JP2012155121A - Toner for electrostatic charge image development, electrostatic charge image developer, toner cartridge, process cartridge, image forming method and image forming apparatus - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner for electrostatic charge image development capable of suppressing generation of color spots.SOLUTION: The toner for electrostatic charge image development contains at least a binder resin and a colorant and has a core-shell structure having a shell layer on a core particle surface. The binder resin in the core particle contains a crystalline polyester resin and an amorphous polyester resin. The shell layer contains a crystalline polyester resin, and by an observation of the shell layer dyed with ruthenium tetraoxide, a proportion of the surface covered with the crystalline polyester resin is 70 to 100% by area. The shell layer has an average thickness of 50 nm or more and less than 100 nm. The present invention also provides an electrostatic charge image developer, a toner cartridge, a process cartridge, an image forming method and an image forming apparatus using the above toner for electrostatic charge image development.

Description

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

A method of visualizing image information through an electrostatic charge image such as electrophotography is currently used in various fields. In electrophotography, an electrostatic charge image is formed on a photoreceptor by charging and exposure processes, the electrostatic latent image is developed with a developer containing toner, and visualized through a transfer and fixing process.
In recent years, due to increasing awareness of the environment, demand for a low environmental load is increasing for full-color image forming apparatuses in electrophotography, and various methods have been proposed.
As conventional electrostatic image developing toners and image forming methods, Patent Documents 1 to 3 shown below are known.
Patent Document 1 discloses an electrostatic charge image developing toner containing core-shell structure type toner particles having a shell layer on the surface of core particles, wherein the shell layer includes a crystalline polyester resin having a softening point of 60 to 120 ° C. A toner for developing an electrostatic charge image is described, which is contained in an amount of 70 to 100% by weight of the total shell layer constituting resin.
Japanese Patent Application Laid-Open No. 2004-228561 discloses an image forming method in which a toner image formed on a first image carrier is transferred to an intermediate transfer member and then further transferred onto a second image carrier. The layer contains a high-lubricating powder in an amount of 20 to 80% by weight of the total weight of the surface layer, and the toner covers at least the low-softening point compound forming the central part and the central part. A toner having particles having an inner layer and a central portion and an upper layer covering the inner layer, and the central portion, the inner layer and the upper layer can be distinguished by ruthenium tetroxide and osmium tetroxide dyeing methods An image forming method characterized by comprising: is described.
Patent Document 3 includes at least a toner for developing an electrostatic charge image, which includes a crystalline polyester and an amorphous polymer as a binder resin, and the surface is coated with a surface layer mainly composed of the amorphous polymer. The content of the crystalline polyester is in the range of 30 to 80% by weight, the ratio of the crystalline polyester contained in the outermost surface of the electrostatic image developing toner is 15 atomic% or less, and the surface layer An electrostatic charge image developing toner is described in which the average thickness of the toner is 0.01 μm or more and 0.5 μm or less.

JP 2005-99079 A Japanese Patent Laid-Open No. 9-190010 JP 2004-191927 A

  An object of the present invention is to provide an electrostatic charge image developing toner capable of suppressing the generation of a color point.

As a result of intensive studies to solve the problems of the prior art, the present inventors have found that the above problems can be solved by means described in the following <1> to <6>.
<1> A core-shell structure including at least a binder resin and a colorant and having a shell layer on a core particle surface, wherein the binder resin in the core particle is made of a crystalline polyester resin and an amorphous resin. The ratio of the surface of the shell layer covered with the crystalline polyester resin in the shell layer observed by dyeing with ruthenium tetroxide is 70 to 100 area. An electrostatic charge image developing toner, wherein the shell layer has an average thickness of 50 nm or more and less than 100 nm,
<2> An electrostatic charge image developer comprising the electrostatic charge image developing toner according to <1> above and a carrier,
<3> a toner cartridge containing at least the electrostatic charge image developing toner according to <2>;
<4> Developing means for developing an electrostatic latent image formed on the surface of the image carrier with an electrostatic image developing toner or an electrostatic image developer to form a toner image, an image carrier, and the surface of the image carrier At least one selected from the group consisting of a charging means for charging the toner and a cleaning means for removing the toner remaining on the surface of the image carrier, and the electrostatic charge image according to the above <1> A developing cartridge or a process cartridge containing the electrostatic charge image developer according to <2>,
<5> A latent image forming step of forming an electrostatic latent image on the surface of the image carrier, and a developing step of developing the electrostatic latent image formed on the surface of the image carrier with a developer containing toner to form a toner image. An electrostatic charge as described in <1> above, comprising: a transfer step of transferring the toner image onto the surface of the transfer member; and a fixing step of fixing the toner image transferred onto the surface of the transfer member. An image forming method using an image developing toner or the electrostatic image developer according to <2> above,
<6> Image carrier, charging unit for charging the image carrier, exposure unit for exposing the charged image carrier to form an electrostatic latent image on the surface of the image carrier, and development including toner Developing means for developing the electrostatic latent image with an agent to form a toner image, transfer means for transferring the toner image from the image holding member to the surface of the transfer target, and toner transferred to the surface of the transfer target And an image forming apparatus using the electrostatic charge image developing toner according to <1> or the electrostatic charge image developer according to <2> as the developer.

According to the invention described in <1> above, it is possible to provide an electrostatic image developing toner capable of suppressing the generation of a color point as compared with the case where this configuration is not provided.
According to the invention described in <2> above, it is possible to provide an electrostatic charge image developer capable of suppressing the generation of a color point as compared with the case where the present configuration is not provided.
According to the invention described in <3>, it is possible to provide a toner cartridge capable of suppressing the generation of color points as compared with the case where the present configuration is not provided.
According to the invention described in <4> above, it is possible to provide a process cartridge capable of suppressing the generation of color points as compared with the case where the present configuration is not provided.
According to the invention described in <5>, it is possible to provide an image forming method capable of suppressing the generation of color points as compared with the case where the present configuration is not provided.
According to the invention described in <6>, it is possible to provide an image forming apparatus capable of suppressing the generation of color points as compared with the case where the present configuration is not provided.

Hereinafter, this embodiment will be described in detail.
In the present embodiment, the description “A to B” represents not only a range between A and B but also a range including A and B at both ends thereof. For example, if “A to B” is a numerical value range, “A or more and B or less” or “B or more and A or less” is represented.

(Electrostatic image developing toner)
The electrostatic image developing toner of the present embodiment (hereinafter also simply referred to as “toner”) has a core-shell structure including at least a binder resin and a colorant and having a shell layer on the surface of the core particles. And the binder resin in the core particles contains a crystalline polyester resin and an amorphous polyester resin, and the shell layer contains a crystalline polyester resin and is observed by dyeing with ruthenium tetroxide. The ratio of the surface covered with the crystalline polyester resin is 70 to 100% by area, and the average thickness of the shell layer is 50 nm or more and less than 100 nm.

  According to Patent Document 1, low-temperature fixing, heat-resistant storage property, prevention of offset, and the like are realized by containing a large amount of crystalline polyester resin in the shell layer of the core-shell structure type toner. However, in the toner described in Patent Document 1, in a system in which heat from the fixing device is easily transferred to the developing device, such as direct transfer, under the circumstances where heat and agitation stress are applied at the same time, external additives are buried or toner is used. In some cases, fusion occurs between the two, which may cause image quality defects such as a color point.

The electrostatic charge image developing toner of the present embodiment contains a crystalline polyester resin and an amorphous polyester resin in the core particles, so that the fixing temperature can be lowered and the fixing device temperature is lowered. Since the heat transmitted from the developing unit to the developing unit is suppressed and the surface is mainly formed of crystalline polyester resin, external addition and toner fusion due to heat and stirring stress in the developing unit are suppressed, and the color point It is estimated that the occurrence of is suppressed.
In addition, the electrostatic charge image developing toner of the present embodiment has an average thickness of the shell layer of 50 nm or more and less than 100 nm, which is thinner than the usual shell peeling, and the crystalline polyester resin peels off and adheres to the photoreceptor. It is estimated that the color point due to can be prevented.

<Shell layer>
The electrostatic charge image developing toner of the present embodiment has a core-shell structure having a shell layer on the surface of core particles, the shell layer contains a crystalline polyester resin, and is observed by dyeing with ruthenium tetroxide. The ratio of the surface covered with the crystalline polyester resin in the shell layer is 70 to 100 area%, and the average thickness of the shell layer is 50 nm or more and less than 100 nm.
The shell layer contains a crystalline polyester resin as a main component, that is, preferably contains 70% by weight or more, more preferably 80% by weight or more, more preferably 95% by weight or more based on the total weight of the shell layer. Is more preferable, and it is particularly preferable that the shell layer is made of a crystalline polyester resin.
The shell layer may contain other toner components such as a colorant in addition to the crystalline polyester resin, but it is preferable not to contain it.

The ratio of the surface covered with the crystalline polyester resin in the shell layer is observed by staining with ruthenium tetroxide.
The dyeing with ruthenium tetroxide is carried out by a known method using ruthenium tetroxide. Specifically, it is preferably measured by the following method.
The toner is dyed by bringing it into contact with a 0.5 wt% ruthenium tetroxide aqueous solution, and the dyed toner is imaged as a still image by using a field emission scanning electron microscope S-4800 manufactured by Hitachi High-Technologies Corporation. The captured toner image is subjected to two-dimensional image processing, and the ratio of the surface of the shell layer covered with the crystalline polyester resin is calculated as an average value of 100 toners. In the dyed toner, the crystalline polyester resin is not dyed and is observed in black in the image, while the non-crystalline polyester resin is dyed and observed in white in the image as compared with the crystalline polyester resin.
When the toner has an external additive, the above operation is preferably performed on the toner from which the external additive has been removed.
The ratio of the surface covered with the crystalline polyester resin in the shell layer observed by dyeing with ruthenium tetroxide is preferably 75 to 100 area%, and more preferably 80 to 100 area%.

The average thickness of the shell layer in the electrostatic image developing toner of the exemplary embodiment is 50 nm or more and less than 100 nm, preferably 50 to 80 nm, and more preferably 60 to 75 nm. Within the above range, the crystalline polyester resin of the shell layer is prevented from peeling off and adhering to the photoreceptor, and the generation of color points in the obtained image is suppressed.
The method for measuring the average thickness of the shell layer is not particularly limited, but it is preferable to measure the cross section of the toner by ruthenium tetroxide, and more specifically, the following method is more preferable.
The toner is embedded in an epoxy resin and sectioned to a thickness of 100 nm by a microtome. The toner may have an external additive, or may not have or be removed. The cross section of the toner is dyed with a 0.5% by weight aqueous solution of ruthenium tetroxide and observed with a scanning electron microscope (TEM). In the cross section of the toner, the thickness of the shell layer is measured from the color contrast.
In this embodiment, the measurement position of the thickness of the shell layer is measured at four positions of the shell layer that intersect two straight lines perpendicular to the approximate center of the toner. It is assumed that the average thickness of the shell layer is calculated by averaging the thickness values of the shell layer measured at four points for each of 100 toners.

<Core particles>
The electrostatic charge image developing toner of the present embodiment has a core-shell structure having a shell layer on the surface of the core particles, and the binder resin in the core particles comprises a crystalline polyester resin and an amorphous polyester resin. Including. When the core particles contain a crystalline polyester resin and an amorphous polyester resin, the toner fixing temperature can be lowered, the heat transmitted from the fixing device to the developing device is suppressed, and the toner is fused in the developing device. Therefore, it is estimated that the generation of color points is suppressed.
The presence of the crystalline polyester resin and the non-crystalline polyester resin can be confirmed by a known method. For example, the glass transition temperature or crystal by component analysis such as resin composition or differential scanning calorimetry (DSC). Examples include measurement of melting point.
The crystalline polyester resin and the non-crystalline polyester resin in the core particles may or may not be compatible with each other, but are compatible or have a microphase separation structure. It is preferable that a microphase separation structure is formed. The microphase separation structure is a state in which two kinds of resins are phase-separated on the order of several hundred nanometers or less. Examples of the microphase separation structure include a sea-island structure and an interpenetrating network structure that are phase-separated on the order of several hundred nanometers or less. Among these, it is preferable to have a sea-island structure in the core particles, and the major axis of the island phase in the sea-island structure is more preferably 150 nm or less, and even more preferably 1 to 150 nm. Moreover, either the crystalline polyester resin or the amorphous polyester resin may form an island in the sea-island structure.
As a method for confirming the sea-island structure of the crystalline polyester resin and the amorphous polyester resin in the core particles, the toner cross section is dyed by the same method as the method for measuring the average thickness of the shell layer, and the core particle portion The method of observing is mentioned.

  In the binder resin in the core particles, the weight ratio of the crystalline polyester resin to the amorphous polyester resin is preferably crystalline polyester resin: noncrystalline polyester resin = 10: 90 to 90:10, It is more preferably 20:80 to 80:20, and further preferably 30:70 to 70:30. Within the above range, the toner fixing temperature can be lowered and the generation of color points is further suppressed.

  Next, a toner constituent material such as a crystalline polyester resin and an amorphous polyester resin used in the present embodiment, a toner manufacturing method, and the like will be described.

<Polyester resin>
In the toner according to the exemplary embodiment, the binder resin in the core particle includes a crystalline polyester resin and an amorphous polyester resin, and the shell layer includes a crystalline polyester resin.
A crystalline polyester resin may be used individually by 1 type, and may use 2 or more types together. The non-crystalline polyester resin may be used alone or in combination of two or more, and is not particularly limited. Moreover, although the same crystalline polyester resin may be used for the core particle and the shell layer, different types of crystalline polyester resins may be used, but the same crystalline polyester resin is preferable.

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

  Examples of the polycondensable monomer used in the polycondensation reaction for synthesizing the polyester resin include polycarboxylic acids and polyols. The polyester resin is preferably a polyester resin obtained using a polycarboxylic acid and a polyol as a polycondensable monomer. Furthermore, among these, it is more preferable to use a dicarboxylic acid as the polyvalent carboxylic acid and to use a diol as the polyol.

  In the present embodiment, the polycarboxylic acid includes polycarboxylic acids such as aliphatic, alicyclic, aromatic, and hydroxycarboxylic acids, and alkyl esters thereof, and the polyol includes polyhydric alcohols, ester compounds thereof, and hydroxy Contains carboxylic acid and the like. The polyester resin can be produced by performing polycondensation by direct esterification reaction or transesterification reaction using a polycondensable monomer. In this case, the polyester resin to be polymerized includes any form such as amorphous (amorphous / non-crystalline) polyester, crystalline polyester, or a mixed form thereof.

The polycarboxylic acid used as the polycondensable monomer is a compound containing two or more carboxy groups in one molecule.
Among these, divalent polycarboxylic acid is a compound containing two carboxy groups in one molecule. For example, oxalic acid, succinic acid, maleic acid, itaconic acid, adipic acid, glutaric acid, β-methyladipic acid , Azelaic acid, sebacic acid, suberic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, tetradecanedicarboxylic acid, octadecanedicarboxylic acid, fumaric acid, citraconic acid, diglycolic acid, glutaconic acid, n-dodecyl Succinic acid, n-dodecenyl succinic acid, isododecyl succinic acid, isododecenyl succinic acid, n-octyl succinic acid, n-octenyl succinic acid, cyclohexanedicarboxylic acid, cyclohexene dicarboxylic acid, cyclohexane-3,5-diene-1,2 -Dicarboxylic acid, malic acid Citric acid, hexahydroterephthalic acid, malonic acid, pimelic acid, tartaric acid, mucoic acid, phthalic acid, isophthalic acid, terephthalic acid, tetrachlorophthalic acid, chlorophthalic acid, nitrophthalic acid, p-carboxyphenylacetic acid, p-phenylenediacetic acid M-phenylene diglycolic acid, p-phenylene diglycolic acid, o-phenylene diglycolic acid, diphenylacetic acid, diphenyl-p, p'-dicarboxylic acid, naphthalene-1,4-dicarboxylic acid, naphthalene-1,5- Examples thereof include dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, anthracene dicarboxylic acid, norbornene-2,3-dicarboxylic acid, adamantane dicarboxylic acid, and adamantane diacetic acid.
Examples of the trivalent or higher polycarboxylic acids include trimellitic acid, pyromellitic acid, naphthalenetricarboxylic acid, naphthalenetetracarboxylic acid, pyrenetricarboxylic acid, pyrenetetracarboxylic acid, mesaconic acid, and lower esters thereof. Etc. Furthermore, although the acid chloride of the said polycarboxylic acid is mentioned, it is not this limitation.
These may be used alone or in combination of two or more. Further, in addition to the aliphatic dicarboxylic acid and aromatic dicarboxylic acid described above, a dicarboxylic acid component having a double bond may be contained.

The polyol used in the present embodiment is a compound containing two or more hydroxyl groups in one molecule. Examples of the diol containing two hydroxyl groups in one molecule include ethylene glycol, propylene glycol, butanediol, butenediol, neopentyl glycol, pentanediol, hexanediol, heptanediol, cyclohexanediol, cyclohexanedimethanol, diethylene glycol, Triethylene glycol, dipropylene glycol, octanediol, nonanediol, decanediol, undecanediol, dodecanediol, tridecanediol, tetradecanediol, octadecanediol, eicosandecanediol, diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol , Polypropylene glycol, polytetramethylene glycol, bisphenol Lumpur A, bisphenol Z, and hydrogenated bisphenol A, and the like.
Examples of the polyol having three or more hydroxyl groups in one molecule include glycerin, pentaerythritol, hexamethylol melamine, hexaethylol melamine, tetramethylol benzoguanamine, and tetraethylol benzoguanamine.
These polyols may be used alone or in combination of two or more.

-Crystalline polyester resin-
In this embodiment, a crystalline polyester resin is included as the binder resin.
As the polycarboxylic acid used to obtain the crystalline polyester resin, among the above carboxylic acids, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, Aliphatic dicarboxylic acids such as 1,9-nonanedicarboxylic acid, 1,10-decanedicarboxylic acid, 1,12-dodecanedicarboxylic acid, 1,14-tetradecanedicarboxylic acid, 1,18-octadecanedicarboxylic acid, sebacic acid, Maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, n-dodecyl succinic acid, n-dodecenyl succinic acid, isododecyl succinic acid, isododecenyl succinic acid, n-octyl succinic acid, n-octenyl succinic acid, these Acid anhydrides, lower esters, and acid chlorides.

Examples of the diol used for obtaining the crystalline polyester resin include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, dipropylene glycol, polypropylene glycol, 1, 4-butanediol, 1,4-butenediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1,18-octadecanediol, 1,14-eicosane Deccan Ol, polytetramethylene ether glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, and polytetramethylene glycol, and the like.
A dihydric or higher polyhydric alcohol is also used in combination. Examples thereof include glycol, pentaerythritol, hexamethylol melamine, hexaethylol melamine, tetramethylol benzoguanamine, and tetraethylol benzoguanamine.

  As the crystalline polyester resin, a polyester resin obtained by reacting 1,9-nonanediol and 1,10-decanedicarboxylic acid, a polyester resin obtained by reacting 1,9-nonanediol and azelaic acid, Polyester resin obtained by reacting cyclohexanediol and adipic acid, polyester resin obtained by reacting 1,9-nonanediol and sebacic acid, obtained by reacting 1,6-hexanediol and sebacic acid Polyester resin, polyester resin obtained by reacting ethylene glycol and succinic acid, polyester resin obtained by reacting ethylene glycol and sebacic acid, and obtained by reacting 1,4-butanediol and succinic acid The polyester resin which can be mentioned can be mentioned. Among these, polyester resins obtained by reacting 1,9-nonanediol and 1,10-decanedicarboxylic acid, polyester resins obtained by reacting 1,9-nonanediol and azelaic acid, -Polyester resins obtained by reacting nonanediol and sebacic acid and polyester resins obtained by reacting 1,6-hexanediol and sebacic acid are preferred.

Among the polyvalent carboxylic acid components, the content of the aliphatic dicarboxylic acid is preferably 80 mol% or more, and more preferably 90% mol or more. When the content of the aliphatic dicarboxylic acid is 80 mol% or more, the polyester resin is excellent in crystallinity and has an appropriate melting point, and therefore toner blocking resistance and image storage stability. And it is excellent in low-temperature fixability.
Among the polyhydric alcohol components, the content of the aliphatic diol component is preferably 80 mol% or more, and more preferably 90% mol or more. When the content of the aliphatic diol component is 80 mol% or more, the polyester resin is excellent in crystallinity and has an appropriate melting point, and thus is excellent in toner blocking resistance, image storage stability, and low-temperature fixability.

-Amorphous polyester resin-
In the present embodiment, a crystalline polyester resin and an amorphous polyester resin are used in combination as the binder resin.
Divalent carboxylic acids used to obtain an amorphous polyester resin include phthalic acid, isophthalic acid, terephthalic acid, tetrachlorophthalic acid, chlorophthalic acid, nitrophthalic acid, malonic acid, mesaconic acid, p-carboxyphenylacetic acid P-phenylene diacetic acid, m-phenylene diglycolic acid, p-phenylene diglycolic acid, o-phenylene diglycolic acid, diphenylacetic acid, diphenyl-p, p′-dicarboxylic acid, naphthalene-1,4-dicarboxylic acid, Naphthalene-1,5-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, anthracene dicarboxylic acid, cyclohexane dicarboxylic acid, cyclohexene dicarboxylic acid, norbornene-2,3-dicarboxylic acid, adamantane dicarboxylic acid, and adamantane diacetic acid It is done.
Examples of the trivalent or higher carboxylic acid include trimellitic acid, pyromellitic acid, naphthalenetricarboxylic acid, naphthalenetetracarboxylic acid, pyrenetricarboxylic acid, and pyrenetetracarboxylic acid.
Moreover, you may use what derived the carboxy group of these polycarboxylic acid to the acid anhydride, acid chloride, or lower ester. The lower ester means an ester with an aliphatic alcohol having 1 to 8 carbon atoms.
Among these, it is preferable to use terephthalic acid and its lower ester, phenylenediacetic acid, phenylenedipropanoic acid, cyclohexanedicarboxylic acid, and the like. 1,4-phenylenediacetic acid, 1,4-phenylenedipropanoic acid, 1,4 -Cyclohexanedicarboxylic acid and the like are more preferable.

As the polyol used for obtaining the amorphous polyester resin, among the above polyols, polytetramethylene glycol, bisphenol A, bisphenol Z, bisphenol S, biphenol, naphthalene diol, adamantanediol, adamantane dimethanol, hydrogen It is preferable to use added bisphenol A, cyclohexanedimethanol, or the like.
The bisphenol is preferably an alkylene oxide adduct, and examples of the alkylene oxide group include an ethylene oxide group, a propylene oxide group, and a butylene oxide, and ethylene oxide and propylene oxide are preferable.

  Among these, it is preferable that the amorphous polyester resin includes an amorphous polyester resin polymerized using a polycondensable monomer having an aromatic group. That is, the amorphous polyester resin is preferably an amorphous polyester resin obtained by polycondensation of a polyol having an aromatic group and / or a polycarboxylic acid having an aromatic group, and has an aromatic group. More preferably, it is an amorphous polyester resin obtained by polycondensation of a diol and / or a dicarboxylic acid having an aromatic group, and an amorphous polyester resin obtained by polycondensation of a diol having an aromatic group More preferably.

It does not specifically limit as said aromatic group, If it contains aromatic groups, such as a phenyl group, a naphthyl group, an anthracenyl group, in the structure, it will not specifically limit. Among these, it is preferable to have a bisphenol skeleton, more preferably a linear polyester resin having a bisphenol skeleton.
The bisphenol skeleton is not particularly limited as long as it is a skeleton composed of two phenol groups. Examples include bisphenol A, bisphenol C, bisphenol E, bisphenol F, bisphenol M, bisphenol P, bisphenol S, and bisphenol Z. However, it is not limited to this. Examples of the skeleton preferably used include bisphenol A, bisphenol C, bisphenol E, bisphenol F, bisphenol M, bisphenol P, bisphenol S, and bisphenol Z, more preferably bisphenol A, bisphenol E, and bisphenol F. More preferred is bisphenol A. That is, the amorphous polyester resin is preferably an amorphous polyester resin polymerized using a polycondensable monomer having a bisphenol A structure.

As a polycondensable monomer used for obtaining an amorphous polyester resin having a bisphenol skeleton, a polyol having a bisphenol skeleton is preferable, and an alkylene oxide adduct of bisphenol or bisphenol is particularly preferable.
Examples of the alkylene oxide include C2-C6 alkylene oxides such as ethylene oxide, propylene oxide, and butylene oxide. Among these, ethylene oxide or propylene oxide is more preferable.
Among these, as the polyol used for obtaining the amorphous polyester resin, an alkylene oxide adduct of bisphenol A is preferable, and an ethylene oxide adduct and a propylene oxide adduct of bisphenol A are more preferable. Further, the alkylene oxide is preferably added in an amount of 2 to 4 mol, more preferably 2 mol or 4 mol, in terms of both ends (total number of moles).

The amorphous polyester resin polymerized by using a polycondensable monomer having an aromatic group is preferably contained in an amount of 30 to 100% by weight, more preferably 50 to 100% by weight based on the whole amorphous polyester resin. Is more preferable, and it is still more preferable to contain 70-100 weight%.
The non-crystalline polyester resin polymerized using the polycondensable monomer having an aromatic group is a total of a monomer unit derived from a polyol and a monomer unit derived from a polycarboxylic acid. In the monomer unit, the monomer unit having an aromatic group is preferably contained in an amount of 30 mol% or more, and more preferably 40 mol% or more.

  As the non-crystalline polyester resin, a polyester resin obtained by reacting an ethylene oxide adduct and / or propylene oxide adduct of bisphenol A with terephthalic acid is preferable, and fumaric acid or dodecenyl succinic acid is further added as a polycarboxylic acid component. And at least one polycarboxylic acid selected from the group consisting of trimellitic anhydride is also preferred.

  Even if each of the polycarboxylic acid and polyol is used alone to produce one kind of polyester resin (crystalline polyester resin or non-crystalline polyester resin), one is one and the other is 2 Two or more species may be used, or two or more species may be used. Moreover, when using hydroxycarboxylic acid for producing polycondensation resin, it may be used individually by 1 type, may use 2 or more types, and may use polycarboxylic acid and a polyol together.

In the present embodiment, the crystalline melting point Tm of the crystalline polyester resin is preferably 50 to 100 ° C, more preferably 50 to 90 ° C, and still more preferably 50 to 80 ° C. The above range is preferable because it is excellent in peelability and low-temperature fixability and can further reduce offset.
Here, for measuring the crystalline melting point of the crystalline polyester resin, a differential scanning calorimeter was used, and JIS K-7121 measured at a heating rate of 10 ° C. per minute from room temperature (20 ° C.) to 180 ° C. : It can obtain | require as a melting peak temperature of the input compensation differential scanning calorimetry shown to 87. The crystalline polyester resin may show a plurality of melting peaks, but in this embodiment, the maximum peak is regarded as the crystalline melting point.

On the other hand, the glass transition temperature (Tg) of the amorphous polyester resin is preferably 30 ° C. or higher, more preferably 30 to 100 ° C., and still more preferably 50 to 80 ° C. If it is in the above range, since it is in a glass state in use, toner particles do not aggregate due to heat and pressure received during image formation, and do not adhere and accumulate in the machine, and stable image forming ability over a long period of time. can get.
Here, the glass transition temperature of the non-crystalline polyester resin refers to a value measured by a method (DSC method) defined in ASTM D3418-82.
Moreover, the measurement of the glass transition temperature in this embodiment can be measured by, for example, “DSC-20” (manufactured by Seiko Denshi Kogyo Co., Ltd.) according to the differential scanning calorimetry, and specifically, about 10 mg of a sample. Is heated at a constant rate of temperature increase (10 ° C./min), and the glass transition temperature is obtained from the intersection of the baseline and the endothermic peak tilt line.

The weight average molecular weight of the crystalline polyester resin is preferably 10,000 to 60,000, more preferably 15,000 to 45,000, and still more preferably 20,000 to 30,000. .
The weight average molecular weight of the amorphous polyester resin is preferably 5,000 to 100,000, more preferably 10,000 to 90,000, and 20,000 to 80,000. Is more preferable.
It is preferable that the weight average molecular weights of the crystalline polyester resin and the non-crystalline polyester resin are within the above ranges because both the image strength and the fixability can be achieved. All of the above weight average molecular weights can be obtained by molecular weight measurement by gel permeation chromatography (GPC) method in which tetrahydrofuran (THF) is soluble. The molecular weight of the resin is calculated using a molecular weight calibration curve prepared with a monodisperse polystyrene standard sample by measuring THF soluble material with THF solvent using TSK-GEL (GMH (manufactured by Tosoh Corporation)) etc. Is done.

The acid value of the crystalline polyester resin and the amorphous polyester resin is preferably 1 to 50 mgKOH / g, more preferably 5 to 50 mgKOH / g, and still more preferably 8 to 50 mgKOH / g. . The above range is preferable because it is excellent in fixing characteristics and charging stability.
If necessary, a monovalent acid such as acetic acid or benzoic acid or a monovalent alcohol such as cyclohexanol benzyl alcohol may be used for the purpose of adjusting the acid value or the hydroxyl value.

In this embodiment, the polycarboxylic acid and polyol which are the above-mentioned polycondensation monomers, and the polymerization reaction with the oligomer and / or prepolymer produced previously can also be included. The prepolymer is not limited as long as it is a polymer that can be melted or uniformly mixed with the monomer.
In this embodiment, the binder resin is a homopolymer of the above-mentioned polycondensation component and two or more monomers including the above-mentioned polycondensation component as long as it contains crystalline and non-crystalline polyester resins. Or a mixture thereof, a graft polymer, a partially branched or crosslinked structure, and the like.

The production method of the polyester resin is not particularly limited, and can be produced by a general polyester polymerization method in which an acid component and an alcohol component are reacted. Examples thereof include direct polycondensation and transesterification. Depending on the type, it will be manufactured separately.
The polyester resin may be produced by subjecting the polyhydric alcohol and polyhydric carboxylic acid to a condensation reaction according to a conventional method. For example, the above polyhydric alcohol and polyvalent carboxylic acid, if necessary, a catalyst, and blended in a reaction vessel equipped with a thermometer, a stirrer, a flow-down condenser, and in the presence of an inert gas (such as nitrogen gas), Heat at 150 to 250 ° C. to continuously remove by-product low-molecular compounds out of the reaction system, stop the reaction when a predetermined acid value is reached, cool, and obtain the desired reactant Manufactured by.

Although there is no restriction | limiting in particular as content of the binder resin in the said core particle, It is preferable that it is 5-95 weight% with respect to the total weight of a core particle, and it is more preferable that it is 20-90 weight%. Preferably, it is 40 to 85 weight%. Within the above range, the fixing property, storage property, powder property, charging property and the like are excellent.
Further, the content of the binder resin in the toner of the exemplary embodiment is not particularly limited, but is preferably 10 to 95% by weight, and preferably 25 to 90% by weight with respect to the total weight of the toner. Is more preferable, and it is still more preferable that it is 45 to 85 weight%. Within the above range, the fixing property, storage property, powder property, charging property and the like are excellent.

Further, the toner of the present embodiment may contain a resin other than the polyester resin as the binder resin, but the content is preferably 20% by weight or less with respect to the total weight of the toner. It is more preferably 10% by weight or less, still more preferably 5% by weight or less, and particularly preferably not contained.
Resins other than polyester resins include styrenes such as styrene and chlorostyrene, monoolefins such as ethylene, propylene, butylene, and isoprene, vinyl esters such as vinyl acetate, vinyl propionate, vinyl benzoate, and vinyl acetate, and methyl acrylate. , Α-methylene aliphatic monocarboxylic acid esters such as ethyl acrylate, butyl acrylate, dodecyl acrylate, octyl acrylate, phenyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, dodecyl methacrylate, vinyl methyl Examples thereof include homopolymers or copolymers of vinyl ethers such as ether, vinyl ethyl ether and vinyl butyl ether, vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and vinyl isopropenyl ketone.

<Colorant>
The toner used in the exemplary embodiment preferably contains a colorant in the core particle and / or shell layer, and contains at least a colorant in the core particle.
Examples of colorants include carbon black, nigrosine, aniline blue, calcoil blue, chrome yellow, ultramarine blue, dupont oil red, quinoline yellow, methylene blue chloride, phthalocyanine blue, malachite green oxalate, lamp black, rose bengal, C.I. I. Pigment red 48: 1, C.I. I. Pigment red 122, C.I. I. Pigment red 57: 1, C.I. I. Pigment red 238, C.I. I. Pigment yellow 97, C.I. I. Pigment yellow 12, C.I. I. Pigment yellow 180, C.I. I. Pigment blue 15: 1, C.I. I. Pigment Blue 15: 3 is a representative example.

  In the toner of this embodiment, the colorant is selected from the viewpoints of hue angle, saturation, brightness, weather resistance, OHP permeability, and dispersibility in the toner. The addition amount of the colorant in the toner is not particularly limited, but is preferably in the range of 4 to 20 parts by weight with respect to 100 parts by weight of the binder resin contained in the toner.

<Release agent>
The toner used in the exemplary embodiment preferably contains a release agent in the core particle and / or shell layer, and more preferably contains at least a release agent in the core particle.
There is no restriction | limiting in particular in the mold release agent used for this embodiment, A well-known thing is used and what is obtained from the following waxes is preferable. Paraffin wax and derivatives thereof, montan wax and derivatives thereof, microcrystalline wax and derivatives thereof, Fischer-Tropsch wax and derivatives thereof, polyolefin wax and derivatives thereof, and the like. Derivatives include oxides, polymers with vinyl monomers, and graft modified products. In addition, alcohols, fatty acids, plant waxes, animal waxes, mineral waxes, ester waxes, acid amides and the like are also used.

The wax used as a release agent is preferably melted at any temperature of 70 to 140 ° C. and exhibits a melt viscosity of 1 to 200 centipoise, more preferably 1 to 100 centipoise. When the melting temperature is 70 ° C. or higher, the change temperature of the wax is sufficiently high, and the blocking resistance and the developability are excellent when the temperature in the copying machine is increased. When the temperature is 140 ° C. or lower, the change temperature of the wax is sufficiently low, it is not necessary to perform fixing at a high temperature, and energy saving is excellent. Further, when the melt viscosity is 200 centipoises or less, the elution from the toner is appropriate and the fixing peelability is excellent.
In the toner of the present exemplary embodiment, the release agent is selected from the viewpoints of fixing properties, toner blocking properties, toner strength, and the like. The addition amount of the release agent is not particularly limited, but is preferably in the range of 2 to 20 parts by weight with respect to 100 parts by weight of the binder resin contained in the toner.

<External additive>
The toner of this embodiment is dried in the same manner as a normal toner for the purpose of imparting fluidity and improving cleaning properties, and then inorganic particles such as silica, alumina, titania and calcium carbonate, and resins such as vinyl resins, polyesters and silicones. The particles can be added to the toner particle surface while being sheared in a dry state and used as an external additive.
In addition, when adhering to the toner surface in an aqueous medium, examples of inorganic particles include silica, alumina, titania, calcium carbonate, magnesium carbonate, and tricalcium phosphate, all of which are usually used as external additives on the toner surface. Can be used by dispersing with an ionic surfactant, polymer acid, or polymer base.

It is preferable that the surface of the inorganic particles is previously hydrophobized. This hydrophobization treatment is more effective for improving the powder fluidity of the toner, as well as the environmental dependency of charging and the resistance to carrier contamination.
The hydrophobizing treatment may be performed by immersing the inorganic particles in a hydrophobizing agent. Although there is no restriction | limiting in particular as said hydrophobic treatment agent, For example, a silane coupling agent, a silicone oil, a titanate coupling agent, an aluminum coupling agent etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together. Among these, silane coupling agents are preferable.

As the silane coupling agent, for example, any of chlorosilane, alkoxysilane, silazane, and a special silylating agent can be used.
Specifically, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, phenyltrichlorosilane, diphenyldichlorosilane, tetramethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, tetraethoxysilane, Methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, diphenyldiethoxysilane, isobutyltriethoxysilane, decyltrimethoxysilane, hexamethyldisilazane, N, O- (bistrimethylsilyl) acetamide, N, N- ( Trimethylsilyl) urea, tert-butyldimethylchlorosilane, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane , Γ-methacryloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-mercapto Examples thereof include propyltrimethoxysilane and γ-chloropropyltrimethoxysilane.

The amount of the hydrophobizing agent varies depending on the type of the inorganic particles and cannot be defined unconditionally, but is preferably 1 to 50 parts by weight with respect to 100 parts by weight of the inorganic particles, and 5 to 20 More preferred are parts by weight. In the present embodiment, commercially available products are also preferably used as the hydrophobic silica particles.
The average particle size (average primary particle size) of the inorganic particles used as the external additive in the toner of the exemplary embodiment is preferably 1 to 500 nm, and more preferably 5 to 300 nm.
The ratio of the external additive mixed with the toner of the exemplary embodiment is not particularly limited, but is preferably 0.01 to 5% by weight, and 0.01 to 2.0% by weight based on the total weight of the toner. % Is more preferable.

<Other additives>
In addition to the components as described above, various components such as an internal additive and a charge control agent can be added to the toner of the exemplary embodiment as necessary.
Examples of the internal additive include metals such as ferrite, magnetite, reduced iron, cobalt, nickel, and manganese, alloys, or magnetic materials such as compounds containing these metals.
Examples of the charge control agent include quaternary ammonium salt compounds, nigrosine compounds, dyes composed of complexes of aluminum, iron, chromium, and triphenylmethane pigments.

The volume average particle size of the toner according to the exemplary embodiment is preferably 2 to 9 μm, and more preferably 3 to 7 μm. Within the above range, the chargeability, developability, and image resolution are excellent.
In addition, the toner of this embodiment preferably has a volume average particle size distribution index GSDv of 1.30 or less. When the volume distribution index GSDv is 1.30 or less, the image resolution is excellent.
In this embodiment, the toner particle size and the value of the volume average particle size distribution index GSDv are measured and calculated as follows. First, the toner particle size distribution measured using a measuring instrument such as Coulter Counter TAII (Beckman Coulter), Multisizer II (Beckman Coulter), etc. A cumulative distribution is drawn from the small diameter side with respect to the volume of the toner particles, and the particle diameter of 16% is defined as the volume average particle diameter D _16v, and the particle diameter of 50% is defined as the volume average particle diameter D _50v. To do. Similarly, the particle size at a cumulative 84% is defined as the volume average particle size D _84v . At this time, the volume average particle size distribution index (GSDv) is calculated using these relational expressions defined as D _84v / D _16v .

In the toner of this embodiment, the shape factor SF1 (= ((absolute maximum length of toner diameter) ² / toner projected area) × (π / 4) × 100) is preferably in the range of 110 to 160, and 125 The range of ~ 140 is more preferable.
Note that the value of the shape factor SF1 indicates the roundness of the toner, which is 100 in the case of a true sphere, and increases as the shape of the toner becomes indefinite. Further, the values required for calculation using the shape factor SF1, that is, the absolute maximum length of the toner diameter and the projected area of the toner are enlarged to 500 times magnification using an optical microscope (Nikon Corporation, Microphoto-FXA). The obtained toner particle image was photographed, and the obtained image information was obtained by introducing the image information into an image analyzer (Luzex III) manufactured by Nireco Co., Ltd. via an interface and performing image analysis. The average value of the shape factor SF1 was calculated based on data obtained by measuring 1,000 toner particles sampled randomly.
When the shape factor SF1 is 110 or more, the generation of residual toner in the transfer process during image formation is suppressed, and the cleaning property when cleaning with a blade or the like is excellent, and as a result image defects are suppressed. On the other hand, when the shape factor SF1 is 160 or less, when the toner is used as a developer, the toner is prevented from being destroyed by the collision with the carrier in the developing device, and as a result, the generation of fine powder is suppressed. As a result, the surface of the photoreceptor is prevented from being contaminated by the release agent component exposed on the toner surface, and not only the charging characteristics are excellent, but also the occurrence of fog caused by fine powder is suppressed.

(Method for producing electrostatic image developing toner)
In the toner manufacturing method of the present embodiment, it is particularly important that the average thickness of the shell layer is 50 nm or more and less than 100 nm.
The toner according to the exemplary embodiment is preferably manufactured by one of the following two methods.
First, in an aqueous medium, a crystalline polyester resin particle having a volume average particle diameter of 50 to 80 nm and an amorphous polyester resin particle having a volume average particle diameter of 50 to 80 nm are aggregated to obtain aggregated particles. An aggregation step, a fusion step in which the aggregated particles are heated and fused, and a shell adhesion step in which crystalline polyester resin particles having a volume average particle size of 50 to 80 nm are adhered to the surface of the fused aggregated particles are arranged in this order. And a method in which the difference in volume average particle size between the crystalline polyester resin particles and the non-crystalline polyester resin particles in the aggregation step is 5 nm or less (hereinafter also referred to as “Production Method A”) is preferable. In the production method A, since the difference between the core resin particles in the aggregation step and the shell resin particles in the shell adhesion step is small, the shell particles do not concentrate in the concave portions of the core aggregation particles, and the resin particle diameter is Since it is sufficiently small, the core agglomerated particles can be thinly covered with shell particles, and the toner of this embodiment is manufactured.
Secondly, an aggregation step of aggregating at least crystalline polyester resin particles and non-crystalline polyester resin particles in an aqueous medium to obtain aggregated particles, a fusion step of heating and aggregating the aggregated particles, A cooling step for cooling the agglomerated particles, a shell adhering step for adhering the crystalline polyester resin particles to the surface of the agglomerated particles, a drying step for drying the agglomerated particles adhering the crystalline polyester resin particles, and the drying A method (hereinafter also referred to as “manufacturing method B”) including a tanning step for tanning the surface of the aggregated particles in this order is preferable. In the production method B, once the core particles are fused and cooled, the surface of the core particles becomes smooth, and the core particles are thinned with the shell particles without concentrating the shell particles in the recesses of the core particles. The toner of this embodiment can be manufactured.
Among these, the production method A is particularly preferable as the production method of the toner of the present exemplary embodiment.
Hereinafter, production methods A and B will be described respectively.

<Production method A>
-Aggregation process-
In the toner production method of the present embodiment, at least a crystalline polyester resin particle having a volume average particle diameter of 50 to 80 nm and an amorphous polyester resin particle having a volume average particle diameter of 50 to 80 nm are aggregated in an aqueous medium. It is preferable that a step of obtaining agglomerated particles is included, and a difference in volume average particle size between the crystalline polyester resin particles and the amorphous polyester resin particles is 5 nm or less.
Moreover, in the aggregation step, core particles having a microphase separation structure of crystalline polyester resin particles and non-crystalline polyester resin particles are easily produced.

In the aggregation step, the crystalline polyester resin particle dispersion, the amorphous polyester resin particle dispersion mixed with each other, and, if necessary, other than the colorant dispersion, the release agent dispersion, and the polyester resin. The particles in the resin particle dispersion are aggregated to form aggregated particles having a desired volume average particle diameter in the core particles. The aggregated particles are formed by heteroaggregation or the like, and a surfactant or an aggregating agent may be added for the purpose of stabilizing the aggregated particles and controlling the particle size / particle size distribution. In addition, the formation of the agglomerated particles is preferably performed by adding an aggregating agent at 10 to 35 ° C. while stirring with a rotary shearing homogenizer.
In the present embodiment, depending on the purpose, at least one of the resin particle dispersion, the colorant dispersion, and the release agent dispersion includes an internal additive, a charge control agent, an inorganic particle, and an organic particle. In addition, other components (particles) such as a lubricant and an abrasive may be dispersed. In that case, other components (particles) may be dispersed in at least one of the binder resin dispersion, the colorant dispersion, and the release agent dispersion, or the resin particle dispersion and the colorant dispersion. You may mix the dispersion liquid which disperse | distributes another component (particle | grains) in the liquid mixture formed by mixing a liquid and a mold release agent dispersion liquid.

[Aqueous medium]
Examples of the dispersion medium in the dispersion such as the resin particle dispersion, the colorant dispersion, and the release agent dispersion include an aqueous medium.
Examples of the aqueous medium used in the present embodiment include water such as distilled water and ion exchange water, and alcohols such as ethanol and methanol. Among these, ethanol and water are preferable, and water such as distilled water and ion-exchanged water is particularly preferable. These may be used individually by 1 type and may use 2 or more types together.
The aqueous medium may contain a water-miscible organic solvent. Examples of the water-miscible organic solvent include acetone and acetic acid.

[Surfactant]
In the exemplary embodiment, a surfactant can be used for the purpose of stabilizing the dispersion of the resin particle dispersion, the colorant dispersion, the release agent dispersion, and the like in the aggregation process, for example, during the production of the toner.
Examples of the surfactant include anionic surfactants such as sulfate ester, sulfonate, phosphate ester, and soap; cationic surfactants such as amine salt type and quaternary ammonium salt type; polyethylene Nonionic surfactants such as glycols, alkylphenol ethylene oxide adducts, polyhydric alcohols and the like can be mentioned. Among these, an ionic surfactant is preferable, and an anionic surfactant and a cationic surfactant are more preferable.

In toners, anionic surfactants generally have a strong dispersing power and are excellent in dispersing resin particles and colorants. Moreover, it is advantageous to use an anionic surfactant as the surfactant for dispersing the release agent.
The nonionic surfactant is preferably used in combination with the anionic surfactant or the cationic surfactant. The said surfactant may be used individually by 1 type, and may be used in combination of 2 or more type.

  Specific examples of anionic surfactants include fatty acid soaps such as potassium laurate, sodium oleate, and castor oil sodium; sulfate esters such as octyl sulfate, lauryl sulfate, lauryl ether sulfate, and nonyl phenyl ether sulfate; lauryl sulfonate , Sodium alkylnaphthalene sulfonate such as dodecylbenzene sulfonate, triisopropyl naphthalene sulfonate, dibutyl naphthalene sulfonate; sulfones such as naphthalene sulfonate formalin condensate, monooctyl sulfosuccinate, dioctyl sulfosuccinate, lauric acid amide sulfonate, oleic acid amide sulfonate Acid salts; lauryl phosphate, isopropyl phosphate, nonylphenyl ether Phosphoric acid esters such as Sufeto; dialkyl sulfosuccinate salts such as sodium dioctyl sulfosuccinate; and sulfosuccinate salts such as lauryl disodium sulfosuccinate, and the like.

  Specific examples of the cationic surfactant include laurylamine hydrochloride, stearylamine hydrochloride, oleylamine acetate, stearylamine acetate, stearylaminopropylamine acetate, and other amine salts; lauryltrimethylammonium chloride, dilauryldimethylammonium Chloride, distearyldimethylammonium chloride, distearyldimethylammonium chloride, lauryldihydroxyethylmethylammonium chloride, oleylbispolyoxyethylenemethylammonium chloride, lauroylaminopropyldimethylethylammonium ethosulphate, lauroylaminopropyldimethylhydroxyethylammonium perchlorate, alkylbenzene Trimethylammonium chloride, Such as quaternary ammonium salts such as quilts trimethyl ammonium chloride.

  Specific examples of nonionic surfactants include alkyl ethers such as polyoxyethylene octyl ether, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether; polyoxyethylene octylphenyl ether, polyoxyethylene Alkyl phenyl ethers such as nonylphenyl ether; alkyl esters such as polyoxyethylene laurate, polyoxyethylene stearate, polyoxyethylene oleate; polyoxyethylene lauryl amino ether, polyoxyethylene stearyl amino ether, polyoxyethylene oleyl Alkylamines such as amino ether, polyoxyethylene soybean amino ether, polyoxyethylene beef tallow amino ether; polyoxy Alkyl amides such as ethylene lauric acid amide, polyoxyethylene stearic acid amide, polyoxyethylene oleic acid amide; vegetable oil ethers such as polyoxyethylene castor oil ether and polyoxyethylene rapeseed oil ether; lauric acid diethanolamide, stearic acid Alkanolamides such as diethanolamide and oleic acid diethanolamide; sorbitan ester ethers such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate Etc.

  The content of the surfactant in each dispersion may be a level that does not hinder the present embodiment, and is generally a small amount, specifically, 0.01 wt% or more and 3 wt% or less. The range is preferably 0.05% by weight or more and 2% by weight or less, more preferably 0.1% by weight or more and 1% by weight or less. Within the above range, each dispersion such as a resin particle dispersion, a colorant dispersion, and a release agent dispersion is stable, does not cause aggregation or release of specific particles, and affects the amount of copper compound added. The effect of the present embodiment can be sufficiently obtained. In general, a suspension-polymerized toner dispersion having a large particle size is stable even when a small amount of a surfactant is used.

[Flocculant]
In the aggregating step, agglomeration is caused by pH change or the like, and particles having a toner particle diameter containing a binder resin and a colorant can be prepared. At the same time, an aggregating agent may be added in order to stably and rapidly aggregate the particles or to obtain aggregated particles having a narrower particle size distribution.
As the flocculant, a compound having a monovalent or higher charge is preferable, and specific examples of the compound include water-soluble surfactants such as the above-mentioned ionic surfactants and nonionic surfactants, hydrochloric acid, sulfuric acid, Acids such as nitric acid, acetic acid, oxalic acid, magnesium chloride, sodium chloride, aluminum sulfate, calcium sulfate, aluminum nitrate, silver nitrate, copper sulfate, sodium carbonate and other inorganic acid metal salts, sodium acetate, potassium formate, sodium oxalate, Examples thereof include aliphatic acids such as sodium phthalate and potassium salicylate, metal salts of aromatic acids, and metal salts of phenols such as sodium phenolate.

In consideration of the stability of the aggregated particles, the stability of the coagulant with respect to heat and time, and the removal during washing, a metal salt of an inorganic acid is preferable as the coagulant in terms of performance and use. Specific examples include metal salts of inorganic acids such as magnesium chloride, sodium chloride, aluminum sulfate, calcium sulfate, aluminum nitrate, silver nitrate, copper sulfate, and sodium carbonate.
The amount of these flocculants to be added varies depending on the valence of the charge, but it is preferable that all of them are small, in the case of monovalent, 3% by weight or less, in the case of divalent, 1% by weight or less, in the case of trivalent Is preferably 0.5% by weight or less. Since the amount of the flocculant is preferably small, it is preferable to use a compound having a large valence.

[Method for producing polyester resin particle dispersion having a volume average particle size of 50 to 80 nm]
The method for producing a crystalline or non-crystalline polyester resin particle dispersion with a volume average particle size of 50 to 80 nm is not particularly limited, but is preferably produced by emulsion polymerization or emulsion. A known emulsion polymerization method and a known emulsification method are used, and examples thereof include a phase inversion emulsification method.
The method for producing a polyester resin particle dispersion by the phase inversion emulsification method comprises stirring and dissolving a polyester resin and a solvent at a temperature near the melting temperature of the crystalline polyester resin or the glass transition temperature of the amorphous polyester resin. A step of making an oil phase, a step of adding a small amount of a basic compound while stirring the oil phase, a step of preparing water by adding water little by little while stirring, and then cooling the emulsion to reduce pressure It is characterized by passing through a solvent step.

Hereinafter, an example is given and demonstrated about the manufacturing method of the polyester resin particle dispersion by the phase inversion emulsification method.
First, a polyester resin and an organic solvent are put into a reaction vessel equipped with a condenser, a stirrer, and a thermometer, and a temperature near the melting point (crystalline melting point) of the crystalline polyester resin or the glass transition temperature of the amorphous polyester resin. The resin is dissolved by heating and stirring. In the crystalline polyester resin, the heating temperature is preferably −15 ° C. to + 15 ° C., more preferably −10 ° C. to + 10 ° C. Further, in the non-crystalline polyester resin, the glass transition temperature is preferably −25 ° C. to + 5 ° C., more preferably −20 ° C. to 0 ° C. In the above embodiment, a resin particle dispersion having a volume average particle size of 50 to 80 nm is stably produced.

Examples of the organic solvent include ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-amyl alcohol, isoamyl alcohol, sec-amyl alcohol, tert-amyl alcohol, 1-ethyl. Alcohols such as -1-propanol, 2-methyl-1-butanol, n-hexanol and cyclohexanol, ketones such as methyl ethyl ketone, methyl isobutyl ketone, ethyl butyl ketone, cyclohexanone and isophorone, ethers such as tetrahydrofuran and dioxane, Ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, 3-methoxybutyl acetate, methyl propionate, propio Esters such as ethyl acid, diethyl carbonate, dimethyl carbonate, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol ethyl ether acetate, diethylene glycol, diethylene glycol monomethyl ether, Diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol ethyl ether acetate, propylene glycol, propylene glycol monomethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol Examples include glycol derivatives such as tilether acetate and dipropylene glycol monobutyl ether, and 3-methoxy-3-methylbutanol, 3-methoxybutanol, acetonitrile, dimethylformamide, dimethylacetamide, diacetone alcohol, ethyl acetoacetate and the like. The
These solvents may be used alone or in combination of two or more.
Further, the amount of these solvents used is preferably 200% by weight or more and 400% by weight or less with respect to the resin amount. In the above embodiment, a sufficient amount of solvent is used with respect to the resin to lower the viscosity during stirring, and a resin particle dispersion having a volume average particle size of 50 to 80 nm can be easily produced.

Next, a basic compound is added to the polyester resin solution to neutralize it. In the present embodiment, the neutralization reaction with the carboxyl group of the polyester resin is the starting force for making aqueous, and the aggregation between particles is prevented by the electric repulsive force between the generated carboxyl anions.
Examples of the basic compound include ammonia and organic amine compounds having a boiling point of 250 ° C. or lower.
Examples of preferred organic amine compounds include triethylamine, N, N-diethylethanolamine, N, N-dimethylethanolamine, aminoethanolamine, N-methyl-N, N-diethanolamine, isopropylamine, iminobispropylamine, ethylamine , Diethylamine, 3-ethoxypropylamine, 3-diethylaminopropylamine, sec-butylamine, propylamine, methylaminopropylamine, dimethylaminopropylamine, methyliminobispropylamine, 3-methoxypropylamine, monoethanolamine, diethanolamine, Examples include triethanolamine, morpholine, N-methylmorpholine, N-ethylmorpholine and the like.

The basic compound is preferably added in an amount that can be at least partially neutralized according to the carboxyl group contained in the polyester resin, that is, 0.2 to 9.0 times the molar equivalent of the carboxyl group. It is more preferable to add 6 to 2.0 times molar equivalent. When it is 0.2 times molar equivalent or more, the effect of adding a basic compound is sufficiently obtained, and when it is 9.0 times molar equivalent or less, the hydrophilicity of the oil phase is appropriate and the particle size distribution is narrow. A dispersion can be obtained.
Next, the phase is reversed by applying stirring shear while adding an aqueous medium to obtain an emulsion of the polyester resin, then the emulsion of the polyester resin is cooled, subjected to a heating operation again, and further subjected to a decompression operation as necessary. By applying and removing the solvent, a resin particle dispersion of the polyester resin can be obtained.

The volume average particle diameter of the resin particle dispersion thus obtained is preferably measured, for example, with a laser diffraction particle size distribution analyzer (LA-700, manufactured by Horiba, Ltd.).
Specific examples of the measuring method include the following methods.
The sample in the state of dispersion is adjusted so as to have a solid content of about 2 g, and ion exchange water is added thereto to make about 40 ml. This is put into the cell until an appropriate concentration is reached, waits for about 2 minutes, and is measured when the concentration in the cell becomes almost stable. The obtained volume average particle diameter for each channel is accumulated from the smaller volume average particle diameter, and the volume average particle diameter (D ₅₀ ) is defined as 50%.

[Production method of colorant dispersion]
The colorant dispersion is formed by dispersing at least a colorant.
The colorant is dispersed by a known method. For example, a rotary-type homogenizer, a ball-type mill, a sand mill, an attritor-type media type dispersing machine, a high-pressure counter-collision type dispersing machine, or the like is preferably used. The colorant may be an ionic surfactant having polarity and dispersed in an aqueous solvent using a homogenizer as described above to produce a colorant particle dispersion. A coloring agent may be used individually by 1 type, and may use 2 or more types together. The volume average particle size of the colorant (hereinafter sometimes simply referred to as an average particle size) is preferably 1 μm or less, more preferably 0.5 μm or less, and 0.01 to 0.5 μm. Is particularly preferred.
In addition, rosin, rosin derivatives, coupling agents, polymer dispersions are added as dispersants to further stabilize the dispersion stability of the colorant in the aqueous medium and lower the energy of the colorant in the toner. Agents and the like.

[Method for preparing release agent dispersion]
The release agent dispersion is formed by dispersing at least a release agent.
The release agent is dispersed by a known method, and for example, a rotary shearing type homogenizer, a media type dispersing machine such as a ball mill, a sand mill, or an attritor, a high pressure opposed collision type dispersing machine or the like is preferably used. The release agent may be a ionic surfactant having polarity and dispersed in an aqueous solvent using a homogenizer as described above to prepare a release agent particle dispersion. In this embodiment, a mold release agent may be used individually by 1 type, and may use 2 or more types together. The average particle size of the release agent particles is preferably 1 μm or less, and more preferably 0.01 to 1 μm.

-Fusion process-
The toner manufacturing method of the present embodiment preferably includes a fusing step of heating and fusing the aggregated particles.
In the fusion step, the fusion is preferably performed under a temperature condition equal to or higher than the glass transition temperature of the non-crystalline polyester resin particles in the aggregated particles. By heating the agglomerated particles, the agglomerated particles change from an irregular shape to a more spherical shape.
The heating temperature in the fusion step is preferably in the range of (glass transition temperature of non-crystalline polyester resin particles + 0-50) ° C., and (glass transition temperature of non-crystalline polyester resin particles + 10-40) ° C. A range is more preferable. Within the above range, a microphase separation structure of the crystalline polyester resin particles and the non-crystalline polyester resin particles can be easily formed.

-Shell adhesion process-
The toner manufacturing method of the present embodiment preferably includes a shell attaching step of attaching crystalline polyester resin particles having a volume average particle diameter of 50 to 80 nm to the surface of the fused aggregated particles.
The addition amount of the crystalline polyester resin particles having a volume average particle diameter of 50 to 80 nm may be adjusted so that the thickness of the shell layer is 50 nm or more and less than 100 nm, but the total weight of the core particles is 100 parts by weight. It is preferably 5 to 10 parts by weight, and more preferably 5 to 8 parts by weight.
In the shell adhesion step, a surfactant or an aggregating agent may be added for the purpose of stabilizing the aggregated particles and controlling the particle size / particle size distribution.

  The toner production method of the present embodiment preferably includes a step of heating the particles to which the crystalline polyester resin particles are adhered after the shell adhesion step. The heating temperature is preferably in the range of (crystalline melting point Tm + 0-20 of crystalline polyester resin particles) ° C. The heating time depends on the heating temperature and thus cannot be defined generally, but it is preferably 5 minutes to 1.5 hours.

-Other processes-
After completion of the shell attaching step, a desired toner may be obtained through an arbitrary washing step, solid-liquid separation step, drying step, external addition step, and the like.
In the washing step, it is preferable to sufficiently perform substitution washing with ion-exchanged water from the viewpoint of chargeability. The solid-liquid separation step is not particularly limited, but suction filtration, pressure filtration, and the like are preferably used from the viewpoint of productivity. Furthermore, the drying process is not particularly limited, but freeze drying, flash jet drying, fluidized drying, vibration fluidized drying, etc. are preferably used from the viewpoint of productivity. In the toner of the present exemplary embodiment, the moisture content after drying is preferably adjusted to 1.0% by weight or less, and more preferably adjusted to 0.5% by weight or less.
The method for externally adding inorganic particles such as silica and titania to the surface of the toner base particles in the external addition step is not particularly limited, and a known method is used, for example, adhesion by a mechanical method or a chemical method. The method of letting it be mentioned.

<Production method B>
-Aggregation process-
The toner production method of the present embodiment preferably includes an aggregating step of aggregating at least the crystalline polyester resin particles and the non-crystalline polyester resin particles in an aqueous medium to obtain aggregated particles.
The aggregation step in the production method B is the same as the aggregation step in the production method A except for the particle size of the resin particles, and the preferred embodiment is also the same.
The volume average particle diameters of the crystalline polyester resin particles and the non-crystalline polyester resin particles in the aggregation step of production method B are each preferably 50 to 400 nm, more preferably 50 to 200 nm, and more preferably 50 nm to less than 100 nm. It is particularly preferred that

-Fusion process-
The toner manufacturing method of the present embodiment preferably includes a fusing step of heating and fusing the aggregated particles.
The fusion step in the production method B is the same as the fusion step in the production method A except for the particle size of the resin particles in the aggregation step, and the preferred embodiment is also the same.

-Cooling process-
The toner manufacturing method of the present embodiment preferably includes a cooling step of cooling the fused aggregated particles.
The temperature in the cooling step may be a temperature lower than the temperature in the fusion step, but is preferably 30 ° C. or less, and more preferably 20 ° C. or less.
The cooling rate in the cooling step is preferably 10 ° C./min or more, more preferably 50 ° C./min or more, and further preferably 80 ° C./min or more.
Although there is no restriction | limiting in particular as the cooling method in the said cooling process, Specifically, the method of adding ice water in a system, ie, a dispersion liquid, is illustrated preferably.

-Shell adhesion process-
The toner manufacturing method of the present embodiment preferably includes a shell attaching step of attaching crystalline polyester resin particles to the surface of the aggregated particles after the cooling step.
In the shell adhesion step, the temperature of the dispersion is preferably −20 ° C. or more and −5 ° C. or less, more preferably −15 ° C. from the glass transition temperature of the amorphous polyester resin used for the core particles. The coagulant is preferably added in a state of −5 ° C. or lower, more preferably −10 ° C. or higher and −5 ° C. or lower from the glass transition temperature. Preferred examples of the flocculant include those described above. In addition to the flocculant, hydrochloric acid, nitric acid, and the like are added to adjust the pH to 3.0 to 5.0, which is preferable because adhesion of the shell can be promoted.
Moreover, in the said shell adhesion process, it is preferable to maintain the said temperature for 0.5 to 24 hours after adding a flocculant. In the above embodiment, the fused aggregated particles, that is, the core particles are impregnated with an aggregating agent, and the shell layer can be easily formed at a low temperature.
In the shell adhesion step, a surfactant may be added for the purpose of stabilizing the aggregated particles and controlling the particle size / particle size distribution.

  The toner production method of the present embodiment preferably includes a step of heating the particles to which the crystalline polyester resin particles are adhered after the shell adhesion step. The heating temperature is preferably −10 ° C. or higher and + 10 ° C. or lower from the glass transition temperature of the amorphous polyester resin used for the core particles, and is −5 ° C. or higher and + 5 ° C. or lower from the glass transition temperature. More preferred. The heating time is preferably 2 to 120 hours, preferably 4 to 60 hours, and more preferably 12 to 48 hours in order to form the shell layer at as low a temperature as possible.

-Drying process-
The toner production method of the present embodiment preferably includes a drying step of drying the aggregated particles to which the crystalline polyester resin particles are adhered.
The drying method in the drying step is not particularly limited, but from the viewpoint of productivity, freeze drying, flash jet drying, fluidized drying, vibration fluidized drying and the like are preferably used.
Further, the toner manufacturing method of the present embodiment includes a solid-liquid separation step of separating the aggregated particles having the crystalline polyester resin particles attached thereto from the dispersion before the drying step, and / or the crystalline polyester. A cleaning step of cleaning the aggregated particles to which the resin particles are attached may be included.
The washing step and the solid-liquid separation step in the production method B are the same as the washing step and the solid-liquid separation step in the production method A, and preferred embodiments are also the same.

-Tanning process-
It is preferable that the toner manufacturing method of the present embodiment includes a tanning step after the drying step for tanning the surface of the dried aggregated particles. By performing the tanning step, a toner having a uniform shell layer can be easily obtained.
As the tanning means in the tanning step, an impact pulverizer is preferably used, and a sample mill is more preferably used.
When using a sample mill, tanning is preferably performed at a rotational speed of 5,000 to 50,000 rpm, more preferably 10,000 to 20,000 rpm.
The tanning time in the tanning step is not particularly limited, but is preferably 5 minutes to 24 hours.

-Other processes-
After the tanning step, a desired toner may be obtained through an optional external addition step.
The external addition step in the production method B is the same as the external addition step in the production method A, and the preferred embodiment is also the same.

(Electrostatic image developer)
The electrostatic image developing toner of this embodiment is suitably used as an electrostatic image developer.
The electrostatic image developer of the exemplary embodiment is not particularly limited except that it contains the electrostatic image developing toner of the exemplary embodiment, and can take an appropriate component composition according to the purpose. When the electrostatic image developing toner of this embodiment is used alone, it is prepared as a one-component electrostatic image developer, and when used in combination with a carrier, it is prepared as a two-component electrostatic image developer.
As a one-component developer, a method in which a charged toner is formed by frictional charging with a developing sleeve or a charging member, and development is performed according to an electrostatic latent image is also applied.

  In the present embodiment, the development method is not particularly defined, but the two-component development method is preferable. In addition, the carrier is not particularly defined as long as the above conditions are satisfied, but examples of the carrier core material include magnetic metals such as iron, steel, nickel, and cobalt, alloys of these with manganese, chromium, rare earth, and the like, and Magnetic oxides such as ferrite and magnetite are mentioned, and from the viewpoint of core material surface properties and core material resistance, ferrite, particularly alloys with manganese, lithium, strontium, magnesium and the like are preferably mentioned.

The carrier used in this embodiment is preferably formed by coating the surface of the core material with a resin. There is no restriction | limiting in particular as said resin, According to the objective, it selects suitably. For example, polyolefin resins such as polyethylene and polypropylene; polyvinyl resins and polyvinylidene resins such as polystyrene, acrylic resins, polyacrylonitrile, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, polyvinyl chloride, polyvinyl carbazole, polyvinyl ether and polyvinyl ketone Vinyl chloride-vinyl acetate copolymer; styrene-acrylic acid copolymer; straight silicone resin composed of organosiloxane bond or modified product thereof; polytetrafluoroethylene, polyvinyl fluoride, polyvinylidene fluoride, polychlorotrifluoroethylene, etc. Fluorine resin; Silicone resin; Polyester; Polyurethane; Polycarbonate; Phenol resin; Urea-formaldehyde resin, Melamine tree , Benzoguanamine resins, urea resins, amino resins such as polyamide resins, epoxy resins, per se known resins and the like. These may be used individually by 1 type and may use 2 or more types together. In the present embodiment, among these resins, it is preferable to use at least a fluorine resin and / or a silicone resin. The use of at least a fluorine-based resin and / or a silicone resin as the resin is advantageous in that the effect of preventing carrier contamination (impaction) due to toner and external additives is high.
In the coating with the resin, it is preferable that resin particles and / or conductive particles are dispersed in the resin. Examples of the resin particles include thermoplastic resin particles and thermosetting resin particles. Among these, thermosetting resins are preferable from the viewpoint of relatively easily increasing the hardness, and resin particles made of nitrogen-containing resin containing N atoms are preferable from the viewpoint of imparting negative chargeability to the toner. In addition, these resin particles may be used individually by 1 type, and may use 2 or more types together. The average particle size of the resin particles is preferably 0.1 to 2 μm, and more preferably 0.2 to 1 μm. When the average particle size of the resin particles is 0.1 μm or more, the resin particles are excellent in dispersibility in the coating, whereas when the average particle size is 2 μm or less, the resin particles are not easily dropped from the coating.

  Examples of the conductive particles include metal particles such as gold, silver, and copper, carbon black particles, and surfaces of titanium oxide, zinc oxide, barium sulfate, aluminum borate, potassium titanate powder, tin oxide, carbon black, metal And particles covered with the like. These may be used individually by 1 type and may use 2 or more types together. Among these, carbon black particles are preferable from the viewpoints of production stability, cost, conductivity, and the like. The type of carbon black is not particularly limited, but carbon black having a dibutyl phthalate (DBP) oil absorption of 50 to 250 ml / 100 g is preferable because of excellent production stability. The coating amount of the resin, the resin particles, and the conductive particles on the surface of the core material is preferably 0.5 to 5.0% by weight, and preferably 0.7 to 3.0% by weight. More preferred.

The method for forming the coating is not particularly limited. For example, the resin particles such as crosslinkable resin particles and / or the conductive particles, and a styrene acrylic resin, a fluorine resin, a silicone resin as a matrix resin, etc. And a method of using a film-forming solution containing the above resin in a solvent.
Specifically, the carrier core material is immersed in the film forming liquid, a spray method in which the film forming liquid is sprayed on the surface of the carrier core material, and the carrier core material is floated by flowing air And kneader coater method in which the film forming solution is mixed and the solvent is removed. Among these, the kneader coater method is preferable in the present embodiment.

  The solvent used for the film forming liquid is not particularly limited as long as it can dissolve only the resin as a matrix resin, and is selected from known solvents such as toluene, Aromatic hydrocarbons such as xylene, ketones such as acetone and methyl ethyl ketone, ethers such as tetrahydrofuran and dioxane, and the like. When the resin particles are dispersed in the coating, since the resin particles and the particles as the matrix resin are uniformly dispersed in the thickness direction and the tangential direction of the carrier surface, the carrier is used for a long time. Even when the coating is worn, it is possible to always maintain the same surface formation as when it is not used, and to maintain a good charge imparting ability for the toner over a long period of time. In the case where the conductive particles are dispersed in the coating, the conductive particles and the resin as the matrix resin are uniformly dispersed in the thickness direction and the tangential direction of the carrier surface. Even if the coating is worn out over a long period of time, the same surface formation as when not in use can be maintained, and carrier deterioration is prevented for a long period of time. In addition, in the case where the resin particles and the conductive particles are dispersed in the coating, the above-described effects are exhibited at the same time.

The electric resistance of the magnetic carrier formed as described above in the state of a magnetic brush under an electric field of 10 ⁴ V / cm is preferably 10 ⁸ to 10 ¹³ Ωcm. When the electric resistance of the magnetic carrier is 10 ⁸ Ωcm or more, the adhesion of the carrier to the image portion on the image carrier is suppressed, and the brush mark is difficult to appear. On the other hand, when the electrical resistance of the magnetic carrier is 10 ¹³ Ωcm or less, the generation of the edge effect is suppressed and a good image quality is obtained.
The volume resistivity is measured as follows.
A measuring jig that is a pair of 20 cm ² circular electrode plates (made of steel) connected to an electrometer (made by KEITHLEY, trade name: KEITHLEY 610C) and a high-voltage power supply (made by FLUKE, trade name: FLUKE 415B). The sample is placed on the lower electrode plate so as to form a flat layer having a thickness of about 1 mm to 3 mm. Next, after the upper electrode plate is placed on the sample, a 4 kg weight is placed on the upper electrode plate in order to eliminate the gap between the samples. In this state, the thickness of the sample layer is measured. Next, the current value is measured by applying a voltage to the bipolar plate, and the volume resistivity is calculated based on the following equation.
Volume resistivity = applied voltage × 20 ÷ (current value−initial current value) ÷ sample thickness In the above formula, the initial current is the current value when the applied voltage is 0, and the current value indicates the measured current value.

  In the two-component electrostatic charge image developer, the mixing ratio of the toner and the carrier of this embodiment is preferably 2 to 10 parts by weight of the toner with respect to 100 parts by weight of the carrier. Moreover, the preparation method of a developing agent is not specifically limited, For example, the method of mixing with a V blender etc. is mentioned.

(Image forming method)
The electrostatic image developer (electrostatic image developing toner) is used in an image forming method of a normal electrostatic image developing system (electrophotographic system).
The image forming method of the present embodiment includes a charging step for charging an image carrier, a latent image forming step for forming an electrostatic latent image on the surface of the image carrier, and an electrostatic latent image formed on the surface of the image carrier. A development step of developing the image with an electrostatic charge image developing toner or an electrostatic charge image developer to form a toner image, a transfer step of transferring the toner image formed on the surface of the image carrier to the surface of the transfer target, And a fixing step of fixing the toner image. In addition, a cleaning process or the like may be included as necessary.
Each of the above steps is a general step per se, and is described in, for example, JP-A-56-40868 and JP-A-49-91231. Note that the image forming method of the present embodiment is carried out by using a known image forming apparatus such as a copying machine or a facsimile machine.

The latent image forming step is a step of forming an electrostatic latent image on the surface of the image carrier.
The developing step is a step of developing the electrostatic latent image with a developer layer on a developer holder to form a toner image. The developer layer is not particularly limited as long as it contains the electrostatic image developer of this embodiment containing the electrostatic image developer of the present embodiment.
The transfer step is a step of transferring the toner image onto a transfer target.
The fixing step is a step of forming a copy image by fixing the toner image transferred onto a recording medium such as recording paper by an optical fixing device or a thermal fixing device.
The cleaning step is a step of removing the electrostatic charge image developer remaining on the image carrier. In the image forming method of the present embodiment, an aspect that further includes a recycling step is preferable.
The recycling step is a step of transferring the electrostatic charge image developing toner collected in the cleaning step to a developer layer. The image forming method including the recycling process is performed using an image forming apparatus such as a toner recycling system type copying machine or facsimile machine. The present invention is also applicable to a recycling system in which the cleaning step is omitted and toner is collected simultaneously with development.
Through such a series of processing steps, a desired duplicate product (printed matter or the like) can be obtained.

(Image forming device)
The image forming apparatus according to the present embodiment includes an image carrier, a charging unit that charges the image carrier, and an exposure unit that exposes the charged image carrier to form an electrostatic latent image on the image carrier. Developing means for developing the electrostatic latent image with an electrostatic charge image developing toner or an electrostatic charge image developer to form a toner image; and transfer means for transferring the toner image from the image carrier to a transfer target; It is preferable to have. In the transfer unit, the transfer may be performed twice or more using an intermediate transfer member. Further, it may have a cleaning means for removing toner remaining on the image carrier.

The configuration described in each step of the image forming method is preferably used for the image carrier and each unit.
As each of the above-described means, a well-known means is used in the image forming apparatus. Further, the image forming apparatus used in the present embodiment may include means and devices other than the above-described configuration. Further, the image forming apparatus used in the present embodiment may simultaneously perform a plurality of the above-described means.

In the present embodiment, a known fixing device is used for fixing. For example, a fixing belt having a low surface energy material typified by a fluororesin component and a silicone-based resin on the surface and a belt shape, as well as the surface. And a fixing roll having a low surface energy material typified by a fluororesin component and a silicone-based resin and having a cylindrical roll shape.
For the purpose of preventing the toner from adhering to the surface of the fixing roll or the fixing belt, for example, the surface of the roll needs to be formed of a material having excellent releasability with respect to the toner, such as silicon rubber or fluorine resin. At this time, it is effective that the releasable liquid such as silicone oil applied to the fixing roll is infinitely small.
Since the toner configuration of the present embodiment exhibits a sufficient fixing latitude, a small amount of releasable liquid such as silicone oil applied to the fixing roll or fixing belt is sufficient. For example, it may be 1 μl or less per A4 sheet. If it is in the above range, transfer and stickiness are suppressed on the material to be fixed, and it is easy to affix tape or write characters with magic, and the fixing surface is smooth, Excellent OHP transparency.

(Toner cartridge and process cartridge)
The toner cartridge of the present embodiment is a toner cartridge that contains at least the electrostatic image developing toner of the present embodiment. The toner cartridge of this embodiment may contain the electrostatic image developing toner of this embodiment as an electrostatic image developer.
Further, the process cartridge according to the present embodiment includes a developing unit that develops an electrostatic latent image formed on the surface of the image carrier with the electrostatic charge image developing toner or the electrostatic charge image developer to form a toner image; And at least one selected from the group consisting of an image carrier, a charging unit for charging the surface of the image carrier, and a cleaning unit for removing toner remaining on the surface of the image carrier. 2 is a process cartridge containing at least the electrostatic image developing toner of the embodiment or the electrostatic image developer of the embodiment.

The toner cartridge of this embodiment is preferably detachable from the image forming apparatus. That is, in the image forming apparatus having a configuration in which the toner cartridge can be attached and detached, the toner cartridge of the present embodiment in which the toner of the present embodiment is stored is preferably used.
Further, the toner cartridge may be a cartridge that stores toner and a carrier, or a cartridge that stores toner alone and a cartridge that stores a carrier independently.

It is preferable that the process cartridge of the present embodiment is attached to and detached from the image forming apparatus.
In addition, the process cartridge according to the present embodiment may include other members such as a static elimination unit as necessary.
As the toner cartridge and the process cartridge, known configurations may be adopted. For example, Japanese Patent Application Laid-Open Nos. 2008-209489 and 2008-233736 are referred to.

  Hereinafter, the present embodiment will be described in detail with reference to examples. However, the present embodiment is not limited only to the following examples.

<Manufacture of resin>
(Measurement of molecular weight distribution)
The molecular weight distribution was performed under the following conditions.
Tosoh Corporation HLC 8120GPC, SC8020 apparatus was used, TSK gei, SuperHMH (6.0 mmID × 15 cm × 2) was used as a column, and THF (tetrahydrofuran) was used as an eluent. As experimental conditions, the sample concentration was 0.5%, and the flow rate was 0.6 ml / min. Sample injection volume 10 μl, measurement temperature 40 ° C., calibration curve was prepared from 10 samples of A500, F1, F10, F80, F380, A2500, F4, F40, F128, F700. The data collection interval in sample analysis was 300 ms.

(Measurement of Tg (glass transition temperature))
Using a differential scanning calorimeter (manufactured by Mac Science: DSC3110, thermal analysis system 001) (hereinafter abbreviated as “DSC”), the temperature was raised from 0 ° C. to 150 ° C. at a rate of 10 ° C./min. Held for 10 minutes, cooled to 150 ° C. to 0 ° C. with liquid nitrogen at 10 ° C./min, held at 0 ° C. for 5 minutes, and again raised from 0 ° C. to 150 at 10 ° C./min. The onset temperature analyzed from the endothermic curve during the second temperature increase was defined as Tg.

(Measurement of acid value)
About 1 g of resin is precisely weighed and dissolved in 80 ml of tetrahydrofuran. Phenolphthalein indicator is added as an indicator, titrated with a 0.1NKOH ethanol solution, and the end point is the color lasting for 30 seconds. From the amount of 0.1NKOH ethanol solution used, the acid value (free contained in 1 g of resin) It is the number of KOH mg necessary to neutralize fatty acids, and was calculated according to JIS K0070; 92.).

(Preparation of crystalline polyester resin (C1))
・ 1,10-dodecanedicarboxylic acid 100 mol%
・ 1,9-nonanediol 100mol%
After putting the above monomer and 0.3% dibutyltin oxide as a catalyst into a heat-dried three-necked flask, the air in the container is brought into an inert atmosphere with nitrogen gas by a depressurization operation, and at 170 ° C. by mechanical stirring. The mixture was stirred and refluxed for 5 hours.
Then, it heated up gradually to 230 degreeC under pressure reduction, stirred for 2 hours, and air-cooled when it became a viscous state, the reaction was stopped, and the crystalline polyester resin (C1) was synthesize | combined.
The acid value was 11.2 mgKOH / g, and the weight average molecular weight (Mw) of the obtained crystalline polyester resin (C1) was 23,000 according to molecular weight measurement by GPC (polystyrene conversion).
Further, when the melting temperature (Tm) of the crystalline polyester resin (C1) was measured by the above-described measurement method using a differential scanning calorimeter (DSC), it showed a clear endothermic peak, and the endothermic peak temperature was 73. It was 2 ° C.

(Preparation of amorphous polyester resin (A1))
・ Bisphenol A ethylene oxide 2mol adduct 10mol%
-Bisphenol A propylene oxide 2 mol adduct 40 mol%
・ Terephthalic acid 25mol%
・ Fumaric acid 15mol%
・ Dodecenyl succinic anhydride 10mol%
・ Trimellitic anhydride 2mol%
In a reaction vessel equipped with a stirrer, a thermometer, a condenser, and a nitrogen gas introduction pipe, a monomer component other than fumaric acid and trimellitic anhydride among the monomer components, and dioctanoic acid tin in a total of 100 parts by weight of the monomer components 0.24 part by weight was added. After reacting at 230 ° C. for 6 hours under a nitrogen gas stream, the temperature was lowered to 200 ° C., and the fumaric acid and trimellitic anhydride were added and reacted for 1 hour. Furthermore, it heated up to 220 degreeC in 4 hours, and superposed | polymerized until it became a desired molecular weight under the pressure of 10 kPa, and the pale yellow transparent amorphous polyester resin (A1) was obtained.
The acid value of this non-crystalline polyester resin (A1) is 11.5 mgKOH / g, the glass transition temperature (Tg) by differential scanning calorimeter (DSC) is 58 ° C., and the weight average molecular weight (Mw) by GPC is 24,000. there were.

<Production of resin particle dispersion>
(Measurement of volume average particle diameter of resin particle dispersion)
It measured using the laser diffraction type particle size distribution measuring apparatus (LA-700, the Horiba Ltd. make). Specifically, the sample in the state of dispersion is adjusted to have a solid content of about 2 g, and ion-exchanged water is added thereto to make about 40 ml. This is put into the cell until an appropriate concentration is reached, waits for about 2 minutes, and is measured when the concentration in the cell becomes almost stable. The volume average particle diameter of each obtained channel was accumulated from the smaller volume average particle diameter, and the volume average particle diameter (D _50v ) was determined when the accumulation reached 50%.

(Preparation of crystalline polyester resin particle dispersion (C1))
In a separable flask equipped with a stirring blade, a condenser, a thermometer, and a water dropping device, 100 parts by weight of the crystalline polyester resin (C1), 330 parts by weight of methyl ethyl ketone (solvent), and 30 parts by weight of isopropyl alcohol (solvent). The mixture was heated to 70 ° C. in a hot water bath, maintained at 70 ° C., and the resin was dissolved while stirring and mixing at 150 rpm.
Thereafter, the stirring rotation speed was set at 190 rpm, the hot water bath was set at 66 ° C., and the mixture was left for 30 minutes to stabilize the temperature.
Next, 200 parts by weight of 10% by weight aqueous ammonia (reagent) was added in 1 minute, mixed for 10 minutes, and then ion-exchanged water (aqueous medium) kept at 66 ° C. was added at a rate of 7 parts by weight / min. A total of 900 parts by weight was dropped and phase-inverted to obtain an emulsion.
After completion of the water dripping, while discharging hot water in the hot water bath, 10 ° C. cold water having the same amount as the discharged hot water was added to the hot water bath, and the flask was cooled to 20 ° C. The cooling rate to 20 ° C. was 1 ° C./min.
800 parts by weight of the cooled emulsion and 500 parts by weight of ion-exchanged water were placed in an eggplant flask, and set in an evaporator (manufactured by Tokyo Rika Kikai Co., Ltd.) equipped with a vacuum control unit via a trap ball.
While rotating the eggplant flask, the mixture was heated at 60 ° C. for 30 minutes in a hot water bath to stabilize the liquid temperature, and then pressure reduction was started. Depressurization condition is the capacity limit speed of the pump from 101 kPa to 50 kPa, depressurize from 50 kPa to 7 kPa in 172 minutes, maintain 7 kPa after reaching 7 kPa, while adjusting the degree of vacuum so that the contents do not bump during the process The solvent was recovered.
When the solvent recovery amount reached 850 parts by weight, the pressure was returned to normal pressure, and the eggplant flask was cooled with water to obtain a crystalline polyester resin particle dispersion (C1).
The volume average particle diameter D _50v of the resin particles in this dispersion was 62 nm. Ion exchange water was added to the obtained dispersion to adjust the solid content concentration to 30% by weight.

(Preparation of crystalline polyester resin particle dispersion (C2))
In a separable flask equipped with a stirring blade, a condenser, a thermometer, and a water dropping device, 100 parts by weight of the crystalline polyester resin (C1), 200 parts by weight of methyl ethyl ketone (solvent), and 25 parts by weight of isopropyl alcohol (solvent). The mixture was heated to 70 ° C. with a hot water bath, maintained at 70 ° C., and the resin was dissolved while stirring and mixing at 140 rpm.
Thereafter, the stirring rotation speed was set to 180 rpm, the hot water bath was set at 66 ° C., and the mixture was left for 30 minutes to stabilize the temperature.
Next, 200 parts by weight of 10% by weight aqueous ammonia (reagent) was added in 1 minute, mixed for 10 minutes, and then ion-exchanged water (aqueous medium) kept at 66 ° C. was added at a rate of 7 parts by weight / min. A total of 900 parts by weight was dropped and phase-inverted to obtain an emulsion.
After completion of the water dripping, while discharging hot water in the hot water bath, 10 ° C. cold water having the same amount as the discharged hot water was added to the hot water bath, and the flask was cooled to 20 ° C. The cooling rate to 20 ° C. was 1 ° C./min.
800 parts by weight of the cooled emulsion and 500 parts by weight of ion-exchanged water were placed in an eggplant flask, and set in an evaporator (manufactured by Tokyo Rika Kikai Co., Ltd.) equipped with a vacuum control unit via a trap ball.
While rotating the eggplant flask, the mixture was heated at 60 ° C. for 30 minutes in a hot water bath to stabilize the liquid temperature, and then pressure reduction was started. Depressurization condition is the capacity limit speed of the pump from 101 kPa to 50 kPa, depressurize from 50 kPa to 7 kPa in 172 minutes, maintain 7 kPa after reaching 7 kPa, while adjusting the degree of vacuum so that the contents do not bump during the process The solvent was recovered.
When the solvent recovery amount reached 850 parts by weight, the pressure was returned to normal pressure, and the eggplant flask was cooled with water to obtain a crystalline polyester resin particle dispersion (C2).
The volume average particle diameter D _50v of the resin particles in this dispersion was ₇₈ nm. Ion exchange water was added to the obtained dispersion to adjust the solid content concentration to 30% by weight.

(Preparation of crystalline polyester resin particle dispersion (C3))
In a separable flask equipped with a stirring blade, a condenser, a thermometer, and a water dropping device, 300 parts by weight of the crystalline polyester resin (C1), 170 parts by weight of methyl ethyl ketone (solvent), and 50 parts by weight of isopropyl alcohol (solvent). The mixture was heated to 70 ° C. with a hot water bath, maintained at 70 ° C., and the resin was dissolved while stirring and mixing at 120 rpm.
Thereafter, the stirring rotation speed was set at 170 rpm, the hot water bath was set at 66 ° C., and the mixture was left for 30 minutes to stabilize the temperature.
Next, 50 parts by weight of 10% by weight aqueous ammonia (reagent) was added in 1 minute, mixed for 10 minutes, and then ion-exchanged water (aqueous medium) kept at 66 ° C. was added at a rate of 7 parts by weight / min. A total of 900 parts by weight was dropped and phase-inverted to obtain an emulsion.
After completion of the water dripping, while discharging hot water in the hot water bath, 10 ° C. cold water having the same amount as the discharged hot water was added to the hot water bath, and the flask was cooled to 20 ° C. The cooling rate to 20 ° C. was 1 ° C./min.
800 parts by weight of the cooled emulsion and 500 parts by weight of ion-exchanged water were placed in an eggplant flask, and set in an evaporator (manufactured by Tokyo Rika Kikai Co., Ltd.) equipped with a vacuum control unit via a trap ball.
While rotating the eggplant flask, the mixture was heated at 60 ° C. for 30 minutes in a hot water bath to stabilize the liquid temperature, and then pressure reduction was started. Depressurization condition is the capacity limit speed of the pump from 101 kPa to 50 kPa, depressurize from 50 kPa to 7 kPa in 172 minutes, maintain 7 kPa after reaching 7 kPa, while adjusting the degree of vacuum so that the contents do not bump during the process The solvent was recovered.
When the solvent recovery amount reached 850 parts by weight, the pressure was returned to normal pressure, and the eggplant flask was cooled with water to obtain a crystalline polyester resin particle dispersion (C3).
The volume average particle diameter D _50v of the resin particles in this dispersion was 101 nm. Ion exchange water was added to the obtained dispersion to adjust the solid content concentration to 30% by weight.

(Preparation of non-crystalline polyester resin particle dispersion (A1))
While maintaining a jacketed reactor equipped with a condenser, a thermometer, a water dropping device, and an anchor blade (manufactured by Tokyo Rika Kikai Co., Ltd .: BJ 30N) at 40 ° C. in a water circulating thermostat, 430 parts by weight of methyl ethyl ketone A mixed solvent with 50 parts by weight of isopropyl alcohol was added, 200 parts by weight of the amorphous polyester resin was added thereto, and the mixture was stirred at 190 rpm with a three-one motor and dissolved to obtain an oil phase.
To this stirred oil phase, 115 parts by weight of a 10% by weight aqueous ammonia solution was dropped for 1 minute, mixed for 10 minutes, and then 900 parts by weight of ion-exchanged water was added dropwise at a rate of 7 parts by weight per minute. Phase inversion emulsification was performed.
800 parts by weight of the obtained emulsified liquid and 500 parts by weight of ion-exchanged water were placed in an eggplant flask and set in an evaporator (manufactured by Tokyo Rika Kikai Co., Ltd.) equipped with a vacuum control unit via a trap ball.
While rotating the eggplant flask, the mixture was heated at 60 ° C. for 30 minutes in a hot water bath to stabilize the liquid temperature, and then pressure reduction was started. The depressurization condition is the capacity limit speed of the pump from 101 kPa to 60 kPa, and the pressure is reduced from 50 kPa to 7 kPa in 250 minutes. After reaching 7 kPa, 7 kPa is maintained and the degree of vacuum is adjusted so that the contents do not bump during the process. The solvent was recovered.
When the solvent recovery amount reached 850 parts by weight, the pressure was returned to normal pressure, and the eggplant flask was cooled with water to obtain an amorphous polyester resin particle dispersion (A1).
The volume average particle diameter D _50v of the resin particles in this dispersion was 61 nm. Then, it adjusted with ion-exchange water and made solid content concentration 20weight%.

(Preparation of non-crystalline polyester resin particle dispersion (A2))
While maintaining a jacketed reaction tank (Tokyo Rika Kikai Co., Ltd .: BJ 30N) equipped with a condenser, a thermometer, a water dropping device, and an anchor blade at 40 ° C. in a water circulation thermostat, 350 parts by weight of methyl ethyl ketone A mixed solvent with 50 parts by weight of isopropyl alcohol was added, 200 parts by weight of the amorphous polyester resin was added thereto, and the mixture was stirred at 160 rpm with a three-one motor and dissolved to obtain an oil phase.
To this stirred oil phase, 60 parts by weight of a 10% by weight aqueous ammonia solution was added dropwise for 1 minute, mixed for 10 minutes, and then 900 parts by weight of ion-exchanged water was added dropwise at a rate of 7 parts by weight per minute. Phase inversion emulsification was performed.
800 parts by weight of the obtained emulsified liquid and 500 parts by weight of ion-exchanged water were placed in an eggplant flask and set in an evaporator (manufactured by Tokyo Rika Kikai Co., Ltd.) equipped with a vacuum control unit via a trap ball.
While rotating the eggplant flask, the mixture was heated at 60 ° C. for 30 minutes in a hot water bath to stabilize the liquid temperature, and then pressure reduction was started. The depressurization condition is the capacity limit speed of the pump from 101 kPa to 60 kPa, and the pressure is reduced from 50 kPa to 7 kPa in 250 minutes. After reaching 7 kPa, 7 kPa is maintained and the degree of vacuum is adjusted so that the contents do not bump during the process. The solvent was recovered.
When the solvent recovery amount reached 850 parts by weight, the pressure was returned to normal pressure, and the eggplant flask was cooled with water to obtain an amorphous polyester resin particle dispersion (A2).
The volume average particle diameter D _50v of the resin particles in this dispersion was 80 nm. Then, it adjusted with ion-exchange water and made solid content concentration 20weight%.

(Preparation of non-crystalline polyester resin particle dispersion (A3))
While maintaining a jacketed reaction tank (Tokyo Rika Kikai Co., Ltd .: BJ 30N) equipped with a condenser, a thermometer, a water dropping device, and an anchor blade at 40 ° C. in a water circulation thermostat, 350 parts by weight of methyl ethyl ketone A mixed solvent with 50 parts by weight of isopropyl alcohol was added, 250 parts by weight of the amorphous polyester resin was added thereto, and the mixture was stirred and dissolved at 130 rpm with a three-one motor to obtain an oil phase.
To this stirred oil phase, 50 parts by weight of a 10 wt% aqueous ammonia solution was added dropwise for 1 minute, mixed for 10 minutes, and then 900 parts by weight of ion-exchanged water was added dropwise at a rate of 7 parts by weight per minute. Phase inversion emulsification was performed.
800 parts by weight of the obtained emulsified liquid and 500 parts by weight of ion-exchanged water were placed in an eggplant flask and set in an evaporator (manufactured by Tokyo Rika Kikai Co., Ltd.) equipped with a vacuum control unit via a trap ball.
While rotating the eggplant flask, the mixture was heated at 60 ° C. for 30 minutes in a hot water bath to stabilize the liquid temperature, and then pressure reduction was started. The depressurization condition is the capacity limit speed of the pump from 101 kPa to 60 kPa, and the pressure is reduced from 50 kPa to 7 kPa in 250 minutes. After reaching 7 kPa, 7 kPa is maintained and the degree of vacuum is adjusted so that the contents do not bump during the process. The solvent was recovered.
When the solvent recovery amount reached 850 parts by weight, the pressure was returned to normal pressure, and the eggplant flask was cooled with water to obtain an amorphous polyester resin particle dispersion (A3).
The volume average particle diameter D _50v of the resin particles in this dispersion was 105 nm. Then, it adjusted with ion-exchange water and made solid content concentration 20weight%.

<Manufacture of toner>
(Measurement of toner particle size distribution)
The volume average particle diameter D _50v and the volume average particle size distribution index GSDv of the toner were measured and calculated as follows. First, with respect to the particle size range (channel) obtained by dividing the toner particle size distribution measured using Multisizer II (manufactured by Beckman Coulter, Inc.), a cumulative distribution is drawn from the smaller diameter side for each toner particle volume. The particle size at 16% was defined as the volume average particle size D _16v, and the particle size at 50% cumulative was defined as the volume average particle size D _50v . Similarly, the particle size at which the accumulation was 84% was defined as the volume average particle size D _84v . At this time, the volume average particle size distribution index (GSDv) was calculated using these relational expressions defined as D _84v / D _16v .

(Measurement of toner shape factor)
The toner shape factor SF1 was measured as follows. The absolute maximum length of the toner diameter and the projected area of the toner were taken using an optical microscope (Nikon Corporation, Microphoto-FXA), and a toner particle image magnified at a magnification of 500 times was taken. And introduced into an image analysis apparatus (Luzex III) manufactured by Nireco Co., Ltd. to perform image analysis. The average value of the shape factor SF1 was calculated based on data obtained by measuring 1,000 toner particles sampled randomly.

(Measurement of crystalline polyester resin coverage on toner surface)
The ratio of the toner surface covered with the crystalline polyester resin in the shell layer was observed by dyeing with ruthenium tetroxide. Specifically, it measured by the following method.
The toner is dyed by bringing it into contact with a 0.5 wt% ruthenium tetroxide aqueous solution, and the dyed toner is imaged as a still image by using a field emission scanning electron microscope S-4800 manufactured by Hitachi High-Technologies Corporation. The captured toner image was subjected to two-dimensional image processing, and the ratio of the surface covered with the crystalline polyester resin in the shell layer was calculated as an average value of 100 toners. In the dyed toner, the crystalline polyester resin was not dyed and was observed in black in the image, whereas the non-crystalline polyester resin was dyed and observed in white in the image as compared to the crystalline polyester resin.

(Measurement of average thickness of shell layer in toner cross section)
The average thickness of the shell layer in the cross section of the toner was measured by dyeing the cross section of the toner with ruthenium tetroxide. Specifically, it measured by the following method.
The toner was embedded in an epoxy resin and sectioned to a thickness of 100 nm by a microtome. The toner may have an external additive, or may not have or be removed. The cross section of the toner is dyed with a 0.5% by weight aqueous solution of ruthenium tetroxide and observed with a scanning electron microscope (TEM). In the cross section of the toner, the thickness of the shell layer was measured from the color contrast.
In this embodiment, the measurement position of the thickness of the shell layer was measured at four positions of the shell layer intersecting with two straight lines perpendicular to the approximate center of the toner. The average value of the shell layer thickness was calculated by averaging the values of the thickness of the shell layer measured at four points for each of 100 toners.

(Preparation of release agent dispersion)
-Mold release agent (Nippon Seiki Co., Ltd., trade name: HNP9, melting point Tw 76.8 ° C): 270 parts by weight-Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd., Neogen RK, active ingredient amount) : 60% by weight): 13.5 parts by weight (as an active ingredient, 3.0% by weight with respect to the release agent)
-Ion-exchanged water: 722 parts by weight The above components were mixed, and the release agent was dissolved at an internal liquid temperature of 120 ° C with a pressure discharge type homogenizer (Gorin homogenizer manufactured by Gorin Co., Ltd.), and then at a dispersion pressure of 5 MPa for 110 minutes. Subsequently, a dispersion treatment was performed at 40 MPa for 350 minutes, followed by cooling to obtain a release agent dispersion.
The volume average particle diameter D _50v of the particles in this dispersion was 220 nm. Thereafter, ion exchange water was added to adjust the solid content concentration to 20.0% by weight to obtain a release agent dispersion.

(Preparation of colorant dispersion)
Cyan pigment (Daiichi Seika Kogyo Co., Ltd .: ECB 301): 200 parts by weight Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd., Neogen SC): 33 parts by weight (active ingredient 60% by weight) 10% by weight based on colorant)
-Ion-exchanged water: 750 parts by weight 270 parts by weight of ion-exchanged water and anionic system in a stainless steel container whose liquid level is about 1/3 of the height of the container when all of the above components are added After adding 20 parts by weight of a surfactant and sufficiently dissolving the surfactant, all the cyan pigment is added, and the mixture is stirred using a stirrer until there is no wet pigment, and sufficiently defoamed. It was. After the defoaming, the remaining ion-exchanged water was added, and the mixture was dispersed for 10 minutes at 5,000 rpm using a homogenizer (manufactured by IKA, Ultra Tarrax T50).
After defoaming, the mixture was dispersed again at 6,000 rpm for 10 minutes using a homogenizer, and then defoamed by stirring for one day with a stirrer. Subsequently, the dispersion was dispersed at a pressure of 240 MPa using a high-pressure impact disperser Ultimateizer (manufactured by Sugino Machine, HJP30006). The dispersion was equivalent to 25 passes in terms of the total charge and the processing capacity of the apparatus. The obtained dispersion was allowed to stand for 72 hours to remove precipitates, and ion exchange water was added to adjust the solid content concentration to 15% by weight.
The volume average particle diameter D _50v of the particles in this colorant dispersion is 119 nm. As the volume average particle diameter D _50v , the average value of three measurement values excluding the maximum value and the minimum value out of the five times measured by Microtrack was used.

(Preparation of aqueous aluminum sulfate solution)
Aluminum sulfate powder (Asada Chemical Co., Ltd .: 17% by weight aluminum sulfate): 35 parts by weight and ion-exchanged water: 1,965 parts by weight are put into a container, and the precipitate disappears at 30 ° C. The mixture was stirred and mixed to prepare an aqueous aluminum sulfate solution.

[Example 1]
(Manufacture of toner (1))
Crystalline polyester resin particle dispersion (C1) 270 parts by weight Amorphous polyester resin particle dispersion (A1) 500 parts by weight Colorant dispersion 70 parts by weight Release agent dispersion 60 parts by weight Ion exchange water 200 parts by weight-anionic surfactant (Dowfax2A1 manufactured by Dow Chemical Co.) 7.0 parts by weight The above components are put in a reaction vessel equipped with a thermometer, pH meter, and stirrer, and homogenizer at a temperature of 25 ° C 125 parts by weight of the prepared aqueous aluminum sulfate solution was added and dispersed for 6 minutes while dispersing at 5,000 rpm with (IKA Japan Co., Ltd .: Ultra Turrax T50). Then, a stirrer and a mantle heater were installed in the reaction vessel, and the temperature of the stirrer was adjusted to 0.2 ° C / min up to 40 ° C, exceeding 40 ° C while adjusting the rotation speed of the stirrer so that the slurry was sufficiently stirred. The temperature was increased at 0.05 ° C./min, and the particle size was measured with Multisizer II (aperture diameter: 50 μm, manufactured by Beckman Coulter, Inc.) every 10 minutes, resulting in a volume average particle size of 5.6 μm. By the way, in order to maintain the temperature and further form a shell layer, 63 parts by weight of the crystalline polyester resin particle dispersion (C1) was added over 5 minutes. After holding for 30 minutes, the pH was adjusted to 9.0 using a 4 wt% aqueous sodium hydroxide solution. Thereafter, while adjusting the pH to 9.0 every 5 ° C., the temperature was raised to 90 ° C. at a temperature rising rate of 1 ° C./min and held at 90 ° C. When the particle shape and surface property were observed with an optical microscope and a scanning electron microscope (FE-SEM) every 15 minutes, the coalescence of the particles was confirmed at 1.5 hours. Cooled to 5 ° C. in 5 minutes.

The cooled slurry was passed through a nylon mesh having an opening of 15 μm to remove coarse powder, and the toner slurry that passed through the mesh was filtered under reduced pressure with an aspirator. The toner remaining on the filter paper is crushed as finely as possible by hand, poured into ion-exchanged water of 10 times the amount of toner at a temperature of 30 ° C., stirred and mixed for 30 minutes, and then filtered under reduced pressure with an aspirator again. Was measured. This operation was repeated until the filtrate had a conductivity of 10 μS / cm or less, and the toner was washed. The washed toner was finely pulverized by a wet dry granulator (Comil) and then vacuum dried in an oven at 35 ° C. for 36 hours to obtain toner particles.
To 100 parts by weight of the obtained toner particles, 1.2 parts by weight of hydrophobic silica (manufactured by Nippon Aerosil Co., Ltd., RX50) and 0.9 parts by weight of hydrophobic titanium oxide (manufactured by Nippon Aerosil Co., Ltd., T805) Were mixed and blended at 13,000 rpm for 30 seconds using a sample mill. Thereafter, the toner (1) was obtained by sieving with a vibration sieve having an opening of 45 μm.
The obtained toner (1) had a volume average particle diameter D _50v of 5.7 μm, a GSDv of 1.22, and a shape factor SF1 of 128. Further, the coverage of the crystalline polyester resin on the toner surface was 98%, and the average thickness of the shell layer in the cross section of the toner was 71 nm.

[Example 2]
(Manufacture of toner (2))
In the production of the toner (1), 63 parts by weight of the crystalline polyester resin particle dispersion (C1) for forming the shell layer, 38.25 parts by weight of the crystalline polyester resin particle dispersion (C1) and the non-crystalline polyester resin particles A toner (2) was produced in the same manner as the toner (1) except that the dispersion (A1) was changed to 6.75 parts by weight.
Toner (2) obtained had a volume average particle diameter D _50v of 5.8 μm, a GSDv of 1.23 and a shape factor SF1 of 127. Further, the coverage of the crystalline polyester resin on the toner surface was 81%, and the average thickness of the shell layer in the cross section of the toner was 72 nm.

Example 3
(Manufacture of toner (3))
In the production of the toner (1), 63 parts by weight of the crystalline polyester resin particle dispersion (C1) for forming the shell layer, 35.1 parts by weight of the crystalline polyester resin particle dispersion (C1) and the non-crystalline polyester resin particles A toner (3) was produced in the same manner as the toner (1) except that the dispersion (A1) was changed to 9.9 parts by weight.
Toner (3) obtained had a volume average particle diameter D _50v of 5.7 μm, a GSDv of 1.23 and a shape factor SF1 of 128. Further, the coverage of the crystalline polyester resin on the toner surface was 75%, and the average thickness of the shell layer in the cross section of the toner was 70 nm.

Example 4
(Manufacture of toner (4))
In the production of the toner (1), 63 parts by weight of the crystalline polyester resin particle dispersion (C1) for forming the shell layer, 32.85 parts by weight of the crystalline polyester resin particle dispersion (C1) and the non-crystalline polyester resin particles A toner (4) was produced in the same manner as the toner (1) except that the dispersion (A1) was changed to 12.15 parts by weight.
Toner (4) obtained had a volume average particle diameter D _50v of 5.6 μm, a GSDv of 1.24 and a shape factor SF1 of 126. Further, the coverage of the crystalline polyester resin on the toner surface was 70%, and the average thickness of the shell layer in the cross section of the toner was 72 nm.

Example 5
(Manufacture of toner (5))
In the production of the toner (1), except that 63 parts by weight of the crystalline polyester resin particle dispersion (C1) for forming the shell layer was changed to 54 parts by weight of the crystalline polyester resin particle dispersion (C1), the toner (1 The toner (5) was produced in the same manner.
Toner (5) obtained had a volume average particle diameter D _50v of 5.6 μm, a GSDv of 1.23 and a shape factor SF1 of 127. Further, the coverage of the crystalline polyester resin on the toner surface was 98%, and the average thickness of the shell layer in the cross section of the toner was 60 nm.

Example 6
(Manufacture of toner (6))
In the production of the toner (1), except that 63 parts by weight of the crystalline polyester resin particle dispersion (C1) for forming the shell layer was changed to 67.5 parts by weight of the crystalline polyester resin particle dispersion (C1). Toner (6) was produced in the same manner as (1).
Toner (6) obtained had a volume average particle diameter D _50v of 5.7 μm, a GSDv of 1.24 and a shape factor SF1 of 128. Further, the coverage of the crystalline polyester resin on the toner surface was 97%, and the average thickness of the shell layer in the toner cross section was 75 nm.

Example 7
(Manufacture of toner (7))
In the production of the toner (1), except that 63 parts by weight of the crystalline polyester resin particle dispersion (C1) for forming the shell layer was changed to 45 parts by weight of the crystalline polyester resin particle dispersion (C1), The toner (7) was produced in the same manner as above.
Toner (7) obtained had a volume average particle diameter D _50v of 5.6 μm, a GSDv of 1.22, and a shape factor SF1 of 129. Further, the coverage of the crystalline polyester resin on the toner surface was 98%, and the average thickness of the shell layer in the toner cross section was 51 nm.

Example 8
(Manufacture of toner (8))
In the production of the toner (1), except that 63 parts by weight of the crystalline polyester resin particle dispersion (C1) for forming the shell layer was changed to 72 parts by weight of the crystalline polyester resin particle dispersion (C1), the toner (1 ) Toner (8) was produced in the same manner.
The obtained toner (8) had a volume average particle diameter D _50v of 5.8 μm, a GSDv of 1.24, and a shape factor SF1 of 126. Further, the coverage of the crystalline polyester resin on the toner surface was 97%, and the average thickness of the shell layer in the cross section of the toner was 79 nm.

Example 9
(Manufacture of toner (9))
In the production of the toner (1), except that 63 parts by weight of the crystalline polyester resin particle dispersion (C1) for forming the shell layer was changed to 90 parts by weight of the crystalline polyester resin particle dispersion (C1), The toner (9) was produced in the same manner as in (1).
The toner (9) obtained had a volume average particle diameter D _50v of 5.8 μm, a GSDv of 1.25, and a shape factor SF1 of 125. Further, the coverage of the crystalline polyester resin on the toner surface was 99%, and the average thickness of the shell layer in the cross section of the toner was 99 nm.

Example 10
(Manufacture of toner (10))
In the production of the toner (1), the crystalline polyester resin particle dispersion (C1) used for the core particles is converted to the crystalline polyester resin particle dispersion (C2), and the amorphous polyester resin particle dispersion (A1) is amorphous. The crystalline polyester resin particle dispersion (A2) was changed from 63 parts by weight of the crystalline polyester resin particle dispersion (C1) for forming the shell layer to 54 parts by weight of the crystalline polyester resin particle dispersion (C2). Toner (10) was produced in the same manner as Toner (1).
The obtained toner (10) had a volume average particle diameter _D50v of 5.7 μm, a GSDv of 1.24, and a shape factor SF1 of 127. Further, the coverage of the crystalline polyester resin on the toner surface was 87%, and the average thickness of the shell layer in the toner cross section was 75 nm.

Example 11
(Manufacture of toner (11))
Crystalline polyester resin particle dispersion (C1) 270 parts by weight Amorphous polyester resin particle dispersion (A1) 500 parts by weight Colorant dispersion 70 parts by weight Release agent dispersion 60 parts by weight Ion exchange water 200 parts by weight-anionic surfactant (Dowfax2A1 manufactured by Dow Chemical Co.) 7.0 parts by weight The above components are put in a reaction vessel equipped with a thermometer, pH meter, and stirrer, and homogenizer at a temperature of 25 ° C 125 parts by weight of the prepared aqueous aluminum sulfate solution was added and dispersed for 6 minutes while dispersing at 5,000 rpm with (IKA Japan Co., Ltd .: Ultra Turrax T50). Then, a stirrer and a mantle heater were installed in the reaction vessel, and the temperature of the stirrer was adjusted to 0.2 ° C / min up to 40 ° C, exceeding 40 ° C while adjusting the rotation speed of the stirrer so that the slurry was sufficiently stirred. The temperature was increased at 0.05 ° C./min, and the particle size was measured with Multisizer II (aperture diameter: 50 μm, manufactured by Beckman Coulter, Inc.) every 10 minutes, resulting in a volume average particle size of 5.6 μm. By the way, after maintaining the temperature, the pH was adjusted to 9.0 using a 4 wt% aqueous sodium hydroxide solution. Thereafter, while adjusting the pH to 9.0 every 5 ° C., the temperature was raised to 90 ° C. at a temperature rising rate of 1 ° C./min and held at 90 ° C. When the particle shape and surface property were observed with an optical microscope and a scanning electron microscope (FE-SEM) every 15 minutes, the coalescence of the particles was confirmed at 1.5 hours. Cooled to 5 ° C. in 5 minutes.

After adding 0.3 M nitric acid to the slurry after cooling to pH 4.5, 25 parts by weight of the prepared aqueous aluminum sulfate solution was added, and then the temperature was adjusted to 20 ° C. 63 parts by weight of crystalline polyester resin particle dispersion (C1) Was maintained for 2 hours while maintaining the temperature.
Thereafter, while stirring the slurry, the temperature was raised to 55 ° C. at a temperature rise of 1 ° C./min, and the temperature was maintained for 5 hours, and then the container was cooled to 20 ° C. with cooling water.
The slurry was passed through a nylon mesh having a mesh size of 15 μm to remove coarse powder, and the toner slurry passed through the mesh was filtered under reduced pressure with an aspirator. The toner remaining on the filter paper is crushed as finely as possible by hand, poured into ion-exchanged water of 10 times the amount of toner at a temperature of 30 ° C., stirred and mixed for 30 minutes, and then filtered under reduced pressure with an aspirator again. Was measured. This operation was repeated until the filtrate had a conductivity of 10 μS / cm or less, and the toner was washed. The washed toner was finely crushed with a wet dry granulator (Comil) and then vacuum-dried in an oven at 35 ° C. for 36 hours.

The particles obtained by drying were tanned at a rotational speed of 13,000 rpm using a sample mill. In the tanning, after stirring for 1 minute, the smoothness of the particle surface was confirmed with a scanning electron microscope (FE-SEM). If the smoothness was insufficient, tanning was performed again. By repeatedly tanning and tanning for a total of 30 minutes, it was confirmed that the particle surface was smooth, and toner particles were obtained.
To 100 parts by weight of the obtained toner particles, 1.2 parts by weight of hydrophobic silica (manufactured by Nippon Aerosil Co., Ltd., RX50) and 0.9 parts by weight of hydrophobic titanium oxide (manufactured by Nippon Aerosil Co., Ltd., T805) Were mixed and blended at 13,000 rpm for 30 seconds using a sample mill. Thereafter, the mixture was sieved with a vibration sieve having an opening of 45 μm to obtain toner (11).
The toner (11) obtained had a volume average particle diameter D _50v of 5.7 μm, a GSDv of 1.23, and a shape factor SF1 of 125. Further, the coverage of the crystalline polyester resin on the toner surface was 99%, and the average thickness of the shell layer in the cross section of the toner was 70 nm.

[Comparative Example 1]
(Manufacture of toner (12))
In the production of the toner (1), 270 parts by weight of the crystalline polyester resin particle dispersion (C1) used for the core particles is 0 parts by weight, and 500 parts by weight of the amorphous polyester resin particle dispersion (A1) is 770 parts by weight. A toner (12) was produced in the same manner as the toner (1) except that the toner (12) was changed.
The toner (12) obtained had a volume average particle diameter D _50v of 5.8 μm, a GSDv of 1.24, and a shape factor SF1 of 128. Further, the coverage of the crystalline polyester resin on the toner surface was 98%, and the average thickness of the shell layer in the cross section of the toner was 73 nm.

[Comparative Example 2]
(Manufacture of toner (13))
In the production of the toner (1), 270 parts by weight of the crystalline polyester resin particle dispersion (C1) used for the core particles is 770 parts by weight, and 500 parts by weight of the amorphous polyester resin particle dispersion (A1) is 0 parts by weight. A toner (13) was produced in the same manner as the toner (1) except that the toner (13) was changed.
The obtained toner (13) had a volume average particle diameter D _50v of 5.7 μm, a GSDv of 1.25, and a shape factor SF1 of 125. Further, the coverage of the crystalline polyester resin on the toner surface was 100%, and the average thickness of the shell layer in the cross section of the toner was not measurable because there was no contrast when the cross section was observed.

[Comparative Example 3]
(Manufacture of toner (14))
In the production of the toner (1), 63 parts by weight of the crystalline polyester resin particle dispersion (C1) for forming the shell layer, 31.5 parts by weight of the crystalline polyester resin particle dispersion (C1) and the non-crystalline polyester resin particles A toner (14) was produced in the same manner as the toner (1) except that the dispersion (A1) was changed to 13.5 parts by weight.
The toner (14) obtained had a volume average particle diameter D _50v of 5.6 μm, a GSDv of 1.24, and a shape factor SF1 of 129. Further, the coverage of the crystalline polyester resin on the toner surface was 69%, and the average thickness of the shell layer in the cross section of the toner was 71 nm.

[Comparative Example 4]
(Manufacture of toner (15))
In the production of the toner (1), the crystalline polyester resin particle dispersion (C1) used for the core particles is converted to the crystalline polyester resin particle dispersion (C3), and the amorphous polyester resin particle dispersion (A1) is amorphous. The crystalline polyester resin particle dispersion (A3) was changed from 63 parts by weight of the crystalline polyester resin particle dispersion (C1) for shell layer formation to 63 parts by weight of the crystalline polyester resin particle dispersion (C3). Toner (15) was produced in the same manner as Toner (1).
The obtained toner (15) had a volume average particle diameter D _50v of 5.9 μm, a GSDv of 1.25, and a shape factor SF1 of 126. Further, the coverage of the crystalline polyester resin on the toner surface was 68%, and the average thickness of the shell layer in the cross section of the toner was 72 nm.

[Comparative Example 5]
(Manufacture of toner (16))
In the production of the toner (1), except that 63 parts by weight of the crystalline polyester resin particle dispersion (C1) for forming the shell layer was changed to 36 parts by weight of the crystalline polyester resin particle dispersion (C1), the toner (1 ) To produce toner (16).
The obtained toner (16) had a volume average particle diameter D _50v of 5.8 μm, a GSDv of 1.25, and a shape factor SF1 of 127. Further, the coverage of the crystalline polyester resin on the toner surface was 94%, and the average thickness of the shell layer in the cross section of the toner was 47 nm.

[Comparative Example 6]
(Manufacture of toner (17))
In the production of the toner (1), except that 63 parts by weight of the crystalline polyester resin particle dispersion (C1) for forming the shell layer was changed to 99 parts by weight of the crystalline polyester resin particle dispersion (C1), the toner (1 ) To produce toner (17).
The toner (17) obtained had a volume average particle diameter D _50v of 5.7 μm, a GSDv of 1.26, and a shape factor SF1 of 128. Further, the coverage of the crystalline polyester resin on the toner surface was 99%, and the average thickness of the shell layer in the cross section of the toner was 101 nm.

  Table 1 summarizes the characteristics of the toners obtained in Examples 1 to 11 and Comparative Examples 1 to 6.

<Manufacture of carriers>
Mn-Mg-Sr ferrite particles (average particle size 40 μm): 100 parts by weight Toluene: 14 parts by weight Styrene / methyl methacrylate copolymer (copolymerization weight ratio 90:10): 2.0 parts by weight Carbon Black (VXC72: manufactured by Cabot Corporation): 0.15 parts by weight The above components excluding ferrite particles and glass beads (φ1 mm, the same amount as toluene) were stirred for 1,200 ppm / 30 min using a sand mill manufactured by Kansai Paint Co., Ltd. A solution for forming a resin coating layer was obtained. Further, this resin coating layer forming solution and ferrite particles were put in a vacuum degassing kneader and the pressure was reduced, and toluene was distilled off / dried to form a resin coated carrier.

<Manufacture of developer>
After adding 40 parts by weight of the toners (1) to (17) to 500 parts by weight of the carrier and blending with a V-type blender for 20 minutes, the aggregates are removed with a vibrating screen having an opening of 212 μm, and a developer 1) to (17) were obtained.

<Evaluation>
(Evaluation of low-temperature fixability)
The developers (1) to (17) are filled in a developing device of an Aeosport C75550I remodeling machine manufactured by Fuji Xerox Co., Ltd. (the fixing machine has been remodeled so that the fixing temperature can be changed), and normal temperature and normal humidity (22 In the environment of 50 ° C. and 50% RH, the fixing roll surface temperature of the fixing device is changed from 60 ° C. to 200 ° C. every 10 ° C., and at each temperature, solid (toner loading: 4.5 g / m ² ) and A thin line image was produced. These images were evaluated as follows.

After making a crease inside the central part of the solid fixed image, wipe it with a non-woven fabric, visually evaluate the destruction of the fixed image, and set the fixing temperature at which there is no problem as the minimum fixing temperature (MFT (° C)). Evaluation was made according to the following criteria.
(Double-circle): MFT <= 110 degreeC ... It has the outstanding low-temperature fixability.
○: 110 ° C. <MFT ≦ 120 ° C. Low temperature fixability.
Δ: 120 ° C. <MFT ≦ 130 ° C. Slightly low-temperature fixability.
×: 130 ° C. <MFT... No superiority in low-temperature fixability.

(Evaluation of color point)
The developers (1) to (17) are filled in a developing device of an Aeosport C75550I remodeling machine manufactured by Fuji Xerox Co., Ltd. (the fixing machine has been remodeled so that the fixing temperature can be changed), and high temperature and high humidity (28 After setting the fixing roll surface temperature of the fixing device to a value that is + 15 ° C. from the minimum fixing temperature MFT of each developer in an environment of 85 ° C. and 85% RH, and outputting one A4 blank sheet Then, 10,000 A4 blank sheets were output while the developing unit was driven, and then one A4 blank sheet similar to the above was output. With respect to the output one sheet and 10,000 sheets after the blank sheet, the blank part color point was visually counted and evaluated according to the following criteria.
◎: 0 white spots ○: 1 to 4 white spots △: 5 to 9 white spots ×: 10 or more white spots

  As shown in Table 2, in Examples 1 to 11, the fixing temperature can be set low, and the generation of color points in the initial and continuous use can be suppressed. On the other hand, in Comparative Examples 1 to 6, the fixing temperature was inevitably set high, and the color point generation could not be suppressed.

Claims (6)

Including at least a binder resin and a colorant,
Having a core-shell structure having a shell layer on the surface of the core particles;
The binder resin in the core particles includes a crystalline polyester resin and an amorphous polyester resin,
The shell layer includes a crystalline polyester resin;
The ratio of the surface covered with the crystalline polyester resin in the shell layer observed by staining with ruthenium tetroxide is 70 to 100 area%,
The electrostatic charge image developing toner, wherein an average thickness of the shell layer is 50 nm or more and less than 100 nm.   An electrostatic charge image developer comprising the electrostatic charge image developing toner according to claim 1 and a carrier.   A toner cartridge containing at least the electrostatic image developing toner according to claim 1. The electrostatic latent image formed on the surface of the image carrier is developed with an electrostatic image developing toner or an electrostatic image developer to form a toner image, and the image carrier and the surface of the image carrier are charged. And at least one selected from the group consisting of a charging means for cleaning, and a cleaning means for removing toner remaining on the surface of the image carrier.
A process cartridge containing the electrostatic charge image developing toner according to claim 1 or the electrostatic charge image developer according to claim 2. A latent image forming step for forming an electrostatic latent image on the surface of the image carrier;
A developing step of forming a toner image by developing the electrostatic latent image formed on the surface of the image carrier with a developer containing toner;
A transfer step of transferring the toner image onto the surface of the transfer target; and
A fixing step of fixing the toner image transferred to the surface of the transfer target,
An image forming method using the electrostatic charge image developing toner according to claim 1 or the electrostatic charge image developer according to claim 2 as the developer. An image carrier,
Charging means for charging the image carrier;
Exposure means for exposing the charged image carrier to form an electrostatic latent image on the surface of the image carrier;
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 from the image carrier to the surface of the transfer target;
Fixing means for fixing the toner image transferred to the surface of the transfer target,
An image forming apparatus using the electrostatic charge image developing toner according to claim 1 or the electrostatic charge image developer according to claim 2 as the developer.