JP5266977B2 - Toner for developing electrostatic image, method for producing toner for developing electrostatic image, developer for electrostatic image, image forming method and image forming apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electrostatic charge image developing toner which exhibits superior pressure-fixing property, at ordinary temperature or by additionally using a small amount of heat energy, is free from occurrence of VOC, is superior in toner strength in a developing machine and obtains a superior fixing image strength, to provide a manufacturing method of the electrostatic charge image developing toner, to provide an electrostatic charge image developer that uses the electrostatic charge image developing toner, and to provide an image forming method and an image forming apparatus. <P>SOLUTION: The electrostatic charge image developing toner contains a block copolymer, comprising a block prepared by polymerizing an ethylenic unsaturated compound, wherein a temperature T(P5) at which the viscosity of the block copolymer becomes 10<SP>4</SP>Pa s is 60&deg;C or more under application pressure 5 kgf/cm<SP>2</SP>of flow tester, a temperature T(P300), at which the viscosity of the block copolymer becomes 10<SP>4</SP>Pa s is &le;80&deg;C, at an applied pressure 300 kgf/cm<SP>2</SP>of flow tester, and these temperatures satisfy the relation: 30&deg;C&le;T(P5)-T(P300)&le;80&deg;C. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

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

  The electrostatic charge image developing toner using an addition polymerization type resin having a random monomer chain and a polycondensation type resin as a binder resin mainly promotes fixing by heating rather than pressure.

In the electrophotographic printing and copying technologies, recently, for the purpose of lower energy, efforts have been made to use pressure fixing (pressure fixing) from the conventional heat energy based fixing method (Patent Document 1). To 4).
Patent Document 1 is composed of toner particles having a particle size in the range of about 0.5 to about 1,000 microns and an agglomeration temperature of at least about 37.8 ° C., and has adhesion with a colorant. An electrostatographic magnetic toner material is disclosed in which a soft solid polymer core material and magnetic particles are encapsulated with a shell material made of a polymer.

  Further, Patent Document 2 discloses a pressure fixing toner comprising a composition containing 30 to 70 parts by weight of a bis fatty acid amide as a binder component.

Patent Document 3 discloses a toner characterized by atomizing a toner material containing polyethylene having a density of 0.94 g / cm ³ or more and a long-chain compound having a carbon chain of C12 to C99 in a molten state. Is disclosed.
In Patent Document 4, in a microcapsule type toner having a core material and an outer wall for coating the core material, the core material has a vinyl-based weight having a weight average molecular weight / number average molecular weight value of 3.5 to 20. There is disclosed a microcapsule type toner characterized by containing a coalescence as a main component.

JP 49-17739 A JP 58-86557 A JP-A-57-201246 JP 61-56355 A

  As described above, various attempts have been made to use waxes, solid core capsule structures, liquid core capsule structures, and the like for pressure fixing of electrostatic image developing toners. However, toners using these waxes have practical problems such as insufficient image strength after fixing and poor scratch resistance (scratch resistance) of a fixed image. This problem also occurs in a toner having a solid capsule structure, and a reduction in strength due to exposure of the soft resin component used for the core material for realizing pressure fixing to the image surface after fixing is inevitable. . In addition, the liquid core capsule has a serious problem in terms of its use environment such as VOC (volatile organic compound) generated in the fixing process.

  The problem to be solved by the present invention is that it exhibits excellent pressure fixability when used in combination with normal temperature or a small amount of heat energy, does not generate VOC, has excellent toner strength in the developing machine, and provides a static image that provides excellent fixed image strength. To provide a charge image developing toner, a method for producing the electrostatic image developing toner, an electrostatic image developer, an image forming method, and an image forming apparatus.

As a result of intensive studies on the above problems by the present inventors, it has been found that the problems can be solved by using the means <1> to <12> described below, and the present invention has been achieved.
<1> includes a block copolymer composed of a block obtained by polymerizing an ethylenically unsaturated compound, and at a flow tester applied pressure of 5 kgf / cm ² , a temperature T at which the viscosity of the block copolymer is 10 ⁴ Pa · s ( P5) is 60 ° C. or higher, and at a flow tester applied pressure of 300 kgf / cm ² , the temperature T (P300) at which the viscosity of the block copolymer becomes 10 ⁴ Pa · s is 80 ° C. or lower, and 30 ° C. ≦ T (P5) -T (P300) ≦ 80 ° C., an electrostatic charge image developing toner,
<2> The electrostatic charge image developing toner according to <1>, wherein the block copolymer has a number average molecular weight of 10,000 to 150,000.
<3> The block copolymer is a diblock copolymer comprising a block A and a block B, the glass transition point Tg (A) of the block A is 60 ° C. or higher, and the glass transition point Tg of the block B ( The toner for developing an electrostatic charge image according to <1> or <2>, wherein B) is 20 ° C. or lower,
<4> The electrostatic image developing toner according to <3>, wherein a difference between the Tg (A) and the Tg (B) is 60 ° C. or more.
<5> The electrostatic charge image developing toner according to <3> or <4>, wherein the block A is a polymer of styrene and / or a derivative thereof,
<6> The electrostatic charge image developing toner according to any one of <1> to <5>, wherein the block copolymer is synthesized by living radical polymerization.
<7> The resin according to any one of <1> to <6>, further including a resin having a Tg of 40 ° C. or higher, wherein the resin is a polymer of an ethylenically unsaturated compound and / or an amorphous polyester. Toner for developing electrostatic image,
<8> Block copolymer resin particle dispersion preparation step for producing an aqueous dispersion of block copolymer resin particles including a block copolymer comprising a block obtained by polymerizing an ethylenically unsaturated compound, dispersed block copolymer The method according to any one of <1> to <7>, further comprising an aggregation step of aggregating the coalesced resin particles to obtain aggregated particles, and a fusion step of fusing the aggregated particles by heating. Production method of toner for developing electrostatic image,
<9> The production method according to <8>, wherein the block copolymer resin particle dispersion preparation step includes an emulsification step by miniemulsion polymerization.
<10> The electrostatic image developing toner according to any one of <1> to <7>, or the electrostatic image developing toner and carrier produced by the production method according to <8> or <9>. An electrostatic charge image developer,
<11> An electrostatic latent image forming step for forming an electrostatic latent image on the surface of the latent image holding member, an electrostatic charge image including the toner or the toner and the carrier as an electrostatic latent image formed on the surface of the latent image holding member. A developing step of developing with a developer to form a toner image, a transferring step of transferring the toner image formed on the surface of the latent image holding member to the surface of the transfer target, and a toner image transferred to the surface of the transfer target A fixing step of fixing by applying pressure or heat and pressure, wherein the toner is the toner for developing an electrostatic charge image according to any one of <1> to <7> or the toner according to <8> or <9>. Or the electrostatic charge image developer according to <10>, wherein the fixing pressure in the fixing step is 5 to 300 kgf. image forming method which is a / cm ²
<12> a latent image holding member, a charging unit for charging the latent image holding member, an exposure unit for exposing the charged latent image holding member to form an electrostatic latent image on the latent image holding member, and a developer. Developing means for developing the electrostatic latent image to form a toner image, transfer means for transferring the toner image from the latent image holding member to the transfer target, and the toner image transferred to the surface of the transfer target A fixing unit that fixes the toner by pressurizing or heating and pressing, wherein the fixing unit has a fixing pressure of 5 to 300 kgf / cm ² , and the toner is any one of <1> to <7>. The toner for developing an electrostatic image, the toner for developing an electrostatic image produced by the production method according to <8> or <9>, or the electrostatic image developer described in <10> is used as the developer. An image forming apparatus.

  According to the present invention, for electrostatic image development that exhibits excellent pressure fixability when used in combination with normal temperature or a small amount of heat energy, does not generate VOC, has excellent toner strength in the developing machine, and provides excellent fixed image strength. A toner, a method for producing the toner for developing an electrostatic charge image, an electrostatic charge image developer, an image forming method, and an image forming apparatus can be provided.

I. Toner for developing an electrostatic image The toner for developing an electrostatic image of the present embodiment (hereinafter also simply referred to as “toner”) includes a block copolymer composed of a block obtained by polymerizing an ethylenically unsaturated compound, and is a flow tester. At an applied pressure of 5 kgf / cm ² , a temperature T (P5) at which the viscosity of the block copolymer becomes 10 ⁴ Pa · s is 60 ° C. or more, and at an applied pressure of 300 kgf / cm ² , the block copolymer The temperature T (P300) at which the viscosity becomes 10 ⁴ Pa · s is 80 ° C. or lower, and 30 ° C. ≦ T (P5) −T (P300) ≦ 80 ° C. The expression “30 ° C. ≦ T (P5) −T (P300) ≦ 80 ° C.” is synonymous with “30 ° C. ≦ {T (P5) −T (P300)} ≦ 80 ° C.”, and “{T The value of (P5) −T (P300)} is synonymous with “30 ° C. or higher and 80 ° C. or lower”.

  In this embodiment, the pressure dependence of the phase transition phenomenon of a block copolymer resin made of an ethylenically unsaturated compound used for a binder resin of toner is utilized. Hereinafter, the toner for developing an electrostatic charge image according to the exemplary embodiment will be described in detail. In addition, in this embodiment, description of numerical ranges, such as "A-B", is synonymous with "A or more and B or less" unless there is particular notice, and it is the same below.

Usually, at room temperature (25 ° C.), in the case of a block copolymer composed of units that are incompatible with each other (synonymous with “block”), the polymer chain has a lamellar structure, a syringe structure, etc. at a certain boundary temperature. It is known to change from a regular structure to a disordered state.
With respect to this boundary temperature, for example, when the temperature is changed from a low temperature to a high temperature region, the boundary temperature of the change from the ordered structure to the disordered state is the UDOT (Upper Disorder to Order Transition) temperature, from the disordered state to the ordered state. The boundary temperature is referred to as LDOT (Lower Order to Order Transition) temperature. Furthermore, in this case, it is reported that the change from the ordered state to the disordered state is accompanied by a large decrease in the melt viscosity of the block copolymer (PJ Flory et al, J. Am. Chem. Soc, 86, 3515). (1964), LP Mcmaster et al, Macromolecules 6,760 (1973), IC Sanchez et al, Macromolecules 11,1145 (1978), C. Yeung et al, Phys. Rev. Lett. 72, 1834 (1994), T. Hino et al, Macromolecules 31, 2636 (1998), H. Hasegawa et al, J. Phys. Chem. Solids 60, 1307 (1999)).

  Furthermore, recently, it has been reported that the phase transition phenomenon of block copolymers due to these temperatures greatly depends on pressure (Du. Yeol. Ryu et al, Phys. RevLett, 90, 235501 (2003)). In this case, the pressure dependence in the phase transition is a phenomenon in which the boundary temperature of the phase transition described above decreases or increases in a state under pressure.

As a result of intensive studies aimed at applying the phase transition phenomenon due to the temperature and pressure of these block copolymers to the toner for developing an electrostatic charge image for pressure fixing, the present inventors have developed an electrostatic image developing toner of this embodiment. Excellent electrostatic fixing performance by using a method for producing an electrostatic charge image developing toner, an electrostatic charge image developer, an image forming method and an image forming apparatus, and an excellent fixability in combination with room temperature or an unprecedented small amount of heat energy. It was found that an image having an excellent fixed image strength can be obtained without impairing the use environment by VOC.
More specifically, the present embodiment utilizes the above-described phenomenon of decrease in UDOT temperature due to pressurization, and is a recording medium (“transfer target”) due to a fixing unit pressure in an image forming apparatus such as an electrophotographic apparatus. Synonymous) Toner for electrostatic image development capable of achieving both excellent fixing property of toner on top and excellent stability in various electrophotographic processes such as development process, method for producing toner for electrostatic image development, electrostatic charge The present invention relates to an image developer, an image forming method, and an image forming apparatus.

<Block copolymer>
In this embodiment, at a flow tester applied pressure of 5 kgf / cm ² , the temperature T (P5) at which the viscosity of the block copolymer is 10 ⁴ Pa · s is 60 ° C. or higher, and the flow tester applied pressure is 300 kgf / cm ^2. The temperature T (P300) at which the viscosity of the block copolymer is 10 ⁴ Pa · s is 80 ° C. or lower.
When T (P5) is less than 60 ° C., the strength of the toner in the developing machine decreases. T (P5) is preferably 80 to 150 ° C, and more preferably 100 to 120 ° C.
T (P300) is 80 ° C. or less, and when this value exceeds 80 ° C., sufficient fixability cannot be obtained, which causes a problem in the fixed image strength. T (P300) is preferably 30 to 80 ° C, more preferably 40 to 70 ° C.
For sufficient fixing performance, it is preferable to fix the toner by using a combination of heating at 60 ° C. or lower and pressure.

T (P5) and T (P300) satisfy the relationship of 30 ° C. ≦ T (P5) −T (P300) ≦ 80 ° C.
When T (P5) -T (P300) is less than 30 ° C., toner fixing failure occurs, and the fixed image strength is poor. Similarly, when T (P5) -T (P300) is higher than 80 ° C., a problem arises in the fixed image strength after fixing due to defective fixing.
In the exemplary embodiment, 30 ° C. ≦ T (P5) −T (P300) ≦ 60 ° C. is preferable, and the range of the above numerical values is preferable from the viewpoint of fixability.

  Here, the flow tester viscosity of the block copolymer was measured using a flow tester CFT-500C (die diameter 0.5 mm) manufactured by Shimadzu Corporation, and a cylindrical sample having a diameter of 1 cm and a thickness of 1 cm was measured from room temperature to 200 ° C. It is a value obtained from an elution curve when measurement is performed at a temperature rising rate of 1 ° C. per minute.

  In order to achieve a sufficient balance between the pressure fixing performance and the toner strength, the block copolymer preferably has a number average molecular weight of 10,000 to 150,000, preferably 20,000 to It is more preferable that it is 100,000, and it is further more preferable that it is 30,000-60,000. Within the above range, it is possible to achieve both image quality characteristics with sufficient fixing properties and excellent toner strength in the developing machine.

Here, the number average molecular weight can be measured, for example, by gel permeation chromatography (HLC-8120GPC, TSK-GEL, GMH column, manufactured by Tosoh Corporation) under the conditions described below.
At a temperature of 40 ° C., a solvent (tetrahydrofuran) is flowed at a flow rate of 1.2 ml per minute, and 3 mg of a tetrahydrofuran sample solution having a concentration of 0.2 g / 20 ml is injected as a sample weight for measurement. When measuring the molecular weight of a sample, select the measurement conditions that fall within the range in which the logarithm of the molecular weight of the calibration curve and the number of counts are linear, using several types of monodisperse polystyrene standard samples. .

The block copolymer is preferably a block copolymer containing the following block A and block B. The glass transition point Tg (A) of the block A is preferably 60 ° C. or higher, and more preferably 70 to 110 ° C. Within the above range, the practical strength as a toner and the image strength after fixing are good.
Moreover, it is preferable that the glass transition point Tg (B) of the said block B is 20 degrees C or less, and it is more preferable that it is -100-10 degreeC. Within the above range, good fixability under pressure can be obtained.
The block A and the block B preferably occupy 60% by weight or more of the entire block copolymer, more preferably 80 to 100% by weight, and the diblock copolymer comprising the block A and the block B More preferably, it is a polymer. When the content of the block A and the block B is within the above range, good fixability under pressure can be obtained.
Moreover, as a ratio of the block A and the block B, the total amount of the block A and the block B is 100% by weight, and the ratio of the block A is preferably 25 to 75% by weight, and 40 to 60% by weight. It is more preferable. Within the above range, the practical strength as a toner and the image strength after fixing are good.
The glass transition point Tg is measured by the method defined in ASTM D3418-82 when a differential scanning calorimeter (DSC) is used to measure from −80 ° C. to 150 ° C. at a rate of temperature increase of 10 ° C. per minute. The measured value.

  Furthermore, the difference (Tg (A) −Tg (B)) between the glass transition point Tg (A) of the homopolymer of block A and the glass transition point Tg (B) of the homopolymer of block B is 60 ° C. or more. Is preferred. Within the above range, sufficient pressure fixability can be obtained, and thermal energy for fixing can be reduced.

The electrostatic image developing toner according to the exemplary embodiment includes a block copolymer including a block obtained by polymerizing an ethylenically unsaturated compound. These block copolymers can be obtained by polymerizing various ethylenically unsaturated compounds.
In the present embodiment, the ethylenically unsaturated compound may be a compound having at least one ethylenically unsaturated bond, and is preferably an addition polymerizable compound, which is anionic polymerizable, cationic polymerizable, and radical polymerizable. Any one of coordination polymerizable compounds may be used, and among them, a radical polymerizable ethylenically unsaturated compound is more preferable.
Examples of radically polymerizable ethylenically unsaturated compounds that can be used in this embodiment include styrenes, (meth) acrylic acid esters (“(meth) acrylic acid ester” and the like are “acrylic acid ester and / or Synonymous with “methacrylic acid ester” and the like hereinafter, and the like), ethylenically unsaturated nitriles, ethylenically unsaturated carboxylic acids, vinyl ethers, vinyl ketones, olefins and the like.

  More specifically, styrenes such as styrene, parachlorostyrene, and α-methylstyrene; methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, hexyl acrylate, lauryl acrylate, 2-ethylhexyl acrylate , [Beta] -carboxyethyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, hexyl methacrylate, lauryl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, and the like; Ethylenically unsaturated nitriles such as acrylonitrile and methacrylonitrile; Ethylenically unsaturated carboxylic acids such as acrylic acid, methacrylic acid and crotonic acid; Vinyl such as vinyl methyl ether and vinyl isobutyl ether Preferred examples include ethers; vinyl ketones such as vinyl methyl ketone, vinyl ethyl ketone and vinyl isopropenyl ketone; and olefins such as isoprene, butene and butadiene. As a block contained in the block copolymer, a homopolymer consisting of any one of these ethylenically unsaturated compounds, a copolymer obtained by copolymerizing two or more of these, and a mixture thereof can be used. Can be used.

Examples of the ethylenically unsaturated compound that can be preferably used for the production of the block A having a Tg (A) of 60 ° C. or higher include styrenes such as styrene, parachlorostyrene, and α-methylstyrene. Among them, styrene is preferable. Can be used.
In addition, as the ethylenically unsaturated compound that can be preferably used for the production of the block B having Tg (B) of 20 ° C. or less, (meth) acrylic acid esters are preferably exemplified, and among them, acrylic acid esters are more preferable. Acrylic acid alkyl esters having an alkyl group of 1 to 8 carbon atoms are more preferable, and methyl acrylate, butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, and the like are particularly preferable.

In the production of the block copolymer of these ethylenically unsaturated compounds, various living polymerization methods such as ionic polymerization method and living radical polymerization method can be used, but in this embodiment, the monomers are used. It is preferable to use the living radical polymerization method because of the ease of the combination.
In this case, as the living radical polymerization method, existing methods such as NMRP (Nitroxide Mediated Radial Polymerization), ATRP (Atom Transfer Radical Polymerization), and RAFT (Reversible Addition Fragmentation Transfer) can be used. Among these, in this embodiment, the NMRP method is preferable.

  As the nitroxide compound used in the NMRP method, a known nitroxide compound used in the living radical polymerization method can be used, and specifically, JP 2004-307502 A, JP 2005-126442 A, and JP 2007. The compounds described in Japanese Patent No. 518843 and Japanese Patent No. 4081112 can be used. In the present embodiment, a monoalkoxyamine represented by the formula (I) can be preferably used.

（式（Ｉ）中、Ｒ₁は炭素数１〜５個の直鎖又は分岐を有するアルキル基を表し、Ｒ₂は水素原子、炭素数１〜８個の直鎖又は分岐を有するアルキル基、炭素数６〜２０のアリール基、アルカリ金属イオン又はアンモニウムイオンを表す。）

(In the formula (I), R ₁ represents a linear or branched alkyl group having 1 to 5 carbon atoms, R ₂ represents a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, Represents an aryl group having 6 to 20 carbon atoms, an alkali metal ion or an ammonium ion.)

R ₁ represents a linear or branched alkyl group having 1 to 5 carbon atoms, preferably a linear alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group.
R ₂ represents a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkali metal ion or an ammonium ion. Examples of the linear or branched alkyl group having 1 to 8 carbon atoms include a methyl group and an ethyl group, examples of the aryl group having 6 to 20 carbon atoms include a phenyl group, and examples of the alkali metal ion include Li. ⁺ , Na ⁺ , K ^{+ and the} like, and ammonium ions include NH ₄ ⁺ , NBu ₄ ⁺ , HNBu ₃ ^{+ and the} like. Among these, in the present embodiment, R ² is preferably a hydrogen atom.

The NMRP method is preferably performed in a nitrogen atmosphere.
The reaction is preferably carried out in the presence or absence of a solvent selected from a solvent, preferably an alcohol such as ethanol, an aromatic solvent, a chlorinated solvent, an ether or a polar aprotic solvent. It is more preferred to react under
The reaction temperature is preferably in the range of 30 to 90 ° C, more preferably in the range of 50 to 90 ° C.

  The amount of the nitroxide compound used can be determined by the number average molecular weight at the end of the polymerization. Usually, the amount of ditrooxide compound to be used can be determined stoichiometrically from the monomer weight and number average molecular weight to be used.

  In this embodiment, the content of the block copolymer is preferably 50 to 99% by weight, and more preferably 70 to 95% by weight, based on 100% by weight of the electrostatic image developing toner. It is preferable for it to be within the above numerical value range because of excellent fixability in pressure or heat and pressure fixing.

<Resin having a Tg of 40 ° C. or higher>
In addition to the block copolymer, the toner for developing an electrostatic charge image of this embodiment preferably further contains a resin having a Tg of 40 ° C. or higher, and more preferably a resin having a Tg of 50 to 80 ° C. By adding a resin having a Tg of 40 ° C. or more to the electrostatic image developing toner, it is possible to further improve the mechanical stability of the toner in the electrophotographic process.
In the present embodiment, an embodiment in which the shell layer of the electrostatic charge image developing toner is formed of a resin having a Tg of 40 ° C. or higher is preferable.

  Preferred examples of the resin include polycondensation resins such as polyester resins and polymers of ethylenically unsaturated compounds. In this case, the polycondensation resin is preferably an amorphous polyester resin or a crystalline polyester resin, and more preferably an amorphous polyester resin in order to improve the mechanical stability of the toner.

  The polyester resin can be produced by performing polycondensation by a direct esterification reaction, a transesterification reaction or the like using a polycondensable monomer such as a polyvalent carboxylic acid, a polyhydric alcohol, or a hydroxycarboxylic acid. In the case of polycondensation, it is preferable to use a polycondensation catalyst in combination in order to promote polycondensation.

  In the present embodiment, the polyvalent carboxylic acid includes aliphatic, alicyclic, and aromatic polyvalent carboxylic acids, their alkyl esters, acid anhydrides, and acid halides. The polyhydric alcohol includes polyhydric alcohols and ester compounds thereof. The alkyl ester of polyvalent carboxylic acid is preferably a lower alkyl ester. The said lower alkyl ester represents the alkyl ester whose carbon number of the alkoxy part of ester is 1-8. Specific examples include methyl ester, ethyl ester, n-propyl ester, isopropyl ester, n-butyl ester, and isobutyl ester.

The polyvalent carboxylic acid that can be used in the present embodiment is a compound containing two or more carboxy groups in one molecule. Among these, dicarboxylic acid is a compound containing two carboxy groups in one molecule. For example, oxalic acid, succinic acid, maleic acid, adipic acid, β-methyladipic acid, azelaic acid, sebacic acid, nonanedicarboxylic acid , Decanedicarboxylic acid, undecanedicarboxylic acid, dodecenyl succinic acid, dodecanedicarboxylic acid, fumaric acid, citraconic acid, diglycolic acid, cyclohexanedicarboxylic acid, cyclohexane-3,5-diene-1,2-dicarboxylic acid, 2,2-di Methylol butanoic acid, malic acid, citric acid, hexahydroterephthalic acid, malonic acid, pimelic acid, tartaric acid, mucoic acid, phthalic acid, isophthalic acid, terephthalic acid, tetrachlorophthalic acid, chlorophthalic acid, nitrophthalic acid, p-carboxyphenyl Acetic acid, p-phenylenediacetic acid, m-phenol Range glycolic acid, p-phenylene diglycolic acid, o-phenylene diglycolic acid, diphenylacetic acid, diphenyl-p, p'-dicarboxylic acid, naphthalene-1,4-dicarboxylic acid, naphthalene-1,5-dicarboxylic acid, naphthalene Examples include -2,6-dicarboxylic acid, anthracene dicarboxylic acid, dodecenyl succinic acid and the like.
Examples of the polyvalent carboxylic acid other than dicarboxylic acid include trimellitic acid, pyromellitic acid, naphthalenetricarboxylic acid, naphthalenetetracarboxylic acid, pyrenetricarboxylic acid, and pyrenetetracarboxylic acid.
These polyvalent carboxylic acids can be used alone or in combination of two or more.

A polyhydric alcohol (polyol) is a compound containing two or more hydroxyl groups in one molecule. Among these, the diol is a compound containing two hydroxyl groups in one molecule, such as ethylene glycol, propylene glycol, butanediol, diethylene glycol, triethylene glycol, hexanediol, cyclohexanediol, octanediol, decanediol, dodecanediol. Bisphenol A ethylene oxide adduct, bisphenol A propylene oxide adduct, bisphenoxy alcohol fluorene (bisphenoxyethanol fluorene), and the like.
Examples of polyols other than diols include glycerin, pentaerythritol, hexamethylol melamine, hexaethylol melamine, tetramethylol benzoguanamine, and tetraethylol benzoguanamine.
These polyhydric alcohols (polyols) can be used alone or in combination of two or more.

In this embodiment, the ethylenically unsaturated compound is a compound having at least one ethylenically unsaturated bond, and may be a monomer having a hydrophilic group and an ethylenically unsaturated bond.
Examples of the hydrophilic group include polar groups, such as acidic polar groups such as carboxy group, sulfo group, and phosphonyl group: basic polar groups such as amino group, amide group, hydroxy group, cyano group, and formyl group. Neutral polar groups and the like can be mentioned, but are not limited thereto.
Among these, acidic polar groups are preferably used for the electrostatic image developing toner of the present embodiment. The presence of the monomer having an acidic polar group and an ethylenically unsaturated bond in a specific range on the surface of the resin particles gives the resin particles cohesion, and the resin particles can be made into a toner. Sufficient chargeability can be imparted to the toner.
Examples of the acidic polar group preferably used include a carboxy group and a sulfo group. Examples of the monomer having an acidic polar group include an α, β-ethylenically unsaturated compound having a carboxy group and an α, β-ethylenically unsaturated compound having a sulfo group. Examples of the α, β-ethylenically unsaturated compound having a carboxy group include acrylic acid, methacrylic acid, fumaric acid, maleic acid, itaconic acid, cinnamic acid, monomethyl maleate, monobutyl maleate, and maleic acid. Mention may be made of monooctyl esters. These monomers may be used individually by 1 type, and may use 2 or more types together.

The resin having a Tg of 40 ° C. or higher is preferably a random copolymer when it is a polymer of an ethylenically unsaturated compound.
Moreover, the resin which contains the ethylenically unsaturated compound which has a hydrophilic group as a monomer unit is preferable, and it is preferable to contain 0.1-10 mol% of ethylenically unsaturated compounds which have a hydrophilic group by copolymerization ratio. Within the above range, a resin having a Tg of 40 ° C. or more is preferable in the production process of the electrostatic charge image developing toner in the aqueous medium because the toner shell layer is easily formed.

  The polycondensation resin such as a polymer of an ethylenically unsaturated compound having a Tg of 40 ° C. or higher and a polyester resin is preferably 50% by weight or less, more preferably 5 to 20% by weight of the total binder resin contained in the toner. . Within the above range, toner durability in the developing machine is improved, and stable image quality characteristics can be obtained.

<Colorant>
The toner for developing an electrostatic charge image of this embodiment preferably contains a colorant.
As the colorant, known ones can be used, and may be arbitrarily selected from the viewpoints of hue angle, saturation, brightness, weather resistance, OHP permeability, and dispersibility in the toner.
Specific examples of colorants that can be used in this embodiment include carbon black, chrome yellow, hansa yellow, benzidine yellow, sren yellow, quinoline yellow, permanent orange GTR, pyrazolone orange, vulcan orange, watch young red, and permanent red. , Brilliantamine 3B, brilliantamine 6B, dapon oil red, pyrazolone red, risor red, rhodamine B rake, lake red C rose bengal, aniline blue, ultramarine blue, calco oil blue, methylene blue chloride, phthalocyanine blue, phthalocyanine green, Various pigments such as malachite green oxalate, titanium black, acridine, xanthene, azo, benzoquinone , Azine, anthraquinone, thioindico, dioxazine, thiazine, azomethine, indico, thioindico, phthalocyanine, aniline black, polymethine, triphenylmethane, diphenylmethane, thiazine, thiazole, xanthene Various dyes such as those of the system can be exemplified.

  Specific examples of the colorant include carbon black, nigrosine dye (C.I. No. 50415B), aniline blue (C.I.No. 50405), and calco oil blue (C.I.No.). .Azoic Blue 3), chrome yellow (C.I.No. 14090), ultramarine blue (C.I.No. 77103), DuPont oil red (C.I.No. 26105), quinoline yellow (C.I. No. 47005), methylene blue chloride (C.I.No. 52015), phthalocyanine blue (C.I.No. 74160), malachite green oxalate (C.I.No. 42000), lamp black (C.I. No. 77266), Rose Bengal (C.I. No. 45435), a mixture thereof It can be preferably used.

The amount of the colorant used is preferably 0.1 to 20% by weight and more preferably 0.5 to 10% by weight with respect to 100% by weight of the toner. Moreover, as a coloring agent, these pigments, dyes, etc. can be used individually by 1 type, or 2 or more types can be used together.
Moreover, when using the magnetic body mentioned later as a black coloring agent, unlike other coloring agents, 12 to 240 weight% can be added.

<Release agent>
The toner for developing an electrostatic charge image of this embodiment preferably contains a release agent.
Specific examples of the release agent that can be used in the present embodiment include, for example, various ester waxes, low molecular weight polyolefins such as polyethylene, polypropylene, and polybutene, silicones that exhibit a softening point by heating, oleic acid amide, erucic acid, and the like. Fatty acid amides such as amides, ricinoleic acid amides, stearic acid amides, plant waxes such as carnauba wax, rice wax, candelilla wax, tree wax, jojoba oil, animal waxes such as beeswax, Examples thereof include mineral-based and petroleum-based waxes such as montan wax, ozokerite, ceresin, paraffin wax, microcrystalline wax, microcrystalline wax, Fischer-Tropsch wax, and modified products thereof.

  In the toner for developing an electrostatic charge image of the exemplary embodiment, the release agent is preferably contained in a range of 1 to 20% by weight, and in a range of 3 to 15% by weight with respect to 100% by weight of the binder resin. It is more preferable to contain. Within the above numerical range, it is possible to achieve both good fixing and image quality characteristics.

<Internal additives and other additives>
For the electrostatic charge image developing toner of the present embodiment, various known internal additives such as a charge control agent, an antioxidant, and an ultraviolet absorber used for this type of toner may be used as necessary. .
Examples of the charge control agent include positively chargeable charge control agents such as nigrosine dyes, quaternary ammonium salt compounds, triphenylmethane compounds, imidazole compounds, and polyamine resins, or chromium, cobalt, aluminum, and iron. Metal-containing azo dyes such as, salicylic acid or metal salts and metal complexes of hydroxycarboxylic acids such as acrylic acid, benzylic acid, chrome, zinc, aluminum, amide compounds, phenol compounds, naphthol compounds, phenolamide compounds, etc. Known charge control agents can be used.

  Further, the electrostatic charge image developing toner of this embodiment may contain a flame retardant or a flame retardant aid as necessary. Examples of flame retardants and flame retardant aids include, but are not limited to, bromine flame retardants that are already widely used, antimony trioxide, magnesium hydroxide, aluminum hydroxide, and ammonium polyphosphate.

Further, when the electrostatic image developing toner of the present embodiment is used as a magnetic toner, magnetic powder may be included. Specifically, a material that is magnetized in a magnetic field is used, but a ferromagnetic powder such as iron, cobalt, or nickel, or a compound such as ferrite or magnetite is used.
In the present embodiment, when toner is obtained in the aqueous phase, it is necessary to pay attention to the water phase transferability of the magnetic material. For example, the surface of the magnetic material may be modified in advance, for example, a hydrophobic treatment may be performed. preferable.

In addition, the electrostatic image developing toner of this embodiment is dried in the same manner as a normal toner for the purpose of imparting fluidity and improving cleaning properties, and then inorganic particles such as silica, alumina, titania, calcium carbonate, and vinyl resins. In addition, resin particles such as polyester and silicone can be added to the toner particle surface while being sheared in a dry state.
In addition, when adhering to the toner surface in an aqueous medium, examples of inorganic particles include silica, alumina, titania, calcium carbonate, magnesium carbonate, tricalcium phosphate, etc. Can be used by dispersing with an ionic surfactant, polymer acid, or polymer base.

<Volume average particle size, particle size distribution, shape factor>
The volume average particle diameter (D _50v ) of the toner for developing an electrostatic charge image of this embodiment is preferably 2 to 10 μm, more preferably 3 to 8 μm, and further preferably 5 to 7 μm. Within the above range, the image quality characteristics after fixing are good.

Further, it is preferable that the toner particle size distribution is narrower. More specifically, the ratio of the 16% diameter (D _16p ) and the 84% diameter (D _84p ) in terms of the smaller number particle size of the toner is expressed as a square root. (GSDp), that is, GSDp represented by the following formula is preferably 1.40 or less, more preferably 1.31 or less, and particularly preferably 1.27 or less. Moreover, it is preferable that GSDp is 1.15 or more.
_{GSDp = {(D 84p) /} (D 16p)} 0.5
If the volume average particle size and GSDp are both in the above ranges, extremely small particles do not exist, and therefore, it is possible to suppress a decrease in developability due to an excessive charge amount of the small particle size toner.

  A Coulter counter [TA-II] type (manufactured by Beckman Coulter, Inc.) can be used to measure the average particle size of particles such as resin particles and toner particles. In this case, measurement can be performed using an optimum aperture depending on the particle size level of the particles. The measured particle diameter is expressed by a volume average particle diameter.

When the particle size is about 5 μm or less, the particle size can be measured using a laser diffraction / scattering particle size distribution measuring device (LA-700, manufactured by Horiba, Ltd.).
The volume average primary particle size, number average particle size distribution index, volume average particle size distribution index, etc. of the produced aggregated particles are, for example, Coulter counter [TA-II] type (manufactured by Beckman Coulter, Inc.), Multisizer, etc. It can be measured with a measuring instrument such as II (manufactured by Beckman Coulter, Inc.). A cumulative distribution is drawn from the smaller diameter side to the particle size range (channel) divided on the basis of the particle size distribution, and the particle size that becomes 16% cumulative is the volume D _16v , the number D _16P , and the cumulative 50%. The particle diameter to be defined is defined as volume D _50v and number D _50P , and the particle diameter to be accumulated 84% is defined as volume D _84v and number D _84P . Using these, the volume average particle size distribution index (GSDv) can be calculated as (D _84v / D _16V ) ^1/2 and the number average particle size distribution index (GSDp) can be calculated as (D _84P / D _16P ) ^1/2 .

  The shape factor SF1 of the electrostatic image developing toner is preferably in the range of 110 to 145, more preferably in the range of 120 to 140. The shape factor SF1 is a shape factor indicating the degree of unevenness on the particle surface, and is calculated by the following equation.

In the formula, ML indicates the maximum length of the particle, and A indicates the projected area of the particle.
As a specific measurement method of SF1, for example, first, an optical microscope image of toner spread on a slide glass is taken into an image analysis device through a video camera, SF1 is calculated for 50 toners, and an average value is obtained. Is mentioned.

II. Method for Producing Toner for Developing Electrostatic Image The method for producing the toner for developing an electrostatic image of the present embodiment (hereinafter also simply referred to as “toner producing method”) is not particularly limited, and the existing kneading and pulverizing method, A process for producing an aqueous dispersion of resin particles including a block copolymer having a block obtained by polymerizing an ethylenically unsaturated compound (hereinafter, referred to as a chemical production method such as turbid polymerization or emulsion aggregation method) (hereinafter, referred to as a polymer dispersion method) , Also referred to as “block copolymer resin particle dispersion preparation step”).
When the toner manufacturing method of the present embodiment includes a block copolymer resin particle dispersion preparation step, an emulsion aggregation method or a suspension method can be preferably used as the toner manufacturing method of the present embodiment.

As a specific example of the production method of the toner for developing an electrostatic charge image of the present embodiment, a block copolymer for producing a block copolymer resin particle dispersion containing a block copolymer having a block obtained by polymerizing an ethylenically unsaturated compound. A production method comprising a step of preparing a polymer resin particle dispersion, an aggregation step of aggregating dispersed block copolymer resin particles to obtain aggregated particles, and a fusion step of heating and aggregating the aggregated particles Can be preferably exemplified.
Hereinafter, a method for producing the electrostatic charge image developing toner of this embodiment will be described.

<Block copolymer resin particle dispersion preparation process>
The block copolymer resin particle dispersion preparation step in this embodiment includes a block copolymer preliminarily polymerized by bulk polymerization, solution polymerization, etc., and then a rotary shear homogenizer, a ball mill having media, a sand mill, a dyno mill, pressure discharge Shear emulsification method that disperses in an aqueous medium with various mechanical high shear forces such as a type disperser (Gorin homogenizer, manufactured by Gorin Inc.), a phase inversion emulsification method in which an aqueous medium is added and phase is changed after the resin is dissolved in an organic solvent, The block copolymer or its precursor (living terminal low molecular weight or block) is mixed with a small amount of an ethylenically unsaturated compound, and after shear emulsification or phase inversion emulsification, the block copolymer is prepared by miniemulsion polymerization or suspension polymerization. An existing dispersion method such as a method of producing a resin particle dispersion can be used.

In miniemulsion polymerization or suspension polymerization, it is preferable not to use an organic solvent for dissolving the block copolymer or its precursor, and the block copolymer or its precursor is used only with a small amount of an ethylenically unsaturated compound. More preferably, it is dissolved.
In the miniemulsion polymerization or suspension polymerization, the ethylenically unsaturated compound to be mixed with the block copolymer is preferably an ethylenically unsaturated compound that becomes a polymer having a Tg of 40 ° C. or higher after polymerization. Specific examples of the ethylenically unsaturated compound include styrene, butyl acrylate and 2-ethylhexyl acrylate.

In the present embodiment, examples of the “aqueous medium” include water such as distilled water and ion exchange water, and the water to which alcohols such as ethanol and methanol are added. Among them, a mixed solution of ethanol and water or water is preferable, and water such as distilled water and ion exchange water is more preferable. These may be used individually by 1 type and may use 2 or more types together.
The aqueous medium may contain a water-miscible organic solvent in addition to the alcohols. Examples of the water-miscible organic solvent include acetone and acetic acid.

  In this embodiment, when the block copolymer is prepared by the NMRP method as described above, the mini-emulsion polymerization method is given as the most preferable aspect from the viewpoint that the resin particle dispersion can be stably prepared without using an organic solvent. be able to.

In preparing resin particle dispersions, various ionic surfactants such as anionic surfactants and cationic surfactants, nonionic surfactants (nonionic surfactants), inorganic dispersants, polymer types It is also possible to use a dispersant or the like.
For example, anionic surfactants include sodium dodecylbenzenesulfonate, sodium alkylnaphthalenesulfonate, sodium arylalkylpolyethersulfonate, 3,3-disulfone-N, N-diphenylurea, 4,4-diazo-bis- Sodium amino-8-naphthol-6-sulfonate, ortho-carboxybenzene-azo-dimethylaniline, 2,2,5,5-tetramethyl-triphenylmethane-4,4-diazo-bis-β-naphthol-6 -Sodium sulfonate, sodium dialkylsulfosuccinate, sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, sodium laurate, sodium caprate, sodium caprylate Um, sodium caproate, potassium stearate, and the like calcium oleate.
Examples of the cationic surfactant include alkylbenzene dimethyl ammonium chloride, alkyl trimethyl ammonium chloride, distearyl ammonium chloride and the like.
Nonionic surfactants include polyethylene oxide, polypropylene oxide, combinations of polypropylene oxide and polyethylene oxide, esters of polyethylene glycol and higher fatty acids, alkylphenol polyethylene oxide, esters of higher fatty acids and polyethylene glycol, higher fatty acids and polypropylene oxide. And water-soluble and oil-soluble surfactants such as esters and sorbitan esters.
Examples of the polymer colloid stabilizer include sodium polycarboxylate and polyvinyl alcohol, and examples of the inorganic dispersant include calcium carbonate. However, these do not limit the present embodiment.
Further, the pH of the aqueous dispersion can be adjusted with sodium hydroxide, potassium hydroxide, ammonia, or the like.

Furthermore, in the miniemulsion method, a small amount of a co-surfactant (Co-Stabilizer) can be used in combination. As the co-surfactant, a co-surfactant which is water-insoluble or hardly soluble and is soluble in the oil phase and used in the conventionally known “miniemulsion polymerization” can be used.
Examples of suitable co-surfactants include alkanes having 8 to 30 carbon atoms such as dodecane, hexadecane and octadecane, alkyl alcohols having 8 to 30 carbon atoms such as lauryl alcohol, cetyl alcohol and stearyl alcohol, and lauryl. C8-C30 alkyl (meth) acrylates such as (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, dodecanethiol, lauryl mercaptan, cetyl mercaptan, stearyl mercaptan, etc. Specific alkanethiols, and other polymers or polyadducts such as polystyrene and polymethyl methacrylate, carboxylic acids, ketones, amines, and the like.

In the case where an addition polymerizable monomer is used in the preparation of the mixed liquid and the phase inversion emulsification, the method for producing the toner for developing an electrostatic charge image according to this embodiment is an addition polymerization of an ethylenically unsaturated compound or the like in the phase inversion emulsification step. A step of polymerizing the polymerizable monomer (hereinafter also referred to as “addition polymerization step”) may be included.
The addition polymerizable monomer is preferably styrene and its derivatives, acrylic ester and its derivatives, methacrylic ester and its derivatives.

  The polymerization method is not particularly limited, but a polymerization method in a normal aqueous medium such as a suspension polymerization method, a dissolution suspension method, a miniemulsion method, a microemulsion method, a multistage swelling method or an emulsion polymerization method including seed polymerization. It is also possible to use two or more polymerization methods in combination.

  For the addition polymerizable monomer, known polymerization methods such as a method using a polymerization initiator, a self-polymerization method by heat, a method using ultraviolet irradiation, etc. can be adopted as the polymerization method. Among these, a polymerization initiator is used. The method used is preferred.

There is no restriction | limiting in particular as a polymerization initiator, A well-known radical polymerization initiator, a cationic polymerization initiator, and an anionic polymerization initiator can be used.
The polymerization initiator includes oil-soluble and water-soluble initiators, and both initiators can be arbitrarily used in consideration of the decomposition temperature, that is, the activation temperature.

The addition polymerizable monomer is preferably a radical polymerizable monomer.
In this case, the radical polymerization initiator includes oil-soluble and water-soluble initiators, but either initiator may be used.
Specific examples of the radical polymerization initiator include 2,2′-azobis (2-methylpropionitrile), 2,2′-azobis (2-methylbutyronitrile), and 2,2′-azobisiso. Butyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethyl-4-methoxyvaleronitrile), 1,1′-azobis (cyclohexanecarbonitrile) ), 2,2′-azobis (2-amidinopropane) hydrochloride azobisnitriles, acetyl peroxide, octanoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, decanoyl peroxide, lauroyl Diacyl peroxide such as peroxide, benzoyl peroxide, di-t-butyl peroxide, t-butyl Dialkyl peroxides such as til-α-cumyl peroxide and dicumyl peroxide, t-butyl peroxyacetate, α-cumyl peroxypivalate, t-butyl peroxyoctoate, t-butylperoxyneodecanoate Peroxyesters such as t-butylperoxylaurate, t-butylperoxybenzoate, di-t-butylperoxyphthalate, di-t-butylperoxyisophthalate, t-butylhydroperoxide, 2,5 Organic peroxides such as hydroperoxides such as dimethylhexane-2,5-dihydroperoxide, cumene hydroperoxide, di-isopropylbenzene hydroperoxide, peroxycarbonates such as t-butylperoxyisopropyl carbonate, Peroxidation Examples thereof include radical polymerization initiators such as inorganic peroxides such as hydrogen, and persulfates such as potassium persulfate, sodium persulfate, and ammonium persulfate. A redox polymerization initiator may be used in combination.

Moreover, you may use a chain transfer agent at the time of addition polymerization.
There is no restriction | limiting in particular as a chain transfer agent, Specifically, what has the covalent bond of a carbon atom and a sulfur atom is preferable, For example, thiols are mentioned preferably.

  When the toner according to the exemplary embodiment is manufactured by the emulsion aggregation method, the method for manufacturing the toner according to the exemplary embodiment includes aggregating the resin particles in a dispersion containing at least the block copolymer resin particle dispersion and preferably a colorant. It is preferable to include a step of obtaining aggregated particles (hereinafter also referred to as “aggregation step”) and a step of heating and aggregating the aggregated particles (hereinafter also referred to as “fusion step”).

As the aggregation step, for example, the resin particle dispersion is preferably mixed with a colorant particle dispersion, a release agent particle dispersion, and the like, and an aggregation agent is added to cause heteroaggregation, thereby agglomerating the toner diameter. The particles are formed, and then heated to a temperature higher than the glass transition temperature or higher than the melting point of the resin particles to fuse and coalesce the aggregated particles, followed by washing and drying. The temperature for fusion / unification is preferably higher than the melting point of the low Tg component of the resin used in the block copolymer or the Tg of the high Tg component.
The medium of each dispersion is preferably an aqueous medium.
In the aggregation step in the present embodiment, other resin particles other than the block copolymer resin particles, preferably a polymer of an ethylenically unsaturated compound and / or a non-crystalline polyester having a Tg of 40 ° C. or higher. Particles may be used.

  In addition, as a dispersion method of the colorant and the release agent, any method such as a rotary shear type homogenizer, a ball mill having a medium, a sand mill, a dyno mill, a homogenizer having a strong shearing ability, or a pressure discharge type disperser (Gorin homogenizer). It is possible to use a general dispersion method such as (manufactured by Gorin Co., Ltd.) and is not limited at all. Further, these colorant particles and release agent particles may be added together with other particle components in a mixed solvent at once, or may be divided and added in multiple stages.

Further, after the aggregation as described above to form the first aggregated particles, the above resin particle dispersion or another resin particle dispersion is further added, and the second shell layer is formed on the surface of the first aggregated particles. It is also possible to form. The material of the second shell layer is preferably a resin having a Tg of 40 ° C. or higher.
In this example, the colorant dispersion is prepared separately. However, when the colorant is mixed in advance with the resin particles, the colorant dispersion is not necessary, and the release agent is the same as this point. is there.

  When the emulsion aggregation method is used in the method for producing an electrostatic charge image developing toner of this embodiment, the aggregation is caused by pH change in the aggregation process, and the particle size of the toner particles containing the binder resin and the colorant is adjusted. can do. At the same time, an aggregating agent may be added in order to stably and rapidly aggregate the particles, or to obtain aggregated particles having a narrower particle size distribution.

  As the flocculant, a compound having a monovalent or higher charge is preferable, and specific examples of the compound include water-soluble surfactants such as the above-mentioned ionic surfactants and nonionic surfactants, hydrochloric acid, sulfuric acid, and the like. Acids such as nitric acid, acetic acid, oxalic acid, magnesium chloride, sodium chloride, aluminum sulfate, calcium sulfate, ammonium sulfate, aluminum nitrate, silver nitrate, copper sulfate, sodium carbonate, inorganic acid metal salts, sodium acetate, potassium formate, sulphate Examples thereof include metal salts of aliphatic acids such as sodium acid, sodium phthalate and potassium salicylate, metal salts of aromatic acids, and metal salts of phenols such as sodium phenoxide.

In consideration of the stability of the aggregated particles, the stability of the coagulant with respect to heat and time, and the removal during washing, a metal salt of an inorganic acid is preferable as the coagulant in terms of performance and use. Specific examples include metal salts of inorganic acids such as magnesium chloride, sodium chloride, aluminum sulfate, calcium sulfate, ammonium sulfate, aluminum nitrate, silver nitrate, copper sulfate, and sodium carbonate.
The amount of these flocculants added varies depending on the valence of the charge, but they are all small, 3% or less for monovalent, 1% or less for divalent, 0 for trivalent. .5% by weight or less. Since the amount of the flocculant is preferably small, it is preferable to use a compound having a large valence.

In the present embodiment, the aggregating method is not particularly limited, and the aggregating method conventionally used in the emulsion aggregation method of electrostatic charge image developing toner, for example, temperature increase, pH change, salt addition For example, a method of reducing the stability of the emulsion by a method such as stirring with a disperser or the like is used.
Further, after the agglomeration treatment, the particle surface may be cross-linked by heat treatment or the like for the purpose of suppressing colorant exudation from the particle surface. In addition, you may remove the used surfactant etc. by water washing | cleaning, acid washing | cleaning, or alkali washing | cleaning as needed.

The median diameter of the resin particles in the other resin particle dispersion that can be used in the present embodiment is preferably 0.1 to 2.0 μm.
Further, the median diameter of the colorant particles of the colorant particle dispersion that can be used in the aggregation step and the median diameter of the release agent particles of the release agent particle dispersion are 0.1 to 2.0 μm. It is preferable.

  In the fusing step, the binder resin in the aggregated particles melts under a temperature condition equal to or higher than the melting point of the low Tg component or the glass transition temperature of the high Tg component of the block copolymer, and the aggregated particles change from amorphous to more spherical. And change. Thereafter, the agglomerated particles are separated from the aqueous medium, and washed and dried as necessary to form toner particles.

  After completion of the aggregation step and the fusion step, a desired toner may be obtained through an arbitrary washing step, solid-liquid separation step, and drying step. In the washing step, it is preferable to sufficiently perform substitution washing with ion-exchanged water from the viewpoint of chargeability. The solid-liquid separation step is not particularly limited, but suction filtration, pressure filtration, and the like are preferably used from the viewpoint of productivity. Furthermore, the drying process is not particularly limited, but freeze drying, flash jet drying, fluidized drying, vibration fluidized drying, etc. are preferably used from the viewpoint of productivity.

In addition, the manufacturing method of the toner for developing an electrostatic charge image according to the exemplary embodiment includes various known internal additives such as a charge control agent, an antioxidant, and an ultraviolet absorber used for this type of toner, if necessary. May be used.
These additives can be added at the time of preparation of the mixture, at the time of emulsification dispersion, at the time of aggregation, or the like, if necessary. The charge control agent is preferably added as an aqueous dispersion or the like. The addition amount of the charge control agent is preferably 1 to 25% by weight, and 5 to 15% by weight with respect to 100% by weight of the oil phase. % Is more preferable. Here, the oil phase is a solid content obtained by removing an organic solvent or the like from components emulsified and dispersed in an aqueous medium.

III. Electrostatic Image Developer The electrostatic image developing toner of the exemplary embodiment can be used as an electrostatic image developer (hereinafter also referred to as “developer”). The developer is not particularly limited except that it contains the toner for developing an electrostatic image, and can have an appropriate component composition depending on the purpose. When the electrostatic image developing toner is used alone, it is prepared as a one-component electrostatic image developer, and when used in combination with a carrier, it is prepared as a two-component electrostatic image developer.
As a one-component developer, a method in which a charged toner is formed by frictional charging with a developing sleeve or a charging member, and development according to an electrostatic latent image can be applied.

  The carrier is not particularly limited, but usually, magnetic particles such as iron powder, ferrite, iron oxide powder, nickel, etc .; the magnetic particles as a core material and the surface thereof as a styrene resin, vinyl resin, ethylene resin, rosin Resin-coated carrier formed by coating a resin such as a resin based on polyester, polyester or melamine, or a wax such as stearic acid, and forming a resin coating layer; a magnetic material obtained by dispersing magnetic particles in a binder resin Examples include a distributed carrier. Among them, the resin-coated carrier is particularly preferable because the chargeability of the toner and the resistance of the entire carrier can be controlled by the configuration of the resin coating layer.

  The mixing ratio of the electrostatic image developing toner of this embodiment and the carrier in the two-component electrostatic image developer is 2 to 10 parts by weight of the electrostatic image developing toner with respect to 100 parts by weight of the carrier. Is preferred. 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.

IV. Image Forming Method and Image Forming Apparatus The electrostatic image developing toner of the present embodiment and the electrostatic image developer of the present embodiment can be used in an image forming method of a normal electrostatic image developing system (electrophotographic system). In particular, it can be preferably used in the image forming method and the image forming apparatus of the present embodiment.

The image forming method of the present embodiment includes an electrostatic latent image forming step of forming an electrostatic latent image on the surface of the latent image holding member, and the electrostatic latent image formed on the surface of the latent image holding member is treated with toner or the toner and carrier. A developing process for forming a toner image by developing with an electrostatic charge image developer, a transfer process for transferring the toner image formed on the surface of the latent image holding body to the surface of the transferred body, and the surface of the transferred body A fixing step of fixing the toner image transferred to the surface by pressing or heating and pressing, wherein the toner is the electrostatic image developing toner of the present embodiment, or the electrostatic image developer is of the present embodiment. An electrostatic charge image developer, wherein the fixing pressure in the fixing step is 5 to 300 kgf / cm ² .
Further, the image forming apparatus of the present embodiment includes a latent image holding member, a charging unit for charging the latent image holding member, and exposing the charged latent image holding member to form an electrostatic latent image on the latent image holding member. An exposure unit for forming, a developing unit for developing the electrostatic latent image with a developer to form a toner image, a transfer unit for transferring the toner image from the latent image holding member to the transfer target, and the transfer target The toner image transferred to the surface has fixing means for fixing by pressurizing or heating and pressurizing, and the fixing pressure when the pressurizing or heating and pressurizing is 5 to 300 kgf / cm ^2. The electrostatic image developing toner of the present embodiment, the electrostatic image developing toner manufactured by the manufacturing method of the present embodiment, or the electrostatic image developer of the present embodiment is used as the developer.
In the transfer step or the transfer means, a transfer step or transfer means for transferring twice or more using an intermediate transfer member may be provided.

  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 the surface of the latent image holding member.
The developing step is a step of developing the electrostatic latent image with a developer layer on a developer carrier to form a toner image. The developer layer is not particularly limited as long as it contains the electrostatic image developer of this embodiment containing the electrostatic image developing toner of the present embodiment.
The transfer step is a step of transferring the toner image onto a transfer target.
In the fixing step, a toner image on a transfer medium such as paper is fixed by pressurizing or heat-pressing the toner image by a heating roller fixing device or the like in which the temperature of the roller or the heating roller is set to a constant temperature to form a copy image. It is a process.

The fixing pressure in the fixing step for fixing the toner image on the transfer medium by pressing or heating and pressing is 5 to 300 kgf / cm ² . When the fixing pressure is less than 5 kgf / cm ² , there is a problem that sufficient fixing property is not achieved and the image strength is practically insufficient. Further, when the fixing pressure exceeds 300 kgf / cm ² , there is a problem that image quality characteristics are deteriorated due to paper wrinkles, paper spread, and the like. Fusing pressure is preferably ^{10~200kgf / cm 2, 20~100kgf / cm} 2 is more preferable. Within the above range, both excellent fixability and image quality characteristics can be achieved.

  In the fixing step, when the image is fixed by heating and pressing, the heating temperature is preferably 40 to 120 ° C, more preferably 50 to 100 ° C.

The image forming process of the present embodiment preferably further includes a cleaning process. The cleaning step is a step of removing the electrostatic charge image developer remaining on the latent image holding member.
In the image forming method of the present embodiment, an aspect that further includes a recycling step is preferable. The recycling step is a step of transferring the electrostatic image developing toner collected in the cleaning step to a developer tank. The image forming method including the recycling step can be performed using an image forming apparatus such as a toner recycling system type copying machine or facsimile machine. The present invention can also be applied to a recycling system in which the cleaning process is omitted and toner is collected simultaneously with development.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, a following example does not limit this invention at all. Hereinafter, “part” means “part by weight” and “%” means “% by weight” unless otherwise specified.

  In the following examples, the volume average particle size was measured by the following method. Moreover, the method described in the above-mentioned description was used for the measurement of molecular weight, glass transition point (Tg), and flow tester viscosity.

<Measurement of volume average particle diameter of particles>
A Coulter counter [TA-II] type (manufactured by Beckman Coulter, Inc.) was used to measure the volume average particle diameter of the particles. In this case, measurement was performed using an optimum aperture depending on the particle size level of the particles. The particle diameter of the measured particle is represented by a volume average particle diameter (μm).
When the particle size of the particles was about 5 μm or less, the measurement was performed using a laser diffraction / scattering particle size distribution analyzer (LA-700, manufactured by Horiba, Ltd.).

<Synthesis of 2-methyl-2- [N- (tert-butyl) -N- (1-diethoxyphosphoryl-2,2-dimethylpropyl) -aminoxy] -propionic acid (MBPAP)>
In a nitrogen purged glass container 500 ml degassed toluene, 35.9 parts CuBr, 15.9 parts copper powder, 86.7 parts N, N, N ′, N ′, N ″ -pentamethyldiethylenetriamine 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 room temperature, after which the reaction medium was filtered and the toluene filtrate was washed twice with a saturated aqueous NH ₄ Cl solution. 2-methyl-2- [N- (tert-butyl) -N- (1-diethoxyphosphoryl-2,2-dimethylpropyl) -aminoxy] -propionic acid MBPAP) was obtained.
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.

<Preparation of release agent particle dispersion>
Ester wax (manufactured by NOF Corporation: WE-2, melting point 65 ° C.): 50 parts Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen RK): 5 parts Ion exchange water: 200 The above components were mixed, heated to 95 ° C., dispersed using a homogenizer (manufactured by IKA: Ultra Tarrax T50), then dispersed with a Manton Gorin high-pressure homogenizer (manufactured by Gorin), and an average particle size of 230 nm. A release agent particle dispersion (release agent concentration: 20% by weight) obtained by dispersing a release agent as described above was prepared.

<Preparation of colorant particle dispersion>
Cyan pigment (Daiichi Seika Kogyo Co., Ltd., Pigment Blue 15: 3 (copper phthalocyanine)): 1,000 parts Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen R): 150 parts Ion-exchanged water: 9,000 parts or more are mixed, dissolved, and dispersed for about 1 hour using a high-pressure impact disperser Ultimateizer (manufactured by Sugino Machine Co., Ltd., HJP30006) to disperse the colorant (cyan pigment). A colorant particle dispersion was prepared. The average particle diameter of the colorant (cyan pigment) in the colorant particle dispersion was 0.15 μm, and the colorant particle concentration was 23% by weight.

Example 1
<Preparation of block copolymer resin (1)>
Add 200 parts of styrene monomer (St) and 14.8 parts of MBPAP to a glass container equipped with a reflux condenser, a nitrogen inlet pipe, and a stirrer, and mix well at 80 ° C. under a nitrogen stream. The styrene was polymerized by raising. The molecular weight was measured at any time by GPC, and when the number average molecular weight of styrene reached 5,100, the amount of residual styrene was measured by the weight loss method and the polymerization rate (conversion rate) was determined to be 99.5%. there were. Thereafter, 212 parts of butyl acrylate (BA) was added, polymerization was continued at 130 ° C., and chain extension with butyl acrylate was performed. When the number average molecular weight of the butyl acrylate block was 5,400 and the sum of the number of styrene chains polymerized first was 10,500, the mixture was cooled to room temperature. The polymer was dissolved in 225 parts of THF and taken out, and dropped into methanol to reprecipitate the block polymer. The precipitate was filtered, washed with methanol, vacuum dried at 40 ° C., and styrene and butyl. An acrylate block copolymer resin (1) was obtained.

  In addition, a styrene homopolymer having a number average molecular weight of 5,100 was prepared by the same operation using 50 parts of styrene and 3.7 parts of MBPAP using the above polymerization apparatus, and after purification in the same manner, the glass transition point (Tg) It was 78 degreeC when the measurement was performed.

  Further, a homopolymer having a number average molecular weight of 5,400 was polymerized in the same manner using 53 parts of butyl acrylate and 3.7 parts of MBPAP, and Tg after purification was confirmed to be -35 ° C.

Further, when the temperature at which the flow tester viscosity of the obtained block copolymer resin (1) was 10 ⁴ Pa · s was measured, it was 95 ° C. (T (P5)) at 5 kgf / cm ² and 300 kgf / cm ² . Was 53 ° C. (T (P300)), and T (P5) -T (P300) was 42 ° C.

<Preparation of resin particle dispersion (1)>
To 400 parts of the block copolymer resin (1), 8.0 parts of sorbitan sesquiolate and 120 parts of methyl ethyl ketone (MEK) in which 0.8 parts of sodium dodecylbenzenesulfonate are dissolved are added, and a reflux condenser, a stirrer, ion The mixture was added to a reactor equipped with a replacement water dropping device and a heating device, and then mixed well at 65 ° C. Then, after heat-mixing at 65 degreeC for 1 hour, 1,000 parts of ion-exchange water were dripped at the speed | rate of 1 part / min, and phase-phase emulsification of the block copolymer resin (1) was performed. Further, the phase-inverted emulsion was cooled and MEK was removed from the emulsion under reduced pressure at 60 ° C. using an evaporator to obtain a resin particle dispersion (1).
The volume average particle diameter of the resin particles in the obtained resin particle dispersion was 205 nm, and the solid content concentration was 42.5%.

<Manufacture of toner particles (1)>
Resin particle dispersion (1): 565 parts (240 parts solid content)
Colorant particle dispersion: 22.87 parts (solid content 5.3 parts)
Release agent particle dispersion: 50 parts (solid content 10 parts)
Among the raw materials, 158 parts (67 parts solids) of the resin particle dispersion (1) were left, and the raw materials were placed in a cylindrical stainless steel container and dispersed and mixed for 30 minutes while applying a shearing force at 8,000 rpm with Ultraturrax. Subsequently, 0.14 part of 10% nitric acid aqueous solution of polyaluminum chloride was dropped as a flocculant. At this time, the pH of the raw material dispersion was controlled in the range of 4.2 to 4.5. The pH was adjusted with 0.3N nitric acid or 1N aqueous sodium hydroxide as required. Thereafter, the raw material dispersion is transferred to a polymerization kettle equipped with a stirrer and a thermometer and heated to promote the growth of adhered aggregated particles at 40 ° C. When the volume average particle diameter reaches 5.0 μm, 158 parts of the separated resin particle dispersion (1) was gradually added afterwards, the temperature was raised to 50 ° C., and the particle diameter was adjusted to 6.1 μm. Further, after raising the pH to 7.5, the temperature was raised to 98 ° C. and held at 98 ° C. for 6 hours, and then the pH was gradually lowered to 6.5, then the heating was stopped and the mixture was allowed to cool. Thereafter, it was sieved with a 45 μm mesh, washed repeatedly with water and then dried with a freeze dryer to obtain toner particles (1).
The volume average particle size of the toner particles (1) was measured using a Coulter Multisizer TA-II type (aperture diameter: 50 μm; manufactured by Beckman Coulter, Inc.). As a result, the particle size was 6.1 μm, and the volume average particle size was The distribution was 1.22.

<Preparation and Evaluation of Electrostatic Charge Image Developer (1)>
To the toner particles (1) thus obtained, 1 part of colloidal silica (Aerosil R972, manufactured by Nippon Aerosil Co., Ltd.) is externally added and mixed using a Henschel mixer, thereby developing an electrostatic charge image developing toner. (1) was obtained.
On the other hand, 100 parts of ferrite particles (manufactured by Powdertech Co., Ltd., EFC50B, average particle size 50 μm) and 1 part of methacrylate resin (Mitsubishi Rayon Co., Ltd., molecular weight 95,000) are combined with 500 parts of toluene into a pressure kneader. After mixing for 15 minutes at room temperature, the temperature is raised to 70 ° C. while mixing under reduced pressure, and after distilling off toluene, cooling and sizing using a 105 μm sieve, a ferrite carrier (resin-coated carrier) Was made.
This ferrite carrier and the electrostatic image developing toner (1) were mixed to prepare a two-component electrostatic image developer (1) having a toner concentration of 7% by weight.

<Toner strength, fixing test, fixed image strength test>
A modified machine of DocuCenterColor f450 manufactured by Fuji Xerox Co., Ltd. was used. As for the fixing device, a two-roll type fixing device capable of adjusting the maximum fixing pressure was modified, and the image-side pressure roll was changed to a high-hardness roll in which a SUS tube was coated with Teflon (registered trademark). The above-mentioned Fuji Xerox S paper was used as the transfer paper.

(Toner strength in the system)
In order to examine the strength of the toner in the system, after continuous printing of 5,000 sheets at an image density of 5%, the toner is visually checked for crushing, destruction, and aggregation in the developing machine as follows. Evaluation was performed.
◯: Level where there is no problem with crushing, destruction, and aggregation of toner △: Level at which crushing, destruction, and aggregation of toner are somewhat observed but no problem in practical use ×: Crushing, destruction, and aggregation of toner are remarkable and practically large Level at which the problem has occurred: As a result of the evaluation of the toner strength in the system using the electrostatic image developing toner (1) and the electrostatic image developer (1), a slight toner collapse is observed, but there is no practical problem. It was level (△).

(Fixability with various fixing pressures)
The fixing pressure of the fixing machine was set to 10 kgf / cm ² , 50 kgf / cm ² , and 100 kgf / cm ² , and then the fixing roll was heated to 60 ° C. to fix the image, and the following evaluation was made regarding the fixing property.
○: No image unevenness (gross unevenness), good adhesion to paper, and no problem level Δ: Although slight image unevenness is observed, adhesion to paper is good and practically no problem ×: Image Uneven level with practical problems in adhesion to paper As a result of the evaluation of fixability using the electrostatic image developing toner (1) and the electrostatic image developer (1), good at all pressures Fixing property (◯).

(Fixed image strength)
The pencil scratch test based on JIS K5400 of the image part after the above 10 kgf / cm ² fixing was performed, and the following determination was performed based on the pencil hardness.
○: Level with no problem at pencil hardness H or higher Δ: Level at which there is no problem with practical use when pencil hardness is HB or higher X: Level with practical problem when pencil hardness is lower than HB Above, electrostatic image developing toner (1) and electrostatic charge As a result of evaluating the strength of the fixed image using the image developer (1), the pencil hardness HB was shown to be a level having no practical problem (Δ).

(Example 2)
<Preparation of block copolymer resin (2)>
In the same manner as in Example 1, a block copolymer resin (2) was produced using 200 parts of styrene monomer, 208 parts of butyl acrylate, and 2.9 parts of MBPAP.
Further, the number average molecular weight of each unit, the total number average molecular weight, and the flow tester temperature reaching 10 ⁴ Pa · s under each pressure were measured in the same manner as in Example 1, and the results are shown in Table 1.
Polymerization of each homopolymer was carried out in the same manner as in Example 1, using 0.73 part of MBPAP for 50 parts of styrene monomer and 0.73 part of MBPAP for 52 parts of butyl acrylate monomer. Asked. The results are shown in Table 1.

<Preparation of resin particle dispersion (2)>
Using the block copolymer resin (2), emulsification was carried out in the same manner as in Example 1 to prepare a resin particle dispersion (2). The volume average particle diameter of the resin particles in the obtained resin particle dispersion was 198 nm, and the solid content concentration was 42.5%.

<Production of toner particles (2)>
Using the resin particle dispersion (2), toner particles (2) were produced in the same manner as in Example 1. As a result of measuring the volume average particle size of the final toner particles, the particle size was 6.2 μm and the volume average particle size distribution was 1.21.

<Preparation and Evaluation of Electrostatic Image Developing Toner (2) and Electrostatic Image Developer (2)>
Using the toner particles (2), an electrostatic image developing toner (2) and an electrostatic image developer (2) were produced in the same manner as in Example 1.

<Toner strength, fixing test, fixed image strength test>
Using the electrostatic image developing toner (2) and the electrostatic image developer (2), the toner strength, fixing test and fixed image strength test were conducted in the same manner as in Example 1. The results are shown in Table 1.

(Example 3)
<Preparation of block copolymer resin (3)>
In the same manner as in Example 1, a block copolymer resin (3) was produced using 200 parts of styrene monomer, 199 parts of methyl acrylate (MA), and 1.9 parts of MBPAP. Further, the number average molecular weight of each unit, the total number average molecular weight, and the flow tester temperature reaching 10 ⁴ Pa · s under each pressure were measured in the same manner as in Example 1, and the results are shown in Table 1.

  Polymerization of each homopolymer was carried out in the same manner as in Example 1 by using 0.48 part of MBPAP for 50 parts of styrene monomer and 0.48 part of MBPAP for 48 parts of methyl acrylate monomer to obtain Tg of each homopolymer. It was. The results are shown in Table 1.

<Preparation of resin particle dispersion (3)>
Using the block copolymer resin (3), emulsification was carried out in the same manner as in Example 1 to prepare a resin particle dispersion (3). The volume average particle size of the resin particles in the obtained resin particle dispersion was 199 nm, and the solid content concentration was 42.5% by weight.

<Manufacture of toner particles (3)>
Using the resin particle dispersion (3), toner particles (3) were produced in the same manner as in Example 1. As a result of measuring the volume average particle size of the toner particles (3), the particle size was 6.1 μm and the volume average particle size distribution was 1.21.

<Production and Evaluation of Toner for Electrostatic Image Development (3) and Electrostatic Charge Image Developer (3)>
Using toner particles (3), an electrostatic image developing toner (3) and an electrostatic image developer (3) were produced in the same manner as in Example 1.

<Toner strength, fixing test, fixed image strength test>
Using the electrostatic image developing toner (3) and the electrostatic image developer (3), the toner strength, fixing test and fixed image strength test were conducted in the same manner as in Example 1. The results are shown in Table 1.

Example 4
<Preparation of block copolymer resin (4)>
In the same manner as in Example 1, 200 parts of styrene monomer, 207 parts of butyl acrylate, and 1.1 parts of MBPAP were used to prepare a block copolymer resin (4). The number average molecular weight of each unit, the total number average molecular weight, and the flow tester temperature reaching 10 ⁴ Pas under each pressure were measured in the same manner as in Example 1, and the results are shown in Table 1.
Polymerization of each homopolymer was carried out in the same manner as in Example 1 by using 0.28 parts of MBPAP for 50 parts of styrene monomer and 0.28 parts of MBPAP for 52 parts of butyl acrylate monomer to obtain the Tg of each homopolymer. It was. The results are shown in Table 1.

<Preparation of resin particle dispersion (4)>
Using the block copolymer resin (4), emulsification was carried out in the same manner as in Example 1 to prepare a resin particle dispersion (4). The volume average particle diameter of the resin particles in the obtained resin particle dispersion was 196 nm, and the solid content concentration was 42.5%.

<Preparation of styrene / butyl acrylate / acrylic acid (AA) random polymer resin particle dispersion (4-2)>
In a reactor equipped with a reflux condenser, a stirrer, a nitrogen inlet, and a monomer dropping port, 3.3 parts of sodium dodecylbenzenesulfonate was dissolved in 3,824 parts of ion-exchanged water, and then 30.6 parts of styrene and butyl acrylate. 9.4 parts, 1.2 parts of acrylic acid dimer, and 0.3 parts of dodecanethiol were added and stirred well at room temperature to stabilize the emulsion (emulsion 1).
Further, 3,000 parts of styrene, 940 parts of butyl acrylate, 120 parts of acrylic acid dimer, 63 parts of dodecanethiol, and 1,327 parts of ion-exchanged water in which 39 parts of sodium dodecylbenzenesulfonate were dissolved in a vessel equipped with a stirrer. The mixture was added and emulsified separately using a homomixer. After emulsification, the stirring was continued gently with a four-paddle stirrer (emulsified liquid 2). After sufficiently replacing nitrogen inside the emulsion 1, the temperature was further increased to 75 ° C. while introducing nitrogen, and 600 parts of 10% aqueous solution of ammonium persulfate (APS) was added thereto, followed by heating for 10 minutes. Thereafter, the emulsion 2 was gradually brought down over 3 hours from the monomer dropping port of the reactor of the emulsion 1 with a pump, and the reaction at 75 ° C. was continued. Further, after completion of the dropwise addition of the emulsion 2, the reaction was continued at 75 ° C. for 3 hours, followed by cooling to obtain a resin particle dispersion (4-2) having a particle size of 200 nm and a solid content concentration of 42.5%. The dispersion was dried and the molecular weight of the polymer was measured. The number average molecular weight was 11,000 and its Tg was 51 ° C.

<Production of toner particles (4)>
In the same manner as in Example 1, 407 parts of the resin particle dispersion (4) was added instead of the resin particle dispersion (1) to be initially added to perform aggregation, and then the resin particle dispersion (1) to be added later was added. Instead, 158 parts of resin particle dispersion (4-2) was used to prepare toner particles (4). As a result of measuring the volume average particle size of the final toner particles, the particle size was 6.3 μm and the volume average particle size distribution was 1.23.

<Preparation and Evaluation of Electrostatic Image Developing Toner (4) and Electrostatic Image Developer (4)>
Using toner particles (4), an electrostatic image developing toner (4) and an electrostatic image developer (4) were prepared in the same manner as in Example 1.

<Toner strength, fixing test, fixed image strength test>
Using the electrostatic image developing toner (4) and the electrostatic image developer (4), the toner strength, fixing test, and fixed image strength test were conducted in the same manner as in Example 1. The results are shown in Table 1.

(Example 5)
<Preparation of block copolymer resin (5)>
In the same manner as in Example 1, 300 parts of styrene monomer, 282 parts of butyl acrylate, and 3.3 parts of MBPAP were used to prepare a block copolymer resin (5). In addition, the number average molecular weight of each unit, the total number average molecular weight, and the flow tester temperature reaching 10 ⁴ Pa · s under each pressure were measured in the same manner as in Example 1, and the results are shown in Table 1.
Polymerization of each homopolymer was carried out in the same manner as in Example 1 by using 0.55 parts of MBPAP for 50 parts of styrene monomer and 0.55 parts of MBPAP for 47 parts of butyl acrylate monomer to obtain the Tg of each homopolymer. It was. The results are shown in Table 1.

<Preparation of resin particle dispersion (5)>
Using the block copolymer resin (5), emulsification was carried out in the same manner as in Example 1 to prepare a resin particle dispersion (5). The volume average particle diameter of the resin particles in the obtained resin particle dispersion was 220 nm, and the solid content concentration was 42.5%.

<Preparation of terephthalic acid (TPA) / bisphenol A ethylene oxide 2-mole adduct (BPAEO) / dodecenyl succinic acid (DSA) resin particle dispersion (5-2)>
(Polyvalent carboxylic acid component)
Terephthalic acid: 70 mol%
Dodecenyl succinic anhydride: 30 mol%
(Polyhydric alcohol component)
Bisphenol A ethylene oxide 2-mol adduct: 100 mol%
A total of 3,000 parts of the polyvalent carboxylic acid component and the polyhydric alcohol component are charged into a 5 liter flask equipped with a stirrer, a nitrogen introduction tube, a temperature sensor, and a rectifying column, and 190 hours are required for 1 hour. After confirming that the reaction system was uniformly stirred, the catalyst Ti (OBu) ₄ (0.003% by weight with respect to the total amount of the polyvalent carboxylic acid component) was added.
Further, while distilling off the generated water, the temperature was increased from the same temperature to 6 hours, and the temperature was raised to 240 ° C., and the dehydration condensation reaction was further continued at 240 ° C. for 12 hours to carry out the polymerization, and the amorphous polyester resin (1) Got. When the molecular weight of the obtained amorphous polyester resin (1) was measured by GPC, the number average molecular weight was 3,980, and the Tg in DSC measurement was 56 ° C.
Using the obtained terephthalic acid / bisphenol A ethylene oxide 2-mol adduct / dodecenyl succinic polyester resin, emulsification was carried out in the same manner as in Example 1 to prepare a resin particle dispersion (5). The volume average particle diameter of the resin particles in the obtained resin particle dispersion was 205 nm, and the solid content concentration was 42.5%.

<Manufacture of toner particles (5)>
In the same manner as in Example 1, 407 parts of the resin particle dispersion (5) is added instead of the resin particle dispersion (1) that is initially added to perform aggregation, and then the resin particle dispersion (1) to be added later is added. Toner particles (5) were prepared using 158 parts of resin particle dispersion liquid (5-2) instead of the above. As a result of measuring the volume average particle size of the final toner particles, the particle size was 6.7 μm and the volume average particle size distribution was 1.25.

<Production and Evaluation of Toner for Electrostatic Image Development (5) and Electrostatic Charge Image Developer (5)>
Using toner particles (5), an electrostatic charge image developing toner (5) and an electrostatic charge image developer (5) were prepared in the same manner as in Example 1.

<Toner strength, fixing test, fixed image strength test>
Using the electrostatic image developing toner (5) and the electrostatic image developer (5), the toner strength, fixing test, and fixed image strength test were conducted in the same manner as in Example 1. The results are shown in Table 1.

(Example 6)
<Preparation of block copolymer resin (6) and resin particle dispersion (6) by miniemulsion>
As in Example 1, bulk polymerization of styrene was first performed using 250 parts of styrene monomer and 3.1 parts of MBPAP to obtain a resin having a number average molecular weight of 31,000. Thereafter, this resin was dissolved in 250 parts of 2-ethylhexyl acrylate (2EHA). Next, 697 parts of ion-exchanged water in which 12 parts of sodium dodecylbenzenesulfonate was dissolved was adjusted to pH 9 with 0.1N sodium hydroxide, and then the 2-ethylhexyl acrylate mixed solution in which the styrene polymer was dissolved was gradually stirred. A suspension was prepared by dropping. This suspension solution was further preliminarily dispersed at room temperature using ultrasonic waves, and then further emulsified and dispersed using an ultrahigh pressure homogenizer (Nanomizer manufactured by Yoshida Kikai Kogyo Co., Ltd.). An emulsion of 25 μm was obtained.
This emulsion was put into a 2 L pressure reactor equipped with a stirrer and subjected to chain extension polymerization of 2-ethylhexyl acrylate under nitrogen pressure (0.5 Mpa) at 120 ° C. for 8 hours to obtain a resin particle dispersion ( 6) was obtained. The reaction product maintained a stable emulsified state, its number average molecular weight was 62,000, solid content concentration was 42.5%, and volume average particle size was 300 nm.
Table 1 shows the results obtained by partially drying the emulsion and measuring the characteristics of the resin. Further, as in Example 1, Tg of styrene and 2-ethylhexyl acrylate homopolymer was determined by separately conducting bulk polymerization using 50 g of styrene and 0.6 g of MBPAP, and 50 g of 2-ethylhexyl acrylate and 0.6 g of MBPAP.

<Manufacture of toner particles (6)>
Using the resin particle dispersion (6), toner particles (6) were produced in the same manner as in Example 1. As a result of measuring the volume average particle size of the final toner particles, the particle size was 6.6 μm and the volume average particle size distribution was 1.21.

<Production and Evaluation of Toner for Electrostatic Image Development (6) and Electrostatic Charge Image Developer (6)>
Using toner particles (6), an electrostatic image developing toner (6) and an electrostatic image developer (6) were produced in the same manner as in Example 1.

<Toner strength, fixing test, fixed image strength test>
Using the electrostatic image developing toner (6) and the electrostatic image developer (6), the toner strength, fixing test and fixed image strength test were conducted in the same manner as in Example 1. The results are shown in Table 1.

(Example 7)
<Preparation of block copolymer resin (7) and resin particle dispersion (7) by miniemulsion>
Similarly to Example 6, miniemulsion polymerization was performed using 250 parts of styrene monomer, 284 parts of hexyl methacrylate (HMA), and 2.9 parts of MBPAP.
In this case, the number average molecular weight in polymerization of styrene was 33,000, the number average molecular weight after chain extension with hexyl methacrylate was 70,500, the solid content concentration was 42.5%, and the volume average particle diameter was 280 nm.

The Tg of each homopolymer was determined using 50 parts of styrene, 57 parts of hexyl methacrylate, and 0.58 parts of MBPAP in the same manner as in Example 6.
The results of measuring the properties of these resins are shown in Table 1.

<Production of toner particles (7)>
Using the resin particle dispersion (7), toner particles (7) were produced in the same manner as in Example 1. As a result of measuring the volume average particle size of the final toner particles, the particle size was 6.3 μm and the volume average particle size distribution was 1.21.

<Preparation and Evaluation of Electrostatic Charge Image Developer (7)>
Using toner particles (7), an electrostatic charge image developing toner (7) and an electrostatic charge image developer (7) were produced in the same manner as in Example 1.

<Toner strength, fixing test, fixed image strength test>
Using the electrostatic image developing toner (7) and the electrostatic image developer (7), the toner strength, fixing test and fixed image strength test were conducted in the same manner as in Example 1. The results are shown in Table 1.

(Comparative Example 1)
<Manufacture of toner particles (8)>
In the same manner as in Example 1, toner particles (8) were produced using the random polymer of styrene / butyl acrylate / acrylic acid used in Example 4 instead of the block copolymer resin (1) of Example 1. . The final toner particles had a volume average particle size of 6.0 μm and a volume average particle size distribution of 1.21. Table 1 summarizes various resin properties of the random polymer used for toner preparation.

<Production and Evaluation of Toner for Electrostatic Image Development (8) and Electrostatic Image Developer (8)>
Using toner particles (8), an electrostatic image developing toner (8) and an electrostatic image developer (8) were produced in the same manner as in Example 1.

<Toner strength, fixing test, fixed image strength test>
Using the electrostatic image developing toner (8) and the electrostatic image developer (8), the toner strength, fixing test and fixed image strength test were conducted in the same manner as in Example 1. The results are shown in Table 1.

(Comparative Example 2)
<Preparation of block copolymer resin (8)>
Similarly to Example 1, a block copolymer resin (8) was produced using 250 parts of styrene, 257 parts of butyl acrylate, and 23.6 parts of MBPAP. The number average molecular weight of each unit, the total number average molecular weight, and the flow tester temperature reaching 10 ⁴ Pa · s under each pressure were measured in the same manner as in Example 1, and the results are shown in Table 1.
Polymerization of each homopolymer was carried out in the same manner as in Example 1 by using 4.7 parts of MBPAP for 50 parts of styrene monomer and 4.7 parts of MBPAP for 51 parts of butyl acrylate monomer to obtain the Tg of each homopolymer. It was. The results are shown in Table 1.

<Preparation of resin particle dispersion (8)>
Using the block copolymer resin (8), emulsification was carried out in the same manner as in Example 1 to prepare a resin particle dispersion (8). The volume average particle diameter of the resin particles in the obtained resin particle dispersion was 189 nm, and the solid content concentration was 42.5%.

<Production of toner particles (9)>
Using the resin particle dispersion (8), toner particles (9) were produced in the same manner as in Example 1. As a result of measuring the volume average particle size of the toner particles (9), the particle size was 6.0 μm and the volume average particle size distribution was 1.21.

<Production and Evaluation of Toner for Electrostatic Image Development (9) and Electrostatic Charge Image Developer (9)>
Using toner particles (9), an electrostatic image developing toner (9) and an electrostatic image developer (9) were produced in the same manner as in Example 1.

<Toner strength, fixing test, fixed image strength test>
Using the electrostatic image developer (9), the toner strength, fixing test, and fixed image strength test were conducted in the same manner as in Example 1. The results are shown in Table 1.

(Comparative Example 3)
<Preparation of block copolymer resin (9)>
Similarly to Example 1, a block copolymer resin (9) was produced using 250 parts of styrene, 273 parts of butyl acrylate, and 1.1 parts of MBPAP. The number average molecular weight of each unit, the total number average molecular weight, and the flow tester temperature reaching 10 ⁴ Pa · s under each pressure were measured in the same manner as in Example 1, and the results are shown in Table 1.
Polymerization of each homopolymer was carried out in the same manner as in Example 1 using 50 parts of MBPAP for 50 parts of styrene monomer and 0.2 part of MBPAP for 55 parts of butyl acrylate monomer to obtain the Tg of each homopolymer. It was. The results are shown in Table 1.

<Preparation of resin particle dispersion (9)>
Using the block copolymer resin (9), emulsification was carried out in the same manner as in Example 1 to prepare a resin particle dispersion (9). The volume average particle diameter of the resin particles in the obtained resin particle dispersion was 268 nm, and the solid content concentration was 42.5%.

<Manufacture of toner particles (10)>
Using the resin particle dispersion (9), toner particles (10) were produced in the same manner as in Example 1. As a result of measuring the volume average particle size of the toner particles (10), the particle size was 6.4 μm and the volume average particle size distribution was 1.21.

<Production and Evaluation of Toner for Electrostatic Image Development (10) and Electrostatic Charge Image Developer (10)>
Using toner particles (10), an electrostatic charge image developing toner (10) and an electrostatic charge image developer (10) were produced in the same manner as in Example 1.

<Toner strength, fixing test, fixed image strength test>
Using the electrostatic image developing toner (10) and the electrostatic image developer (10), the toner strength, fixing test, and fixed image strength test were conducted in the same manner as in Example 1. The results are shown in Table 1.

(Comparative Example 4)
<Preparation of block copolymer resin (10)>
Similarly to Example 1, a block copolymer resin (10) was produced using 250 parts of styrene, 243 parts of butyl methacrylate (BMA), and 17.2 parts of MBPAP. The number average molecular weight of each unit, the total number average molecular weight, and the flow tester temperature reaching 10 ⁴ Pas under each pressure were measured in the same manner as in Example 1, and the results are shown in Table 1.
Polymerization of each homopolymer was carried out in the same manner as in Example 1, using 8.6 parts of MBPAP for 50 parts of styrene monomer and 8.6 parts of MBPAP for 49 parts of butyl methacrylate monomer, to determine the Tg of each homopolymer. It was. The results are shown in Table 1.

<Preparation of resin particle dispersion (10)>
Using the block copolymer resin (10), emulsification was carried out in the same manner as in Example 1 to prepare a resin particle dispersion (10). The volume average particle diameter of the resin particles in the obtained resin particle dispersion was 288 nm, and the solid content concentration was 42.5%.

<Manufacture of toner particles (11)>
Using the resin particle dispersion (10), toner particles (11) were produced in the same manner as in Example 1. As a result of measuring the volume average particle size of the toner particles (11), the particle size was 6.5 μm and the volume average particle size distribution was 1.21.

<Production and Evaluation of Toner for Electrostatic Image Development (11) and Electrostatic Charge Image Developer (11)>
Using toner particles (11), an electrostatic charge image developing toner (11) and an electrostatic charge image developer (11) were produced in the same manner as in Example 1.

<Toner strength, fixing test, fixed image strength test>
Using the electrostatic image developer (10), the toner strength, fixing test, and fixed image strength test were conducted in the same manner as in Example 1. The results are shown in Table 1.

  As described above, as is clear from the examples and comparative examples, the block copolymer resin obtained by polymerizing the ethylenically unsaturated compound is excellent in pressure fixing performance, and excellent fixing with a combination of a small amount of heat energy and pressure that has not been conventionally available. Therefore, it is possible to provide a toner for developing an electrostatic charge image, a developer, an image forming method, and an image forming apparatus capable of achieving excellent properties and obtaining an excellent fixed image strength without impairing the use environment by VOC.

Claims (14)

An AB type diblock copolymer comprising block A and block B , which is obtained by polymerizing an ethylenically unsaturated compound,
At a flow tester applied pressure of 5 kgf / cm ² , the temperature T (P5) at which the viscosity of the diblock copolymer becomes 10 ⁴ Pa · s is 60 ° C. or higher,
At a flow tester applied pressure of 300 kgf / cm ² , the temperature T (P300) at which the viscosity of the diblock copolymer is 10 ⁴ Pa · s is 80 ° C. or less,
A toner for developing electrostatic images, wherein 30 ° C. ≦ T (P5) −T (P300) ≦ 80 ° C. The electrostatic image developing toner according to claim 1, wherein the number average molecular weight of the diblock copolymer is 10,000 to 150,000. The said diblock copolymer WHEREIN: The glass transition point Tg (A) of the block A is 60 degreeC or more, The glass transition point Tg (B) of the block B is 20 degrees C or less, The Claim 1 or 2 Toner for developing electrostatic images.   The electrostatic image developing toner according to claim 3, wherein a difference between the Tg (A) and the Tg (B) is 60 ° C. or more.   The ratio of the block A to the total amount of the diblock copolymer is 40 to 60% by weight, and the ratio of the block B to 60 to 40% by weight (however, the total amount of the block A and the block B is The toner for electrostatic charge development according to claim 1, wherein the toner is 100% by weight. Wherein block A is a polymer of styrene and / or a derivative thereof, an electrostatic image developing toner according to any one of claims 1 to 5.   The toner for developing an electrostatic charge image according to claim 1, wherein the block B is a polymer of (meth) acrylic acid ester.   The electrostatic image developing toner according to claim 1, wherein the block A is a styrene polymer and the block B is a butyl acrylate polymer. The toner for developing an electrostatic charge image according to any one of claims 1 to 8, wherein the diblock copolymer is synthesized by living radical polymerization. A block copolymer resin particle dispersion producing step for producing an aqueous dispersion of diblock copolymer resin particles comprising a block copolymer comprising a block obtained by polymerizing an ethylenically unsaturated compound;
Agglomeration step of aggregating the dispersed block copolymer resin particles to obtain agglomerated particles; and
Claim 1-9 any one method of producing an electrostatic charge image developing toner according to the, characterized in that it comprises a fusion step of fusing by heating the aggregated particles. The manufacturing method of Claim 10 with which the said block copolymer resin particle dispersion liquid preparation process includes the emulsification process by miniemulsion polymerization. An electrostatic charge image developing toner comprising the electrostatic charge image developing toner according to any one of claims 1 to 9, or the electrostatic charge image developing toner produced by the production method according to claim 10 or 11 , and a carrier. Agent. An electrostatic latent image forming step for forming an electrostatic latent image on the surface of the latent image holding member;
A developing step of developing a toner image by developing the electrostatic latent image formed on the surface of the latent image carrier with an electrostatic charge image developer containing toner or the toner and a carrier;
A transfer step of transferring the toner image formed on the surface of the latent image holding member to the surface of the transfer target; and
A fixing step of fixing the toner image transferred to the surface of the transfer target by pressing or heating and pressing;
The toner is an electrostatic charge image developing toner according to any one of claims 1 to 9, or an electrostatic charge image developing toner produced by the production method according to claim 10 or 11 , or the electrostatic charge image developing toner. The charge image developer is the electrostatic charge image developer according to claim 12 ,
The image forming method, wherein a fixing pressure in the fixing step is 5 to 300 kgf / cm ² . Latent image carrier,
Charging means for charging the latent image holding member;
Exposure means for exposing the charged latent image holding member to form an electrostatic latent image on the latent image holding member;
Developing means for developing the electrostatic latent image with a developer to form a toner image;
Transfer means for transferring the toner image from the latent image holding member to a transfer target; and
A fixing unit that fixes the toner image transferred to the surface of the transfer medium by pressing or heating and pressing;
The fixing pressure of the fixing means is 5 to 300 kgf / cm ² ;
The toner for developing an electrostatic charge image according to any one of claims 1 to 9, the toner for developing an electrostatic image produced by the production method according to claim 10 or 11 , or the developer as the toner. The electrostatic image developer according to claim 12 is used.
Image forming apparatus.