JP5401966B2 - Toner for developing electrostatic image and method for producing the same, developer for developing electrostatic image, toner cartridge, process cartridge, and image forming apparatus - Google Patents

Description

  The present invention relates to a toner for developing an electrostatic image and a method for producing the same, a developer for developing an electrostatic image, a toner cartridge, a process cartridge, and an image forming apparatus.

  A so-called xerographic image forming apparatus includes an electrophotographic photosensitive member (hereinafter sometimes referred to as “photosensitive member”), a charging device, an exposure device, a developing device, and a transfer device, and forms an image by an electrophotographic process using them. Is done. In recent years, xerographic image forming apparatuses have been further improved in speed, image quality, and lifetime due to technological progress of each member and system. In addition, consumables such as toner are required to have a long life and high functionality, while those composed of structures and materials with a low environmental load have been required.

  As a material with little environmental load, a material with high biodegradability is mentioned, for example. In particular, in recent years, in order to achieve high functionality, there has been an active study of producing toner by a wet manufacturing method, but in order to reduce the environmental impact of the material that flows into the waste water at the time of production, In particular, there is a demand for safe materials with a small amount of outflow and environmental loads.

  These degradable material studies have been used in various studies (see Patent Documents 1, 2, and 3). In Patent Document 1, a charge control agent contains a sulfate ester type surfactant. In Patent Literature 2, a biodegradable resin having a low melting point is contained. Patent Document 3 is also a toner made of a decomposable new resin. In addition, an attempt to reduce the environmental load by achieving a so-called long life by investigating an electrophotographic photoreceptor having a protective layer is also active (see Patent Document 4).

In addition, from the viewpoint of reducing the amount of waste toner, a recycling system that recycles the collected toner is actively studied. Specifically, a method of treating the toner base particles with hot air (see Patent Document 7), a study of improving the Tg of the resin (glass transition temperature and toner release agent (see Patent Document 5), and improving the additive dynamic friction coefficient) (See Patent Document 6), and attempts to improve the resin molecular weight and water content (see Patent Document 9) have been made.
JP 2000-347461 A JP 2007-114607 A JP 2005-154698 A JP-A-9-68826 JP-A-7-84406 Japanese Patent Laid-Open No. 11-95477 JP 2000-181118 A JP 2000-181119 A JP 2001-147551 A

  The purpose of the present invention is to suppress changes in toner deformation, surface wear, destruction, etc., even when used continuously, as compared with the case without this configuration. A toner in which the additive is appropriately embedded in the toner surface resin to prevent dropping, and the effect of the additive is maintained. Further, a manufacturing method thereof, a developer for developing an electrostatic image using the toner, a toner cartridge, The object is to provide a process cartridge and an image forming apparatus.

The above-mentioned subject is achieved by the following present invention.
That is, the invention according to claim 1
It contains a resin containing a crosslinked polyester resin and a non-crosslinked polyester resin, a colorant, a and, the volume ratio of alcohol and water 1: dissolution fraction when dissolved in a mixed solution of 1, the total weight of the toner der 5.0% or less than 0.5% with respect to is,
When dynamic viscoelasticity measurement is performed on the toner particles under an angular velocity of 6.28 rad and a temperature change condition of 1 ° C./min, a storage elastic modulus G ′ during a temperature rising process from 30 ° C. to 170 ° C. is measured. The G ′ change width in the temperature rising process from 60 ° C. to 140 ° C. is 10 ^{2 to} 10 ⁵ Pa and the G ′ change width in the temperature rising process from 150 ° C. to 170 ° C. is 10 ³ Pa or less. the toner for developing an electrostatic image Ru Oh.

The invention according to claim 2
The electrostatic charge image developing toner according to claim 1 , wherein the resin in the toner contains a biodegradable dispersant.
The invention according to claim 3
The electrostatic charge image developing toner according to claim 2 , wherein the biodegradable dispersant is derived from a manufacturing process of the toner.
The invention according to claim 4
A resin particle dispersion in which resin particles containing a biodegradable dispersant are dispersed in at least one and a colorant particle dispersion in which colorant particles are dispersed are mixed, and the resin particles and the colorant particles are aggregated and heated. The electrostatic image developing toner according to claim 2 or 3 obtained by fusing and uniting.

The invention according to claim 5
2. The oxide particle coverage on the toner surface is 50% or more and 95% or less when the toner surface contains two or more kinds of oxide particles as an additive and the toner surface is measured by an X-ray photoelectron spectrometer. The electrostatic image developing toner according to claim 4 .
The invention according to claim 6
6. The electrostatic image developing toner according to claim 5 , wherein the difference in hardness between the maximum hardness and the minimum hardness of the two or more kinds of oxide particles is 4 or more and 8 or less.

The invention according to claim 7 provides:
A resin particle dispersion adjusting step for adjusting a resin particle dispersion in which resin particles are dispersed;
A colorant particle dispersion adjusting step of adjusting a colorant particle dispersion in which the colorant particles are dispersed;
A mixed solution adjusting step of mixing the resin particle dispersion and the colorant particle dispersion to adjust a mixed solution containing the resin particles and the colorant particles;
An aggregated particle adjusting step of adjusting aggregated particles in which the resin particles and the colorant particles are aggregated;
A fusion and coalescence step of fusing and coalescing the aggregated particle dispersion in which the agglomerated particles are dispersed above the glass transition temperature of the resin particles; and
Cooling to a temperature below the glass transition temperature of the resin particles,
A biodegradable dispersing agent includes at least one process of fusing and coalescing and fusing and coalescing by heating above the glass transition temperature of the resin particles, and cooling to a temperature below the glass transition temperature of the resin particles. And a step of adjusting the pH of the liquid to a range of 7 or more and 11 or less by adding a basic compound.

The invention according to claim 8 provides:
An electrostatic charge image developing developer comprising the electrostatic charge image developing toner according to any one of claims 1 to 6 .
The invention according to claim 9 is:
Desorbed in an image forming apparatus having a developing unit, the toner to be supplied to a developing unit is accommodated, the toner is for developing an electrostatic charge image according to any one of claims 1 to 6 A toner cartridge that is toner.
The invention according to claim 10 is:
A process cartridge comprising a developing holder and containing the developer for developing an electrostatic charge image according to claim 8 .

The invention according to claim 11 is:
A latent image carrier,
An electrostatic latent image forming means for forming an electrostatic latent image on the surface of the latent image holding member;
Developing means for developing the electrostatic latent image with a developer containing toner to form a toner image;
Transfer means for transferring the toner image formed on the latent image holding member to the surface of a recording medium;
Toner removing means for removing residual toner remaining on the surface of the latent image holding member,
The image forming apparatus according to claim 8 , wherein the developer is an electrostatic charge image developing developer.
The invention according to claim 12
The image forming apparatus according to claim 11 , further comprising: a residual toner collecting / supplying unit that collects the residual toner removed by the toner removing unit and supplies the collected residual toner to the developing unit.
The invention according to claim 13 is:
Layer constituting the outermost surface of the latent image holding member comprises a resin having a three-dimensional crosslinked structure, an image forming apparatus according to claim 11 or claim 12.

According to the first aspect of the present invention, when the solubility when dissolved in the ethanol / water mixed solution is within the range, a flexible layer that can be dissolved on the toner surface as compared with those outside the range, or Since an appropriate amount of the layer having a low degree of crosslinking is provided, deformation of the toner is suppressed, and further changes in the toner surface properties such as surface wear and destruction are suppressed. When an additive is used in combination, a toner is provided in which the additive is appropriately embedded in the toner surface resin to prevent dropping and the effect of the additive is maintained.
According to the first aspect of the present invention, since the toner interior is sufficiently tough and the surface is kept flexible as compared with a toner that does not contain both crosslinked and non-crosslinked polyester resins as the resin, the toner surface Since the additive particles present in the material are appropriately embedded and difficult to move on the surface, the dropping of the additive is suppressed, and the effect of the additive can be maintained for a longer period. In addition, the interparticle surface layer is controlled more flexibly than the case where the dynamic viscoelasticity is not controlled within the range of this embodiment, and the shape variation of the toner particles is suppressed.

According to the second aspect of the present invention, compared to the case where the resin does not contain a dispersant, a flexible layer that can be dissolved on the toner surface is formed, and the additive is well embedded in the toner surface to prevent dropping. The effect of the additive is maintained.
According to the third aspect of the present invention, compared to a case where a biodegradable dispersant is not used in the manufacturing process, a flexible layer that can be dissolved on the toner surface is formed, and the additive is well embedded in the toner surface. Dropping is suppressed and the effect of the additive is maintained.
According to the invention of claim 4 , compared to a production method that does not include a biodegradable dispersant and a production method that fuses and coalesces resin particles and colorant particles, the toner surface A flexible layer that can be dissolved in the toner is formed, and the additive is well embedded in the toner surface to prevent the dropping, and the effect of the additive is maintained.

According to the fifth aspect of the invention, compared to the case where two or more kinds of oxide particles are not included, the oxide particles are embedded in the surface of the toner particles and the dropping is suppressed, and the effect of the additive is prolonged. Maintained for a long time. In addition, more particles can be obtained in which variation in the amount of the additive between the toner particles is suppressed as compared with the case where the coverage of the oxide particles on the toner particle surface is not controlled within the range.
According to the sixth aspect of the invention, compared to a case where the hardness difference between two or more kinds of oxide particles is not controlled within the above range, the particles having high hardness are appropriately embedded in the toner particle surface, and dropout is suppressed. In addition, since particles having low hardness can be present with reduced variation, the effect of the additive is improved, and particle variation is further suppressed.

According to the invention of claim 7 , the surface of the toner particle is compared with the case where the step of adding a biodegradable dispersant or the step of adjusting the pH to 7 or more and 11 or less with a basic compound is not included. A layer having high flexibility can be formed so as to be in contact with the toner, and the additive particles existing on the toner surface are appropriately embedded and hardly fall off, so that the effect of the additive is maintained for a longer period of time.
According to the eighth aspect of the invention, the toner particle shape and additives in the developer for developing an electrostatic charge image are compared with the case where the amount of the toner particles dissolved in the mixture of alcohol and water is out of the range. The effect lasts longer.
According to the ninth aspect of the invention, the toner particle shape and additives in the developer for developing an electrostatic charge image are compared with the case where the amount of the toner particles dissolved in the mixture of alcohol and water is out of the range. The effect lasts longer.
According to the tenth aspect of the present invention, the toner particle shape and the effect of the additive are maintained for a longer period of time as compared with the case where the amount of toner particles dissolved in the mixture of alcohol and water is out of the range.
According to the invention of claim 11 , the effect of the toner particle shape and the additive lasts longer than the case where the dissolution amount of the toner particles in the mixed liquid of alcohol and water is out of the range, and the toner particles can be used for a long time. A high quality image is formed.

According to the twelfth aspect of the present invention, even with the configuration including the residual toner collecting and supplying means, the effects of the toner particle shape and the additive are maintained, and a high-quality image is formed over a long period of time.
According to the thirteenth aspect of the present invention, even if a latent image carrier having a high surface height is used, the effects of the toner particle shape and the additive are maintained, and a high-quality image is formed over a long period of time.

Hereinafter, the present invention will be described in detail.
<Toner for electrostatic image latent image>
The toner particles in the electrostatic image developing toner of the present embodiment (hereinafter sometimes simply referred to as “toner”) contain a binder resin and a colorant, and other additives such as a release agent as required. An agent may be included. When the toner particles are dissolved in a mixed solution of alcohol and water at a volume ratio of 1: 1 (hereinafter sometimes referred to as “alcohol / water mixed solution”), the dissolution fraction is based on the total mass of the toner particles. 0.5% or more and 5.0% or less.
However, in this embodiment, when the binder resin contains a crosslinked polyester resin and a non-crosslinked polyester resin, and the dynamic viscoelasticity measurement is performed on the toner particles under a temperature change condition of an angular velocity of 6.28 rad and 1 ° C. per minute. When the storage elastic modulus G ′ in the temperature rising process from 30 ° C. to 170 ° C. is measured, the G ′ change width in the temperature rising process from 60 ° C. to 140 ° C. is 10 ^{2 to} 10 ⁵ Pa, and A toner having a G ′ variation width of 10 ³ Pa or less in a temperature rising process from 150 ° C. to 170 ° C. is applied.

In the present embodiment, the toner particles having a dissolution fraction in the above range when dissolved in a mixed solution of alcohol and water in a volume ratio of 1: 1 have a flexible layer formed on the surface of the toner particles. The flexible layer is continuously thin on the surface, has little variation in thickness, and supports that the inside of the toner particles has a sufficient elastic modulus. Additives such as external additives added to the toner surface Among them, the particles having high hardness are appropriately embedded in a flexible layer to suppress falling off and suppress uneven distribution of other additives.
In particular, even when used repeatedly in a toner recycling system or when the surface of a photoconductor having a high hardness surface layer is cleaned at a high pressure, destruction of toner particles and occurrence of deformation are suppressed, and blade wear is suppressed. In addition, when the toner is fixed, it melts from the soft layer on the surface, so that even a highly elastic toner can sufficiently adhere to the paper.
In addition, the additive added to the toner particle surface does not move or drop off, and the additive is stably maintained without dropping for a long period of time compared to the case where the additive does not have the flexible layer on the toner particle surface. Therefore, mutual charging (also referred to as abnormal charging) between the toner used in a harsh environment and the toner not subjected to stress hardly occurs. When an image is formed using an electrostatic charge image developer containing the toner particles, an image is formed. The concentration is stable. This effect is particularly remarkable on thick paper that is difficult to control density, paper that has large unevenness, and the like.

Although it is not clear why the toner particles can be controlled to have a dissolution fraction of 0.5% or more and 5.0% or less when dissolved in a 1: 1 mixed solution of alcohol and water in volume ratio, So guessed.
It is considered that the precise control of the degree of ionic crosslinking and the degree of chemical bonding on the surface of the toner particles has an influence because the dissolution fraction is in the specific range. Thus, among the whole toner particles, the dissolution fraction of 0.5% or more and 5.0% or less means that the above-mentioned weight on the particle surface can be dissolved, and the remaining resin components constituting the particles are It shows that it is stable against the liquid mixture.
As one embodiment for achieving the dissolution fraction, for example, a biodegradable dispersant may be used for adjusting toner particles. According to this aspect, the biodegradable dispersant is present in a region in contact with the surface of the resin constituting the toner particles. By taking this aspect, the resin is not reduced in ionic cross-linking inside the toner particles. Since the dispersant itself existing on the surface and the area in contact with the surface is also decomposed, the action of this dispersant does not penetrate into the inside of the particle. Therefore, a flexible layer exists on the surface of the toner particles and the area in contact with the surface.
Furthermore, by using a basic compound such as NaOH, KOH, Ca (OH) ₂ , ammonia, amine, etc. and a biodegradable dispersant, the dispersant acts uniformly on each toner particle, It is presumed that variation in the dissolution fraction between toner particles is suppressed.

  At this time, since the added biodegradable dispersant is decomposed in the production process of the toner, the amount of the biodegradable dispersant remaining in the produced toner is small. Therefore, compared to the case where a large amount of the dispersant remains in the toner as in the case of using another dispersant, the toner has fewer impurities, so the durability of the toner, the electrical characteristics, the image quality of the formed image, etc. Is estimated to be good. Conversely, even when a large amount of dispersant is added compared to the case where other dispersants are used, the amount of the dispersant (that is, impurities) remaining in the toner is small, so that the toner characteristics and image quality are good. Presumed to be.

  In addition, since the biodegradable dispersant is decomposed during the toner production process, the waste water generated by the toner production contains a lot of decomposition products generated after the biodegradable dispersant is decomposed. Since the content of itself is small, it is estimated that the wastewater treatment cost is reduced.

  In addition, in order to reduce environmental impact, stress on toner particles increases in a recycling system that repeatedly uses toner, and a system that has a three-dimensional cross-linked photoconductor with increased surface hardness as a long-life electrophotographic photoconductor. In order to deal with the system, toner particles having a high elastic modulus with improved durability are used, but an additive added to the surface of the toner particles having a high elastic modulus due to stress applied to the toner particles. It tends to be unevenly distributed or desorbed by pressure. On the other hand, in the toner particles of this embodiment, the additive was appropriately buried in the soft layer on the surface, and the uneven distribution and detachment were suppressed, so that the toner particles were stressed in a severe environment for a long time. Even in this case, the particle change is suppressed, and the effect of the additive is maintained.

  In a further embodiment, two or more kinds of oxide particles having different hardnesses are used as additives to be added to the toner particles, but in this embodiment, the high hardness particles are appropriately buried and fixed in a flexible layer on the toner particle surface. As a result, the surface of the toner is protected, and the more flexible dispersion state of the other additives is controlled so as not to vary. By defining the difference in hardness between the two or more kinds of oxide particles within the range, the surface of the photoconductor is cleaned while protecting both the photoconductor and the blade and also has a polishing action.

Hereinafter, the configuration of this aspect will be described.
-A mixed solution of alcohol and water in a volume ratio of 1: 1 (alcohol / water mixed solution)-
In this embodiment, the alcohol / water mixed solution is a mixture of alcohol and water at a volume ratio of 1/1. When the amount of alcohol is large, the solution penetrates to the inside of the toner particles, making it difficult to compare the surface and the area in contact therewith, and when the amount of water is large, the wettability such as toner surface polarity is affected. This makes comparison difficult. The alcohol here is an alcohol having a relatively short alkyl chain length, more specifically, an alcohol having up to about 5 carbon atoms, specifically, for example, methyl alcohol, ethyl alcohol, linear or branched butyl. Examples thereof include alcohol, propyl alcohol having a straight chain or branched chain, and methyl alcohol, ethyl alcohol, and the like are preferable from the viewpoint of measurement accuracy for accurately extracting the toner surface.

-Dissolution rate when dissolved in alcohol / water mixed solution-
In the present embodiment, the dissolution fraction when dissolved in an alcohol / water mixed solution is 10 wt% of toner particles after adjusting the mixed solution and added by a rotating device such as a ball mill at room temperature (25 ° C.). After mixing and stirring for 30 minutes to 30 minutes, solid-liquid separation is performed. The dissolved content in the liquid is air-dried, the weight is measured, and the ratio to the amount of toner charged is calculated.
When the dissolution fraction is lower than the above range, it is presumed that the whole toner particles are hard, or that the inside is soft and the surface is hard, that is, there are few soft layers soluble in the mixed solution on the surface. When exceeding the said range, the case where the whole toner particle is flexible, or the case where the surface flexible layer is thicker than the target thickness is estimated.

  There is no particular limitation on the method for obtaining toner particles having a defined amount of a flexible layer that is dissolved in an alcohol / water mixed solution on the surface, which is defined by the physical property values of the present embodiment. For example, the toner particles are adjusted. In the process, the method using the biodegradable dispersant described above, the method of changing the surface and the resin constituting the region in contact with the center of the particle, and reducing the crosslink density, molecular weight, and glass transition temperature of the surface Alternatively, there is a method in which the toner surface is washed with highly alkaline washing water or the like to reduce the cross-linking density of the particle surface resin with which the washing water comes into contact.

Hereinafter, details will be described by taking as an example a method of using a biodegradable dispersant for adjusting toner particles, which is a typical method for obtaining toner particles of the present embodiment.
-Biodegradable dispersant and its addition method-
In the present embodiment, the biodegradable dispersant is a biological substance such as a hydrolysis or a microorganism in which a bond of a functional group is cleaved and a reaction in which water molecules are divided into H ⁺ and OH ⁻ is added to the cleavage site. This refers to biodegradation that is converted into carbon dioxide or water by reaction.
The biodegradable dispersant and production method that can be used in this embodiment will be described in detail below.

  The toner particles of the present embodiment are preferably a resin particle dispersion adjusting step for adjusting a resin particle dispersion in which resin particles are dispersed, and a colorant particle dispersion for adjusting a colorant particle dispersion in which colorant particles are dispersed. An adjustment step, a mixed solution adjustment step of mixing the resin particle dispersion and the colorant particle dispersion to adjust a mixed solution containing the resin particles and the colorant particles, and the resin particles and the colorant particles An agglomerated particle adjusting step for adjusting the agglomerated particles, an aggregating particle dispersion in which the agglomerated particles are dispersed, a fusion and coalescence step for fusing and coalescing by heating above the glass transition temperature of the resin particles; A step of cooling to a temperature lower than the glass transition temperature of the resin particles, wherein a fusion / merging step of fusing and coalescing by heating above the glass transition temperature of the resin particles. As at least one step of cooling the resin particles to the glass transition temperature or lower, the step of adding a biodegradable dispersant and the addition of a basic compound bring the pH of the liquid to a range of 7 or more and 11 or less. It is important to include a process of adjusting.

As a mode for carrying out the method of adding the biodegradable dispersant, that is, the step of adding the biodegradable dispersant, the fusion and coalescence process in which the elastic modulus of the whole toner particles is lowered and the heating is performed at a temperature higher than the resin glass transition temperature. However, it can also be used when it is added in the step of cooling to the glass transition temperature or lower after fusion and coalescence.
When adding the biodegradable dispersant, the pH in the system is adjusted to a range of 7 or more and 11 or less with a basic compound such as sodium hydroxide, potassium hydroxide, ammonia or amine in order to allow the dispersant to work without variation. Preferably, the solubility of the biodegradable dispersant is improved by adjusting the pH in the system to the above range. Therefore, there is no variation among the toner particles, and the biodegradable dispersant is uniformly applied to any toner particle. It becomes possible to act.

When the above step includes a step of adding a biodegradable dispersant, a flexible layer having no thickness variation is formed on the toner surface. The reason is not clear, but is presumed as follows.
The biodegradable dispersant is added in the process of heating to the resin glass transition temperature, so that it decomposes by heating. Concentrates on the contact area, contributes to particle stabilization, and the alcohol component gently contributes to a decrease in the degree of cross-linking of the toner surface and surface polarity. Therefore, a flexible layer having a low degree of ion bridge and a low resin entanglement density is formed on the surface layer as compared with the inside of the toner.

Among the biodegradable dispersants used in the present embodiment, ether carboxylic acids, derivatives thereof, and salts thereof (hereinafter sometimes referred to as “ether carboxylic acid compounds”) are preferable.
When an ether carboxylic acid compound is used as the biodegradable dispersant, the toner constituent components are blended more uniformly and the secondary effect of reducing impurities is achieved. The reason is not clear, but is presumed as follows.
The ether carboxylic acid compound dissolves in the solvent while coordinating ionic impurities (particularly cationic impurities) in the mixed solution. In other words, the ether carboxylic acid compound suppresses the ionic impurities from being taken into the aggregated particles, and dissolves in the aqueous solvent while the ionic impurities are selectively unevenly distributed on the toner surface. It is presumed that the impurities in the toner are reduced by discharging to the outside.
On the other hand, when a monoamine or diamine complexing agent is used as a biodegradable dispersant in addition to the ether carboxylic acid compound, the dispersibility of the ether carboxylic acid acting on the surface is improved. Further, the complexing agent itself reduces the degree of ionic crosslinking and resin crosslinking on the particle surface, so that the surface becomes more flexible.

  Further, since the ether carboxylic acid compound exhibits hydrolyzability, for example, when toner is prepared by a wet process, the ether carboxylic acid compound is gradually decomposed by optimizing the conditions during the preparation of the toner, so that the water phase is separated from the toner surface. Even when the toner cleaning process is simplified or when a large amount of biodegradable dispersant is contained, the ether carboxylic acid compound hardly remains in the toner, and the electrical characteristics and the like are maintained over a long period of time. Toner is obtained.

  Specific examples of ether carboxylic acid compounds include alkyl ether carboxylic acid compounds (alkyl ether carboxylic acids, derivatives thereof, and salts thereof), and hydroxy ether carboxylic acid compounds (hydroxy ether carboxylic acids, derivatives thereof, and Of these, hydroxyalkyl ether carboxylic acid compounds are preferable from the viewpoint of allowing them to selectively exist on the toner surface.

As the alkyl ether carboxylic acid, a linear or branched alkyl group having 4 to 22 carbon atoms is preferable. More specifically, for example, propyl ether acetic acid, octyl ether acetic acid, decyl ether acetic acid, Examples include lauryl ether acetic acid and myristyl ether acetic acid.
Specific examples of the alkyl ether carboxylic acid derivative include, for example, propyl ether acetate, propyl ether acetate, octyl ether acetate, octyl ether acetate, decyl ether acetate, decyl ether acetate, lauryl ether acetate. Lauryl ether acetic acid amide, myristyl ether acetic acid ester, myristyl ether acetic acid amide and the like.

Hydroxy ether carboxylic acid is an ether carboxylic acid that is preferably used for further improving the dispersibility of the pigment and the release agent, and hydroxy ether carboxylic acid containing an alkyl group having 4 to 22 carbon atoms is preferably used.
More specifically, examples of the hydroxy ether carboxylic acid include hydroxy ethyl ether acetic acid, hydroxy propyl ether acetic acid, hydroxy octyl ether acetic acid, hydroxy decyl ether acetic acid, hydroxy lauryl ether acetic acid, hydroxymyristyl ether acetic acid and the like.
Specifically, the derivative of the hydroxy ether carboxylic acid is preferably, for example, a linear or branched alkyl group having 4 to 22 carbon atoms, a hydroxy ether carboxylic acid ester containing an alkenyl group, or a hydroxy ether carboxylic acid amide. Hydroxyethyl ether acetate, hydroxyethyl ether acetate, hydroxypropyl ether acetate, hydroxypropyl ether acetate, hydroxyoctyl ether acetate, hydroxyoctyl ether acetate, hydroxydecyl ether acetate, hydroxy lauryl ether acetate, hydroxy lauryl Examples include ether acetates and hydroxymyristyl ether acetates.
Specific examples of salts of alkyl ether carboxylic acid, hydroxy ether carboxylic acid, or derivatives thereof include, for example, sodium salt, potassium salt, magnesium salt, ammonium salt, lower alkanolamine (mono, di, triethanolamine). Examples include salt.

  In addition, when a biodegradable dispersant is used, it is preferable to use a monoamine type or diamine type complexing agent in combination. By using a complexing agent in combination, the action of the dispersing agent can be made uniform, and the action of the complexing agent itself can make the toner surface more flexible, or it can suppress fluctuations in the charging properties of the toner particles themselves. Or improve. The complexing agent is preferably a biodegradable complexing agent from the viewpoint of being difficult to remain in the toner and easy to process.

  Specific examples of the monoamine type complexing agent include aspartic acid monoacetic acid (ASMA), aspartic acid diacetic acid (ASDA), aspartic acid monopropionic acid (ASMP), iminodisuccinic acid (IDSA), 2-sulfo. Methyl aspartic acid (SMAS), 2-sulfoethyl aspartic acid (SEAS), glutamic acid diacetic acid (GLDA), 2-sulfomethyl glutamic acid (SMGL), 2-sulfoethyl glutamic acid (SEGL), methyliminodiacetic acid (MIDA), α -Alanine diacetic acid (α-ALDA), β-alanine diacetic acid (β-ALDA), serine diacetic acid (SEDA), isoserine diacetic acid (ISDA), phenylalanine diacetic acid (PHDA), anthranilic acid diacetic acid (ANDA), Sulfanilic acid diacetic acid (SLDA), Taurine di Acid (Tuda), such as sulfomethyl diacetate (sMDA) or alkali metal salts or ammonium salts thereof. When the molecule has an asymmetric carbon, (S) -aspartic acid monoacetic acid, (S) -aspartic acid diacetic acid, (S) -aspartic acid monopropionic acid, (S, S) -iminodisuccinic acid, (S , R) -iminodisuccinic acid, (S) -2-sulfomethylaspartic acid, (S) -2-sulfoethylaspartic acid, (S) -glutamic acid diacetic acid, (S) -2-sulfomethylglutamic acid, (S) -2-Sulfoethylglutamic acid, (S) -α-alanine diacetic acid, (S) -serine diacetic acid, (S) -phenylalanine diacetic acid, or alkali metal salts thereof are preferred from the viewpoint of degradability.

  Diamine type complexing agents include (S, S) -ethylenediamine diglutaric acid, 1,3-propanediamine diglutaric acid, 2-hydroxy-1,3-propanediamine disuccinic acid, 2-hydroxy-1, Examples include 3-propanediamine diglutaric acid or alkali metal salts or ammonium salts thereof.

  The toner particles of this embodiment obtained through the above steps contain a biodegradable dispersant in the resin. The total content of the biodegradable dispersant in the toner particles is preferably 0.5% by mass or more and 5% by mass or less, more preferably 0.7% by mass or more and 4% by mass or less with respect to the toner particles. More preferably, it is at least 3.5% by mass. Since the biodegradable dispersant is gradually decomposed during the toner manufacturing process, the content of the biodegradable dispersant remaining in the toner particles can be kept low. For this reason, deterioration of toner characteristics and image quality due to the remaining dispersant is suppressed.

  When a biodegradable dispersant is used in combination with a monoamine type or diamine type complexing agent, the content of the biodegradable dispersant in the toner is 0.5 to 2 times the content of the complexing agent in the toner. The following are preferable, 0.5 times or more and 1.7 times or less are more preferable, and 0.7 times or more and 1.5 times or less are more preferable.

Identification and content measurement of the biodegradable dispersant contained in the toner are performed as follows.
Specifically, first, trimethylsilylation of the toner is performed as follows. 1 g of toner is dispersed in 5 ml of acetone (solvent), 25 ml of ion-exchanged water is added and mixed, and solid-liquid separation is performed. 10 ml of trimethylchlorosilane was added to the obtained solution and stirred at room temperature (25 ° C.) for 3 hours to perform a coupling reaction (trimethylsilylation treatment), which is used as a measurement sample.
Next, the measurement sample is measured under the following conditions using the following pyrolysis gas chromatography mass spectrometer, and the biodegradable dispersant is identified and the content is measured.
・ Model: Hitachi N-5000 (quadrupole type)
Column: GLscience DB-1 (0.25 mm × 30 m × 0.25 μm)
-Curie Point Pyrolyzer measurement method (400 ° C)
・ Temperature increase program: Hold at 60 ° C for 5 minutes, then heat up at 5 ° C / minute and hold at 200 ° C for 5 minutes

The complexing agent can be identified and measured for content by HPLC analysis, NMR spectrum analysis, or the like.
High-performance liquid chromatograph (HPLC) analysis is performed by analyzer: LC-08 manufactured by Nippon Analytical Industries, Ltd., column: Inertsil ODS3 (Φ4.6 × 250 mm), detector: differential refractometer, ultraviolet absorption detector (254 nm). The measurement conditions are eluent: chloroform, flow rate of 1.0 mL / min, and 1 g of toner dissolved in 10 mL of chloroform as a measurement sample is used.
The NMR spectrum analysis is performed using a ¹ H-NMR apparatus: JNM-AL400 (manufactured by JEOL Ltd.), and the measurement conditions are a 5 mm glass tube, a 3 wt% heavy aqueous solution, and a measurement temperature: 25 ° C. In addition, a measurement sample is used in which the carrier is detached from the developer, the toner is dissolved in an organic solvent, and the binder resin is separated by filtration or the like.

As a preferable physical property of the toner particles of this embodiment, when dynamic viscoelasticity measurement is performed under an angular velocity of 6.28 rad and a temperature change condition of 1 ° C. per minute, storage in a temperature rising process from 30 ° C. to 170 ° C. is performed. When the elastic modulus G ′ is measured, the G ′ change width in the temperature raising process from 60 ° C. to 140 ° C. is 10 ^{2 to} 10 ⁵ Pa and G in the temperature raising process from 150 ° C. to 170 ° C. 'The change width is 10 ³ Pa or less. This indicates that the change range is large in the relatively low temperature region and the change range is small in the high temperature region of 150 ° C. or higher, and the toner particles have excellent low temperature fixability and cause further undesired deformation in the high temperature region. Indicates difficult.
The storage elastic modulus of the toner particles of this embodiment was determined from dynamic viscoelasticity measured by a sine wave vibration method. For measurement of dynamic viscoelasticity, an ARES measuring apparatus manufactured by Rheometric Scientific was used. For measurement of dynamic viscoelasticity, a toner was molded into a tablet and then set on an 8 mm diameter parallel plate. After normal force was set to 0, sinusoidal vibration was applied at a vibration frequency of 6.28 rad / sec. The measurement started from 30 ° C and continued to 200 ° C.
The measurement time interval was 30 seconds and the temperature rise was 1 ° C./min. Further, before the measurement, the stress dependency of the strain amount was confirmed at intervals of 10 ° C. from 20 ° C. to 100 ° C., and the strain amount range in which the stress and the strain amount at each temperature are in a linear relationship was obtained. During measurement, the amount of strain at each measurement temperature is maintained within the range of 0.01% to 0.5%, and the stress and strain are controlled to have a linear relationship at all temperatures. From the results of these measurements The storage modulus was determined.

-Binder resin-
In the toner of this embodiment, it is preferable to use a crystalline resin as a binder resin. Moreover, it is particularly preferable to use an amorphous resin in combination as necessary.
In the present embodiment, “crystalline resin” means a resin having a clear endothermic peak (a peak where the half-value width of the endothermic peak is 10 ° C. or less) in differential scanning calorimetry (DSC). "Crystalline resin" means a resin that does not have the above-mentioned clear peak. In addition, regardless of whether the resin is a crystalline resin or an amorphous resin, the weight average molecular weight of the binder resin is particularly preferably 10,000 or more, and the weight average molecular weight is usually preferably in the range of 15000 to 50000.
As the crystalline resin, for example, a polyester resin, a crystalline vinyl resin, or the like can be used. As the amorphous resin, for example, a polyester resin, a polyurethane resin, an epoxy resin, a polyol resin, or the like is used. Hereinafter, the binder resin used in the present invention will be described separately for a crystalline resin and an amorphous resin.

(Crystalline resin)
The content of the crystalline resin contained in the toner particles is preferably in the range of 2% by mass to 30% by mass, and more preferably in the range of 3% by mass to 15% by mass. If the content of the crystalline resin is less than 2% by weight, fixing in a low temperature region may be difficult. Further, if the content of the crystalline resin exceeds 30% by mass, gloss unevenness is likely to occur or filming is likely to occur particularly when fixing is performed in an intermediate temperature range or a high temperature range. . The toner of the present embodiment preferably has an external additive added as will be described later. In this specification, the toner before the external additive is added may be referred to as “toner particles”.

The melting temperature of the crystalline resin is preferably in the range of 45 ° C. or higher and 110 ° C. or lower, more preferably in the range of 50 ° C. or higher and 100 ° C. or lower, and still more preferably in the range of 55 ° C. or higher and 90 ° C. or lower.
When the melting temperature is lower than 45 ° C., it becomes difficult to store the toner, and when it exceeds 110 ° C., fixing in a low temperature range (hereinafter sometimes referred to as “low temperature fixability”) may be difficult. In addition, the melting temperature of crystalline resin means what was calculated | required by the method based on ASTMD3418-8.

  Further, the number average molecular weight (Mn) of the crystalline resin is preferably 5000 or more, and more preferably 7000 or more. If the number average molecular weight (Mn) is less than 7000, the toner may penetrate into the surface of a recording medium such as paper at the time of fixing to cause uneven fixing, or the resistance to bending of the fixed image may be reduced. .

  As described above, crystalline polyester resin, crystalline vinyl resin, etc. are used as the crystalline resin. However, the adhesiveness to the paper and the charging property at the time of fixing, and the melting temperature satisfying the above range can be easily achieved. From the viewpoint of being obtained, it is preferable to use a crystalline polyester resin. In particular, an aliphatic crystalline polyester resin is more preferable because a resin having a desired melting temperature is easily obtained.

  Examples of the crystalline vinyl resin include amyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, and (meth) acrylic. Decyl acid, undecyl (meth) acrylate, tridecyl (meth) acrylate, myristyl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, oleyl (meth) acrylate, (meth) acrylic acid Examples thereof include vinyl resins using long-chain alkyl such as behenyl and alkenyl (meth) acrylic acid esters. In the present specification, the description “(meth) acryl” means that both “acryl” and “methacryl” are included.

On the other hand, the crystalline polyester resin is synthesized from a carboxylic acid (dicarboxylic acid) component and an alcohol (diol) component.
Hereinafter, the carboxylic acid component and the alcohol component will be described in more detail. In the present specification, the “crystalline polyester resin” also means a copolymer obtained by copolymerizing other components in a proportion of 50% by mass or less with respect to the main chain of the crystalline polyester resin.

  The carboxylic acid component is preferably an aliphatic dicarboxylic acid, and particularly preferably a linear carboxylic acid. For example, succinic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelic acid, sebacic acid, 1,9-nonanedicarboxylic acid, 1,10-decanedicarboxylic acid, 1,11-undecanedicarboxylic acid Acid, 1,12-dodecanedicarboxylic acid, 1,13-tridecanedicarboxylic acid, 1,14-tetradecanedicarboxylic acid, 1,16-hexadecanedicarboxylic acid, 1,18-octadecanedicarboxylic acid, etc., or lower alkyl esters thereof, Acid anhydrides can be mentioned but are not limited to these.

  The carboxylic acid component preferably contains a constituent component of a dicarboxylic acid component having a double bond in addition to the aliphatic dicarboxylic acid component described above. The dicarboxylic acid component having a double bond includes a component derived from a lower alkyl ester or acid anhydride of a dicarboxylic acid having a double bond, in addition to a component derived from a dicarboxylic acid having a double bond. Is also included.

  The dicarboxylic acid having a double bond is preferably used in order to prevent hot offset at the time of fixing because the entire resin can be crosslinked using the double bond. Examples of the dicarboxylic acid include, but are not limited to, fumaric acid, maleic acid, 3-hexenedioic acid, and 3-octenedioic acid. Moreover, these lower alkyl esters, acid anhydrides, etc. are also mentioned. Among these, fumaric acid, maleic acid and the like are preferable in terms of cost.

  The content of the carboxylic acid component other than these aliphatic dicarboxylic acid components (dicarboxylic acid component having a double bond and / or dicarboxylic acid component having a sulfonic acid group) in the carboxylic acid component is 1 component mol% or more and 20 Constituent mol% is preferable, and 2 constituent mol% or more and 10 constituent mol% is more preferable.

When the content is less than 1 mol%, the use of a pigment as a colorant may deteriorate the dispersibility of the pigment in the toner base particles.
Further, when a toner is produced using the emulsion polymerization aggregation method, the emulsion particle diameter in the dispersion becomes large, and it may be difficult to adjust the toner diameter by aggregation. On the other hand, if it exceeds 20 component mol%, the crystallinity of the crystalline polyester resin is lowered, the melting temperature is lowered, and the image storage stability may be deteriorated. Further, when a toner is produced using an emulsion polymerization aggregation method, the emulsion particle size in the dispersion may be too small to dissolve in water, and latex may not be generated. In the present invention, “constituent mol%” refers to a percentage when each constituent component (carboxylic acid component, alcohol component) in the polyester resin is 1 unit (mol).

  On the other hand, the alcohol component is preferably an aliphatic diol, such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7. -Heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14 -Tetradecanediol, 1,18-octadecanediol, 1,20-eicosanediol and the like are exemplified, but not limited thereto.

  The alcohol component preferably has an aliphatic diol component content of 80 constituent mol% or more, and includes other components as necessary. As the alcohol component, the content of the aliphatic diol component is more preferably 90 constituent mol% or more.

  When the content is less than 80 mol%, the crystallinity of the polyester resin is lowered and the melting temperature is lowered, so that toner blocking resistance, image storage stability, and low-temperature fixability may be deteriorated. On the other hand, examples of other components included as necessary include diol components having a double bond and diol components having a sulfonic acid group.

  Examples of the diol having a double bond include 2-butene-1,4-diol, 3-butene-1,6-diol, 4-butene-1,8-diol, and the like. On the other hand, examples of the diol having a sulfonic acid group include 1,4-dihydroxy-2-sulfonic acid benzene sodium salt, 1,3-dihydroxymethyl-5-sulfonic acid benzene sodium salt, and 2-sulfo-1,4. -Butanediol sodium salt and the like.

  In the case of adding an alcohol component other than these linear aliphatic diol components (a diol component having a double bond and / or a diol component having a sulfonic acid group), the content in the alcohol component is one component mole. % Or more and 20 component mol% is preferable, and 2 component mol% or more and 10 component mol% is more preferable. When the content is less than 1 component mol%, pigment dispersion may be poor, the emulsified particle size may be increased, and adjustment of the toner diameter by aggregation may be difficult. On the other hand, if it exceeds 20 component mol%, the crystallinity of the polyester resin is lowered, the melting temperature is lowered, and the storage stability of the image is deteriorated. It may not occur.

  The method for producing the crystalline polyester resin is not particularly limited and can be produced by a general polyester polymerization method in which a carboxylic acid component and an alcohol component are reacted. Examples thereof include direct polycondensation and transesterification. Produced separately depending on the type of monomer. The molar ratio (acid component / alcohol component) when the acid component reacts with the alcohol component varies depending on the reaction conditions and the like, and cannot be generally stated, but is usually about 1/1.

  The crystalline polyester resin can be produced at a polymerization temperature of 180 ° C. or higher and 230 ° C. or lower. The reaction system is reduced in pressure as necessary, and the reaction is carried out while removing water and alcohol generated during condensation. When the monomer is not dissolved or compatible at the reaction temperature, a solvent having a high boiling point may be added as a solubilizer and dissolved. In the polycondensation reaction, the dissolution auxiliary solvent is distilled off. If a monomer with poor compatibility is present in the copolymerization reaction, the monomer with poor compatibility and the monomer and the carboxylic acid component or alcohol component to be polycondensed are condensed in advance and then polycondensed together with the main component. Good.

  Examples of the catalyst used in the production of the crystalline polyester resin include alkali metal compounds such as sodium and lithium; alkaline earth metal compounds such as magnesium and calcium; zinc, manganese, antimony, titanium, tin, zirconium, Examples include metal compounds such as germanium; phosphorous acid compounds, phosphoric acid compounds, and amine compounds. Specific examples include the following compounds.

  For example, sodium acetate, sodium carbonate, lithium acetate, calcium acetate, zinc stearate, zinc naphthenate, zinc chloride, manganese acetate, manganese naphthenate, titanium tetraethoxide, titanium tetrapropoxide, titanium tetraisopropoxide, titanium tetra Butoxide, antimony trioxide, triphenylantimony, tributylantimony, tin formate, tin oxalate, tetraphenyltin, dibutyltin dichloride, dibutyltin oxide, diphenyltin oxide, zirconium tetrabutoxide, zirconium naphthenate, zirconyl carbonate, zirconyl acetate, zirconyl stearate , Zirconyl octylate, germanium oxide, triphenyl phosphite, tris (2,4-di-t-butylphenyl) phosphite Ethyltriphenylphosphonium bromide, triethylamine, compounds such as triphenyl amine.

  Among the catalysts containing metal elements capable of taking the valences of 2 or more listed above, calcium acetate is preferred from the viewpoint that it is easier to achieve both low-temperature fixability and gloss unevenness suppressing effect at a high level. It is preferable to use manganese acetate.

In addition to the above polymerizable monomers, compounds having shorter chain alkyl groups, alkenyl groups, aromatic rings and the like are also used for the purpose of adjusting the melting temperature and molecular weight of the crystalline resin.
Specific examples include, for example, dicarboxylic acids, alkyldicarboxylic acids such as succinic acid, malonic acid, and oxalic acid, and phthalic acid, isophthalic acid, terephthalic acid, homophthalic acid, 4,4′-bibenzoic acid, 2, Aromatic dicarboxylic acids such as 6-naphthalenedicarboxylic acid and 1,4-naphthalenedicarboxylic acid, nitrogen-containing aromatic dicarboxylic acids such as dipicolinic acid, dinicotinic acid, quinolinic acid, and 2,3-pyrazinedicarboxylic acid, and diols In the case of short chain alkyl diols such as succinic acid, malonic acid, acetone dicarboxylic acid, diglycolic acid, etc., and in the case of short chain alkyl vinyl polymerizable monomers, methyl (meth) acrylate, ( Short chain alkyls such as ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and alkenyl (Meth) acrylic acid esters, vinyl nitriles such as acrylonitrile and methacrylonitrile, vinyl ethers such as vinyl methyl ether and vinyl isobutyl ether, vinyl methyl ketone, vinyl ethyl ketone, vinyl isopropenyl ketones, ethylene, propylene, butadiene And olefins such as isoprene. These polymerizable monomers may be used individually by 1 type, and may use 2 or more types together.

(Non-crystalline resin)
In the toner of the exemplary embodiment, a non-crystalline resin may be used together with a crystalline resin as a binder resin.
The molecular weight of the amorphous resin to be used is not particularly limited, but when the toner is produced by using an emulsion polymerization aggregation method described later, an amorphous resin having a high weight average molecular weight (Mw) (high It is preferable to use a non-crystalline resin (low molecular weight component) having a low molecular weight component and a molecular weight component.

  In this case, Mw of the high molecular weight component is preferably 30000 or more and 300000 or less, more preferably 30000 or more and 200000 or less, and particularly preferably 35000 or more and 150,000 or less. By controlling the Mw of the high molecular weight component within the above range, it is more efficiently compatible with the crystalline resin, and further, separation from the crystalline resin once compatible is suppressed.

On the other hand, the Mw of the low molecular weight component is preferably 8000 or more and 25000 or less, more preferably 8000 or more and 22000 or less, and particularly preferably 9000 or more and 20000 or less.
By controlling the Mw of the high molecular weight component within the above range, the inclusion of the high molecular weight component in the toner particles is improved when the aggregated particles obtained by aggregating the raw material components by the emulsion polymerization aggregation method are heated and fused. The exposure of the crystalline resin to the toner particle surface is prevented.

As described above, when the high molecular weight component and the low molecular weight component are mixed and used, the blending ratio of both is preferably in the range of high molecular weight component / low molecular weight component = 35/65 to 95/5, and 40/60 The range of thru | or 90/10 is more preferable, and the range of 50/50 thru | or 85/15 is still more preferable.
The high molecular weight component preferably contains alkenyl succinic acid or its anhydride and trimellitic acid or its anhydride as its constituent monomers. Alkenyl succinic acid or its anhydride is more easily compatible with crystalline polyester resin due to the presence of highly hydrophobic alkenyl groups.

  In the present embodiment, the molecular weight distribution uses Tosoh Corporation HLC-8120GPC, SC-8020 apparatus, the column uses TSK gei, SuperHM-H (6.0 mm ID × 15 cm × 2), and THF (tetrahydrofuran) as an eluent. ). The measurement conditions were a sample concentration of 0.5% and a flow rate of 0.6 ml / min. Sample injection volume 10 μl, measurement temperature 40 ° C., calibration curve is A-500, F-1, F-10, F-80, F-380, A-2500, F-4, F-40, F-128, Made from 10 samples of F-700. The data collection interval in sample analysis was 300 ms.

  Examples of the alkenyl succinic acid component include n-dodecenyl succinic acid, isododecenyl succinic acid, n-octenyl succinic acid, acid anhydrides, acid chlorides thereof, and lower alkyl esters having 1 to 3 carbon atoms. By containing a trivalent or higher polyvalent carboxylic acid, the polymer chain takes a crosslinked structure. By taking a cross-linked structure, an effect of fixing the crystalline polyester resin once compatible and making it difficult to separate is obtained. Examples of trivalent or higher polyvalent carboxylic acids include hemimellitic acid, trimellitic acid, trimesic acid, merophanic acid, planitic acid, pyromellitic acid, merit acid, 1,2,3,4-butanetetracarboxylic acid and These acid anhydrides, acid chlorides and lower alkyl esters having 1 to 3 carbon atoms can be mentioned.

There is no restriction | limiting in particular in the manufacturing method of an amorphous polyester resin, It manufactures with the above-mentioned general polyester polymerization method. As the carboxylic acid component used for the synthesis of the amorphous polyester resin, various dicarboxylic acids mentioned for the crystalline polyester resin are used.
As the alcohol component, various diols used for the synthesis of the amorphous polyester resin are used. In addition to the aliphatic diols mentioned for the crystalline polyester resin, for example, bisphenol A, bisphenol A ethylene oxide adduct, bisphenol A Propylene oxide adducts, hydrogenated bisphenol A, bisphenol S, bisphenol S ethylene oxide adducts, bisphenol S propylene oxide adducts, and the like are used. Furthermore, it is particularly preferable to use bisphenol S derivatives such as bisphenol S, bisphenol S ethylene oxide adduct, and bisphenol S propylene oxide adduct from the viewpoints of toner manufacturability, heat resistance, and transparency. Further, both the carboxylic acid component and the alcohol component may contain a plurality of components, and in particular, bisphenol S has an effect of improving heat resistance.

(Binder resin crosslinking treatment, etc.)
Next, the amorphous resin used as the binder resin, the crosslinking treatment of the crystalline resin used as necessary, and the copolymerization component used in the synthesis of the binder resin will be described.
In synthesizing the binder resin, other components can be copolymerized, and a compound having a hydrophilic polar group is used. As a specific example, when the binder resin is a polyester resin, for example, dicarboxylic acid compounds in which an aromatic ring such as sulfonyl-terephthalic acid sodium salt or 3-sulfonylisophthalic acid sodium salt is directly substituted are mentioned. When the binder resin is a vinyl resin, for example, unsaturated aliphatic carboxylic acids such as (meth) acrylic acid and itaconic acid, glycerin mono (meth) acrylate, fatty acid-modified glycidyl (meth) acrylate, and zinc mono (meth) acrylate , Zinc di (meth) acrylate, 2-hydroxyethyl (meth) acrylate, polyethylene glycol (meth) acrylate, esters of (meth) acrylic acid and alcohols such as polypropylene glycol (meth) acrylate, ortho, meta, para Examples include styrene derivatives having a sulfonyl group at any of the positions, sulfonyl group-substituted aromatic vinyls such as sulfonyl group-containing vinyl naphthalene, and the like.

In addition, a crosslinking agent may be added to the binder resin as necessary for the purpose of preventing uneven glossiness, uneven color development, hot offset, and the like during fixing in a high temperature region.
Specific examples of the crosslinking agent include aromatic polyvinyl compounds such as divinylbenzene and divinylnaphthalene, divinyl phthalate, divinyl isophthalate, divinyl terephthalate, divinyl homophthalate, divinyl trimesate / trivinyl, and naphthalene dicarboxylic acid. Polyvinyl esters of aromatic polycarboxylic acids such as divinyl and divinyl biphenyl carboxylate, divinyl esters of nitrogen-containing aromatic compounds such as divinyl pyridine dicarboxylate, unsaturated heterocyclic compounds such as pyrrole and thiophene, pyromutic acid Vinyl esters of unsaturated heterocyclic compounds such as vinyl, vinyl furancarboxylate, vinyl pyrrole-2-carboxylate, vinyl thiophenecarboxylate, butanediol methacrylate, hexanediol acrylate, octanedio (Meth) acrylic acid esters of linear polyhydric alcohols such as dimethacrylate, decanediol acrylate and dodecanediol methacrylate, branching and substitution such as neopentyl glycol dimethacrylate, 2-hydroxy, 1,3-diacryloxypropane Polyhydric alcohol (meth) acrylic acid esters, polyethylene glycol di (meth) acrylate, polypropylene polyethylene glycol di (meth) acrylates, divinyl succinate, divinyl fumarate, vinyl / divinyl maleate, divinyl diglycolate, itacon Vinyl / divinyl acetate, divinyl acetone dicarboxylate, divinyl glutarate, divinyl 3,3′-thiodipropionate, divinyl aconite / trivinyl, divinyl adipate, dipimelate Cycloalkenyl, divinyl suberate, azelate, divinyl sebacate, divinyl dodecanedioate divinyl, the polyvinyl esters of polycarboxylic acids such as oxalic acid divinyl and the like.

  In particular, in the crystalline polyester resin, for example, unsaturated polycarboxylic acids such as fumaric acid, maleic acid, itaconic acid, trans-aconitic acid, etc. are copolymerized in the polyester, and then the multiple bond portions in the resin are bonded together, Or you may use the method of bridge | crosslinking using another vinyl type compound. In addition, these crosslinking agents may be used individually by 1 type, and may be used in combination of 2 or more types.

  As a method of cross-linking with these cross-linking agents, a method of polymerizing and cross-linking with a cross-linking agent in a step of polymerizing a polymerizable monomer (monomer) may be used, or an unsaturated portion may be left in the binder resin to bind the resin. Alternatively, the unsaturated portion may be cross-linked by a cross-linking reaction after the polymerization of the polymer or after the toner preparation.

  When the binder resin is a polyester resin, the polymerizable monomer is polymerized by condensation polymerization. As the polycondensation catalyst, known ones can be used. Specific examples include titanium tetrabutoxide, dibutyltin oxide, germanium dioxide, antimony trioxide, tin acetate, zinc acetate, tin disulfide and the like. It is done. When the binder resin is a vinyl resin, the polymerizable monomer is polymerized by radical polymerization.

  The initiator for radical polymerization is not particularly limited as long as it undergoes emulsion polymerization. Specifically, hydrogen peroxide, acetyl peroxide, cumyl peroxide, tert-butyl peroxide, propionyl peroxide, benzoyl peroxide, chlorobenzoyl peroxide, dichlorobenzoyl peroxide, bromomethylbenzoyl peroxide, lauroyl peroxide , Ammonium persulfate, sodium persulfate, potassium persulfate, diisopropyltetralin hydroperoxide, 1-phenyl-2-methylpropyl-1-hydroperoxide, pertriphenylacetic acid-tert-butyl hydroperoxide, tert-butyl formate, Peroxides such as tert-butyl peracetate, tert-butyl perbenzoate, tert-butyl perphenylacetate, tert-butyl permethoxyacetate, tert-butyl perN- (3-toluyl) carbamate, 2,2 '-Azobisp Bread, 2,2′-dichloro-2,2′-azobispropane, 1,1′-azo (methylethyl) diacetate, 2,2′-azobis (2-amidinopropane) hydrochloride, 2,2 ′ -Azobis (2-amidinopropane) nitrate, 2,2'-azobisisobutane, 2,2'-azobisisobutyramide, 2,2'-azobisisobutyronitrile, 2,2'-azobis-2- Methyl methylpropionate, 2,2′-dichloro-2,2′-azobisbutane, 2,2′-azobis-2-methylbutyronitrile, dimethyl 2,2′-azobisisobutyrate, 1,1′-azobis (1 -Sodium methylbutyronitrile-3-sulfonate), 2- (4-methylphenylazo) -2-methylmalonodinitrile, 4,4'-azobis-4-cyanovaleric acid, 3,5-dihy Roxymethylphenylazo-2-methylmalonodinitrile, 2- (4-bromophenylazo) -2-allylmalonodinitrile, 2,2′-azobis-2-methylvaleronitrile, 4,4′-azobis-4 -Dimethyl cyanovalerate, 2,2'-azobis-2,4-dimethylvaleronitrile, 1,1'-azobiscyclohexanenitrile, 2,2'-azobis-2-propylbutyronitrile, 1,1'- Azobis-1-chlorophenylethane, 1,1′-azobis-1-cyclohexanecarbonitrile, 1,1′-azobis-1-cycloheptanenitrile, 1,1′-azobis-1-phenylethane, 1,1 ′ -Azobiscumene, 4-nitrophenylazobenzyl cyanoacetate ethyl, phenylazodiphenylmethane, phenylazotriphenylmeth Tan, 4-nitrophenylazotriphenylmethane, 1,1′-azobis-1,2-diphenylethane, poly (bisphenol A-4,4′-azobis-4-cyanopentanoate), poly (tetraethylene glycol) -2,2'-azobisisobutyrate) and the like, 1,4-bis (pentaethylene) -2-tetrazene, 1,4-dimethoxycarbonyl-1,4-diphenyl-2-tetrazene and the like Can be mentioned. These polymerization initiators are also used as initiators during the crosslinking reaction.

  As the binder resin, mainly the crystalline polyester resin and the non-crystalline polyester resin have been described above. However, other styrenes such as styrene, parachlorostyrene, α-methylstyrene, etc. Acrylic monomers such as methyl acrylate, ethyl acrylate, n-propyl acrylate, butyl acrylate, lauryl acrylate, 2-ethylhexyl acrylate; methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, Methacrylic monomers such as lauryl methacrylate and 2-ethylhexyl methacrylate; ethylenically unsaturated acid monomers such as acrylic acid, methacrylic acid and sodium styrenesulfonate; and vinyl nitriles such as acrylonitrile and methacrylonitrile Vinyl vinyl ether, vinyl Vinyl ethers such as isobutyl ether; vinyl ketones such as vinyl methyl ketone, vinyl ethyl ketone and vinyl isopropenyl ketone; homopolymers of olefin monomers such as ethylene, propylene and butadiene, and two or more of these monomers Copolymers combined or a mixture thereof, and further, non-vinyl condensation resins such as epoxy resins, polyester resins, polyurethane resins, polyamide resins, cellulose resins, polyether resins, or the like and the vinyl resins A mixture, a graft polymer obtained by polymerizing a vinyl monomer in the presence of these, and the like are used.

  As will be described later, when the toner of this embodiment is prepared by the emulsion polymerization aggregation method (that is, when the resin particle dispersion is adjusted by the emulsion polymerization method in the process of preparing the toner by the aggregation / unification method), The adhesion resin is prepared as a resin particle dispersion. The resin particle dispersion can be easily obtained by an emulsion polymerization method and a polymerization method similar to a heterogeneous dispersion system. The resin particle dispersion is obtained by a method in which a polymer previously polymerized by a solution polymerization method, a cage polymerization method, or the like is added to a solvent in which the polymer is not dissolved together with a stabilizer and mechanically mixed and dispersed.

For example, when synthesizing a vinyl resin, an ionic surfactant is used, and a resin particle dispersion is preferably obtained by emulsion polymerization or seed polymerization using an ionic surfactant and a nonionic surfactant in combination. Is made.
Examples of the surfactant used herein include anionic surfactants such as sulfate ester, sulfonate, phosphate, and soap; cationic surfactants such as amine salt type and quaternary ammonium salt type; Nonionic surfactants such as polyethylene glycols, alkylphenol ethylene oxide adducts, alkyl alcohol ethylene oxide adducts, polyhydric alcohols, and various graft polymers, etc., are not particularly limited. Absent.

  When preparing a resin particle dispersion by emulsion polymerization, a small amount of unsaturated acid such as acrylic acid, methacrylic acid, maleic acid, styrene sulfonic acid, etc. is added as a part of the monomer component to the particle surface. A protective colloid layer can be formed, which is particularly preferable because it becomes soap-free polymerization.

-Release agent-
The toner of the exemplary embodiment preferably contains a release agent. As the release agent, a known release agent for toner can be used. For example, low molecular weight polyolefins such as polyethylene, polypropylene, and polybutene; Fatty acid amides such as silicones, oleic acid amide, erucic acid amide, ricinoleic acid amide, stearic acid amide; plant waxes such as carnauba wax, rice wax, candelilla wax, tree wax, jojoba oil; animals such as beeswax System wax; mineral wax such as montan wax, ozokerite, ceresin, paraffin wax, microcrystalline wax, Fischer-Tropsch wax, petroleum wax, and modified products thereof.

  The content of the release agent in the toner particles is preferably in the range of 0.5% by mass or more and 50% by mass or less, more preferably in the range of 1% by mass or more and 30% by mass or less, and 5% by mass or more and 15% by mass or less. A range is more preferred. If the content is less than 0.5% by mass, oil-less fixing may be difficult. If the content exceeds 50% by mass, the release agent may not easily bleed out onto the image surface when fixing, and the image In some cases, the release agent tends to stay therein, and the transparency of the image may be deteriorated.

The average dispersion diameter of the release agent dispersed and contained in the toner is preferably in the range of 0.3 μm to 0.8 μm, and preferably in the range of 0.4 μm to 0.8 μm. More preferred.
When the average dispersion diameter of the release agent is less than 0.3 μm, the releasability may be insufficient, and this tendency tends to become more remarkable particularly when the process speed is fast. On the other hand, when the thickness exceeds 0.8 μm, the transparency may be lowered when the OHP sheet is used, and the release agent component may be exposed to the toner surface.

Further, the standard deviation of the dispersion diameter of the release agent is preferably 0.05 or less, and more preferably 0.04 or less. When the standard deviation of the dispersion diameter of the release agent exceeds 0.05, the release property, transparency when using the OHP sheet, and exposure of the release agent to the toner surface may be adversely affected.
The average dispersion diameter of the release agent dispersed and contained in the toner is obtained by analyzing a TEM (transmission electron microscope) photograph of a cross section of the toner particle with an image analysis apparatus (Lusex image analysis apparatus manufactured by Nireco). It is obtained by calculating the average value of the dispersion diameter (= (major axis + minor axis) / 2) of the release agent in individual toner particles, and the standard deviation is obtained based on the individual dispersion diameters obtained at this time. It was.

Further, the exposure rate of the release agent on the toner particle surface is preferably in the range of 5 atom% to 12 atom%, and more preferably in the range of 6 atom% to 11 atom%.
When the exposure rate is less than 5 atom%, particularly when performing high-speed image formation with a process speed of 200 mm / s or more, fixability may deteriorate when fixing in a high temperature range, and when the exposure rate exceeds 12 atom%. In long-term use, the developability and transferability may be deteriorated due to uneven distribution of external additives or embedding in toner particles.

Here, the exposure rate of the release agent on the toner particle surface was determined by XPS (X-ray photoelectron spectroscopy) measurement.
The XPS measurement was performed using JPS-9000MX manufactured by JEOL Ltd. as a measuring device, using an MgKα ray as an X-ray source, setting an acceleration voltage to 10 kV, and an emission current to 30 mA.
Then, from the C1S spectrum obtained under the above conditions, the amount of the release agent on the toner surface was quantified by peak-separating components due to the release agent on the toner surface. In the peak separation, the measured C1S spectrum is separated into each component using curve fitting by the least square method. As the component spectrum serving as a base for separation, a C1S spectrum obtained by independently measuring the release agent, the binder resin, and the crystalline resin used for the preparation of the toner was used.

-Colorant-
The toner of this embodiment contains a colorant.
Examples of the colorant used in the present embodiment include carbon black, chrome yellow, hansa yellow, benzidine yellow, sren yellow, quinoline yellow, permanent orange GTR, pyrazolone orange, vulcan orange, watch young red, permanent red, and brilliantamine 3B. , Brilliantamine 6B, Dupont Oil Red, Pyrazolone Red, Resol Red, Rhodamine B Lake, Lake Red C, Rose Bengal, Aniline Blue, Ultramarine Blue, Calco Oil Blue, Methylene Blue Chloride, Phthalocyanine Blue, Phthalocyanine Green, Malachite Green Oxalate Various pigments such as acridine, xanthene, azo, benzoquinone, azine, anthraquino 1 type or 2 or more types of various dyes such as thioindico, dioxazine, thiazine, azomethine, indico, phthalocyanine, aniline black, polymethine, triphenylmethane, diphenylmethane, and thiazole You may use together.

In addition, a colorant that has been surface-modified with rosin, polymer, or the like is also used. The surface-modified colorant is stabilized in the colorant dispersion, and after the colorant is dispersed to the desired average particle size in the colorant dispersion, it is mixed with the resin particle dispersion. At this time, it is advantageous in that the colorant does not aggregate in the aggregated particle forming process and the like, and a good dispersion state is maintained. On the other hand, the colorant that has been subjected to an excessive surface modification treatment may be released without being aggregated with the resin particles in the aggregated particle forming step. For this reason, the surface modification treatment is performed under selected optimum conditions.
Examples of the polymer used for the surface treatment of the colorant include acrylonitrile polymer and methyl methacrylate polymer.

  The conditions for surface modification are generally a polymerization method in which a monomer is polymerized in the presence of a colorant (pigment), a colorant (pigment) is dispersed in a polymer solution, and the solubility of the polymer is lowered to reduce the colorant (pigment). ) A phase separation method that precipitates on the surface is used.

  The content of the colorant is preferably in the range of 1% by mass to 20% by mass with respect to the entire toner particles.

-Other additive components-
When the toner of this embodiment is used as a magnetic toner, magnetic powder is contained. Examples of the magnetic powder used here include metals such as ferrite, magnetite, reduced iron, cobalt, nickel, and manganese, alloys, or these metals. And the like. Furthermore, various charge control agents that are usually used, such as quaternary ammonium salts, nigrosine compounds and triphenylmethane pigments, may be added as necessary.

  The toner of this embodiment may be internally added with inorganic particles as necessary. The inorganic particles having a center particle of 5 nm or more and 30 nm or less and the inorganic particle having a center particle diameter of 30 nm or more and 100 nm or less are contained in a range of 0.5 mass% or more and 10 mass% or less with respect to the toner. More preferable in terms of durability.

  Examples of the inorganic particles include silica, hydrophobized silica, titanium oxide, alumina, calcium carbonate, magnesium carbonate, tricalcium phosphate, colloidal silica, cationic surface-treated colloidal silica, and anion surface-treated colloidal silica. These inorganic particles are dispersed in advance in the presence of an ionic surfactant using an ultrasonic disperser or the like, and it is more preferable to use colloidal silica which does not require this dispersion treatment.

  When the added amount of the inorganic particles is less than 0.5% by mass, not only the addition of the inorganic particles does not provide sufficient toughness at the time of melting the toner, but not only the releasability in oilless fixing can be improved, but also when the toner is melted. The coarse dispersion of the toner particles in the toner increases only the viscosity, and as a result, the spinnability is deteriorated, so that the peelability in oilless fixing may be impaired. On the other hand, if it exceeds 10% by mass, sufficient toughness can be obtained, but the fluidity at the time of melting the toner is greatly reduced, and the gloss of the image may be impaired.

-Additives (external additives)-
A known additive (external additive) may be externally added to the electrostatic image developing toner of the exemplary embodiment. As the external additive, inorganic particles such as silica, alumina, titania, calcium carbonate, magnesium carbonate, and tricalcium phosphate are used. For example, as fluidity aids and cleaning aids, inorganic particles such as silica, alumina, titania and calcium carbonate, and resin particles such as vinyl resin, polyester and silicone are used. The method for adding the external additive is not particularly limited, but may be added to the toner particle surface by applying a shearing force in a dry state.

The toner of the exemplary embodiment preferably contains two or more types of external additives having different Mohs hardnesses, particularly two or more types of oxide particles having different Mohs hardnesses. By containing two or more types of external additives with different Mohs hardnesses, external additives with low Mohs hardness (low hardness external additives) protect the surface of electrophotographic photoreceptors (image carriers), cleaning blades, etc. And alleviate the adhesion of discharge products. The external additive having a high Mohs hardness (high hardness external additive) is appropriately buried in the flexible layer on the surface of the toner particle of the present embodiment and fixed on the surface of the particle, and the discharge adhered to the surface of the electrophotographic photoreceptor. Polish products uniformly. At this time, since the high-hardness additive is hardly detached from the toner particle surface, damage to the blade and the like is also suppressed. Further, cleaning is performed while suppressing surface scratches and uneven wear that cause image defects.
The toner according to the exemplary embodiment preferably includes three or more types of external additives having different Mohs hardnesses. That is, in addition to the advantages of the above-mentioned high hardness additive and low hardness additive, further addition of a medium Mohs hardness additive results in a medium hardness due to the influence of a high hardness external additive embedded in the toner surface. Additives are difficult to embed in the toner particles and maintain the structure as an external additive, so even if they are used repeatedly for a long time and in harsh environments, the charge difference between stress toner and fresh toner is suppressed and abnormal Charging is unlikely to occur.
The Mohs hardness is a value represented by a Mohs hardness of 1 to 10.

The Mohs hardness of the low-hardness external additive is preferably 2 or more and 6 or less, and more preferably 3 or more and 5 or less in that the effect of protecting the surface of the electrophotographic photoreceptor is exhibited.
Further, the Mohs hardness of the high-hardness external additive is preferably 7 or more and 9 or less, and preferably 7.5 or more in that the effect of strongly polishing the discharge product and the like attached to the surface of the electrophotographic photoreceptor is exhibited. 8.5 or less is more preferable.
Further, when a medium hardness external additive is used, the Mohs hardness is preferably 4.6 or more and 7.0 or less, and more preferably 5.0 or more and 6.5 or less from the viewpoint of maintaining the structure.
Here, when two or more kinds of oxide particles are included as an additive, the difference in hardness between the maximum hardness and the minimum hardness of the included oxide particles is set to 4 or more and 8 or less, thereby adding different kinds of hardness as described above. The effect of the agent is further improved.

Preferred combinations of the low-hardness external additive and the high-hardness external additive when containing two types of external additives having different Mohs hardness include calcium carbonate and alumina, calcium sulfate and zirconia, calcium fluoride and silicon nitride, and the like. Can be mentioned.
Preferred combinations of low-hardness and high-hardness external additives when three types of external additives with different Mohs hardness are included are combinations of calcium carbonate, silica and alumina, calcium sulfate, titania and zirconia, etc. Is mentioned.

The content ratio of the low hardness external additive and the high hardness external additive (low hardness external additive: high hardness external additive, mass ratio) is preferably 20:80 to 80:20, preferably 30:70 to 70: 30 is more preferable. The content ratio of the low-hardness external additive, medium-hardness external additive, and high-hardness external additive is preferably 10:10:80 to 45:45:10, and 15:15:70 to 42.5. : 42.5: 15 is more preferable.
The total content of external additives in the toner according to the exemplary embodiment is preferably 0.8 parts by mass or more and 3.5 parts by mass or less, and more preferably 1 part by mass or more and 2.5 parts by mass or less with respect to 100 parts by mass of the toner. preferable.
When two or more kinds of oxide particles are contained as an additive, the coverage of the oxide particles on the toner surface is 50% or more and 95% or less when the toner surface is measured by an X-ray photoelectron spectrometer (XPS). It is preferably 55% or more and 90% or less. The measuring method of the oxide particle coverage by XPS (X-ray photoelectron spectroscopy) is as follows.
The XPS measurement was performed using JPS-9000MX manufactured by JEOL Ltd. as a measuring device, using an MgKα ray as an X-ray source, setting an acceleration voltage to 10 kV, and an emission current to 30 mA. The coverage was calculated in advance by measuring the measured value of the oxide fine particles alone as 100% and converting the measurement result of the toner particles. This measurement condition can be applied regardless of the type of oxide particles used as the external additive.

-Toner characteristics-
The volume average particle diameter D50v of the toner particles of the present embodiment is preferably in the range of 3 μm to 7 μm. If the thickness is less than 3 μm, the chargeability may be insufficient and scattering to the surroundings may occur to cause image fogging. If the thickness exceeds 7 μm, the resolution of the image may be reduced, and it may be difficult to achieve high image quality. The volume average particle diameter D50v is more preferably in the range of 5 μm to 6.5 μm.

  Further, the volume average particle size distribution index GSDv of the toner is preferably 1.28 or less. If GSDv exceeds 1.28, the sharpness and resolution of the image may decrease. On the other hand, the number average particle size distribution index GSDp is preferably 1.30 or less. When the GSDp exceeds 1.30, the ratio of the small particle size toner is increased, and thus there may be a very large influence from the viewpoint of reliability in addition to the initial performance. That is, as is conventionally known, since the adhesion force of small-diameter toner is large, electrostatic control is likely to be difficult, and when a two-component developer is used, it tends to remain on the carrier. In this case, if mechanical force is repeatedly applied, carrier contamination may be caused, and as a result, deterioration of the carrier may be promoted.

  Particularly in the transfer process, among the toners developed on the image carrier, it is difficult to transfer the small diameter component, resulting in poor transfer efficiency, resulting in increased waste toner and poor image quality. . As a result of these problems, there are cases where toners that are not electrostatically controlled and reverse-polar toners increase, which may contaminate the surroundings. In particular, the charging roll accumulates these uncontrolled toners via an image carrier or the like, which may cause charging failure.

Further, since the toner having a small diameter component tends to have insufficient inclusion of the crystalline resin, filming on the image holding member may be caused. On the other hand, a toner having a large particle size component may cause toner cracking in the developing machine, deflation from the developing machine, image quality deterioration due to charging failure, and the like.
The volume average particle size distribution index GSDv is more preferably 1.25 or less, and the number average particle size distribution index GSDp is more preferably 1.25 or less.

Here, the volume average particle diameter D50v of the toner and various particle size distribution indexes are measured using Coulter Multisizer II (manufactured by Beckman-Coulter), and the electrolyte is measured using ISOTON-II (manufactured by Beckman-Coulter). To do.
In measurement, a measurement sample is added in a range of 0.5 mg to 50 mg in 2 ml of a 5% by weight aqueous solution of a surfactant such as sodium alkylbenzenesulfonate as a dispersant. This is added to 100 ml to 150 ml of electrolyte.
The electrolytic solution in which the sample is suspended is subjected to a dispersion treatment for 1 minute with an ultrasonic disperser, and the particle size distribution of particles having a particle size in the range of 2 μm to 50 μm is obtained using the Multisizer II type with an aperture diameter of 100 μm. taking measurement. The number of particles to be sampled is 50,000.

For the particle size range (channel) divided on the basis of the particle size distribution measured in this way, the cumulative distribution is drawn from the smaller diameter side for the volume and number, respectively, and the cumulative particle size average particle size is 16%. Diameter D16v, cumulative number average particle diameter D16p, cumulative volume average particle diameter 50v is cumulative volume average particle diameter 50v, cumulative number average particle diameter D50p, cumulative volume average particle diameter D84v is cumulative volume average particle diameter D84v, cumulative number average The particle size is defined as D84p.
Here, the volume average particle size distribution index (GSDv) is defined as (D84v / D16v) ^1/2 and the number average particle size distribution index (GSDp) is defined as (D84p / D16p) ^1/2 .

  Further, the average circularity of the toner is preferably in the range of 0.940 to 0.980. If the average circularity is less than the above range, the shape becomes indeterminate, and transferability, durability, fluidity, and the like may decrease. On the other hand, if the above range is exceeded, the ratio of the spherical particles increases and the cleaning property may become difficult. The average circularity is more preferably in the range of 0.950 or more and 0.970 or less.

  In the case of a toner containing a crystalline resin, the average circularity is spherical (when the average circularity is closer to 1), and the spherical toner with a large amount of crystalline resin component may increase. Filming due to accumulation, member deterioration due to torque increase, and filming on the image carrier may occur. On the other hand, when it is on the irregular side (when the average circularity is closer to 0), it may cause toner cracking in the developing machine, and the crystalline resin component may be exposed at the cracked interface, thereby impairing charging properties, etc. There is.

The average circularity of the toner is measured by a flow type particle image analyzer FPIA-2000 (manufactured by Toa Medical Electronics Co., Ltd.). As a specific measurement method, 0.1 to 0.5 ml of a surfactant, for example, alkylbenzesulfonate is added as a dispersant to 100 to 150 ml of water from which impure solids have been removed in advance, and a measurement sample is further added. Add about 0.1g to 0.5g.
The suspension in which the measurement sample is dispersed is subjected to a dispersion treatment for 1 to 3 minutes with an ultrasonic wave disperser, and the average circularity of the toner is measured with the above apparatus with a dispersion concentration of 3000 to 10,000 / μl.

  The glass transition temperature Tg of the toner of the present embodiment is not particularly limited, but a range of 45 ° C. or more and 60 ° C. is preferably selected. Below the above range, problems such as toner storage stability, fixed image storage stability, and durability in the actual machine may occur. If it is higher than the above range, problems such as an increase in the fixing temperature and an increase in the temperature required for granulation may occur.

  In addition, Tg is measured based on ASTMD3418-8 using a DSC measuring machine (differential thermal analyzer DSC60A, manufactured by Shimadzu Corporation). The temperature correction of the detection part of the apparatus uses the melting points of indium and zinc, and the correction of heat quantity uses the heat of fusion of indium. As the sample, an aluminum pan is used, an empty pan is set as a control, and the measurement is performed at a heating rate of 10 ° C./min.

The charge amount of the electrostatic image developing toner of the present embodiment is preferably in the range of 10 μC / g to 40 μC / g, more preferably in the range of 15 μC / g to 35 μC / g in absolute value. When it is less than 10 μC / g, background stains are likely to occur, and when it exceeds 40 μC / g, the image density may be easily lowered.
The ratio of the charge amount in the summer (28 ° C., 85% RH) of the electrostatic image developing toner to the charge amount in the winter (10 ° C., 30% RH) is preferably 0.5 or more and 1.5 or less. 0.7 or more and 1.3 or less are more preferable. When this ratio is out of the above range, the toner is highly dependent on the environment, and the charging property is not stable, which is not preferable in practice.

-Toner production method-
As a toner production method, for example, after preparing a resin particle dispersion by an aggregation / unification method (emulsion polymerization / forced emulsification / phase inversion emulsification method, etc.) and a colorant dispersion in which a colorant is dispersed in a solvent, , These are mixed to form agglomerates corresponding to the toner particle diameter and heated to fuse and coalesce into a toner, and a suspension polymerization method (release agent, colorant, etc. is required) The component used according to the method is suspended together with a polymerizable monomer that forms a binder resin such as a crystalline resin, and a method of producing a toner by polymerizing the polymerizable monomer), a dissolution suspension method ( A compound having an ionic dissociation group, a binder resin such as a crystalline resin, and a toner constituent material such as a release agent are dissolved in an organic solvent and dispersed in an aqueous solvent in a suspended state, and then the organic solvent is removed. And a wet manufacturing method such as a manufacturing method using a toner.

Hereinafter, an aggregation / unification method will be described as an example of a toner manufacturing method according to the present exemplary embodiment.
The toner manufacturing method in the present embodiment includes, for example, a resin particle dispersion adjusting step for adjusting a resin particle dispersion in which resin particles are dispersed, and a colorant particle dispersion for adjusting a colorant particle dispersion in which colorant particles are dispersed. A liquid adjustment step, a mixed solution adjustment step of mixing a resin particle dispersion and a colorant particle dispersion to adjust a mixed solution containing the resin particles and the colorant particles, and an aggregated particle in which the resin particles and the colorant particles are aggregated An agglomerated particle adjusting step for adjusting, and an aggregating particle dispersion in which the agglomerated particles are dispersed are heated to a temperature equal to or higher than the glass transition temperature of the resin particles to fuse and coalesce.
Moreover, you may include other processes, such as the mold release agent particle dispersion liquid adjustment process which adjusts the mold release agent particle dispersion liquid which disperse the mold release agent particle as needed.

  In addition, for the purpose of satisfying the physical property that the toner particles of the present embodiment are dissolved in the alcohol / water mixed solution at a prescribed dissolution rate, a fusion / union step of fusing and uniting by heating above the glass transition temperature, At least one step of cooling the resin particles to the glass transition temperature or lower includes a step of adding a biodegradable dispersant and a step of adjusting the pH to a range of 7 to 11 by adding a basic compound. As described above, the inclusion is preferable.

  The amount of the biodegradable dispersant added is preferably 1 part by mass or more and 20 parts by mass or less, more preferably 2 parts by mass or more and 18 parts by mass or less, with respect to 100 parts by mass of the resin particles (binder resin). More preferably, it is at least 15 parts by mass. Biodegradable dispersants are decomposed during the toner manufacturing process (for example, agglomeration process, coalescence and coalescence process, etc.) and are less likely to remain in the manufactured toner. At most, toner characteristics and image quality are good.

When a hydroxy ether carboxylic acid compound is used as the biodegradable dispersant, the addition amount of the hydroxy ether carboxylic acid compound is preferably 0.5 parts by mass or more and 15 parts by mass or less with respect to 100 parts by mass of the resin particles. 10 mass parts or less are more preferable, and 1.5 mass parts or more and 5 mass parts or less are still more preferable.
Moreover, when using together a hydroxy ether carboxylic acid compound and a complexing agent as a biodegradable dispersant, the total addition amount is preferably 1 part by mass or more and 10 parts by mass or less, and 2 parts by mass with respect to 100 parts by mass of the resin particles. It is more preferably 9 parts by mass or less, and further preferably 3 parts by mass or more and 8 parts by mass or less.

When the addition amount of the hydroxy ether carboxylic acid compound and the addition amount of the complex compound are lower than the above range, the flexibility of the toner surface may be reduced, and as a result, the adhesion variation of the additive on the toner surface increases, For example, there are cases in which electrical characteristics deteriorate, fogging occurs, filming on a photoconductor scratch, or the like occurs in the early stage of toner use.
On the other hand, when the addition amount of the ether carboxylic acid compound and the addition amount of the complexing agent exceed the above ranges, the surface flexibility can be obtained, but the residual amount of the dispersant itself in the toner may increase. In some cases, the process becomes complicated for the removal, or the dispersant remains in the toner without being removed, and as a result of long-term use, the image quality such as fogging may be affected.

When the hydroxy ether carboxylic acid compound and the complexing agent are used in combination as the biodegradable dispersant, the addition amount of the ether carboxylic acid compound is preferably 2 to 7 times the addition amount of the complexing agent. It is more preferably 2 times or more and 6 times or less, and further preferably 3 times or more and 5.5 times or less.
When the biodegradable dispersant is added in a plurality of steps, it is preferable that the total amount added in each step is in the above range.

Hereinafter, each step will be specifically described. In addition, the overlapping part in the description regarding the biodegradable dispersant described above may be omitted.
(Resin particle dispersion adjustment process)
As described above, when the emulsion polymerization method or the like is used in the synthesis of the binder resin, the resin resin dispersion is obtained in the state of the resin particle dispersion.

On the other hand, in the case of obtaining a binder resin by polymerizing in advance by a solution polymerization method, a bulk polymerization method, etc., as described above, the obtained binder resin and the stabilizer are added to a solvent and mixed mechanically. By dispersing, a resin particle dispersion can be obtained. That is, for example, it is performed by applying a shearing force to a solution obtained by mixing an aqueous medium and a binder resin by a disperser. At that time, particles may be formed by heating to lower the viscosity of the resin component. A dispersant may be used for stabilizing the dispersed resin particles.
Furthermore, if the binder resin is oily and can be dissolved in a solvent having a relatively low solubility in water, the resin is dissolved in those solvents and dispersed in water together with a dispersant and a polymer electrolyte, and then heated or decompressed. Then, the resin particle dispersion may be prepared by evaporating the solvent.

Examples of the disperser include a homogenizer, a homomixer, a pressure kneader, an extruder, and a media disperser.
Examples of the aqueous medium include water such as distilled water and ion-exchanged water; alcohols; and the like.

  Examples of the dispersant include water-soluble polymers such as polyvinyl alcohol, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, sodium polyacrylate, and sodium polymethacrylate; sodium dodecylbenzenesulfonate, sodium octadecylsulfate, and oleic acid. Anionic surfactants such as sodium, sodium laurate, potassium stearate, cationic surfactants such as laurylamine acetate, stearylamine acetate, lauryltrimethylammonium chloride, zwitterionic surfactants such as lauryldimethylamine oxide, Polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl amine, etc. Surfactants such as on-surfactants; and the like are; tricalcium phosphate, aluminum hydroxide, calcium sulfate, calcium carbonate, inorganic salts such as barium carbonate.

  Among the above, it is preferable to use a biodegradable dispersant as the dispersant. However, if the mixed solution contains a biodegradable dispersant, only a dispersant other than the biodegradable dispersant may be used. In addition, a biodegradable dispersant and a dispersant other than the biodegradable dispersant may be used in combination.

  The content of the resin particles contained in the resin particle dispersion is desirably in the range of 10% by mass to 50% by mass, and more desirably in the range of 20% by mass to 40% by mass. When the content is less than 10% by mass, the particle size distribution is widened and the toner characteristics may be deteriorated. On the other hand, if it exceeds 50% by mass, uniform stirring becomes difficult, and it may be difficult to obtain a toner having a narrow particle size distribution and uniform characteristics.

The volume average particle size of the resin particles in the resin particle dispersion is desirably 1 μm or less, and more desirably 0.01 μm or more and 1 μm or less. If the average particle size of the resin particles exceeds 1 μm, the particle size distribution of the finally obtained toner may be broadened, or free particles may be generated, leading to a decrease in performance and reliability.
On the other hand, when the average particle diameter of the resin particles is within the above range, the above disadvantages are eliminated, uneven distribution among the toners is reduced, dispersion in the toners is improved, and variations in performance and reliability are reduced. It is advantageous. The volume average particle size of the resin particles is measured using, for example, a laser diffraction particle size distribution measuring device (manufactured by Shimadzu Corporation, SALD2000A).

(Colorant particle dispersion adjustment process)
As a method for dispersing the colorant in the solvent, an arbitrary method such as a rotary shear type homogenizer, a ball mill having a medium, a sand mill, or a dyno mill is adopted.
Examples of the solvent include the same solvents as the aqueous solvent used in the resin particle dispersion.

The volume average particle diameter of the colorant particles is preferably 0.8 μm or less, and more preferably 0.05 μm or more and 0.5 μm or less.
If the volume average particle size of the colorant particles exceeds 0.8 μm, the particle size distribution of the finally obtained toner may be widened, or free particles may be generated, resulting in a decrease in performance and reliability. . Further, when the average particle diameter of the colorant particles is smaller than 0.05 μm, not only the colorability in the toner is lowered but also the shape controllability, which is one of the characteristics of the aggregation / unification method, is impaired. In some cases, a toner having a shape close to a sphere cannot be obtained.

Further, the proportion of coarse particles having a volume average particle size of 0.8 μm or more in the colorant particle dispersion is preferably less than 10% by number, and more preferably close to 0% by number. The presence of the coarse particles may impair the stability of the formed aggregated particles in the aggregated particle forming step. In addition, coarse colored particles may be liberated or the particle size distribution may be widened.
Further, the proportion of fine particles having a volume average particle size of 0.05 μm or less in the colorant particle dispersion is preferably 5% by number or less. The presence of the fine particles impairs the shape controllability of the toner particles in the coalescence and coalescence process, and the average circularity of 0.940 or less may not be obtained.

On the other hand, when the average particle diameter, coarse particles, and fine particles of the colorant are within the above ranges, the above disadvantages are eliminated and the uneven distribution of the components among the toners is reduced, and the dispersion of the components in the toners is improved. This is advantageous in that variations in performance and reliability are reduced.
The volume average particle diameter of the colorant particles is also measured using a laser diffraction particle size distribution measuring apparatus (manufactured by Shimadzu Corporation, SALD2000A).

(Release agent particle dispersion adjustment process)
The release agent particle dispersion is prepared by dispersing it in the above aqueous solvent together with a polymer electrolyte such as an ionic surfactant, polymer acid, polymer base, etc., heating it above the melting temperature, and applying a strong shearing force. The particles are formed using a homogenizer or a pressure discharge type dispersing machine.

(Mixed solution adjustment process)
The mixed solution is prepared by mixing the resin particle dispersion, the colorant particle dispersion, and other dispersions such as a release agent particle dispersion as necessary. At this time, the release agent particle dispersion may be added at once in the mixed solution adjustment step, or may be divided and added in multiple stages.

(Aggregated particle adjustment process)
In the aggregated particle adjustment step, the mixed solution is heated to form aggregated particles in which the particles in the mixed solution are aggregated. Note that the heating is desirably performed in a temperature range lower than the melting temperature of the crystalline resin (a temperature lower by 20 ° C. to 10 ° C. than the melting temperature of the crystalline resin).

Aggregated particles are formed by stirring with a rotary shearing homogenizer. Specifically, for example, an aggregating agent is added at 20 ° C. to 30 ° C. to make the pH of the raw material dispersion acidic (eg, pH = 2.8). Is made by
The flocculant used in the agglomerated particle forming step can take a valence of 2 or more in addition to a surfactant having a reverse polarity to the surfactant used as a dispersant added to the raw material dispersion, that is, an inorganic metal salt. A metal complex containing a metal element is preferably used. In particular, the use of a metal complex is particularly preferable because the amount of the surfactant used can be reduced and the charging characteristics are improved.

  Examples of the inorganic metal salt include metal salts such as calcium chloride, calcium nitrate, barium chloride, magnesium chloride, zinc chloride, aluminum chloride, and aluminum sulfate, and polyaluminum chloride, polyaluminum hydroxide, and calcium polysulfide. Examples thereof include inorganic metal salt polymers. Of these, aluminum salts and polymers thereof are particularly preferred. In order to obtain a sharper particle size distribution, the valence of the inorganic metal salt is bivalent than monovalent, trivalent than bivalent, trivalent than trivalent, and tetravalent than trivalent. The inorganic metal salt polymer is more suitable.

  Examples of the metal complex containing a metal element capable of taking a valence of 2 or more include a metal salt of aminocarboxylic acid. Specifically, calcium salts, magnesium salts, iron salts, aluminum salts and the like based on known chelates such as ethylenediaminetetraacetic acid, propanediaminetetraacetic acid, nitriletriacetic acid, triethylenetetraminehexaacetic acid, diethylenetriaminepentaacetic acid and the like are listed. It is done.

The inorganic metal salt is preferably dispersed in a solvent to form an inorganic particle dispersion, which is added to the mixed solution in advance in the mixed solution preparation step and simultaneously aggregated. As a result, the inorganic metal salt effectively acts on the molecular chain terminal of the binder resin and contributes to the formation of a crosslinked structure.
The inorganic particle dispersion is prepared by an arbitrary method, for example, using a ball mill, a sand mill, an ultrasonic disperser rotary shearing type homogenizer, or the like.

  The inorganic particle dispersion may be added stepwise in the aggregated particle forming step, or may be added continuously. These methods are effective in dispersing the metal ion component in the inorganic particle dispersion from the toner surface to the inside. When adding stepwise, it is particularly preferable to add the dispersion at a slow rate of about 0.1 g / m or less when adding continuously in three steps or more.

  The amount of the inorganic particle dispersion added varies depending on the type of metal required and the degree of formation of the crosslinked structure, but is in the range of 0.5 to 10 parts by mass with respect to 100 parts by mass of the binder resin. It is preferable to set it in a range of 1 part by mass or more and 5 parts by mass or less.

In the agglomerated particle forming step, toner particles are prepared by adjusting the type and amount of inorganic metal salt or metal complex containing a metal element capable of taking a valence of 2 or more in a range that does not affect the formation of agglomerated particles. You may control content of the metal element which can take the valence more than bivalence contained in it.
In addition, from the viewpoint that it is easier to achieve both a low-temperature fixability and a gloss unevenness suppressing effect at a high level, it is preferable to use aluminum sulfate, polyaluminum chloride, or calcium chloride among the aggregating agents listed above. It is.

The aggregated particle forming step may include an attaching step as necessary. In the attaching step, the coating layer is formed by attaching resin particles to the surface of the aggregated particles (core particles) formed through the above-described aggregated particle forming step. Thereby, a toner having a so-called core layer and a core / shell structure covering the core layer is obtained.

  The coating layer is usually formed by additionally adding a resin particle dispersion containing non-crystalline resin particles to the dispersion in which aggregated particles (core particles) are formed in the aggregated particle forming step. In addition, when the amorphous resin is used in addition to the crystalline resin in the step of forming the core particles, the non-crystalline resin used in the adhesion step may be the same as that used in the aggregated particle forming step. It may be.

  In general, the adhesion process is used when a toner having a so-called core / shell structure in which a crystalline resin as a main component is contained as a binder resin together with a release agent, and the main purpose thereof is the core layer. The purpose is to suppress the exposure of the release agent and the crystalline resin contained on the toner surface, and to supplement the strength of the toner particles, which is insufficient with the core layer alone.

(Fusion / unification process)
In the fusion / unification step performed after the aggregated particle forming step, the pH of the suspension containing the aggregated particles formed through these steps is in a desired range (pH is 2.5 or more and pH 5.5 or less). Thus, after the progress of aggregation is stopped, the aggregated particles are fused by heating.

The pH is adjusted by adding an acid and / or alkali. Although an acid is not specifically limited, The aqueous solution which contains inorganic acids, such as hydrochloric acid, nitric acid, and a sulfuric acid, in 0.1 to 50 mass% is preferable. The alkali is not particularly limited, but an aqueous solution containing an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide in the range of 0.1% by mass to 50% by mass is preferable.
In the pH adjustment, if a local pH change occurs, local aggregated particles themselves may be destroyed or local excessive aggregation may be caused, and the shape distribution may be deteriorated. In particular, the larger the scale, the greater the amount of acid and / or alkali. In general, there is only one place where the acid and alkali are added, so that if the treatment is performed for the same time, the concentration of acid and alkali at the place where the scale is increased increases.

  After performing the composition control described above, the aggregated particles are heated and fused. In the fusion, the agglomerated particles are fused by heating at a temperature of 10 ° C. to 30 ° C. or higher from the melting temperature of the crystalline resin (or the glass transition temperature of the amorphous resin when an amorphous resin is used). Let

The cross-linking reaction may be performed with other components during the heating at the time of fusion or after the fusion is completed. Further, a crosslinking reaction may be performed simultaneously with the fusion. When the crosslinking reaction is performed, the above-described crosslinking agent and polymerization initiator are used in the production of the toner.
The polymerization initiator may be preliminarily mixed with the dispersion at the stage of preparing the raw material dispersion, or may be incorporated into the aggregated particles in the aggregated particle forming step. Furthermore, it may be introduced after the fusion / unification step or after the fusion / unification step. In the case of introduction after the aggregated particle forming step, the adhering step, the fusing / merging step, or the fusing / merging step, a solution in which the polymerization initiator is dissolved or emulsified is added to the dispersion. These polymerization initiators may be added with known crosslinking agents, chain transfer agents, polymerization inhibitors and the like for the purpose of controlling the degree of polymerization.

(Washing, drying process, etc.)
After completing the coalescence and coalescence process of aggregated particles, the desired toner particles are obtained through any washing process, solid-liquid separation process, and drying process. It is desirable to do. Moreover, although there is no restriction | limiting in particular in a solid-liquid separation process, From the point of productivity, suction filtration, pressure filtration, etc. are suitable. Further, the drying process is not particularly limited, but freeze drying, flash jet drying, fluidized drying, vibration fluidized drying and the like are preferably used from the viewpoint of productivity. Further, the various external additives described above are added to the toner particles after drying as necessary.

<Developer for developing electrostatic image>
The developer for developing an electrostatic charge image of the present embodiment (hereinafter sometimes referred to as “developer”) includes the toner of the present embodiment, and other components may be blended depending on the purpose. .
Specifically, when the toner of this embodiment is used alone, it becomes a one-component electrostatic image developing developer, and when used in combination with a carrier, it becomes a two-component electrostatic image developing developer. The toner concentration in the developer is preferably in the range of 1% by mass to 10% by mass.

  Here, the carrier is not particularly limited, and examples thereof include known carriers. For example, the core material described in JP-A-62-39879, JP-A-56-11461 or the like is coated with a resin layer. A known carrier such as a prepared carrier (resin-coated carrier) is used.

Examples of the core material of the resin-coated carrier include moldings such as iron powder, ferrite, and magnetite, and the average diameter is about 30 μm or more and 200 μm or less.
Examples of the coating resin for forming the coating layer include styrenes such as styrene, parachlorostyrene, and α-methylstyrene, methyl acrylate, ethyl acrylate, n-propyl acrylate, lauryl acrylate, and 2-ethylhexyl acrylate. , Α-methylene fatty acid monocarboxylic acids such as methyl methacrylate, n-propyl methacrylate, lauryl methacrylate and 2-ethylhexyl methacrylate, nitrogen-containing acrylics such as dimethylaminoethyl methacrylate, vinyl nitriles such as acrylonitrile and methacrylonitrile Vinyl pyridines such as 2-vinyl pyridine and 4-vinyl pyridine, vinyl ethers such as vinyl methyl ether and vinyl isobutyl ether, vinyl methyl ketone, vinyl ethyl ketone, vinyl isopropenyl ketone and other vinyl ethers. Nyl ketones, olefins such as ethylene and propylene, homopolymers such as vinyl-based fluorine-containing monomers such as vinylidene fluoride, tetrafluoroethylene and hexafluoroethylene, or copolymers comprising two or more monomers, methyl silicone, Examples thereof include silicones such as methylphenyl silicone, polyesters containing bisphenol and glycol, epoxy resins, polyurethane resins, polyamide resins, cellulose resins, polyether resins, polycarbonate resins and the like. These resins may be used alone or in combination of two or more.

  The amount of the coating resin is preferably in the range of 0.1 to 10 parts by mass and more preferably in the range of 0.5 to 3.0 parts by mass with respect to 100 parts by mass of the core material. For the production of the carrier, for example, a heating kneader, a heating Henschel mixer, a UM mixer, or the like can be used. Depending on the amount of the coating resin, a heating fluidized rolling bed, a heating kiln, or the like may be used. . The mixing ratio of the toner and the carrier in the electrophotographic developer is not particularly limited, and is selected according to the purpose.

<Image forming method>
Next, an image forming method using the developer of this embodiment will be described.
As a method for forming an image using the toner of the present embodiment, a known electrophotographic method is used. Specifically, the surface of a latent image holding member (hereinafter sometimes referred to as “image holding member”). An electrostatic latent image forming step for forming an electrostatic latent image on the toner, a developing step for developing the electrostatic latent image with a developer containing toner to form a toner image, and a transfer for transferring the toner image to a recording medium. Preferably, the method includes a step and a fixing step of fixing the toner image to the recording medium.
In addition to these steps, a known process used in an electrophotographic image forming method may be combined. For example, a toner that removes residual toner remaining on the surface of the image carrier after the transfer process is completed. It may include a removing step and a residual toner collecting and supplying step of collecting the residual toner removed in the toner removing step and supplying the collected residual toner to the developing unit. The residual toner supplied to the developing means is reused (recycled) as developer toner.

  Here, the electrostatic latent image forming step is a step of forming an electrostatic latent image by charging the surface of the image carrier with a charging means and then exposing the image carrier with a laser optical system or an LED array. is there. Examples of the charging unit include a non-contact type charger such as corotron and scorotron, and a contact type that charges the image carrier surface by applying a voltage to a conductive member that is in contact with the image carrier surface. Any type of charger may be used. However, a contact charging type charger is preferable from the viewpoint that the amount of ozone generated is small, environmentally friendly, and excellent printing durability. In the contact charging type charger, the shape of the conductive member may be any of a brush shape, a blade shape, a pin electrode shape, a roller shape, and the like, and is not limited. Note that the latent image forming step is not limited to the above-described embodiment.

  In the developing step, a developer carrier having a developer layer containing at least toner on the surface thereof is brought into contact with or close to the surface of the image carrier, and toner particles are formed on the electrostatic latent image on the surface of the image carrier. Is a step of forming a toner image on the surface of the image carrier. The development method is performed using a known method, and examples of the development method when the developer is a two-component developer include a cascade method and a magnetic brush method. The developing method is not limited to the above-described mode.

  The transfer step is a step of transferring a toner image formed on the surface of the image carrier to a recording medium. The transfer process may be a system in which a toner image is directly transferred onto a recording medium such as paper, or a system in which the toner image is transferred onto a recording medium such as paper after being transferred onto a drum-like or belt-like intermediate transfer member. The transfer method is not limited to the above-described mode.

  For example, a corotron is used as a transfer device (transfer means) that transfers the toner image from the image carrier to paper or the like. The corotron is effective as a means for charging the paper, but a high voltage of several kV must be applied and a high voltage power source is required to give the target charge to the paper as the recording medium. In addition, ozone is generated by corona discharge, which causes deterioration of rubber parts and the image carrier. Therefore, contact transfer that transfers a toner image onto a sheet by pressing a conductive transfer roll having an elastic material against the image carrier. The method is preferred. The transfer device is not limited to the above-described embodiment.

  The toner removal step (cleaning step) is a step in which a blade, brush, roll, or the like is brought into direct contact with the surface of the image carrier to remove toner, paper dust, dust, etc. adhering to the surface of the image carrier.

  The most commonly employed method is a blade cleaning method in which a rubber blade such as polyurethane is pressed against the image carrier. On the other hand, a magnetic brush method in which a magnet is fixedly arranged inside, a cylindrical non-magnetic sleeve that rotates on the outer periphery is provided, and a magnetic carrier is held on the sleeve surface to collect toner, A method may be used in which conductive resin fibers or animal hairs are arranged so as to be rotated in a roll shape, and a bias having a polarity opposite to that of the toner is applied to the roll to remove the toner. In the former magnetic brush system, a cleaning pretreatment corotron may be provided. The cleaning method is not limited to the above-described mode.

  The fixing step is a step of fixing the toner image transferred on the surface of the recording medium by a fixing unit. As the fixing means, a heat fixing apparatus using a heat roll is preferably used. The heat fixing device includes a fixing roller having a heater lamp for heating inside a cylindrical metal core, a so-called release layer formed on the outer peripheral surface by a heat resistant resin film layer or a heat resistant rubber film layer, and the fixing roller. The pressure roller or the pressure belt is arranged in pressure contact with the roller and has a layer containing a heat-resistant elastic material formed on the outer peripheral surface of the cylindrical metal core or the surface of the belt-like base material. In the toner image fixing process, a recording medium on which a toner image is formed is passed through a contact portion formed by a fixing roller and a pressure roller or a pressure belt, and heat of binder resin, additives, etc. in the toner is passed. Fix by melting. However, the fixing method is not limited to the above-described mode.

In the case of producing a full-color image, each of the plurality of image holding bodies has a developer holding body for each color, and a latent image forming step using each of the plurality of image holding bodies and the developer holding bodies, and a toner image Through a series of steps including a forming step, a transfer step, and a cleaning step, each color toner image for each step is sequentially stacked on the same recording medium surface, and the stacked full-color toner images are thermally fixed in the fixing step. An image forming method is preferably used.
By using the developer of this embodiment in the image forming method, stable development, transfer, and fixing performance can be obtained even in a tandem system suitable for, for example, small size and high color speed.

<Image forming apparatus, toner cartridge>
The image forming apparatus of the present embodiment includes an image carrier, a charging unit that charges the surface of the image carrier, an electrostatic latent image forming unit that forms an electrostatic latent image on the charged surface of the image carrier, Developing means for developing the electrostatic latent image with the developer to form a toner image, transfer means for transferring the toner image to the surface of the recording medium, and fixing for fixing the toner image transferred to the surface of the recording medium And a toner removing means for removing the toner remaining on the surface of the image carrier after transfer, wherein the developer is the developer of the present embodiment described above. Since the image forming apparatus of the present embodiment uses the developer of the present embodiment, a high-quality image is formed over a long period of time.

  The image forming apparatus according to the present exemplary embodiment may further include a residual toner collecting / supplying unit that collects the residual toner removed by the toner removing unit and supplies the collected residual toner to the developing unit. In the present embodiment, since the developer of the present embodiment is used as the developer, the durability of the toner is high, and a high-quality image can be formed over a long period of time even when the toner is reused.

  Hereinafter, the image forming apparatus of this embodiment will be described in detail with reference to the drawings. In addition, the same code | symbol is provided to the member which has the substantially same function throughout all the drawings, and the overlapping description may be abbreviate | omitted.

-First embodiment-
FIG. 1 is a configuration diagram illustrating an image forming apparatus according to the first embodiment. The image forming apparatus shown in FIG. 1 is a quadruple tandem full-color image forming apparatus, and each color of yellow (Y), magenta (M), cyan (C), and black (K) based on color-separated image data. Are provided with first to fourth image forming units 10Y, 10M, 10C, and 10K (image forming means) of an electrophotographic system for outputting the above image. These image forming units (hereinafter simply referred to as “units”) 10Y, 10M, 10C, and 10K are juxtaposed at a predetermined distance in the horizontal direction. The units 10Y, 10M, 10C, and 10K may be process cartridges that are detachable from the main body of the image forming apparatus.

  Above each of the units 10Y, 10M, 10C, and 10K, an intermediate transfer belt 20 as an intermediate transfer member is extended through each unit. The intermediate transfer belt 20 is provided by being wound around a driving roller 22 and a support roller 24 that are in contact with the inner surface of the intermediate transfer belt 20 that are spaced apart from each other from the left to the right in the drawing. It is designed to travel in the direction toward 10K. The support roller 24 is biased in a direction away from the drive roller 22 by a spring or the like (not shown), and necessary tension is applied to the intermediate transfer belt 20 wound around both. Further, an intermediate transfer member cleaning device 30 is provided on the side of the image carrier of the intermediate transfer belt 20 so as to face the driving roller 22.

  Further, each of the developing devices (developing means) 4Y, 4M, 4C, and 4K of each unit 10Y, 10M, 10C, and 10K contains developer containing toner of four colors of yellow, magenta, cyan, and black. Yes. Further, toners of four colors, yellow, magenta, cyan, and black, stored in the toner cartridges 8Y, 8M, 8C, and 8K are supplied to the developing devices 4Y, 4M, 4C, and 4K, respectively.

  Since the first to fourth units 10Y, 10M, 10C, and 10K have the same configuration, the first unit that forms a yellow image disposed on the upstream side in the intermediate transfer belt traveling direction here. 10Y will be described as a representative. Note that the second to fourth units are given the same reference numerals with magenta (M), cyan (C), and black (K) instead of yellow (Y) in the same parts as the first unit 10Y. Description of 10M, 10C, 10K is omitted.

The first unit 10Y has a photoreceptor 1Y (latent image holder) that acts as an image holder. Details of the image carrier will be described later. Around the photoreceptor 1Y, an electrostatic latent image is obtained by exposing the surface of the photoreceptor 1Y to a predetermined potential by a charging roller 2Y, and exposing the charged surface by a laser beam 3Y based on the color-separated image signal. A developing device 4Y (developing unit) for supplying the charged toner to the electrostatic latent image and developing the electrostatic latent image, and the developed toner image is transferred to the intermediate transfer belt. A primary transfer roller 5Y for transferring (temporary transfer) onto 20 and a cleaning device (toner removing means) 6Y for removing the toner remaining on the surface of the photoreceptor 1Y after the primary transfer are sequentially arranged.
The primary transfer roller 5Y is disposed inside the intermediate transfer belt 20, and is provided at a position facing the photoreceptor 1Y. Further, a bias power source (not shown) for applying a primary transfer bias is connected to each of the primary transfer rollers 5Y, 5M, 5C, and 5K. Each bias power source varies the transfer bias applied to each primary transfer roller under the control of a control unit (not shown).

Hereinafter, an operation of forming a yellow image in the first unit 10Y will be described. First, prior to the operation, the surface of the photoreceptor 1Y is charged to a potential of about −600V to −800V by the charging roller 2Y.
The photoreceptor 1Y is formed by laminating a photosensitive layer on a conductive substrate (volume resistivity at 20 ° C .: 1 × 10 ⁻⁶ Ωcm or less). This photosensitive layer usually has a high resistance (a resistance equivalent to that of a general resin), but has a property that the specific resistance of the portion irradiated with the laser beam changes when irradiated with the laser beam 3Y. Therefore, a laser beam 3Y is output to the surface of the charged photoreceptor 1Y via the exposure device 3 in accordance with yellow image data sent from a control unit (not shown). The laser beam 3Y is applied to the photosensitive layer on the surface of the photoreceptor 1Y, whereby an electrostatic latent image of a yellow print pattern is formed on the surface of the photoreceptor 1Y.

The electrostatic latent image is an image formed on the surface of the photoreceptor 1Y by charging, and the specific resistance of the irradiated portion of the photosensitive layer is lowered by the laser beam 3Y, and the charged charge on the surface of the photoreceptor 1Y is reduced. On the other hand, it is a so-called negative latent image formed by the charge remaining in the portion not irradiated with the laser beam 3Y.
The electrostatic latent image formed on the photoreceptor 1Y in this way is rotated to a predetermined development position as the photoreceptor 1Y travels. At this development position, the electrostatic latent image on the photoreceptor 1Y is visualized (developed) by the developing device 4Y.

  Developer including yellow toner is accommodated in the developing device 4Y. The yellow toner is triboelectrically charged by being agitated inside the developing device 4Y, and has a charge of the same polarity (negative polarity) as the charged charge on the photoreceptor 1Y, and a developer roll (developer holder). Is held on. As the surface of the photoreceptor 1Y passes through the developing device 4Y, the yellow toner is electrostatically attached to the latent image portion on the surface of the photoreceptor 1Y, and the latent image is developed with the yellow toner. . The photoreceptor 1Y on which the yellow toner image is formed continues to run at a predetermined speed, and the toner image developed on the photoreceptor 1Y is conveyed to a predetermined primary transfer position.

When the yellow toner image on the photoreceptor 1Y is conveyed to the primary transfer, a predetermined primary transfer bias is applied to the primary transfer roller 5Y, and the electrostatic force directed from the photoreceptor 1Y to the primary transfer roller 5Y generates a toner image. The toner image on the photoreceptor 1 </ b> Y is transferred onto the intermediate transfer belt 20. The transfer bias applied at this time is a (+) polarity opposite to the polarity (−) of the toner, and is controlled to about +10 μA by the control unit (not shown) in the first unit 10Y, for example.
On the other hand, the toner remaining on the photoreceptor 1Y is removed and collected by the cleaning device 6Y.

Further, the primary transfer bias applied to the primary transfer rollers 5M, 5C, and 5K after the second unit 10M is also controlled according to the first unit.
Thus, the intermediate transfer belt 20 onto which the yellow toner image has been transferred by the first unit 10Y is sequentially conveyed through the second to fourth units 10M, 10C, and 10K, and the toner images of the respective colors are superimposed and transferred in a multiple manner.

  The intermediate transfer belt 20 onto which the four color toner images have been transferred in a multiple manner through the first to fourth units is disposed on the intermediate transfer belt 20, the support roller 24 in contact with the inner surface of the intermediate transfer belt 20, and the image holding surface side of the intermediate transfer belt 20. The secondary transfer roller 26 is formed to a secondary transfer portion. On the other hand, the recording medium P (transfer object) is fed at a predetermined timing into a gap where the secondary transfer roller 26 and the intermediate transfer belt 20 are pressed against each other via a supply mechanism, and a predetermined secondary transfer bias is supported. Applied to the roller 24. The transfer bias applied at this time is a (−) polarity that is the same polarity as the polarity (−) of the toner, and an electrostatic force from the intermediate transfer belt 20 toward the recording medium P is applied to the toner image, so The toner image is transferred onto the recording medium P. Note that the secondary transfer bias at this time is determined according to the resistance detected by a resistance detecting means (not shown) for detecting the resistance of the secondary transfer portion, and is voltage-controlled.

Thereafter, the recording medium P is sent to a fixing device (fixing means) 28, the toner image is heated, and the color-superposed toner image is melted and fixed on the recording medium P. The recording medium P on which the color image has been fixed is unloaded to the discharge unit, and a series of color image forming operations is completed.
The image forming apparatus exemplified above is configured to transfer the toner image to the recording medium P via the intermediate transfer belt 20, but is not limited to this configuration, and the toner image is directly transferred from the photoconductor. It may be a structure that is transferred to a recording sheet.

  The image forming apparatus shown in FIG. 1 is an image forming apparatus having a configuration in which the toner cartridges 8Y, 8M, 8C, and 8K are attached to and detached from each other. The developing devices 4Y, 4M, 4C, and 4K each have their respective developing devices (colors). And a toner supply pipe (not shown). Further, when the amount of toner stored in the toner cartridge is low, this toner cartridge may be replaced.

-Second Embodiment-
FIG. 2 is a cross-sectional view schematically showing a basic configuration of an image forming apparatus according to another preferred embodiment (second embodiment).
The image forming apparatus shown in FIG. 2 employs a system in which the developer according to this embodiment is supplied to the developer storage container in the developing unit as required by the developer supplying unit.

  In the image forming apparatus shown in FIG. 2, the residual toner removed from the surface of the latent image holding member by the cleaning blade of the cleaning means (toner removing means) is collected and supplied to the developing means, whereby the residual toner is reused. The toner reclaim method is adopted.

  As shown in FIG. 2, the image forming apparatus 100 according to the present embodiment includes an electrostatic latent image holding body 110 (latent image holding body) that rotates clockwise as indicated by an arrow a, and an electrostatic latent image. Above the holding body 110, the charging means 120 is provided relative to the electrostatic latent image holding body 110 and charges the surface of the electrostatic latent image holding body 110 negatively, and the electrostatic latent image charged by the charging means 120 An electrostatic latent image forming unit 130 for writing an image to be formed with a developer (toner) on the surface of the holding body 110 to form an electrostatic latent image, and a downstream side of the electrostatic latent image forming unit 130 are provided. A developing unit 140 that forms a toner image on the surface of the electrostatic latent image holding member 110 by attaching toner to the electrostatic latent image formed by the electrostatic latent image forming unit 130; Travel in the direction indicated by arrow b while touching, and hold electrostatic latent image The endless belt-shaped intermediate transfer belt 150 for transferring the toner image formed on the surface of the 110 and the surface of the electrostatic latent image holding body 110 after the toner image is transferred to the intermediate transfer belt 150 are neutralized to the surface. A neutralization unit 160 that makes it easy to remove the remaining transfer residual toner, and a cleaning unit 170 (toner removal unit) that cleans the surface of the electrostatic latent image holding member 110 to remove the transfer residual toner.

  The charging unit 120, the electrostatic latent image forming unit 130, the developing unit 140, the intermediate transfer belt 150, the neutralizing unit 160, and the cleaning unit 170 are arranged in a clockwise direction on the circumference surrounding the electrostatic latent image holding body 110. It is installed.

  The intermediate transfer belt 150 is tensioned and held from the inside by the stretching rollers 150A and 150B, the backup roller 150C, and the driving roller 150D, and is driven in the direction of the arrow b as the driving roller 150D rotates. At a position opposite to the electrostatic latent image holder 110 inside the intermediate transfer belt 150, the intermediate transfer belt 150 is positively charged, and the toner on the electrostatic latent image holder 110 is placed on the outer surface of the intermediate transfer belt 150. A primary transfer roller 151 that adsorbs the toner is provided. On the outer side below the intermediate transfer belt 150, the recording medium P is positively charged and pressed against the intermediate transfer belt 150, thereby transferring the toner image formed on the intermediate transfer belt 150 onto the recording medium P. A transfer roller 152 is provided to face the backup roller 150C.

  Below the intermediate transfer belt 150, a recording medium supply device 153 that supplies the recording medium P to the secondary transfer roller 152 and a recording medium P on which a toner image is formed on the secondary transfer roller 152 are conveyed. Fixing means 180 for fixing the toner image is provided.

  The recording medium supply device 153 includes a pair of conveying rollers 153A and a guide slope 153B that guides the recording medium P conveyed by the conveying rollers 153A toward the secondary transfer roller 152. On the other hand, the fixing unit 180 includes a fixing roller 181 that is a pair of heat rollers for fixing the toner image by heating and pressing the recording medium P on which the toner image has been transferred by the secondary transfer roller 152, and fixing. A conveyance conveyor 182 that conveys the recording medium P toward the roller 181.

  The recording medium P is conveyed in the direction indicated by the arrow c by the recording medium supply device 153, the secondary transfer roller 152, and the fixing unit 180.

  In the vicinity of the intermediate transfer belt 150, an intermediate transfer body cleaning unit 154 having a cleaning blade for removing toner remaining on the intermediate transfer belt 150 after the toner image is transferred to the recording medium P by the secondary transfer roller 152 is provided. It has been.

  Hereinafter, the developing unit 140 will be described in detail. The developing unit 140 is disposed in the developing region so as to face the electrostatic latent image holding member 110, and includes, for example, a toner charged to a negative (−) polarity and a carrier charged to a positive (+) polarity. A developer accommodating container 141 for accommodating the component developer is included. The developer container 141 includes a developer container main body 141A and a developer container cover 141B that closes the upper end of the developer container main body 141A.

  The developer container main body 141A has a developing roll chamber 142A for storing the developing roll 142 therein, and is adjacent to the first stirring chamber 143A and the first stirring chamber 143A adjacent to the developing roll chamber 142A. 144A of 2nd stirring chambers. In the developing roll chamber 142A, a layer thickness regulating member 145 for regulating the layer thickness of the developer on the surface of the developing roll 142 when the developer containing container cover 141B is mounted on the developer containing container main body 141A. Is provided.

  The first stirring chamber 143A and the second stirring chamber 144A are partitioned by a partition wall 141C. Although not shown, the longitudinal direction of the partition wall 141C of the first stirring chamber 143A and the second stirring chamber 144A (developing device) (Longitudinal direction) Both ends are provided with passages, and the first stirring chamber 143A and the second stirring chamber 144A constitute a circulation stirring chamber (143A + 144A).

  The developing roll 142 is disposed in the developing roll chamber 142A so as to face the electrostatic latent image holding body 110. Although not shown, the developing roll 142 is provided with a sleeve outside a magnetic roll (fixed magnet) having magnetism. The developer in the first stirring chamber 143A is adsorbed on the surface of the developing roll 142 by the magnetic force of the magnetic roll and is transported to the developing area. Further, the roll axis of the developing roll 142 is rotatably supported by the developer container main body 141A. Here, the developing roll 142 and the electrostatic latent image holding body 110 rotate in the opposite directions, and the developer adsorbed on the surface of the developing roll 142 at the facing portion advances by the electrostatic latent image holding body 110. The sheet is conveyed to the development area from the same direction as the direction.

  A bias power supply (not shown) is connected to the sleeve of the developing roll 142 so that a predetermined developing bias is applied (in this embodiment, an alternating electric field is applied to the developing region. , Applying a bias in which the AC component (AC) is superimposed on the DC component (DC)).

  The first stirring chamber 143A and the second stirring chamber 144A are provided with a first stirring member 143 (stirring / conveying member) and a second stirring member 144 (stirring / conveying member) that transport the developer while stirring. The first agitating member 143 includes a first rotating shaft extending in the axial direction of the developing roll 142, and an agitating / conveying blade (protrusion) fixed in a spiral manner on the outer periphery of the rotating shaft. Similarly to the first stirring member 143, the second stirring member 144 is also configured by a second rotating shaft and a stirring / conveying blade (protrusion). The stirring member is rotatably supported by the developer container main body 141A. The first stirring member 143 and the second stirring member 144 are arranged such that the developer in the first stirring chamber 143A and the second stirring chamber 144A is conveyed in the opposite directions by rotation thereof. .

One end of a developer supply means 146 for appropriately supplying a supply developer including supply toner and a supply carrier to the second agitation chamber 144A is connected to one end side in the longitudinal direction of the second agitation chamber 144A. A developer cartridge 147 containing a supply developer is connected to the other end of the developer supply means 146.
As described above, the developing unit 140 appropriately supplies the supply developer from the developer cartridge 147 through the developer supplying unit 146 to the developing unit 140 (second stirring chamber 144A).

  Here, in this embodiment, the configuration using the developer cartridge 147 containing the supply developer of the present invention has been described as an example. However, the developer cartridge 147 is a cartridge that contains supply toner alone. It may be a separate body from the cartridge that individually stores the supply carrier.

  Next, the cleaning unit 170 will be described in detail. The cleaning unit 170 includes a housing 171 and a cleaning blade 172 disposed so as to protrude from the housing 171. The cleaning blade 172 is a plate-like member extending in the extending direction of the rotation axis of the electrostatic latent image holding body 110, and is rotated in the rotation direction (arrow) from the transfer position by the primary transfer roller 151 in the electrostatic latent image holding body 110. a direction) A tip end portion (hereinafter referred to as an edge portion) is provided in pressure contact with the downstream side and the downstream side in the rotational direction from the position where the charge is removed by the charge removal means 160.

  The cleaning blade 172 is not transferred onto the intermediate transfer belt 150 by the primary transfer roller 151 by rotating the electrostatic latent image holding body 110 in a predetermined direction (arrow a direction). Foreign matter such as retained untransferred residual toner and paper dust of the recording medium P is dammed and removed from the electrostatic latent image holder 110.

  Further, a transport member 173 is disposed at the bottom of the housing 171, and toner particles (developer) removed by the cleaning blade 172 are developed on the downstream side of the transport direction of the transport member 173 in the housing 171 by the developing unit 140. One end of a supply conveying means 174 for supplying to is connected. The other end of the supply / conveyance unit 174 is connected to join the developer supply unit 146.

  As described above, the cleaning unit 170 transports the untransferred residual toner particles to the developing unit 140 (second stirring chamber 144A) through the supply transport unit 174 in accordance with the rotation of the transport member 173 provided at the bottom of the housing 171. A toner reclaim method is employed in which the developer (toner) contained in the container is stirred and conveyed for reuse.

-Latent image carrier-
Next, a latent image holding member (image holding member) constituting the image forming apparatus in the present embodiment will be described.
As the image carrier, a known photoreceptor (electrophotographic photoreceptor) having at least a photosensitive layer on a conductive support is used, but an organic photoreceptor is preferably used. In this case, the layer constituting the outermost surface of the image carrier, for example, the protective layer, preferably contains a resin having a crosslinked structure. As the resin having a crosslinked structure, for example, a phenol resin, a urethane resin, and a siloxane resin are used, and a siloxane resin and a phenol resin are most preferable.

In the present embodiment, it is preferable that the layer constituting the outermost surface of the image carrier includes a resin having a three-dimensional crosslinked structure. Since the layer constituting the outermost surface containing a resin having a three-dimensional crosslinked structure has high strength, it has high durability against wear and scratches, and the image carrier has a long life. However, since the surface of the holder is not easily worn, it has a drawback that it is difficult to remove the adhered toner component.
On the other hand, in order to ensure the cleaning property, for example, when the cleaning blade is brought into contact with the image carrier at a high contact pressure, the torque is increased at the contact portion between the cleaning blade and the image carrier and the image is held. The toner remaining on the body surface may be easily destroyed. Further, when the toner is destroyed, the toner constituting material adheres to the surface of the image holding member, and the charge fluctuation may easily occur. However, the toner of the present embodiment has high surface flexibility, and the inside has sufficient elasticity, so it has high durability and excellent strength, so that the external additive added to the toner surface is buried or dispersed. Therefore, abnormal charging between toners due to a change in the structure of the toner and uneven wear on the surface of the photoreceptor due to the removal of the additive are suppressed. In addition, even when combined with a method of recycling and reusing toner, the toner has high durability and high structure maintainability, so that an image with good image quality can be formed over a long period of time.
Note that the three-dimensional crosslinked structure of the resin contained in the surface protective layer is observed as follows.
Regarding the elements peculiar to the surface layer, ion etching was performed for 180 seconds under the conditions of an acceleration voltage of 400 ± 10 V and a degree of vacuum (3 ± 1) × 10 ⁻² Pa in an Ar atmosphere, and the surface was subjected to X-ray photoelectron analysis. It can be judged from the difference in the abundance (Atom%) of the specific element. It can be judged that the smaller the difference is, the stronger and more uniform the crosslinked structure of the surface protective layer is. Specific elements include, for example, Si, Ti, Al and the like, and other elements C, O, N, etc. that form a protective layer by having a crosslinked structure are also made uniform in the depth direction. , Value fluctuations are small.
Generally, if the difference between before and after the abundance before ion etching is within 10%, it is considered to have a crosslinked structure.

<Process cartridge>
The process cartridge of this embodiment includes at least a developer holder, and uses the developer of this embodiment as a developer. In addition, an image carrier, a charging unit, a toner removing unit, and the like may be provided.

  FIG. 3 is a schematic configuration diagram showing a preferred example of a process cartridge containing the developer according to the present embodiment. The process cartridge 200 includes a photosensitive member 107 (latent image holding member), a charging roller 108, a developing device 111 including a developer holding member 111A, a photosensitive member cleaning device 113 (toner removing unit), and an opening 118 for exposure. , And the opening 117 for static elimination exposure is combined and integrated using the mounting rail 116.

  The process cartridge 200 is detachable from an image forming apparatus main body including a transfer device 112, a fixing device 115, and other components (not shown). It forms a forming apparatus. Reference numeral 300 denotes a recording paper (recording medium).

  The process cartridge shown in FIG. 3 includes a charging roller 108, a developing device 111, a cleaning device (cleaning means) 113, an opening 118 for exposure, and an opening 117 for static elimination exposure. May be combined selectively. In the process cartridge of the present embodiment, if the developer holding member 111A is provided, the photosensitive member 107, the charging roller 108, the developing device 111, the cleaning device 113, the opening 118 for exposure, and the discharge exposure. You may provide at least 1 sort (s) selected from the group comprised from the opening part 117. FIG.

<Toner cartridge>
The toner cartridge according to this embodiment is detached from an image forming apparatus having at least a developing unit, and stores a developer containing toner to be supplied to the toner image forming unit. The toner is in the form. It should be noted that at least the toner may be stored in the toner cartridge of the present embodiment, and for example, a developer may be stored depending on the mechanism of the image forming apparatus.

  Therefore, in the image forming apparatus having a configuration in which the toner cartridge can be freely attached and detached, the storability is maintained even in the toner cartridge in which the container is miniaturized by using the toner cartridge containing the toner of the present embodiment. Can be fixed at low temperature while maintaining high image quality.

EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated concretely, this invention is not limited only to the Example shown below.
However, Example 8 and Example 9 below are Reference Example 8 and Reference Example 9.
In the examples, “parts” and “%” mean “parts by mass” and “% by mass” unless otherwise specified.

<Measuring method of various characteristics>
First, methods for measuring physical properties of toners and the like used in Examples and Comparative Examples will be described.
(Molecular weight of resin)
The molecular weight distribution of the resin was performed under the following conditions. GPC uses “HLC-8120GPC, SC-8020 (manufactured by Tosoh Corporation)”, and the column uses two “TSKgel, SuperHM-H (6.0 mm ID × 15 cm, manufactured by Tosoh Corporation)” THF (tetrahydrofuran) was used as an eluent. As experimental conditions, an experiment was performed using a sample concentration of 0.5%, a flow rate of 0.6 ml / min, a sample injection amount of 10 μl, a measurement temperature of 40 ° C., and an IR detector. The calibration curve is “polystylen standard sample TSK standard” manufactured by Tosoh Corporation: “A-500”, “F-1”, “F-10”, “F-80”, “F-380”, “A-2500”. ”,“ F-4 ”,“ F-40 ”,“ F-128 ”, and“ F-700 ”.

(Volume average particle diameter of resin particles, colorant particles, etc.)
Volume average particle diameters of resin particles (resin particles), colorant particles, and the like were measured with a laser diffraction particle size measuring instrument (SALD2000A, manufactured by Shimadzu Corporation).

(Resin melting temperature, glass transition temperature)
The melting temperature of the toner and the crystalline polyester resin and the glass transition temperature of the toner and the amorphous resin were determined from the respective maximum peaks measured according to ASTM D3418-8. The glass transition temperature was the temperature at the intersection of the extension line of the base line and the rising line in the endothermic part, and the melting temperature was the temperature at the top of the endothermic peak.
For the measurement, a differential scanning calorimeter (DSC-60A with automatic cooler, manufactured by Shimadzu Corporation) was used.

<Preparation of developer>
The developer was produced by first producing a toner and a carrier, and using them. In producing the toner, first, a resin particle dispersion, a colorant dispersion, and a release agent dispersion were produced, and toner particles were produced using them. Next, it was used to produce a toner and a developer.

-Preparation of non-crystalline polyester resin (A1) and non-crystalline resin particle dispersion (a1)-
In a heat-dried two-necked flask, 20 mol parts of polyoxyethylene (2,0) -2,2-bis (4-hydroxyphenyl) propane and polyoxypropylene (2,2) -2,2-bis (4 -Hydroxyphenyl) propane 80 mol part, terephthalic acid 15 mol part, fumaric acid 67 mol part, n-dodecenyl succinic acid 3 mol part, trimellitic acid 25 mol part, and these acid components (terephthalic acid, n After adding 0.05 mol part of dibutyltin oxide to the total number of moles of dodecenyl succinic acid, trimellitic acid and fumaric acid), introducing nitrogen gas into the container and maintaining the inert atmosphere to raise the temperature The copolycondensation reaction is carried out at 150 ° C. to 230 ° C. for 12 to 20 hours, and then gradually reduced in pressure at 210 ° C. to 250 ° C. to combine the amorphous polyester resin (A1). It was. The weight average molecular weight Mw of this resin was 70000, and the glass transition temperature Tg was 65 ° C.

  3000 parts of the obtained non-crystalline polyester resin, 10000 parts of ion-exchanged water, and 90 parts of surfactant sodium dodecylbenzenesulfonate were charged into an emulsification tank of a high-temperature and high-pressure emulsifier (Cabitron CD1010, slit: 0.4 mm). Then, after heating and melting at 130 ° C., it was dispersed at 110 ° C. at a flow rate of 3 L / m at 10,000 rpm for 30 minutes, passed through a cooling tank, and then a non-crystalline resin particle dispersion (high temperature / high pressure emulsifier (Cabitron CD1010 slit 0 .4 mm) was recovered to obtain an amorphous resin particle dispersion (a1).

In a heat-dried two-necked flask, 35 mol parts of polyoxyethylene (2,0) -2,2-bis (4-hydroxyphenyl) propane and polyoxypropylene (2,2) -2,2-bis (4 -Hydroxyphenyl) propane 65 mol parts, terephthalic acid 80 mol parts, n-dodecenyl succinic acid 15 mol parts, trimellitic acid 10 mol parts, and these acid components (terephthalic acid, n-dodecenyl succinic acid, trimellitic acid 0.05 mol part of dibutyltin oxide with respect to the total number of moles), and nitrogen gas was introduced into the container to maintain an inert atmosphere and the temperature was raised. A time copolycondensation reaction was performed, and then the pressure was gradually reduced from 210 ° C. to 250 ° C. to synthesize an amorphous polyester resin (B1).
The weight average molecular weight (Mw) of this resin was 16000, and the glass transition temperature Tg was 60 ° C. Thereafter, a high-temperature / high-pressure emulsification apparatus (Cabitron CD1010) was prepared under the same conditions as in the preparation of the amorphous resin dispersion (A1). , Slit: 0.4 mm) to obtain a crystalline resin particle dispersion (b1).

-Preparation of crystalline polyester resin (C1) and crystalline resin particle dispersion (c1)-
Into a heat-dried three-necked flask, 40 mol parts of 1,9-nonanediol, 60 mol parts of dodecanedicarboxylic acid, and 0.05 mol parts of dibutyltin oxide as a catalyst were added, and the air in the container was reduced by a depressurization operation. Was placed in an inert atmosphere with nitrogen gas, and stirred at 180 ° C. for 2 hours with mechanical stirring. Thereafter, the temperature was gradually raised to 230 ° C. under reduced pressure, and the mixture was stirred for 5 hours. When it became a viscous state, it was air-cooled, the reaction was stopped, and a crystalline polyester resin (B1) was synthesized. This resin had a weight average molecular weight Mw of 23000 and a melting temperature Tm of 74 ° C.
Thereafter, a crystalline resin particle dispersion (c1) was obtained using a high-temperature and high-pressure emulsification apparatus (Cabitron CD1010, slit: 0.4 mm) under the same conditions as in the preparation of the amorphous resin dispersion (A1).

-Preparation of colorant particle dispersion (1)-
-Cyan pigment (manufactured by Dainichi Seika Co., Ltd., Pigment Blue 15: 3 (copper phthalocyanine)): 1000 parts-Anionic surfactant (sodium lauryl sulfate, manufactured by Wako Pure Chemical Industries): 150 parts-Ion-exchanged water: 4000 parts

  Disperse colorant particles by mixing and dissolving the above and dispersing the colorant (cyan pigment) particles by dispersing for about 1 hour using a high-pressure impact disperser Ultimateizer (manufactured by Sugino Machine Co., Ltd., HJP30006). Liquid (1) was prepared. The volume average particle size of the colorant (cyan pigment) particles in the colorant particle dispersion was 0.15 μm, and the colorant particle concentration was 20%.

-Preparation of release agent particle dispersion (1)-
Fischer-Tropsch wax (Nippon Seisaku Co., Ltd., HNP51 100 parts) Anionic surfactant (Nippon Yushi Co., Ltd., Newlex R): 2 parts ・ Ion-exchanged water: 300 parts The above ingredients are heated to 95 ° C. and homogenizer (IKA's Ultra Turrax T50) is used to disperse, then a pressure discharge type gorin homogenizer (Gorin) to disperse a release agent having a volume average particle size of 200 nm. A particle dispersion (1) (release agent concentration: 20% by mass) was prepared.

[Production of toner]
-Production of Toner A1-
(Production of toner particles)
Non-crystalline resin particle dispersion (a1): 180 parts Non-crystalline resin particle dispersion (b1): 140 parts Crystalline resin particle dispersion (c1): 80 parts Colorant particle dispersion (1) : 50 parts Release agent particle dispersion: 60 parts Aluminum sulfate (manufactured by Wako Pure Chemical Industries): 5 parts 0.3 M nitric acid aqueous solution: 50 parts Ion exchange water: 500 parts

  Among the above components, the amorphous resin particle dispersions (a1) and (b1) and the crystalline resin particle dispersion (c1) are first accommodated in a round stainless steel flask, and lauryl is an active agent having biodegradability. It is mixed and stirred with 10 parts of a 20% aqueous solution of sodium sulfate (manufactured by Wako Pure Chemical Industries, Ltd.). Thereafter, the other components described above were added and dispersed using a homogenizer (manufactured by IKA, Ultra Tarrax T50), and then heated to 45 ° C. with stirring in an oil bath for heating. After maintaining at 48 ° C., when it was confirmed that aggregated particles having an average particle diameter of about 5.2 μm were formed, an additional amorphous resin particle dispersion (a1): 50 parts, (b1) : After adding 50 parts of the mixed solution, the mixture was further maintained for 30 minutes.

  Subsequently, a 1N aqueous sodium hydroxide solution was gently added until pH 7.0 was reached, and then sodium dodecane-1,12-diol acetate ether ether (Bulite SHAA hydroxy ether carboxyl produced by Sanyo Kasei) was used as a biodegradable dispersant. 5 parts of acid) and 5 parts of Kirest E20 (Hydroxyiminodiacetic acid 2Na) manufactured by Kirest Co. as a complexing agent were added, and the glass transition temperature of the amorphous resin and the glass resin melted while stirring was continued. It heated to 90 degreeC which is more than temperature, and hold | maintained at the temperature for 2 hours. Then, it is cooled to 35 ° C. which is lower than the glass transition temperature of the amorphous resin and the melting temperature of the crystalline resin, the reaction product is filtered, washed with ion-exchanged water, and then dried using a vacuum dryer. Toner particles were obtained.

(External additive treatment)
Thereafter, 1.0 part of calcium carbonate (Takehara Chemical Industry Co., Ltd. (SL1500) Mohs hardness: 2.0), alumina (Sumitomo Chemical Co., Ltd., AKP30) as external additives with respect to 100 parts of the obtained toner base particles Mohs hardness: 9.0) 0.5 part, silica (AEROSIL 0.5 parts of R 812 Aerosil, Mohs hardness: 7.0) were mixed with a Henschel mixer and externally added to obtain toner A1.

-Production of Toner A2-
In preparation of toner A1, except that polyoxyethylene lauryl ether sodium acetate (Burelite LCA manufactured by Sanyo Kasei Co., Ltd.) was used as a biodegradable dispersant in place of dodecane-1,12-diol sodium acetate ether. A toner A2 was obtained in the same manner as in the preparation of the toner A1.

-Production of Toner A3-
In the production of the toner A1, the toner A1 was used except that an equivalent amount of sodium polyoxyethylene tridecyl ether acetate (Burelite ECA) was used as a biodegradable dispersant instead of sodium dodecane-1,12-diol acetate. A toner A3 was obtained in the same manner as in the above.

-Production of Toner A4-
A toner A4 was obtained in the same manner as in the preparation of the toner A1, except that in the preparation of the toner A1, the addition amount of the biodegradable dispersant (dodecane-1,12-diol sodium ether acetate) was changed to 7 parts. .

-Production of Toner A5-
In the preparation of the toner A1, a 1N sodium hydroxide aqueous solution was added under the condition of pH 5.0, and the addition amount of the biodegradable dispersant (dodecane-1,12-diol ether sodium acetate) was changed from 5 parts to 1 part. A toner A5 was obtained in the same manner as in the preparation of the toner A1, except that the toner A1 was changed.

-Production of Toner A6-
In preparation of toner A1, the amount of the amorphous resin particle dispersion (a1) added together with the colorant particle dispersion (1) is changed from 180 parts to 120 parts, and the addition of the amorphous resin particle dispersion (b1). A toner A6 was produced in the same manner as the toner A1, except that the amount was changed from 140 parts to 200 parts.

-Production of Toner A7-
In preparation of toner A1, the amount of the amorphous resin particle dispersion (a1) added together with the colorant particle dispersion (1) is changed from 180 parts to 200 parts, and the addition of the amorphous resin particle dispersion (b1). A toner A7 was obtained in the same manner as in the preparation of the toner A1, except that the amount was changed from 140 parts to 120 parts.

-Production of Toner A8-
In preparation of toner A1, the amount of the amorphous resin particle dispersion (a1) added together with the colorant particle dispersion (1) is changed from 180 parts to 80 parts, and the addition of the amorphous resin particle dispersion (b1). A toner A8 was obtained in the same manner as in the preparation of the toner A1, except that the amount was changed from 140 parts to 240 parts.

-Production of Toner A9-
In the preparation of toner A1, the amount of the amorphous resin particle dispersion (a1) added together with the colorant particle dispersion (1) is changed from 180 parts to 240 parts, and the amount of the amorphous resin particle dispersion (b1) added. The toner A9 was obtained in the same manner as in the preparation of the toner A1, except that the toner was changed from 140 parts to 80 parts.

-Production of Toner A10 (Comparative Toner)-
In the preparation of the toner A1, 5 parts of alkylbenzene sulfonic acid (Neogen RK) which is a biodegradable dispersant is used as a biodegradable dispersant in place of 5 parts of sodium dodecane-1,12-diol acetate ether. A toner A10 was obtained in the same manner as in the preparation of the toner A1, except that

-Production of Toner A11-
In preparation of the toner A1, as an external additive, instead of a mixture of 1.0 part of calcium carbonate, 0.5 part of alumina, and 0.5 part of silica, 0.3 part of calcium carbonate, 0.2 part of alumina, Toner A11 was obtained in the same manner as Toner A1, except that 0.3 part of silica mixed with a Henschel mixer was externally added.

-Production of Toner A12-
In the preparation of the toner A1, as an external additive, instead of a mixture of 1.0 part of calcium carbonate, 0.5 part of alumina, and 0.5 part of silica, 0.7 part of calcium carbonate, 0.6 part of alumina, Toner A12 was obtained in the same manner as Toner A1, except that 0.6 part of silica mixed with a Henschel mixer was externally added.

-Production of Toner A13-
In the preparation of the toner A1, as an external additive, instead of a mixture of 1.0 part of calcium carbonate, 0.5 part of alumina, and 0.5 part of silica, 0.1 part of calcium carbonate, 0.2 part of alumina, Toner A12 was obtained in the same manner as Toner A1, except that 0.1 part of silica mixed with a Henschel mixer was externally added.

-Production of Toner A14-
In the preparation of toner A1, 0.9 parts of calcium carbonate, 1 part of alumina, and silica were used as external additives in place of a mixture of 1.0 part of calcium carbonate, 0.5 part of alumina, and 0.5 part of silica. Toner A14 was obtained in the same manner as Toner A1, except that 0.9 part of the mixture mixed with a Henschel mixer was externally added.

-Production of Toner A15-
Toner A15 was obtained in the same manner as Toner A1, except that in the preparation of Toner A1, hydroxyapatite (Mohs hardness 5 manufactured by Junsei Kagaku) was mixed and added in place of calcium carbonate used as an external additive.

-Production of Toner 16-
Toner A16 was prepared in the same manner as toner A1, except that calcium sulfate dihydrate (Morse hardness 2 manufactured by Junsei Kagaku) was mixed and added in place of calcium carbonate used as an external additive in the preparation of toner A1. Obtained.

-Production of Toner 17-
In the preparation of the toner A1, the toner A17 was added in the same manner as the toner A1, except that calcium fluoride was used instead of calcium carbonate as an external additive, and the mixture was changed so as not to add alumina. Obtained.

-Production of Toner 18-
In the preparation of the toner A1, except that talc (made by Junsei Chemical) was used as an external additive instead of calcium carbonate, and boron carbide (made by Junsei Chemical) was changed instead of alumina and mixed and added externally, In the same manner, Toner A18 was obtained.

Table 1 shows the types and contents of biodegradable dispersants contained in toner A1 to toner A18.
-Evaluation of toner particles-
Further, 10% by mass of the obtained toner particles were added to a 1: 1 mixed solution of methanol / water, and mixed and stirred for 20 minutes by a rotating device such as a ball mill at room temperature (25 ° C.), followed by solid-liquid separation. The dissolved content in the liquid is air-dried, the weight is measured, the ratio with respect to the amount of toner charged is calculated, and the results of determining the dissolved fraction are also shown in Table 1 below. From this result, it can be seen that the toner A10 prepared without using a biodegradable dispersant has a dissolution fraction of 6.1 and is a comparative toner particle outside the scope of the present invention.
Further, the toner surface was measured with an X-ray photoelectron spectrometer under the above conditions, and the coverage of the external additive (oxide particles) on the toner surface was determined. The results are also shown in Table 1 below.

[Preparation of carrier]
100 parts of ferrite particles (Powder Tech, average particle size: 50 μm) and 2.5 parts of methyl methacrylate resin (Mitsubishi Rayon, weight average molecular weight: 95000) are placed in a pressure kneader together with 500 parts of toluene, and After stirring and mixing at 25 ° C. for 15 minutes, the temperature was raised to 70 ° C. while mixing under reduced pressure. After toluene was distilled off, the mixture was cooled and classified using a sieve having an opening of 105 μm. Coated carrier).

[Developer preparation]
The ferrite carrier and each of the toners A1 to A18 were mixed to prepare two-component developers (Developer 1 to Developer 18) having a toner concentration of 7% by mass.

<Production of photoconductor>
(Photoreceptor-1)
The cylindrical Al substrate was polished by a centerless polishing apparatus, and the 10-point average surface roughness Rz was 0.6 μm. As a cleaning process, the cylinder was degreased, etched with a 2% by mass sodium hydroxide solution for 1 minute, neutralized, and further washed with pure water. Next, as an anodizing treatment step, an anodized film (current density 1.0 A / dm ² ) was formed on the cylinder surface with a 10 mass% sulfuric acid solution. After washing with water, sealing was performed by dipping in a 1% by mass nickel acetate solution at 80 ° C. for 20 minutes. Furthermore, pure water washing | cleaning and the drying process were performed. In this manner, a 7 μm anodic oxide film was formed on the surface of the aluminum cylinder.

  One part of titanyl phthalocyanine having a strong diffraction peak at a Bragg angle (2θ ± 0.2 °) of X-ray diffraction spectrum on this aluminum substrate of 27.2 ° is polyvinyl butyral (ESREC BM-S, Sekisui Chemical). After mixing with 1 part and 100 parts of n-butyl acetate and treating with glass beads for 1 hour with a paint shaker to disperse, the resulting coating solution was dip coated on the undercoat layer at 100 ° C. for 10 minutes. A heat generation layer having a thickness of 0.15 μm was formed by heating and drying.

  Next, 2 parts of a benzidine compound (the following compound 1) having the following structure and 2.5 parts of a polymer compound (the following compound 2, viscosity average molecular weight: 39,000, n represents the number of repetitions) are 20 parts of chlorobenzene. The coating solution dissolved in was applied on the charge generation layer by a dip coating method, and heated at 110 ° C. for 40 minutes to form a charge transport layer having a thickness of 20 μm.

  Furthermore, 5 parts of the following compound 4, 7 parts of resol type phenol resin (PL-4852, manufactured by Gunei Chemical Co., Ltd.), 0.03 part of methylphenylpolysiloxane, and 20 parts of isopropanol are mixed and dissolved, and a protective layer is obtained. A forming coating solution was obtained. This coating solution was applied onto the charge transport layer of the image carrier by dip coating, and dried at 130 ° C. for 40 minutes to form a protective layer (outermost surface layer) having a thickness of 3 μm, thereby obtaining a photoreceptor.

(Preparation of photoconductor 2)
100 parts of zinc oxide (manufactured by Teika Co., Ltd., SMZ-017N) and 500 parts of toluene were mixed with stirring, 2 parts of a silane coupling agent (Nihon Unicar Co., Ltd., A1100) was added and stirred for 5 hours. Thereafter, toluene was distilled off under reduced pressure and baked at 120 ° C. for 2 hours to obtain surface-treated zinc oxide.

  35 parts of this surface-treated zinc oxide, 15 parts of a curing agent blocked isocyanate (Sumitomo Bayern Urethane Co., Ltd., Sumidur 3175) and 6 parts of butyral resin (Sekisui Chemical Co., Ltd., BM-1) 44 parts of tomethyl ethyl ketone are mixed, Dispersion was obtained by dispersing for 2 hours in a sand mill using glass beads of 1 mmφ. As a catalyst, 0.005 part of dioctyltin dilaurate and 17 parts of a silicone resin (GE Toshiba Silicone, Tospearl 130) were added to the resulting dispersion to obtain a coating solution for an undercoat layer.

  This coating solution was applied onto an 84 mm drawn tube base material made of JIS A3003 alloy by a wet coating method, and dried and cured at 160 ° C. for 100 minutes to obtain an undercoat layer having a thickness of 20 μm.

  Chlorogallium phthalocyanine having strong diffraction peaks on the undercoat layer at X-ray diffraction spectra of Bragg angles (2θ ± 0.2 °) of 7.4 °, 16.6 °, 25.5 ° and 28.3 ° 1 part is mixed with 1 part of polybutyral resin (manufactured by Sekisui Chemical Co., Ltd., BM-S) and 100 parts of butyl acetate, dispersed with a glass bead for 1 hour in a paint shaker, and the resulting coating solution is placed on the undercoat layer. The film was dipped and dried by heating at 100 ° C. for 10 minutes to form a charge generation layer having a thickness of about 0.15 μm.

  Next, a coating solution for charge transport in which 3 parts of a polymer compound (compound 2) and 2 parts of a benzidine compound (compound 1) are dissolved in 20 parts of tetrahydrofuran is dipped on the charge generation layer, A charge transport layer was obtained, and an electrophotographic photoreceptor 2 was obtained.

(Preparation of photoreceptor 3)
Japanese Patent Laid-Open No. 2006-0330278 [0238] Compound 3 and Compound 4 are each 2 parts and 0.05 parts of tetramethoxysilane, 5 parts of isopropyl alcohol, 3 parts of tetrahydrofuran, and 0.3 part of distilled water. After dissolution, 0.05 part of an ion exchange resin (Amberlyst 15E) was added thereto, and the mixture was stirred at room temperature for hydrolysis for 24 hours.

The ion exchange resin was filtered and separated from the obtained liquid, and 0.04 part of aluminum trisacetylacetonate and 0.02 part of 3,5-di-tert-butyl-4-hydroxytoluene were used with respect to 2 parts of the obtained filtrate. The liquid obtained by adding parts was designated as surface protective layer-forming coating solution A. This surface protective layer forming coating solution A was applied on the charge transport layer of the image carrier before forming the protective layer in the photoreceptor 1 by a dipping coating method, and dried at room temperature for 30 minutes, It was cured by heat treatment at 150 ° C. for 1 hour. In this way, a surface protective layer having a thickness of about 3 μm was formed, and this was used as a photoreceptor 3.
It was confirmed by the above method whether or not the protective layer in the photoreceptor 1 to the photoreceptor 3 contains a resin having a three-dimensional crosslinked structure, and the results are shown in Table 2.

<Example 1 to Example 17, Comparative Example 1>
(Evaluation)
Fuji Xerox printer DocuCenter Color 400CP remodeling machine (process speed 350 mm / s, mounted with the photosensitive member shown in Table 1, charging means, latent image forming means, toner image forming means, transfer means, fixing means, cleaning means, residual toner The image forming test (image coverage density 5%) in a high-temperature and high-humidity (28 ° C., 85% RH) environment using a developer containing toner shown in Table 1. Then, an image forming test for 100,000 sheets was performed in an environment of low temperature and low humidity (10 ° C., 15% RH). Furthermore, abnormal chargeability of residual toner collected after a total of 400,000 image formation tests under the same conditions in a high temperature and high humidity environment and a low temperature and low humidity environment, the deformation toner rate, the image quality of the formed image, the surface condition of the photoreceptor The change of the cleaning blade was evaluated according to the following criteria.

-Judgment of abnormal charge level-
After running 400,000 sheets, the toner collected for cleaning was collected, and foreign matters such as paper dust were removed with a 200 μm net. Then, a developer was produced under the same conditions as the developer used for running the actual machine. The charging performance of the prepared developer and the developer before use in the actual machine evaluation was compared with the idle evaluation (3 m) of the developing machine. The results are shown in the table.
◎: After 10 seconds idling, the difference in charge level after running the actual machine and before evaluation use is very good within 2μc ○: After 10 seconds idling, the difference in charge level after running the actual machine and before evaluation use is 3μc to 5μc Good in the following:-: The difference in charging level between 5 μc and 10 μc after running on the actual machine until idling for 20 seconds is recovered to 3 μc or more and 5 μc or less after that; Δ: The charging level difference is 5 μc even after idling for 30 seconds 10 μc or less, recovered to 5 μc or more and 10 μ or less in 60 seconds.
×: Even after 60 seconds, there is a difference of 10 μc or more and there is no recovery

-Image quality evaluation-
The image quality of the formed image was visually evaluated. The results are shown in Table 2.
◎: Image has no streaks and omissions, good reproducibility for fine lines and halftones ○: Image has no streaks and omissions, fine line reproduction is good, gradation is reduced in halftones, but no problem in practical use No streak or missing, good fine line reproduction, slightly reduced, halftone gradation decreased, but no problem in practical use. Δ: Slight white point missing is seen in the image, but recovery is possible with several sheets. Within the acceptable range.
×: White streaks and white spot missing occur remarkably in the image, and 50 or more are required until recovery

-Change of cleaning blade-
Changes in the cleaning blade were observed with a 100 × laser microscope. The evaluation criteria are as follows, and the results are shown in Table 2.
A: Both the image and non-image areas are good without wear.
○: There is a difference between the image portion and the non-image portion, but there is no problem in actual use.
○-: Slight level at which wear is observed in the image area but there is no influence on the image, or there is a density-decreasing part, but it is recovered immediately by turning from the developing machine.
Δ +: Wear is large in a region where the image density is high, but is within an allowable range.
Δ: Large wear in the image area, which may cause a problem depending on the image density.
X: A defective cleaning occurs, causing a problem on the image.

From Table 2, Example 1 to Example 17 have a smaller toner abnormal charge rate after the image formation test than Comparative Example 1, and the change in the cleaning blade and the image quality of the formed image are both good. It can be seen that even after the image formation test, the deterioration of the physical properties of the toner due to the deformation of the toner and the dropping of the external additive is suppressed.
Among these, in Examples 1 and 2 in which all of the dissolution fraction of the toner, the range of change in the storage elastic modulus, and the coverage of the oxide particles on the toner surface are within the preferable ranges, the effects are obtained. Is found to be good.

1 is a schematic configuration diagram illustrating an example of an image forming apparatus of the present invention. It is a schematic block diagram which shows another example of the image forming apparatus of this invention. It is a schematic block diagram which shows an example of the process cartridge of this invention.

Explanation of symbols

1Y, 1M, 1C, 1K, 107, 110 Photosensitive member (latent image holding member)
2Y, 2M, 2C, 2K, 108, 120 Charging roller 3Y, 3M, 3C, 3K, 130 Laser beam (electrostatic latent image forming means)
3, 110 Exposure device 4Y, 4M, 4C, 4K, 111, 140 Developing device (developing means)
5Y, 5M, 5C, 5K Primary transfer rollers 6Y, 6M, 6C, 6K, 113, 170 Photoconductor cleaning device (toner removing means)
8Y, 8M, 8C, 8K Toner cartridge 10Y, 10M, 10C, 10K Unit 26 Secondary transfer roller (transfer means)
28, 115 Fixing device (fixing means)
100 Image forming apparatus 112 Transfer apparatus 147 Developer cartridge (toner cartridge)
200 process cartridge,
P Recording paper (transfer object)

Claims (13)

A resin containing a crosslinked polyester resin and a non-crosslinked polyester resin, containing toner particles comprising a colorant, a and, the toner volume ratio of particles of alcohol and water 1: dissolution when dissolved in 1 mixed solution fraction is state, and are 0.5% or more than 5.0% relative to the total weight of the toner particles,
When dynamic viscoelasticity measurement is performed on the toner particles under an angular velocity of 6.28 rad and a temperature change condition of 1 ° C./min, a storage elastic modulus G ′ during a temperature rising process from 30 ° C. to 170 ° C. is measured. The G ′ change width in the temperature rising process from 60 ° C. to 140 ° C. is 10 ^{2 to} 10 ⁵ Pa and the G ′ change width in the temperature rising process from 150 ° C. to 170 ° C. is 10 ³ Pa or less. toner for developing an electrostatic charge image Ru Oh. In the resin in the toner, biodegradable claim 1 toner according containing the dispersant. The electrostatic image developing toner according to claim 2 , wherein the biodegradable dispersant is derived from a manufacturing process of the toner. A resin particle dispersion in which resin particles containing a biodegradable dispersant are dispersed in at least one and a colorant particle dispersion in which colorant particles are dispersed are mixed, and the resin particles and the colorant particles are aggregated and heated. The electrostatic image developing toner according to claim 2 or 3 obtained by fusing and coalescing. The oxide particle coverage on the toner surface is 50% or more and 95% or less when the toner surface contains two or more oxide particles as an additive and the toner surface is measured by an X-ray photoelectron spectrometer. The toner for developing an electrostatic charge image according to claim 4 . 6. The electrostatic image developing toner according to claim 5 , wherein the difference in hardness between the maximum hardness and the minimum hardness of the two or more kinds of oxide particles is 4 or more and 8 or less. A resin particle dispersion adjusting step for adjusting a resin particle dispersion in which resin particles are dispersed;
A colorant particle dispersion adjusting step of adjusting a colorant particle dispersion in which the colorant particles are dispersed;
A mixed solution adjusting step of mixing the resin particle dispersion and the colorant particle dispersion to adjust a mixed solution containing the resin particles and the colorant particles;
An aggregated particle adjusting step of adjusting aggregated particles in which the resin particles and the colorant particles are aggregated;
A fusion and coalescence step of fusing and coalescing the aggregated particle dispersion in which the agglomerated particles are dispersed above the glass transition temperature of the resin particles; and
Cooling to a temperature below the glass transition temperature of the resin particles,
A biodegradable dispersing agent includes at least one process of fusing and coalescing and fusing and coalescing by heating above the glass transition temperature of the resin particles, and cooling to a temperature below the glass transition temperature of the resin particles. And a process for adjusting the pH of the liquid to a range of 7 to 11 by adding a basic compound. Electrostatic image comprising a toner for developing electrostatic image developer according to any one of claims 1 to 6. Desorbed in an image forming apparatus having a developing unit, the toner to be supplied to a developing unit is accommodated, the toner is for developing an electrostatic charge image according to any one of claims 1 to 6 A toner cartridge that is toner. A process cartridge comprising a developing holder and containing the developer for developing an electrostatic charge image according to claim 8 . A latent image carrier,
An electrostatic latent image forming means for forming an electrostatic latent image on the surface of the latent image holding member;
Developing means for developing the electrostatic latent image with a developer containing toner to form a toner image;
Transfer means for transferring the toner image formed on the latent image holding member to the surface of a recording medium;
Toner removing means for removing residual toner remaining on the surface of the latent image holding member,
The image forming apparatus according to claim 8 , wherein the developer is a developer for developing an electrostatic image according to claim 8 . The image forming apparatus according to claim 11 , further comprising: a residual toner collecting / supplying unit that collects the residual toner removed by the toner removing unit and supplies the collected residual toner to the developing unit. Layer constituting the outermost surface of the latent image holding member comprises a resin having a three-dimensional crosslinked structure, the image forming apparatus according to claim 11 or claim 12.

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