JP2002328489A - Electrostatic charge image developing toner, method for producing the toner and image forming method using the toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrostatic charge image developing toner excellent in uniformity of halftone, ensuring low fog, having good anti-offsetting property and not causing filming on a photoreceptor and to provide a method for producing the toner and an image forming method using the toner. SOLUTION: The electrostatic charge image developing toner has toner particles manufactured through a step for fusing resin particles comprising a polymer having a polymerizable monomer A containing Si or F as a polymer component A and a polymerizable monomer B having an acidic polar group as a polymer component B on the surfaces of colored particles containing a bonding resin and a colorant by a salting out-fusion method and a step for adding metal oxide particles subjected to hydrophobic processing.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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

[0002]

2. Description of the Related Art Conventionally, as a non-magnetic one-component developing method,
For example, JP-A-63-21946, JP-A-63-27946
The methods described in 1374 and Japanese Patent No. 277453 are known. This method includes a toner conveying member (also referred to as a toner carrier), a toner layer regulating member and a toner replenishing auxiliary member, and the toner replenishing auxiliary member and the toner conveying member, and the toner layer regulating member and the toner conveying member contact each other. In this method, a non-magnetic toner having a reduced thickness is supplied to the surface of the electrostatic latent image forming body to develop the latent image by a developing device having the above configuration. In this method, the non-magnetic toner is charged by frictional charging between the non-magnetic toner and the toner conveying member or the toner layer regulating member.

In the case of using this method, there has been a problem that, when used for a long time, the toner fluidity changes, and toner conveyance unevenness is apt to occur. As a result, the image tends to be uneven. In addition, fog and the like easily occur during long-term use, particularly under high temperature and high humidity, and a solution to this problem is required. One of the reasons why this phenomenon occurs is that the toner is likely to fuse to a member for conveying the toner or a member for regulating the toner layer, and as a result, the triboelectric charging property is reduced. It is believed that the charge amount of the magnetic toner decreases.

Therefore, the charging characteristics of the toner as described above,
As a technique for improving environmental characteristics, for example,
As described in JP-A-310882, the ratio of the number of fluorine atoms to the number of carbon atoms calculated from the X-ray photoelectron spectroscopy analysis of the toner is 0.002 to 0.300, and a component of 1000 or less in the molecular weight distribution. Is 0 to 10.
0% by mass, and the dry toner has a circle-equivalent number average diameter of 2 to 10 μm, and the toner has an average circularity of 0.920 to
A toner having a circularity standard deviation of less than 0.040 at 0.995 is disclosed.

However, the above-mentioned toner is obtained by suspension-polymerizing a polymerizable monomer having a bond between a carbon atom and a fluorine atom with a styrene monomer or the like, and the fluorine atom is present only on the toner surface. Therefore, the stability of the charge on the surface of the toner is not good, and there is a problem that the sharpness of the image quality is caused. Further, it is difficult in the manufacturing method to provide a sufficient fluorine concentration on the surface of the toner.

[0006] Japanese Patent Application Laid-Open No. 2000-305311 discloses that polytetrafluoroethylene, a copolymer containing tetrafluoroethylene, a fluoropolyether and a compound containing a perfluoroalkyl group having a specific average dispersed particle diameter and melt viscosity are selected. An electrophotographic toner containing fine particles of a low molecular weight fluorine compound is disclosed.

However, the toner described above is obtained by externally adding and mixing fluororesin particles to a toner produced by an emulsion polymerization method, and the fluororesin particles are not sufficiently fixed to the toner particles. Is a photoconductor,
There is a problem that the fixing heating member is easily contaminated.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to provide an electrostatic image development which is excellent in uniformity of halftone, has low fog, has good anti-offset properties, and does not cause filming of a photosensitive member. An object of the present invention is to provide a toner for use, a method for producing the toner, and an image forming method using the toner.

[0009]

The above objects of the present invention have been attained by the following items 1 to 16.

[0010] 1. Resin particles having a polymer having a polymerizable component A of a polymerizable monomer A having a silicon atom or a fluorine atom and a polymerizable component B of a polymerizable monomer B having an acidic polar group, a binder resin and a colorant. Salting out on the surface of the colored particles
A toner for developing an electrostatic image, wherein toner particles are produced through a step of adding hydrophobic metal oxide particles after fusing by a fusion method.

2. 2. The electrostatic image developing toner according to item 1, wherein the polymerizable monomer A is represented by the general formula (1).

3. 2. The electrostatic image developing toner according to item 1, wherein the polymerizable monomer A is represented by the general formula (2).

4. The resin particles are characterized by containing the polymer component A of the polymerizable monomer A in a ratio of 20% by mass to 80% by mass and the polymer component B of the polymerizable monomer B in a ratio of 2% by mass to 20% by mass. 4. The toner for developing an electrostatic charge image according to any one of the above items 1 to 3.

5. The volume average particle size of the resin particles is 30 nm or more
The toner for developing an electrostatic charge image according to any one of the above items 1 to 4, wherein the toner has a softening point of 80 to 170 ° C and a Tg (glass transition temperature) of 35 to 80 ° C.

6. The mass ratio ((s) / (s + Mp) × 10) between the mass (S) of the resin particles and the mass (Mp) of the colored particles.
0)% is 0.2% to 12%, the toner for developing an electrostatic image according to any one of the above items 1 to 5, wherein

[7] The crushing strength index of the toner is 0.1 to 0.1.
7. The toner for developing an electrostatic image according to any one of the above items 1 to 6, wherein

8. The resin particles are produced by emulsion polymerization or miniemulsion polymerization, and at the time of the polymerization reaction, at least one compound selected from thioglycerin or the compound represented by the general formula (3) is used as a chain transfer agent. The above 1 characterized in that it is produced through a process
8. The toner for developing an electrostatic image according to any one of items 7 to 7.

9. Resin particles, from the surface to the inside,
The electrostatic image according to any one of the above items 1 to 8, wherein the polymer A has a particle structure in which the concentration of the polymer A as a polymerization component of the polymerizable monomer A changes continuously or discontinuously. Development toner.

10. The toner contains a crystalline compound, and one or more endothermic peaks in differential thermal analysis due to the crystalline compound are present at 60 ° C. to 120 ° C., and the endothermic amount of the endothermic peak is 4 J / g to 30 J. / G, the toner for developing an electrostatic image according to any one of the above items 1 to 9.

11. Resin particles having a polymer having a polymerizable component A of a polymerizable monomer A having a silicon atom or a fluorine atom and a polymerizable component B of a polymerizable monomer B having an acidic polar group, a binder resin and a colorant. Having a process of adding toner particles to the surface of the colored particles containing the particles by fusing with a salting-out / fusing method and then adding hydrophobic metal oxide particles to form toner particles. Manufacturing method of toner.

[12] 11. In producing the toner for developing an electrostatic image according to any one of the above items 1 to 10,
A toner for developing electrostatic images, characterized by using the production method described in (1).

13. A developing roll and a toner supply member for supplying a toner for developing an electrostatic image onto the development roll, a non-magnetic toner supplied to the development roll from the toner supply member, and a toner layer formed on the development roll is formed. In an image forming method using a one-component developing device for performing development using a non-magnetic toner, any one of the above-described 1 to 10 is used as the non-magnetic toner.
13. An image forming method, comprising using the toner for developing an electrostatic image according to item 13.

14. A latent image forming step of forming a latent image on the latent image carrier, a developing step of visualizing the latent image using toner, and a toner image formed on the latent image carrier on a transfer target. An image forming method comprising: a transfer step of transferring; and a fixing step of heating and fixing the toner image on the transfer target body using a heating member and a pressure member.
11. An image forming method, wherein the electrostatic charge image developing toner according to any one of 10 to 10, wherein the heating member has an elastic layer.

[15] 15. The image forming method according to the above 14, wherein at least one of the heating member and the pressing member is a belt.

Hereinafter, the present invention will be described in detail. The resin particles according to the present invention have a polymerization component A of a polymerizable monomer A having a silicon atom or a fluorine atom, and a polymerization component B of a polymerizable monomer B having an acidic polar group.

The polymerizable monomer A having a silicon atom or a fluorine atom according to the present invention will be described.

As the polymerizable monomer A according to the present invention, monomers represented by the general formulas (1) and (2) are preferably used.

In the general formula (1), as the alkyl group having at least one fluorine atom represented by R ² , an alkyl group represented by-(CH ₂ ) _n -Rf is preferably used. Among them, n is preferably an integer of 1 to 10, and more preferably 2 to 4. Rf is an alkyl group having at least one fluorine atom.
The number of carbon atoms constituting f is preferably from 1 to 21, and more preferably a linear or branched fluoroalkyl group or perfluoroalkyl group having 6 to 10 carbon atoms is preferably used.

In the general formula (1), as the alkyl group having at least one silicon atom represented by R ² , an alkyl group represented by — (CH ₂ ) _n —Rsi is preferably used. Among them, n is preferably an integer of 1 to 10, and more preferably 2 to 4. Further, Rsi represents a group having at least one silicon atom, and among these, a trimethoxysilyl group, a triethoxysilyl group, a monoethoxydimethylsilyl group, a methylethoxysilyl group and the like are preferably used.

In the general formula (2), examples of the substituent having 1 to 13 carbon atoms represented by R and R ⁵ include a branched or linear alkyl group (for example, a methyl group, an ethyl group, Propyl, butyl, pentyl, iso-
Pentyl group, 2-ethyl-hexyl group, octyl group, decyl group, etc.), alkenyl group having 3 to 10 carbon atoms (eg, 2-propenyl group, 3-butenyl group, 1-methyl-
3-propenyl group, 3-pentenyl group, 1-methyl-3
-Butenyl group, 4-hexenyl group, etc.), having 7 to 7 carbon atoms
And 10 aralkyl groups (eg, benzyl group, phenethyl group, etc.).

In the general formula (2), the alkyl group having 1 to 8 carbon atoms represented by R ³ may be, for example, a branched or straight chain, but may be a methyl group, an ethyl group, a propyl group,
Examples thereof include a butyl group, a pentyl group, an iso-pentyl group, a 2-ethyl-hexyl group, and an octyl group.

Hereinafter, specific examples of the polymerizable monomer (A) represented by the general formula (1) or (2) will be shown, but the present invention is not limited thereto.

(1-1) CH ₂ ＣC (CH ₃ ) CO ₂ CH ₂ CF ₃ (1-2) CH ₂ ＣC (CH ₃ ) CO ₂ CH ₂ (CF ₂ ) ₂ H (1-3) _{CH 2 = C (CH 3)} CO 2 CH 2 CF 2 CF 3 (1-4) CH 2 = CHCO 2 CH 2 CF 3 (1-5) CH 2 = CHCO 2 CH 2 (CF 2) 2 H (1 -6) CH ₂ ＣＨCHCO ₂ CH ₂ CF ₂ CF ₃ (1-7) β- (perfluorooctylethyl) acrylate (1-8) β- (perfluorooctylethyl) methacrylate (1-9) β- ( (1-10) β- (perfluoroisononylethyl) methacrylate (2-1) CH ₂ ＣＨCHCO ₂ CH ₂ CH ₂ —Si (OCH
₃ ) ₃ (2-2) CH ₂ ＣC (CH ₃ ) CO ₂ (CH ₂ ) ₃ -Si
(OCH ₃ ) ₃ (2-3) CH ₂ ＣＨCHCO ₂ CH ₂ CH ₂ —Si (OCH
_{2 CH 3) 3 (2-4)} CH 2 = C (CH 3) CO 2 (CH 2) 3 -Si
(OCH ₃ ) ₃ (2-5) CH ₂ ＣＨCHCO ₂ CH ₂ CH ₂ —Si (OCH
_{2 CH 3) 3 (2-6)} CH 2 = CHCO 2 (CH 2) 3 -Si (OCH
_{2 CH 3) 3 (2-7)} CH 2 = C (CH 3) CO 2 (CH 2) 4 -Si
_{(OCH 3) 3 (2-8)} CH 2 = CHCO 2 (CH 2) 4 -Si (OCH
_{3) 3 (2-9) CH 2} = C (CH 3) CO 2 (CH 2) 4 -Si
_{(OCH 2 CH 3) 3 (} 2-10) CH 2 = CHCO 2 (CH 2) 4 -Si (OC
_{H 2 CH 3) 3 (2-11} ) CH 2 = CHCO 2 (CH 2) 4 -Si (CH
_{3) 2 (OCH 2 CH 3} ) (2-12) (CH 2 = CHCO 2 CH 2 CH 2) 2 -Si
(CH ₃ ) (OC ₂ H ₅ ) In the present invention, these can be used alone or in combination of two or more.

The polymerizable monomer B having an acidic polar group according to the present invention will be described. Examples of the polymerizable monomer B having an acidic polar group include an α, β-ethylenically unsaturated compound having a carboxyl group and an α, β-ethylenically unsaturated compound having a sulfo group.

Examples of the α, β-ethylenically unsaturated compound having a carboxyl group include acrylic acid, methacrylic acid, fumaric acid, maleic acid, itaconic acid, cinnamic acid, maleic acid monobutyl ester and maleic acid monobutyl ester. Octyl esters and their metal salts such as Na and Zn are exemplified.

Examples of the α, β-ethylenically unsaturated compound having a sulfo group include sulfonated styrene and its Na salt, allyl sulfosuccinic acid, octyl allyl sulfosuccinate, and their Na salts. .

Of these, methacrylic acid and acrylic acid are particularly preferably used. The compounds described above can be used alone or in combination of two or more.

The resin particles according to the present invention preferably contain a polymerization component C of another vinyl polymerizable monomer (C).

The vinyl polymerizable monomer (C) according to the present invention includes a styrene monomer and a (meth) acrylate monomer.

Examples of the styrene monomer include styrene, o-methylstyrene, m-methylstyrene, p-
Methylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, p-ethylstyrene,
p-n-butylstyrene, p-tert-butylstyrene, p-n-hexylstyrene, p-n-octylstyrene, p-n-nonylstyrene, p-n-decylstyrene, p-n-dodecylstyrene, 2 And styrene-based monomers such as 3,4-dimethylstyrene and 3,4-dichlorostyrene, and derivatives thereof.

Examples of the (meth) acrylate monomers include methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, phenyl acrylate, methyl methacrylate, and ethyl methacrylate. Butyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, ethyl β-hydroxyacrylate, propyl γ-aminoacrylate, stearyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, and the like.

Examples of the vinyl ester monomer include vinyl acetate, vinyl propionate, and vinyl benzoate. Examples of the vinyl ether monomer include vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether, and vinyl phenyl ether. And the like.

Of these, butyl acrylate and methyl methacrylate are particularly preferred. These can be used alone or in combination of two or more.

The resin particles according to the present invention are prepared by fusing the resin particles to the surface of the colored particles containing a binder resin and a colorant by a salting out / fusing method, together with the hydrophobicized metal oxide particles. The effects described in the present invention can be obtained because the toner fluidity and transportability are stabilized, and the toner particles are fused without being separated or separated from the colored particles.

In the resin particles according to the present invention, the constitution of the above-mentioned polymerizable component of the polymerizable monomer A, the polymerizable component of the polymerizable monomer B and the polymerizable component of the other vinyl polymerizable monomer (C) From the viewpoint of preferably achieving the effects described in the present invention, the ratio is determined by polymerization of the polymerization component A of the polymerizable monomer A, the polymerization component B of the polymerizable monomer B, and the polymerization of the other vinyl polymerizable monomer (C). Based on the total weight of component C, the polymerization component A is preferably from 20% to 80% by weight, more preferably 25% by weight.
% By mass to 70% by mass, and the polymerization component B is preferably 2% by mass to 20% by mass, more preferably 3% by mass.
１２12% by mass.

Further, as described in the ninth aspect, the concentration of the polymer A containing the polymerizable component of the polymerizable monomer A, which is a component of the resin particles, increases from the surface of the resin particles to the inside. Alternatively, the temperature may decrease from the surface of the resin particles to the inside.

In preparing the toner particles, it is particularly preferable that the concentration of the polymer A increases from the surface to the inside of the resin particles from the viewpoint of enhancing the adhesiveness of the resin particles to the colored particles.

Polymer A as a polymerization component of polymerizable monomer A
Specifically, the resin particles whose concentration changes vary by adding a polymerization initiator to a dispersion liquid in which polymerizable monomers A, B and C are mixed at a constant ratio, and starting polymerization to prepare a seed. A, B of
And the ratio of C to the seed is changed and added dropwise to complete the polymerization.

As an example, after a polymerization initiator solution is added to a polymerizable monomer dispersion containing A and B to form a core portion of resin particles, a polymerizable monomer containing no A or containing no main component is formed. It can be manufactured by dropping a monomer to form a shell portion.

Here, the polymer A, which is a polymer component of the polymerizable monomer A, may be a homopolymer (also referred to as a homopolymer) of the polymerizable monomer A, or may be combined with other polymerizable monomers. May be used.

Further, the resin particles according to the present invention preferably have a discontinuous layer such as a core-shell structure, wherein the resin constituting the resin layer of the core or the resin layer of the shell is a constituent component. The polymerizable component of the polymerizable monomer A is 2
0 mass% to 80 mass%, the polymerization component of the polymerizable monomer B is 2
It is preferable to contain it in a ratio of from 20% by mass to 20% by mass.

The concentration of the polymer A containing the polymerizable component of the polymerizable monomer A, which is a component of the resin particles as described above, is increased in the concentration on the surface or inside of the resin particles, Conversely, the composition analysis of resin particles having a low height and resin particles having a discontinuous layer such as a core-shell structure is performed by X-ray photoelectron spectroscopy (ESCA or ESCA) from the particle surface to the inside of the particle while etching from the particle surface. It can be measured by performing analysis using XPS.

The resin particles according to the present invention have a volume average particle size of 30 to 400 nm and a softening point of 80 to 170 ° C.
° C and Tg (glass transition temperature) are preferably 35 to 80 ° C, more preferably 70 nm in volume average particle size.
１２０120 nm, softening point 90 ° C.-120 ° C., Tg (glass transition temperature) 40 ° C.-60 ° C.

By adjusting the volume average particle diameter, softening point, and Tg (glass transition temperature) of the resin particles according to the present invention to fall within the above ranges, the effects described in the present invention can be obtained, and the sharpness can be obtained. A good image can be formed continuously from the beginning, and the durability of the developing member can be improved.

The volume average particle size according to the present invention can be measured using a Coulter Counter TA-II, a Coulter Multisizer, SLAD1000 (laser diffraction type particle size measuring device manufactured by Shimadzu Corporation) or the like.

The glass transition temperature (Tg) is measured by a differential calorimetric analysis method, for example, using a DSC curve. Here, it measured using DSC-7 (made by Perkin Elmer). The measurement conditions were as follows: temperature rise and cooling conditions: after leaving at 0 ° C. for 1 minute, 10 ° C. /
The temperature is raised to 200 ° C. for 1 minute (first temperature rising process).
Next, after leaving at 200 ° C. for 1 minute, it is cooled to 0 ° C. at a rate of 10 ° C./min (first cooling step). Next, after leaving at 0 ° C. for 1 minute, the temperature is raised to 200 ° C. at a rate of 10 ° C./min (second temperature raising step). The value measured by the onset method in the second heating process, that is, the intersection between the baseline of the peak and the straight line of the maximum slope of the peak was defined as the glass transition temperature.

The softening point according to the present invention can be measured with a flow tester. Load is 200N, die diameter 1mm,
After the pellet having a height of 10 mm and a height of 12 mm is left at 80 ° C. for 300 seconds, the measurement is performed at a heating rate of 6 ° C./min by a 5 mm offset method.

Further, as these resins, those having a number average molecular weight (Mn) of 1,000 to 100,000 and a weight average molecular weight (Mw) of 2,000 to 1,000,000 as measured by gel permeation chromatography are preferred. Further, as the molecular weight distribution, those having Mw / Mn of 1.5 to 100, particularly 1.8 to 70 are preferable.

The resin particles according to the present invention are preferably prepared by an emulsion polymerization method or a mini-emulsion polymerization method, and more preferably, a chain transfer agent represented by the general formula (3) is used during polymerization. Thereby, the molecular weight and the molecular weight distribution of the resin described above can be adjusted to preferable ranges.

Here, the emulsion polymerization method or miniemulsion polymerization method used for producing the resin particles according to the present invention will be described.

The emulsion polymerization method used in the present invention means that a monomer (also referred to as a monomer) is formed at a critical micelle formation concentration (hereinafter, referred to as “critical micelle formation concentration”).
In the presence of an emulsifier (also referred to as a surfactant) having a concentration of not less than CMC), the mixture is emulsified and dispersed by a mechanical dispersing means such as a homogenizer, and then a water-soluble polymerization initiator is mainly added, followed by polymerization. This is a method of forming resin fine particles and then producing resin particles of a desired size by association.

The mini-emulsion polymerization method used in the present invention is a form of the emulsion polymerization method, and is a method of emulsifying at an emulsifier concentration of CMC or less. The polymerization initiator used at this time may be water-soluble or oil-soluble. For example, an oil-soluble polymerization initiator or a functional compound is allowed to coexist with a polymerizable monomer, and the polymerization is carried out in the presence of an emulsifier having a concentration of CMC or less. By performing the dispersion and polymerization in a controlled manner, the molecular diffusion of the functional additive and the like in the monomer particles is suppressed, and the polymerization proceeds only in the monomer oil droplets. It is particularly preferable because resin particles reliably contained therein can be obtained.

Specifically, in each of the above polymerization methods, a monomer (monomer) solution in which a chain transfer agent and, if necessary, a release agent is dissolved is dispersed in an aqueous medium. The molecular weight adjustment by the agent is performed, after preparing resin particles containing a release agent or the like as necessary, the resin particles, on the surface of the colored particles containing a binder resin and a colorant,
The toner for developing an electrostatic image of the present invention is prepared by fusing using a salting out / fusing method and then adding toner particles subjected to hydrophobic treatment to produce toner particles.

The chain transfer agent represented by the general formula (3) used when preparing the resin particles of the present invention will be described.

In the general formula (3), examples of the divalent hydrocarbon group having 1 to 10 carbon atoms represented by R ⁶ include an alkylene group, an alkenylene group and an alkynylene group. , Ethylene, propylene, butylene, trimethylene, tetramethylene, pentamethylene, octamethylene, hexamethylene, ethylethylene, propenylene, vinylene and the like.

These substituents may be unsubstituted or have further substituents. In the general formula (3), examples of the hydrocarbon group having 2 to 15 carbon atoms represented by R ⁷ include a branched or linear alkyl group (eg, a methyl group, an ethyl group, a propyl group, a butyl group) Pentyl, iso-pentyl, 2-ethyl-hexyl, octyl, decyl, etc.), alkenyl (eg, 2-propenyl, 3
-Butenyl group, 1-methyl-3-propenyl group, 3-pentenyl group, 1-methyl-3-butenyl group, 4-hexenyl group and the like, and aralkyl groups (for example, benzyl group, phenethyl group and the like).

Examples of the compound represented by the general formula (3) include thioglycolic acid esters and 3-mercaptopropionic acid esters, and are preferred. Specifically, thioglycolic acid esters include ethyl thioglycolate, butyl thioglycolate, t-butyl thioglycolate, 2-ethylhexyl thioglycolate, octyl thioglycolate, isooctyl thioglycolate, decyl thioglycolate , Dodecyl thioglycolate, thioglycolic acid ester of ethylene glycol, thioglycolic acid ester of neopentyl glycol, thioglycolic acid ester of trimethylolpropane, thioglycolic acid ester of pentaerythritol, and thioglycolic acid ester of sorbitol. And 3-mercaptopropionic acid esters such as ethyl ester, octyl ester, decyl ester, dodecyl ester, pentaerythritol tetrakis-ester , Ethylene glycol 3-mercaptopropionic acid ester, neopentyl glycol 3-
Mercaptopropionate, 3-mercaptopropionate of trimethylolpropane, 3-mercaptopropionate of pentaerythritol,
And sorbitol 3-mercaptopropionate.

Among the above-mentioned chain transfer agents, more preferably used is 3-mercaptopropionate, and particularly preferably used is n-octyl-
3-mercaptopropionate.

The amount of the chain transfer agent represented by the general formula (3) is preferably from 0.01% by mass to 5% by mass, more preferably from 0.03% by mass to 5% by mass of the polymerizable monomer. 3
% By mass.

The resin particles according to the present invention are preferably produced by the emulsion polymerization method or mini-emulsion polymerization method described above, and the polymerization initiator used for initiating the polymerization reaction is preferably a water-soluble initiator. , For example, persulfates (eg, potassium persulfate, ammonium persulfate, etc.),
Examples include azo compounds (for example, 4,4'-azobis-4-cyanovaleric acid and salts thereof, 2,2'-azobis (2-amidinopropane) salts, etc.), peroxide compounds and the like. Further, the above radical polymerization initiator can be used as a redox initiator in combination with a reducing agent, if necessary. Use of a redox-based initiator has preferred aspects such as an increase in polymerization activity, a reduction in polymerization temperature, and a reduction in polymerization time.

The polymerization temperature is not particularly limited as long as it is higher than the minimum radical generation temperature of the polymerization initiator.
To 90 ° C. However, by using a polymerization initiator which starts at room temperature in combination with hydrogen peroxide and a reducing agent (such as ascorbic acid), polymerization can be performed at room temperature or higher.

The reaction temperature varies depending on the type of the monomer and the polymerization initiator used, but it is usually preferably in the range of 30 to 80 ° C. The reaction time is up to the point at which the monomer component disappears, but usually 3 to 20 hours is preferable. The polymerization is carried out in a weakly acidic atmosphere,
To 6 are preferable. The solids content is at least 25%, preferably at least 35%.

The toner for developing an electrostatic image (hereinafter, also simply referred to as toner) according to the present invention will be described.

The toner of the present invention is obtained by salting out the resin particles described above onto the surface of the colored particles containing the binder resin and the colorant.
It is characterized in that it is produced through a step of adding metal oxide particles subjected to hydrophobic treatment after fusion by a fusion method.

The metal oxide particles according to the present invention will be described. Examples of the constituent material of the metal oxide particles according to the present invention include silicon oxide, titanium oxide, aluminum oxide, zinc oxide, zirconium oxide, cerium oxide, tungsten oxide, antimony oxide, copper oxide, tellurium oxide, and manganese oxide. Of these, titanium oxide is particularly preferably used.

The above-mentioned hydrophobic treatment of the metal oxide particles may be, for example, a coating treatment with a metal oxide such as aluminum, silicon or zinc, or various kinds of coupling agents.
It is preferable to perform a hydrophobic treatment with an organic substance such as a fatty acid compound.

The silane coupling agent, which is an example of the coupling agent, is used for improving the degree of hydrophobicity, environmental dependency and fluidity, and may be a water-soluble one.

As such a silane coupling agent, the chemical structural formula R _n SiX _4-n (where n is an integer of 0 to 3 and R is a hydrogen atom, an organic group such as an alkyl group and an alkenyl group) And X represents a hydrolyzing group such as a chlorine atom, a methoxy group and an ethoxy group.), And any type of chlorosilane, alkoxysilane, silazane, and special silylating agent can be used. Although it is possible to use them, alkoxysilanes are particularly preferred.
Examples of the alkoxysilane include vinyltrimethoxysilane, propyltrimethoxysilane, i-butyltrimethoxysilane, n-butyltrimethoxysilane, and n
-Hexyltrimethoxysilane, n-octyltrimethoxysilane, n-dodecyltrimethoxysilane, phenyltrimethoxysilane, 3-glycoxypropyltrimethoxysilane, and the like, and the number of carbon atoms in the hydrocarbon group is 2 to 2. Ten are preferred. Among them, i-butyltrimethoxysilane and n-butyltrimethoxysilane are particularly preferred.

The treatment amount is 10 to 100% by mass, preferably 20 to 70% by mass, based on 100% by mass of the metal oxide.

From the viewpoint of improving transferability, reducing separation from toner particles, and preventing contamination of the charging member and the transfer member, the number average particle diameter of the metal oxide particles according to the present invention is 3%.
It is necessary to use one having a thickness of 5 to 140 nm, but one having a range of 50 to 110 nm is preferably used. Here, the measurement of the number average particle size of the metal oxide particles is as follows:
It can be measured using a Coulter Counter TA-II, Coulter Multisizer, SLAD1000 (Shimadzu Corporation laser diffraction particle size analyzer) or the like.

The toner of the present invention must have a crushing strength index defined below in order to obtain effects such as low fog, anti-offset properties, filming of the photoreceptor, and a decrease in the minimum fixing temperature. It is preferably from 0.1 to 0.8, more preferably from 0.2 to 0.5.

Here, in the present invention, the “crush strength index” is an index indicating the crushability of toner particles, and is an index obtained by the following method.

(Measurement Method of Crushing Strength Index of Toner) 30 g of toner (sample) and glass beads “GB503M”
100 g (Toshiba Barotini Co., particle size: 2 mm) was placed in a 2-liter polyethylene pot, mixed and stirred for 60 seconds with a turbular mixer, and glass beads were separated and removed with a 330-mesh test sieve. And
Before and after mixing and stirring, 2 to 4
The number ratio (%) of small particles of μm is measured and calculated by the following equation.

Crushing strength index = (N−N ₀ ) / 60 where N is the number% of small particles of 2 to 4 μm after mixing and stirring, and N ₀ is 2 to 4 μm before mixing and stirring.
% Of small particles of

The “% by number of small particles” is a value measured using a Coulter Multisizer. Specifically, an interface (manufactured by Nikkaki) for outputting a particle size distribution and a personal computer are used by using a Coulter Multisizer. It was calculated by measuring the volume distribution of toner of 2 μm or more (for example, 2 to 40 μm) using an aperture of 100 μm in the Coulter Multisizer.

Next, the shape of the toner of the present invention will be described in detail. The toner particles used in the present invention have developability,
In order to obtain fine line reproducibility and stable cleaning properties, the coefficient of variation of the shape factor is preferably 16% or less,
More preferably, the number variation coefficient in the number particle size distribution is 27% or less.

The shape factor of the toner of the present invention will be described. In the toner of the present invention, the proportion of toner particles having a shape coefficient in the range of 1.2 to 1.6 is 65% by number or more, the coefficient of variation of the shape coefficient is 16% or less, and the number in the number particle size distribution is The coefficient of variation is 27% or less. Here, the shape factor of the toner of the present invention is represented by the following equation, and indicates the degree of roundness of the toner particles.

Shape factor = ((maximum diameter / 2) ² × π) / projected area Here, the maximum diameter is defined as a parallel image when a projected image of a toner particle on a plane is sandwiched between two parallel lines. Means the width of the particle at which the distance between the particles becomes maximum. The projection area refers to the area of the projected image of the toner particles on the plane. In the present invention, the shape factor can be determined by taking a photograph in which the toner particles are magnified 2,000 times with a scanning electron microscope, and then referring to the “SCCANNING IMAGE ANALYZE” based on the photograph.
R "(manufactured by JEOL Ltd.) was used to analyze photographic images. In this case, the shape factor of the present invention was measured by using the above formula using 100 toner particles.

The variation coefficient of the shape factor of the toner particles will be described. “Variation coefficient of shape coefficient” which is one variable indicating the uniform shape of the toner particles is calculated from the following equation.

Coefficient of variation of toner shape coefficient = (S1 /
K) × 100 (%) In the formula, S1 represents a standard deviation of the shape factor of 100 toner particles, and K represents an average value of the shape factor.

As a basic condition for achieving high image quality, the variation coefficient of the shape factor of the toner particles according to the present invention is as follows.
The toner of 16% or less is preferable, but the variation coefficient of the shape factor is preferably 14% or less in order to further promote higher image quality.

In order to uniformly control the shape factor of the toner and the variation coefficient of the shape factor without variation in lots,
In the step of preparing (polymerizing) the resin particles (polymer particles) constituting the toner of the present invention and fusing and controlling the shape of the resin particles, the characteristics of the toner particles (colored particles) being formed are appropriately monitored and monitored. The end time of the process is determined.

The number particle size distribution and the number variation coefficient of the toner of the present invention will be described. The number particle size distribution and the number variation coefficient of the toner according to the present invention are measured with a Coulter Counter TA-II or a Coulter Multisizer (manufactured by Coulter Corporation). In the present invention, a Coulter Multisizer was used and connected to an interface (manufactured by Nikkaki Co., Ltd.) for outputting a particle size distribution and a personal computer. The aperture used in the Coulter Multisizer is 100 μm
The particle size distribution and the average particle size were calculated by measuring the volume diameter and the number diameter of 2 μm or more using the above. The number particle size distribution represents the relative frequency of the toner particles with respect to the particle size, and the number average particle size refers to the cumulative 5 in the number particle size distribution.
It represents a diameter of 0%, that is, Dn50.

The number variation coefficient in the number particle size distribution of the toner is calculated from the following equation. Number variation coefficient = [S / Dn] × 100 (%) where S represents a standard deviation in the number particle size distribution, and Dn
Indicates a number average particle size (μm).

The number variation coefficient of the toner of the present invention is preferably 27% or less, more preferably 25% or less. By adjusting the number variation coefficient to 27% or less, the gap of the transferred toner layer is reduced, the fixability is improved, and the offset is less likely to occur. Further, it is possible to obtain favorable effects such as a sharp charge amount distribution, a high transfer efficiency, and an improvement in image quality.

The method of controlling the number variation coefficient is not particularly limited. For example, a method of classifying toner particles by wind force can be used. However, in order to reduce the number variation coefficient, classification in a liquid is effective. It is a target. As a method for classification in the liquid, there is a method in which a centrifugal separator is used, the number of rotations is controlled, and the toner particles are separated and collected according to a sedimentation velocity difference caused by a difference in toner particle diameter.

The inventors of the present invention have focused on the minute shapes of the individual toner particles, and as a result, the shape of the corners of the toner particles has changed and become round inside the developing device. Promoted the burying of the external additive, and decreased the change in the amount of charge, the fluidity, and the stability of transportation. When electric charge is applied to toner particles by frictional charging, it is presumed that the external additive tends to be buried particularly at corners, and the toner particles are likely to be non-uniformly charged. That is, the ratio of toner particles having no corners is set to 50% by number or more,
By using toner composed of toner particles whose number variation coefficient in the number particle size distribution is controlled to 27% or less, it is possible to form a high-quality image over a long period of time with excellent developability and fine line reproducibility. Was found.

Further, it has been found that even when the toner is made to have a specific shape and the shape is made uniform, the external additive does not bury, and the charge amount distribution becomes sharp. That is, the percentage of toner particles having a shape coefficient in the range of 1.2 to 1.6 is 65% by number or more, and the variation coefficient of the shape coefficient is 16%.
It has also been found that the use of the following toners makes it possible to form a high quality image over a long period of time with excellent developability and fine line reproducibility.

The toner of the present invention will be described with respect to toner particles having no corners. Here, the toner particles having no corners refer to toner particles having substantially no projections on which electric charges are concentrated or projections that are easily worn by stress, that is, as shown in FIG. When the major axis of the toner particle T is L, a circle C having a radius (L / 10) is rolled inward while being in contact with the peripheral line of the toner particle T at one point. The case where the toner does not substantially protrude outside the toner T is referred to as “toner particles having no corners”.
“Cases that do not substantially protrude” refer to cases where there are no more than one protrusion having a protruding circle.

The term "major axis of toner particles" refers to the width of a particle at which the distance between the parallel lines becomes maximum when the projected image of the toner particles on a plane is sandwiched between two parallel lines. FIGS. 1B and 1C show projected images of toner particles having corners, respectively.

The measurement of the toner having no corners was performed as follows. First, a photograph in which the toner particles are enlarged by a scanning electron microscope is taken, and further enlarged to obtain a 15,000-fold photographic image. Next, the presence or absence of the corners is measured for this photographic image. This measurement was performed for 1000 toner particles.

In the toner of the present invention, the proportion of toner particles having no corners is preferably at least 50% by number, more preferably at least 70% by number. When the ratio of the toner particles having no corners is 50% by number or more, it is difficult to generate fine particles due to stress with the developer conveying member, and it is possible to suppress so-called contamination on the surface of the developer conveying member. As a result, the charge amount distribution is sharpened, the chargeability is stabilized, and effects such as good image quality can be formed over a long period are amplified.

The method for obtaining a toner having no corners is not particularly limited. For example, as described above, as a method of controlling the shape coefficient, a method of spraying toner particles into a hot air flow, a method of repeatedly applying mechanical energy by an impact force in a gas phase, or a method of dissolving a toner It can be obtained by adding to a solvent that does not contain and giving a swirling flow.

In the toner according to the present invention, when the particle size of the toner particles is D (μm), the natural logarithm lnD
Is plotted on the horizontal axis, and in the histogram showing the number-based particle size distribution obtained by dividing the horizontal axis into a plurality of classes at intervals of 0.23, the relative frequency (m1) of the toner particles included in the most frequent class
It is preferable that the toner has a sum (M) of 70% or more of the relative frequency (m2) of the toner particles included in the class having the second highest frequency after the mode.

When the sum (M) of the relative frequency (m1) and the relative frequency (m2) is 70% or more, the dispersion of the particle size distribution of the toner particles is narrowed. Thus, the occurrence of selective development can be reliably suppressed.

In the present invention, the histogram showing the number-based particle size distribution is obtained by plotting a natural logarithm lnD (D: particle size of individual toner particles) in a plurality of classes (0 to 0) at intervals of 0.23.
0.23: 0.23 to 0.46: 0.46 to 0.69:
0.69 to 0.92: 0.92 to 1.15: 1.15
1.38: 1.38 to 1.61: 1.61 to 1.84:
1.84 to 2.07: 2.07 to 2.30: 2.30 to
2.53: a histogram showing the number-based particle size distribution divided into 2.53 to 2.76..., Which is a particle size data of a sample measured by a Coulter Multisizer according to the following conditions. Is transferred to a computer via an I / O unit, and the computer creates the program using a particle size distribution analysis program.

[Measurement conditions] 1: Aperture: 100 μm 2: Sample preparation method: Electrolyte [ISOTON II (manufactured by Coulter Scientific Japan)] 50-1
An appropriate amount of a surfactant (neutral detergent) is added to 00 ml and stirred, and 10 to 20 mg of a measurement sample is added thereto. This system is prepared by subjecting it to a dispersion treatment with an ultrasonic disperser for 1 minute.

Next, the particle size of the toner of the present invention will be described. The particle size of the toner used in the present invention is 2 to 9 μm in number average particle size, preferably 4.0 to 8.5 μm, and more preferably 4.5 to 8 μm. This particle size can be controlled by the concentration of the coagulant (salting agent), the amount of the organic solvent added, the fusing time, and the composition of the polymer in the method for producing the toner.

When the number average particle size is 2 to 9 μm, the transfer efficiency is increased, the halftone image quality is improved, and the image quality of fine lines and dots is improved. The calculation of the particle size distribution of the toner and the measurement of the number average particle size are performed using a Coulter Counter TA.
-II, Coulter Multisizer (both from Coulter), SLAD1100 (Shimadzu Corporation laser diffraction particle size analyzer) and the like. In the present invention, measurement and calculation are performed using a Coulter Multisizer, an interface for outputting a particle size distribution (manufactured by Nikkaki Co., Ltd.), and a personal computer connected.

The toner particles according to the present invention preferably have a sea-island structure. That the toner particles have a sea-island structure means that regions having different luminances can be confirmed in the toner particles in a cross-sectional photograph of the toner particles taken by a transmission electron microscope. That is, according to the transmission electron microscope, the toner particles according to the present invention have granular islands (a phase of a crystalline substance and a colorant) having different luminances in a continuous phase (the binder resin phase forms a sea). Phase) is preferably present.

Further, from the results of observation with an electron microscope, factors specifying the sea-island structure in the toner particles, such as the number of islands in one toner particle, the shape factor of the island, the horizontal diameter of the island, can be obtained as numerical values.

Here, the luminance in the transmission electron micrograph is caused by a difference in the crystal state of each element constituting the toner particles, that is, a crystalline material used as a binder resin, a colorant, and other additives. This is caused by visualizing the difference in the generated electron beam transmittance.Generally, the colorant is photographed at a lower luminance because the electron beam transmittance is lower than that of the binder resin, and the crystalline substance is more than the binder resin. There is a tendency for images to be shot closer to high brightness.

In electron micrographs, low luminance means 0 when a luminance signal of a pixel is divided into 256 gradations.
~ 99 gradations, medium brightness is 80 ~ 160
In the range of gradations and high luminance are those in the range of 127 to 255 gradations, but in the present invention, if they are relative, that is, if the above-mentioned components of the toner particles can be distinguished by photographs, respectively. It is not necessarily limited to the above range. For example, for an island of crystalline material,
When a section for transmission electron microscopy observation is placed in an environment of 80 to 120 ° C., the section flows out and is observed as a hole, so that it can be easily distinguished from a colorant island.

As described above, in the present invention, by identifying each component in the toner particles based on the luminance, it is possible to visually determine and identify the sea as the sea and the island as the island by an electron micrograph. The luminance information is converted into visually identifiable image information by an image analysis device installed in the electron microscope apparatus.

In the toner of the present invention, the toner particles preferably have a sea-island structure, and those having an island-free region along the outer periphery of the toner particles are preferably used. The toner particles having the above-mentioned sea-island structure will be specifically described with reference to the schematic sectional view of the toner particles shown in FIG.

In the schematic sectional view of FIG. 2, a region indicated by length a and depth b along the outer periphery of the cross section of the toner particle is a region not including an island.

The toner particles according to the present invention have a depth of 100 to 2 in the region along the outer periphery of the cross section of the toner particles.
One having a region of 00 nm and a length of 500 to 6000 nm that does not include an island at all is preferably used.

As described above, by preventing the island from being present in the specific region along the outer periphery of the toner particle, it is possible to effectively prevent the island from spilling out from the toner particle, and to further improve the crystallinity added to the toner particle. It is presumed that the substance and the colorant can be appropriately dispersed in the particles, and the crystalline substance can be effectively exuded at the time of pressure fixing.

The toner particles according to the present invention preferably have a sea-island structure from the result of observation with a transmission electron microscope. However, a crystalline substance added to the toner particles (for example, the release agent described above) Are islands of a crystalline substance, and the colorant is an island of the colorant. It is preferable that a plurality of islands are formed for each type of additive. The properties described so far are properties of the same kind, ie, between islands of crystalline material or between islands of colorant, not between islands of different types.

Since the islands of different additives, that is, the islands of the crystalline substance and the islands of the colorant, have different luminances, they can be easily identified in an electron micrograph and an image analyzer for calculating the above-mentioned characteristics. Is set so that a characteristic value between different types of islands is not erroneously calculated. Regarding the islands in the toner particles of the present invention, the islands of the crystalline substance are specified by the Feret diameter, the shape factor of the islands, and the number of islands present per toner particle. , Which are specified by the area of a Voronoi polygon described later.

The transmission electron microscope apparatus capable of observing the structure of the toner particles of the present invention is usually sufficiently observed with a model well known to those skilled in the art.
000 type (manufactured by Topcon Corporation) "and the like. In the present invention, the values obtained from the results of transmission electron micrographs such as the number of islands in the toner particles, which are the features of the present invention, are obtained from the projected surface of 1,000 or more toner particles at a magnification of 10,000 times. It is calculated.

In the present invention, a photographing method using a transmission electron microscope is performed by a generally known method performed when measuring toner particles. That is, as a specific method for measuring the tomographic plane of the toner, the toner may be sufficiently dispersed in a room-temperature curable epoxy resin, and then embedded and cured, or dispersed in styrene fine powder having a particle size of about 100 nm. After pressure molding, the obtained block is dyed with ruthenium tetroxide or osmium tetroxide in combination, and then a flaky sample is cut out using a microtome with diamond teeth and transmitted. The tomographic morphology of the toner was photographed using an electron microscope (TEM). From the photograph, the shape of the crystalline substance region in the toner particles was visually confirmed, and an image photographed by an image processing apparatus “Luzex F” (manufactured by Nireco Corporation) provided in the electron microscope apparatus. The value of the Voronoi polygon of the island portion in the toner particle is obtained by the arithmetic processing of the information.

By the above method, the structure such as the sea-island structure of the toner particles according to the present invention is specified.

In the present invention, the crystalline substance constituting the island portion is an organic compound having a melting point, and is preferably a hydrocarbon compound containing an ester group in the compound structure. The melting point of the crystalline substance in the toner particles of the present invention is a temperature lower than the softening point of the toner, specifically, preferably 130 ° C. or lower. The organic compound preferably has an ester group in its structure, and includes a crystalline polyester compound.

In the toner of the present invention, DSC and the like can be used as a method for confirming that the crystalline substance constituting the island portion has a melting point. Some of those having crystallinity can be confirmed by means such as an X-ray diffractometer.

Further, the crystalline substance contained in the toner of the present invention includes those exhibiting a function as a release agent at the time of image formation.

In the toner of the present invention, in order to reduce the melt viscosity and improve the adhesiveness to a transfer material such as paper and the offset resistance, the crystalline substance must have a melting point of 50 to 130 ° C. The temperature is more preferably 60 ° C to 120 ° C.

Here, the melting point of a crystalline substance refers to a value measured by a differential calorimeter (DSC).
The temperature at which the maximum endothermic peak measured when the temperature is raised from 0 ° C. to 200 ° C. at a rate of 10 ° C./min (first temperature raising step) is defined as the melting point. The melting point is determined by an endothermic peak (P
1) ".

As a specific measuring device of the melting point, DSC-7 manufactured by Perkin Elmer Co., Ltd. can be mentioned.
A specific method of measuring the melting point by a differential calorimeter (DSC) is as follows. The temperature at which the maximum endothermic peak is measured at this time is defined as the endothermic peak P1 in the first heating process. Then, after leaving at 200 ° C. for 1 minute, the temperature is lowered under the condition of 10 ° C./min, and the temperature showing the maximum exothermic peak measured at that time is defined as the exothermic peak P2 in the first cooling process.

The crystalline substance used in the toner of the present invention has an endothermic peak (P1) in the first temperature raising process by DSC.
Is present at 60 ° C to 120 ° C, particularly 65 ° C to 100 ° C. The heat absorption of P1 is 4 J to 30 J /
g is preferable.

By including a crystalline substance having the above-mentioned thermal characteristics, an excellent offset prevention effect (wide fixing temperature range) and an excellent fixing property (high fixing rate) can be exhibited. In order to exhibit the effects of the present invention, it is preferable that the binder resin and the crystalline substance exist in a state where they are separated from each other.

That is, the crystalline substance dissolves sharply, and as a result, the melt viscosity of the whole toner can be reduced, and the fixability can be improved. Also,
The presence of the phases separated from each other makes it possible to suppress a decrease in the elastic modulus on the high temperature side, so that the offset resistance is not impaired.

The toner used in the present invention is a toner in which resin particles containing a crystalline substance are fused in an aqueous medium, and the crystalline substance is appropriately aggregated by an aging step to form a sea-island structure. Is preferred. By salting out / fusing the resin particles containing the crystalline substance in the resin particles with the colorant particles in the aqueous medium, a toner in which the crystalline substance is finely dispersed can be obtained. here,
The aging step refers to a step of continuing stirring at a temperature within the range of the melting point of the crystalline substance ± 20 ° C. even after the fusion of the resin particles.

In the toner of the present invention, low molecular weight polypropylene (number average molecular weight = 1500 to 9000), low molecular weight polyethylene and the like are preferable as the crystalline substance having a releasing function, and particularly preferable is represented by the following formula. It is an ester compound.

R _1- (OCO-R ₂ ) _{n In the} formula, n is an integer of 1 to 4, preferably 2 to 4, more preferably 3 to 4, and particularly preferably 4. R ₁ , R
₂ represents a hydrocarbon group which may have a substituent. R ₁
Has 1 to 40 carbon atoms, preferably 1 to 20 carbon atoms, and more preferably 2 to 5 carbon atoms. R ₂ has 1 to 40 carbon atoms, preferably 16 to 30 carbon atoms, and more preferably 18 to 26 carbon atoms.

Next, examples of typical compounds are shown below.

[0137]

Embedded image

[0138]

Embedded image

In the present invention, a crystalline polyester can also be used as the crystalline substance. Examples of the crystalline polyester include aliphatic diols and aliphatic dicarboxylic acids (including acid anhydrides and acid chlorides). ) Is preferred.

The diol used to obtain the crystalline polyester includes ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol,
4-butanediol, 1,4-butenediol, neopentyl glycol, 1,5-pentane glycol, 1,
6-hexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, bisphenol A, bisphenol Z, hydrogenated bisphenol A, and the like. it can.

The dicarboxylic acids used to obtain the crystalline polyester include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, speric acid, azelaic acid, sebacic acid, maleic acid, fumaric acid , Citraconic acid, itaconic acid, glutacoic acid, n-dodecyl succinic acid, n-dodecenyl succinic acid, isododecyl succinic acid, isododecenyl succinic acid, n-octyl succinic acid, n-octenyl succinic acid, these acid anhydrides or Acid chlorides can be mentioned.

Particularly preferred crystalline polyesters include polyesters obtained by reacting 1,4-cyclohexanedimethanol with adipic acid, polyesters obtained by reacting 1,6-hexanediol with sebacic acid, and ethylene glycol. And succinic acid, polyester obtained by reacting ethylene glycol and sebacic acid, and polyester obtained by reacting 1,4-butanediol and succinic acid. Among them, a polyester obtained by reacting 1,4-cyclohexanedimethanol with adipic acid is most preferred.

The addition amount of the above compound is 1 to 30% by mass, preferably 2 to 20% by mass, more preferably 3 to 15% by mass based on the whole toner.

As the toner particles of the present invention, particles having a sea-island structure in which a colorant or the like constitutes a separated phase in a binder resin phase are preferably used. As a scale to represent, the occupation state of the island portion of the toner particles in the sea-island structure is indicated by the area of a Voronoi polygon obtained by Voronoi division.

Further, since the effects described in the present invention such as improvement of the transfer rate, uniformity of halftone, and elimination of dust of fine dots are obtained, the toner particles according to the present invention are defined as follows. It is preferable that the average value of the area of such a Voronoi polygon (also called a Voronoi polyhedron) falls within a specific range. Here, the Voronoi polygon will be described.

The area of the Voronoi polygon according to the present invention is
The occupation state of the island portion in the toner particles is shown. A Voronoi polygon or a Voronoi polyhedron is, for example, as described in the Encyclopedia of Physical and Chemical Sciences of Iwanami, when two or more points are dispersed in space or on a plane.
By dividing the whole space into a polyhedron or the whole plane into a polygon by creating an equal plane and a perpendicular bisector, the polyhedron thus formed is called a Voronoi polyhedron, and the polygon is called a Voronoi polygon, Such division of a space or plane is called Voronoi division.

FIG. 3 shows a Voronoi polygon (Voronoi polyhedron).
1 shows an example of the toner particles according to the present invention, which is divided according to the present invention.

That is, in the present invention, attention is paid to the center of gravity of the islands existing in the toner particles, and polygons are formed by vertical bisectors formed by connecting the centers of gravity of the adjacent islands. Is calculated by an image analyzer installed in the electron microscope apparatus based on the photograph taken by the transmission electron microscope.

Here, a large Voronoi polygon area means that the distance between the centers of gravity of adjacent islands is large, that is, the occupation state of the island portion in the particle. It shows a sparse state. Also, a Voronoi polygon having a small area indicates that the distance between the centers of gravity of adjacent islands is short and close, that is, the island is occupied by particles in a dense state.

In the present invention, with respect to the Voronoi polygon of the island portion in the toner particles, measurement was performed for 1,000 toners, and the average value of the area of the Voronoi polygon was calculated.

The Voronoi polygon is mathematically defined in general by the following equation.

<< Area of Voronoi Polygon >> Two-dimensional space R
N independent points P in a two- or three-dimensional space R3
(I) Voronoi polygon V (i) for (1 ≦ i ≦ N)
V (i) = ｛X || XP (i) | <| XP (j) |
where X and P are position vectors, and | | indicates a distance in Euclidean space.

It is assumed that V (i) thus defined forms a Voronoi polygon in R2 and a Voronoi polyhedron in R3. When V (i) and V (j) are adjacent to each other, the boundary of the Voronoi polygon is determined. Is defined as a part of a perpendicular bisector of a line connecting the points P (i) and P (j). The Euclidean space is as defined and described in the Dictionary of Mathematical Sciences and the like.

The center of gravity of the toner particles of the present invention and the center of gravity of each island in the toner particles are obtained from the moment of the image, and are automatically calculated by the image analyzer installed in the transmission electron microscope. You. Here, the barycentric coordinates of the toner particles are obtained by multiplying a luminance value of a small area at an arbitrary point of the toner particle by a coordinate value of the arbitrary point. Then, for all coordinates existing in the entire toner particle, the product of the luminance and the coordinate value is obtained, and the sum of the products is calculated as the luminance of the toner particle (the sum of the luminance values at each coordinate point obtained as described above). It is required by dividing. Similarly, the center of gravity of the island is calculated by calculating the luminance at an arbitrary coordinate point in the island. As described above, both the barycentric coordinates of the toner particles of the present invention and the barycentric coordinates of each island present in the toner particles are calculated based on the brightness at each arbitrary point, that is, from the brightness of the image.

In the present invention, the average value of the area of the Voronoi polygon formed by the perpendicular bisector between the centers of gravity of adjacent islands in the toner particles is 20,000 to 120,000 nm.
² and the coefficient of variation of the average value of the area is 25%
The following are preferred. In the present invention, the coefficient of variation of the area of the Voronoi polygon is calculated by the following equation.

Coefficient of variation of Voronoi polygon area = ｛S4
/ K4｝ × 100 (%) In the formula, S4 indicates the standard deviation of the area of the Voronoi polygon of the island portion existing in the toner particles, and K4 indicates the average value of the area of the Voronoi polygon.

The average value of the Voronoi polygon area of adjacent islands in the toner particles according to the present invention is more preferably 40,000 to 100,000 nm ² , and the coefficient of variation is 20%. It is as follows.

The average value of the area of the Voronoi polygon formed by the perpendicular bisector between the centers of gravity of the adjacent islands in the toner particles according to the present invention is 20,000 to 120,000 nm.
^Although it is within the range of ² , the one out of this range results in unfavorable occupation of the islands in the toner particles.For example, the colorant present as the islands in the particles has an effect on the toner particles. It is not preferable because it is difficult to find the effect of the present invention.

The variation coefficient of the average value of the area of the Voronoi polygon formed by the adjacent islands in the toner particles according to the present invention specifies the variation in the area of the Voronoi polygon, that is, the variation coefficient of the area of the Voronoi polygon. The variation in the occupation state of the islands is specified, and the variation coefficient of the average value of the area of the Voronoi polygons is preferably 25% or less, more preferably 20% or less. When the coefficient of variation is 0%, that is, a state where there is no variation in the average value of the area of the Voronoi polygon, in other words, a state where there is no variation in the occupation state of the islands in the toner particles, There is no need for the occupancy to be the same.

Further, in the present invention, the area of the Voronoi polygon formed by islands existing within a specific range from the center of gravity of the toner particles is larger than the area of the Voronoi polygon formed by islands existing outside the range. Preferably, it is small. That is, in the present invention, the average value of the area of the Voronoi polygon formed by the islands located outside the radius of 1000 nm from the center of gravity of the toner particles is the average value of the area of the Voronoi polygon formed by the islands located within the radius of 1000 nm. This means that in the toner particles, it is preferable that the dispersed state of the islands is sparse at a place somewhat away from the center of gravity of the toner particles. By satisfying this condition, in the toner according to the present invention, the effects achieved by the present invention can be more effectively obtained by appropriately dispersing the islands in the toner particles.

In the present invention, the islands are appropriately dispersed, the islands are appropriately spaced from each other, the islands are not unevenly distributed in the toner particles, and the colorant is effectively added to the toner particles. From, the area of the Voronoi polygon is 160,000
It is preferable that 5 to 30 islands having a nm ² or more exist in one toner particle.

(Molecular Weight Distribution of Resin Particle and Toner) The peak or shoulder of the molecular weight distribution of the toner of the present invention is 10%.
0.00-1,000,000, and 1,000-5
It is preferable that the peak is present at a molecular weight distribution of 100,000 to 1,000,000.
00, 25,000-150,000 and 1,000-
Preferably it is present at 50,000.

The molecular weight of the resin particles is from 100,000 to
A resin containing at least a high molecular weight component having a peak or shoulder in a region of 1,000,000 and a low molecular weight component having a peak or shoulder in a region of 1,000 to less than 50,000 is preferable, and more preferably a resin. Is
It is preferable to use an intermediate molecular weight resin having a peak or shoulder at a portion of 15,000 to 100,000.

The above-mentioned method for measuring the molecular weight of the toner or the resin is based on the GP using THF (tetrahydrofuran) as a solvent.
Measurement by C (gel permeation chromatography) is good. That is, 1.0 ml of THF is added to 0.5 to 5 mg, more specifically, 1 mg of a measurement sample, and the mixture is stirred at room temperature using a magnetic stirrer or the like to be sufficiently dissolved. Then, pore size 0.45
After treatment with a 0.50 μm membrane filter,
Inject into GPC. GPC measurement conditions are as follows: stabilize the column at 40 ° C., flow THF at a flow rate of 1.0 ml per minute, and inject about 100 μl of a 1 mg / ml concentration sample for measurement. The column is preferably used in combination with a commercially available polystyrene gel column. For example, Shodex GPC KF-801, 80 manufactured by Showa Denko KK
2, 803, 804, 805, 806, 807 and TSKgel G1000H, G200 manufactured by Tosoh Corporation
0H, G3000H, G4000H, G5000H, G
6000H, G7000H, TSK guard co
and the like. As the detector, a refractive index detector (IR detector) or U
Preferably, a V detector is used. In measuring the molecular weight of a sample, the molecular weight distribution of the sample is calculated using a calibration curve created using monodispersed polystyrene standard particles. It is preferable to use about 10 polystyrenes for preparing a calibration curve.

(Developer) The toner of the present invention may be used as a one-component developer or a two-component developer, but is particularly preferably used as a non-magnetic one-component developer.

In the case where the toner of the present invention contains a fluorine atom as the component a, X is used to sufficiently bring out the effects of the present invention.
In the measurement by line photoelectron spectroscopy (referred to as ESCA or XPS), a peak exists at 689.0 to 692.0 eV, and the ratio of the number of fluorine atoms to the number of carbon atoms calculated from the peak intensity is 0.001 to 0.001. It is preferably 0.04. Particularly preferably, 690.5 to 6
A peak exists at 91.0 eV, and the ratio of the number of fluorine atoms to the number of carbon atoms calculated from the peak intensity is 0.0
01 to 0.002.

Further, the toner of the present invention exhibits a high fixing property and contains a crystalline compound in order to avoid the offset phenomenon described in JP-A-8-328295. One or more endothermic peaks in the differential thermal analysis due to the compound exist at 60 to 120 ° C,
It is preferable that the heat absorption is 4 J to 30 J / g.

Next, a method for producing the toner of the present invention will be described. The toner of the present invention is obtained by polymerizing at least a polymerizable monomer in an aqueous medium, and this manufacturing method prepares resin particles by polymerizing the polymerizable monomer by a suspension polymerization method. Alternatively, emulsion polymerization or mini-emulsion polymerization of the monomer is performed in a liquid (in an aqueous medium) to which an emulsion of the necessary additives is added to prepare fine resin particles, and if necessary, charged. After adding controllable resin particles,
It is manufactured by a method of adding an organic solvent, a coagulant such as salts and the like, and coagulating and fusing the resin particles.

<< Shape and Production Method >><Emulsion Polymerization Method> As a method for producing the toner of the present invention, a method in which resin particles are prepared by salting out / fusion in an aqueous medium can also be mentioned. Although this method is not particularly limited, for example, Japanese Patent Application Laid-Open No. 5-2652
52, JP-A-6-329947 and JP-A-9
-15904 can be mentioned.
That is, a method of salting out, aggregating, and fusing a plurality of fine particles composed of a resin and a colorant, or a dispersion particle of a constituent material such as a resin particle and a colorant, particularly dispersing these in water using an emulsifier After that, a coagulant having a critical coagulation concentration or more is added and salted out, and at the same time, the formed polymer itself is heated and fused at a temperature of the glass transition temperature or more to gradually grow the particle size while forming fused particles. When the target particle size is reached, add a large amount of water to stop the particle size growth, further heat and stir to smooth the particle surface to control the shape, and heat the particles in a fluid state while keeping the particles wet. By drying, the toner of the present invention can be formed.
Here, a solvent such as alcohol which is infinitely soluble in water may be added together with the coagulant.

In the method for producing a toner according to the present invention, the composite resin fine particles and the colorant particles formed through the step of dissolving the crystalline substance in at least the polymerizable monomer and polymerizing the polymerizable monomer are used. It is obtained by salting out / fusing. The toner of the present invention dissolves a crystalline substance in a polymerizable monomer. The crystalline substance may be dissolved or dissolved, or may be dissolved and dissolved.

The method for producing the toner of the present invention is to salt out / fuse the composite resin fine particles obtained by the multi-stage polymerization method and the colorant particles. The multi-stage polymerization method will be described below.

<< Method for Producing Composite Resin Particles Obtained by Multistage Polymerization Method >> The method for producing the toner of the present invention comprises the following steps.

1: a multi-stage polymerization step; 2: a salting-out / fusing step of salting-out / fusing the composite resin particles and the colorant particles to obtain toner particles; 3: a step of dispersing the toner particles from a dispersion system of the toner particles. Filter out,
A filtration / washing step of removing a surfactant or the like from the toner particles; 4: a drying step of drying the washed toner particles; and 5: a step of adding an external additive to the dried toner particles. .

Hereinafter, each step will be described in detail. [Multi-stage polymerization step] The multi-stage polymerization step is a polymerization method carried out to expand the molecular weight distribution of the resin particles in order to obtain a toner in which offset has been prevented. That is, in order to form phases having different molecular weight distributions in one resin particle, the polymerization reaction is performed in multiple stages, and the obtained resin particles have a molecular weight gradient from the center of the particle toward the surface layer. It is intended to be formed. For example, a method in which a high molecular weight resin particle dispersion is obtained first, and then a low molecular weight surface layer is formed by newly adding a polymerizable monomer and a chain transfer agent.

In the present invention, it is preferable to employ a multi-stage polymerization method of three-stage polymerization or more from the viewpoint of production stability and crushing strength of the obtained toner. Hereinafter, two-stage polymerization and three-stage polymerization, which are typical examples of the multi-stage polymerization, will be described. In the toner obtained by such a multi-stage polymerization reaction, those having a molecular weight as low as the surface layer are preferable from the viewpoint of crushing strength.

<Two-Step Polymerization Method> In the two-step polymerization method, a central part (nucleus) formed from a high molecular weight resin containing a crystalline substance is used.
And a method of producing composite resin particles comprising an outer layer (shell) formed of a low molecular weight resin.

The method will be described in detail. First, a crystalline substance is dissolved in a monomer to prepare a monomer solution, and the monomer solution is added to an aqueous medium (for example, an aqueous solution of a surfactant).
After the oil droplets are dispersed therein, this system is subjected to a polymerization treatment (first stage polymerization) to prepare a dispersion of high molecular weight resin particles containing a crystalline substance.

Next, a polymerization initiator and a monomer for obtaining a low molecular weight resin are added to the dispersion of the resin particles, and the monomer is subjected to a polymerization treatment (second stage polymerization) in the presence of the resin particles. Is performed to form a coating layer made of a low molecular weight resin (monomer polymer) on the surface of the resin particles.

<Three-Stage Polymerization Method> In the three-stage polymerization method, a central portion (nucleus) formed from a high molecular weight resin, an intermediate layer containing a crystalline substance, and an outer layer (shell) formed from a low molecular weight resin are used. This is a method for producing composite resin particles. The toner of the present invention exists as the composite resin particles as described above.

The method will be described in detail. First, a dispersion of resin particles obtained by a polymerization treatment (first-stage polymerization) according to a conventional method is added to an aqueous medium (for example, an aqueous solution of a surfactant). Along with the addition, a monomer solution obtained by dissolving a crystalline substance in a monomer is dispersed in the aqueous medium in oil droplets, and then the system is subjected to a polymerization treatment (second-stage polymerization). A coating layer (intermediate layer) made of a resin (monomer polymer) containing a crystalline substance is formed on the surface of the particles (core particles) to form composite resin particles (high molecular weight resin / intermediate molecular weight resin). Prepare a dispersion.

Next, a polymerization initiator and a monomer for obtaining a low-molecular-weight resin are added to the obtained dispersion of the composite resin particles, and the monomer is subjected to a polymerization treatment (first step) in the presence of the composite resin particles. By performing the three-stage polymerization, a coating layer made of a low-molecular-weight resin (monomer polymer) is formed on the surfaces of the composite resin particles. In the above method, the incorporation of an intermediate layer is preferable because the crystalline substance can be finely and uniformly dispersed.

One feature of the method for producing a toner according to the present invention is to polymerize a polymerizable monomer in an aqueous medium. That is, when forming resin particles (core particles) or a coating layer (intermediate layer) containing a crystalline substance, the crystalline substance is dissolved in a monomer, and the resulting monomer solution is oiled in an aqueous medium. In this method, latex particles are obtained by dispersing droplets, adding a polymerization initiator to the system, and performing a polymerization treatment.

The aqueous medium referred to in the present invention is water 50 to 10
A medium comprising 0% by mass and 0 to 50% by mass of a water-soluble organic solvent. Examples of the water-soluble organic solvent include, for example, methanol, ethanol, isopropanol, butanol,
Acetone, methyl ethyl ketone, tetrahydrofuran and the like can be exemplified, and an alcohol-based organic solvent which does not dissolve the obtained resin is preferable.

As a polymerization method suitable for forming resin particles or a coating layer containing a crystalline substance, a crystalline substance is dissolved in an aqueous medium obtained by dissolving a surfactant having a concentration equal to or lower than the critical micelle concentration. The monomer solution dissolved in the monomer is dispersed in oil droplets using mechanical energy to prepare a dispersion, and a water-soluble polymerization initiator is added to the obtained dispersion, and the oil is dispersed in the oil droplets. A method of radical polymerization (hereinafter, referred to as a “mini-emulsion method” in the present invention) can be mentioned, and the effect of the present invention can be more exerted, which is preferable. In addition,
In the above method, an oil-soluble polymerization initiator may be used instead of or together with the water-soluble polymerization initiator.

According to the mini-emulsion method in which oil droplets are formed mechanically, unlike a normal emulsion polymerization method, the crystalline substance dissolved in the oil phase is less detached, and the resin particles or the coating layer to be formed are formed. A sufficient amount of crystalline material can be introduced into the inside.

Here, the disperser for dispersing oil droplets by mechanical energy is not particularly limited, and for example, a stirrer “CLEARMIX” equipped with a high-speed rotating rotor (M -Technic Co., Ltd.), an ultrasonic disperser, a mechanical homogenizer, a Menton-Gaulin and a pressure homogenizer. Further, the dispersion particle diameter is 1
0 nm to 1000 nm, preferably 50 nm to 1 nm.
000 nm, more preferably 30 nm to 300 nm. Here, by giving a distribution to the dispersed particle diameter, the phase separation structure of the crystalline substance in the toner particles, that is, the Feret diameter, the shape coefficient, and the variation coefficient thereof may be controlled.

As other polymerization methods for forming the resin particles containing the crystalline substance or the coating layer, known methods such as an emulsion polymerization method, a suspension polymerization method, and a seed polymerization method can be used. . In addition, these polymerization methods can also be employed to obtain resin particles (core particles) or coating layers constituting the composite resin particles, which do not contain a crystalline substance.

The particle diameter of the composite resin particles obtained in this polymerization step is 10 n in terms of mass average particle diameter measured using an electrophoretic light scattering photometer “ELS-800” (manufactured by Otsuka Electronics Co., Ltd.).
It is preferably in the range of m to 1000 nm.

Also, the glass transition temperature (T
g) is preferably in the range of 48 to 74 ° C, more preferably 52 to 64 ° C. The softening point of the composite resin particles is preferably in the range of 95 to 140 ° C.

The toner of the present invention is obtained by forming a resin layer formed by fusing resin particles on a surface of a resin and colored particles by a salting out / fusion method. explain.

[Salt-out / fusion step] In the salt-out / fusion step, the composite resin particles obtained by the multi-stage polymerization step and the colorant particles are subjected to salt-out / fusion (the salt-out / fusion step). At the same time) to obtain irregular (non-spherical) toner particles.

The salting out / fusion in the present invention means that salting out (aggregation of particles) and fusion (loss of interface between particles) occur simultaneously, or salting out and fusion occur simultaneously. Act. In order to simultaneously carry out the salting-out and the fusion, the particles (composite resin particles, colorant particles) under a temperature condition not lower than the glass transition temperature (Tg) of the resin constituting the composite resin particles.
Need to be aggregated.

In this salting-out / fusion step, together with the composite resin particles and the colorant particles, internal additive particles (fine particles having a number average primary particle diameter of about 10 to 1000 nm) such as a charge control agent are salted out / fused. May be. Also, the colorant particles
The surface may be modified, and a conventionally known surface modifier may be used.

[Maturation Step] The ripening step is a step subsequent to the salting-out / fusion step. After the resin particles are fused, the temperature is kept near the melting point of the crystalline substance, preferably at ± 20 ° C. In this step, the crystalline substance is phase-separated by continuing the stirring at an intensity of. In this step, it is possible to control the Feret diameter and the shape coefficient of the crystalline substance and the coefficient of variation thereof.

The colorant particles are subjected to salting-out / fusion treatment in a state of being dispersed in an aqueous medium. The aqueous medium in which the colorant particles are dispersed is preferably an aqueous solution in which a surfactant is dissolved at a concentration equal to or higher than the critical micelle concentration (CMC).

The disperser used for dispersing the colorant particles is not particularly limited, but is preferably a stirrer “CLEARMIX (CLEARM) equipped with a high-speed rotating rotor.
MIX) "(manufactured by M Technique Co., Ltd.), an ultrasonic disperser, a pressure disperser such as a mechanical homogenizer, a Menton-Gaulin, a pressure type homogenizer, and a medium disperser such as a Getzman mill and a diamond fine mill.

In order to salt out / fuse the composite resin particles and the colorant particles, a salting-out agent having a critical coagulation concentration or more (coagulant) is added to the dispersion in which the composite resin particles and the colorant particles are dispersed. ) And heating the dispersion above the glass transition temperature (Tg) of the composite resin particles.

The temperature range suitable for salting out / fusing is (Tg + 10) to (Tg + 50 ° C.), and particularly preferably (Tg + 15) to (Tg + 40 ° C.). Further, in order to effectively perform the fusion, an organic solvent which is infinitely soluble in water may be added.

Further, in the present invention, after the resin particles and the colorant are salted out, aggregated and fused in an aqueous medium to obtain colored particles (referred to as toner particles in the present invention), the toner particles are dispersed in an aqueous medium. When separating from the medium, the separation is preferably performed at a temperature equal to or higher than the Kraft point of the surfactant present in the aqueous medium, and more preferably at a temperature in the range of Kraft point to (Kraft point + 20 ° C.). preferable.

The above-mentioned Krafft point is a temperature at which an aqueous solution containing a surfactant starts to become cloudy, and the Krafft point is measured as follows.

<< Measurement of Kraft Point >> A solution was prepared by adding an actually used amount of a coagulant to an aqueous medium, ie, a surfactant solution, used in the steps of salting out, coagulation, and fusion. For 5 days. The solution was then heated gradually with stirring until it became clear. The temperature at which the solution became clear is defined as the Krafft point.

From the viewpoint of suppressing excessive charging of the toner particles and imparting a uniform charging property, in particular, in order to stabilize and maintain the charging property with respect to the environment, the toner for developing an electrostatic image of the present invention comprises: The metal elements described above (in the form of metal,
Metal ions, etc.) in the toner of 250 to 20
The content is preferably 000 ppm, more preferably 800 to 5000 ppm.

In the present invention, the total value of the divalent (trivalent) metal element used for the coagulant and the monovalent metal element added as the coagulation terminator described later is 350 to 35,000 pp.
m is preferable. The measurement of the residual amount of metal ions in the toner is performed using a fluorescent X-ray analyzer "System 3270"
It can be determined by measuring the intensity of fluorescent X-rays emitted from a metal species of a metal salt used as a coagulant (for example, calcium derived from calcium chloride) using [Rigaku Denki Kogyo]. As a specific measuring method, a plurality of toners having a known content ratio of the coagulant metal salt are prepared, and 5 g of each toner is pelletized, and the content ratio (mass ppm) of the coagulant metal salt and the metal type of the metal salt are determined. The relationship (calibration curve) with the fluorescent X-ray intensity (peak intensity) from the sample is measured. Next, the toner (sample) whose content ratio of the coagulant metal salt is to be measured is similarly pelletized, and the fluorescent X-ray intensity from the metal species of the coagulant metal salt is measured. Quantity "can be determined.

[Filtration / Washing Step] In this filtration / washing step, a filtration treatment for filtering the toner particles from the dispersion system of the toner particles obtained in the above step, Washing treatment for removing extraneous substances such as surfactants and salting-out agents from the aggregates). Here, the filtration method is not particularly limited, such as a centrifugal separation method, a reduced pressure filtration method using a Nutsche method, a filtration method using a filter press, or the like.

[Drying Step] This step is a step of drying the washed toner particles.

[0206] Examples of the drier used in this step include a spray drier, a vacuum freeze drier, a reduced-pressure drier, and the like, and a stationary shelf drier, a movable shelf drier, a fluidized bed drier, a rotary drier. It is preferable to use a type dryer, a stirring type dryer and the like.

The water content of the dried toner particles is preferably 5% by mass or less, more preferably 2% by mass or less. In the case where the dried toner particles are aggregated by a weak attractive force between the particles, the aggregate may be crushed. Here, as the crushing device, a mechanical crushing device such as a jet mill, a Henschel mixer, a coffee mill, and a food processor can be used.

The toner of the present invention forms composite resin particles in the absence of a colorant, adds a dispersion of the colorant particles to a dispersion of the composite resin particles, and combines the composite resin particles with the colorant particles. It is preferably prepared by salting out / fusing.

As described above, by performing the preparation of the composite resin particles in a system in which no colorant is present, the polymerization reaction for obtaining the composite resin particles is not hindered. Therefore, according to the toner of the present invention, the excellent offset resistance is not impaired, and the fixing device is not stained or the image is not stained due to the accumulation of the toner.

Further, as a result of reliably performing the polymerization reaction for obtaining the composite resin particles, no monomer or oligomer remains in the obtained toner particles. No unpleasant odor is generated in the heat fixing step.

Furthermore, since the surface characteristics of the obtained toner particles are uniform and the charge amount distribution is sharp, an image having excellent sharpness can be formed for a long period of time. According to such a toner having a uniform composition, molecular weight, and surface characteristics among toner particles, good adhesion (high fixing strength) to an image support is maintained in an image forming method including a fixing step by a contact heating method. Meanwhile, the offset resistance and the anti-winding property can be improved, and an image having an appropriate gloss can be obtained.

Next, each component used in the toner manufacturing process will be described in detail. (Polymerizable monomer) As a polymerizable monomer for producing the resin (binder) used in the present invention, a hydrophobic monomer is an essential component, and a crosslinkable monomer is optionally used. Used. It is desirable that the structure contains at least one monomer having an acidic polar group or a monomer having a basic polar group as described below.

(1) Hydrophobic monomer The hydrophobic monomer constituting the monomer component is not particularly limited, and a conventionally known monomer can be used. In addition, one kind or a combination of two or more kinds can be used so as to satisfy required characteristics.

Specifically, monovinyl aromatic monomers,
It is possible to use (meth) acrylate monomers, vinyl ester monomers, vinyl ether monomers, monoolefin monomers, diolefin monomers, halogenated olefin monomers, and the like. it can.

Examples of the vinyl aromatic monomer include, for example,
Styrene, o-methylstyrene, m-methylstyrene,
p-methylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, p-ethylstyrene, p-n-butylstyrene, p-tert-butylstyrene, p-n-hexylstyrene, p-n- Styrene-based monomers such as octylstyrene, pn-nonylstyrene, pn-decylstyrene, pn-dodecylstyrene, 2,4-dimethylstyrene, and 3,4-dichlorostyrene, and derivatives thereof. .

Examples of (meth) acrylic ester monomers include acrylic acid, methacrylic acid, methyl acrylate,
Ethyl acrylate, butyl acrylate, acrylic acid-2
-Ethylhexyl, cyclohexyl acrylate, phenyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, ethyl β-hydroxyacrylate, γ-aminopropyl acrylate, methacrylic acid Stearyl, dimethylaminoethyl methacrylate,
And diethylaminoethyl methacrylate.

Examples of the vinyl ester monomers include vinyl acetate, vinyl propionate, and vinyl benzoate. Examples of the vinyl ether monomers include vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether, and vinyl phenyl ether. And the like.

The monoolefin monomers include ethylene, propylene, isobutylene, 1-butene and 1-butene.
Examples thereof include pentene and 4-methyl-1-pentene, and examples of the diolefin-based monomer include butadiene, isoprene, and chloroprene.

(2) Crosslinkable monomer A crosslinkable monomer may be added to improve the properties of the resin particles. Examples of the crosslinkable monomer include those having two or more unsaturated bonds such as divinylbenzene, divinylnaphthalene, divinyl ether, diethylene glycol methacrylate, ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, and diallyl phthalate.

(3) Monomer having acidic polar group Examples of the monomer having an acidic polar group include (a) an α, β-ethylenically unsaturated compound having a carboxyl group, and
(B) α, β-ethylenically unsaturated compounds having a sulfonic acid group.

Examples of the α, β-ethylenically unsaturated compound having a carboxyl group include acrylic acid, methacrylic acid, fumaric acid, maleic acid, itaconic acid, cinnamic acid, maleic acid monobutyl ester, and maleic acid monobutyl ester. Examples thereof include octyl esters, and metal salts thereof such as Na and Zn.

Examples of the α, β-ethylenically unsaturated compound having a sulfonic acid group include sulfonated styrene and its Na salt, allyl sulfosuccinic acid, octyl allyl sulfosuccinate, and Na salt thereof. it can.

(4) Monomer having a basic polar group Examples of the monomer having a basic polar group include (i) an amine group or a quaternary ammonium group having 1 to 1 carbon atoms.
2, preferably 2 to 8, particularly preferably 2, (meth) acrylic esters of aliphatic alcohols, (ii) (meth)
Acrylamide or optionally 1 to 1 carbon atoms on N
(Meth) acrylamide mono- or di-substituted by an alkyl group of 18, (iii) vinyl compound substituted by a heterocyclic group having N as a ring member, and (iv) N, N-diallyl-alkylamine or A quaternary ammonium salt can be illustrated. Among them, (i) the (meth) acrylic acid ester of an aliphatic alcohol having an amine group or a quaternary ammonium group is preferable as the monomer having a basic polar group.

Examples of the (meth) acrylate of an aliphatic alcohol having an amine group or a quaternary ammonium group (i) include dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, Quaternary ammonium salts of four compounds, 3-dimethylaminophenyl acrylate, 2-hydroxy-
Examples thereof include 3-methacryloxypropyltrimethylammonium salt.

Examples of (ii) (meth) acrylamide or mono- or dialkyl-substituted (meth) acrylamide include acrylamide, N-butylacrylamide, N, N-dibutylacrylamide, piperidylacrylamide, methacrylamide, -Butylmethacrylamide, N, N-dimethylacrylamide, N-octadecylacrylamide and the like.

Examples of the vinyl compound (iii) substituted with a heterocyclic group having N as a ring member include vinylpyridine,
Vinyl pyrrolidone, vinyl-N-methylpyridinium chloride, vinyl-N-ethylpyridinium chloride and the like can be mentioned.

Examples of (iv) N, N-diallyl-alkylamine include N, N-diallylmethylammonium chloride, N, N-diallylethylammonium chloride and the like.

(Chain transfer agent) For the purpose of adjusting the molecular weight, a known chain transfer agent can be used. The chain transfer agent is not particularly limited, for example, octyl mercaptan, dodecyl mercaptan,
A compound having a mercapto group such as tert-dodecyl mercaptan is used. In particular, a compound having a mercapto group is preferably used because it suppresses odor at the time of heat-fixing, provides a toner having a sharp molecular weight distribution, and is excellent in storage stability, fixing strength, and offset resistance. Preferred are, for example, ethyl thioglycolate,
The mercapto group of propyl thioglycolate, propyl thioglycolate, butyl thioglycolate, t-butyl thioglycolate, 2-ethylhexyl thioglycolate, octyl thioglycolate, decyl thioglycolate, dodecyl thioglycolate, and ethylene glycol A compound having a mercapto group of neopentyl glycol and a compound having a mercapto group of pentaeristol. Among these, from the viewpoint of suppressing odor during toner heat fixing, n-octyl-
3-mercaptopropionate is particularly preferred.

(Surfactant) In order to carry out the miniemulsion polymerization using the above-mentioned polymerizable monomer, it is preferable to disperse oil droplets in an aqueous medium using a surfactant. Surfactants that can be used at this time are not particularly limited, but the following ionic surfactants can be mentioned as examples of suitable compounds.

Examples of the ionic surfactant include sulfonates (sodium dodecylbenzenesulfonate,
Sodium arylalkyl polyether sulfonate,
3,3-disulfonediphenylurea-4,4-diazo-
Sodium bis-amino-8-naphthol-6-sulfonate, ortho-carboxybenzene-azo-dimethylaniline, 2,2,5,5-tetramethyl-triphenylmethane-4,4-diazo-bis-β-naphthol -6
Sodium sulfonate), sulfate salts (sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, etc.),
Fatty acid salts (sodium oleate, sodium laurate, sodium caprate, sodium caprylate, sodium caproate, potassium stearate, calcium oleate, etc.) are exemplified.

In the present invention, the following general formula (A):
The surfactant represented by (B) is particularly preferably used. General formula (A) R ₁ (OR ₂ ) _n OSO ₃ M General formula (B) R ₁ (OR ₂ ) _n SO ₃ M In the formula, R ₁ Represents an alkyl group or an arylalkyl group having 6 to 22 carbon atoms, preferably an alkyl group or an arylalkyl group having 8 to 20 carbon atoms, more preferably an alkyl group or an arylalkyl group having 9 to 16 carbon atoms. is there.

Examples of the alkyl group having 6 to 22 carbon atoms represented by R ₁ include n-hexyl group, n-heptyl group, n-octyl group, n-decyl group, n-undecyl group and n-hexadecyl. Groups, cyclopropyl group, cyclopentyl group, cyclohexyl group, and the like. Examples of the arylalkyl group represented by R1 include a benzyl group, a diphenylmethyl group, a cinnamyl group, a styryl group, a trityl group, a phenethyl group, and the like.

In the general formulas (1) and (2), R ₂ represents an alkylene group having 2 to 6 carbon atoms, preferably an alkylene group having 2 to 3 carbon atoms. Carbon atoms represented by R ₂ 2
Examples of the alkylene groups 6 to 6 include an ethylene group, a trimethylene group, a tetramethylene group, a propylene group, and an ethylethylene group.

In the general formulas (1) and (2), n is 1 to
It is an integer of 11, preferably 2 to 10, more preferably 2 to 5, and particularly preferably 2 to 3. Further, as a monovalent metal element represented by M, sodium,
Potassium, lithium and the like can be mentioned. Among them, sodium is preferably used.

Specific examples of the surfactants represented by formulas (1) and (2) are shown below, but the present invention is not limited thereto.

Compound (101): C ₁₀ H ₂₁ (OCH ₂ CH ₂ ) ₂ OSO ₃
Na compound (102): C ₁₀ H ₂₁ (OCH ₂ CH ₂ ) ₃ OSO ₃
Na compound (103): C ₁₀ H ₂₁ (OCH ₂ CH ₂ ) ₂ SO ₃ N
a Compound (104): C ₁₀ H ₂₁ (OCH ₂ CH ₂ ) ₃ SO ₃ N
a Compound (105): C ₈ H ₁₇ (OCH ₂ CH (CH ₃ )) ₂
OSO ₃ Na compound (106): C ₁₈ H ₃₇ (OCH ₂ CH ₂ ) ₂ OSO ₃
In the present invention, from the viewpoint of maintaining the charge retention function of the toner in a good state, suppressing fogging under high temperature and high humidity, and improving transferability, and suppressing an increase in charge amount under low temperature and low humidity, From the viewpoint of stabilizing the development amount, the content of the surfactant represented by the general formulas (1) and (2) in the toner for developing an electrostatic image is preferably from 1 to 1000 ppm, more preferably from 1 to 1000 ppm. It is 5 to 500 ppm, particularly preferably 7 to 100 ppm.

In the present invention, by setting the amount of the surfactant to be contained in the toner within the above-mentioned range, the chargeability of the toner for developing an electrostatic image of the present invention is not affected by the environment and is always influenced by the environment. , Can be applied and maintained in a uniform and stable state.

The content of the surfactant represented by the above general formulas (1) and (2) contained in the toner for developing an electrostatic image of the present invention is calculated by the following method. .

One gram of the toner is dissolved in 50 ml of chloroform, and the surfactant is extracted from the chloroform layer with 100 ml of ion-exchanged water. The extracted chloroform layer was extracted again with 100 ml of ion-exchanged water to obtain a total of 200 ml of an extract (aqueous layer).
Dilute to 00 ml.

This diluent was used as a test solution in accordance with JIS 33
According to the method specified in Section 636, the color is developed with methylene blue, the absorbance is measured, and the content of the surfactant in the toner is measured from a separately prepared calibration curve.

In addition, the fields represented by the general formulas (1) and (2)
The structure of the surfactant is based on the above extract ¹Using H-NMR
Analysis and structure determination.

In the present invention, a metal salt can be preferably used as a coagulant in the step of salting out, coagulating, and fusing resin particles from a dispersion of resin particles prepared in an aqueous medium. More preferably, a trivalent metal salt is used as a flocculant. The reason is that a divalent or trivalent metal salt is preferable to a monovalent metal salt because the critical aggregation concentration (coagulation value or coagulation point) is smaller.

In the present invention, nonionic surfactants can also be used. Specific examples include polyethylene oxide, polypropylene oxide, a combination of polypropylene oxide and polyethylene oxide, an ester of polyethylene glycol and higher fatty acid, and an alkylphenol. Examples include polyethylene oxide, esters of higher fatty acids and polyethylene glycol, esters of higher fatty acids and polypropylene oxide, and sorbitan esters.

In the present invention, these surfactants are mainly used as an emulsifier at the time of emulsion polymerization, but may be used for other steps or other purposes.

(Aggregating Agent) In the present invention, a metal salt can be preferably used as an aggregating agent in the step of salting out, aggregating, and fusing resin particles from a dispersion of resin particles prepared in an aqueous medium. It is further preferable to use a divalent or trivalent metal salt as a flocculant. The reason is that a divalent or trivalent metal salt is preferable to a monovalent metal salt because the critical aggregation concentration (coagulation value or coagulation point) is smaller.

The coagulant used in the present invention is, for example, a monovalent metal salt such as a salt of an alkali metal such as sodium, potassium or lithium, for example, a salt of an alkaline earth metal such as calcium or magnesium, or a manganese or copper salt. Examples thereof include divalent metal salts and trivalent metal salts such as iron and aluminum.

Specific examples of these metal salts are shown below.
Examples of the monovalent metal salt include sodium chloride, potassium chloride, and lithium chloride. Examples of the divalent metal salt include calcium chloride, zinc chloride, copper sulfate, magnesium sulfate, and manganese sulfate. Examples thereof include aluminum chloride and iron chloride. These are appropriately selected depending on the purpose, but are preferably divalent or trivalent metal salts having a low critical aggregation concentration.

The critical flocculation concentration referred to in the present invention is an index relating to the stability of the dispersion in the aqueous dispersion, and indicates the concentration of the flocculant added when the flocculant is added. This critical aggregation concentration varies greatly depending on the latex itself and the dispersant. For example, it is described in Seizo Okamura et al., Polymer Chemistry 17, 601 (1960).
According to these descriptions, the value can be known.
As another method, a desired salt is added to the target particle dispersion at a different concentration, and the ζ potential of the dispersion is measured.
ζIt is also possible to set the salt concentration at the point where the potential starts to change as the critical aggregation concentration.

In the present invention, the polymer fine particle dispersion is treated using a metal salt so as to have a concentration higher than the critical aggregation concentration. At this time, of course, add the metal salt directly,
The addition as an aqueous solution is arbitrarily selected depending on the purpose. In the case of adding as an aqueous solution, the added metal salt needs to be at or above the critical aggregation concentration of the polymer particles with respect to the volume of the polymer particle dispersion and the total volume of the metal salt aqueous solution.

In the present invention, the concentration of the metal salt may be not less than the critical coagulation concentration, but is preferably 1.
It is added twice or more, more preferably 1.5 times or more.

(Colorant) The toner of the present invention is obtained by salting out / fusing the composite resin particles and the colorant particles. Examples of the colorant (colorant particles subjected to salting out / fusion with the composite resin particles) constituting the toner of the present invention include various inorganic pigments, organic pigments, and dyes.
Conventionally known inorganic pigments can be used. Specific inorganic pigments are exemplified below.

Examples of black pigments include furnace black, channel black, acetylene black,
Carbon black such as thermal black and lamp black, and magnetic powder such as magnetite and ferrite are also used.

These inorganic pigments can be used alone or in combination of two or more as desired. The amount of the pigment to be added is 2 to 20% by mass, preferably 3 to 15% by mass, based on the polymer.

When used as a magnetic toner, the above-described magnetite can be added. In this case, from the viewpoint of imparting predetermined magnetic characteristics, 20 to 6
It is preferable to add 0% by mass.

As the organic pigment and dye, conventionally known organic pigments and dyes can be used, and specific organic pigments and dyes are exemplified below.

As the pigment for magenta or red,
For example, C.I. I. Pigment Red 2, C.I. I. Pigment Red 3, C.I. I. Pigment Red 5, C.I. I.
Pigment Red 6, C.I. I. Pigment Red 7,
C. I. Pigment Red 15, C.I. I. Pigment Red 16, C.I. I. Pigment Red 48: 1, C.I.
I. Pigment Red 53: 1, C.I. I. Pigment Red 57: 1, C.I. I. Pigment Red 122, C.I.
I. Pigment Red 123, C.I. I. Pigment Red 139, C.I. I. Pigment red 144, C.I. I.
Pigment Red 149, C.I. I. Pigment Red 1
66, C.I. I. Pigment Red 177, C.I. I. Pigment Red 178, C.I. I. Pigment Red 222
And the like.

Examples of orange or yellow pigments include C.I. I. Pigment Orange 31, C.I.
I. Pigment Orange 43, C.I. I. Pigment Yellow 12, C.I. I. Pigment Yellow 13, C.I. I.
Pigment Yellow 14, C.I. I. Pigment Yellow 15, C.I. I. Pigment Yellow 17, C.I. I. Pigment Yellow 93, C.I. I. Pigment Yellow 9
4, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 180, C.I. I. Pigment Yellow 1
85, C.I. I. Pigment yellow 155, C.I. I. Pigment Yellow 156 and the like.

Examples of the green or cyan pigments include:
For example, C.I. I. Pigment Blue 15, C.I. I. Pigment Blue 15: 2, C.I. I. Pigment Blue 1
5: 3, C.I. I. Pigment Blue 16, C.I. I. Pigment Blue 60, C.I. I. Pigment Green 7 and the like.

As the dye, for example, C.I. I. Solvent Red 1, 49, 52, 58, 63
111, 122, C.I. I. Solvent Yellow 1
9, 44, 77, 79, 81, 82, 9
3, 98, 103, 104, 112, 16
2, C.I. I. Solvent Blue 25, 36, 60
70, 93, 95, etc., and mixtures thereof can also be used.

These organic pigments and dyes can be used alone or in combination of two or more as desired.
The amount of the pigment added is 2 to 20% by mass based on the polymer.
And preferably 3 to 15% by mass.

The colorant (colorant particles) constituting the toner of the present invention may be surface-modified. As the surface modifier, a conventionally known one can be used, and specifically, a silane coupling agent, a titanium coupling agent, an aluminum coupling agent and the like can be preferably used. Examples of the silane coupling agent include alkoxysilanes such as methyltrimethoxysilane, phenyltrimethoxysilane, methylphenyldimethoxysilane, and diphenyldimethoxysilane, siloxanes such as hexamethyldisiloxane, γ-chloropropyltrimethoxysilane, and vinyltrimethoxysilane. Chlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane,
γ-ureidopropyltriethoxysilane and the like. As the titanium coupling agent, for example, TTS, 9S, 38S, 41B, 46B, 55, 138, which are commercially available under the trade name of “Plenact” manufactured by Ajinomoto Co., Inc.
S-1, 238S, etc., commercial products A-1 and B-
1, TOT, TST, TAA, TAT, TLA, TO
G, TBSTA, A-10, TBT, B-2, B-4,
B-7, B-10, TBSTA-400, TTS, TO
A-30, TSDMA, TTAB, TTOP and the like. As the aluminum coupling agent, for example,
"Plenact AL-M" manufactured by Ajinomoto Co. and the like.

The addition amount of these surface modifiers is preferably from 0.01 to 20% by mass, more preferably from 0.1 to 5% by mass, based on the colorant. As a method for modifying the surface of the colorant particles, there is a method in which a surface modifier is added to a dispersion of the colorant particles, and the system is heated and reacted. The colorant particles surface-modified in this way are:
It is obtained by filtration, washing and filtering with the same solvent are repeated, followed by drying.

The image forming method of the present invention will be described.
An image forming method according to the present invention includes a latent image forming step of forming a latent image on a latent image carrier, a developing step of developing the latent image using toner, and forming the latent image on the latent image carrier. In an image forming method, a transfer step of transferring a toner image onto a transfer body, and a fixing step of heating and fixing the toner image on the transfer body using a heating member, wherein the toner is the toner of the present invention. Wherein the heating member has an elastic layer. According to the image forming method of the present invention, since the toner of the present invention is used, offset resistance and OH
Excellent transparency and high image quality without unpleasant glare.

The elastic layer of the heating member has a role of improving image quality, and is made of a material such as silicone rubber or fluorine rubber. The thickness of the elastic layer can be appropriately selected according to the purpose, but is preferably 0.5 to 5.0 mm.

Preferably, the heating member has a release layer. The release layer is preferably formed of a material having excellent releasability from the toner, for example, a fluorine-based resin, for the purpose of preventing the toner from adhering. Specific examples of the fluororesin include, for example, a copolymer of tetrafluoroethylene and perfluoroalkyl vinyl ether, a copolymer of tetrafluoroethylene and ethylene, and a copolymer of tetrafluoroethylene and hexafluoroethylene. Preferred are mentioned. The thickness of the release layer can be appropriately selected according to the purpose, but is preferably 10 to 60 μm.

In this case, it is preferable that the releasing liquid such as silicone oil applied to the heating member is not applied.
It is effective that the amount is as small as possible even if applied. The release liquid is effective for fixing latitude, but is transferred to the transfer-receiving material to be fixed, so it has stickiness, and it is not possible to attach a tape or write characters with magic. There's a problem. This is remarkable for OHP. In addition, since the release liquid cannot make the surface of the fixing surface smooth, it also causes a decrease in OHP transparency. In the configuration of the toner of the present invention, the release liquid such as silicone oil applied to the fixing roll may be slight in order to exhibit sufficient fixing latitude. For example, A4
It may be 1 μl or less per sheet. With the above range, the above-mentioned problems can be substantially avoided. In addition, in the configuration of the toner of the present invention, since a sufficient fixing latitude is exhibited without applying a releasing liquid, the releasing liquid applying mechanism can be omitted to save space.

In the case where the heating member is constituted by two rolls, the roll surface in contact with the toner image on the transfer member may be more concave than the other roll surface to form a nip. This is preferable because the transfer-receiving body is hardly wound around the roll. For example, if the thickness of the elastic layer of the roll that contacts the toner image on the
mm, the thickness of the elastic layer on the other roll is 1 mm
Alternatively, the hardness of the elastic layer with the same thickness can be achieved by setting a lower roll in contact with the toner image on the transfer-receiving member and applying a load. With this configuration, the discharge direction of the transfer target immediately after passing through the fixing roll is a direction away from the roll that is in contact with the toner image on the transfer target, and winding is unlikely to occur.

From the viewpoint of power consumption, it is preferable that the heating member is constituted by a single roll and a belt, and the roll is in contact with the toner image on the transfer object because the heat capacity of the belt is small. The material of the belt is preferably a heat-resistant material such as tetrafluoroethylene or polyimide. The layer thickness of the belt is preferably 2 mm or less, and the surface is preferably coated with a fluorine resin equivalent to the heating member. In addition, by applying pressure from the inside of the belt to the roll in contact with the toner image on the transfer target from the inside of the belt with a pressure roll or the like to form a recess, the discharge direction of the transfer target immediately after passing through the fixing roll can be changed. This is a direction away from the roll that is in contact with the toner image on the transfer member, and is preferable because winding is less likely to occur.

The surface temperature of the heating member is preferably 30 ° C. or higher, more preferably 50 ° C. or higher, than the temperature at the DSC endothermic peak of the wax contained in the toner of the present invention. If the surface temperature is not higher than the DSC endothermic peak temperature of the wax by 30 ° C. or more, the wax may not be able to sufficiently exhibit the releasing effect.

When a contact type such as a thermocouple is used as the temperature control sensor of the heating member, the surface of the heating member is easily worn in the structure of the present invention, unlike the conventional type in which a large amount of a releasing liquid is applied. Therefore, if the position of the temperature control sensor is present in the image portion, the image quality becomes defective. The non-image portion includes not only a portion through which the sheet does not pass but also an end portion where the toner is not transferred onto the sheet.

Hereinafter, an image forming apparatus used in the image forming method of the present invention will be described with reference to FIG. The image forming apparatus used in the image forming method of the present invention is not limited to the one shown in FIG.

FIG. 4A is a schematic sectional view showing the structure near the developing device according to the embodiment, and FIG. 4B is a sectional view of a main part thereof.
As shown in the figure, the developing device 3 (also referred to as a developing device 3) is configured such that a developing sleeve (developer carrier) 140 faces the photosensitive drum (electrostatic latent image carrier) 1, Is provided at a position close to the peripheral surface of. A positioning member (polyester film having a thickness of 0.1 mm) 160 is interposed between the developing sleeve 140 and the photosensitive drum 1, whereby a gap (a gap) between the developing sleeve 140 and the photosensitive drum 1 is formed. ) The distance Ds is set to a predetermined value.

The non-magnetic one-component toner used in the present invention is accommodated in the hopper 120 of the developing device 3, and is conveyed through the developing device 3 by a screw, a stirring blade or the like.
The developing sleeve 140 is reached. The toner that has reached the developing sleeve 140 is charged to a predetermined polarity by friction with a regulating member (eg, a SUS (stainless steel) plate having a thickness of 0.1 mm) 150 and is carried in a thin layer on the peripheral surface of the developing sleeve 140. You. The thickness of this thin layer is determined by the material and pressing force of the regulating member 150, but in this example, the peripheral speed of the photosensitive drum 1 is 100 mm / sec, the peripheral speed of the developing sleeve 140 is 200 mm / sec. Developing sleeve 1
By setting the pressing force for pressing 40 at 10 to 100 N / m, about 1.5 layers (thickness of about 1.5 toner particles) are obtained. The toner is charged to a predetermined polarity by frictional charging with the regulating member 150 and the developing sleeve 14 is charged.
The process supported in a thin layer on the peripheral surface of the 0 is, for example,
Since it is known as described in JP-B-63-15580, its description is omitted.

The developing sleeve 140 is formed in a cylindrical shape (eg, 17 mm in diameter) using a flexible material having conductivity (eg, a polyamide resin having a thickness of 1 mm).
Inside the developing sleeve 140, the drive roller 1 whose diameter is slightly smaller than the developing sleeve 140 (eg, 16 mm in diameter)
When the drive roller 130 rotates in the direction of the arrow, the developing sleeve 140 is driven by the frictional force between the outer peripheral surface of the drive roller 130 and the inner peripheral surface of the developing sleeve 140 and rotates in the same direction. It is configured as follows. Further, as described above, since the developing sleeve 140 is flexible and has a slightly larger diameter than the driving roller 130, there is a slight slack. The slack is regulated by the regulating member 150 and a guide belt (not shown) so as to occur on the side facing the photosensitive drum 1. Therefore, a part of the pressing force from the developing sleeve 140 is absorbed by the slack, and as a result, the developing sleeve 1
The pressing force applied from the developing sleeve 140 to the positioning member 160 inserted between the photosensitive drum 1 and the photosensitive drum 1 is relatively low.

The toner carried in a thin layer on the peripheral surface of the developing sleeve 140 is conveyed with the rotation of the developing sleeve 140 and reaches the developing area Da. The developing area Da is defined by the action of an electric field formed by the developing bias voltage Vb applied from the developing bias power supply device and the alternating voltage so that the toner on the peripheral surface of the developing sleeve 140 is developed.
Is an area where the electrostatic latent image on the peripheral surface of the photosensitive drum 1 is developed by flying from the peripheral surface of the photosensitive drum 1. This area is also an area within the nip width Da between the developing sleeve 140 and the photosensitive drum 1. The developing bias power supply device includes a DC voltage power supply that outputs a set value of the developing bias voltage Vb (eg, about −500 V) and an alternating electric field (eg, Vpp 2.0).
(kV, frequency 2 kHz).

For the process of developing the electrostatic latent image on the photoconductor by converting the toner flying from the developing sleeve into a powder cloud by an alternating electric field, for example, the basics and applications of electrophotographic technology (edited by the Electrophotographic Society, Corona As described on pages 158 to 170 of the company, the description is omitted. Vpp means a peak-to-peak voltage which is a difference between a peak and a valley of the amplitude of the alternating voltage waveform.

In the present embodiment, the photosensitive drum 1 is a photoconductive drum having a surface composed of a negatively charged organic photosensitive member and rotating at a constant speed in the direction of the arrow in the figure. The photosensitive drum 1 has a uniform potential (eg, -8) by a charging device (not shown).
After being charged to about 00V, it is exposed by an optical head such as a laser to attenuate the potential (eg, about -100V). That is, an electrostatic latent image is formed. When the electrostatic latent image reaches the development area Da, the toner that has been turned into a powder cloud as described above adheres to the potential attenuation portion,
Development takes place.

The positioning member 160 is in contact with the developing sleeve 140 so that its front edge (lower end in the figure) 16a is located within the developing area Da and is parallel to the longitudinal direction of the developing area Da. The developing sleeve 140 is interposed at a position on the upstream side in the rotation direction (the position on the upper half side in the figure) between the photosensitive drum 1 and the developing sleeve 140. Thereby, the gap distance Ds between the developing sleeve 14 and the photosensitive drum 1 is set to a predetermined value, and
Since the leading edge 16a is provided along the longitudinal direction, the gap distance Ds is set to an appropriate value over the entire image width. As described above, the positioning member 160 is a polyester film having a thickness of 0.1 mm as described above, but is not limited to the polyester film. The material may be selected in consideration of the balance with the frictional charging of the toner.For example, by using a charging series material having a polarity opposite to the charging polarity of the toner, the frictional charging by the regulating member 150 is assisted or promoted. You may comprise. Also, 2
As a layer structure, the surface in contact with the developing sleeve 140 is made of a conductive material, and by applying a voltage having the same polarity as the charging polarity of the toner, the toner is prevented from adhering and the charging of the toner is assisted. You may.

In the present embodiment, the positioning member 160 is
As shown, it is provided on the upstream side of the rotation of the developing sleeve 140 and the photosensitive drum 1 and shields the upstream part in the developing area Da, but is provided on the downstream side and is provided on the downstream side in the developing area Da. May be shielded. In the case where the positioning member 160 is provided on the upstream side as in this example, the positioning member 160 is provided along the rotation direction, so that the resistance received from the developing sleeve 140 and the photosensitive drum 1 is reduced, which causes a problem in toner flying. There is an effect that it is difficult. Even when at least one of the developing sleeve 140 and the photosensitive drum 1 has flexibility or elasticity, the gap distance Ds
Has an effect that can be set to an appropriate value.

Next, the leading edge 16 of the positioning member 160
The relationship between the position of “a”, the gap distance Ds between the developing sleeve 140 and the photosensitive drum 1, and the toner adhesion amount will be described.
The flying of the toner from the surface of the developing sleeve 140 and the formation of the powder cloud are mainly determined by the gap distance Ds, the width Da of the developing region in the rotation direction, and the developing bias voltage Vb. When an alternating electric field is formed, the amplitude difference voltage Vp-p of the applied voltage waveform also contributes. When a flying type developing device is configured, it is relatively easy to improve the accuracy on the power supply side, but it is difficult to stably secure the gap distance Ds. Therefore, in this example, the positioning member 160 is used.

Although the gap distance Ds can be easily set to an appropriate value by the positioning member 160 as described above, a part of the developing region (the upper part in the illustrated example) is shielded by the presence of the positioning member 160. Would.
For this reason, the amount of toner adhered on the photosensitive drum 1 is reduced, which causes a problem that the development density is reduced. In order to obtain a sufficient print image density, it is sufficient that the toner adhering amount is 0.7 mg / cm ² or more, and the developing nip width D is 1.5 mm or more.
By ensuring a, a sufficient amount of toner adhered can be obtained.

Therefore, it is necessary to set the position of the leading edge 16a of the positioning member 160 within a range where the developing nip width Da is 1.5 mm or more.

The above example can be variously modified. For example, an amplitude voltage difference Vp for forming an alternating electric field
p is about 100 to 3000 V, and its frequency is 1
A triangular wave or a rectangular wave can be used as the waveform at about 00 to 10 kHz. Further, the thickness of the positioning member 160 may be about 0.01 to 0.5 mm, and may be used in combination with the above-described alternating electric field. Magnetic toner can be used instead of non-magnetic toner. Further, a developing roller may be used instead of the flexible developing sleeve, and the photoconductor may be configured to have elasticity. Further, by detaching the positioning member 160 in the non-image printing area, it can be used as a simultaneous development cleaning device.

FIG. 5 is a schematic diagram showing an example of a color electrophotographic image forming apparatus. First, second, third and fourth image forming units P are provided in the main body of the color electrophotographic image forming apparatus.
a, Pb, Pc and Pd are installed in parallel. Each image forming unit has the same configuration, and forms visible images (toner images) of different colors.

The image forming units Pa, Pb, Pc and Pd are:
Each has a dedicated electrostatic latent image carrier (electrophotographic photosensitive drum) 1a, 1b, 1c and 1d. Electrophotographic photoreceptor drums (may be abbreviated as photoreceptor drums) 1a, 1a formed by image forming portions Pa, Pb, Pc and Pd
The images on b, 1c and 1d are transferred onto a recording material (transfer material, image support) carried and conveyed on a recording material carrier 18 moving adjacent to each image forming section. Further, the image on the recording material is fixed by heating and pressing in a fixing unit (fixing device) 10, and the recording material is discharged to a tray 61.

Next, the latent image forming section in each image forming section will be described. Photoconductor drums 1a, 1b, 1c, 1d
Around the discharge lamps 21a, 21b, 21
c, 21d, drum chargers 2a, 2b, 2c, 2d, laser beam exposure device 17 as image exposure means, and potential sensors 22a, 22b, 22c, 22d.
The photosensitive drums 1a, 1b, 1c, and 1d whose charges have been removed by the charge removing exposure lamps 21a, 21b, 21c, and 21d are uniformly charged by drum chargers 2a, 2b, 2c, and 2d. , An electrostatic latent image is formed on the photosensitive drums 1a, 1b, 1c, and 1d by color separation according to the image signal. In the image forming apparatus of the present invention, in addition to the laser beam exposure device 17 described above, a plurality of light levels other than OFF in a basic image unit (pixel) such as an LED array exposure device are used as image exposure means. A well-known multi-value exposure means capable of irradiating the light can be suitably used.

The electrostatic latent image on the photosensitive drum is developed by a developing means to become a visible image. That is, the developing means
Developing units 3a, 3b, and 3 filled with a predetermined amount of cyan, magenta, yellow, and black developers, respectively.
c, 3d, and the photosensitive drums 1a, 1b,
The electrostatic latent images formed on 1c and 1d are developed into visible images (toner images).

Next, the transfer section will be described. The recording material held in the recording material cassette 60 is fed to the recording material carrier 18 via a registration roller.

When this recording material carrier 18 starts to rotate,
The recording material is conveyed from the registration roller onto the recording material carrier 18. At this time, the image writing signal turns ON,
First electrophotographic photosensitive drum 1 at appropriate timing
An image is formed on a.

A transfer charger 4a and a transfer pressing member 41a are provided below the first electrophotographic photosensitive drum 1a, and a uniform pressing force is applied to the photosensitive drum by the transfer pressing member 41a. The transfer charger 4a applies an electric field to transfer the toner image on the photosensitive drum 1a onto a recording material. At this time, the recording material is the recording material carrier 1
8, the recording material is conveyed to the second image forming portion Pb, and the next transfer is performed. Hereinafter, the third and fourth image forming units Pc, P
The recording material to which the toner image formed by d is transferred is
The charge is removed by the separation charger (separation pole) 9, separated from the recording material carrier 18 by the attenuation of the electrostatic attraction force, and conveyed to the fixing unit (fixing unit) 10.

The fixing section 10 includes a fixing roller 71, a pressure roller 72, heat-resistant cleaning members 73 and 74 for cleaning the rollers 71 and 72, and rollers 71 and 7 respectively.
The fixing device 71 includes heaters 75 and 76 for heating the heating roller 2, an oil application roller 77 for applying a release agent oil such as dimethyl silicone to the fixing roller 71, an oil reservoir 78 for supplying the oil, and a thermistor 79 for controlling the fixing temperature. ing.

After the transfer, the photosensitive drums la, lb, lc,
The toner and the like remaining on the photoconductor cleaning unit 5
a, 5b, 5c and 5d to prepare for the next latent image formation. Further, the toner and the like remaining on the image support 8 are removed by the belt static eliminator 12 to remove the electrostatic attraction force, and then removed by the cleaning device 62 provided with a nonwoven fabric in this example. As the cleaning device 62, a rotating fur brush, a blade, a device using these in combination, or the like is also used.

As a preferred fixing method used in the present invention, a so-called contact heating method will be described with reference to FIGS.

FIGS. 7 and 8 are schematic sectional views each showing one embodiment of the fixing device used in the present invention.

In the present invention, in particular, as the contact heating method, a heat pressure fixing method, a heat roll fixing method, and a pressure contact heat fixing method in which fixing is performed by a rotating pressing member including a fixedly arranged heating element are used. I can give it.

The hot roll fixing method shown in FIGS. 7 and 8 is often made of iron, aluminum or the like whose surface is coated with tetrafluoroethylene or a polytetrafluoroethylene-perfluoroalkoxyvinyl ether copolymer. And a lower roller made of silicone rubber or the like. A typical example of the heat source is one having a linear heater and heating the surface temperature of the upper roller to about 120 to 200 ° C. In the fixing section, pressure is applied between the upper roller and the lower roller to deform the lower roller and form a so-called nip. Nip width is 1 to 10m
m, preferably 1.5 to 7 mm. Fixing linear velocity is 40
mm / sec to 600 mm / sec is preferred.

A fixing cleaning mechanism may be provided for use. As this method, a method in which a silicone oil is supplied to a roller or a film after fixing, or a method in which a silicone oil-impregnated pad, roller, web or the like is used for cleaning can be used.

Next, a description will be given of a method of fixing by a rotating pressing member including a fixedly disposed heating element used in the present invention.

This fixing system is a system in which a heating member fixedly arranged and a pressing member which is in pressure contact with the heating member and closely adheres a transfer material to the heating member via a film via a film are used to perform pressure-contact heating and fixing.

In this press-contact heat fixing device, the heating element has a smaller heat capacity than a conventional heating roller, and has a linear heating section in a direction perpendicular to the direction in which the transfer material passes. Is 100 to 300 ° C.

Incidentally, the press-contact heat fixing means fixing an unfixed toner image by pressing the unfixed toner image against a heating source, such as a method of passing a transfer material containing unfixed toner between a heating member and a pressing member as usually used. How to By doing so, heating is performed quickly, so that the fixing speed can be increased.
It is difficult to control the temperature and so-called toner offset, in which the toner adheres and remains on the portion where the unfixed toner is directly pressed against, such as the surface of the heating source, is likely to occur, and the transfer material is liable to be entangled in the fixing device and other troubles are likely to occur. There is also a problem.

In this fixing method, the low heat capacity linear heating element fixedly supported by the apparatus has a thickness of 0.2 to 5.0 mm.
0 mm, more preferably 0.5 to 3.5 mm and width 10
A resistance material is applied to an alumina substrate having a length of 240 to 400 mm and a length of 240 to 400 mm, and is supplied with electricity from both ends.

Energization is performed at a cycle of 100 V DC 15 to 25 ms.
The pulse width of ec is changed to give a pulse width corresponding to the temperature and the amount of energy release controlled by the temperature sensor. In the case of the temperature T1 detected by the temperature sensor in the low heat capacity linear heating element, the surface temperature T2 of the film facing the resistance material is lower than T1. Here, T1 is preferably 120 to 220 ° C., and the temperature of T2 is T1
Is preferably 0.5 to 10 ° C. lower than the temperature of
Further, the film material surface temperature T3 at a portion where the film is separated from the toner surface is substantially equal to T2. The film is moved in the direction of the central arrow in FIG. 9A by contacting the heating body whose energy and temperature are controlled in this manner. Those used as fixing films have a thickness of 1
A conductive material is added to a heat-resistant film of 0 to 35 μm, for example, polyester, polyperfluoroalkoxy vinyl ether, polyimide, or polyetherimide, and in many cases, a fluororesin such as Teflon (R) to form a release agent layer.
It is an endless film coated with １５15 μm.

In driving the film, a driving force and tension are applied by a driving roller and a driven roller, and the film is transported in the direction of the arrow without wrinkles and twists. The linear velocity of the fixing device is preferably 40 to 600 mm / sec.

The pressure roller has a rubber elastic layer such as silicone rubber with high releasability, is pressed against a heating body via a film material, and rotates under pressure.

In the above description, an example using an endless film has been described. However, as shown in FIG. 9B, a film sheet feeding shaft and a winding shaft are used, and an endless film material is used. Good. Further, it may be a simple cylindrical member having no drive roller or the like inside.

The fixing device may be provided with a cleaning mechanism. As a cleaning method, a method of supplying various silicone oils to the fixing film or a method of cleaning with a pad, a roller, a web, or the like impregnated with various silicone oils is used.

As the silicone oil, polydimethylsiloxane, polymethylphenylsiloxane, polydiphenylsiloxane and the like can be used. Further, a siloxane containing fluorine can also be suitably used.

Next, FIG. 9 shows an example of a sectional view of the structure of this fixing device. In FIG. 9A, reference numeral 84 denotes a low-heat-capacity linear heating element fixedly supported by the apparatus. As an example, a resistance material 86 is attached to an alumina substrate 85 having a height of 1.0 mm, a width of 10 mm, and a length of 240 mm. Is applied to a width of 1.0 mm, and electricity is supplied from both ends in the longitudinal direction.

The energization is performed, for example, at DC 100 V, usually at a period of 2
It has a pulse-like waveform of 0 msec, is controlled by a signal from the temperature detecting element 87, and is maintained at a predetermined temperature. For this reason, the pulse width is changed in accordance with the energy release amount, and the range is, for example, 0.5 to 5 msec.

[0311] The transfer material 94 carrying the unfixed toner image 93 is brought into contact via the film 88 moving to the heating element 84 controlled in this way, and the toner is thermally fixed.

[0312] The film 88 used here moves without wrinkles while being tensioned by the driving roller 89 and the driven roller 90. Reference numeral 95 denotes a pressure roller having a rubber elastic layer formed of silicone rubber or the like, and presses the heating body through the film at a total pressure of 0.4 to 2.0 N. Unfixed toner image 93 on transfer material 94
Are guided to the fixing section by the entrance guide 96, and a fixed image is obtained by heating.

Although the endless belt has been described above, as shown in FIG. 9B, a film sheet feeding shaft 91 and a winding shaft 92 may be used, and the fixing film may be endless.

[0314]

EXAMPLES The present invention will be described below in detail with reference to examples, but embodiments of the present invention are not limited thereto. In the description, “parts” means “parts by mass”.

Example 1 << Production Example of Resin Particles >> (Production of Resin Particles S1) 430 parts of deionized water was put into a separable flask equipped with a thermometer, a reflux condenser, a stirrer and a monomer charger. After replacing oxygen with nitrogen gas, the temperature was raised to 70 ° C., and 5 parts of potassium persulfate (KPS) was added and stirred.

A separable flask equipped with the same apparatus as above was prepared, and 44 parts of methyl methacrylate (MMA) and 44 parts of n-butyl acrylate were used as vinyl polymerizable monomers. (1-1)
100 parts of (2,2,2-trifluoroethyl methacrylate), as a polymerizable monomer B having an acidic polar group,
12 parts of methacrylic acid, n-octyl- as a chain transfer agent
1 part of 3-mercaptopropionate emulsified with 480 parts of deionized water and 9 parts of an anionic surfactant (sodium dodecylbenzenesulfonate: SDS) 5
% As a seed, added to a separable flask containing potassium persulfate, and polymerized for 20 minutes.

Further, the remaining emulsion was continuously dropped into the flask over 5 hours. After further reacting at 75 ° C. for 3 hours, the mixture was cooled to 50 ° C., diluted 5 times with ion-exchanged water, and adjusted to pH 8 with aqueous ammonia to obtain resin particles S1.

(Production of Resin Particles S2 to S5 and S8) In the production of the resin particles S1, the polymerizable monomer A, the polymerizable monomer B, and the vinyl polymerizable monomer were as shown in Table 1. Resin particles S2 to S5 and S8 were produced in the same manner, except for the change.

(Production of Resin Particles S6) 998 parts of deionized water was placed in a separable flask equipped with a thermometer, a reflux condenser, a stirrer, and a monomer charger, and oxygen was replaced with nitrogen gas. After warming, 5 parts of potassium persulfate was added and stirred.

A separable flask equipped with the same apparatus as above was prepared, and 44 parts of methyl methacrylate (MMA) and 44 parts of n-butyl acrylate were used as vinyl polymerizable monomers. (1-1) 2,
100 parts of 2,2-trifluoroethyl methacrylate,
As a polymerizable monomer B, 12 parts of methacrylic acid, 1 part of n-octyl-3-mercaptopropionate as a chain transfer agent were emulsified with 191 parts of deionized water and 2.2 parts of SDS. The mixture was added to a separable flask containing potassium persulfate and polymerized for 20 minutes. Further, the remaining emulsion was continuously dropped into the flask over a period of 1.5 to 2 hours to form a core.

Thereafter, the reaction was carried out for 1 hour.
As a vinyl polymerizable monomer, methyl methacrylate (M
MA) 44 parts, n-butyl acrylate 44 parts, methacrylic acid 12 parts as polymerizable monomer B, n-octyl-3-mercaptopropionate 1 as a chain transfer agent
The emulsion emulsified in the above portion was continuously dropped into the above-mentioned 3 liter separable flask over 1 to 2 hours to form a shell portion.

After further reacting at 75 ° C. for 2 hours, the mixture was cooled to 50 ° C. and adjusted to pH 8 with aqueous ammonia to obtain resin particles S6 having a core-shell structure.

(Production of Resin Particles S7) In a separable flask equipped with a thermometer, a reflux condenser, a stirrer, and a monomer charger, 998 parts of deionized water was placed, oxygen was replaced with nitrogen gas, and the temperature was raised to 72 ° C. After warming, 5 parts of potassium persulfate was added and stirred.

A separable flask equipped with the same apparatus as above was prepared, and as a vinyl polymerizable monomer, 44 parts of methyl methacrylate (MMA), 44 parts of n-butyl acrylate, and as a polymerizable monomer B, methacrylic monomer was used. 12 parts of acid,
As a chain transfer agent, 1 part of n-octyl-3-mercaptopropionate was added to 191 parts of deionized water and SDS 2.2.
Using 5% of the emulsion emulsified in the above portion as a seed, the mixture was added to a separable flask containing the above potassium persulfate and polymerized for 20 minutes. Further, the remaining emulsion was continuously dropped into the flask over a period of 1.5 to 2 hours to form a core.

Thereafter, the reaction was carried out for 1 hour.
As a vinyl polymerizable monomer, methyl methacrylate (M
MA) 44 parts, n-butyl acrylate 44 parts, as polymerizable monomer A, compound (1-1) (2,2,2-trifluoroethyl methacrylate) 100 parts, as polymerizable monomer B, 12 parts of methacrylic acid, n as a chain transfer agent
One emulsified with 1 part of -octyl-3-mercaptopropionate was continuously dropped into the flask containing potassium persulfate over 1 to 2 hours to form a shell portion.

Then, the mixture was further reacted at 75 ° C. for 2 hours, cooled to 50 ° C., and adjusted to pH 8 with aqueous ammonia to obtain resin particles S7 having a core-shell structure.

Table 1 shows a list of the composition, physical properties, and the like of the obtained resin particles S1 to S8.

[0328]

[Table 1]

<< Preparation of Latex >> (Preparation of Latex 1HML) (1) Preparation of core particles (first-stage polymerization): 5000 m equipped with a stirrer, a temperature sensor, a cooling pipe, and a nitrogen introducing device.
of a surfactant solution (aqueous medium) prepared by dissolving 7.08 g of the anionic surfactant shown below in 3010 g of ion-exchanged water was charged into a 1 l separable flask, and then placed under a nitrogen stream.
The temperature in the flask was raised to 80 ° C. while stirring at a stirring speed of 0 rpm.

(101) C ₁₀ H ₂₁ (OCH ₂ CH ₂ ) ₂ OSO ₃ Na A polymerization initiator (potassium persulfate) was added to this surfactant solution.
An initiator solution prepared by dissolving 9.2 g in ion-exchanged water (200 g) was added, and the temperature was adjusted to 75 ° C.
g, 19.9 g of n-butyl acrylate and 10.9 g of methacrylic acid were added dropwise over 1 hour, and the system was heated and stirred at 75 ° C. for 2 hours to carry out polymerization (first polymerization). Latex (a dispersion of resin particles composed of a high molecular weight resin) was prepared. This is designated as “latex (1H)”.

(2) Formation of Intermediate Layer (Second Stage Polymerization): In a flask equipped with a stirrer, styrene 10
As a crystalline substance, a monomer mixture comprising 5.6 g, 30.0 g of n-butyl acrylate, 6.2 g of methacrylic acid, and 5.6 g of n-octyl-3-mercaptopropionate was used as a crystalline substance in Table 19). Compound (hereinafter, referred to as
It is referred to as "exemplary compound 19." 9) 9g was added and 9
The mixture was heated to 0 ° C. and dissolved to prepare a monomer solution.

On the other hand, an anionic surfactant (the above formula (1)
01)) A surfactant solution obtained by dissolving 1.6 g in 2700 ml of ion-exchanged water was heated to 98 ° C., and the latex (1H) as a dispersion of core particles was added to the surfactant solution.
Was added in an amount of 28 g in terms of solid content, and then a mechanical dispersing machine having a circulation route “CLEARMIX”
The monomer solution of Exemplified Compound 19) was mixed and dispersed for 8 hours using (manufactured by M Technique) to prepare a dispersion liquid (emulsion liquid) containing emulsified particles (oil droplets).

Next, to this dispersion liquid (emulsion liquid) were added an initiator solution obtained by dissolving 5.1 g of a polymerization initiator (KPS) in 240 ml of ion-exchanged water, and 750 ml of ion-exchanged water. Polymerization (second-stage polymerization) is carried out by heating and stirring at 12 ° C. for 12 hours, and latex (a dispersion of composite resin particles having a structure in which the surface of resin particles made of a high molecular weight resin is coated with an intermediate molecular weight resin) is used. Obtained. This is referred to as “latex (1HM)”.

The latex (1HM) was dried and observed with a scanning electron microscope. As a result, it was found that particles (40%) of which the main component was Exemplified Compound 19 which was not surrounded by the latex.
0 nm to 1000 nm) was observed.

(3) Formation of outer layer (third stage polymerization): An initiator obtained by dissolving 7.4 g of a polymerization initiator (KPS) in 200 ml of ion-exchanged water in the latex (1HM) obtained as described above. The solution was added, and a monomer mixture consisting of 300 g of styrene, 95 g of n-butyl acrylate, 15.3 g of methacrylic acid, and 10.4 g of n-octyl-3-mercaptopropionate was added under a temperature condition of 80 ° C.
It was dropped over time. After completion of the dropping, polymerization (third stage polymerization) is carried out by heating and stirring for 2 hours.
Cooled to 8 ° C. and latex (having a central portion composed of a high molecular weight resin, an intermediate layer composed of an intermediate molecular weight resin, and an outer layer composed of a low molecular weight resin, and the intermediate layer has exemplified compound 19).
Was obtained. This latex is referred to as “latex (1HML)”.

<< Preparation of Colored Particles >> (Preparation of Colored Particles 1 to 8) This latex (1HML)
Are 138,000, 80,0
The composite resin particles have peak molecular weights of 00 and 13,000, and the weight average particle size of the composite resin particles is 122
nm.

39.0 g of SDS was added to 1600 of ion-exchanged water.
of the C.I. solution with stirring. I.
Pigment red 122 (420.0 g) is gradually added, and then subjected to a dispersion treatment using “CLEARMIX” (manufactured by M Technique Co., Ltd.), whereby a dispersion of colorant particles (hereinafter referred to as “colorant dispersion 1”) Was prepared. When the particle size of the colorant particles in this colorant dispersion was measured using an electrophoretic light scattering photometer “ELS-800” (manufactured by Otsuka Electronics Co., Ltd.), the weight average particle size was 89.
nm.

Latex 1 HML 420.7 g (in terms of solid content), 900 g of ion-exchanged water, and 166 g of the colorant dispersion 1 were mixed with a temperature sensor, a cooling pipe, a nitrogen introducing device,
The mixture was stirred in a reaction vessel (four-necked flask) equipped with a stirrer. After adjusting the temperature in the container to 30 ° C., a 5 mol / liter aqueous sodium hydroxide solution was added to the solution to adjust the pH to 8 to 10.0.

Next, magnesium chloride hexahydrate 1
An aqueous solution in which 2.1 g was dissolved in 1,000 ml of ion-exchanged water was added over 10 minutes at 30 ° C. with stirring. After standing for 3 minutes, heating was started, and the temperature of the system was raised to 90 ° C. over 6 to 60 minutes to generate associated particles. In this state, the particle size of the associated particles was measured with a “Coulter counter TA-II”, and when the number average particle size reached 5 μm, 40.2 g of sodium chloride was added to 100 parts of ion-exchanged water.
An aqueous solution dissolved in 0 ml was added to temporarily stop the particle growth, and colored particles 1 were obtained.

Further, by controlling the pH of the agglomeration step, the temperature of the aging treatment step, the aging time, and the stirring intensity, the crystalline substance, the colorant dispersion state, the shape, and the variation coefficient of the shape coefficient are controlled. By arbitrarily adjusting the variation coefficient of the toner particle size and the particle size distribution by classification in the liquid,
8 was obtained.

<< Production Examples of Toner >> (Production of Toners 1 to 8) Colored particles 1 to 8 obtained above
While adjusting the mass ratio ((s) / (s + Mp) × 100)% of the mass (S) of the resin particles to the mass (Mp) of the colored particles, the resin particles were adjusted to the values shown in Table 4. S1
Each of the dispersions of S8 was added, and the mixture was further heated and stirred at a liquid temperature of 98 ° C. for 2 hours as an aging treatment, and an aqueous solution in which 40.2 g of sodium chloride was dissolved in 1,000 ml of ion-exchanged water was added to grow particles. Was temporarily stopped, and the mixture was heated and stirred at a liquid temperature of 98 ° C. for 1 to 4 hours to continue the fusion of the particles (ripening step).

Then, the mixture was cooled to 30 ° C., hydrochloric acid was added to adjust the pH to 2.0, and stirring was stopped. The generated associated particles were filtered, washed repeatedly with ion exchanged water at 45 ° C., and then dried with warm air at 40 ° C., and 0.8 parts by mass of hydrophobic silica and 1.0 part by mass of hydrophobic titanium oxide were added. Then, the peripheral speed of the rotating blade of a 10-liter Henschel mixer was set to 30 m / s and mixed for 25 minutes to obtain toners 1 to 8.

(Production of Comparative Toner 1)
In Comparative Example 1, a comparative toner 1 was obtained in the same manner except that the dispersion of the resin particles S1 was not added.

In the production of the above-described toner, the shape and particle size of the above-described colored particles are not changed at all by the addition of an external additive.

(Production of Comparative Toner 2) A dispersion of the resin particles S1 was dried by a spray drying method to obtain resin particles S1 powder.

(Formulation 1) Styrene acrylic resin 100 parts C.I. I. pigment. red 122 10 parts Resin particles S1 powder 2 parts Exemplified compound 19) 8 parts The above composition 1 is premixed with a Henschel mixer, extruded and kneaded with a twin screw, pulverized with a jet pulverizer, classified with an air classifier, and then classified. 0.8 parts by mass of hydrophobic silica and 1.0 parts by mass of hydrophobic titanium oxide were added, and the peripheral speed of the rotating blade of the Henschel mixer was set to 30 m / s, followed by mixing for 25 minutes to obtain Comparative Toner 2.

(Production of Comparative Toner 3) 150 parts of toluene was placed in a reaction vessel and heated to a reflux temperature. A mixture of 75 parts of styrene, 25 parts by weight of 1H, 1H-perfluoro-n-octyl acrylate, and 2 parts of tert-butylperoxybenzoate was added dropwise, and the solution polymerization was completed in 7 hours under reflux of toluene. The toluene was distilled off under reduced pressure to obtain a compound (A).

In a 2-liter four-necked flask equipped with a high-speed stirrer TK-type homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), 600 parts of ion-exchanged water and 0.1 ml of 0.1. lmol / liter-
500 parts of an aqueous solution of Na ₃ PO ₄ are charged, and the number of rotations is 1200.
It was adjusted to 0 rpm and heated to 70 ° C. here,
70 parts of a 1.0 mol / liter-CaCl ₂ aqueous solution was added to prepare an aqueous dispersion medium containing a minute hardly water-soluble dispersion stabilizer (calcium phosphate).

On the other hand, styrene 82 parts 2-ethylhexyl acrylate 18 parts C.I. I. pigment. red122 10 parts Exemplified compound 19) 8 parts Compound (A) 2 parts The above mixture was treated with an attritor (manufactured by Mitsui Kinzoku Co., Ltd.) to obtain 3 parts.
After dispersing for time, 3 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) was added to prepare a polymerizable monomer composition.

Next, the polymerizable monomer composition was put into the aqueous dispersion medium, and the mixture was stirred at 10 ° C. under a nitrogen atmosphere at an internal temperature of 70 ° C. while maintaining the rotation speed of a high-speed stirrer at 12,000 rpm.
After stirring for minutes, the polymerizable monomer composition was granulated. Thereafter, the stirring was changed to a propeller stirring blade, and the mixture was maintained at the same temperature for 10 hours while stirring at 50 rpm to complete the polymerization. After completion of the polymerization, the suspension was cooled, and then diluted hydrochloric acid was added to remove the dispersion stabilizer. Further, after repeating water washing several times, drying is performed, and then 0.8 parts by mass of hydrophobic silica and 1.0 parts by mass of hydrophobic titanium oxide are added, and the peripheral speed of the rotor of the Henschel mixer is set to 30 m / s. Then, the mixture was mixed for 25 minutes to obtain Comparative Toner 3.

(Production of Comparative Toner 4) Comparative Toner 1
2 parts of the resin particle S1 powder was added to 100 parts of the mixture, and mixed with a Henschel mixer for 10 minutes to obtain Comparative Toner 4.

The physical property data (number average particle diameter, shape coefficient, coefficient of variation of shape coefficient, ratio of colored particles without corners, variation of number distribution) of each of the toners 1 to 8 and comparative toners 1 to 4 manufactured above. Table 2 shows the coefficient, the sum of m1 and m2).

[0353]

[Table 2]

[0354]

[Table 3]

[0355]

[Table 4]

The toners 1 to 8 and the colored particles 1 shown in Table 2
When the respective physical property data of No. 8 are compared, the physical property data are the same. The reason is that, in the production of the colored particles according to the present invention, the resin particles and the colorant are monitored during the salting out / fusion step and the shape control step, and the reaction is controlled by controlling the number of rotations of the stirring and the heating time. The variation coefficient of the shape and the shape factor is controlled, and the variation coefficient of the particle size and the particle size distribution is adjusted.

An external additive is added to the thus-obtained colored particles to produce toner particles. The external additive gives a physical change to the colored particles only by fixing to the surface of the toner particles. Therefore, the physical properties (shape, particle size, etc.) of the obtained toner particles are the same as the physical properties of the colored particles.

<Production of Photoconductor P1> The following coating solution was applied on a cylindrical conductive support having a length of 380 mm and a diameter of 60 mm to prepare photoconductor P1.

<Undercoat Layer> Titanium chelate compound (TC-750: manufactured by Matsumoto Pharmaceutical Co., Ltd.) 30 g Silane coupling agent (KBM-503: manufactured by Shin-Etsu Chemical Co., Ltd.) 17 g 2-propanol 150 ml Cylindrical conductive using the above coating solution Film thickness of 0.
It was applied to a thickness of 5 μm.

<Charge Generating Layer> Y-type titanyl phthalocyanine (titanyl phthalocyanine having a maximum peak at 27.2 ° at a Bragg angle of 2θ (± 0.2 °) by Cu-Kα characteristic X-ray diffraction spectrum measurement) 60 g Silicone Modified butyral resin (X-40-1211M: manufactured by Shin-Etsu Chemical Co., Ltd.) 700 g 2-butanone 2000 ml The above materials were mixed and dispersed using a sand mill for 10 hours to prepare a charge generating layer coating liquid. This coating solution was applied on the undercoat layer by a dip coating method to form a charge generation layer having a thickness of 0.2 μm.

<Charge Transport Layer> Charge transport material (N- (4-methylphenyl) -N- {4- (β-phenylstyryl) phenyl} -p-toluidine) 225 g Polycarbonate (viscosity average molecular weight 30,000) 300 g Antioxidant (Exemplified Compound 1-3) 6 g Dichloromethane 2000 ml The above materials were mixed and dissolved to prepare a charge transport layer coating solution. This coating solution was applied on the charge generation layer by a dip coating method to form a charge transport layer having a dry film thickness of 20 μm.

<Protective Layer> Methyltrimethoxysilane 150 g Dimethyldimethoxysilane 30 g Reactive charge transporting compound (Exemplary Compound B-1) 15 g Polyvinylidene fluoride particles (volume average particle size 0.2 μm) 10 g Antioxidant (Exemplary compound) 2-1) 0.75 g 2-propanol 75 g 3% acetic acid 5 g The above materials were mixed to prepare a coating solution for a resin layer. A 2 μm-thick resin layer was formed on the charge transporting layer by a circular amount-regulating coating device on the charge transporting layer, and cured by heating at 120 ° C. for 1 hour to form a siloxane resin layer. Produced.

[0363]

Embedded image

[0364]

Embedded image

[0365]

Embedded image

Next, a photoreceptor P1 and the toner described above were placed in a digital copying machine (having corona charging, laser exposure, reversal development, electrostatic transfer, nail separation, and cleaning blade) having the image forming process shown in FIG. Was directly mounted as a developer and evaluated. The above digital copying machine was evaluated under the following conditions.

(Charging Condition) Charging device: Scorotron charger, initial charging potential was -750
Adjusted to V (Exposure condition) Set the exposure amount to make the exposure part potential -50V.

(Developing conditions) DC bias; -550 V Transfer pole; corona charging system The fixing device shown in FIG. 6 was used. The linear velocity was 120 mm / sec, and the fixing device cleaning mechanism and the silicone oil supply mechanism were not mounted.
The fixing temperature is controlled by the surface temperature of the heating roller.
The temperature was set to ° C.

The copying conditions were as follows: high temperature and high humidity environment (30 ° C., 80
% RH), and the following evaluation items were evaluated.

In the evaluation, a character image having a pixel rate of 7%, a portrait image of a person, a solid white image, and a solid black image each having an equal size of 1/4 were copied on A4 neutral paper.
The following evaluation was performed.

<Evaluation Items> (Uniformity of Halftone) The uniformity (non-uniformity) of the halftone image due to the change in toner transportability after 500,000 consecutive copies was evaluated. It was visually evaluated in four stages as described below.

A: Uniform image without unevenness B: Extremely thin streak-like unevenness present C: Several streak-like thin unevennesses exist, but there is no practical problem D: Several streak-like unevennesses are clear The existence evaluation ranks described above were A to C, and D was rejected.

(Fog) Using a solid white image,
The occurrence of fog after 10,000 copies was visually evaluated. The evaluation was performed in three ranks.

◎: No fog occurred O: Occasionally fogged (practical) ×: Continuous fog (offset resistance) After continuous printing of 1000 sheets on A4 size transfer paper, white paper was printed and offset And the toner stain on the surface of the heat roller was visually evaluated. The transfer paper used for evaluation was thick paper of high quality paper 200 g / m ² , and was 0.3 mm in width and 1 mm in length parallel to the paper advancing direction (heat roller circumferential direction).
A 50 mm line image was formed.

A: Image offset and toner stain on the heat roller are not observed at all. O: No image offset occurs, but toner stain is on the heat roller. X: Image offset is confirmed.

As for the evaluation rank, ◎ and ○ are passed, and x is rejected. (Photoreceptor Filming) The presence or absence of filming was determined by visually observing the photoreceptor surface after 500,000 consecutive copies described above.

Table 5 shows the obtained evaluation results.

[0378]

[Table 5]

As can be seen from Table 5, the sample of the present invention has excellent halftone uniformity, low fog, good offset resistance, and good toner filming property of the photoreceptor, as compared with the comparative sample. Is also very good.

[0380]

According to the present invention, excellent halftone uniformity, low fog, and good offset resistance are obtained.
In addition, it was possible to provide a toner for developing an electrostatic image without filming of the photoreceptor, a method for producing the toner, and an image forming method using the toner.

[Brief description of the drawings]

FIG. 1 is a schematic diagram illustrating a toner without a corner or with a corner.

FIG. 2 is a schematic view illustrating an example of a toner particle having a sea-island structure according to the present invention.

FIG. 3 is a schematic diagram in which toner particles having a sea-island structure according to the present invention are divided by Voronoi polygons.

FIG. 4 is a cross-sectional view illustrating an example of an image forming apparatus applied to the present invention.

FIG. 5 is a schematic sectional view illustrating an example of a color electrophotographic image forming apparatus.

FIG. 6 is a schematic sectional view showing one embodiment of a fixing device used in the present invention.

FIG. 7 is a schematic sectional view showing another embodiment of the fixing device used in the present invention.

FIG. 8 is a schematic sectional view showing another embodiment of the fixing device used in the present invention.

FIG. 9 is a schematic sectional view showing another embodiment of the fixing device used in the present invention.

[Explanation of symbols]

1, 1a, 1b, 1c, 1d Electrostatic latent image carrier (electrophotographic photosensitive drum, photosensitive drum) 2a, 2b, 2c, 2d Drum charger 3, 3, a, 3b, 3c, 3d Developing device 4a, 4b , 4c, 4d Transfer chargers 41a, 41b, 41c, 41d Transfer pressing member 5a, 5b, 5c, 5d Photoconductor cleaning unit 10 Fixing unit (fixing unit) 16a Tip edge 17 Laser beam exposure device 21a, 21b, 21c, 21d Static elimination exposure lamp 22a, 22b, 22c, 22d Potential sensor 160 Positioning member Da Development nip width Pa, Pb, Pc, Pd Image forming section 8 Image holder 11 Core of heating roll 12, 20 Heating roll 12a Coating of heating roll Layer 13 Heating member 21 Core of pressure roll 22 Coating layer of pressure roll 37 Heat generating member 38 Release protective layer T Toner image 40 Heating member 41, 211, 221 Core metal 42, 212 Elastic layer (silicone resin layer) 43, 213, 222 Release layer (fluororesin layer) 44, 214, 223 Heater 45 Temperature sensor 50 Endless belt 51-53 Instruction roller 54 Base plate 55 Pressing assist pad 56 Pressing pad 71, 72 Heating roller 73, 74 Heat resistant cleaning member 75, 76 Heater 77 Oil application roller 78 Oil reservoir 79 Thermistor 210 Heating roller 220 Pressure roller

 ────────────────────────────────────────────────── ─── Continuing from the front page (72) Inventor Yasuko Yamauchi 2970 Ishikawacho, Hachioji-shi, Tokyo Konica Corporation F-term (reference) 2H005 AA01 AA06 AA15 AB06 CA02 CA11 CA12 CA14 EA03 EA05 EA07 EA10 FA07 2H033 AA09 BA11 BA42 BA49 BA57 BA58 BB05 BB06 BB12 BB13 BB14 BB18 BB30 BB33 BB34 BE03 CA07 CA27

Claims (15)

[Claims] 1. A resin particle comprising a polymer having a polymerizable component A of a polymerizable monomer A having a silicon atom or a fluorine atom and a polymerizable component B of a polymerizable monomer B having an acidic polar group. Salting out on the surface of colored particles containing resin and colorant
A toner for developing an electrostatic image, wherein toner particles are produced through a step of adding hydrophobic metal oxide particles after fusing by a fusion method. 2. The electrostatic image developing toner according to claim 1, wherein the polymerizable monomer A is represented by the following general formula (1). Embedded image [Wherein, R ¹ represents a hydrogen atom or a methyl group, and R ² represents
Represents an alkyl group having at least one fluorine atom or at least one silicon atom. ] 3. The electrostatic image developing toner according to claim 1, wherein the polymerizable monomer A is represented by the following general formula (2). Embedded image [Wherein, R represents a substituent having 1 to 13 carbon atoms;
³ represents an alkyl group having 1 to 8 carbon atoms, and R ⁴ represents a hydrogen atom or a substituent having 1 to 13 carbon atoms. However, R ⁴ may be the same or different. R ⁵ represents an alkylene group having 1 to 8 carbon atoms. a represents 0, 1 or 2, and b is an integer of 1 to 3. However, the total value of a + b is 1-3. n represents 0 or 1. ] 4. The resin particles contain 20% by mass to 80% by mass of the polymerizable component A of the polymerizable monomer A and 2% by mass to 20% by mass of the polymerizable component B of the polymerizable monomer B. The electrostatic image developing toner according to claim 1, wherein: 5. The resin particles having a volume average particle diameter of 30 nm to 4 nm.
The toner for developing an electrostatic image according to claim 1, wherein the toner has a softening point of 80 ° C. to 170 ° C. and a Tg (glass transition temperature) of 35 ° C. to 80 ° C. 6. 6. A mass ratio of the mass (s) of the resin particles to the mass (Mp) of the colored particles ((s) / (s + Mp) × 100).
% Is 0.2% to 12%.
6. The toner for developing an electrostatic image according to any one of items 5 to 5. 7. The toner has a crushing strength index of 0.1 to 0.8.
The electrostatic image developing toner according to any one of claims 1 to 6, wherein 8. The resin particles are produced by emulsion polymerization or miniemulsion polymerization, and at the time of the polymerization reaction, link at least one compound selected from thioglycerin or a compound represented by the following general formula (3). 2. A process according to claim 1, wherein the process is carried out using a transfer agent.
8. The toner for developing an electrostatic image according to any one of items 7 to 7. Formula (3) HS-R ⁶ -COOR ⁷ [wherein, R ⁶ represents a divalent group having 1 to 10 carbon atoms, R ⁷ represents a hydrocarbon group having from 2 to 15 carbon atoms. ] 9. The resin particles having a particle structure in which the concentration of the polymer A as a polymerization component of the polymerizable monomer A changes continuously or discontinuously from the surface to the inside. Item 10. The electrostatic image developing toner according to any one of Items 1 to 8. 10. The toner contains a crystalline compound, and one or more endothermic peaks in differential thermal analysis due to the crystalline compound are present at 60 ° C. to 120 ° C., and the endothermic amount of the endothermic peak is The electrostatic image developing toner according to any one of claims 1 to 9, wherein the toner content is 4 J / g to 30 J / g. 11. A resin particle comprising a polymer having a polymerization component A of a polymerizable monomer A having a silicon atom or a fluorine atom and a polymerization component B of a polymerizable monomer B having an acidic polar group. Salting out on the surface of colored particles containing resin and colorant
A method for producing a toner for developing an electrostatic image, comprising a step of adding metal oxide particles subjected to a hydrophobic treatment after fusing by a fusion method to produce toner particles. 12. A method for producing the toner for developing an electrostatic image according to claim 1, wherein
A toner for developing an electrostatic image, wherein the toner according to claim 1 is used. 13. A developing roll and a toner supply member for supplying a toner for developing an electrostatic image onto the development roll, wherein a non-magnetic toner is supplied to the development roll from the toner supply member and formed on the development roll. An image forming method using a one-component developing device for performing development using a formed toner layer, wherein the non-magnetic toner is the toner for developing an electrostatic image according to any one of claims 1 to 10. Image forming method. 14. A latent image forming step of forming a latent image on a latent image carrier, a developing step of developing the latent image using toner, and a step of developing a toner image formed on the latent image carrier. An image forming method comprising: a transfer step of transferring a toner image onto a transfer target; and a fixing step of heating and fixing the toner image on the transfer target using a heating member and a pressure member.
11. An image forming method, wherein the electrostatic charge image developing toner according to any one of 10 to 10, wherein the heating member has an elastic layer. 15. The image forming method according to claim 14, wherein at least one of the heating member and the pressing member is a belt.