JP5817443B2 - Electrostatic image developing toner, electrostatic image developer, toner cartridge, process cartridge, image forming apparatus, and image forming method - Google Patents

Description

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

  Patent Document 1 includes 40 to 99% by weight of an amorphous polymer block made of polyester containing 1 to 50 mol% of a trifunctional or higher polyfunctional monomer component, and 1 to 1 of crystalline polymer block made of polyester. A toner for electrostatic image development is disclosed, wherein a block copolymer or graft copolymer containing 60% by weight in a molecule is used as a binder resin.

  Patent Document 2 includes, as a main component, a block copolymer or graft copolymer obtained by chemically bonding a crystalline polyester and an amorphous vinyl polymer having a functional group that forms a bond with the crystalline polyester. A toner for electrostatic image development is disclosed, wherein a ratio Mw / Mn of a weight average molecular weight Mw to a number average molecular weight Mn of the amorphous vinyl polymer is 3.5 or more. ing.

Patent Document 3, a polyester block composed by condensing an aliphatic diol and dicarboxylic acid, the weight-average molecular weight 3 × 10 ³ ~ containing polyester blocks formed by condensing an alicyclic diol and dicarboxylic acids in the molecule There is disclosed a resin composition for toner, characterized by comprising a 5 × 10 ⁴ polyester block copolymer as a main component.

  Patent Document 4 discloses a toner mainly composed of a resin and provided with an external additive, wherein the resin is mainly composed of a polyester resin, and the polyester resin is mainly composed of a block copolymer. The block polyester includes a crystalline block obtained by condensing a diol component and a dicarboxylic acid component, and is more crystalline than the crystalline block. Of the external additive contained in the toner, the ratio of those free from the surface of the toner particles is 0.1 to 5 wt%. Toner is disclosed.

  Patent Document 5 discloses an electrostatic charge image developing toner comprising at least a binder resin, a colorant, and a release agent, and the binder resin includes a polyester resin and a block copolymer having a polyolefin skeleton. An electrostatic charge image developing toner is disclosed.

Japanese Patent Laid-Open No. 62-299859 JP-A 63-027855 JP 2001-324832 A JP 2004-138920 A JP 2010-102117 A

  An object of the present invention is to provide a toner for developing an electrostatic image having excellent strength.

The above problem is solved by the following means. That is,
The invention according to claim 1
An electrostatic charge image developing toner comprising a triblock copolymer in which an amorphous polyester polymer block A, a crystalline acrylate polymer block B, and an amorphous vinyl polymer block C are block polymerized in this order.

The invention according to claim 2
2. The electrostatic image developing toner according to claim 1, wherein the number average molecular weight of the crystalline acrylate polymer block B is 10% to 60% with respect to the number average molecular weight of the entire triblock copolymer. is there.

The invention according to claim 3
The electrostatic image developing toner according to claim 1, wherein the crystalline acrylate polymer block B includes a repeating unit derived from at least one of stearyl acrylate and behenyl acrylate.

The invention according to claim 4
4. The electrostatic image developing toner according to claim 1, wherein the non-crystalline vinyl polymer block C includes a repeating unit derived from at least one of styrene and a derivative thereof. 5. .

The invention according to claim 5
An electrostatic charge image developer comprising the electrostatic charge image developing toner according to claim 1.

The invention according to claim 6
The toner for developing an electrostatic charge image according to any one of claims 1 to 4, containing the toner,
The toner cartridge is detachable from the image forming apparatus.

The invention according to claim 7 provides:
A developing means for accommodating the electrostatic charge image developer according to claim 5 and developing the electrostatic charge image formed on the image carrier as a toner image by the electrostatic charge image developer,
It is a process cartridge that can be attached to and detached from the image forming apparatus.

The invention according to claim 8 provides:
An image carrier,
Charging means for charging the image carrier;
An electrostatic charge image forming means for forming an electrostatic charge image on the surface of the charged image carrier;
Developing means for containing the electrostatic charge image developer according to claim 5 and developing the electrostatic charge image formed on the image carrier as a toner image by the electrostatic charge image developer;
Transfer means for transferring a toner image formed on the image carrier onto a transfer target;
Fixing means for fixing the toner image transferred onto the transfer medium;
An image forming apparatus.

The invention according to claim 9 is:
A charging step for charging the image carrier;
An electrostatic charge image forming step of forming an electrostatic charge image on the surface of the charged image carrier;
A developing step of developing the electrostatic image formed on the image carrier as a toner image with the electrostatic image developer according to claim 5;
A transfer step of transferring a toner image formed on the image carrier onto a transfer target;
A fixing step of fixing the toner image transferred onto the transfer medium;
Is an image forming method.

  According to the first aspect of the invention, the electrostatic charge image development is superior in strength compared to the case where a diblock copolymer obtained by block polymerization of the amorphous polyester polymer block A and the crystalline acrylate polymer block B is used. Toner is provided.

  According to the second aspect of the present invention, compared with the case where the ratio of the number average molecular weight of the crystalline acrylate-based polymer block B to the number average molecular weight of the entire triblock copolymer is out of the range, the strength and low temperature of the toner are reduced. Provided is a toner for developing an electrostatic image that is compatible with fixability.

  According to the third aspect of the invention, there is provided an electrostatic charge image developing toner excellent in strength compared to the case where the crystalline acrylate polymer block B does not contain a repeating unit derived from at least one of stearyl acrylate and behenyl acrylate. Provided.

  According to the fourth aspect of the invention, compared to the case where the non-crystalline vinyl polymer block C does not contain a repeating unit derived from at least one of styrene and its derivatives, the electrostatic image development is excellent in low-temperature fixability. Toner is provided.

  According to the invention of claim 5, compared to the case where a toner for developing an electrostatic image using a diblock copolymer obtained by block polymerization of an amorphous polyester polymer block A and a crystalline acrylate polymer block B is applied. An electrostatic charge image developer excellent in strength is provided.

  According to the inventions according to claim 6, claim 7, claim 8 and claim 9, a diblock copolymer obtained by block polymerization of an amorphous polyester polymer block A and a crystalline acrylate polymer block B is used. The present invention provides a toner cartridge, a process cartridge, an image forming apparatus, and an image forming method capable of obtaining an image having an excellent strength as compared with the case where the electrostatic charge image developing toner is applied.

1 is a schematic configuration diagram illustrating an example of an image forming apparatus according to an exemplary embodiment. It is a schematic block diagram which shows an example of the process cartridge which concerns on this embodiment.

  Hereinafter, an embodiment which is an example of the present invention will be described in detail.

(Static image developing toner)
The electrostatic image developing toner according to this embodiment (hereinafter sometimes referred to as “toner”) includes an amorphous polyester polymer block A (hereinafter sometimes referred to as “block A”) and a crystalline acrylate-based toner. A triblock copolymer obtained by block polymerization of a polymer block B (hereinafter sometimes referred to as “block B”) and an amorphous vinyl polymer block C (hereinafter sometimes referred to as “block C”) in this order. It is comprised including.

The toner according to the exemplary embodiment has excellent strength due to the above configuration. In particular, in this embodiment, in place of the triblock copolymer, compared to the case where a diblock copolymer obtained by block polymerization of an amorphous polyester polymer block A and a crystalline acrylate polymer block B is used, the strength is increased. It will be excellent.
The reason for this is not clear, but in the present embodiment, a block copolymer having high strength is obtained by sandwiching both ends of the block B with non-crystalline polymer blocks (the block A and the block C). It is presumed that the strength of the toner using the block copolymer is also increased.

  By applying the toner according to the present embodiment to an image forming apparatus or the like (that is, a toner cartridge, a process cartridge, an image forming apparatus, and an image forming method), an image having excellent strength can be obtained.

Further, in this embodiment, since the triblock copolymer has an amorphous vinyl polymer block, a polymer that does not have the amorphous vinyl polymer block instead of the triblock copolymer is used. Compared to the case of using a coalescence, it has excellent low-temperature fixability (for example, fixability at a fixing temperature of 120 ° C. or lower). This is presumably because the compatibility of the crystalline acrylate block and the amorphous polyester block is improved by having the amorphous vinyl polymer block.
That is, in this embodiment, by using the triblock copolymer, the toner has excellent mechanical strength as well as excellent low-temperature fixability.

  Further, in this embodiment, since the triblock copolymer has a crystalline acrylate polymer block, its melting characteristics are sharper and its melting than a polymer that does not have the crystalline acrylate polymer block. Lower viscosity later. Furthermore, by having a crystalline acrylate polymer block, the charging stability of the toner is better than other crystalline resins due to the excellent electrical properties derived from the crystalline structure. That is, in this embodiment, the triblock copolymer has a crystalline acrylate-based polymer block as a binder resin for toner, so that excellent charging stability is imparted.

In the present embodiment, the number average molecular weight of the block B (hereinafter sometimes referred to as “M _B ”) is the number average molecular weight of the entire triblock copolymer (hereinafter sometimes referred to as “M _T ”). On the other hand, it is preferably 10% or more and 60% or less. By the ratio of the _{M B} with respect to the _{M T (i.e., (M B / M T)} × 100 (%)) is in the above range, as compared with the case where outside the above range, the strength of the toner and low-temperature fixability Is realized. Specifically, the ratio of the M _B for said M _T is excellent low-temperature fixability as compared with the case lower than the above range, excellent strength of the toner as compared with the case higher than the above range.

In this case, in this embodiment liquid, the triblock copolymer may be used alone as the binder resin, or may be used in combination with other resins.
As content of the said triblock copolymer in the case of using other binder resin together, 40 mass% or more and 95 mass% or less are mentioned with respect to the whole binder resin, for example, 50 mass% or more and 90 mass% are desirable. % Or less, and more desirably 60% by mass or more and 85% by mass or less.

In this embodiment, it is desirable that the block B includes a repeating unit derived from at least one of stearyl acrylate and behenyl acrylate. That is, it is desirable that the block B is a polymer block in which a monomer containing at least one of stearyl acrylate and behenyl acrylate is polymerized. Thereby, compared to the case where neither stearyl acrylate nor behenyl acrylate is used (particularly, when alkyl acrylate having a smaller number of carbon atoms in the alkyl group is used instead of stearyl acrylate and behenyl acrylate), the mechanical strength is excellent. A toner having excellent heat storage properties can be obtained.
In this case, by using a crystalline resin having a longer carbon number, a stronger crystal structure is formed, and when at least one of stearyl acrylate and behenyl acrylate is used, the melting temperature of block B is increased, and triblock copolymer It is considered that the heat resistance of the coalescence is improved, and the heat storage property and mechanical strength of the toner are excellent.
Then, by applying a toner containing a triblock copolymer using at least one of stearyl acrylate and behenyl acrylate to an image forming apparatus or the like, aggregation of the toner in the developing machine is suppressed, and image storability is added in addition to image strength. A good image can be obtained.

  Moreover, in this embodiment, it is more desirable that the block B includes both a repeating unit derived from stearyl acrylate and a repeating unit derived from behenyl acrylate. That is, it is desirable that the block B is a block of a copolymer obtained by copolymerizing monomers including both stearyl acrylate and behenyl acrylate. By using both stearyl acrylate and behenyl acrylate, the melting temperature of block B is more strictly controlled than when only one of them is used, and the low-temperature fixability, heat storage property and mechanical strength of the toner are controlled. It becomes easy to realize at a high level.

  In this embodiment, it is desirable that the block C includes a repeating unit derived from at least one of styrene and its derivatives. That is, the block C is preferably a polymer block obtained by polymerizing a monomer containing at least one of styrene and its derivatives. As a result, the toner has excellent low-temperature fixability as compared with a case where neither styrene nor a derivative thereof is used (that is, only a vinyl monomer having no styrene skeleton is used). In this case, it is considered that the compatibility of the crystalline acrylate-based polymer block with the other block units is reduced because the polarity of the block C with respect to the crystalline acrylate-based polymer block becomes too high by not using styrene or its derivative. It is done. Therefore, it is presumed that the polarity of the block C can be suppressed by using at least one of styrene and its derivatives, and as a result, good low-temperature fixability can be obtained.

  Hereinafter, the configuration of the toner according to the exemplary embodiment will be described in detail.

  The toner according to the exemplary embodiment includes toner particles and, if necessary, an external additive.

First, toner particles will be described.
The toner particles include, for example, the triblock copolymer as a binder resin, and, if necessary, a colorant, a release agent, and other additives.

The triblock copolymer will be described.
The triblock copolymer is a copolymer obtained by block polymerization of an amorphous polyester polymer block A, a crystalline acrylate polymer block B, and an amorphous vinyl polymer block C in this order.

Here, “crystallinity” refers to a material having a clear endothermic peak rather than a stepwise endothermic amount change in thermal analysis measurement using differential scanning calorimetry (DSC). Moreover, it has a diffraction peak derived from the crystal structure by X-ray analysis. On the other hand, “non-crystalline” means that in a thermal analysis measurement using differential scanning calorimetry (DSC), it has not a clear endothermic peak but only a step-like endothermic change. Yes, it refers to the property of thermoplasticizing at a temperature above the glass transition temperature. Moreover, the thing which does not have a diffraction peak by X-ray analysis is pointed out.
Specifically, for example, a crystalline polymer means that the half-value width of an endothermic peak when measured at a heating rate of 10 ° C./min is within 10 ° C., and an amorphous polymer is It means a polymer having a full width at half maximum exceeding 10 ° C. or a polymer having no clear endothermic peak.

The amorphous polyester polymer block A will be described.
The block A is a non-crystalline polymer block having a polyester structure, and specifically includes, for example, a polycondensation block of a polyvalent carboxylic acid and a polyhydric alcohol.

  Among the polyvalent carboxylic acids, examples of the divalent carboxylic acid having an unsaturated group (for example, a vinyl group) include fumaric acid, maleic acid, maleic anhydride, citraconic acid, mesaconic acid, and 2-pentenedioic acid. , Methylene succinic acid, and lower (1 to 5 carbon atoms) alkyl esters thereof.

  Examples of other divalent carboxylic acids include alkyl succinic acid, alkenyl succinic acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, Dibasic acids such as naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, cyclohexanedicarboxylic acid, malonic acid, mesaconic acid, their anhydrides, and their lower levels (1 to 5 carbon atoms) Examples include alkyl esters.

Among the polyvalent carboxylic acids, examples of trivalent or higher carboxylic acids include 1,2,4-benzenetricarboxylic acid (trimellitic acid), 1,2,5-benzenetricarboxylic acid, 1,2,4- Naphthalene tricarboxylic acid, anhydrides thereof, lower alkyl esters thereof and the like can be mentioned.
These polyvalent carboxylic acids may be used alone or in combination of two or more.

Examples of the polyhydric alcohol include bisphenol A, hydrogenated bisphenol A, ethylene oxide and / or propylene oxide adduct of bisphenol A, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, ethylene glycol, diethylene glycol, propylene glycol. , Dipropylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol and the like.
Examples of the trivalent or higher alcohol include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol and the like.
In addition to polyhydric alcohols, monovalent acids such as acetic acid and benzoic acid, and monohydric alcohols such as cyclohexanol and benzyl alcohol are also used together for the purpose of adjusting the acid value and hydroxyl value, if necessary. May be.
These polyhydric alcohols may be used alone or in combination of two or more.

The number average molecular weight of the block A (hereinafter sometimes referred to as “M _A ”) is, for example, 2000 or more and 20000 or less, more preferably 3000 or more and 15000 or less, and further preferably 5000 or more and 10,000 or less. .

  The number average molecular weight is measured by gel permeation chromatography (GPC). The molecular weight measurement by GPC is performed with a THF solvent using a Tosoh GPC / HLC-8120 as a measuring device and a Tosoh column / TSKgel Super HM-M (15 cm). The number average molecular weight is calculated from the measurement result using a molecular weight calibration curve prepared with a monodisperse polystyrene standard sample. The same applies hereinafter.

  The number average molecular weight of the block A of the triblock copolymer is the number average molecular weight of the resin before blocking, the block B is the number average molecular weight before polymerization (before chain extension), and the block C is block B. Is obtained by subtracting the molecular weight of block B before chain extension from the number average molecular weight after chain extension (after polymerization of block C). In this case, when the chain is extended from the block C and the block B is polymerized, the opposite is true.

As a glass transition temperature of the block A, the range of 50 degreeC or more and 70 degrees C or less is mentioned, for example, More preferably, they are 53 degreeC or more and 65 degrees C or less, More preferably, they are 55 degreeC or more and 63 degrees C or less.
The said glass transition temperature is measured by the method (DSC method) prescribed | regulated to ASTMD3418-82, for example. The same applies hereinafter.

The crystalline acrylate polymer block B will be described. The block B is a crystalline polymer block having an acrylic resin structure. Specifically, for example, the side chain has 16 or more alkyl chains at room temperature. As described above, a polymer of an acrylate monomer having a melting point is desirable, and a copolymer with another radical polymerizable monomer may be used as long as the crystal structure can be maintained and a desired melting point can be obtained.

Here, the block B exhibits crystallinity from the viewpoint of low-temperature fixability, and has a melting temperature of 37 ° C. or higher (preferably 45 ° C. or higher and 80 ° C. or lower) from the viewpoint of toner strength or heat storage. It is good to have.
The said melting temperature is measured by the method (DSC method) prescribed | regulated to ASTMD3418-82, for example.
Specifically, the melting temperature by DSC is measured according to ASTM D3418 using a differential scanning calorimeter (DSC-50) manufactured by Shimadzu Corporation equipped with an automatic tangential processing system. The measurement conditions are shown below.
Sample: 3 to 15 mg, preferably 5 to 10 mg
Measurement method: Place the sample in an aluminum pan and use an empty aluminum pan as a reference.
Temperature curve: Temperature rise I (20 ° C. to 180 ° C., temperature rise rate 10 ° C./min)
In the temperature curve obtained by the above measurement, the peak temperature of the endothermic curve measured at the time of temperature rise is obtained and set as the melting temperature.

Examples of the acrylate ester that becomes a crystalline polymer satisfying the above properties by polymerization include an acrylate ester having an alkyl group having 16 to 25 carbon atoms (preferably an alkyl group having 18 to 22 carbon atoms). It is done.
Among the acrylic esters, examples of the acrylic ester include hexadecyl acrylate, heptadecyl acrylate, octadecyl acrylate (stearyl acrylate), nonadecyl acrylate, eicosyl acrylate, heneicosyl acrylate, docosyl acrylate (behenyl acrylate). , Tricosyl acrylate, tetracosyl acrylate, pentacosyl acrylate and the like.
Only one acrylate monomer may be used, or two or more acrylate monomers may be used in combination.

Among the specific examples of the acrylic ester, stearyl acrylate and behenyl acrylate are particularly preferable.
That is, as described above, the block B may be a polymer block obtained by polymerizing at least one monomer selected from stearyl acrylate and behenyl acrylate.
The block B is particularly preferably a polymer block composed of a copolymer of stearyl acrylate and behenyl acrylate. As a ratio of stearyl acrylate and behenyl acrylate used in the copolymer, behenyl acrylate may be in the range of 60% by mass to 95% by mass in the total weight of stearyl acrylate and behenyl acrylate, and more preferably 70% by mass. % Or more and 90 mass% or less may be sufficient.

The number average molecular weight of the block B _{(M B),} for example, include 2000 to 30,000, more preferably 5,000 or more than 15,000, still more preferably 8000 or more 13500 or less.
The number average molecular weight of the entire triblock copolymer ratio of the _{M B} for _{(M T) (i.e., (M B / M T)} × 100 (%)), the range of 60% or less 10% or more as described above It may be 15% or more and 50% or less, and may be 17% or more and 40% or less.

The non-crystalline vinyl polymer block C will be described. The block C is a non-crystalline polymer block having a vinyl resin structure. Specifically, for example, a non-polymerized vinyl monomer is polymerized. Examples include a block of a crystalline polymer.
The vinyl monomer is a monomer having a vinyl group, and examples thereof include a monomer having a styrene skeleton (that is, styrene or a derivative thereof). As described above, the vinyl monomer preferably includes at least a monomer having a styrene skeleton. In that case, the ratio of the monomer having a styrene skeleton to the whole monomer used for the polymerization of the block C includes, for example, a range of 50% by mass to 100% by mass, and more preferably 70% by mass or more. The range may be 95% by mass or less.

Examples of the monomer having a styrene skeleton include styrene and alkyl-substituted styrene (for example, α-methylstyrene, vinylnaphthalene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2-ethylstyrene, 3 -Ethyl styrene, 4-ethyl styrene, etc.), halogen-substituted styrene (for example, 2-chlorostyrene, 3-chlorostyrene, 4-chlorostyrene, etc.), divinylbenzene and the like.
Among these, styrene is preferable.

Examples of other vinyl monomers include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, butyl acrylate, and 2-ethylhexyl acrylate.
Only one vinyl monomer may be used, or two or more vinyl monomers may be used in combination.

The number average molecular weight of the block C (hereinafter sometimes referred to as “M _C ”) is, for example, from 1000 to 20000, and may be from 3000 to 15000, or from 5000 to 13000. .
The number average molecular weight of the entire triblock copolymer _{(M T)} wherein _{M C} ratio _{(i.e., (M C / M T)} × 100 (%)) of the relative as, for example a range of 15% or more than 60% More preferably, it may be 20% or more and 50% or less.
Moreover, as a glass transition temperature of the block C, the range of 50 to 100 degreeC is mentioned, for example, 55 to 80 degreeC may be sufficient and 58 to 65 degreeC may be sufficient.

Other items of the triblock copolymer will be described.
The number average molecular weight (M _T ) of the triblock copolymer is, for example, from 10,000 to 80,000, may be from 15,000 to 60,000, and may be from 18,000 to 30,000.

The fact that the block A, the block B, and the block C are block polymerized in the triblock copolymer is confirmed by, for example, structural analysis and thermal analysis.
Specifically, for example, the structure of each component contained in the polymer is confirmed by structural analysis such as NMR measurement or IR measurement, and each component is block polymerized by thermal analysis such as DSC measurement. Is confirmed. For example, as a result of DSC measurement of the polymer, the glass transition temperature of the amorphous polyester, the melting temperature of the crystalline acrylate polymer, and the glass transition temperature of the amorphous vinyl polymer were observed separately. In this case, the measured polymer is confirmed to be a triblock copolymer of an amorphous polyester block, a crystalline acrylate polymer block, and an amorphous vinyl polymer block.

A method for synthesizing the triblock copolymer will be described.
The triblock copolymer is synthesized, for example, by the following method.
Specifically, for example, first, an acrylate monomer (for example, the (meth) acrylic acid ester or the like) that becomes a crystalline polymer by polymerization is used, for example, using a living control agent (for example, a nitrooxide stable radical compound). Polymerization is performed by a living radical polymerization method. At that time, a nitrooxy radical such as 2-methyl-2- [N- (tert-butyl) -N- (1-diethoxyphosphoryl-2,2-dimethylpropyl) -aminoxy] -propionic acid is introduced into a carboxyl group in the molecule. By supplementing (stabilizing) with a compound containing a living radical initiator, a block B in which one terminal is a living radical starting point and the other terminal is a carboxy group is obtained.

  Next, a vinyl monomer (for example, styrene) that becomes an amorphous polymer by polymerization is added to the block B, and chain extension is performed from the living start point to radically polymerize the block C from the end of the block B. Thus, a diblock copolymer of block B and block C can be easily obtained.

On the other hand, separately, for example, by adjusting the ratio of the acid component and the alcohol component in a general polyester polymerization method (for example, direct polycondensation, transesterification method, etc.) in which a polycarboxylic acid and a polyhydric alcohol are reacted, Block A which is an alcoholic hydroxyl group is formed.
Then, a hydroxyl group at one end of the block A and a carboxy group at the end on the block B side of the diblock copolymer are subjected to a condensation reaction so that the block A, the block B, and the block C are in this order. A bound triblock copolymer is obtained.
A triblock copolymer is synthesized as described above.

In the present embodiment, as the binder resin, a resin other than the triblock copolymer (other binder resin) may be used in combination.
Examples of other binder resins include known resins such as polyester resins, vinyl resins, styrene / acrylic resins, epoxy resins, polyester resins, polyurethane resins, polyamide resins, cellulose resins, polyether resins, and polyolefin resins. Can be mentioned.
In the case where other resins are used in combination, the above-mentioned value of M _T , preferably obtained by adding the number average molecular weight of the other resins used as M _T, is (M _B / M _T ) × 100 (%)) Similar effects can be obtained by being in the range.
As content of the said triblock copolymer in the case of using other binder resin together, 40 mass% or more and 95 mass% or less are mentioned with respect to the whole binder resin, for example, 50 mass% or more and 90 mass% are desirable. % Or less, and more desirably 60% by mass or more and 85% by mass or less.

The colorant will be described.
The colorant is not particularly limited as long as it is a known colorant. For example, carbon black such as furnace black, channel black, acetylene black, and thermal black, inorganic pigments such as bengara, bitumen, and titanium oxide, fast yellow, disazo Azo pigments such as yellow, pyrazolone red, chelate red, brilliant carmine, para brown, phthalocyanine pigments such as copper phthalocyanine, metal-free phthalocyanine, flavantron yellow, dibromoanthrone orange, perylene red, quinacridone red, dioxazine violet Examples thereof include cyclic pigments.

  As the colorant, a surface-treated colorant may be used as necessary, or it may be used in combination with a dispersant. A plurality of colorants may be used in combination.

  As content of a coloring agent, the range of 1 to 30 mass parts is desirable with respect to 100 mass parts of binder resin.

The release agent will be described.
Examples of mold release agents include hydrocarbon waxes; natural waxes such as carnauba wax, rice wax, and candelilla wax; synthetic or mineral / petroleum waxes such as montan wax; ester types such as fatty acid esters and montanic acid esters. Wax; and the like, but is not limited thereto.

  The melting point of the release agent is preferably 50 ° C. or higher, and more preferably 60 ° C. or higher, from the viewpoint of storage stability. Further, from the viewpoint of offset resistance, the temperature is desirably 110 ° C. or less, and more desirably 100 ° C. or less.

  The content of the release agent is preferably in the range of 2 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the binder resin.

Other additives will be described.
Examples of other additives include magnetic substances, charge control agents, inorganic powders, and the like.

The characteristics of the toner particles will be described.
The toner particles may be toner particles having a single layer structure, or toner particles having a so-called core / shell structure including a core (core particle) and a coating layer (shell layer) covering the core. May be.
In the case of toner particles having a core / shell structure, for example, the coating layer (shell layer) is configured to include the triblock copolymer, while the core body (core particle), together with the triblock copolymer, As needed, it is good to make it comprise a coloring agent, a mold release agent, and another additive.

The volume average particle diameter of the toner particles is, for example, 2.0 μm or more and 10 μm or less, and preferably 4.0 μm or more and 8.0 μm or less.
As a method for measuring the volume average particle diameter of the toner particles, 0.5 mg to 50 mg of a measurement sample is added to 2 ml of a 5% by weight aqueous solution of a surfactant, preferably sodium alkylbenzenesulfonate as a dispersant. The electrolyte was added to 100 ml to 150 ml. The electrolytic solution in which the measurement sample is suspended is subjected to a dispersion treatment for 1 minute with an ultrasonic disperser, and the particle size of the particle size is measured with the Coulter Multisizer II type (manufactured by Beckman-Coulter) using an aperture having an aperture diameter of 100 μm. Is a particle size distribution of particles in the range of 2.0 μm or more and 60 μm or less. The number of particles to be measured is 50,000.
For the particle size range (channel) obtained by dividing the obtained particle size distribution, the volume cumulative distribution is subtracted from the small particle size side, and the particle size that becomes 50% cumulative is defined as the volume average particle size D50v.

The external additive will be described.
Examples of the external additive include inorganic particles. Examples of the inorganic particles include SiO ₂ , TiO ₂ , Al ₂ O ₃ , CuO, ZnO, SnO ₂ , CeO ₂ , Fe ₂ O ₃ , MgO, BaO, and CaO. , K ₂ O, Na ₂ O, ZrO ₂ , CaO.SiO ₂ , K ₂ O. (TiO ₂ ) _n , Al ₂ O ₃ .2SiO ₂ , CaCO ₃ , MgCO ₃ , BaSO ₄ , MgSO _{4 and the} like. .

The surface of the external additive may be hydrophobized in advance. The hydrophobic treatment is performed, for example, by immersing inorganic particles in a hydrophobic treatment agent. The hydrophobizing agent is not particularly limited, and examples thereof include silane coupling agents, silicone oils, titanate coupling agents, aluminum coupling agents and the like. These may be used individually by 1 type and may use 2 or more types together.
The amount of the hydrophobizing agent is usually about 1 part by mass or more and about 10 parts by mass with respect to 100 parts by mass of the inorganic particles, for example.

  The external addition amount of the external additive is preferably 0.5 parts by mass or more and 2.5 parts by mass or less with respect to 100 parts by mass of the toner particles.

A toner manufacturing method according to this embodiment will be described.
First, toner particles may be produced by a dry process (for example, a kneading and pulverization method), a wet process (for example, an aggregation coalescence method, a suspension polymerization method, a solution suspension granulation method, a solution suspension method, a solution emulsion aggregation method, or the like. ). There is no restriction | limiting in particular in these manufacturing methods, A well-known manufacturing method is employ | adopted.

  The toner according to the exemplary embodiment is manufactured, for example, by adding an external additive to the dry toner particles and mixing them. Mixing may be performed, for example, with a V blender, a Henschel mixer, a Ladyge mixer, or the like. Further, if necessary, coarse toner particles may be removed using a vibration classifier, a wind classifier, or the like.

(Electrostatic image developer)
The electrostatic charge image developer according to the exemplary embodiment includes at least the toner according to the exemplary embodiment.
The electrostatic image developer according to this embodiment may be a one-component developer including only the toner according to this embodiment, or may be a two-component developer mixed with the toner and a carrier.

  There is no restriction | limiting in particular as a carrier, A well-known carrier is mentioned. Examples of the carrier include a resin-coated carrier, a magnetic dispersion carrier, a resin dispersion carrier, and the like.

  In the two-component developer, the mixing ratio (mass ratio) of the toner according to the exemplary embodiment and the carrier is preferably in the range of toner: carrier = 1: 100 to 30: 100, and about 3: 100 to 20: 100. The range of is more desirable.

(Image forming apparatus / image forming method)
Next, the image forming apparatus / image forming method according to the present embodiment will be described.
An image forming apparatus according to the present embodiment includes an image carrier, a charging unit that charges the image carrier, an electrostatic image forming unit that forms an electrostatic image on the surface of the charged image carrier, and an electrostatic image development. A developing means for accommodating the developer and developing the electrostatic image formed on the image carrier as a toner image by the electrostatic image developer, and transferring the toner image formed on the image carrier onto the transfer target And a fixing unit that fixes the toner image transferred onto the transfer target. The electrostatic image developer according to the present embodiment is applied as the electrostatic image developer.

  In the image forming apparatus according to the present embodiment, for example, the part including the developing unit may have a cartridge structure (process cartridge) that is detachable from the image forming apparatus. As the process cartridge, for example, A process cartridge that accommodates the electrostatic charge image developer according to the exemplary embodiment and includes a developing unit is preferably used.

  The image forming method according to the present embodiment contains a charging step for charging the image carrier, an electrostatic charge image forming step for forming an electrostatic charge image on the surface of the charged image carrier, and an electrostatic charge image developer. A developing step of developing the electrostatic image formed on the image carrier as a toner image with an electrostatic charge image developer, and a transfer step of transferring the toner image formed on the image carrier onto the transfer target; And a fixing step of fixing the toner image transferred onto the transfer medium. And as the electrostatic charge image developer, the electrostatic charge image developer according to the present embodiment is applied.

  Hereinafter, an example of the image forming apparatus according to the present embodiment will be described, but the present invention is not limited thereto. The main parts shown in the figure will be described, and the description of the other parts will be omitted.

  FIG. 1 is a schematic configuration diagram showing a four-tandem color image forming apparatus. The image forming apparatus shown in FIG. 1 is a first to first electrophotographic method that outputs yellow (Y), magenta (M), cyan (C), and black (K) images based on color-separated image data. Fourth image forming units 10Y, 10M, 10C, and 10K (image forming means) are provided. These image forming units (hereinafter sometimes simply referred to as “units”) 10Y, 10M, 10C, and 10K are arranged in parallel at a predetermined distance from each other in the horizontal direction. The units 10Y, 10M, 10C, and 10K may be process cartridges that are detachable from the main body of the image forming apparatus.

Above each of the units 10Y, 10M, 10C, and 10K, an intermediate transfer belt 20 as an intermediate transfer member is extended through each unit. The intermediate transfer belt 20 is provided by being wound around a driving roller 22 and a support roller 24 that are in contact with the inner surface of the intermediate transfer belt 20 that are spaced apart from each other from the left to the right in the drawing. The vehicle travels in the direction toward the unit 10K. A force is applied to the support roller 24 in a direction away from the drive roller 22 by a spring or the like (not shown), and tension is applied to the intermediate transfer belt 20 wound around the both. Further, an intermediate transfer member cleaning device 30 is provided on the side of the image carrier of the intermediate transfer belt 20 so as to face the driving roller 22.
Further, each of the developing devices (developing means) 4Y, 4M, 4C, and 4K of the units 10Y, 10M, 10C, and 10K has yellow, magenta, cyan, and black contained in the toner cartridges 8Y, 8M, 8C, and 8K. The toner including the four color toners is supplied.

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

The first unit 10Y includes a photoreceptor 1Y that functions as an image holding member. Around the photosensitive member 1Y, a charging roller 2Y for charging the surface of the photosensitive member 1Y to a predetermined potential, and the charged surface is exposed by a laser beam 3Y based on the color-separated image signal to form an electrostatic charge image. An exposure device (electrostatic image forming means) 3 for forming, a developing device (developing means) 4Y for supplying the charged toner to the electrostatic image and developing the electrostatic image, and transferring the developed toner image onto the intermediate transfer belt 20 A primary transfer roller 5Y (primary transfer unit) that performs the transfer and a photoconductor cleaning device (cleaning unit) 6Y that removes toner remaining on the surface of the photoconductor 1Y after the primary transfer are sequentially arranged.
The primary transfer roller 5Y is disposed inside the intermediate transfer belt 20, and is provided at a position facing the photoreceptor 1Y. Further, a bias power source (not shown) for applying a primary transfer bias is connected to each of the primary transfer rollers 5Y, 5M, 5C, and 5K. Each bias power source varies the transfer bias applied to each primary transfer roller under the control of a control unit (not shown).

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

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

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

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

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

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

Thereafter, the recording paper P is sent to the pressure contact portions (nip portions) of the pair of fixing rolls in the fixing device (roll-type fixing unit) 28, and the toner image is fixed on the recording paper P, thereby forming a fixed image.
Examples of the transfer target to which the toner image is transferred include plain paper, OHP sheet, and the like used for electrophotographic copying machines and printers.
In order to further improve the smoothness of the image surface after fixing, it is desirable that the surface of the transfer target is also smooth. For example, coated paper in which the surface of plain paper is coated with resin, art paper for printing, etc. Preferably used.

The recording paper P on which the color image has been fixed is carried out toward the discharge unit, and a series of color image forming operations is completed.
The image forming apparatus exemplified above is configured to transfer the toner image onto the recording paper P via the intermediate transfer belt 20, but is not limited to this configuration, and the toner image is directly transferred from the photoreceptor. It may be a structure that is transferred to a recording sheet.

<Process cartridge, toner cartridge>
FIG. 2 is a schematic configuration diagram showing an embodiment of a preferred example of a process cartridge containing an electrostatic charge image developer according to this embodiment. In the process cartridge 200, a charging roller 108, a developing device 111, a photoconductor cleaning device 113, an opening 118 for exposure, and an opening 117 for static elimination exposure are combined using a mounting rail 116 together with the photoconductor 107. , And integrated. In FIG. 2, reference numeral 300 denotes a transfer target.
The process cartridge 200 is detachable from an image forming apparatus including a transfer device 112, a fixing device 115, and other components not shown.

  The process cartridge 200 shown in FIG. 2 includes a charging device 108, a developing device 111, a cleaning device 113, an opening 118 for exposure, and an opening 117 for static elimination exposure. May be combined. In the process cartridge according to the present embodiment, in addition to the photosensitive member 107, the charging device 108, the developing device 111, the cleaning device (cleaning means) 113, the opening 118 for exposure, and the opening 117 for static elimination exposure. At least one selected from the group consisting of:

  Next, the toner cartridge according to this embodiment will be described. The toner cartridge according to the present exemplary embodiment is a toner cartridge that is detachably attached to the image forming apparatus and stores at least a replenishment electrostatic image developing toner to be supplied to a developing unit provided in the image forming apparatus.

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

  Hereinafter, although an embodiment explains this embodiment in detail, this embodiment is not limited to these examples at all. In the following description, “part” and “%” are all based on mass unless otherwise specified.

[Preparation of resin particle dispersion]
<Synthesis of Triblock Copolymer 1>
(Synthesis of living control agent)
In a nitrogen purged glass vessel with a reflux condenser, 500 parts degassed toluene, 35.9 parts CuBr, 15.9 parts copper powder, 86.7 parts N, N, N ′, N ′, N ”-Pentamethyldiethylenetriamine was introduced and with stirring, 580 parts degassed toluene, 42.1 parts 2-bromo-2-methylpropionic acid and 78.9 parts N-tert-butyl-N— ( 1-Diethylphosphono-2,2-dimethylpropyl) nitroxide was introduced and stirred for 90 minutes at 25 ° C. Thereafter, the reaction medium was filtered, and the toluene filtrate was further washed twice with a saturated aqueous NH ₄ Cl solution. The obtained solid was washed with pentane, vacuum-dried, and the living control agent 2-methyl-2- [N- (tert-butyl) -N- (1-diethoxyphosphoryl-2,2-dimethylpro (Pyr) -aminoxy] -propionic acid (hereinafter sometimes referred to as “MBPAP”).
The molar mass of the prepared MBPAP determined by mass spectrometry was 381.44 g / mol (C ₁₇ H ₃₆ NO ₆ P), which was confirmed to be the target product.

(Synthesis of diblock copolymer 1 of block B and block C)
In a glass container equipped with a reflux condenser, a nitrogen inlet tube, and a stirrer, 83.0 parts of stearyl acrylate monomer and 3.9 parts of MBPAP are dissolved in 183 parts of toluene, and mixed well at 80 ° C. under a nitrogen stream. The polymer used as the block B was obtained by heating up temperature to 110 degreeC and superposing | polymerizing a stearyl acrylate monomer for 8 hours. When the molecular weight was measured by GPC as needed, the number average molecular weight was 8120, which was within 5% of the theoretical value 8118, indicating good living controllability. Moreover, it was 49 degreeC when the melting | fusing point was measured with the differential scanning calorimeter (DSC).

  Thereafter, after the temperature was lowered to 80 ° C., 53 parts of a styrene monomer was dropped and the temperature was raised again to 110 ° C., and polymerization was continued for 8 hours to extend the chain. A diblock copolymer was obtained. When the molecular weight of the polymer was measured, the total number average molecular weight was 13300, and the total number average molecular weight derived from the styrene polymer block obtained by subtracting the molecular weight of the block B was 5100, which is a difference within 5% from the theoretical value 5183. Chain extension was performed. Its melting point was 49 ° C., unchanged from that before chain extension.

  The diblock copolymer was dissolved in 100 parts of THF and taken out, dropped into methanol to reprecipitate the diblock copolymer 1, the precipitate was filtered, and further washed with methanol. The diblock copolymer was purified by vacuum drying at.

(Synthesis of polymer 1 to be block A)
In a heat-dried two-necked flask, 25 mol parts of polyoxyethylene (2,0) -2,2-bis (4-hydroxyphenyl) propane (BPAEO = bisphenol A ethylene oxide adduct), polyoxypropylene (2,2 ) -2,2-bis (4-hydroxyphenyl) propane (BPAPO = bisphenol A propylene oxide adduct) 25 mol parts, 27.1 mol parts terephthalic acid (TPA), 10 mol parts n-dodecenyl succinic acid (DSA), 10 mol parts of fumaric acid (FA) and 0.05 mol parts of dibutyltin oxide were added, and after introducing nitrogen gas into the container and keeping the temperature in an inert atmosphere, the temperature was raised to 150 ° C. to 230 ° C. for 12 hours to 20 hours. A time co-condensation polymerization reaction is performed, and then the pressure is gradually reduced at 210 ° C. to 250 ° C. to synthesize a polymer that becomes block A It was. It was 8010 when the number average molecular weight of the obtained polymer was measured. Further, when the hydroxyl group (OHV) of the resin was measured by the acetic anhydride method of JIS K3342, it was 20.7 mgKOH / g, and it was confirmed that almost all molecular terminals were hydroxyl groups.

(Polymerization of diblock copolymer and polymer to be block A)
In a glass vessel equipped with a reflux condenser, a nitrogen inlet tube, and a stirrer, 136 parts of the B and C diblock copolymer 1 obtained above and 30 parts of the polymer to be block A were added to 166 parts of toluene at 50 ° C. Then, 2.7 parts of dicyclocarbodiimide (DCC) and 0.17 part of dimethylaminopyridine (DMAP) were added and reacted at 50 ° C. for 2 hours.
The number average molecular weight of the obtained polymer was measured to be 21300. The triblock polymer having each block unit of A, B, and C in which the reaction of the block A and the diblock copolymer of B and C reacted well. 1 was obtained.

When the obtained triblock copolymer was subjected to thermal analysis by the above method, the glass transition temperature of block A, the melting temperature of block B, and the glass transition temperature of block C were observed separately. From the results, it was confirmed that the obtained polymer was a triblock copolymer.
Moreover, about the obtained triblock copolymer, the result of having measured the number average molecular weight of each block (Block A, Block B, and Block C) and the melting temperature of Block B by the said method is shown in Table 1. .

<Preparation of resin particle dispersion 1>
3000 parts by weight of the obtained triblock copolymer 1, 10000 parts by weight of ion-exchanged water, and 90 parts by weight of sodium dodecylbenzenesulfonate were charged into an emulsification tank of a high-temperature, high-pressure emulsifier (Cabitron CD1010). After being melted by heating to 130 ° C., the resin particle dispersion 1 was dispersed at 110 ° C. for 30 minutes at a flow rate of 3 L / m and 10000 rpm, passed through a cooling tank, solid content 30%, and the volume average particle diameter D50v of the resin particles was 115 nm. Produced.

<Synthesis of Triblock Copolymer 2>
(Synthesis of diblock copolymer 2 of block B and block C)
The diblock copolymer of block B and block C was used except that 51.2 parts of behenyl acrylate monomer were used instead of 83.1 parts of stearyl acrylate monomer, 3.9 parts of MBPAP, and styrene monomer of component C were changed to 122 parts. The diblock copolymer 2 was synthesized in the same manner as the polymer 1.

(Synthesis of polymer 2 to be block A)
A polymer 2 to be block A was obtained in the same manner as in the previous method except that the BPAEO used was changed to 25 mol parts, 25 mol parts of BPAPO, 24.3 mol parts of TPA, 10 mol parts of DSA, and 10 mol parts of FA. The OHV was 27.9 mgKOH / g, and it was confirmed that the terminal was almost OH group.

(Polymerization of diblock copolymer 2 and polymer 2 to be block A)
Obtained diblock copolymer 2: 173 parts, 22 parts of the block A polymer 2 obtained above were triblocked by the above method using 195 parts of toluene, 2.7 parts of DCC, and 0.2 part of DMAP. Copolymer 2 was synthesized.

  Table 1 shows the results obtained by measuring the number average molecular weight of each block and the melting temperature of block B for the obtained triblock copolymer by the above method.

<Preparation of resin particle dispersion 2>
Resin particle dispersion having a solid content of 30% and a resin particle volume average particle diameter D50v of 105 nm, except that triblock copolymer 2 was used instead of triblock copolymer 1, as in resin particle dispersion 1. Liquid 2 was prepared.

<Synthesis of Triblock Copolymer 3>
(Synthesis of diblock copolymer 3 of block B and block C)
Similar to the synthesis of the triblock copolymer 1, 16.6 parts of stearyl acrylate monomer and 66.4 parts of behenyl acrylate monomer are used in place of 83.0 parts of stearyl acrylate monomer, and 3.1 parts of MBPAP is added. The diblock copolymer 3 was synthesized in the same manner as the diblock copolymer 1 of the block B and the block C except that the styrene monomer of C was changed to 98 parts.

(Polymerization of diblock copolymer 3 and polymer 2 to be block A)
Obtained diblock copolymer 3: 181 parts and 17 parts of the block A polymer 2 obtained above by triblock copolymer by the above method using 195 parts of toluene, 2.2 parts of DCC and 0.2 part of DMAP. Polymer 3 was synthesized.

  Table 1 shows the results obtained by measuring the number average molecular weight of each block and the melting temperature of block B for the obtained triblock copolymer by the above method.

<Preparation of resin particle dispersion 3>
Resin particle dispersion having a solid content of 30% and a resin particle volume average particle diameter D50v of 108 nm, as in the resin particle dispersion 1, except that the triblock copolymer 3 was used instead of the triblock copolymer 1 Liquid 3 was prepared.

<Synthesis of Triblock Copolymer 4>
(Synthesis of diblock copolymer 4 of block B and block C)
Similar to the synthesis of triblock copolymer 1, 10.3 parts of stearyl acrylate monomer and 41.2 parts of behenyl acrylate monomer were used instead of 83.0 parts of stearyl acrylate monomer, and 3.9 parts of MBPAP, component A diblock copolymer 4 was synthesized in the same manner as the diblock copolymer 1 of block B and block C, except that the styrene monomer of C was changed to 146 parts of styrene and 3.7 parts of acrylic acid.

(Polymerization of diblock copolymer 4 and polymer 1 to be block A)
Triblock by the above method using 205.5 parts of the obtained diblock copolymer 4 and 28 parts of the obtained block A polymer 1 using 233 parts of toluene, 2.7 parts of DCC and 0.2 part of DMAP. Block copolymer 4 was synthesized.

  Table 1 shows the results obtained by measuring the number average molecular weight of each block and the melting temperature of block B for the obtained triblock copolymer by the above method.

<Preparation of resin particle dispersion 4>
Resin particle dispersion having a solid content of 30% and a resin particle volume average particle diameter D50v of 120 nm, except that triblock copolymer 4 was used instead of triblock copolymer 1, as in resin particle dispersion 1. Liquid 4 was prepared.

<Synthesis of Triblock Copolymer 5>
(Synthesis of diblock copolymer 5 of block B and block C)
Similar to the synthesis of the triblock copolymer 1, 10 parts of stearyl acrylate monomer and 40 parts of behenyl acrylate monomer are used instead of 83.0 parts of stearyl acrylate monomer, 6.3 parts of MBPAP, and styrene monomer of component C The diblock copolymer 5 was synthesized in the same manner as the diblock copolymer 1 of the block B and the block C except that was changed to 215 parts.

(Synthesis of polymer 3 to be block A)
A polymer 3 to be block A was obtained in the same manner as in the previous method, except that the BPAEO used was changed to 25 mole parts, 25 mole parts of BPAPO, 27.3 mole parts of TPA, 10 mole parts of DSA, and 10 mole parts of FA. The OHV was 13.0 mg KOH / g, and it was confirmed that the terminal was almost OH group.

(Polymerization of diblock copolymer 5 and polymer 3 to be block A)
Diblock copolymer 5 obtained: 265 parts, 73 parts of the block A polymer 3 obtained above were added to the triblock copolymer by the above method using 338 parts of toluene, 4.4 parts of DCC and 0.3 part of DMAP. Polymer 5 was synthesized.

  Table 1 shows the results obtained by measuring the number average molecular weight of each block and the melting temperature of block B for the obtained triblock copolymer by the above method.

<Adjustment of resin particle dispersion 5>
Resin particle dispersion having a solid content of 30% and a resin particle volume average particle diameter D50v of 113 nm, except that triblock copolymer 5 is used instead of triblock copolymer 1, as in resin particle dispersion 1. Liquid 5 was produced.

<Synthesis of Triblock Copolymer 6>
(Synthesis of diblock copolymer 6 of block B and block C)
Similar to the synthesis of the triblock copolymer 1, 18 parts of stearyl acrylate monomer and 72 parts of behenyl acrylate monomer were used instead of 83.0 parts of stearyl acrylate monomer, and 2.7 parts of MBPAP and styrene monomer of component C were used. The diblock copolymer 6 was synthesized in the same manner as the diblock copolymer 1 of the block B and the block C except that was changed to 36 parts.

(Polymerization of diblock copolymer 6 and polymer 2 to be block A)
126 parts of the obtained diblock copolymer 6 and 15 parts of the block A polymer 2 obtained above were triblock copolymerized by the above method using 141 parts of toluene, 1.9 parts of DCC, and 0.1 part of DMAP. Polymer 6 was synthesized.

  Table 2 shows the results of measuring the number average molecular weight of each block and the melting temperature of block B by the above-described method for the obtained triblock copolymer.

<Adjustment of resin particle dispersion 6>
Resin particle dispersion having a solid content of 30% and a resin particle volume average particle diameter D50v of 106 nm, except that triblock copolymer 6 was used instead of triblock copolymer 1, as in resin particle dispersion 1. Liquid 6 was produced.

<Synthesis of Triblock Copolymer 7>
(Synthesis of diblock copolymer 7 of block B and block C)
Similar to the synthesis of the triblock copolymer 1, 18 parts of stearyl acrylate monomer and 72 parts of behenyl acrylate monomer were used instead of 83.0 parts of stearyl acrylate monomer, and 2.7 parts of MBPAP and a styrene monomer of component C were used. The diblock copolymer 7 was synthesized in the same manner as the diblock copolymer 1 of the block B and the block C, except that was changed to 29 parts.

(Polymerization of diblock copolymer 7 and polymer 2 to be block A)
Diblock copolymer 7: 119 parts, 14 parts of the block A polymer 2 obtained above were triblocked by the above method using 133 parts of toluene, 1.9 parts of DCC, and 0.1 part of DMAP. Copolymer 7 was synthesized.

  Table 2 shows the results of measuring the number average molecular weight of each block and the melting temperature of block B by the above-described method for the obtained triblock copolymer.

<Preparation of resin particle dispersion 7>
Resin particle dispersion having a solid content of 30% and a resin particle volume average particle size D50v of 110 nm, except that triblock copolymer 7 was used instead of triblock copolymer 1, Liquid 7 was produced.

<Synthesis of Triblock Copolymer 8>
(Synthesis of diblock copolymer 8 of block B and block C)
Similar to the synthesis of the triblock copolymer 1, 10 parts of stearyl acrylate monomer and 40 parts of behenyl acrylate monomer are used in place of 83.0 parts of stearyl acrylate monomer, 7.7 parts of MBPAP, and styrene monomer of component C The diblock copolymer 8 was synthesized in the same manner as the diblock copolymer 1 of the block B and the block C except that was changed to 314 parts.

(Polymerization of diblock copolymer 8 and polymer 3 to be block A)
Diblock copolymer 8: 364 parts, 90 parts of the block A polymer 3 obtained above were trimethylated by the above method using 454 parts of toluene, 5.4 parts of DCC, and 0.5 part of DMAP. Block copolymer 8 was synthesized.

  Table 2 shows the results of measuring the number average molecular weight of each block and the melting temperature of block B by the above-described method for the obtained triblock copolymer.

<Adjustment of resin particle dispersion 8>
Resin particle dispersion having a solid content of 30% and a resin particle volume average particle diameter D50v of 104 nm, except that triblock copolymer 8 was used instead of triblock copolymer 1, in the same manner as resin particle dispersion 1. Liquid 8 was produced.

<Synthesis of Triblock Copolymer 9>
(Synthesis of diblock copolymer 9 of block B and block C)
Similar to the synthesis of the triblock copolymer 1, 83 parts of hexadecyl acrylate was used instead of 83.0 parts of stearyl acrylate monomer, and 3.9 parts of MBPAP and the styrene monomer of component C were changed to 56.5 parts. Except that, diblock copolymer 9 was synthesized in the same manner as diblock copolymer 1 of block B and block C.

(Polymerization of diblock copolymer 9 and polymer 1 to be block A)
Obtained diblock copolymer 9: 139.5 parts, 29 parts of the block A polymer 1 obtained above were used with 168.5 parts of toluene, 2.7 parts of DCC, and 0.2 part of DMAP. Triblock copolymer 9 was synthesized by the above method.

  Table 2 shows the results of measuring the number average molecular weight of each block and the melting temperature of block B by the above-described method for the obtained triblock copolymer.

<Preparation of resin particle dispersion 9>
Resin particle dispersion having a solid content of 30% and a resin particle volume average particle diameter D50v of 123 nm, except that triblock copolymer 9 was used instead of triblock copolymer 1, as in resin particle dispersion 1. Liquid 9 was prepared.

<Synthesis of Triblock Copolymer 10>
(Synthesis of diblock copolymer 10 of block B and block C)
Similar to the synthesis of the triblock copolymer 1, 16.6 parts of stearyl acrylate monomer and 66.4 parts of behenyl acrylate monomer were used instead of 83.0 parts of stearyl acrylate monomer, and 4.2 parts of MBPAP, component A diblock copolymer 10 was synthesized in the same manner as the diblock copolymer 1 of the block B and the block C except that 57 parts of MMA monomer was used instead of the styrene monomer of C.

(Polymerization of diblock copolymer 10 and polymer 1 to be block A)
Obtained diblock copolymer 10: 140 parts, 30 parts of the block A polymer 1 obtained as described above were triturated by the above method using 170 parts of toluene, 3.0 parts of DCC, and 0.2 part of DMAP. Block copolymer 10 was synthesized.

  Table 2 shows the results of measuring the number average molecular weight of each block and the melting temperature of block B by the above-described method for the obtained triblock copolymer.

<Adjustment of resin particle dispersion 10>
Resin particle dispersion having a solid content of 30% and a resin particle volume average particle diameter D50v of 119 nm, except that triblock copolymer 10 was used instead of triblock copolymer 1, Liquid 10 was produced.

<Adjustment of Triblock Copolymer 11: Mixture of Triblock Resin and Normal Polyester>
(Synthesis of polyester resin 4)
Polyester having a number average molecular weight of 23,570 in the same manner as the method of polymer 1 in the previous period except that the BPAEO used is changed to 25 mol parts, BPAPO 25 mol parts, TPA 29.0 mol parts, DSA 10 mol parts, FA 10 mol parts. Resin 4 was obtained.

  30 parts of the obtained polyester resin 4 and 70 parts of the triblock copolymer 3 obtained in Example 3 at a temperature of 100 ° C. using a table type kneader (PBV-01 manufactured by Irie Trading Co., Ltd.) After performing melt mixing, the mixture was cooled to 25 ° C. to obtain a triblock copolymer resin 11.

<Adjustment of resin particle dispersion 11>
Resin particles having a solid content of 30% and a volume average particle diameter D50v of the resin particles of 121 nm are the same as in the resin particle dispersion 1 except that the triblock copolymer resin 11 is used instead of the triblock copolymer 1 Dispersion 11 was prepared.

<Synthesis of Comparative Resin 1>
100 parts of a solution in which 83 parts of behenyl acrylate monomer and 5.8 parts of MBPAP are dissolved in 83 parts of toluene are added to a glass vessel equipped with a reflux condenser, a nitrogen inlet tube, and a stirrer. After mixing, the temperature was raised to 110 ° C. and the behenyl acrylate monomer was polymerized for 8 hours to obtain an acrylate polymer.
The obtained acrylate polymer was purified by the same method as the purification of the diblock copolymer in the synthesis of the triblock copolymer 1, and then the polymer was dried. When the molecular weight of the polymer was measured by GPC after drying, the number average molecular weight was 5023, and the melting temperature was 60 ° C.
30 parts of the obtained resin was the previous period, and 70 parts of the polyester resin was melt-mixed at a temperature of 100 ° C. in a table type kneader in the same manner as in Example 11, and then cooled to 25 ° C. Comparative resin 1 was obtained by melt mixing polyester and polyester.

<Adjustment of resin particle dispersion 12>
A resin particle dispersion 11 having a solid content of 30% and a volume average particle diameter D50v of the resin particles of 116 nm is obtained in the same manner as in the resin particle dispersion 1, except that the comparative resin 1 is used instead of the triblock copolymer 1. Produced.

<Synthesis of Comparative Resin 2>
In a heat-dried two-necked flask, 94.3 mole parts of 1,12-dodecanedicarboxylic acid, 100 mole parts of 1,9-nonanediol, and 0.05 mole part of dibutyltin oxide were introduced, and nitrogen gas was introduced into the container. After maintaining the temperature in an inert atmosphere and raising the temperature, a copolycondensation reaction is carried out at 150 ° C. to 180 ° C. for 3 hours, and then gradually reduced in pressure to increase the weight of 1,12-dodecanedicarboxylic acid and 1,9-nonanediol. A condensate was synthesized. When the molecular weight of the obtained polycondensate was measured, the number average molecular weight was 6030, and its melting temperature was 70 ° C.
After 40 parts of the obtained polycondensate and 60 parts of the above polyester resin were melt-mixed at a temperature of 100 ° C. with a desktop kneader (PBV-01 manufactured by Irie Trading Co., Ltd.), the mixture was cooled to 25 ° C., Comparative resin 2 was obtained.

<Preparation of resin particle dispersion 13>
A resin particle dispersion 13 having a solid content of 30% and a resin particle volume average particle diameter D50v of 278 nm was obtained in the same manner as in the resin particle dispersion 1, except that the comparative resin 2 was used instead of the triblock copolymer 1. Produced.

<Synthesis of Comparative Resin 3>
(Synthesis of polymer to be block B)
To a glass vessel equipped with a reflux condenser, a nitrogen inlet tube, and a stirrer, 100 parts of a solution in which 80 parts of stearyl acrylate monomer and 3.8 parts of MBPAP are dissolved in 80 parts of toluene are added, and the mixture is heated at 80 ° C. under a nitrogen stream. The polymer which becomes block B was obtained by mixing well and raising the temperature to 110 ° C. to polymerize the stearyl acrylate monomer for 8 hours.

(Polymerization of polymer to be block A and polymer to be block B)
80 parts of the resulting polymer to be block B and 31 parts of the block A polymer 1 obtained above were diblock copolymerized by the above method using 110 parts of toluene, 2.7 parts of DCC, and 0.1 part of DMAP. The combined resin was synthesized to obtain Comparative Resin 3.
Table 3 shows the results obtained by measuring the number average molecular weight of each block and the melting temperature of block B for the obtained diblock copolymer by the above method.

<Adjustment of resin particle dispersion 14>
A resin particle dispersion 14 having a solid content of 30% and a volume average particle diameter D50v of the resin particles of 124 nm is obtained in the same manner as in the resin particle dispersion 1, except that the comparative resin 3 is used instead of the triblock copolymer 1. Produced.

<Synthesis of Comparative Resin 4>
50 parts of the diblock copolymer of block A and block B obtained with the comparative resin 3 and the previous period, and 50 parts of polyester resin were melt-mixed at a temperature of 100 ° C. in a table type kneader in the same manner as in Example 11. Thereafter, the mixture was cooled to 25 ° C. to obtain a comparative resin 4 in which a crystalline polymer homopolymer and polyester were melt-mixed.

<Adjustment of resin particle dispersion 15>
A resin particle dispersion 15 having a solid content of 30% and a resin particle volume average particle diameter D50v of 120 nm was prepared in the same manner as in the resin particle dispersion 1, except that the comparative resin 4 was used instead of the triblock copolymer 1. Produced.

[Preparation of colorant dispersion]
Carbon black (Regal 330 Cabot) 45 parts by mass, ionic surfactant Neogen R (Daiichi Kogyo Seiyaku) 5 parts by mass, ion-exchanged water 200 parts by mass are mixed and dissolved, and homogenizer (IKA Ultra Tarrax) is used for 10 minutes. Dispersion was then performed using an optimizer to obtain a colorant dispersion having a solid content of 20% and a center particle size (volume average particle size) of 245 nm.

[Preparation of release agent dispersion]
Paraffin wax (manufactured by Nippon Seiki Co., Ltd., HNP0190) 45 parts by mass of ionic surfactant Neogen R (Daiichi Kogyo Seiyaku) and 200 parts by mass of ion-exchanged water are heated to 120 ° C., and pressure discharge type gorin homogenizer Dispersion treatment was performed to obtain a release agent dispersion having a solid content of 20% and a center particle size (volume average particle size) of 219 nm.

[Example 1]
500 parts by weight of the resin particle dispersion 1, 85 parts by weight of the colorant dispersion, 94 parts by weight of the release agent dispersion, 5 parts by weight of aluminum sulfate (manufactured by Wako Pure Chemical Industries, Ltd.), and sodium dodecylbenzenesulfonate 10 parts by mass, 50 parts by mass of 0.3 M nitric acid aqueous solution, and 500 parts by mass of ion-exchanged water were accommodated in a round stainless steel flask, and a homogenizer (Ultra Turrax T-50 manufactured by IKA) was used. After using and dispersing, the mixture was heated to 50 ° C. with stirring in an oil bath for heating. After maintaining at 50 ° C. and confirming that aggregated particles having a volume average particle size of about 5.5 μm were formed, 233 parts by mass of the additional resin particle dispersion 1 was added, and further maintained for 30 minutes.

  Subsequently, a 1N aqueous sodium hydroxide solution was added until pH 8.0 was reached, and then the mixture was heated to 85 ° C. and kept for 1 hour while stirring was continued. The reaction product was filtered, washed with ion exchange water, and then dried using a vacuum dryer to obtain toner particles.

  Then, 1.5 parts by mass of hydrophobic silica (manufactured by Cabot, TS720) was added to 50 parts by mass of the obtained toner particles, and blended with a sample mill to obtain a toner.

[Example 2 to Example 11]
Toner particles were obtained in the same manner as in Example 1, except that the resin particle dispersion 2 to the resin particle dispersion 11 were used instead of the resin particle dispersion 1.
Then, 1.5 parts by mass of hydrophobic silica (manufactured by Cabot, TS720) was added to 50 parts by mass of the obtained toner particles, and blended with a sample mill to obtain a toner.

[Comparative Example 1 to Comparative Example 4]
Toner particles were obtained in the same manner as in Example 1 except that the resin particle dispersion liquid 12 to the resin particle dispersion liquid 15 were used instead of the resin particle dispersion liquid 1, respectively.
Then, 1.5 parts by mass of hydrophobic silica (manufactured by Cabot, TS720) was added to 50 parts by mass of the obtained toner particles, and blended with a sample mill to obtain a comparative toner.

[Evaluation]
(Development of developer)
Using the toner obtained in each example and the comparative toner, a developer was prepared as follows.
First, 100 parts of ferrite particles (manufactured by Powder Tech Co., Ltd., average particle size 50 μm) and 1.5 parts of methyl methacrylate resin (manufactured by Mitsubishi Rayon Co., Ltd., molecular weight 95,000, component ratio of 10,000 or less) are added together with 500 parts of toluene. Place in a pressure kneader and stir and mix at 25 ° C. for 15 minutes, then raise the temperature to 70 ° C. while mixing under reduced pressure to distill off toluene, then cool and classify using a 105 μm sieve to obtain a resin-coated ferrite carrier. Obtained.
Then, the resin-coated ferrite carrier and toner were mixed to produce a developer having a toner concentration of 7% by mass.

(Characteristic evaluation)
Using the developer, toner was evaluated using a DocuPrint C2425 remodeling machine manufactured by Fuji Xerox Co., Ltd. This printer uses a blade cleaner for cleaning the transfer residual toner on the photoconductor. Moreover, plain paper (C2 paper manufactured by Fuji Xerox Co., Ltd.) was used as the transfer target. The obtained results are shown in Tables 1 to 3.

-Toner strength-
The toner strength was evaluated as follows.
After continuous printing of 3,000 solid images with an area ratio of 50%, the toner is crushed by the cleaning blade on the photosensitive member of the printer, and the toner filming (generation of film-like streaks due to the crushed toner) is visually and photosensitized. The residual toner on the body and the blade portion were confirmed by microscopic observation.
The evaluation criteria are as follows.
○: No filming and toner crushing is not observed.
Δ: No filming, but slight toner crushing at a level causing no practical problem is observed in the blade portion.
X: Filming due to toner crushing is observed on the photoreceptor, which is a practical problem.

-Aggregation in developer unit-
The aggregation in the developing unit was evaluated as follows.
The developer was idled for 1 hour without printing, and the presence or absence of toner aggregation was visually observed, and the developer was sampled and the presence or absence of toner aggregation was confirmed with a microscope.
The evaluation criteria are as follows.
○: Aggregation is hardly observed.
Δ: A level where no agglomeration is observed but a practical problem occurs.
X: Level at which significant aggregation is observed and there is a practical problem.

-Toner charging stability-
The toner charging stability was evaluated as follows.
The developer is weighed into a glass bottle with a lid, seasoned for 24 hours under high temperature and high humidity (temperature 28 ° C, humidity 85%) and low temperature and low humidity (temperature 10 ° C, humidity 15%). The charge amount (μc / g) of the toner after stirring and shaking for 5 minutes was measured with a blow-off charge amount measuring device.
The evaluation criteria are as follows.
◯: The charge amount is 15 μC / g or more, and there is almost no difference in charge amount between the two environments.
Δ: The charge amount is 15 μC / g or more, but a slight difference due to the environment is observed, but there is no practical problem.
X: The charge amount is 15 μC / g or less, and the environmental difference is remarkably problematic.

-Low temperature fixability-
The low temperature fixability was evaluated as follows.
After fixing the toner on the fixing roll of the fixing machine from 80 ° C. to 200 ° C., fixing the image (40 mm × 50 mm 100% solid image) every 10 ° C. The temperature at which the image peeling at the eye part was observed and no image peeling occurred was defined as the minimum fixing temperature. Using this method, the lowest fixing temperature was used to evaluate its low temperature fixability.
The evaluation criteria are as follows.
○: Fixing at a fixing temperature of 80 ° C. to 120 ° C. Δ: When the fixing temperature is higher than 120 ° C. and not higher than 140 ° C. ×: When the fixing temperature is higher than 140 ° C.

-Image gloss unevenness-
Image gloss unevenness was evaluated as follows.
The image gloss uniformity was visually observed on the image fixed at + 30 ° C. from the lowest fixing temperature, and the following evaluation was performed.
The evaluation criteria are as follows.
◯: Level where image gloss is uniform and no problem △: Level where slight unevenness is observed but no problem for practical use ×: Level where image gloss is uneven and practically problematic

-Fixed image strength-
The fixed image strength was evaluated as follows.
The image at the lowest fixing temperature was subjected to a pencil scratch test based on JIS K5400, and the following determination was made based on the pencil hardness.
○: Pencil hardness H or higher and no problem at all.
Δ: Some image defects occur when the pencil hardness is H, but if it is less than H, defects do not occur and there is no practical problem.
X: An image defect was caused at a pencil hardness of less than H, which was a practically problematic level.

-Fixed image storage stability-
The fixed image storability was evaluated as follows.
Two recording papers on which a fixed image was formed at the lowest fixing temperature were left to stand for 7 days in a state in which a load of 100 g / cm ² was applied in an environment of a temperature of 60 ° C. and a humidity of 85% with the image surfaces overlapped. The superimposed images were peeled off, the images were fused between the recording papers, and the presence or absence of transfer in the non-image area was visually observed and evaluated according to the following evaluation criteria.
・ ○: No problem in image storability ・ △: Some change was observed but no problem in practical use ・ ×: Large change was observed and practical use was not possible

  The above evaluation results are shown in Tables 1 to 3. In Tables 1 to 3, “Ac” indicates acrylate, “St” indicates styrene, “AA” indicates acrylic acid, and “−” indicates that the component is not used or is a target value. Indicates that does not exist.

  From the above results, it can be seen that both the toner strength and the fixed image strength are better in this embodiment than in the comparative example.

1Y, 1M, 1C, 1K, 107 photoconductor (image carrier)
2Y, 2M, 2C, 2K, 108 Charging roller 3Y, 3M, 3C, 3K Laser beam 3, 110 Exposure device 4Y, 4M, 4C, 4K, 111 Developing device (developing means)
5Y, 5M, 5C, 5K Primary transfer rollers 6Y, 6M, 6C, 6K, 113 Photoconductor cleaning device (cleaning means)
8Y, 8M, 8C, 8K Developer cartridge 10Y, 10M, 10C, 10K Unit 20 Intermediate transfer belt 22 Drive roller 24 Support roller 26 Secondary transfer roller (transfer means)
28, 115 Fixing device (fixing means)
30 Intermediate transfer member cleaning device 112 Transfer device 116 Mounting rail 117 Opening 118 for static elimination exposure Opening 200 for exposure Process cartridge,
P, 300 Recording paper (transfer object)

Claims (9)

  An electrostatic image developing toner comprising a triblock copolymer obtained by block polymerization of an amorphous polyester polymer block A, a crystalline acrylate polymer block B, and an amorphous vinyl polymer block C in this order.   2. The electrostatic image developing toner according to claim 1, wherein the crystalline acrylate polymer block B has a number average molecular weight of 10% to 60% with respect to the number average molecular weight of the entire triblock copolymer.   The electrostatic image developing toner according to claim 1, wherein the crystalline acrylate polymer block B includes a repeating unit derived from at least one of stearyl acrylate and behenyl acrylate.   4. The electrostatic charge image developing toner according to claim 1, wherein the amorphous vinyl polymer block C includes a repeating unit derived from at least one of styrene and a derivative thereof. 5.   An electrostatic charge image developer comprising the electrostatic charge image developing toner according to claim 1. The toner for developing an electrostatic charge image according to any one of claims 1 to 4, containing the toner,
A toner cartridge to be attached to and detached from the image forming apparatus. A developing means for accommodating the electrostatic charge image developer according to claim 5 and developing the electrostatic charge image formed on the image carrier as a toner image by the electrostatic charge image developer,
A process cartridge attached to and detached from the image forming apparatus. An image carrier,
Charging means for charging the image carrier;
An electrostatic charge image forming means for forming an electrostatic charge image on the surface of the charged image carrier;
Developing means for containing the electrostatic charge image developer according to claim 5 and developing the electrostatic charge image formed on the image carrier as a toner image by the electrostatic charge image developer;
Transfer means for transferring a toner image formed on the image carrier onto a transfer target;
Fixing means for fixing the toner image transferred onto the transfer medium;
An image forming apparatus comprising: A charging step for charging the image carrier;
An electrostatic charge image forming step of forming an electrostatic charge image on the surface of the charged image carrier;
A developing step of developing the electrostatic image formed on the image carrier as a toner image with the electrostatic image developer according to claim 5;
A transfer step of transferring a toner image formed on the image carrier onto a transfer target;
A fixing step of fixing the toner image transferred onto the transfer medium;
An image forming method comprising: