JP5954218B2 - Electrostatic image developing toner, electrostatic image developer, toner cartridge, developer 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 developer cartridge, a process cartridge, an image forming apparatus, and an image forming method.

  A method for visualizing image information through an electrostatic latent image (electrostatic image) such as electrophotography is currently used in various fields. Conventionally, in electrophotography, an electrostatic image is formed on a photosensitive member or electrostatic recording member using various means, and particles called toner are attached to the electrostatic image to develop the electrostatic image. A method is generally used in which a toner image (development image) is visualized through a plurality of steps of transferring the toner image onto the surface of a transfer medium and fixing it by heating or the like.

In recent years, the demand for energy saving has been increasing, and a technique for improving low-temperature fixability has been studied in order to reduce power consumption during toner fixing.
For example, Patent Document 1 discloses that a weight average molecular weight 3 × 10 containing a polyester block obtained by condensing an aliphatic diol and a dicarboxylic acid and a polyester block obtained by condensing an alicyclic diol and a dicarboxylic acid in the molecule. ^A resin composition for toner is disclosed, which is characterized by comprising a ^{3 to} 5 × 10 ⁴ polyester block copolymer as a main component.
Patent Document 2 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 a block copolymer. A block polyester composed of a non-crystalline polyester having a lower crystallinity than the block polyester, the block polyester comprising a crystalline block formed by condensing a diol component and a dicarboxylic acid component, and the crystalline block It has an amorphous block with low crystallinity, and the proportion of the external additive contained in the toner that is free from the surface of the toner particles is 0.1 to 5 wt%. Toner is disclosed.

In Patent Document 3, in a toner comprising a crystalline resin B having a crystalline block structure and an amorphous block structure and a weight average molecular weight of 10,000 to 50,000, and a resin A, the molecular weight of the resin A is set to be the same as that of the crystalline resin B. A toner is disclosed that has a molecular weight of at least twice the molecular weight of the amorphous block.
Patent Document 4 includes a polyester block copolymer having a crystalline polyester block and an amorphous polyester block, and a binder resin containing a polymer of an ethylenically unsaturated compound, and a flow tester applied pressure of 5 kgf / in cm ^2, the viscosity of the binding resin becomes 10 ⁴ Pa · s temperature T (P5) is not less 110 ° C. or higher, the flow tester applied pressure 300 kgf / cm ^2, the binder viscosity is 10 ⁴ Pa resin A toner for developing an electrostatic charge image is disclosed in which the temperature T (P300) at which s is 80 ° C. or lower and 30 ° C. ≦ T (P5) −T (P300) ≦ 80 ° C. is disclosed.

JP 2001-324832 A JP 2004-138920 A JP 2005-148554 A JP 2010-60651 A

  An object of the present invention is to provide a toner for developing an electrostatic image excellent in image strength and low-temperature fixability.

The above-described problems of the present invention have been solved by means described in the following <1> and <7> to <12>. It is described below together with <2> to <6> which are preferred embodiments.
<1> At least a polyester block copolymer is included, the polyester block copolymer has an amorphous block and a crystalline block, and both ends of the polyester block copolymer are amorphous blocks. An electrostatic charge image developing toner,
<2> The toner for developing an electrostatic charge image according to the above <1>, wherein the polyester block copolymer includes a polyester block copolymer in which the total number of amorphous blocks and crystalline blocks is 5 or more,
<3> The electrostatic image developing toner according to the above <1> or <2>, wherein the total amount of the crystalline blocks in the polyester block copolymer is 33% or more by weight.
<4> The electrostatic image developing toner according to any one of <1> to <3>, further comprising an amorphous polyester resin,
<5> The electrostatic image developing toner according to the above <4>, wherein the ratio of the polyester block copolymer to the amorphous polyester resin is in the range of 80:20 to 30:70 by weight.
<6> The electrostatic charge image according to any one of the above <1> to <5>, wherein the glass transition temperature (Tg) of the amorphous block in the polyester block polymer is 50 ° C. or higher. Developing toner,
<7> An electrostatic charge image developer comprising the electrostatic charge image developing toner according to any one of <1> to <6> above, and a carrier,
<8> A toner cartridge which is detachable from the image forming apparatus and contains the electrostatic charge image developing toner according to any one of <1> to <6> above,
<9> A developer cartridge containing the electrostatic charge image developer according to <7> above,
<10> a process cartridge comprising a developer holder that contains the electrostatic charge image developer according to <7> and holds and conveys the electrostatic charge image developer;
<11> An image carrier, a charging unit for charging the image carrier, an 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 A fixing unit for fixing an image, wherein the developer is the toner for developing an electrostatic charge image according to any one of <1> to <6> or the static image according to <7>. An image forming apparatus which is a charge image developer;
<12> A latent image forming step for forming an electrostatic latent image on the surface of the image carrier, and development for forming the toner image by developing the electrostatic latent image formed on the surface of the image carrier with a developer containing toner. And a fixing step of fixing the toner image transferred to the surface of the transfer medium, wherein the developer includes the above <1> to <6> An image forming method using the electrostatic image developing toner according to any one of 6> or the electrostatic image developer according to <7> above.

According to the invention described in <1> above, it is possible to provide a toner for developing an electrostatic charge image that is superior in image strength and low-temperature fixability as compared with the case where the present configuration is not provided.
According to the invention described in the above <2>, the static block having excellent low-temperature fixability as compared with the case of not including the polyester block copolymer in which the total number of the amorphous blocks and the crystalline blocks is 5 or more. A toner for developing a charge image can be provided.
According to the invention described in the above <3>, the electrostatic charge image having excellent low-temperature fixability as compared with the case where the total amount of the crystalline blocks in the polyester block copolymer is less than 33% by weight. A developing toner can be provided.
According to the invention described in <4> above, it is possible to provide a toner for developing an electrostatic image that is superior in image strength and low-temperature fixability as compared with a case where an amorphous polyester resin is not further included.
According to the invention described in <5> above, the charging characteristics are higher than when the ratio of the polyester block copolymer to the amorphous polyester is outside the range of 80:20 to 30:70 by weight. It is possible to provide a toner for developing an electrostatic image excellent in the above.
According to the invention described in <6> above, the image strength is more excellent as compared with the case where any of the glass transition temperatures (Tg) of the amorphous blocks in the polyester block polymer is less than 50 ° C. In addition, a toner for developing an electrostatic image can be provided.
According to the invention described in <7> above, it is possible to provide an electrostatic image developer excellent in image strength and low-temperature fixability as compared with the case where the present configuration is not provided.
According to the invention described in <8> above, a toner cartridge is provided that contains toner for developing an electrostatic image that is superior in image strength and low-temperature fixability as compared with the case where the present configuration is not provided. can do.
According to the invention described in <9>, a developer cartridge containing an electrostatic charge image developer excellent in image strength and low-temperature fixability as compared with the case where the present configuration is not provided is provided. can do.
According to the invention described in <10>, there is provided a process cartridge containing an electrostatic charge image developer excellent in image strength and low-temperature fixability as compared with the case where the present configuration is not provided. be able to.
According to the invention described in <11> above, it is possible to provide an image forming apparatus excellent in image strength and low-temperature fixability as compared with the case where the present configuration is not provided.
According to the invention described in <12> above, it is possible to provide an image forming method excellent in image strength and low-temperature fixability as compared with the case where the present configuration is not provided.

Hereinafter, the present embodiment will be described.
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.

(Static image developing toner)
The electrostatic image developing toner of the present embodiment (hereinafter also simply referred to as “toner”) includes at least a polyester block copolymer, and the polyester block copolymer includes an amorphous block and a crystalline block. And the terminal of the polyester block copolymer is an amorphous block.

The inventors of the present invention have prepared a polyester block having a non-crystalline (hereinafter also referred to as “non-crystalline”) block and a crystalline block, and the terminal of which is an amorphous block, in the toner for developing an electrostatic image. It has been found that by containing a polymer, a toner for developing an electrostatic image having excellent image strength (image strength) and low-temperature fixability can be obtained. The detailed mechanism of the obtained image strength and low temperature fixability is unknown, but in the case of a crystalline resin alone or a block polymer having a crystalline resin block at the end, intermolecular interaction between crystalline sites It is presumed that the strength is weak and sufficient strength cannot be obtained. On the other hand, in the case of a block polymer having an amorphous block at the terminal, it is presumed that an intermolecular interaction acts between the amorphous blocks and becomes stronger and sufficient image strength can be obtained. On the other hand, when the toner is melted, the crystalline resin block part melts, the effect of plasticizing the amorphous resin block part, the effect of dispersing the amorphous resin block part in the melted crystalline resin block, etc. It is assumed that fixability is achieved at a lower temperature.
Regarding the image strength, the interaction between the non-crystalline block sites in the block resin also occurs between the block polymer having the non-crystalline block site at the terminal and the non-crystalline resin. Since the strength is stronger than that of the block copolymer, it is presumed that a stronger image strength can be obtained with a toner containing a block polymer having an amorphous block site at the terminal and an amorphous resin.

<Polyester block copolymer>
The electrostatic image developing toner of the present embodiment contains a polyester block copolymer, the polyester block copolymer has an amorphous block and a crystalline block, and the terminal of the polyester block copolymer is A non-crystalline block. Hereinafter, such a block copolymer is also referred to as a “specific block copolymer”.

The specific block copolymer used in this embodiment has one or more crystalline blocks and two or more non-crystalline blocks because both ends are non-crystalline blocks.
Although the specific block copolymer contains a plurality of non-crystalline blocks, the plurality of non-crystalline blocks may be the same or different, and are not particularly limited. From the viewpoint of synthesis, it is preferable that any two or more non-crystalline blocks in the specific block copolymer are non-crystalline blocks having the same type of monomer unit.
Similarly, the specific block copolymer may contain a plurality of crystalline blocks, but the plurality of crystalline blocks may be the same or different, and is not particularly limited. From the viewpoint of synthesis, it is preferable that any two or more crystalline blocks in the specific block copolymer are crystalline blocks having the same type of monomer unit.
The crystalline block in the specific block copolymer is preferably a crystalline polyester block, and the non-crystalline block in the specific block copolymer is preferably a non-crystalline polyester block.

The specific block copolymer preferably has a structure in which a crystalline block and an amorphous block repeat each other.
The specific block copolymer is preferably a linear block copolymer, more preferably a block copolymer having a structure represented by the formula (1).
A (BA) _n BA (1)
In formula (1), each A independently represents an amorphous block, each B independently represents a crystalline block, and n represents an integer of 0 or more.
In the formula (1), n is preferably 0 to 10, more preferably 0 to 7, still more preferably 0 to 4, and particularly preferably 1 to 4. The above embodiment is more excellent in low-temperature fixability.
In addition, the toner for developing an electrostatic charge image according to the exemplary embodiment preferably includes a polyester block copolymer including a polyester block copolymer in which the total number of non-crystalline blocks and crystalline blocks is 5 or more. It is more preferable to include a polyester block copolymer in which the total number of blocks and crystalline blocks is 5 or more and 11 or less. The above embodiment is more excellent in low-temperature fixability.
Further, the toner for developing an electrostatic charge image according to the exemplary embodiment includes 50% by weight or more of a polyester block copolymer in which the total number of amorphous blocks and crystalline blocks is 5 or more with respect to the total weight of the polyester block copolymer. The polyester block copolymer preferably contains 50% by weight or more of a polyester block copolymer in which the total number of non-crystalline blocks and crystalline blocks is 5 or more and 11 or less. The above embodiment is more excellent in low-temperature fixability.

The total amount of the crystalline blocks in the specific block copolymer is preferably 25% or more by weight, more preferably 33% or more, still more preferably 33 to 80%, and more preferably 55 to 80%. % Is particularly preferred. The above embodiment is more excellent in low-temperature fixability.
There is no restriction | limiting in particular as a measuring method of content of the crystalline block in a specific block copolymer, or an amorphous block, What is necessary is just to measure by a well-known method. For example, a method of separating and analyzing the binder resin from the toner can be mentioned. As a specific separation method, a method in which a toner is dissolved in a solvent such as tetrahydrofuran and separated using preparative GPC can be considered. Furthermore, by using the ¹ H-NMR, ¹³ C-NMR, and mass spectrum of the resin separated in this way, the composition of the resin can be measured. From the comparison of the signal intensity, the block copolymer The ratio inside can be measured. In addition, by observing the chemical shift of ¹³ C-NMR (carbon nuclear magnetic resonance) at the bonding site between the crystalline block site and the amorphous block site, it is possible to confirm that the block copolymer is present. is there.

The glass transition temperature (Tg) of the amorphous block in the specific block copolymer is preferably 50 ° C or higher, more preferably 50 ° C or higher and 100 ° C or lower, and 50 ° C or higher and 90 ° C or lower. More preferably. Within the above range, the charging characteristics are excellent.
The melting temperature of the crystalline block in the specific block copolymer is preferably in the range of 40 ° C. or higher and 120 ° C. or lower, more preferably in the range of 50 ° C. or higher and 90 ° C. or lower, and 50 ° C. or higher and 75 ° C. or lower. More preferably, the temperature is in the range of ℃ or less. Within the above range, the storage stability of the toner and the storage stability of the toner image after fixing are excellent, and the low-temperature fixability is improved.
The glass transition temperature may be measured by a known method, for example, the method defined by ASTM D3418-82 (DSC method).
For the measurement of the melting temperature, a differential scanning calorimeter (DSC) was used, and the input compensated differential scanning calorimetry shown in JIS K-7121 when measuring from room temperature to 150 ° C. at a heating rate of 10 ° C. per minute. It can be determined as the melting peak temperature.

The weight average molecular weight (Mw) of the specific block copolymer is preferably 10,000 or more and 150,000 or less, more preferably 20,000 or more and 100,000 or less, and 25,000 or more and 80,000. More preferably, it is as follows. In the above embodiment, the low-temperature fixability is excellent and the solubility during the synthesis reaction is excellent, so that the synthesis is easy.
The number average molecular weight (Mn) of the specific block copolymer is preferably 5,000 or more and 75,000 or less, and more preferably 10,000 or more and 40,000 or less. In the above embodiment, the low-temperature fixability is excellent and the solubility during the synthesis reaction is excellent, so that the synthesis is easy.

The number average molecular weight of the amorphous block in the specific block copolymer is preferably 1,000 or more and 20,000 or less, more preferably 1,500 or more and 10,000 or less, and 1,500 or more and 4 or less. More preferably, it is 1,000 or less. The above embodiment is more excellent in low-temperature fixability.
Further, the number average molecular weight of the crystalline block in the specific block copolymer is preferably 1,500 or more and 15,000 or less, more preferably 1,500 or more and 10,000 or less, and 1,500 or more. More preferably, it is 7,500 or less. The above embodiment is more excellent in low-temperature fixability.

Here, the measurement of the number average molecular weight (Mn) of the resin was carried out by calculating the acid value and the hydroxyl value of the resin terminal and calculating from those values.
That is, when the acid value of the resin is A (mg KOH / g) and the hydroxyl value is B (mg KOH / g),
Mn = 2 × 56.11 × 1000 ÷ (A + B)
As the number average molecular weight (Mn).
The acid value was determined by dissolving the resin in tetrahydrofuran and titrating with an automatic potentiometric titrator in accordance with JIS K2501-2003 method.
Meanwhile, according to JIS K0070 method, the hydroxyl value is determined by heating and dissolving the resin in pyridine / acetic anhydride to acetylate the hydroxyl group and titrate the acetic anhydride that was not used for acetylation with sodium hydroxide. Asked.
The weight average molecular weight (Mw) is measured by using the Mw / Mn ratio obtained using gel permeation chromatography (GPC) and multiplying the number average molecular weight described above by the Mw / Mn ratio obtained by GPC. did. Gel permeation chromatography (GPC) is determined using a polystyrene standard. As the GPC, Tosoh Co., Ltd. HLC-8120 GPC system, TSK guardcolumn Super H-H, and TSKgel SuperHM-H are connected in series. And measured at a sample concentration of 0.5% by weight using tetrahydrofuran medium at 40 ° C. and 0.6 mm / min, and analyzed and determined using software attached to the system. The polystyrene standard is “polystyrene standard sample TSK standard” manufactured by Tosoh Corporation: “A-500”, “F-1”, “F-10”, “F-80”, “F-380”, Ten samples of “A-2500”, “F-4”, “F-40”, “F-128”, and “F-700” were used.

In the present embodiment, the “crystallinity” in the crystalline resin or the crystalline block means that the differential scanning calorimetry (DSC) has a clear endothermic peak, not a stepwise endothermic amount change. Specifically, it means that the half-value width of the endothermic peak when measured at a heating rate of 10 ° C./min is within 15 ° C.
On the other hand, a resin or block having a half width exceeding 15 ° C. or a resin or block in which no clear endothermic peak is observed is an amorphous resin or an amorphous block.

  In a polyester resin (including a polyester block, the same applies hereinafter) that can be used in the present embodiment, the polyvalent carboxylic acid that can be used as the polycondensable monomer has two or more carboxyl groups in one molecule. It is a compound to contain. Among these, dicarboxylic acid is a compound containing two carboxyl groups in one molecule. For example, oxalic acid, glutaric acid, succinic acid, maleic acid, adipic acid, β-methyladipic acid, azelaic acid, sebacic acid, Nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, fumaric acid, citraconic acid, diglycolic acid, cyclohexane-3,5-diene-1,2-carboxylic acid, hexahydroterephthalic acid, malonic acid, pimeline Acid, phthalic acid, isophthalic acid, terephthalic acid, tetrachlorophthalic acid, chlorophthalic acid, nitrophthalic acid, p-carboxyphenylacetic acid, p-phenylenediacetic acid, m-phenylenediglycolic acid, p-phenylenediglycolic acid, o- Phenylene diglycolic acid, diphenylacetic acid, diph Nyl-p, p′-dicarboxylic acid, naphthalene-1,4-dicarboxylic acid, naphthalene-1,5-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, anthracene dicarboxylic acid, cyclohexanedicarboxylic acid and the like can be mentioned. . Examples of the polyvalent carboxylic acid other than dicarboxylic acid include trimellitic acid, pyromellitic acid, naphthalenetricarboxylic acid, naphthalenetetracarboxylic acid, pyrenetricarboxylic acid, and pyrenetetracarboxylic acid. Moreover, you may use what derived the carboxyl group of these carboxylic acid into the acid anhydride, mixed acid anhydride, acid chloride or ester.

  Moreover, the polyol which can be used for this embodiment is a compound which contains two or more hydroxyl groups in 1 molecule. Among these, the diol is a compound containing two hydroxyl groups in one molecule. For example, ethylene glycol, propylene glycol, butanediol, diethylene glycol, hexanediol, cyclohexanediol, octanediol, nonanediol, decanediol, dodecanediol, Polytetramethylene glycol, bisphenol A, bisphenol Z, hydrogenated bisphenol A, cyclohexanedimethanol, ethylene oxide (EO) and / or propylene oxide (PO) adducts of bisphenol A, EO and / or PO adducts of bisphenol Z, etc. Can be mentioned. Examples of polyols other than diols include glycerin, pentaerythritol, hexamethylol melamine, hexaethylol melamine, tetramethylol benzoguanamine, and tetraethylol benzoguanamine.

In this embodiment, a polycondensate of hydroxycarboxylic acid can be used. Hydroxycarboxylic acid is a compound having both a hydroxyl group and a carboxyl group in the molecule.
Examples of the hydroxycarboxylic acid include aromatic hydroxycarboxylic acids and aliphatic hydroxycarboxylic acids, but it is preferable to use aliphatic hydroxycarboxylic acids. Specific examples include hydroxyheptanoic acid, hydroxyoctanoic acid, hydroxydecanoic acid, hydroxyundecanoic acid, malic acid, citric acid, tartaric acid, mucoic acid, and lactic acid.
The polyester resin that can be used in the present embodiment can easily obtain an amorphous polyester resin or a crystalline polyester resin by a combination of these polycondensable monomers.

  As the polyvalent carboxylic 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, speric acid, azelaic acid, sebacic acid Maleic acid, fumaric acid, citraconic acid, itaconic acid, glutamic 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 or acid chlorides can be mentioned.

Examples of the polyol used for obtaining the crystalline polyester resin include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,4. , Butenediol, neopentyl glycol, 1,5-pentane glycol, 1,6-hexane glycol, 1,9-nonanediol, 1,12-dodecanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol , Dipropylene glycol, polyethylene glycol, polypropylene glycol and the like.
In addition, a crystalline polyester resin obtained by ring-opening polymerization of a cyclic monomer such as caprolactone is preferable because the crystal melting point is in the vicinity of 60 ° C. and is suitable for a toner.

As the polyvalent carboxylic acid used to obtain the non-crystalline polyester resin, among the polyvalent carboxylic acids described above, the dicarboxylic acids include phthalic acid, isophthalic acid, terephthalic acid, tetrachlorophthalic acid, chlorophthalic acid. Acid, nitrophthalic acid, p-carboxyphenylacetic acid, p-phenylenediacetic acid, m-phenylenediglycolic acid, p-phenylenediglycolic acid, o-phenylenediglycolic acid, diphenylacetic acid, diphenyl-p, p'-dicarboxylic acid And naphthalene-1,4-dicarboxylic acid, naphthalene-1,5-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, anthracene dicarboxylic acid, cyclohexanedicarboxylic acid, and tetrapropenyl succinic acid. Examples of the polyvalent carboxylic acid other than dicarboxylic acid include trimellitic acid, pyromellitic acid, naphthalenetricarboxylic acid, naphthalenetetracarboxylic acid, pyrenetricarboxylic acid, and pyrenetetracarboxylic acid. Moreover, you may use what derived the carboxyl group of these carboxylic acid into the acid anhydride, the acid chloride, or ester.
Among these, it is preferable to use terephthalic acid, its lower ester, diphenylacetic acid, cyclohexanedicarboxylic acid, tetrapropenyl succinic acid, its anhydride, and the like. The lower ester means an ester of an aliphatic alcohol having 1 to 8 carbon atoms.

In addition, as the polyol used for obtaining the amorphous polyester resin, among the above polyols, in particular, polytetramethylene glycol, bisphenol A, bisphenol Z, hydrogenated bisphenol A, cyclohexanedimethanol, EO of bisphenol A and It is preferable to use a PO adduct, EO of bisphenol Z, and / or a PO adduct.
Further, a polycondensate of hydroxycarboxylic acid can be used as the amorphous resin, and specific examples thereof include hydroxyheptanoic acid, hydroxyoctanoic acid, hydroxydecanoic acid, hydroxyundecanoic acid, and lactic acid. Of these, lactic acid is preferably used.

In addition, an amorphous resin or a crystalline resin can be easily obtained by combining the above polycondensable monomers.
In order to produce one type of polycondensation resin, each of the polyvalent carboxylic acid and polyol may be used alone or in combination of two or more, each of which may be used alone or in combination of two or more. You may use each. Moreover, when using hydroxycarboxylic acid in order to produce 1 type of polycondensation resin, 1 type may be used individually, 2 or more types may be used, and polyvalent carboxylic acid and a polyol may be used together.

  The polyester resin can be used in any combination of the monomer components described above, for example, polycondensation (Chemical Doujin), polymer experiment (polycondensation and polyaddition: Kyoritsu Publishing Co., Ltd.) and polyester. It can be synthesized using a conventionally known method described in Resin Handbook (edited by Nikkan Kogyo Shimbun Co., Ltd.), and can be used alone or in combination, such as a transesterification method or a direct polycondensation method. .

-Manufacturing method of block copolymer-
The method for producing the specific block copolymer having a crystalline block and an amorphous block is not particularly limited, but a crystalline block resin and an amorphous block resin are used, and the terminal functional groups of these resins are used. In consideration of reactivity, it is preferable to select from various methods. However, when manufacturing a specific block copolymer, it is necessary to consider so that a terminal may become an amorphous block.
Specifically, for example, the specific block copolymer can be produced by the following method.

First, there is a method in which an excessive amount of non-crystalline block resin is used with respect to the crystalline block resin. Each of the crystalline block resin and the non-crystalline block resin may have a group that reacts with each other at the terminal. For example, a combination of a carboxy group and a hydroxy group is preferable. Among these, an embodiment using a polyester resin for a crystalline block having two or more carboxy groups at the terminal and a polyester resin for a non-crystalline block having two hydroxy groups at the terminals is preferable. In addition, the reaction between the terminals may be performed in the presence of a known condensing agent and a catalyst. For example, a method of adding N, N′-dicyclohexylcarbodiimide and 4-dimethylaminopyridine is preferable. .
In addition, as a method of synthesizing a polyester resin having a carboxy group at the terminal, when synthesizing a polyester resin, the molar amount of the carboxy group of the acid component is used in excess of the molar amount of the hydroxy group of the alcohol component. The method of doing is mentioned.
Similarly, when synthesizing a polyester resin having a hydroxyl group at the terminal, the polyester resin is synthesized by using an excess amount of the hydroxyl group of the alcohol component rather than the molar amount of the carboxyl group of the acid component. The method of doing is mentioned.

Moreover, after making a binder react with crystalline resin for blocks, the method of making non-crystalline block resin react is mentioned preferably.
As the binder, various known binders can be used, for example, polyhydric carboxylic acid, polyhydric alcohol, polyfunctional isocyanate, polyfunctional epoxy compound, polyfunctional acid anhydride, etc. The addition reaction can be performed. Among these, polyfunctional acid anhydrides are preferable.
Specifically, for example, a polyfunctional acid anhydride is reacted with a crystalline block polyester resin having two or more hydroxy groups at the terminal, and the resulting crystalline block polyester resin having an acid anhydride group at the terminal is obtained. A method of reacting a polyester resin for an amorphous block with two hydroxy groups at the ends is preferred.

  In the above, the production of the ABA type block copolymer is mainly exemplified. However, for example, by changing the resin to a block copolymer as the raw material, other ABABA type block copolymers may be used. A specific block copolymer having a structure is easily produced.

<Amorphous polyester resin>
The toner for developing an electrostatic charge image of this embodiment preferably contains an amorphous polyester resin. In the above embodiment, the image strength and the low-temperature fixability are excellent.
The amorphous polyester resin may be contained singly or in combination of two or more.
There is no restriction | limiting in particular as an amorphous polyester resin, As the raw material, the polycondensable monomer mentioned above is mentioned preferably. Among them, as the polycarboxylic acid component, terephthalic acid and lower esters thereof, diphenylacetic acid, cyclohexanedicarboxylic acid, tetrapropenyl succinic acid, and anhydrides thereof are preferable, terephthalic acid, tetrapropenyl succinic acid, and anhydrides thereof are more preferable. As the polyol component, polytetramethylene glycol, bisphenol A, bisphenol Z, hydrogenated bisphenol A, cyclohexanedimethanol, EO and / or PO adduct of bisphenol A, EO and / or PO adduct of bisphenol Z are preferable, Hydrogenated bisphenol A, EO and / or PO adducts of bisphenol A are more preferred.
The glass transition temperature (Tg) of the amorphous polyester resin is preferably 50 ° C. or higher, more preferably 50 ° C. or higher and 100 ° C. or lower, and further preferably 50 ° C. or higher and 80 ° C. or lower. Within the above range, the charging characteristics are excellent.
The weight average molecular weight (Mw) of the amorphous polyester resin is preferably 5,000 or more and 150,000 or less, more preferably 8,000 or more and 100,000 or less, and 10,000 or more and 50,000. More preferably, it is as follows. In the above embodiment, the low-temperature fixability is excellent and the solubility during the synthesis reaction is excellent, so that the synthesis is easy.

The ratio of the polyester block copolymer and the non-crystalline polyester resin in the electrostatic image developing toner of the present embodiment is preferably in the range of 90:10 to 20:80 by weight, and 80: The range of 20-30: 70 is more preferable, and the range of 45: 55-30: 70 is more preferable. Within the above range, the charging characteristics are excellent.
Further, the total content of the polyester block copolymer and the non-crystalline polyester resin in the toner for developing an electrostatic charge image of the exemplary embodiment is 90 to 100% by weight with respect to the total binder resin content in the toner. It is preferable that it is 95 to 100 weight%, and it is still more preferable that it is 100 weight%.

<Other binder resins>
In this embodiment, as the binder resin constituting the toner, in addition to the specific block copolymer and the amorphous polyester resin, other binder resins may be contained.
Other binder resins are not particularly limited, and specific examples include polystyrene, styrene butadiene based polymers, styrene acrylic polymers, and crystalline polyester resins. In addition, you may perform modification | denaturation of urethane, urea, and other epoxies. However, in consideration of compatibility during heating, a polyester resin is preferable.

The content of the binder resin (including the specific block copolymer and the non-crystalline polyester resin) in the toner of the exemplary embodiment is not particularly limited, but is 10 to 95% by weight based on the total weight of the toner. It is preferably 25 to 90% by weight, more preferably 45 to 85% by weight. Within the above range, the fixing property, the charging property and the like are excellent.
The specific block copolymer can be qualitatively and quantitatively determined by a known method after the specific block copolymer is isolated from the toner by various separation methods (filtration, liquid separation, reprecipitation, etc.).

<Colorant>
The toner for developing an electrostatic charge image of the present embodiment preferably contains a colorant for the purpose of coloring an image to be obtained.
There is no restriction | limiting in particular as a coloring agent used, A well-known coloring agent is mentioned, It can select suitably according to the objective. One colorant may be used alone, or two or more colorants of the same system may be mixed and used. Further, two or more kinds of different colorants may be mixed and used. Further, these colorants may be used after surface treatment.

  As the colorant to be used, pigments and dyes of various colors are used, and specific examples include the following. Examples of the black pigment include carbon black, copper oxide, manganese dioxide, aniline black, activated carbon, nonmagnetic ferrite, and magnetite. Examples of yellow pigments include yellow lead, zinc yellow, yellow iron oxide, cadmium yellow, chrome yellow, Hansa yellow, Hansa yellow 10G, benzidine yellow G, benzidine yellow GR, selenium yellow, quinoline yellow, permanent yellow NCG, and the like. it can.

Examples of the orange pigment include red mouth yellow lead, molybdenum orange, permanent orange GTR, pyrazolone orange, Vulcan orange, benzidine orange G, indanthrene brilliant orange RK, indanthrene brilliant orange GK and the like. Red pigments include Bengala, cadmium red, red lead, mercury sulfide, watching red, permanent red 4R, risor red, brilliant carmine 3B, brilliant carmine 6B, pyrazolone red, rhodamine lake B, lake red C, rose bengal and eosin red. And alizarin lake.
Examples of blue pigments include bitumen, cobalt blue, alkali blue lake, Victoria blue lake, fast sky blue, indanthrene blue BC, ultramarine blue, phthalocyanine blue, and phthalocyanine green. Examples of purple pigments include manganese purple, fast violet B, and methyl violet lake.
Examples of the green pigment include chromium oxide, chromium green, pigment green B, malachite green lake, and final yellow green G.
Examples of white pigments include zinc white, titanium oxide, antimony white, and zinc sulfide. Examples of extender pigments include barite powder, barium carbonate, clay, silica, white carbon, talc, and alumina white.

  Examples of the dye include various dyes such as basic, acidic, dispersed, and direct dyes, such as nigrosine, methylene blue, rose bengal, and quinoline yellow.

  With respect to these colorants, for example, a dispersion of colorant particles can be prepared using a media type dispersing machine such as a rotary shearing homogenizer, a ball mill, a sand mill, or an attritor, or a high-pressure opposed collision type dispersing machine. Further, these colorants can be dispersed in an aqueous system by a homogenizer using a polar surfactant.

  Further, the colorant used in the toner of the exemplary embodiment is selected from the viewpoints of hue angle, saturation, brightness, weather resistance, light resistance, OHP permeability, and dispersibility in the toner. The colorant is preferably 0.1 to 40 parts by weight, particularly 0.5 to 20 parts by weight, based on the total solid weight of the toner, in order to ensure color developability at the time of fixing. preferable. However, when a magnetic material is used as the black colorant, it is preferably added in the range of 12 to 48% by weight, and more preferably in the range of 15 to 40% by weight.

  Further, the center diameter (median diameter) of the colorant particles contained in the toner is preferably in the range of 100 nm to 330 nm, and more preferably in the range of 100 nm to 200 nm. By setting the center diameter within such a range, it is possible to ensure transparency and color developability when an image is formed on the OHP. The center diameter of the colorant particles is measured with a laser diffraction particle size distribution analyzer (LA-700, manufactured by Horiba, Ltd.).

  In addition, each color toner such as yellow toner, magenta toner, cyan toner, and black toner can be obtained by appropriately selecting the type of the colorant.

<Release agent>
The electrostatic image developing toner of the present embodiment preferably contains a release agent.
The release agent is generally used for the purpose of improving release properties. Specific examples of the release agent include low molecular weight polyolefins such as polyethylene, polypropylene, and polybutene; silicones having a softening point by heating; fatty acid amides such as oleic acid amide, erucic acid amide, ricinoleic acid amide, and stearic acid amide Plant waxes such as carnauba wax, rice wax, candelilla wax, tree wax, jojoba oil; animal waxes such as beeswax; montan wax, ozokerite, ceresin, paraffin wax, microcrystalline wax, Fischer-Tropsch wax, etc. Mineral / petroleum waxes; ester waxes such as fatty acid esters, montanic acid esters, and carboxylic acid esters. In this embodiment, these mold release agents may be used individually by 1 type, and may use 2 or more types together.

This is dispersed in water with a polymer electrolyte such as an ionic surfactant, a polymer acid or a polymer base, heated to a temperature higher than the melting point, and a homogenizer or pressure discharge type disperser (Gorin homogenizer, The release agent dispersion used in the aggregated particle forming step of adjusting the aggregated particle dispersion can be obtained by dispersing the particles in a fine particle shape having a diameter of 1 μm or less with Gorin Co., Ltd. In addition, the particle diameter of the obtained release agent dispersion liquid can be measured, for example with a laser diffraction type particle size distribution measuring apparatus (LA-700, manufactured by Horiba, Ltd.).
The addition amount of the release agent is preferably 0.5 to 50% by weight, more preferably 1 to 30% by weight, and 5 to 15% by weight with respect to the total amount of toner particles. Is more preferable.

<Other ingredients>
Other components that can be used in the electrophotographic toner of the present embodiment are not particularly limited and may be appropriately selected depending on the purpose. For example, known components such as inorganic particles, organic particles, internal additives, charge control agents, and the like are known. Various additives etc. are mentioned.

Inorganic particles are generally used for the purpose of improving the fluidity of toner.
Examples of inorganic particles include silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, silica sand, clay, mica, wollastonite, diatomaceous earth, cerium chloride, Examples thereof include particles such as bengara, chromium oxide, cerium oxide, antimony trioxide, magnesium oxide, zirconium oxide, silicon carbide, and silicon nitride. Among these, silica particles are preferable, and silica particles that have been hydrophobized are particularly preferable.

  The average primary particle diameter (number average particle diameter) of the inorganic particles is preferably in the range of 1 to 1,000 nm, and the addition amount (external addition) is 0.01 to 20 with respect to 100 parts by weight of the toner. A range of parts by weight is preferred.

  Organic particles are generally used for the purpose of improving cleaning properties, transfer properties, and sometimes charging properties. Examples of the organic particles include particles such as polystyrene, polymethyl methacrylate, polyvinylidene fluoride, and polystyrene-acrylic copolymer.

Examples of the internal additive include metals such as ferrite, magnetite, reduced iron, cobalt, nickel and manganese, alloys, and magnetic materials such as compounds containing these metals.
The charge control agent is generally used for the purpose of improving the chargeability. Examples of the charge control agent include salicylic acid metal salts, metal-containing azo compounds, nigrosine and quaternary ammonium salts.

The toner base particles used in the exemplary embodiment are not particularly limited by the production method, and a known method can be used. Specific examples include the following methods.
The production of the toner base particles is obtained by, for example, a kneading and pulverizing method in which a binder resin, a colorant, and a release agent, a charge control agent, and the like are kneaded, pulverized, and classified, respectively; To change the shape of the particles by mechanical impact force or thermal energy; dispersion of emulsified binder resin, dispersion of colorant, and release agent, charge control agent, etc. if necessary An emulsion aggregation method in which toner particles are obtained by mixing, aggregating and heating and fusing the solution; emulsion polymerization of a polymerizable monomer of a binder resin, and a formed dispersion, a colorant, a release agent, and , An emulsion polymerization aggregation method to obtain toner particles by mixing with a dispersion such as a charge control agent, if necessary, and then fusing and heat-fusing; a polymerizable monomer for obtaining a binder resin, a colorant, A suspension polymerization method in which a release agent and, if necessary, a solution such as a charge control agent are suspended in an aqueous solvent for polymerization; Resin and a colorant, releasing agent, and dissolution suspension method and granulated with a solution such as a charge control agent is suspended in an aqueous solvent optionally; or the like can be used. In addition, a manufacturing method may be performed in which the toner base particles obtained by the above method are used as a core, and aggregated particles are further adhered and heat-fused to have a core-shell structure.
Among these, the toner of the exemplary embodiment is preferably a toner (emulsion aggregation toner) obtained by an emulsion aggregation method or an emulsion polymerization aggregation method.

  The toner base particles produced as described above preferably have a volume average particle diameter in the range of 2 to 8 μm, and more preferably in the range of 3 to 7 μm. When the volume average particle size is 2 μm or more, the fluidity of the toner is good and sufficient charging ability is imparted from the carrier, so that fogging in the background portion and density reproducibility are unlikely to occur. . Further, when the volume average particle size is 8 μm or less, the effect of improving the reproducibility, gradation and graininess of fine dots is good, and a high-quality image can be obtained. In addition, the said volume average particle diameter is measured with measuring machines, such as Coulter multisizer II (made by Beckman-Coulter company), for example.

  The toner base particles are preferably pseudo-spherical from the viewpoint of improving developability and transfer efficiency and improving image quality. The sphericity of the toner base particles can be expressed by using the shape factor SF1 of the following formula, but the average value (average shape factor) of the shape factor SF1 of the toner base particles used in this embodiment is 145. Is preferably in the range of 115 or more and less than 140, and more preferably in the range of 120 or more and less than 140. When the average value of the shape factor SF1 is less than 145, good transfer efficiency is obtained and the image quality is excellent.

In the above formula, ML represents the maximum length of each toner base particle, and A represents the projected area of each toner base particle.
The average value of the shape factor SF1 (average shape factor) is obtained by taking 1,000 toner images magnified 250 times from an optical microscope to an image analyzer (LUZEX III, manufactured by Nireco Corporation), and the maximum From the length and the projected area, the value of the SF1 can be obtained and averaged for each particle.

(Electrostatic image developer)
The toner for developing an electrostatic charge image of this embodiment is suitably used as an electrostatic charge image developer.
The electrostatic image developer of this embodiment is not particularly limited except that it contains the electrostatic image developing toner of this embodiment, and can take an appropriate component composition depending on the purpose. When used alone, the toner for developing an electrostatic image of this embodiment 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. Further, the carrier is not particularly defined as long as the above conditions are satisfied. 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 resin coating, 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 in terms of good production stability, cost, conductivity and the like. The type of carbon black is not particularly limited, but carbon black having a 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, or a silicone resin as a matrix resin. And a method of using a film-forming liquid 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, when the said resin particle and the said electroconductive particle are disperse | distributed to the said film, the above-mentioned effect is exhibited simultaneously.

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 electrical resistance (volume specific resistance) 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 weight of 4 kg 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 an electrostatic image developing system (electrophotographic system).
The image forming method of the present embodiment includes a latent image forming step of forming an electrostatic latent image on the surface of the image carrier, and developing the electrostatic latent image formed on the surface of the image carrier with a developer containing toner. A developing step for forming a toner image, a transferring step for transferring the toner image to the surface of the transfer target, and a fixing step for fixing the toner image transferred to the surface of the transfer target. The toner for developing an electrostatic charge image of the embodiment or the electrostatic charge image developer of the embodiment is used.
In addition, the image forming method of the present embodiment may further include a cleaning process for cleaning the electrostatic charge image developer remaining on the image carrier.

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 can be carried out by using a known image forming apparatus such as a copying machine or a facsimile machine.
The electrostatic latent image forming step is a step of forming an electrostatic latent image on an image carrier (photoconductor).
The developing step is a step of developing the electrostatic latent image with a developer layer on a developer holding member to form a toner image. The developer layer is not particularly limited as long as it contains the electrostatic image developing toner of this embodiment.
The transfer step is a step of transferring the toner image onto a transfer target. Examples of the transfer medium in the transfer process include an intermediate transfer medium and a recording medium such as paper.
In the fixing step, for example, there is a method of forming a copy image by fixing the toner image transferred onto the transfer paper by a heating roller fixing device in which the temperature of the heating roller is set to a constant temperature.
The cleaning step is a step of cleaning the electrostatic charge image developer remaining on the image carrier.
In the image forming method of the present embodiment, it is more preferable that the cleaning step includes a step of removing the electrostatic charge image developer remaining on the image carrier with a cleaning blade.
As the recording medium, known media can be used, for example, paper used for electrophotographic copying machines, printers, OHP sheets, etc. For example, the surface of plain paper is made of resin, etc. Coated coated paper, art paper for printing, and the like can be suitably used.

  The image forming method of the present embodiment may further include a recycling step. The recycling step is a step of transferring the electrostatic image developing toner collected in the cleaning step to the 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. Further, the present invention may be applied to a recycling system that collects toner simultaneously with development.

(Image forming device)
The image forming apparatus according to this 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 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 holding member to the surface of the transferred body; and the transferred body Fixing means for fixing the toner image transferred on the surface, and the developer for developing an electrostatic image of the present embodiment or the electrostatic image developer of the present embodiment is used as the developer. . In addition, the image forming apparatus according to the present embodiment may further include a cleaning unit that cleans the image carrier.
The image forming apparatus of the present embodiment is not particularly limited as long as it includes at least the image carrier, the charging unit, the exposure unit, the developing unit, the transfer unit, and the fixing unit as described above. In addition, cleaning means, static elimination means, and the like may be included as necessary.
In the transfer unit, the transfer may be performed twice or more using an intermediate transfer member. Examples of the transfer medium in the transfer unit include an intermediate transfer medium and a recording medium such as paper.

The image carrier and each of the above-described units can preferably use the configurations described in the respective steps of the image forming method. As each of the above-described means, a known means in the image forming apparatus can be used. In addition, the image forming apparatus according to the present embodiment may include means and devices other than the above-described configuration. Further, the image forming apparatus according to the present embodiment may simultaneously perform a plurality of the above-described means.
Examples of the cleaning means for cleaning the electrostatic charge image developer remaining on the image holding member include a cleaning blade and a cleaning brush, and a cleaning blade is preferable.
Preferred examples of the cleaning blade material include urethane rubber, neoprene rubber, and silicone rubber.

(Toner cartridge, developer cartridge, and process cartridge)
The toner cartridge of this embodiment is a toner cartridge that contains at least the toner for developing an electrostatic charge image of this embodiment.
The developer cartridge of this embodiment is a developer cartridge that contains at least the electrostatic charge image developer of this embodiment.
The process cartridge of the present embodiment is a process cartridge including a developer holder that contains the electrostatic charge image developer of the present embodiment and holds and conveys the electrostatic charge image developer. The electrostatic latent image formed on the surface is developed with the electrostatic charge image developing toner or the electrostatic charge 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 cleaning means for removing the toner remaining on the surface of the image carrier, and the electrostatic charge image developing toner of this embodiment, or The process cartridge preferably contains at least the electrostatic charge image developer of the present 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.
The developer cartridge of the present embodiment is not particularly limited as long as it contains the electrostatic charge image developer containing the electrostatic charge image developing toner of the present embodiment. The developer cartridge is, for example, attached to and detached from an image forming apparatus including a developing unit, and includes the electrostatic image developer according to the present embodiment as a developer to be supplied to the developing unit. Is stored.
The developer cartridge may be a cartridge that stores toner and a carrier, or may be a cartridge that stores toner alone and a cartridge that stores a carrier separately.
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, although this embodiment is described in detail with examples, this embodiment is not limited in any way. In the following description, “parts” means “parts by weight” unless otherwise specified.

<Measurement of number average molecular weight (Mn) of resin>
The number average molecular weight (Mn) of the resin was determined by calculating the acid value and hydroxyl value of the resin terminal and calculating from those values.
That is, when the acid value of the resin is A (mg KOH / g) and the hydroxyl value is B (mg KOH / g),
Mn = 2 × 56.11 × 1000 ÷ (A + B)
The number average molecular weight (Mn) was calculated as
The acid value was determined by dissolving the resin in tetrahydrofuran and titrating with an automatic potentiometric titrator in accordance with JIS K2501-2003 method.
Meanwhile, according to JIS K0070 method, the hydroxyl value is determined by heating and dissolving the resin in pyridine / acetic anhydride to acetylate the hydroxyl group and titrate the acetic anhydride that was not used for acetylation with sodium hydroxide. Asked.

<Measurement of weight average molecular weight (Mw) of resin>
The weight average molecular weight (Mw) of the resin is calculated by using the Mw / Mn ratio obtained using gel permeation chromatography (GPC) and multiplying the aforementioned number average molecular weight by the Mw / Mn ratio obtained by GPC. did. Gel permeation chromatography (GPC) is determined using a polystyrene standard. As the GPC, Tosoh Co., Ltd. HLC-8120 GPC system, TSK guardcolumn Super H-H, and TSKgel SuperHM-H are connected in series. The sample was measured at 40 ° C. and 0.6 mm / min using a tetrahydrofuran medium at a sample concentration of 0.5% by weight, and was analyzed and determined using software attached to the system. The polystyrene standard is “polystyrene standard sample TSK standard” manufactured by Tosoh Corporation: “A-500”, “F-1”, “F-10”, “F-80”, “F-380”, Ten samples of “A-2500”, “F-4”, “F-40”, “F-128”, and “F-700” were used.

<Measurement of resin particle in resin dispersion or glass transition temperature of resin>
A differential scanning calorimeter (manufactured by Shimadzu Corporation, DSC50) was used to measure the glass transition temperature Tg of the resin.

<Synthesis Example 1-1; Synthesis of Crystalline Resin (C1) (also referred to as “Crystalline Part (C1)”, the same shall apply hereinafter)>
In a reaction vessel, 113 parts of 1,9-nonanediol as alcohol component, 172.7 parts of dodecanedioic acid as acid component and 0.7 part of dibutyltin oxide as catalyst were heated at 150 ° C. for 4 hours under nitrogen flow. . Subsequently, the inside of the container was depressurized (7 kPa) and dehydrated at 150 ° C. for 4 hours. Furthermore, it returned to nitrogen stream, and it heated at 175 degreeC for 12 hours, and obtained the crystalline part (C1). The number average molecular weight of the crystalline part (C1) was 5,000, the weight average molecular weight was 11,900, and Tm was 72 ° C.

<Synthesis Example 1-2; Synthesis of Crystalline Resin (C2)>
A crystalline part (C2) was obtained in the same manner as in Synthesis Example 1-1 except that the amount of 1,9-nonanediol added was 111 parts. The number average molecular weight of the crystalline part (C2) was 3,800, the weight average molecular weight was 9,000, and Tm was 70 ° C.

<Synthesis Example 1-3; Synthesis of Crystalline Resin (C3)>
A crystalline part (C3) was obtained in the same manner as in Synthesis Example 1-1 except that the amount of 1,9-nonanediol added was 117 parts. The number average molecular weight of the crystalline part (C3) was 9,500, the weight average molecular weight was 23,300, and Tm was 71 ° C.

<Synthesis Example 1-4; Synthesis of Crystalline Resin (C4)>
A crystalline part (C4) was obtained in the same manner as in Synthesis Example 1-1 except that 1,6-hexanediol was used as the alcohol component, and 62 parts of 1,6-hexanediol and 115 parts of dodecanedioic acid were used. The number average molecular weight of the crystalline part (C4) was 6,000, the weight average molecular weight was 14,500, and Tm was 71 ° C.

<Synthesis Example 1-5; Synthesis of Crystalline Resin (C5)>
A crystalline part (C5) was obtained in the same manner as in Synthesis Example 1-1 except that 1,12-dodecanediol was used as the alcohol component, and 109 parts of 1,12-dodecanediol and 115 parts of dodecanedioic acid were used. The number average molecular weight of the crystalline part (C5) was 4,900, the weight average molecular weight was 11,600, and Tm was 80 ° C.

<Synthesis Example 2-1; Synthesis of Amorphous Resin (A1) (also referred to as “Amorphous Part (A1)”, the same shall apply hereinafter)>
In the reaction vessel, 49 parts of bisphenol A-EO adduct, 162 parts of bisphenol A-PO adduct as alcohol components, 83 parts of terephthalic acid as acid components, and 12.5 parts of tetrapropenyl succinic anhydride as catalysts Dibutyltin oxide 0.7 part was put, and it heated at 250 degreeC under nitrogen stream for 4 hours. Subsequently, the inside of a container was pressure-reduced (7 kPa), and it spin-dry | dehydrated over 4 hours at 250 degreeC, and obtained the amorphous part (A1). This amorphous part (A1) had a number average molecular weight of 3,400, a weight average molecular weight of 7,900, and a Tg of 55 ° C.

<Synthesis Example 2-2; Synthesis of Amorphous Resin (A2)>
Synthesis Example 2-1 except that 47 parts of bisphenol A-EO adduct and 154 parts of bisphenol A-PO adduct were used as the alcohol component, 83 parts of terephthalic acid and 12 parts of tetrapropenyl succinic anhydride were used as the acid component. Similarly, an amorphous part (A2) was obtained. This amorphous part (A2) had a number average molecular weight of 4,900, a weight average molecular weight of 11,100, and a Tg of 62 ° C.

<Synthesis Example 2-3; Synthesis of Amorphous Resin (A3)>
In the same manner as in Synthesis Example 2-1, except that 44 parts of bisphenol A-EO adduct and 144 parts of bisphenol A-PO adduct were used as the alcohol component and 83 parts of terephthalic acid were used as the acid component, the non-crystalline part ( A3) was obtained. This amorphous part (A3) had a number average molecular weight of 4,600, a weight average molecular weight of 9,000, and a Tg of 68 ° C.

<Synthesis Example 2-4; Synthesis of Amorphous Resin (A4)>
As alcohol component, 46.5 parts of bisphenol A-EO adduct, 111 parts of bisphenol A-PO adduct, 28 parts of hydrogenated bisphenol A, 83 parts of terephthalic acid as acid component, 15.7 parts of tetrapropenyl succinic anhydride A non-crystalline part (A4) was obtained in the same manner as in Synthesis Example 2-1. This amorphous part (A4) had a number average molecular weight of 7,700, a weight average molecular weight of 17,100, and a Tg of 65 ° C.

<Synthesis Example 2-5; Synthesis of Amorphous Resin (A5)>
As the alcohol component, 27.9 parts of bisphenol A-EO adduct, 91.2 parts of bisphenol A-PO adduct, 50 parts of terephthalic acid as acid component, and 18.8 parts of tetrapropenyl succinic anhydride, In the same manner as in Synthesis Example 2-1, an amorphous part (A5) was obtained. This amorphous part (A5) had a number average molecular weight of 8,000, a weight average molecular weight of 18,500, and a Tg of 55 ° C.

<Synthesis Example 2-6; Synthesis of Amorphous Resin (A6)>
The alcohol component is 21 parts of bisphenol A-EO adduct, 63 parts of bisphenol A-PO adduct, 20 parts of hydrogenated bisphenol A, 50 parts of terephthalic acid, and 13 parts of tetrapropenyl succinic anhydride as acid components. In the same manner as in Synthesis Example 2-1, an amorphous part (A6) was obtained. This amorphous part (A6) had a number average molecular weight of 7,500, a weight average molecular weight of 16,500, and a Tg of 70 ° C.

<Synthesis Example 3-1; Synthesis of Block Copolymer (B1)>
45 parts of crystalline part (C1), 36.6 parts of non-crystalline part (A1) and 0.5 part of dimethylaminopyridine were dissolved in 100 parts of toluene. The mixture was heated to 40 ° C., 9.2 parts of dicyclohexylcarbodiimide was added, and stirring was continued for 2 hours. The obtained reaction product was purified by reprecipitation using tetrahydrofuran as a good solvent and methanol as a poor solvent to obtain a block copolymer (B1). The number average molecular weight of this block copolymer (B1) was 12,500, and the weight average molecular weight was 39,000.

<Synthesis Example 3-2; Synthesis of Block Copolymer (B2)>
30 parts of crystalline part (C2), 59.6 parts of non-crystalline part (A2) and 0.45 part of dimethylaminopyridine were dissolved in 180 parts of toluene. The mixture was heated to 40 ° C., 8.4 parts of dicyclohexylcarbodiimide was added, and stirring was continued for 2 hours. The obtained reaction product was purified by reprecipitation using tetrahydrofuran as a good solvent and methanol as a poor solvent to obtain a block copolymer (B2). The number average molecular weight of this block copolymer (B2) was 8,200, and the weight average molecular weight was 23,500.

<Synthesis Example 3-3; Synthesis of Block Copolymer (B3)>
55 parts of crystalline part (C3), 46.6 parts of non-crystalline part (A3) and 0.3 part of dimethylaminopyridine were dissolved in 200 parts of toluene. The mixture was heated to 40 ° C., 6 parts of dicyclohexylcarbodiimide was added, and stirring was continued for 2 hours. The obtained reaction product was purified by reprecipitation using tetrahydrofuran as a good solvent and methanol as a poor solvent to obtain a block copolymer (B3). The number average molecular weight of this block copolymer (B3) was 7,500, and the weight average molecular weight was 19,000.

<Synthesis Example 3-4; Synthesis of Block Copolymer (B4)>
In a reaction vessel, 40 parts of crystalline part (C4) and 3.3 parts of 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride are placed and 10 kPa. The pressure was reduced below, and the mixture was heated and stirred at 120 ° C. for 1.5 hours. Under nitrogen flow, 0.19 part of dimethylaminopyridine was added and heated at 160 ° C. for 2 hours. Next, the temperature was lowered to 120 ° C., 65 parts of the amorphous part (A4) was added and stirred for 1 hour, and then heated again to 160 ° C. and stirred for 2 hours to obtain a block polymer (B4). The number average molecular weight of this block copolymer (B4) was 9,500, and the weight average molecular weight was 22,000.

<Synthesis Example 3-5; Synthesis of Block Copolymer (B5)>
In a reaction vessel, 55 parts of crystalline part (C4) and 4.6 parts of 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride are placed and 10 kPa. The pressure was reduced below, and the mixture was heated and stirred at 120 ° C. for 1.5 hours. Under nitrogen flow, 0.19 part of dimethylaminopyridine was added and heated at 160 ° C. for 2 hours. Next, the temperature was lowered to 120 ° C., 47 parts of an amorphous part (A3) was added and stirred for 1 hour, and then heated again to 160 ° C. and stirred for 2 hours to obtain a block polymer (B5). The number average molecular weight of this block copolymer (B5) was 12,500, and the weight average molecular weight was 32,000.

<Synthesis Example 3-6; Synthesis of Block Copolymer (B6)>
55 parts of crystalline part (C3), 22.1 parts of non-crystalline part (A1) and 0.3 part of dimethylaminopyridine were dissolved in 150 parts of toluene. The mixture was heated to 40 ° C., 5.8 parts of dicyclohexylcarbodiimide was added, and stirring was continued for 2 hours. The obtained reaction product was purified by reprecipitation using tetrahydrofuran as a good solvent and methanol as a poor solvent to obtain a block copolymer (B6). This block copolymer (B6) had a number average molecular weight of 21,000 and a weight average molecular weight of 62,000.

<Synthesis Example 3-7; Synthesis of Block Copolymer (B7)>
55 parts of crystalline part (C3), 33.6 parts of non-crystalline part (A3) and 0.3 part of dimethylaminopyridine were dissolved in 180 parts of toluene. The mixture was heated to 40 ° C., 5.9 parts of dicyclohexylcarbodiimide was added, and stirring was continued for 2 hours. The resulting reaction product was purified by reprecipitation using tetrahydrofuran as a good solvent and methanol as a poor solvent to obtain a block copolymer (B7). The number average molecular weight of this block copolymer (B7) was 12,500, and the weight average molecular weight was 34,000.

<Synthesis Example 3-8; Synthesis of Block Copolymer (B8)>
Into the reaction vessel, 50 parts of an amorphous part (A3) and 6 parts of 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride are placed and 10 kPa or less. The mixture was heated to 120 ° C. for 1.5 hours and stirred. Under nitrogen flow, 0.19 part of dimethylaminopyridine was added, and the mixture was heated and stirred at 160 ° C. for 4 hours to obtain a block polymer (B8). This block copolymer (B8) had a number average molecular weight of 16,000 and a weight average molecular weight of 38,000.

<Synthesis Example 3-9; Synthesis of Block Copolymer (B9)>
In a reaction vessel, 30.2 parts of amorphous part (A3), 3.7 parts of 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride The pressure was reduced to 10 kPa or less, and the mixture was heated and stirred at 120 ° C. for 1.5 hours. Under nitrogen flow, 0.17 part of dimethylaminopyridine was added and heated at 160 ° C. for 2 hours. Next, the temperature was lowered to 120 ° C., 55 parts of the crystal part (C4) was added and stirred for 1 hour, and then heated again to 160 ° C. and stirred for 2 hours to obtain a block polymer (B9). The number average molecular weight of this block copolymer (B9) was 14,000, and the weight average molecular weight was 36,000.

-Preparation of toner base particles-
(Toner Production Example 1; Production of Toner (T1))
100 parts of block copolymer (B1), 6.4 parts of cyan pigment, and 10 parts of wax were dissolved / dispersed in 225 parts of chloroform and 104 parts of ethyl acetate to obtain an oil phase. On the other hand, 2.5 parts of carboxymethyl cellulose and 80 parts of calcium carbonate were dissolved / dispersed in 533 parts of water to obtain an aqueous phase. A dispersion suspension in which the oil phase was dispersed and suspended in water was prepared using T25 ULTRA-TURRAX (manufactured by IKA). This dispersion suspension was allowed to stand at room temperature (25 ° C.) for 5 days to remove the organic solvent component. The dispersion suspension thus obtained was washed with hydrochloric acid to remove calcium carbonate, and then repeatedly washed with sufficient water to obtain a toner (T1).

(Toner Production Example 2: Production of Toner (T2))
A toner (T2) was obtained in the same manner as in Toner Production Example 1 except that the block copolymer (B2) was used instead of the block copolymer (B1).

(Toner Production Example 3; Production of Toner (T3))
A toner (T3) was obtained in the same manner as in Toner Production Example 1 except that the block copolymer (B3) was used instead of the block copolymer (B1).

(Toner Production Example 4; Production of Toner (T4))
A toner (T4) was obtained in the same manner as in Toner Production Example 1, except that the block copolymer (B4) was used instead of the block copolymer (B1).

(Toner Production Example 5; Production of Toner (T5))
A toner (T5) was obtained in the same manner as in Toner Production Example 1 except that the block copolymer (B5) was used instead of the block copolymer (B1).

(Toner Production Example 6; Production of Toner (T6))
Toner (T6) was prepared in the same manner as in Toner Production Example 1 except that 50 parts of block copolymer (B1) and 50 parts of amorphous resin (A5) were used instead of 100 parts of block copolymer (B1). )

(Toner Production Example 7; Production of Toner (T7))
Toner (T7) was prepared in the same manner as in Toner Production Example 1 except that 30 parts of block copolymer (B6) and 70 parts of amorphous resin (A6) were used instead of 100 parts of block copolymer (B1). )

(Toner Production Example 8; Production of Toner (T8))
Toner (T8) was prepared in the same manner as in Toner Production Example 1 except that 40 parts of block copolymer (B7) and 60 parts of amorphous resin (A5) were used instead of 100 parts of block copolymer (B1). )

(Toner Production Example 9; Production of Toner (T9))
Toner (T9) was prepared in the same manner as in Toner Production Example 1 except that 75 parts of block copolymer (B2) and 25 parts of amorphous resin (A6) were used instead of 100 parts of block copolymer (B1). )

(Toner Production Example 10; Production of Toner (T10))
Toner (T10) was obtained in the same manner as in Toner Production Example 1, except that 40 parts of block copolymer (B3) and 60 parts of amorphous resin (A5) were used.

(Toner Production Example 11; Production of Toner (T11))
Toner (T11) in the same manner as in Toner Production Example 1, except that 60 parts of amorphous resin (A5) and 40 parts of crystalline resin (C3) were used instead of 100 parts of block copolymer (B1). Got.

(Toner Production Example 12; Production of Toner (T12))
A toner (T12) was obtained in the same manner as in Toner Production Example 1, except that 100 parts of the amorphous resin (A5) was used instead of 100 parts of the block copolymer (B1).

(Toner Production Example 13; Production of Toner (T13))
A toner (T13) was obtained in the same manner as in Toner Production Example 1 except that the block copolymer (B8) was used instead of the block copolymer (B1).

(Toner Production Example 14; Production of Toner (T14))
A toner (T14) was obtained in the same manner as in Toner Production Example 1 except that the block copolymer (B9) was used instead of the block copolymer (B1).

<Low-temperature fixability evaluation (minimum fixing temperature evaluation)>
The developer for developing an electrostatic charge image using each of the obtained toners (T1) to (T14) was filled in a developing device of a color copying machine DocuCentreColor 400 (manufactured by Fuji Xerox Co., Ltd.) from which the fixing device was taken out. A developer filled with a developer for developing an electrostatic charge image is allowed to stand for 24 hours in an environment of a temperature of 25 ° C. and a humidity of 50%, and then adjusted so that the applied toner amount becomes 0.75 mg / cm 2 to obtain an unfixed image. Output. The output image was a solid image in which the image density of 50 mm × 50 mm was 100%, and the paper used was “C2R” (Fuji Xerox Interfield Co., Ltd.).
To fix the image, the fixing device taken out from the color copier DocuCenter IIC2200 (manufactured by Fuji Xerox Co., Ltd.) was modified so that the roll temperature of the fixing device could be changed, and the sheet conveying speed of the fixing device was 250 mm / second. Under the conditions, the above-mentioned unfixed image was fixed by changing the temperature of the fixing device from 100 ° C. to 220 ° C. by 5 ° C. to obtain a fixed image.
The minimum fixing temperature was evaluated as a temperature at which a low temperature offset does not occur.
The evaluation criteria are as follows.
A: Minimum wearing temperature of 90 ° C. or lower ○: Minimum fixing temperature of 90 ° C. or higher and 140 ° C. or lower ×: Minimum fixing temperature of 140 ° C. or higher

<Image strength evaluation (scratch resistance evaluation)>
For each toner, an image fixed at the minimum fixing temperature + 15 ° C. is selected from the images obtained in the low-temperature fixability evaluation, and the paper is lightly bent with the output image inside, and a load of 200 g / cm is applied. The output image was creased over a period of minutes. The image was opened and the crease portion was rubbed with a waste cloth while applying a load of 7.5 g / cm to remove the missing image, and then the image defect at the fold portion was evaluated.
The evaluation criteria are as follows.
◎: No missing image ○: Partially missing image ×: Severe missing image

<Evaluation of charging characteristics>
Toners (T1) to (T14) thus obtained were weighed in 1.5 parts of toner and 30 parts of ferrite particles (average particle diameter 35 μm) coated with styrene / methyl methacrylate resin in a glass bottle with a lid, and then high temperature and high humidity. After seasoning for 24 hours at a lower temperature (temperature of 28 ° C. and humidity of 85%), the mixture was stirred and shaken with a turbula mixer for 15 minutes. The charge amount (μC / g) of the toner was measured with a blow-off charge amount measuring device.
The evaluation criteria are as follows.
A: 25-55 μC / g
○: 20 to 24 μC / g
X: Less than 20 μC / g

In addition, the estimated structure of the block copolymer in Table 1 is the number average molecular weight and the weight average molecular weight of the block copolymer, the ratio of the crystalline block to the amorphous block, the ratio (content) of the crystalline block, the raw material This is an estimated structure of the main component of the block copolymer (50% by weight or more of the block copolymer) estimated from the structure and amount, and the synthesis method.
Further, the block copolymers (B1) to (B7) are block copolymers each having a non-crystalline block, and the block copolymers (B8) and (B9) are both crystalline at the terminal. It is a block copolymer which is a functional block.

Claims (10)

Including at least a polyester block copolymer and an amorphous polyester resin ,
The polyester block copolymer has an amorphous block and a crystalline block;
Both ends of the polyester block copolymer, Ri amorphous blocks der,
The polyester block copolymer contains 50% by weight or more of a block copolymer having a structure represented by the formula (1) based on the total weight of the polyester block copolymer;
The toner for developing an electrostatic charge image, wherein the polyester block copolymer has a weight average molecular weight of 20,000 or more and 100,000 or less .
A (BA) _n BA (1)
In formula (1), each A independently represents an amorphous block, each B independently represents a crystalline block, and n represents an integer of 1 to 4. The electrostatic image developing toner according to claim 1, wherein the total amount of the crystalline blocks in the polyester block copolymer is 33% or more by weight. The polyester ratio of the block copolymer and the non-crystalline polyester resin, the weight ratio 80: 20 to 30: in the range of 70, toner according to claim 1 or 2. Wherein also the glass transition temperature of the amorphous block of the polyester block polymer (Tg) of any, at 50 ° C. or higher, according to claim 1 for electrostatic image development toner according to any one of the three. Claim 1 or one for toner according to 4, and an electrostatic image developer which comprises a carrier. A toner cartridge which is detachable from an image forming apparatus and contains the toner for developing an electrostatic charge image according to any one of claims 1 to 4 . A developer cartridge containing the electrostatic charge image developer according to claim 5 . A process cartridge comprising a developer holder that contains the electrostatic image developer according to claim 5 and that holds and conveys the electrostatic image 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,
The developer is the electrostatic image developing toner according to any one of claims 1-4, or the image forming apparatus is an electrostatic charge image developer according to claim 5. A latent image forming step of forming an electrostatic latent image on the surface of the image carrier;
A development 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;
A transfer step of transferring the toner image onto the surface of the transfer target;
Fixing a toner image transferred to the surface of the transfer target,
An image forming method using the electrostatic image developing toner according to any one of claims 1 to 4 or the electrostatic image developer according to claim 5 as the developer.