particles, in each of which a surface layer B containing a resin (b) is formed on the surface of a toner base particle A containing a binder resin (a), a coloring agent, and wax at least. The binder resin (a) principally consists of polyester. The resin (b) includes a reactant between a diol constituent and a diisocyanate constituent at least. A nitrogen content (n) by an X-ray photoelectron spectroscopy analysis (ESCA) of the toner particle surface is less than 7.0 atomic% and 2.0 atomic% and more. Average roughness Ra of the toner particle surface is less than 5.0 nm and 1.0 nm or more. Toner mean circularity of the toner particle measured by a flow type particle image measurement device is less than 1.000 and 0.970 or more. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an electrophotographic toner that can be used in a wide range of output devices such as copying machines, printers, facsimiles, and light printing systems using image forming methods such as electrophotography and electrostatic recording.

Conventionally, many methods are known as electrophotographic methods. Electrophotography generally uses a photoconductive substance, forms an electrical latent image on an image carrier (photoreceptor) by various means, and then develops the latent image with toner to make it visible. An image is formed and, if necessary, a toner image is transferred to a transfer material such as paper, and then the toner image is fixed on the transfer material by heat / pressure to obtain a copy.
As a method for visualizing an electric latent image, a magnetic two-component developing method comprising a magnetic toner and a carrier, a non-magnetic two-component developing method comprising a non-magnetic toner and a carrier, and a non-magnetic toner using external particles added only. In general, a magnetic one-component developing system and a magnetic one-component developing system using a magnetic toner are widely used.

In recent years, copying apparatuses using such an electrophotographic method have been strictly pursued to be smaller, lighter, faster, and more reliable. Moreover, it has begun to be used not only as a copier for office processing for copying original documents, but also for copying high-definition images such as digital printers or graphic designs for computer output.
Furthermore, in addition to the viewpoint of miniaturization, there is a user's desire to stably output a large number of high-quality images with better color reproducibility and higher quality than ever before for printed or copied materials. The current situation is strengthening. In order to realize these desires, it is necessary to clear various technical problems, and various toner manufacturing methods have been proposed accordingly.

One measure to improve image quality in electrophotography is that the toner particle size is generally reduced. However, the conventional pulverization method has a particle size due to problems with equipment and energy efficiency. Therefore, it is difficult to cope with further particle size reduction.
In addition, since the particle shape is irregular, the toner is further pulverized by stirring or contact stress in the developing device, and fine particles are generated or the fluidizing agent is embedded in the toner surface, so that the image quality is improved. The phenomenon of decreasing has occurred.
Furthermore, due to its shape, the fluidity as powder is poor, a large amount of fluidizing agent is required, and the filling rate into the toner bottle is low, which is an obstacle to downsizing.
Under such circumstances, since a toner shape closer to a spherical shape is being demanded, many toners obtained by a wet method such as a suspension polymerization method and an emulsion aggregation method are recently available in the market. Used.
In the suspension polymerization method, since droplets are formed in an aqueous system and toner particles are obtained by a polymerization reaction, it is possible to manufacture without requiring a great deal of energy for reducing the particle size. In addition, there is an advantage that it is easy to produce particles that are nearly spherical as compared with the toner of the pulverization method described above. In particular, making the toner spherical is suitable in terms of improving transfer characteristics and stabilizing charging characteristics, and has recently been established as an indispensable technique for creating full-color images.

On the other hand, energy saving is also considered as a major technical issue in electrophotographic devices, and the amount of heat applied to the fixing device has been greatly reduced, and the toner can be fixed with lower energy and low temperature fixability. Excellent properties are being demanded.
In general, for a toner obtained by the pulverization method described above, a polyester-based binder resin having a high sharp melt property is often used for general purposes. In the pulverization method, since a binder resin is heated and melted using a biaxial melt kneader or the like and a kneading step is performed together with other materials, any so-called thermoplastic resin can be used as a binder resin without any restrictions.
On the other hand, when a toner is obtained from a vinyl monomer by a suspension polymerization method or an emulsion aggregation method, toner particles close to a true sphere can be produced, but it is difficult to obtain a sharp melt property like a polyester resin. Therefore, it is difficult for the toner obtained by the suspension polymerization method to realize low-temperature fixability.

Therefore, as a wet method in which a sharp melt polyester resin can be used, a resin component is dissolved in an organic solvent that is immiscible with water, and this solution is dispersed in an aqueous phase to form oil droplets. A so-called “dissolution suspension method” for producing a spherical toner has been proposed (for example, Patent Document 1).
According to this method, it is possible to easily obtain a spherical polyester toner having a small particle diameter by using polyester having excellent low-temperature fixability as a binder resin.
In addition, in the dissolution suspension method as described above, for the purpose of further improving low-temperature fixability and heat-resistant storage stability, it is composed of one or more film-like shell layers made of polyurethane resin and a core layer made of resin. A method for preparing a core-shell type toner has been proposed. (For example, Patent Documents 2 and 3).
However, even if it is suitable for low-temperature fixability by using a sharp melt polyester resin in these wet methods, it is difficult to obtain a nearly spherical shape as much as the toner obtained by the above-mentioned polymerization method, and the transferability is improved. Moreover, it is in a situation where it has not reached a sufficiently satisfactory level in terms of stabilization of charging.

In such a core-shell type (capsule type) toner, it is considered that the material characteristics constituting the outermost shell (shell phase) of the toner greatly affect the fixing characteristics.
In particular, if the outermost shell cannot be formed with a uniform film thickness, the outer shell is easily affected by the resin characteristics used for the inner shell (core phase) and exhibits unstable fixing characteristics. On the other hand, even if the outermost shell is formed with a uniform film thickness, if it has uneven surface properties with many irregularities, the heat-resistant storage stability is weak, and the toner tends to clump on the block when left for a long time. In addition, charging performance caused by friction between toner particles tends to be unstable. Furthermore, when an additive such as inorganic fine particles is added to supplement the fluidity, the additive is concentrated in the concave portion, and the influence on the development surface that the desired fluidity becomes difficult to obtain is increased.
In terms of improving the chargeability of such a capsule-type toner, proposals have been made to define the amount of nitrogen that acts as a charged portion on the toner surface (for example, Patent Documents 4, 5, 6, and 7).
However, although the above proposal defines the amount of nitrogen on the toner surface, it is all derived from a colorant, and the amount of nitrogen calculated by X-ray photoelectron spectroscopy (ESCA) or the like is also 0.05 to 1.3 atomic. %. In the above proposal, the regulation of the amount of nitrogen calculates the ratio of the amount of nitrogen between the toner surface and the inside of the toner, and the relationship between the amount of nitrogen present on the toner surface and the charging characteristics is always described. It wasn't.
In the case of a toner made by a wet method as described above, the low-temperature fixability can be improved by using a polyester resin having a sharp melt property. Therefore, it is strongly desired that the toner be a capsule type with a smooth surface and close to a true sphere to further improve heat-resistant storage stability, developability and transferability.
JP 2006-154686 A JP 2006-206848 A JP 2006-226851 A JP 2001-117264 A JP 2003-295493 A JP 2004-139003 A Japanese Patent Laying-Open No. 2005-099846

  It is an object of the present invention to provide a toner having improved low-temperature fixability, developability, and transferability in the toner having the capsule-type toner particles.

The above object can be achieved by the following configuration.
That is, the present invention provides a capsule-type toner having a surface layer (B) containing a resin (b) on the surface of toner base particles (A) containing at least a binder resin (a), a colorant, and a wax. In the toner having particles, the binder resin (a) is a resin mainly composed of polyester, and the resin (b) is a resin containing at least a reaction product of a diol component and a diisocyanate component, The nitrogen amount (n) by X-ray photoelectron spectroscopy (ESCA) of the toner particle surface is 2.0 atomic% or more and less than 7.0 atomic%, and the average roughness (Ra) of the toner particle surface is 1.0 nm or more and 5 The toner is characterized by having an average circularity measured by a flow type particle image measuring apparatus for toner particles of 0.970 or more and less than 1.000. That.

  According to a preferred embodiment of the present invention, it is possible to achieve both low-temperature fixability and heat-resistant storage stability by obtaining a capsule-type toner having a surface layer on the surface of the toner base particles by a dissolution suspension method. Further, according to a preferred embodiment of the present invention, a toner image having a uniform surface property and a toner having a high average circularity is provided together to provide a visible image excellent in developability and transferability. It was.

Hereinafter, the present invention will be described in more detail with reference to preferred embodiments of the present invention.
The toner of the present invention is a capsule-type toner having a surface layer (B) containing a resin (b) on the surface of toner base particles (A) containing at least a binder resin (a), a colorant, and a wax. A toner having particles, wherein the binder resin (a) is a resin mainly composed of polyester, and the resin (b) is a resin containing at least a reaction product of a diol component and a diisocyanate component, and toner particles The nitrogen amount (n) by surface X-ray photoelectron spectroscopy (ESCA) is 2.0 atomic% or more and less than 7.0 atomic%, and the average roughness (Ra) of the toner particle surface is 1.0 nm or more and less than 5.0 nm. The average circularity measured by the flow type particle image measuring device for toner particles is 0.970 or more and less than 1.000.

The amount of nitrogen (n) by X-ray photoelectron spectroscopy (ESCA) on the surface of the toner particles used in the toner of the present invention is 2.0 atomic% or more and less than 7.0 atomic%. Preferably they are 2.5 atomic% or more and less than 7.0 atomic%, More preferably, they are 2.5 atomic% or more and less than 6.5 atomic%.
By setting the amount of nitrogen on the toner particle surface measured by X-ray photoelectron spectroscopic analysis (hereinafter referred to as ESCA) to be 2.0 atomic% or more and less than 7.0 atomic%, the toner of the present invention has only fixability. Therefore, it is possible to achieve stabilization of heat resistant storage stability and triboelectric chargeability. In particular, the presence of concentrated nitrogen-containing groups having a high charge-providing property on the surface of the toner particles dramatically improves the frictional charging performance between the toner particles and makes the toner particles more stable.
When the nitrogen amount is less than 2.0 atomic%, it becomes difficult to form the capsule toner in the present invention. Therefore, the toner particles are likely to coalesce in a high temperature and high humidity environment (for example, 30 ° C./80% RH) or for a long period of storage, and image defects such as a decrease in developability and white spots on the image are likely to occur. In addition, the toner particles are likely to be charged up, resulting in a decrease in the density of the resulting visible image, and the result that the image quality such as image unevenness in the halftone portion is significantly impaired.
On the other hand, when the nitrogen amount is 7.0 atomic% or more, the charge amount is likely to be lowered, and thus, a phenomenon such as fogging in a non-image area and toner dropping from a developing device is likely to occur. Further, since the hardness (melting characteristics) of the resin (b) increases, there is a concern that low temperature offset is likely to occur when using an on-demand fixing machine or a high-speed fixing machine.

The average roughness (Ra) of the toner particle surface used in the toner of the present invention is 1.0 nm or more and less than 5.0 nm, preferably 1.5 nm or more and less than 4.5 nm, more preferably 1. 5 nm or more and less than 4.0 nm.
The
The average circularity of the toner particles used in the toner of the present invention measured by a flow type particle image measuring device is 0.960 or more and less than 1.000, preferably 0.965 or more and less than 0.990. More preferably, it is 0.965 or more and less than 0.985.
The average roughness and average circularity of the toner particle surface are important for further improving developability and transferability. In particular, in the above-mentioned capsule-type toner particles, the average roughness and the average circularity improve the developability and transferability without impairing the charging characteristics obtained by defining the amount of nitrogen on the surface of the toner particles. Is important.

By smoothing the average roughness (Ra) of the toner particle surface in the range of 1 nm or more and less than 5 nm, the contact opportunities between the toner particles can be equalized. Even when inorganic fine particles are added to the toner particles, they are not embedded in the recesses, etc., so that the functionality of the external additive itself (fluidity, charge imparting properties, etc.) is not lost, and it can be demonstrated. easy.
If the average roughness (Ra) of the toner particle surface is 5 nm or more, the surface layer (B) may be peeled off from the stress received by the stirring member in the developing machine, thereby fusing or contaminating the photosensitive member. May occur. Moreover, since the thickness of the surface layer tends to be disturbed, the storage stability tends to deteriorate. Furthermore, external additive fine particles and the like as auxiliary agents are easily embedded in the recesses formed on the toner particle surfaces, and it is difficult to obtain desired charging characteristics and fluidity.
On the other hand, if the average roughness (Ra) of the toner particle surface is less than 1 nm, the unevenness of the toner particles is too small, and the cleaning performance such as turning over of the cleaning blade and passing through of the toner is remarkably lowered.
Examples of means for smoothing the average roughness (Ra) of the toner particle surface in the range of 1 nm or more and less than 5 nm include controlling the contents of a diol component and a diisocyanate component described later. It is also a feature of the present invention that the surface property of the surface layer (B) can be controlled by controlling the content ratio of the diol component and the diisocyanate component, which are components of the resin (b).
On the other hand, it is also possible to obtain the desired surface properties according to the present invention by heat-treating the emulsified dispersion after granulation at an arbitrary temperature.

By increasing the average circularity in the range of 0.970 or more and less than 1.000, the number of contact points between the toner particles is reduced, the release effect is enhanced, and the charge imparting ability is high in the range of the nitrogen amount. Even in such a case, it is possible to always provide high transfer characteristics because toner separation can be provided stably.
If the circularity of the toner particles is less than 0.970, not only the contact characteristics between the toner particles are increased, but the transfer characteristics are deteriorated, and the external additive fine particles are embedded in the recesses as in the average roughness of the toner particles. As a result, it becomes difficult to obtain desired charging characteristics and fluidity.

In order to achieve a nitrogen amount (n) by ESCA on the toner particle surface of 2.0 atomic% or more and less than 7.0 atomic%, the surface layer (B) is 1.0% of the toner base particles (A). It is preferable that it is more than mass% and less than 15.0 mass%. The amount of nitrogen is the amount of nitrogen on the surface of the toner particles, and it is considered that the amount of nitrogen greatly depends on the ratio of the surface layer (B).
When the ratio of the surface layer (B) is smaller than 1.0% by mass, the shape of the capsule is insufficient, and the above-described problems are likely to occur. On the other hand, when the ratio of the surface layer (B) is 15.0% by mass or more, the properties of the surface layer (B) are strongly reflected even at the time of fixing, and it is difficult to exhibit the characteristics of the core. Further, since toner particles are likely to be united and integrated, there is a possibility that the scattering of toner particles, the dropping of a button, and the like may be worsened.
In order to fully exhibit the effects of the present invention, the surface layer (B) is preferably 2.0% by mass or more and less than 12.0% by mass with respect to the toner base particles (A). More preferably, it is more than mass% and less than 10.0 mass%.

Furthermore, as a means for achieving the nitrogen content, it is preferable that the content of the diisocyanate component in the resin (b) is in the range of 20.0 mass% or more and less than 40.0 mass%.
The amount of nitrogen (n) by ESCA on the surface of the toner particles depends mainly on the content of the nitrogen component in the surface layer (B) of the toner particles. Therefore, the content of the diisocyanate component in the resin (b) constituting the surface layer (B) is particularly important.
If the content of the diisocyanate component is less than 20% by mass, the nitrogen amount (n) is likely to be less than 2.0 atomic%, which greatly affects the granulation properties of the toner particles. That is, the granulating property is remarkably deteriorated, and the developability is likely to be deteriorated due to generation of coarse powder, coalescence of fine particles, or the like. Furthermore, there is a possibility that the average circularity and surface properties of the toner particles may be rapidly deteriorated. In the development process, after adding inorganic fine particles for the purpose of imparting charge or fluidity to the toner particles, the toner surface There is a concern about durability problems due to burying or liberation of external additives in
On the other hand, when the content of the diisocyanate component is 40% by mass or more, the nitrogen amount (n) is likely to be 7.0 atomic% or more. In this case, the average circularity and the surface texture can be maintained in a relatively good state, but the charge amount is likely to be rapidly reduced, and adverse effects such as toner scattering to the image portion and dropping of the image are likely to occur.
In general, the toner tends to be hard due to an increase in the diisocyanate component. As a result, the melting characteristics of the surface layer (B) are increased, and this tends to cause a low temperature offset.
In order to exert the effects in the present invention, the content of the diisocyanate component in the resin (b) is preferably 23% by mass or more and less than 38% by mass, more preferably 25% by mass or more and less than 35% by mass. .

The diol component in the resin (b) preferably contains at least an aliphatic diol component, and the content of the aliphatic diol component is preferably 20% by mass or more based on the total diol component. The content is preferably 25% by mass or more, more preferably 30% by mass or more.
This makes it possible to achieve the average roughness (Ra) of the toner particle surface of 1 nm or more and less than 5 nm and the average circularity of the toner particles of 0.970 or more and less than 1.000.
In particular, since the diol component constituting the polyester of the binder resin (a) and the diol component in the resin (b) both contain an aliphatic diol, the binder resin (a) and the resin (b) The affinity is increased, and the surface smoothness of the toner particles can be increased. Furthermore, since the adhesion between the surface layer (B) and the toner base particles (A) is increased and stable capsule-type toner can be formed, the circularity per toner particle tends to be increased.

Next, the structure of the surface layer (B) used for this invention is demonstrated.
The surface layer (B) contains the resin (b). The resin (b) is a resin having a moderate affinity for a solvent and containing at least a reaction product of a diol component and a diisocyanate component in view of water dispersibility, adjustment of viscosity, ease of alignment of particle diameter, and the like. The resin (b) is preferably a resin containing a reaction product in which a diol component and a diisocyanate component are formed by urethane bonds. The resin (b) particularly preferably contains a polyurethane resin having polyester as a constituent element.

As a diol component used for the said resin (b), the following are mentioned, for example.
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.);
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.);
Alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adducts of the above alicyclic diols; and polylactone diols (poly ε-caprolactone diol, etc.), polybutadiene diols, etc.
The alkyl part of the above-described alkylene glycol may be linear or branched. In the present invention, an alkylene glycol having a branched structure can also be preferably used. Among these, an alkyl structure is preferable in view of solubility (affinity) in ethyl acetate, and an alkylene glycol having 2 to 12 carbon atoms is preferably used.

Moreover, it is preferable that the said diol component contains the diol component which has a carboxylic acid group or a sulfonic acid group in a side chain.
Examples of the diol component having a carboxylic acid group in the side chain include dihydroxylcarboxylic acids such as dimethylolacetic acid, dimethylolpropionic acid, dimethylolbutanoic acid, dimethylolbutyric acid, and dimethylolpentanoic acid, and metal salts thereof.
Examples of the diol component having a sulfonic acid group in the side chain include sulfoisophthalic acid, 3- (2,3-dihydroxypropoxy) -1-propanesulfonic acid, N, N-bis (2-hydroxyethyl) -2-aminoethanesulfone. Examples thereof include acids and metal salts thereof.
Diols having a carboxylic acid group, a sulfonic acid group, a salt of a carboxylic acid group or a salt structure of a sulfonic acid group in the side chain as described above are 10 mol% or more of monomers forming a reaction product of a diol component and a diisocyanate component. It is preferably contained in an amount of 50 mol% or less, more preferably 20 mol% or more and 30 mol% or less.
When the amount of the diol is less than 10 mol%, the dispersibility of the fine particles is deteriorated and the granulation property may be remarkably impaired. On the other hand, when it is more than 50 mol%, the reaction product of the diol component and the diisocyanate component may be dissolved in the aqueous medium depending on the case, so that a sufficient function as a dispersant may be achieved.

In the present invention, a polyester having a hydroxyl group at the end can also be used as a suitable diol component.
At this time, the molecular weight (number average molecular weight) of the polyester whose terminal is a hydroxyl group is 3000 or less, more preferably 2000 or less.
When the molecular weight of the polyester is increased more than the above, problems such as poor reactivity with the isocyanate-terminated compound and excessively strong polyester properties become soluble in ethyl acetate.
The polyester described above is 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%. Is preferred.
When the terminal polyester is more than 10 mol%, the reaction product of the diol component and the diisocyanate component may become soluble in ethyl acetate.
On the other hand, if the polyester content is less than 1 mol%, the reaction product of the diol component and the diisocyanate component becomes too hard and the fixing property is hindered, or the affinity with the binder resin is lowered and the surface layer becomes It may be difficult to form.

  Furthermore, when the affinity between the resin (b) and the binder resin (a) is increased and the adhesion between the surface layer (B) and the toner base particles (A) is considered, the above-mentioned polyester having a terminal hydroxyl group is ethylene. It may have an ether bond modified with oxide, propylene oxide or the like.

On the other hand, as a diisocyanate component used for resin (b), the following are mentioned, for example.
Carbon number (excluding carbon in NCO group, the same shall apply hereinafter) 6 to 20 aromatic diisocyanate, C2 to C18 aliphatic diisocyanate, C4 to C15 alicyclic diisocyanate, C8 to C15 aroma Hydrocarbon diisocyanates and modified products of these diisocyanates (urethane groups, carbodiimide groups, allophanate groups, urea groups, burette groups, uretdione groups, uretoimine groups, isocyanurate groups, oxazolidone group-containing modified products), and these 2 A mixture of more than seeds.

Specific examples of the aromatic diisocyanate include the following.
1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 1,5-naphthylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate (TDI), crude tolylene diisocyanate, 2,4 ′ -Diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI), crude MDI [crude diaminophenylmethane [condensation product of formaldehyde and aromatic amine (aniline) or a mixture thereof] and the like].

Specific examples of the aliphatic diisocyanate include the following.
Ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 1,6,11-undecane triisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanatomethyl carbonate Aliphatic isocyanates such as proate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate, 2-isocyanatoethyl-2,6-diisocyanatohexanoate;

Specific examples of the alicyclic diisocyanate include the following.
Isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4′-diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), bis (2-isocyanatoethyl) -4-cyclohexene-1, 2-dicarboxylate, 2,5-norbornane diisocyanate, 2,6-norbornane diisocyanate.

Specific examples of the aromatic hydrocarbon diisocyanate include the following.
m-xylylene diisocyanate, p-xylylene diisocyanate (XDI), α, α, α ′, α′-tetramethylxylylene diisocyanate (TMXDI).

Examples of the modified diisocyanate include urethane group, carbodiimide group, allophanate group, urea group, burette group, uretdione group, uretoimine group, isocyanurate group, and oxazolidone group-containing modified product.
Specifically, 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 of these [for example, modified MDI and urethane-modified TDI ( In combination with an isocyanate-containing prepolymer). Among these, preferred are 6-15 aromatic diisocyanates, aliphatic diisocyanates having 4-12 carbon atoms, and alicyclic diisocyanates having 4-15 carbon atoms, and particularly preferred are TDI, MDI, HDI, water. Attached MDI and IPDI.

  Furthermore, in the present invention, in addition to the diisocyanate component described above, a trifunctional or higher functional isocyanate compound can also be used. Examples of the trifunctional or higher functional isocyanate compound include polyallyl polyisocyanate (PAPI), 4,4 ′, 4 ″ -triphenylmethane triisocyanate, m-isocyanatophenylsulfonyl isocyanate, and p-isocyanatophenylsulfonyl isocyanate. Is mentioned.

The resin (b) can be used in combination with a reaction product of an amino compound and an isocyanate compound, that is, a compound having a so-called urea bond, in addition to the resin composed of a reaction product of the diol component and the diisocyanate component.
Examples of amines that can be used in the present invention include diamine, 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, triamine, triethylamine, diethylenetriamine and 1,8-diamino-4-amino Methyl octane.
Furthermore, some resins such as vinyl resins and epoxy resins may be used in combination.

In the present invention, in order to achieve a toner that can be fixed at a low temperature or light pressure, the binder resin (a) is a resin mainly composed of polyester. Here, the main component means that the polyester occupies 50% by mass or more with respect to the total amount of the binder resin.
This is because the sharp melt property of polyester is suitable for low-temperature fixability, and when applied to a color toner, it is possible to exhibit excellent color mixing properties.

The following are mentioned as a monomer component which comprises the said polyester.
As an alcohol component, Preferably it is C2-C8, More preferably, C2-C6 aliphatic alcohol is mentioned.
Examples of the aliphatic alcohol having 2 to 8 carbon atoms include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, Preferred examples include linear diols such as neopentyl glycol, 1,4-butenediol, 1,7-heptanediol, and 1,8-octanediol.

On the other hand, carboxylic acid components include aromatic polycarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, fumaric acid, maleic acid, adipic acid, succinic acid, dodecenyl succinic acid, octenyl succinic acid. Aliphatic polycarboxylic acids such as succinic acid substituted with an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms, anhydrides of these acids, and alkyls of these acids (1 carbon atom) -8) Esters and the like.
The carboxylic acid component preferably contains an aromatic polyvalent carboxylic acid compound from the viewpoint of chargeability, and the content thereof is preferably 30 to 100 mol%, and 50 to 100 mol% in the carboxylic acid component. Is more preferable.
The raw material monomer may contain a trihydric or higher polyhydric alcohol and / or a trivalent or higher polyvalent carboxylic acid compound.

Furthermore, in this invention, it is preferable that 50 mass% or more in all the diol components which comprise polyester which is a main component of binder resin (a) is an aliphatic diol.
This is for the following reason.
(1) To make the average roughness (Ra) and average circularity of the toner particle surface suitable for the aliphatic diol in the above-mentioned resin (b).
(2) By using an aliphatic diol for the binder resin (a), the adhesion between the surface layer (B) and the toner base particles (A) is enhanced, and a more stable capsule-type toner configuration can be obtained. Because it becomes.
When the aliphatic diol is less than 50% by mass, the adhesion between the surface layer (B) and the toner base particles (A) is lowered, and the heat resistant storage stability tends to be lowered.
In order to further enhance the above effect in the present invention, the preferred amount of the aliphatic diol is 60% by mass or more, more preferably 70% by mass or more.

  Further, the binder resin (a) used in the toner of the present invention may contain a styrene-acrylic resin, a mixed resin of polyester and styrene acrylic, an epoxy resin, etc. in addition to the above-mentioned polyester as the main component.

The binder resin (a) preferably has a peak molecular weight measured by gel permeation chromatography (GPC) of 8000 or less, more preferably less than 5500.
Furthermore, the ratio of molecular weight of 100,000 or more is preferably 5.0% or less, more preferably 1.0% or less.
When the peak molecular weight is 8000 or more, or when the ratio of the molecular weight is 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%, from the standpoint of exhibiting sharp melt properties.
When adjusting the molecular weight of the toner as described above, a binder resin having two or more kinds of molecular weights may be mixed and used.

The toner base particles (A) used in the toner of the present invention contain a wax together with a binder resin and a colorant in order to further improve the fixability.
Examples of the wax used in the present invention include the following.
Low molecular weight polyethylene, low molecular weight polypropylene, low molecular weight olefin copolymer, aliphatic hydrocarbon wax such as microcrystalline wax, paraffin wax, Fischer-Tropsch wax; oxide of aliphatic hydrocarbon wax such as oxidized polyethylene wax; fat A wax mainly composed of a fatty acid ester such as an aromatic hydrocarbon ester wax; and a partially or fully deoxidized fatty acid ester such as a deoxidized carnauba wax; a partial ester of a fatty acid and a polyhydric alcohol such as behenic acid monoglyceride A methyl ester compound having a hydroxyl group obtained by hydrogenating vegetable oils and fats.

The wax particularly preferably used in the present invention is, 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 preferred.
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 linear saturated fatty acid and a long-chain linear saturated alcohol. The long-chain linear saturated fatty acid is represented by the general formula C _n H _{2n + 1} COOH, and those with n = about 5 to 28 are preferably used. The long-chain linear saturated alcohol is preferably represented by C _n H _{2n + 1} OH, where n = about 5 to 28.
Specific examples of the long-chain linear saturated fatty acid include capric acid, undecyl acid, lauric acid, tridecyl acid, myristic acid, palmitic acid, pentadecylic acid, heptadecanoic acid, tetradecanoic acid, stearic acid, nonadecanoic acid, aramonic acid, Examples include behenic acid, lignoceric acid, serotic acid, heptacosanoic acid, montanic acid, and melicic acid.
On the other hand, specific examples of the long-chain linear saturated alcohol include amyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, capryl alcohol, nonyl alcohol, decyl alcohol, undecyl alcohol, lauryl alcohol, tridecyl alcohol, and myristyl alcohol. Pentadecyl alcohol, cetyl alcohol, heptadecyl alcohol, stearyl alcohol, nonadecyl alcohol, eicosyl alcohol, seryl alcohol, heptadecanool and the like.
Examples of the ester wax having two or more ester bonds per molecule include, for example, trimethylolpropane tribehenate, pentaerythritol tetrabehenate, pentaerythritol diacetate dibehenate, glycerin tribehenate, Examples thereof include 18-octadecanediol-bis-stearate, polyalkanol esters (tristearyl trimellitic acid, distearyl maleate and the like.
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 dibehenylamide, etc.), polyalkylamides (trimellitic acid tristearylamide, etc.), dialkyl ketones (distearyl ketone), etc. It may be made.

Among the above, more preferable waxes are synthetic ester waxes composed of long-chain straight-chain fatty acids and long-chain straight-chain saturated alcohols, or natural waxes based on the above esters.
The reason for this is not clear, but it is thought that the mobility in the molten state is increased due to the wax having a linear structure. In other words, it is necessary for the wax to permeate into the toner surface layer through a relatively polar substance such as polyester as a binder resin or a reaction product of diol and diisocyanate on the surface layer at the time of fixing. Therefore, it seems that it is advantageous that the wax has a linear structure as much as possible in order to pass between such highly polar substances.

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

In the present invention, it is also one of preferable modes to use a hydrocarbon wax other than the ester wax as needed.
Examples of hydrocarbon waxes other than the ester wax include petroleum-based natural waxes such as paraffin wax, microcrystalline wax, petrolatum, and derivatives thereof, Fischer-Tropsch wax, polyolefin wax, and derivatives thereof (polyethylene wax, polypropylene wax, etc. ) And natural waxes such as ozokerite and ceresin.

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

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

Examples of the colorant used in the toner of the present invention include the following.
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 can be 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 can be 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. I. Acid Blue 45.
Examples of the dye include the following. C. I. Solvent Blue 25, 36, 60, 70, 93, 95. These can be used alone or in combination of two or more.

  The following are mentioned as a black pigment. Metal oxides such as furnace black, channel black, acetylene black, thermal black, lamp black and other carbon black, magnetite, ferrite.

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

In the present invention, a charge control agent can be used as necessary. The charge control agent may be contained in the toner base particles (A) or in the surface layer (B).
Examples of the charge control agent include the following. Nigrosine dyes, triphenylmethane dyes, metal-containing azo complex dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts (including fluorine-modified quaternary ammonium salts), alkylamides, simple substances of phosphorus Alternatively, a compound, a simple substance or compound of tungsten, a fluorine-based activator, a salicylic acid metal salt, and a salicylic acid derivative metal salt.
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

In the present invention, the toner preferably has a weight average particle diameter (D4) of 3.0 to 8.0 μm. When the toner is replaced in the developing device, the fluctuation of the particle size of the toner is reduced, and the contamination of the member such as the dropping of the toner from the development site is less likely to occur. This is because an image is easily obtained.
In general, it is said that high-resolution and high-quality images can be obtained as the toner particle size is smaller in order to improve the image quality of electrophotography. Tend to be disadvantageous in terms of image quality such as roughness.
In the toner having a capsule structure as in the present invention, when the weight average particle diameter of the toner is smaller than 3.0 μm, the toner filming on the developing sleeve or the like and the fusion of the toner to the peripheral member are performed. It becomes easy to generate. Furthermore, it becomes difficult to construct a capsule structure, and problems such as an increase in irregularly shaped toner particles and a sharp deterioration in heat-resistant storage stability are likely to occur.
In particular, when more so-called ultrafine toner of 0.6 to 2 μm is present, toner packing around the regulating member is likely to occur, and as a result, fusion is likely to occur.
On the other hand, when the weight average particle diameter (D4) of the toner is larger than 8.0 μm, the output of the line image or the like is likely to be scattered or dropped, and the fine line reproducibility is likely to be inferior. .

In the present invention, the following method can be suitably used as a method for easily preparing the toner particles.
That is, the toner particles are obtained by 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 containing the resin (b) are dispersed. The toner particles are preferably obtained by dispersing a product or dispersion, removing the solvent from the obtained dispersion, and drying. Moreover, it is preferable to contain a tertiary amine compound in the aqueous medium and / or the organic medium. In the above preparation method, it is aimed that the fine particles containing the resin (b) also function as a dispersant when suspending the liquid material of the toner composition. By adopting this preparation method, 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.

Solvents that can be used as an organic medium for dissolving the binder resin, etc., are hydrocarbon solvents such as ethyl acetate, xylene, hexane, halogenated hydrocarbon solvents such as methylene chloride, chloroform, dichloroethane, methyl acetate, ethyl acetate, Examples include ester solvents such as 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 wax and pigment are also preferably dispersed in an organic solvent. That is, a wax and a pigment that have been mechanically pulverized in advance by wet or dry method are dispersed in an organic solvent to prepare a wax dispersion and a pigment dispersion, respectively.
With regard to waxes and pigments, the dispersibility can also be improved by adding respective dispersants, resins, and the like. Since these differ depending on the wax, pigment, binder resin, and organic solvent used, it is preferable to select and use them appropriately.
These oil dispersions, wax dispersions, pigment dispersions, and organic media are blended in desired amounts and dispersed to produce an oil phase.

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 preferred method to mix an appropriate amount of the organic solvent used in the oil phase in the aqueous medium used in the present invention. This seems to have the effect of enhancing the droplet stability during granulation and making the oil phase more easily suspended in the aqueous medium.
Examples of the tertiary amine compound contained in the aqueous medium and / or the organic medium include triethylamine. By using the tertiary amine compound, it is possible to obtain the effect of improving the droplet stability during granulation. The content of the tertiary amine compound is preferably 0.5 to 0.8% by mass with respect to the solid content. The tertiary amine compound can be used alone or in combination of two or more.

  In the present invention, it is preferable to disperse the fine particles containing the resin (b) in an aqueous medium. The fine particles containing the resin (b) are used in a desired amount according to the stability of the oil phase in the next step and the encapsulation of the toner base particles (A).

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

Examples of the main surfactant include an anionic surfactant, a cationic surfactant, an amphoteric surfactant, and a nonionic surfactant. These can be arbitrarily selected according to the polarity at the time of toner particle formation.
Anionic surfactants such as alkylbenzene sulfonates, α-olefin sulfonates, phosphate esters; amine salt types such as alkylamine salts, aminoalcohol fatty acid derivatives, polyamine fatty acid derivatives, imidazolines, alkyltrimethylammonium salts, dialkyls Quaternary ammonium salt type cationic surfactants such as dimethylammonium salts, alkyldimethylbenzylammonium salts, pyridinium salts, alkylisoquinolinium salts, benzethonium chloride; nonionic surface actives such as fatty acid amide derivatives and polyhydric alcohol derivatives Agents: amphoteric surfactants such as alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine and N-alkyl-N, N-dimethylammonium betaine.

Examples of the dispersant include acids such as acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid or maleic anhydride, or acrylic acid β- Hydroxyethyl, β-hydroxyethyl methacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate, γ-hydroxypropyl acrylate, γ-hydroxypropyl methacrylate, 3-chloro-2-hydroxypropyl acrylate, 3-chloro-2-hydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerol monoacrylate, glycerol monomethacrylate, N-methylolacrylamide, (Meth) acrylic monomers containing hydroxyl groups such as N-methylolmethacrylamide; vinyl alcohol or ethers with vinyl alcohol such as vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether; vinyl acetate, propion Esters of compounds containing vinyl alcohol and a carboxyl group such as vinyl acid and vinyl butyrate; Acrylamide, methacrylamide, diacetone acrylamide or methylol compounds thereof; Acid chlorides such as acrylic acid chloride and methacrylic acid chloride; Vinyl pyridine , Homopolymers or copolymers having a nitrogen atom such as vinylpyrrolidone, vinylimidazole, ethyleneimine or the like, or heterocycles thereof; 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. Polyoxyethylenes; and celluloses such as methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, and the like.
When a dispersant is used, the dispersant can remain on the surface of the toner particles, but it is preferable from the charged surface of the toner to be removed by dissolution, washing or the like.

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. Therefore, the dispersion stabilizer surrounds the oil droplets formed by finely dispersing the organic medium with high shearing force to prevent the oil droplets from reaggregating and stabilize.
As the dispersion stabilizer, inorganic dispersion stabilizers and organic dispersion stabilizers can be used. In the case of inorganic dispersion stabilizers, the toner particles are granulated in the state of adhering to the particle surface after dispersion, so that they have an affinity with the solvent. Those which can be removed by acids such as hydrochloric acid without any other substances 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.

The dispersion method used when preparing the toner particles is not particularly limited, and general-purpose devices such as a low-speed shearing method, a high-speed shearing method, a friction method, a high-pressure jet method, and an ultrasonic wave can be used, but the dispersion particle size is 2 to 20 μm. In order to achieve the degree, a high-speed shearing type is preferable.
There is no restriction | limiting in particular as a stirring apparatus which has a rotary blade, If it is a general thing as an emulsifier and a disperser, it can be used.
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.), slasher, trigonal wet pulverizer (made by Mitsui Miike Chemical Co., Ltd.), Cavitron (made by Eurotech), fine flow mill Examples include continuous type emulsifiers (made by Taiheiyo Kiko Co., Ltd.), batch types such as Claremix (made by M Technique Co., Ltd.), fill mix (made by Tokushu Kika Kogyo Co., Ltd.), and continuous two-way emulsifiers. .
When a high-speed shearing disperser is used, the rotational speed is not particularly limited, but is usually 1000 to 30000 rpm, preferably 3000 to 20000 rpm.
In the case of a batch system, the dispersion time is usually 0.1 to 5 minutes. The temperature during dispersion is usually 10 to 150 ° C. (under pressure), preferably 10 to 100 ° C.

In order to remove the organic solvent from the obtained emulsified dispersion, a method in which the temperature of the entire system is gradually raised and the organic solvent in the droplets is completely removed by evaporation can be employed.
Alternatively, the emulsified dispersion can be sprayed into a dry atmosphere to completely remove the water-insoluble organic solvent in the droplets to form toner particles, and the aqueous dispersant can be removed by evaporation together.
In that case, the dry atmosphere in which the emulsified dispersion is sprayed is generally a gas heated with air, nitrogen, carbon dioxide gas, combustion gas, etc., particularly various air streams heated to a temperature higher than the boiling point of the highest boiling solvent used. Used.
Sufficient quality can be obtained even in a short time such as spray dryer, belt dryer or rotary kiln.
When the particle size distribution at the time of emulsification dispersion is wide, 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.
It is preferable to remove the dispersant and the like used from the obtained dispersion as much as possible, but it is more preferable to carry out it simultaneously with the classification operation.

Inclusion of an aliphatic diol component in the diol component constituting the resin (b) and the diol component constituting the polyester of the binder resin (a) as described above improves the average circularity of the toner particles, and It is possible to improve the surface smoothness. On the other hand, in the method for preparing toner particles, it is possible to further provide a heating step after removing the organic solvent. Accordingly, by providing the heating step, it is possible to smooth the toner particle surface and adjust the sphericity of the toner particles.
In addition, classification operation can be performed in the preparation method. The classification operation includes removing fine particles in a liquid by a cyclone, a decanter, centrifugation, or the like. Of course, the classification operation may be performed after obtaining the powder after drying, but it is preferable in the liquid to perform the classification operation. The obtained unnecessary fine particles or coarse particles 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 toner of the present invention, inorganic fine particles can be preferably used as an external additive for assisting the fluidity, developability and chargeability of the toner.
The primary particle diameter of the inorganic fine particles is preferably 5 nm to 2 μm, and more preferably 5 nm to 500 nm. Moreover, it is preferable that the specific surface area by BET method of an inorganic fine particle is 20-500 m < ² > / g.
The use ratio of the inorganic fine particles is preferably 0.01 to 5 parts by mass, and more preferably 0.01 to 2.0 parts by mass with respect to 100 parts by mass of the toner particles. The inorganic fine particles may be used alone or in combination of a plurality of types.

Specific examples of the inorganic fine particles include the following.
Silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, tin oxide, silica sand, clay, mica, wollastonite, diatomaceous earth, chromium oxide, cerium oxide, bengara , Antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, silicon nitride.
The external additive is preferably made hydrophobic by using a surface treatment agent in order to prevent deterioration of flow characteristics and charging characteristics under high humidity.
Examples of the surface treatment agent include a silane coupling agent, a silylating agent, a silane coupling agent having a fluorinated alkyl group, an organic titanate coupling agent, an aluminum coupling agent, silicone oil, and modified silicone oil. .

  Further, the toner of the present invention is a fatty acid metal such as zinc stearate, calcium stearate, stearic acid, etc. as an external additive (cleaning improver) for removing the developer after transfer remaining on the photoreceptor or primary transfer medium. Organic fine particles such as salts, polymer fine particles, polymer fine particles produced by soap-free emulsion polymerization such as polymethyl methacrylate fine particles or polystyrene fine particles, methacrylate esters and acrylate copolymer, silicone, benzoguanamine, nylon, etc. Examples thereof include polymer particles. The polymer fine particles preferably have a relatively narrow particle size distribution and a volume average particle size of 0.01 to 1 μm.

  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 ratio of the magnetic carrier to the toner in the developer is 1 to 10 toners per 100 parts by mass of the magnetic carrier. Part by mass 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.

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

<Method for Measuring Nitrogen Content (n) on Toner Particle Surface>
The amount of nitrogen (n) on the toner particle surface was calculated by performing a surface composition analysis by X-ray photoelectron spectroscopy (ESCA). The ESCA apparatus and measurement conditions are as follows.
Device used: Quantum 2000 Scanning ESCA Microprobe manufactured by PHI (Physical Electronics Industries, Inc.)
Analysis method: Narrow analysis Measurement condition: X-ray source: N (50 μ12.5 W15 KV)
Photoelectron Angle: 45 °
Pass Energy: 46.95 eV
Measurement range: φ50μm
Measurement time: 15-30 minutes

From the peak intensity of the N element measured under the above conditions, the surface atomic concentration (atomic%) was calculated using a relative sensitivity factor provided by PHI.

<Method for Measuring Average Roughness (Ra) of Toner Particle Surface>
The average roughness (Ra) of the toner particle surface was measured using a scanning probe microscope.
The measurement conditions and measurement method are shown below.

Probe station: SPI3800N (manufactured by Seiko Instruments Inc.)
・ Measurement unit: SPA400
・ Measurement mode: DFM (resonance mode) shape image ・ Cantilever: SI-DF40P
・ Resolution: Number of X data 256
: Number of Y data 128

In the present invention, an area of 1 μm square on the toner particle surface was measured. The area to be measured was a 1 μm square area at the center of the toner particle surface measured with a scanning probe microscope. As toner particles to be measured, toner particles having a particle diameter equal to the weight average particle diameter (D4) measured by the Coulter counter method described later were randomly selected. The measured data was subjected to secondary correction. Five or more different toner particles were measured, and the average value of the obtained data was calculated to obtain the average roughness (Ra) of the toner particle surface.
The average roughness (Ra) obtained as described above is obtained by extending the centerline average roughness Ra defined in JIS B0601 to three dimensions so that it can be applied to the measurement surface. It is calculated.

Ｆ（Ｘ，Ｙ）：全測定データの示す面
Ｓ_０ ：指定面が理想的にフラットであると仮定したときの面積
Ｚ_０ ：指定面内のＺデータ（指定面に対して垂直方向のデータ）の平均値
指定面とは、本発明においては１μｍ四方の測定エリアを意味する。

F (X, Y): Surface indicated by all measurement data S ₀ : Area when the specified surface is assumed to be ideally flat Z ₀ : Z data in the specified surface (data perpendicular to the specified surface) In the present invention, the designated surface means a measurement area of 1 μm square.

In a toner in which an external additive is externally added to the toner particles, it is necessary to remove the external additive when the surface of the toner particles is measured using a scanning probe microscope. Specific examples of the method include the following methods.
1) Put 45 mg of toner particles into a sample bottle and add 10 ml of methanol.
2) Disperse the sample for 1 minute with an ultrasonic cleaner to separate the external additive.
3) The toner particles and the external additive are separated by suction filtration (10 μm membrane filter). In the case of a toner containing a magnetic material, only the supernatant liquid may be separated by fixing the toner particles by applying a magnet to the bottom of the sample bottle.
4) Perform the above 2) and 3) three times in total, and the obtained toner particles are sufficiently dried at room temperature using a vacuum dryer.
After observing the toner particles from which the external additive has been removed with a scanning electron microscope and confirming that the external additive has been removed, the surface of the toner particles can be observed with a scanning probe microscope. If the external additive is not sufficiently removed, the above 2) and 3) are repeated until the external additive is sufficiently removed, and then the surface of the toner particles is observed with a scanning probe microscope.
Another method for removing the external additive in place of the above 2) and 3) is a method of dissolving the external additive with an alkali. As the alkali, an aqueous sodium hydroxide solution is preferred.

<Measuring method of average circularity of toner particles>
The average circularity of the toner particles is used as a simple method for quantitatively expressing the shape of the toner particles. The average circularity of the toner particles was measured with a flow type particle image analyzer “FPIA-3000 type” (manufactured by Sysmex Corporation) under the measurement and analysis conditions during the calibration operation.
The measurement principle of the flow-type particle image analyzer “FPIA-3000 type” (manufactured by Sysmex Corporation) is to capture flowing particles as a still image and perform image analysis. The sample added to the sample chamber is fed into the flat sheath flow cell by the sample suction syringe. The sample fed into the flat sheath flow is sandwiched between sheath liquids to form a flat flow. The sample passing through the flat sheath flow cell is irradiated with strobe light at 1/60 second intervals, and the flowing particles can be photographed as a still image. Further, since the flow is flat, the image is taken in a focused state. The particle image is captured by a CCD camera, and the captured image is subjected to image processing at an image processing resolution of 512 × 512 (0.37 × 0.37 μm per pixel), and the contour of each particle image is extracted, Projected area, perimeter, etc. are measured.
Next, the projected area S and the perimeter L of each particle image are obtained. Using the area S and the peripheral length L, the equivalent circle diameter and the circularity are obtained. The equivalent circle diameter is the diameter of a circle having the same area as the projected area of the particle image, and the circularity is a value obtained by dividing the circumference of the circle obtained from the equivalent circle diameter by the circumference of the projected particle image. Defined and calculated by the following formula.

Circularity C = 2 × (π × S) ^1/2 / L

When the particle image is a perfect circle, the degree of circularity is 1.000, and the degree of circularity becomes smaller as the degree of unevenness on the outer periphery of the particle image increases.
After calculating the circularity of each particle, the range of the circularity of 0.2 to 1.0 is divided into 800, and the average circularity is calculated using the number of measured particles.
As a specific measurement method, 0.02 g of a surfactant, preferably an alkylbenzene sulfonate, is added to 20 ml of ion-exchanged water, and then 0.02 g of a measurement sample is added, an oscillation frequency of 50 kHz, electrical output. Dispersion treatment was performed for 2 minutes using a 150 W tabletop type ultrasonic cleaner disperser (for example, “VS-150” (manufactured by Velvo Crea Co., Ltd.)) to obtain a dispersion for measurement. It cooled suitably so that temperature might be 10 to 40 degreeC.
For the measurement, the above-mentioned flow type particle image analyzer equipped with a standard objective lens (10 ×) was used, and a particle sheath “PSE-900A” (manufactured by Sysmex Corporation) was used as the sheath liquid. The dispersion prepared according to the above procedure is introduced into the flow type particle image analyzer, 3000 toner particles are measured in the total count mode in the HPF measurement mode, and the binarization threshold at the time of particle analysis is 85%. The analysis particle diameter was limited to a circle equivalent diameter of 2.00 μm or more and 200.00 μm or less, and the average circularity of the toner was determined.
In the measurement, automatic focus adjustment was performed using standard latex particles (for example, Duke Scientific 5200A diluted with ion-exchanged water) before the measurement was started. Thereafter, it is preferable to perform focus adjustment every two hours from the start of measurement.
In the examples of the present application, a flow type particle image analyzer that has been issued a calibration certificate issued by Sysmex Corporation is used, and the analysis particle diameter is limited to a circle equivalent diameter of 2.00 μm or more and 200.00 μm or less. Measured under the measurement and analysis conditions when the calibration certificate was received.

<Method for Measuring Weight Average Particle Diameter (D4) of Toner Particles>
The weight average particle diameter (D4) of the toner particles was measured using a Coulter counter Multisizer II (manufactured by Coulter) according to the operation manual of the apparatus. As the electrolytic solution, approximately 1% NaCl aqueous solution was prepared using primary sodium chloride, but ISTON R-II (manufactured by Coulter Scientific Japan Co.) can be used as the electrolytic solution.
As a measurement method, 0.1 to 5 ml of a surfactant (preferably alkylbenzene sulfonate) was added as a dispersant to 100 to 150 ml of the electrolytic aqueous solution, and 2 to 20 mg of a measurement sample was further added. The electrolytic solution in which the sample was suspended was subjected to dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes. The dispersed sample suspension electrolyte is subjected to the above-mentioned apparatus equipped with a 100 μm aperture, and the volume and number of toner particles having a particle diameter of 2.00 to 40.30 μm are measured for each channel. Distribution and number distribution were calculated. The weight average particle diameter (D4) of the toner particles based on the weight obtained from the volume distribution of the toner particles (the median value of each channel is a representative value for each channel) was determined.
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. 00μm; 8.00 to 10.08 μm; 10.08 to 12.70 μm; 12.70 to 16.00 μm; 16.00 to 20.20 μm; 20.20 to 25.40 μm; 25.40 to 32.00 μm; 13 channels of 32.00-40.30 μm were used.

<Measuring method of molecular weight distribution, peak molecular weight, and number average molecular weight by gel permeation chromatograph (GPC) of tetrahydrofuran (THF) soluble matter such as resin>
Molecular weight distribution, peak molecular weight, and number average molecular weight determined by gel permeation chromatography (GPC) of a soluble portion of tetrahydrofuran (THF) such as resin were measured under the following conditions.
The measurement sample is prepared as follows.
A sample (resin etc.) and THF were mixed at a concentration of about 0.5 to 5 mg / ml (about 5 mg / ml) and left at room temperature for several hours (5 to 6 hours). And the sample were mixed well until the unity of the sample disappeared. Furthermore, it left still for 12 hours or more (24 hours) at room temperature. At this time, the time from the start of mixing the sample and THF to the end of standing was set to 24 hours or longer. Then, a sample processing filter (pore size 0.45 to 0.5 μm, Mysori Disc H-25-2 [manufactured by Tosoh Corp.], Excro Disc 25CR [manufactured by Gelman Science Japan Ltd.] can be preferably used) Was used as a GPC sample.
Stabilize the column in a 40 ° C. heat chamber, flow THF at a flow rate of 1 ml / min through the column at this temperature, and adjust the sample concentration to 0.5-5 mg / ml. Measurements were made by injecting 50-200 μl of 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 a calibration curve prepared from several monodisperse polystyrene standard samples and the number of counts. As a standard polystyrene sample for preparing a calibration curve, Pressure Chemical Co. Manufactured by Toyo Soda Kogyo Co., Ltd. and having molecular weights of 6 × 10 ² , 2.1 × 10 ³ , 4.0 × 10 ³ , 1.75 × 10 ⁴ , 5.1 × 10 ⁴ , 1.1 × 10 ⁵ , 3.9 × 10 ⁵ , 8.6 × 10 ⁵ , 2.0 × 10 ⁶ , 4.48 × 10 ⁶ were used. An RI (refractive index) detector was used as the detector. In addition, as a column, in order to measure the molecular weight area | region of 1 * 10 < ³ > -2 * 10 < ⁶ > appropriately, it used in combination several commercially available polystyrene gel columns. The measurement conditions of GPC in the present invention are as follows.

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

<Measurement method of maximum endothermic peak temperature and melting point of toner particles, wax, etc.>
The maximum endothermic peak temperature of toner particles and wax was measured under the following conditions using DSC-7 (manufactured by Perkin Elmer) according to ASTM (D3418-82).

Temperature curve: Temperature increase I (30 ° C. to 200 ° C., temperature increase rate 10 ° C./min)
Temperature drop I (200 ° C-30 ° C, temperature drop rate 10 ° C / min)
Temperature increase II (30 ° C. to 200 ° C., temperature increase rate 10 ° C./min)

The measurement sample was accurately weighed 5 mg. It is put in an aluminum pan, and an empty aluminum pan is used as a reference. The measuring range is between 30 ° C. and 200 ° C., the heating rate is 10 ° C./min, and normal temperature and humidity (23 ° C./50% RH). The measurement was performed.
The maximum endothermic peak temperature was the temperature at the top of the peak with the highest endotherm among the peaks in the process of temperature increase II. The melting point was the same value as the maximum endothermic peak temperature.

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not restrict | limited at all to this. In addition, the number of parts in the following composition is part by mass unless otherwise specified.

(Production example of resin A)
1,2-propylene glycol 70 in a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introducing tube
0 parts, 716 parts of dimethyl terephthalate, 180 parts of adipic acid, and 3 parts of tetrabutoxytitanate as a condensation catalyst were allowed to react at 180 ° C. for 8 hours while distilling off the methanol produced under air reflux.
Next, while gradually raising the temperature to 230 ° C., the reaction is performed for 4 hours while distilling off propylene glycol and water generated under nitrogen reflux, and further the reaction is performed under a reduced pressure of 5 to 20 mmHg. It was taken out at the time. The recovered propylene glycol was 316 parts. The taken-out resin was cooled to room temperature, and then pulverized and finely divided to obtain Resin A.

(Production example of resin B)
1,2-propylene glycol 55 in a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube
7 parts, 569 parts of dimethyl terephthalate, 184 parts of adipic acid, and 3 parts of tetrabutoxy titanate as a condensation catalyst were allowed to react at 180 ° C. for 8 hours while distilling off the methanol produced under air reflux.
Next, while gradually raising the temperature to 230 ° C., the reaction was performed for 4 hours while distilling off propylene glycol and water generated under nitrogen reflux, and the reaction was further performed under reduced pressure of 5 to 20 mmHg to recover 175 parts of propylene glycol. Next, the mixture was cooled to 180 ° C., 121 parts of trimellitic anhydride was added, reacted for 2 hours under normal pressure sealing, reacted at 220 ° C. normal pressure, taken out when the softening point reached 180 ° C., cooled to room temperature, and ground. Then, resin B was obtained by making fine particles.

(Synthesis method of resin C)
345 parts of bisphenol A / ethylene oxide (EO) 2-mole adduct, 168 parts of isophthalic acid, and 2 parts of dibutyltin oxide are placed in a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe and reacted at normal pressure for 8 hours. Furthermore, after reacting under reduced pressure of 10 to 15 mmHg for 5 hours, the mixture was cooled to 110 ° C., and 20 parts of isophorone diisocyanate was added in toluene and reacted at 110 ° C. for 5 hours.
Next, the solvent was removed under reduced pressure, and the reaction vessel was taken out. After cooling to room temperature, pulverized fine particles were obtained to obtain a resin C which is a urethane-modified polyester resin.

(Synthesis method of resin D)
Bisphenol A · ethylene oxide (EO) 2-mole adduct 670 parts and terephthalic acid dimethyl ester 210 parts were polymerized at 200 ° C. for 8 hours under normal pressure, and further reacted for 5 hours under reduced pressure of 10-15 mmHg. Then, 20 parts of phthalic anhydride was added thereto and reacted for 2 hours.
After removing the solvent, the resin D was taken out from the reaction vessel and pulverized into fine particles to obtain an unmodified polyester resin D.

(Synthesis method of resin E)
229 parts of styrene, 231 parts of n-butyl acrylate, 14 parts of acrylic acid, 50 parts of 2-butanone (solvent) are placed in a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, and 2,2 as a polymerization initiator. -8 parts of azobis (2,4-dimethylvaleronitrile) was dissolved and polymerized at 60 ° C for 8 hours to prepare a polymerizable monomer composition. 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, pulverized fine particles were obtained to obtain Resin E, which is a linear vinyl resin.

(Preparation of wax dispersion 1)
Carnauba wax (melting point: 72 ° C.) 50 parts by mass Wax dispersion medium (I) 30 parts by mass Ethyl acetate 420 parts by mass The above raw materials are put into a reaction vessel equipped with a thermometer and stirring blades, and the system is heated to 78 ° C. It was sufficiently dissolved by heating.
Next, the system was gradually cooled to 30 ° C. over 1 hour while gently stirring at 50 rpm to crystallize the wax into fine particles, and then wet pulverized with a bead mill to obtain wax dispersion 1.
The wax dispersion medium is obtained by the following production method.
[Method for Producing Wax Dispersion Medium (I)]
In an autoclave reaction vessel equipped with a thermometer and a stirrer, 600 parts by mass of xylene and 120 parts by mass of low density polyethylene having a maximum endothermic peak temperature of 110 ° C. were sufficiently dissolved and subjected to nitrogen substitution. Thereafter, a mixed solution of 1992 parts by mass of styrene, 168 parts by mass of acrylonitrile, 240 parts by mass of monobutyl maleate, 78 parts by mass of di-t-butylperoxyhexahydroterephthalate and 455 parts by mass of xylene was dropped at 175 ° C. over 3 hours. Further, the polymerization was carried out by maintaining at this temperature for 30 minutes. Next, the solvent was removed to obtain a wax dispersion medium (I) as a graft reaction product.

(Preparation of wax dispersion 2)
-Paraffin wax (melting point 75 ° C) 50 parts by mass-Wax dispersion medium (I) 30 parts by mass-Ethyl acetate 420 parts by mass A wax dispersion 2 was obtained from the process.

(Preparation of Colorant Dispersion 1)
-Resin A 22.5 parts by mass-Copper phthalocyanine pigment (CI Pigment Blue 15: 3) 22.5 parts by mass-Ethyl acetate 55.0 parts by mass The mixture was put into a glass container and dispersed for 5 hours with a paint shaker to obtain a colorant dispersion 1.

(Preparation of colorant dispersion 2)
Resin B 22.5 parts by mass Copper phthalocyanine pigment (CI Pigment Blue 15: 3) 22.5 parts by mass Ethyl acetate 55.0 parts by mass The mixture was put into a glass container and dispersed for 5 hours with a paint shaker to obtain a colorant dispersion 2.

(Preparation of Liquid Toner Composition 1)
-Resin A 68.0 parts by mass-Resin C 17.0 parts by mass-Colorant dispersion 1 20.0 parts by mass-Wax dispersion 1 50.0 parts by mass-Ethyl acetate 50.0 parts by mass-Triethylamine 0.55 Part by mass The above was put into a beaker, stirred at 2000 rpm for 3 minutes with a disper disperser (manufactured by Tokushu Kika Co., Ltd.), and dissolved sufficiently to prepare a liquid toner composition 1. When the dispersion was confirmed with a microscope, the dispersibility of the pigment and the wax was good.

(Preparation of Liquid Toner Composition 2)
Resin B 50.0 parts by mass Resin D 45.0 parts by mass Colorant dispersion 1 20.0 parts by mass Wax dispersion 1 50.0 parts by mass Ethyl acetate 50.0 parts by mass Triethylamine 0.55 Part by mass The above was put into a beaker, stirred at 2000 rpm for 3 minutes with a disper disperser (manufactured by Tokushu Kika Co., Ltd.) and sufficiently dissolved to prepare a liquid toner composition 2. When the dispersion was confirmed with a microscope, the dispersibility of the pigment and the wax was good.

(Preparation of Liquid Toner Composition 3)
Resin A 68.0 parts by weight Resin D 17.0 parts by weight Colorant Dispersion 2 20.0 parts by weight Wax Dispersion 1 50.0 parts by weight Ethyl acetate 50.0 parts by weight Triethylamine 0.55 Part by mass The above was put into a beaker, stirred for 3 minutes at 2000 rpm with a disper disperser (manufactured by Tokushu Kika Co., Ltd.) and sufficiently dissolved to prepare a liquid toner composition 3. When the dispersion was confirmed with a microscope, the dispersibility of the pigment and the wax was good.

(Preparation of Liquid Toner Composition 4)
-Resin A 17.0 parts by mass-Resin C 68.0 parts by mass-Colorant dispersion 1 20.0 parts by mass-Wax dispersion 2 50.0 parts by mass-Ethyl acetate 50.0 parts by mass-Triethylamine 0.55 Part by mass The above was put into a beaker, stirred at 2000 rpm for 3 minutes with a disper disperser (manufactured by Tokushu Kika Co., Ltd.), and dissolved sufficiently to prepare a liquid toner composition 4. When the dispersion was confirmed with a microscope, the dispersibility of the pigment and the wax was good.

(Preparation of liquid toner composition 5)
-Resin E 85.0 parts by mass-Colorant dispersion 1 20.0 parts by mass-Wax dispersion 1 50.0 parts by mass-Ethyl acetate 50.0 parts by mass-Triethylamine 0.55 parts by mass Then, the mixture was stirred for 3 minutes at 2000 rpm with a disper disperser (manufactured by Tokushu Kika Co., Ltd.) and dissolved sufficiently to prepare liquid toner composition 5. When the dispersion was confirmed with a microscope, the dispersibility of the pigment and the wax was good.

(Preparation of Liquid Toner Composition 6)
-Resin C 85.0 parts by mass-Colorant dispersion 1 20.0 parts by mass-Wax dispersion 1 50.0 parts by mass-Ethyl acetate 50.0 parts by mass-Triethylamine 0.55 parts by mass Then, the mixture was stirred for 3 minutes at 2000 rpm with a disper disperser (manufactured by Tokushu Kika Co., Ltd.) and dissolved sufficiently to prepare a liquid toner composition 6. When the dispersion was confirmed with a microscope, the dispersibility of the pigment and the wax was good.

(Preparation of resin fine particle dispersion 1)
-250.0 parts by mass of a polyester diol having a number average molecular weight of about 2000, obtained from a mixture of 1,4-butanediol and terephthalic acid (molar ratio 1: 1)-9.0 parts by mass of 1,2-propylene glycol

-Dimethylolpropanoic acid 80.0 parts by mass-3- (2,3-dihydroxypropoxy) -1-propanesulfonic acid
5.0 parts by mass / acetone 500.0 parts by mass The above raw materials were charged into a reaction vessel equipped with a stir bar and a thermometer, reacted at 60 ° C. for 1 hour, and then 200.0 parts by mass of isophorone diisocyanate was added. The mixture was reacted at 60 ° C. for 10 hours and cooled to obtain a reaction product. The reaction product was emulsified dropwise with stirring at 500 rpm in 1000 parts by mass of ion-exchanged water to prepare a fine particle dispersion. Further, an aqueous solution in which 50 parts by mass of triethylamine was dissolved in 100 parts by mass of 10% ammonia water was added, and an extension reaction was performed by reacting at 50 ° C. for 4 hours. Further, ion-exchanged water was added until the solid content became 20% by mass to obtain a resin fine particle dispersion 1.

(Preparation of resin fine particle dispersion 2)
-250.0 parts by mass of a polyester diol having a number average molecular weight of about 1000, obtained from a mixture of 1,4-butanediol and adipic acid (molar ratio 1: 1)-10.0 parts by mass of 1,2-propylene glycol

-Dimethylolpropanoic acid 130.0 parts by mass-3- (2,3-dihydroxypropoxy) -1-propanesulfonic acid
10.0 parts by mass / acetone 1000.0 parts by mass The above raw materials were charged into a reaction vessel equipped with a stir bar and a thermometer, reacted at 60 ° C. for 1 hour, and then 250.0 parts by mass of isophorone diisocyanate was added. The mixture was reacted at 60 ° C. for 10 hours and cooled to obtain a reaction product. The reaction product was emulsified dropwise with stirring at 500 rpm in 1000 parts by mass of ion-exchanged water to prepare a fine particle dispersion. Furthermore, an elongation reaction was carried out by adding an aqueous solution in which 60 parts by mass of triethylamine was dissolved in 100 parts by mass of 10% ammonia water and reacting at 50 ° C. for 4 hours. Further, ion exchange water was added until the solid content became 20% by mass to obtain a resin fine particle dispersion 2.

(Preparation of resin fine particle dispersion 3)
Resin fine particle dispersion 3 was obtained in the same manner as in the preparation of resin fine particle dispersion 2, except that 120.0 parts by mass of isophorone diisocyanate was added.

(Preparation of resin fine particle dispersion 4)
A polyester having a number average molecular weight of about 2000, obtained from a mixture of 1,2-propylene glycol, ethylene glycol and 1,4-butanediol in a 40:50:10 molar ratio and an equimolar mixture of terephthalic acid and isophthalic acid. Diol 90.0 parts by mass · Bisphenol A · EO (2 mol adduct) 60.0 parts by mass

-Dimethylolpropionic acid 85.0 parts by mass-Acetone 1000.0 parts by mass The above raw materials were charged into a reaction vessel equipped with a stir bar and a thermometer, reacted at 60 ° C for 1 hour, and then isophorone diisocyanate 130.0 masses Part was added, reacted at 60 ° C. for 10 hours and cooled to obtain a reaction product. The reaction product was emulsified dropwise with stirring at 500 rpm in 1000 parts by mass of ion-exchanged water to prepare a fine particle dispersion. Furthermore, an elongation reaction was carried out by adding an aqueous solution in which 60 parts by mass of triethylamine was dissolved in 100 parts by mass of 10% ammonia water and reacting at 50 ° C. for 4 hours. Further, ion-exchanged water was added until the solid content became 20% by mass to obtain a resin fine particle dispersion 4.

(Preparation of resin fine particle dispersion 5)
A polyester having a number average molecular weight of about 2000, obtained from a mixture of 1,2-propylene glycol, ethylene glycol and 1,4-butanediol in a 40:50:10 molar ratio and an equimolar mixture of terephthalic acid and isophthalic acid. Diol 24.0 parts by mass / Bisphenol A / EO (2 mol adduct) 60.0 parts by mass

-Dimethylolpropionic acid 85.0 parts by mass-Acetone 1000.0 parts by mass The above raw materials were charged in a reaction vessel equipped with a stir bar and a thermometer, reacted at 60 ° C for 1 hour, and then isophorone diisocyanate 100.0 masses Part was added, reacted at 60 ° C. for 10 hours and cooled to obtain a reaction product. The reaction product was emulsified dropwise with stirring at 500 rpm in 1000 parts by mass of ion-exchanged water to prepare a fine particle dispersion. Furthermore, an elongation reaction was carried out by adding an aqueous solution in which 60 parts by mass of triethylamine was dissolved in 100 parts by mass of 10% ammonia water and reacting at 50 ° C. for 4 hours. Further, ion exchange water was added until the solid content became 20% by mass to obtain a resin fine particle dispersion 5.

(Preparation of resin fine particle dispersion 6)
150.0 parts by mass of a polyester diol having a number average molecular weight of about 1000, obtained from a mixture of 1,4-butanediol and adipic acid (molar ratio 1: 1)
・ Dimethylolpropionic acid 40.0 parts by mass Acetone 1000.0 parts by mass The above raw materials were charged into a reaction vessel equipped with a stir bar and a thermometer, reacted at 60 ° C. for 1 hour, and then isophorone diisocyanate 100.0 masses Part was added, reacted at 60 ° C. for 10 hours and cooled to obtain a reaction product. The reaction product was emulsified dropwise with stirring at 500 rpm in 1000 parts by mass of ion-exchanged water to prepare a fine particle dispersion. Furthermore, an elongation reaction was carried out by adding an aqueous solution in which 60 parts by mass of triethylamine was dissolved in 100 parts by mass of 10% ammonia water and reacting at 50 ° C. for 4 hours. Further, ion exchange water was added until the solid content became 20% by mass to obtain a resin fine particle dispersion 6.

(Preparation of resin fine particle dispersion 7)
A polyester having a number average molecular weight of about 2000, obtained from a mixture of 1,2-propylene glycol, ethylene glycol and 1,4-butanediol in a 40:50:10 molar ratio and an equimolar mixture of terephthalic acid and isophthalic acid. Diol 30.0 parts by mass / Bisphenol A / EO (2 mol adduct) 150.0 parts by mass

・ Dimethylolpropionic acid 15.0 parts by mass Acetone 1000.0 parts by mass

The above raw materials are charged in a reaction vessel equipped with a stir bar and a thermometer, reacted at 60 ° C. for 1 hour, then 200.0 parts by mass of isophorone diisocyanate is added, reacted at 60 ° C. for 10 hours and cooled to cool the reaction product. Obtained. The reaction product was dropped and emulsified with stirring at 500 rpm in 1000 parts by mass of ion-exchanged water to prepare a fine particle dispersion. Further, an aqueous solution in which 10 parts by mass of triethylamine was dissolved in 100 parts by mass of 10% aqueous ammonia was added, and an extension reaction was performed by reacting at 50 ° C. for 4 hours. Further, ion exchange water was added until the solid content became 20% by mass to obtain a resin fine particle dispersion 7.

(Preparation of resin fine particle dispersion 8)
In the preparation of the resin fine particle dispersion 1, a resin fine particle dispersion 8 was obtained in the same manner except that 50.0 parts by mass of isophorone diisocyanate was added.

(Preparation of resin fine particle dispersion 9)
In the preparation of resin fine particle dispersion 1, resin fine particle dispersion 9 was obtained in the same manner except that 285.0 parts by mass of isophorone diisocyanate was added.

(Preparation of resin fine particle dispersion 10)
-10.0 parts by mass of a polyester diol having a number average molecular weight of about 1000, obtained from a mixture of 1,4-butanediol and adipic acid (molar ratio 1: 1)-Bisphenol A-EO (2-mole adduct) 0 parts by mass
-Dimethylolpropionic acid 120.0 parts by mass-acetone 1000.0 parts by mass The above raw materials were charged into a reaction vessel equipped with a stir bar and a thermometer, reacted at 60 ° C for 1 hour, and then isophorone diisocyanate 100.0 masses Part was added, reacted at 60 ° C. for 10 hours and cooled to obtain a reaction product. The reaction product was dropped and emulsified with stirring at 500 rpm in 1000 parts by mass of ion-exchanged water to prepare a fine particle dispersion. Further, an aqueous solution in which 10 parts by mass of triethylamine was dissolved in 100 parts by mass of 10% aqueous ammonia was added, and an extension reaction was performed by reacting at 50 ° C. for 4 hours. Further, ion-exchanged water was added until the solid content became 20% by mass to obtain a resin fine particle dispersion 10.

(Preparation of inorganic fine particle dispersion 1)
After warming the _0.1M-Na 3 PO ₄ aqueous solution 500g to put to 60 ° C. in deionized water 700 g, and stirred at 12,000rpm using a TK-type homomixer (manufactured by Tokushu Kika Kogyo). To this, 75 g of 1.0 M CaCl ₂ aqueous solution was gradually added to obtain an inorganic fine particle dispersion 1 containing Ca ₃ (PO ₄ ) ₂ .

<Example 1>
(Emulsification ~ Granulation ~ Solvent removal process)
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 255.0. Mass parts ・ Resin fine particle dispersion 1 15.0 mass parts ・ Carboxymethylcellulose sodium 1.0 mass part ・ 50% aqueous solution of sodium dodecylbenzenesulfonate 25.0 mass parts ・ Ethyl acetate 30. 0 part by mass Next, the number of revolutions of the TK homomixer was increased to 10,000 rpm, 200.0 parts by mass of [Liquid toner composition 1] was added, and stirring was continued for 2 minutes for suspension.
Furthermore, a stirring blade was set in the container, the temperature inside the system was raised to 35 ° C. while stirring at 200 rpm, and ethyl acetate was distilled off over 5 hours in a state where the pressure was reduced to 500 mmHg, and a resin dispersion (D1) was obtained. Obtained.

(Washing to drying process)
The resin dispersion (D1) was filtered and reslurried in 500 parts by mass of ion-exchanged water. The system was stirred and hydrochloric acid was added until the system reached PH4 and stirred for 5 minutes.
The slurry was filtered again, 200 parts by mass of ion exchange water was added, and the operation of stirring for 5 minutes was repeated three times to remove the organic residue remaining in the system, and a toner filter cake was obtained.
The filter cake was dried with a hot air dryer at 40 ° C. for 20 hours and sieved with a mesh having an opening of 75 μm, and [Toner Particles 1] having an average particle size of 5.6 μm was obtained. The surface layer (B) of the toner particles 1 was 7.5% by mass with respect to the toner base particles (A). Furthermore, when the nitrogen amount (n) of the X-ray photoelectron spectroscopic analysis (ESCA) of the toner particle surface was measured, it was 6.1 atomic%. Table 1 shows the physical properties of the toner particles 1.

<Preparation of Toner 1>
1.0 part by mass of hydrophobic silica having an average particle diameter of 20 nm and 1.5 parts by mass of monodispersed silica having an average particle diameter of 110 nm are added to 100 parts by mass of the obtained [Toner Particle 1]. The toner 1 was obtained by external addition and mixing using a Henschel mixer (Mitsui Mine).

<Preparation of two-component developer 1>
A two-component developer 1 was prepared by mixing 8 parts by mass of the above [Toner 1] and 92 parts by mass of a silicone carrier-coated ferrite carrier having an average particle diameter of 35 μm.

The following two-component developer was subjected to the following image evaluation test using a color laser copier (CLC5000: manufactured by Canon Inc., see FIG. 1) modified to the following electrophotographic process conditions. In addition, as a test paper, color laser copier paper: A4 (manufactured by Canon Sales Co., Ltd.) which is a CLC recommended paper was used. Moreover, when there is no description in particular in the following, it measured by the normal temperature normal humidity environment (23 degreeC / 60% RH). The results are shown in Table 2.
(1) Image density fluctuation (initial and after 100,000 sheets endurance output)
The image pattern shown in FIG. 3 is imaged in a low temperature and low humidity environment (20 ° C./10% RH) and a high temperature and high humidity environment (30 ° C./80% RH). Was measured.
The image density was an average of five points ([1] to [5] in the figure), and the image density was measured with an X-Rite color reflection densitometer (X-rite 500 Series; X-Rite). The difference between the initial image density value and the image density after printing 100,000 sheets from the initial stage was defined as the fluctuation range, and expressed as A to D below. As for the fluctuation range, both environments were compared and a bad (large) value was adopted.
(Evaluation criteria)
A: The fluctuation range is 0 or more and less than 0.1 (no image density fluctuation)
B: Fluctuation range of 0.1 or more and less than 0.2 (practical problem level)
C: Fluctuation range 0.2 or more and less than 0.3 (fluctuation range can be visually confirmed and slightly problematic)
D: Fluctuation range of 0.3 or more (a level that causes practical problems)

(2) Transfer efficiency (transfer characteristics)
FIG. 4 shows a monochromatic mode in which the potential contrast of the photoconductor is adjusted so that the toner loading on the photoconductor is 0.55 mg / cm ² under a normal temperature and normal humidity environment (23 ° C./60% RH). An image pattern was output.
The image density (a) transferred onto the transfer paper and the residual transfer density (b) on the photoreceptor were measured using an X-Rite color reflection densitometer (X-rite 500 Series; X-Rite). Regarding the residual transfer density on the photoconductor, the residual toner layer on the photoconductor is fixed and peeled off with a transparent adhesive tape (Cello Tape (registered trademark); manufactured by Nichiban Co., Ltd.), and is applied to the white background portion of the transfer image. The residual transfer density was measured. (Separately, only cello tape (registered trademark) was applied to the white background, and the reflection density of the tape itself was measured and subtracted as background)
From the image density, the transfer efficiency (transfer characteristics) represented by the following formula (3) was determined. The transfer current was adjusted so as to maximize the transfer efficiency.
(Evaluation criteria)
95% or higher (no problem level)
90% or more, less than 95% (a level where there is no practical problem)
80% or more, less than 90% (image quality is slightly inferior, but usable level)
Less than 80% (impractical level)

(3) Evaluation of frictional charging characteristics (chargeability) The above two-component developer is put in a plastic bottle with a lid, and is shaken four times per second with a shaker (YS-LD: manufactured by Yayoi Co., Ltd.). Shake at speed for 1 minute to charge the developer.
Next, the triboelectric charge amount is measured by the apparatus for measuring the triboelectric charge amount shown in FIG. In FIG. 2, about 0.5 to 1.5 g of the developer described above is placed in a metal measuring container 2 having a 500 mesh screen 3 at the bottom, and a metal lid 4 is formed. The total mass of the measurement container 2 at this time is weighed and is defined as W1 (g). Next, in the suction device 1 (at least the insulator is in contact with the measurement container), the pressure of the vacuum gauge 5 is set to 250 mmAq by suction from the suction port 7 and adjusting the air volume control valve 6. In this state, suction is performed for 2 minutes to remove the toner particles by suction.
The potential of the electrometer 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 the following formula (4).

Formula (4): Triboelectric charge amount of sample (mC / kg) = C × V / (W1-W2)


In addition, the evaluation of the triboelectric charging property in the present invention is performed by using the measurement method described above, and evaluating the difference value (absolute value) between the measured value when shaken for 1 minute and the measured value when shaken for 5 minutes. went.
For those showing a stable charging characteristic, the difference value is small, and those showing an unstable charging characteristic (charge-up or charge-down) tend to have a large difference value.
(Evaluation criteria)
Less than 5 (no problem level)
5 or more, but less than 10 (slightly worsening, but practically no problem)
10 or more (impractical level)

(4) Highlight reproducibility An image with an image density of 0.3 to 0.6 measured using an X-Rite color reflection densitometer (X-Rite 500 Series; X-Rite) is output, and the density is uniform. The degree of property and roughness is visually evaluated.
(Evaluation criteria)
A: A good output image with excellent uniformity of image density.
B: Although the image density uniformity is slightly lacking, it is a level that causes no problem in practical use.
C: An output image with poor and uniform image density, which is a practically problematic level.
D: An output image with extremely poor uniformity of image density, which is not suitable for practical use.

(5) Fog Fog (reflectance) (%) is the color laser copier paper (standard paper): A4 (Canon Sales) reflectance (%) and the non-image part reflectance (%) of the sample. It measured using the reflectometer (REFRECOMETER MODEL TC-6DS; Tokyo Denshoku Co., Ltd. make), and computed from following formula (5). The reflectometer was equipped with an amber filter. Smaller values indicate less fog.
Note that the reflectance (%) of the non-image portion of the sample is the above-described color laser copier paper (standard paper), and the image pattern image shown in FIG. 3 is output. ] (%) Of the part (non-image part) was measured with the above-mentioned reflectometer and taken as the average value.
Formula (5): fog (reflectance) (%) = reflectance of standard paper (%) − reflectance of non-image part of sample (%)
(Evaluation criteria)
A: The fog is less than 1.0%, which is a good level.
B: The fog is 1.0% or more and less than 2.0%, which is a level having no practical problem.
C: The fog is 2.0% or more and less than 4.0%, which is a practically problematic level.
D: The fog is 4.0% or more, which is a practically impossible level.

(6) Toner Scattering Visually observe the degree of contamination by toner around the developing device and the developing device in the main body after the endurance output of 100,000 line images with a printing rate of 5% or more and less than 10%.
(Evaluation criteria)
A: No contamination by toner around the developing device and the developing device in the main body is observed.
B: Stain due to a small amount of toner is observed in the developing device, but there is no practical problem.
C: Contamination due to toner around the developing device and the developing device in the main body is observed, and this is a practically problematic level.
D: The periphery of the developing device and the developing device in the main body is significantly soiled with toner, adversely affecting the function of the main body, and cannot be used practically.

(7) Fixing property The fixing device of the above-mentioned CLC5000 (manufactured by Canon Inc.) was manually modified so that the fixing temperature could be set, and a fixing test was conducted.
First, the development contrast was adjusted so that the amount of toner applied on paper was 0.60 mg / cm ² , and an unfixed image having the image pattern shown in FIG. 4 was created.
Next, in a normal temperature and normal humidity environment (23 ° C./60% RH), the set temperature of the fixing device was sequentially increased by 10 ° C. from 100 ° C., and the fixing test was performed up to a temperature range where no offset or wrapping occurred.

(7-1) Measurement of Gross Max Value A fixed image of the image pattern shown in FIG. 4 is created at each of the above set temperatures, and the gloss values of five points ([1] to [5] in FIG. 4) in the image are measured. The average value (gross average value) was calculated. The maximum gloss average value at each set temperature was defined as the gross Max value, and the evaluation was performed as follows.
The gloss value was measured using a gloss meter PG-3G (Nippon Denshoku Industries Co., Ltd.). The incident angle was 75 degrees.
(Evaluation criteria)
A: Glossiness: 40 or more B: Glossiness: 30 or more, less than 40 C: Glossiness: 20 or more, less than 30 D: Glossiness: 15 or more, less than 20 There are C and D levels that are impossible for practical use.

(7-2) Low temperature fixing start temperature (low temperature fixability)
A fixed image having the image pattern shown in FIG. 4 was prepared at each of the set temperatures. From the rear end to the front end of the image, the image density before and after rubbing was rubbed 5 times with a soft thin paper (trade name “Dasper”, manufactured by Ozu Sangyo Co., Ltd.) while applying a load of 4.9 kPa. Were measured, and the image density reduction rate ΔD (%) was calculated by the following equation. The temperature at which ΔD (%) was less than 1% was determined as the fixing start temperature. Note that the image density is an X-Rite color reflection densitometer (X-rite).
500 Series; X-Rite).

(7-3) Evaluation of high temperature offset property High temperature offset property was evaluated according to the above fixability evaluation except that the set temperature of the fixing device was increased by 10 ° C in order from 120 ° C. The temperature at which offset (peeling) or winding occurred was defined as the high temperature offset generation temperature.

(8) Heat-resistant storage characteristics About 10 g of toner was put in a 100 ml polycup, left at 50 ° C. for 3 days, and then visually evaluated. The evaluation criteria are as follows.
(Evaluation criteria)
A: Aggregates are not seen. (no problem)
B: Although aggregates are seen, they break apart easily. (No problem in practical use)
C: Aggregates can be grasped and do not collapse easily. (Unusable level)

<Example 2>
In the same manner as in Example 1 [Preparation of aqueous phase], except that [Resin fine particle dispersion 1] is changed to [Resin fine particle dispersion 2], toner particles 2, toner 2 and two-component developer 2 are the same. Was prepared.
The surface layer (B) of the toner particles 2 was 7.5% by mass with respect to the toner base particles (A). Further, the nitrogen amount (n) of X-ray photoelectron spectroscopic analysis (ESCA) on the toner particle surface was measured and found to be 5.2 atomic%. Table 1 shows the physical properties of the toner particles 2.
Further, image evaluation with the two-component developer 2 was performed in the same manner as in Example 1. The results are shown in Table 2.

<Example 3>
Toner particles 3, toner 3 and two-component developer 3 are the same except that [resin fine particle dispersion 1] is changed to [resin fine particle dispersion 3] in [Adjustment of aqueous phase] in Example 1. Was prepared.
The surface layer (B) of the toner particles 3 was 7.5% by mass with respect to the toner base particles (A). Further, the nitrogen amount (n) measured by X-ray photoelectron spectroscopy (ESCA) on the toner particle surface was 5.1 atomic%. Table 1 shows the physical properties of the toner particles 3.
Further, image evaluation with the two-component developer 3 was performed in the same manner as in Example 1. The results are shown in Table 2.

<Example 4>
In [Adjustment of aqueous phase] in Example 1, except that [Resin fine particle dispersion 1] is changed to [Resin fine particle dispersion 4] and the content is changed from 15.0 parts by mass to 8.0 parts by mass. Similarly, toner particles 4, toner 4 and two-component developer 4 were prepared.
The surface layer (B) of the toner particles 4 was 4.0% by mass with respect to the toner base particles (A). Further, the nitrogen amount (n) of X-ray photoelectron spectroscopic analysis (ESCA) of the toner particle surface was measured and found to be 3.6 atomic%. Table 1 shows the physical properties of the toner particles 4.
Further, image evaluation with the two-component developer 4 was performed in the same manner as in Example 1. The results are shown in Table 2.

<Example 5>
In [Adjustment of aqueous phase] in Example 1, [Resin fine particle dispersion 1] is changed to [Resin fine particle dispersion 5] and the content is changed from 15.0 parts by mass to 4.6 parts by mass. Similarly, toner particles 5, toner 5 and two-component developer 5 were prepared.
The surface layer (B) of the toner particles 5 was 2.3% by mass with respect to the toner base particles (A). Further, the amount of nitrogen (n) measured by X-ray photoelectron spectroscopy (ESCA) on the toner particle surface was 2.4 atomic%. Table 1 shows the physical properties of the toner particles 5.
Further, image evaluation with the two-component developer 5 was performed in the same manner as in Example 1. The results are shown in Table 2.

<Example 6>
In Example 5, the same procedure is performed except that [resin fine particle dispersion 5] is changed to [resin fine particle dispersion 6] and the content is changed from 4.6 parts by mass to 6.8 parts by mass. 6 and two-component developer 6 were prepared. Table 1 shows the physical properties of the toner particles 6. Further, image evaluation with the two-component developer 6 was performed in the same manner as in Example 1. The results are shown in Table 2.

<Example 7>
In Example 1, toner particles 7, toner 7, and two-component developer 7 were prepared in the same manner except that [liquid toner composition 1] was changed to [liquid toner composition 2]. Table 1 shows the physical properties of the toner particles 7. In addition, image evaluation with the two-component developer 7 was performed in the same manner as in Example 1. The results are shown in Table 2.

<Example 8>
In the same manner as in Example 1, except that [Liquid toner composition 1] is changed to [Liquid toner composition 3] and the content is changed from 15.0 parts by mass to 15.6 parts by mass, 8 and two-component developer 8 were prepared. Table 1 shows the physical properties of the toner particles 8. Further, image evaluation with the two-component developer 8 was performed in the same manner as in Example 1. The results are shown in Table 2.

<Example 9>
In the same manner as in Example 1, except that [Resin fine particle dispersion 1] is changed to [Resin fine particle dispersion 3] and the content is changed from 15.0 parts by mass to 28.2 parts by mass, 9 and a two-component developer 9 were prepared. Table 1 shows the physical properties of the toner particles 9. In addition, image evaluation with the two-component developer 9 was performed in the same manner as in Example 1. The results are shown in Table 2.

<Example 10>
In the same manner as in Example 1, except that [Resin fine particle dispersion 1] is changed to [Resin fine particle dispersion 7] and the content is changed from 15.0 parts by mass to 8.6 parts by mass, 10 and two-component developer 10 were prepared. Table 1 shows the physical properties of the toner particles 10. Further, image evaluation with the two-component developer 10 was performed in the same manner as in Example 1. The results are shown in Table 2.

<Example 11>
In Example 1, the content of [resin fine particle dispersion 1] is changed from 15.0 parts by mass to 10.6 parts by mass, and [Liquid toner composition 1] is changed to [Liquid toner composition 6]. Except for the above, toner particles 11, toner 11 and two-component developer 11 were prepared in the same manner. Table 1 shows the physical properties of the toner particles 11. Further, image evaluation with the two-component developer 11 was performed in the same manner as in Example 1. The results are shown in Table 2.

<Comparative Example 1>
Toner particles 12, toner 12 and two-component developer 11 were prepared in the same manner as in Example 1, except that [Resin fine particle dispersion 1] was changed to [Inorganic fine particle dispersion 1]. Table 1 shows the physical properties of the toner particles 12. In addition, image evaluation with the two-component developer 12 was performed in the same manner as in Example 1.

<Comparative Example 2>
In Example 3, the same procedure was followed except that [Resin fine particle dispersion 3] was changed to [Resin fine particle dispersion 8] and the content was changed from 15.0 parts by mass to 13.4 parts by mass. 13 and two-component developer 13 were prepared. Table 1 shows the physical properties of the toner particles 13. Further, image evaluation with the two-component developer 13 was performed in the same manner as in Example 1. The results are shown in Table 2.

<Comparative Example 3>
In Example 1, the [aqueous phase] was changed to the following composition:
-Ion-exchanged water 97.0 parts by mass-Resin fine particle dispersion 9 14.3 parts by mass-Sodium carboxymethyl cellulose 1.0 part by mass-0.1% aqueous solution of sodium dodecylbenzenesulfonate 10.0 parts by mass-Ethyl acetate 8 Toner particles 14, toner 14 and two-component developer 14 were prepared in the same manner except that the amount of addition of [liquid toner composition 1] was 85.0 parts by mass. Table 1 shows the physical properties of the toner particles 14. In addition, image evaluation with the two-component developer 14 was performed in the same manner as in Example 1. The results are shown in Table 2.

<Comparative example 4>
In [Preparation of aqueous phase] in Example 1, the same procedure is performed except that the content of [resin fine particle dispersion 1] is changed from 15.0 parts by mass to 1.6 parts by mass. And a two-component developer 15 was prepared.
Table 1 shows the physical properties of the toner particles 15. Further, image evaluation with the two-component developer 15 was performed in the same manner as in Example 1. The results are shown in Table 2.

<Comparative Example 5>
Toner particles 16, toner 16 and two-component developer 16 were prepared in the same manner as in Example 1 except that the emulsified dispersion after suspension was heat-treated at 80 ° C. for 30 minutes.
Table 1 shows the physical properties of the toner particles 16. Further, image evaluation with the two-component developer 16 was performed in the same manner as in Example 1. The results are shown in Table 2.

<Comparative Example 6>
In Example 1, toner particles 17, toner 17 and two-component developer 17 were prepared in the same manner except that [resin fine particle dispersion 1] was changed to [resin fine particle dispersion 10]. Table 1 shows the physical properties of the toner particles 17. In addition, image evaluation with the two-component developer 17 was performed in the same manner as in Example 1. The results are shown in Table 2.

<Comparative Example 7>
In Example 1, toner particles 18, toner 18 and two-component developer 18 were prepared in the same manner except that [liquid toner composition 1] was changed to [liquid toner composition 4]. Table 1 shows the physical properties of the toner particles 18. Further, image evaluation with the two-component developer 18 was performed in the same manner as in Example 1. The results are shown in Table 2.

<Comparative Example 8>
The following materials were mixed with a Henschel mixer, and the resulting mixture was melt-kneaded with a twin-screw extruder while suctioning with a vent port connected to a suction pump. This melt-kneaded product was roughly crushed with a speed mill to obtain a 1 mm mesh pass crushed product.
Further, after finely pulverizing with a jet mill, the classification operation with a multi-division classifier (elbow jet) was repeated twice to prepare toner particles 19. A toner 19 and a two-component developer 19 were prepared in the same manner as in Example 1 except that the toner particles 19 were used. Table 1 shows the physical properties of the toner particles 19. Further, image evaluation with the two-component developer 19 was performed in the same manner as in Example 1. The results are shown in Table 2.
Resin A 80.0 parts by mass Resin B 20.0 parts by mass Carnauba wax (melting point 72 ° C.) 5.0 parts by mass Copper phthalocyanine pigment (CI Pigment Blue 15: 3) 10.0 parts by mass 20.0 parts by mass of filtered and dried product of resin fine particle dispersion 1

In Table 1 above,
(1) “Diisocyanate amount in resin (b)” indicates the amount of isocyanate in the total resin content (excluding solutions such as water) in preparing the resin fine particle dispersion.
(2) “Fatty acid diol component / total diol component in resin (b)” indicates the amount ratio of the aliphatic component in the alcohol component in the resin fine particles,
(3) “Fatty acid diol component / total diol component” of the toner base particle (A) indicates the amount ratio of the aliphatic component in the alcohol component in the liquid toner composition.

Cross-sectional schematic diagram of Color Laser Copier CLC5000 (Canon) Schematic diagram of triboelectric charge measuring device Pattern diagram in image evaluation Pattern diagram in image evaluation

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 Electrometers 4A to 4D Photoconductors 9A to 9D Developers 21A to 21D Charging devices 22A to 22D Laser Units 23A to 23D Transfer blade 24 Transfer belt 25 Fixing devices 26A to 26D Cleaner 27 Transfer material

Claims (7)

A toner having capsule-type toner particles having a surface layer (B) containing a resin (b) on the surface of toner base particles (A) containing at least a binder resin (a), a colorant, and a wax. And
The binder resin (a) is a resin mainly composed of polyester,
The resin (b) is a resin containing at least a reaction product of a diol component and a diisocyanate component,
The nitrogen amount (n) by X-ray photoelectron spectroscopy (ESCA) of the toner particle surface is 2.0 atomic% or more and less than 7.0 atomic%,
The average roughness (Ra) of the toner particle surface is 1.0 nm or more and less than 5.0 nm,
A toner having an average circularity measured by a flow type particle image measuring apparatus for toner particles of 0.970 or more and less than 1.000.   The toner according to claim 1, wherein the surface layer (B) is 1.0% by mass or more and less than 15.0% by mass with respect to the toner base particles (A).   The toner according to claim 1, wherein the content of the diisocyanate component in the resin (b) is 20.0% by mass or more and less than 40.0% by mass.   The diol component in the resin (b) contains at least an aliphatic diol component, and the content of the aliphatic diol component is 20% by mass or more based on the total diol component. The toner according to claim 1.   The toner according to any one of claims 1 to 4, wherein 50% by mass or more of all diol components constituting the polyester which is a main component of the binder resin (a) is an aliphatic diol.   The toner particles are obtained by 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 containing the resin (b) are dispersed. 6. The toner according to claim 1, wherein the toner is obtained by dispersing the dispersion, removing the solvent from the obtained dispersion, and drying the dispersion.   The toner according to claim 6, wherein a tertiary amine compound is contained in the aqueous medium and / or the organic medium.

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