JP2002072563A - Electrostatic latent image developing toner, method for manufacturing the toner, method for forming image and device for image formation - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrostatic latent image developing toner produced by the so-called polymerization method, having a small particle size, which suppresses generation of odor during thermal fixing and will not cause problems of odors and which is superior in fixing property, and to provide a method for manufacturing the toner, a method for forming images and a device for image formation. SOLUTION: The electrostatic latent image developing toner is obtained by preparing resin particles through polymerization of a radical polymerizable monomer composition, containing a chain transfer agent expressed by general formula (1) in a water-based medium and then salting out/melting the resin particles in a water-based medium.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a toner for developing an electrostatic latent image used in a printer, a copying machine, a facsimile, and the like, a method for producing the toner, an image forming method using the toner, and an image forming apparatus. is there.

[0002]

2. Description of the Related Art At present, an electrostatic latent image developing method represented by an electrophotographic method is widely used in an image forming method of a printer, a copying machine, a facsimile or the like.

[0003] The reason for this is that it is a highly complete method for stably obtaining a high-speed and high-quality image, but some problems still remain. One of them is that it is necessary to control the molecular weight distribution of the toner resin from the viewpoint of stabilizing the fixing property of the toner. For example, in order to suppress high-temperature offset, it is necessary to improve the elastic modulus at high temperature, and it is preferable to increase the high molecular weight component. on the other hand,
In order to improve the adhesiveness to an image forming support (recording material or recording paper) such as paper, it is preferable to increase the low molecular weight component. In order to satisfy such contradictory functions, it is necessary to increase the molecular weight distribution of the resin.

On the other hand, it is desired to reduce the particle size of the toner for developing an electrostatic latent image from the viewpoint of high image quality. In recent years, polymerization toners have been actively developed as a method for producing small particle size toners. In this polymerization method toner, a method of preparing an irregularly shaped toner by associating or salting out / fusing resin particles and colorant particles as needed, or dispersing a radical polymerizable monomer and a colorant, Next, there is a method in which droplets are dispersed in an aqueous medium or the like so as to have a desired toner particle diameter, and suspension polymerization is performed.

In any case, it is necessary to adjust the molecular weight distribution of the toner resin in order to improve the fixability.
When a chain transfer agent is used to control the molecular weight distribution to reduce the molecular weight, mercaptans, particularly dodecyl mercaptan, are used as a suitable chain transfer agent. However, this material has a peculiar odor, and there is a problem that the chain transfer agent remaining at the time of heat fixing volatilizes and odor is generated.

The problem of the odor has not been particularly considered to be a problem in the so-called pulverization method toner, which is produced by melt-kneading a resin and a colorant after synthesis, and then pulverizing the cooled block-shaped material again. However, the above-mentioned polymerization method for producing a toner having a small particle diameter suddenly raises a problem during image formation.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a toner for developing electrostatic latent images of a so-called polymerization method, which suppresses the generation of odor during thermal fixing, does not cause an odor problem, and has an improved fixing property. Excellent, small particle size toner for electrostatic latent image development,
An object of the present invention is to provide a method for manufacturing the toner, an image forming method, and an image forming apparatus.

[0008]

The object of the present invention can be achieved by adopting one of the following constitutions.

1. A resin particle prepared by polymerizing a radically polymerizable monomer composition containing the chain transfer agent represented by the general formula (1) in an aqueous medium, and obtained by salting out / fusion in an aqueous medium. A toner for developing an electrostatic latent image, comprising:

[0010] 2. A resin particle prepared by polymerizing a radically polymerizable monomer composition containing the chain transfer agent represented by the general formula (2) in an aqueous medium, and being obtained by salting out / fusing in an aqueous medium. A toner for developing an electrostatic latent image, comprising:

3. Resin particles prepared by polymerizing a radically polymerizable monomer composition containing a chain transfer agent represented by the general formula (1) in an aqueous medium are subjected to salting out / fusion in an aqueous medium. Of producing an electrostatic latent image developing toner.

4. Resin particles prepared by polymerizing a radically polymerizable monomer composition containing a chain transfer agent represented by the general formula (2) in an aqueous medium are subjected to salting out / fusion in an aqueous medium. Of producing an electrostatic latent image developing toner.

5. It is obtained by subjecting a composition in which a colorant is dispersed in a radical polymerizable monomer composition containing the chain transfer agent represented by the general formula (1) to suspension polymerization in an aqueous medium. An electrostatic latent image developing toner.

6. It is obtained by subjecting a composition in which a colorant is dispersed in a radical polymerizable monomer composition containing the chain transfer agent represented by the general formula (2) to suspension polymerization in an aqueous medium. An electrostatic latent image developing toner.

[0015] 7. A composition in which a colorant is dispersed in a radically polymerizable monomer composition containing the chain transfer agent represented by the general formula (1) is subjected to suspension polymerization in an aqueous medium. A method for producing an image developing toner.

8. A composition comprising a radically polymerizable monomer composition containing the chain transfer agent represented by the general formula (2) and a colorant dispersed therein is subjected to suspension polymerization in an aqueous medium. A method for producing an image developing toner.

9. Secondary particles obtained by aggregating resin particles and colorant particles prepared by polymerizing a radically polymerizable monomer composition containing the chain transfer agent represented by the general formula (1) in an aqueous medium are used. A toner for developing an electrostatic latent image, which is obtained by fusing.

10. Secondary particles obtained by aggregating resin particles and colorant particles prepared by polymerizing a radically polymerizable monomer composition containing a chain transfer agent represented by the general formula (2) in an aqueous medium are used. A toner for developing an electrostatic latent image, which is obtained by fusing.

11. Secondary particles obtained by aggregating resin particles and colorant particles prepared by polymerizing a radically polymerizable monomer composition containing the chain transfer agent represented by the general formula (1) in an aqueous medium are used. A method for producing a toner for developing an electrostatic latent image, wherein the toner is fused.

[12] Secondary particles obtained by aggregating resin particles and colorant particles prepared by polymerizing a radically polymerizable monomer composition containing a chain transfer agent represented by the general formula (2) in an aqueous medium are used. A method for producing a toner for developing an electrostatic latent image, wherein the toner is fused.

13. 11. An image formed by using the toner for developing an electrostatic latent image according to any one of the items 1, 2, 5, 6, 9, and 10, and thermally fixing an image transferred onto a recording material. Image forming method.

14. 11. An image formed by using the toner for developing an electrostatic latent image according to any one of the items 1, 2, 5, 6, 9, and 10, and thermally fixing an image transferred onto a recording material. Image forming apparatus.

As a result of intensive studies by the present inventors, the present invention has been completed by elucidating the essential difference between the kneading method and the polymerization method.

That is, a so-called pulverized toner is formed into a toner by melt-kneading a resin and a colorant, followed by pulverization and classification. In this step, the resin is heated above the melting temperature and at the same time, a large share is applied by a kneading device such as a twin screw extruder, so that the resin is sufficiently heated above the softening point of the resin. For this reason, the chain transfer agent present in the resin is vaporized by this heat, so that almost no simple substance can be present alone in the final toner. On the other hand, a so-called polymerization toner does not go through this melt-kneading step, and when prepared by a radical polymerization method, the heating is limited to a maximum of about 100 ° C., which is the boiling point of water. As a result, it was presumed that a trace amount of the chain transfer agent remained and vaporized at the temperature at the time of fixing, causing a problem of odor.

In other words, it can be said that a very small amount of the chain transfer agent causes the odor in the polymerization toner.

The present inventors have conducted intensive studies in order to solve the above-mentioned problems. As a result, the object of the present invention is to provide the following general formula in the radical polymerizable monomer composition in the process of producing resin particles of a polymerization toner. It has been clarified that this can be achieved by including the chain transfer agent represented by (1). That is, the polymerized toner produced by using the chain transfer agent represented by the following general formula (1) can suppress the odor at the time of fixing the toner and exhibit excellent fixing properties.

[0027]

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In the formula, Q is a polyvalent organic group, X ₁ is a carbonyl group or —CONH—, A ₁ and A ₂ are alkylene groups having 1 to 8 carbon atoms, X ₂ is an oxygen atom, a sulfur atom or —NH—. , Z
Is a chain transfer group, p, q, r, and x are each 0 or 1, m
Represents an integer of 1 to 50, and n represents an integer of 2 to 100, and when n is 2 or more, the contents in [] and () may be the same or different.

Q represents a residue obtained by removing a hydroxyl group from a polyhydric alcohol or a polyhydric phenol;
Residues excluding the OOH group are exemplified.

Examples of the polyhydric alcohol include cyclic groups such as ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, cyclohexanediol and cyclohexanedimethanol. A dihydric alcohol having 2 to 10 carbon atoms which may have glycerin, trimethylolpropane, trimethylolethane,
C3-C12 trihydric alcohols such as hexanetriol, pentaerythritol, methyl glycoside,
C4-20 tetrahydric alcohols such as diglycerin,
Furthermore, pentitols such as xylitol and adonitol, hexitols such as sorbitol, mannitol, iditol, talitol and dulcitol, and sugars such as sucrose, glucose, fructose, crehalose and lactose can be mentioned. Examples of the polyhydric phenol include monocyclic polyhydric phenols such as pyrogallol, hydroquinone, and phloroglucin, and bisphenols such as bisphenol A. Examples of the polycarboxylic acid include maleic acid, fumaric acid, succinic acid, adipic acid, sebacic acid, malonic acid, azelaic acid, mesaconic acid, citraconic acid, glutaconic acid, isododecenyl succinic acid, and n-dodecenyl succinic acid. Divalent aliphatic dicarboxylic acids which may have a side chain having 2 to 40 carbon atoms, aromatic dicarboxylic acids having 8 to 20 carbon atoms such as phthalic acid, isophthalic acid, and terephthalic acid; 1,2,4-butane Tricarboxylic acid, 1,
Trivalent or higher aliphatic carboxylic acids such as 2,5-hexanetricarboxylic acid, tetra (methylenecarboxyl) methane, 1,2,7,8-octanetetracarboxylic acid, and 1,2,4-cyclohexanetricarboxylic acid; Examples thereof include tri- or higher-valent aromatic polycarboxylic acids such as 2,4-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, and pyromellitic acid.

Z represents SH, SR, SSR or a halogenated methyl group, and R represents an alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group or an alkoxy group. Preferred is SH.

When Q is a polyhydric alcohol or polyphenol residue, p = 0, and when Q is a polycarboxylic acid residue, p = 1. When p = 0, x = and q are 0 or 1, respectively, and r = 0. When p = 1, x = 0, and q and r are each 0 or 1. Further, n is preferably 2 to 8, and m is preferably 1 to 30.

The following are specific examples of the compound represented by the general formula (1). When p = 0, x = 0, q = 0, r = 0 Polyoxyethylene glycol-di-2-mercaptoethyl ether can be mentioned.

When p = 0, x = 1, q = 1, and r = 0, there may be mentioned triethanolamine-ε-caprolactone adduct-tri-3-mercaptopropionate and the like.

When p = 0, x = 1, q = 0, r = 0: triethanolamine-ε-caprolactone adduct-tri-2-mercaptoethyl ether and the like can be mentioned.

When p = 0, x = 0, q = 1, r = 0 Polyoxyethylene glycol di-3-mercaptopropionate, polyoxypropylene glycol di-3-mercaptopropionate, pentaerythritol Examples thereof include tetra-3-mercaptopropionic acid ester of ethylene oxide 20 mol adduct.

In the above, p = 0, x = 0, q = 0,
When r = 0, p = 0, x = 1, q = 1, and when r = 0, it is preferable that p = 0, x = 1, q = 0, and r = 0, and particularly preferably, p = 0. , X = 0, q = 0, r = 0.

Similarly, the object of the present invention can be achieved by including a chain transfer agent represented by the following general formula (2).

[0039]

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In the formula, Q is a polyvalent organic group, and A ₂ is a group having 1 to 1 carbon atoms.
An alkylene group of 8, Z is a chain transfer group, p and q are each 0 or 1, and p and q are not simultaneously 1;
m represents an integer of 2 to 20, and when n is 2 or more, the contents in [] may be the same or different.

Q is a residue obtained by removing a hydroxyl group from a polyhydric alcohol or a polyhydric phenol;
Residues excluding the OOH group are exemplified.

Examples of the polyhydric alcohol include cyclic groups such as ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, cyclohexanediol, and cyclohexanedimethanol. A dihydric alcohol having 2 to 10 carbon atoms which may have glycerin, trimethylolpropane, trimethylolethane,
C3-C12 trihydric alcohols such as hexanetriol, pentaerythritol, methyl glycoside,
C4-20 tetrahydric alcohols such as diglycerin,
Furthermore, pentitols such as xylitol and adonitol, hexitols such as sorbitol, mannitol, iditol, talitol and dulcitol, and sugars such as sucrose, glucose, fructose, crehalose and lactose can be mentioned. Examples of the polyhydric phenol include monocyclic polyhydric phenols such as pyrogallol, hydroquinone, and phloroglucin, and bisphenols such as bisphenol A. Examples of the polycarboxylic acid include maleic acid, fumaric acid, succinic acid, adipic acid, sebacic acid, malonic acid, azelaic acid, mesaconic acid, citraconic acid, glutaconic acid, isododecenyl succinic acid, and n-dodecenyl succinic acid. Divalent aliphatic dicarboxylic acids which may have a side chain having 2 to 40 carbon atoms, aromatic dicarboxylic acids having 8 to 20 carbon atoms such as phthalic acid, isophthalic acid, and terephthalic acid; 1,2,4-butane Tricarboxylic acid, 1,
Trivalent or higher aliphatic carboxylic acids such as 2,5-hexanetricarboxylic acid, tetra (methylenecarboxyl) methane, 1,2,7,8-octanetetracarboxylic acid, and 1,2,4-cyclohexanetricarboxylic acid; Examples thereof include tri- or higher-valent aromatic polycarboxylic acids such as 2,4-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, and pyromellitic acid.

Z represents SH, SR, SSR or a halogenated methyl group, and R represents an alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group or an alkoxy group. Preferred is SH.

When Q is a polyhydric alcohol or polyhydric phenol residue, p = 0, and when Q is a polycarboxylic acid residue, p = 1. Preferably, p and q are simultaneously 0. Further, m is preferably 2 to 8.

The following are specific examples of the compound represented by the general formula (2). When p = 0 and q = 0, ethylene glycol-di-2-mercaptoethyl ether, trimethylolpropane-tri-2-mercaptoethylether, and pentaerythritol-tetra-2-mercaptoethylether can be mentioned.

P = 1, q = 0 maleic acid-di-2-mercaptoethyl ester, fumaric acid-di-2-mercaptoethyl ester, adipic acid-di-2-mercaptoethyl ester, terephthalic acid-di-2- Mercaptoethyl ester and the like can be mentioned.

The amount of the chain transfer agent used in the present invention is 0.01 to 5% by mass of the total polymerizable monomer.
In the present invention, a chain transfer agent other than the general formula (1) or (2) may be used in combination, if necessary.

The molecular weight distribution of the resin obtained by polymerization of the radically polymerizable monomer composition in the presence of the chain transfer agent represented by the general formula (1) or (2) is 100,000 to
It is preferable to use a resin containing both a high molecular weight component having a peak or shoulder in the region of 1,000,000 and a low molecular weight component having a peak or shoulder in the region of 1,000 to less than 20,000.

The method for measuring the molecular weight of a resin by GPC is a measurement by GPC (gel permeation chromatography) using THF as a solvent. That is, 1 ml of THF is added to 0.5 to 5 mg, more specifically, 1 mg of the measurement sample, and the mixture is stirred at room temperature using a magnetic stirrer or the like to be sufficiently dissolved. Then
After treating with a membrane filter having a pore size of 0.45 to 0.50 μm, the mixture is injected into GPC. The GPC measurement conditions were as follows: the column was stabilized at 40 ° C., THF was flowed at a flow rate of 1 ml per minute, and a sample having a concentration of 1 mg / ml was reduced to about 1%.
Inject 00 μl and measure. The column is preferably used in combination with a commercially available polystyrene gel column. For example, Shodex GPC K manufactured by Showa Denko KK
F-801, 802, 803, 804, 805, 80
6, 807 and TSKgelG1 manufactured by Tosoh Corporation
000H, G2000H, G3000H, G4000
H, G5000H, G6000H, G7000H, TS
Combinations of K guard columns and the like can be mentioned. As a detector, a refractive index detector (I
R detector) or a UV detector may be 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.

[0050]

BEST MODE FOR CARRYING OUT THE INVENTION The toner of the present invention is prepared by suspension polymerization or emulsion polymerization of monomers in a liquid to which an emulsion of necessary additives is added to produce fine polymer particles. And an organic solvent, a coagulant, or the like is added thereto to cause association. A method of preparing by mixing and dispersing with a dispersion liquid such as a release agent and a colorant necessary for the composition of the toner at the time of association, and dispersing toner constituent components such as a release agent and a colorant in a monomer. And then emulsion polymerization. Here, the association means that a plurality of resin particles and colorant particles are fused.

The aqueous medium in the present invention means a medium containing at least 50% by mass of water.

That is, as a typical production method, a coloring agent and a releasing agent, a charge controlling agent,
Further, various constituent materials such as a polymerization initiator are added, and the various constituent materials are dissolved or dispersed in the polymerizable monomer using a homogenizer, a sand mill, a sand grinder, an ultrasonic disperser or the like. The polymerizable monomer in which these various constituent materials are dissolved or dispersed is dispersed in an aqueous medium containing a dispersion stabilizer into oil droplets of a desired size as a toner using a homomixer, a homogenizer, or the like. Thereafter, the stirring mechanism is moved to a reaction device, which is a stirring blade described later, and heated to cause the polymerization reaction to proceed. After completion of the reaction, the toner of the present invention is prepared by removing the dispersion stabilizer, filtering, washing and drying.

Further, as a method for producing the toner of the present invention, a method in which resin particles are prepared by association or fusion in an aqueous medium can also be mentioned. Although this method is not particularly limited, for example, Japanese Patent Application Laid-Open No. 5-265
252, JP-A-6-329947, and JP-A-9-15904.

That is, a method of associating a plurality of dispersed particles of a constituent material such as a resin particle and a colorant, or a plurality of fine particles composed of a resin and a colorant, particularly, after dispersing these in water using an emulsifier, At the same time as adding a coagulant having a critical coagulation concentration or more and salting out, simultaneously forming a fused particle by heating and fusing at a temperature equal to or higher than the glass transition temperature of the formed polymer itself, gradually growing the particle size, At the particle size, add a large amount of water to stop the particle size growth, and further heat and stir to smooth the particle surface and control the shape.
The toner of the present invention can be formed by heating and drying the particles in a fluidized state in a water-containing state. Here, an organic solvent that is infinitely soluble in water may be added together with the coagulant.

As the polymerizable monomer constituting the resin, styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, p-chlorostyrene, 3,4- Dichlorostyrene,
p-phenylstyrene, p-ethylstyrene, 2,4-
Dimethylstyrene, p-tert-butylstyrene, p
-N-hexylstyrene, pn-octylstyrene,
pn-nonylstyrene, pn-decylstyrene, p
Styrene or a styrene derivative such as -n-dodecylstyrene, methyl methacrylate, ethyl methacrylate,
N-butyl methacrylate, isopropyl methacrylate,
Methacrylate derivatives such as isobutyl methacrylate, t-butyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, lauryl methacrylate, phenyl methacrylate, diethylaminoethyl methacrylate, and dimethylaminoethyl methacrylate. , Methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, t-butyl acrylate, isobutyl acrylate,
Acrylic ester derivatives such as n-octyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, lauryl acrylate, phenyl acrylate, and the like, olefins such as ethylene, propylene, and isobutylene, vinyl chloride, vinylidene chloride, and vinyl bromide , Vinyl fluoride such as vinyl fluoride and vinylidene fluoride; vinyl esters such as vinyl propionate, vinyl acetate and vinyl benzoate; vinyl ethers such as vinyl methyl ether and vinyl ethyl ether; vinyl methyl ketone and vinyl ethyl ketone , Vinyl ketones such as vinyl hexyl ketone, N-vinyl compounds such as N-vinyl carbazole, N-vinyl indole, N-vinyl pyrrolidone, vinyl compounds such as vinyl naphthalene and vinyl pyridine, acrylonitrile, Acrylonitrile, there are acrylic acid or methacrylic acid derivatives such as acrylamide. These vinyl monomers can be used alone or in combination.

It is more preferable to use a polymerizable monomer constituting the resin in combination with one having an ionic dissociation group. For example, those having a substituent such as a carboxyl group, a sulfonic acid group, and a phosphoric acid group as a constituent group of a monomer, specifically, acrylic acid, methacrylic acid, maleic acid, itaconic acid, cinnamic acid, and fumaric acid. Acid, maleic acid monoalkyl ester, itaconic acid monoalkyl ester, styrenesulfonic acid, allylsulfosuccinic acid, 2-acrylamido-2-methylpropanesulfonic acid, acid phosphooxyethyl methacrylate, 3
-Chloro-2-acid phosphooxypropyl methacrylate and the like.

Further, divinylbenzene, ethylene glycol dimethacrylate, ethylene glycol diacrylate, diethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, triethylene glycol diacrylate, neopentyl glycol dimethacrylate,
Polyfunctional vinyls such as neopentyl glycol diacrylate can be used to form a crosslinked resin.

These polymerizable monomers can be polymerized using a radical polymerization initiator. In this case, an oil-soluble polymerization initiator can be used in the suspension polymerization method. As the oil-soluble polymerization initiator, 2,2'-azobis- (2,4
-Dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 1,1'-azobis (cyclohexane-1-carbonitrile), 2,2'-azobis-4-methoxy-2,4-dimethylvalero Azo or diazo polymerization initiators such as nitrile and azobisisobutyronitrile, benzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl peroxycarbonate, cumene hydroperoxide, t-butyl hydroperoxide, di-t-butyl peroxide , Dicumyl peroxide, 2,4-dichlorobenzoyl peroxide, lauroyl peroxide, 2,2-bis-
Examples thereof include peroxide-based polymerization initiators such as (4,4-t-butylperoxycyclohexyl) propane and tris- (t-butylperoxy) triazine, and polymer initiators having a peroxide in a side chain. .

When the emulsion polymerization method is used, a water-soluble radical polymerization initiator can be used. Examples of the water-soluble polymerization initiator include persulfates such as potassium persulfate and ammonium persulfate, azobisaminodipropane acetate, azobiscyanovaleric acid and salts thereof, and hydrogen peroxide.

Examples of the dispersion stabilizer include tricalcium phosphate, magnesium phosphate, zinc phosphate, aluminum phosphate, calcium carbonate, magnesium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, and calcium sulfate. , Barium sulfate,
Bentonite, silica, alumina and the like can be mentioned. Further, a surfactant generally used as a surfactant such as polyvinyl alcohol, gelatin, methyl cellulose, sodium dodecylbenzenesulfonate, ethylene oxide adduct, and higher alcohol sodium sulfate can be used as a dispersion stabilizer.

As the resin excellent in the present invention, a resin having a glass transition point of 20 to 90 ° C. is preferable and a softening point of 8
The thing of 0-220 ° C is preferred. The glass transition point is measured by a differential calorimetric analysis method, and the softening point can be measured by a Koka flow tester. Furthermore, these resins have a number average molecular weight (Mn) of 10 as measured by gel permeation chromatography.
00 to 100000, weight average molecular weight (Mw) 200
Those having 0 to 1,000,000 are preferred. Further, as a molecular weight distribution, Mw / Mn is 1.5 to 100, particularly 1.8.
-70 are preferred.

The flocculant to be used is not particularly limited, but those selected from metal salts are preferably used. Specifically, as a monovalent metal, for example, a salt of an alkali metal such as sodium, potassium, and lithium, and as a divalent metal, for example, a salt of an alkaline earth metal such as calcium and magnesium, or a divalent metal such as manganese or copper Salt,
Examples include salts of trivalent metals such as iron and aluminum, and specific salts include sodium chloride, potassium chloride, lithium chloride, calcium chloride, zinc chloride, copper sulfate, magnesium sulfate, and manganese sulfate. Can be.
These may be used in combination.

It is preferable that these coagulants are added at a concentration higher than the critical coagulation concentration. The critical aggregation concentration is an index relating to the stability of the aqueous dispersion, and indicates the concentration at which aggregation occurs when a coagulant is added. This critical aggregation concentration is
It varies greatly depending on the emulsified component and the dispersant itself. For example, Seizo Okamura et al.
7, 601 (1960), edited by The Society of Polymer Science, Japan, and the like, and a detailed critical aggregation concentration can be determined.
As another method, a desired salt is added to the target particle dispersion at a different concentration, the 、 (zeta) potential of the dispersion is measured, and the salt concentration at which this value changes is defined as the critical aggregation concentration. You can also ask.

The addition amount of the coagulant of the present invention may be not less than the critical coagulation concentration, but is preferably 1.2 to the critical coagulation concentration.
It is better to add it at least twice, more preferably at least 1.5 times.

The solvent which is infinitely soluble means a solvent which is infinitely soluble in water. The solvent which does not dissolve the formed resin in the present invention is selected.
Specifically, methanol, ethanol, propanol,
Examples thereof include alcohols such as isopropanol, t-butanol, methoxyethanol and butoxyethanol, nitriles such as acetonitrile, and ethers such as dioxane. Particularly, ethanol, propanol and isopropanol are preferred.

The amount of the solvent to be dissolved infinitely is 1 to 100% by volume based on the polymer-containing dispersion to which the flocculant is added.
Is preferred.

In order to make the shape uniform, it is preferable to prepare a colored particle, and after the filtration, a slurry in which 10% by mass or more of water is present in the particle is fluidized and dried. Those having a polar group in the polymer are preferred. It is considered that the reason for this is that the existing water exerts an effect of slightly swelling the polymer in which the polar group is present, so that it is particularly easy to make the shape uniform.

The toner of the present invention contains at least a resin and a colorant, but may contain a releasing agent or a charge control agent as a fixing property improving agent, if necessary. Further, an external additive composed of inorganic fine particles, organic fine particles, and the like may be added to the toner particles containing the resin and the colorant as main components.

As the colorant used in the toner of the present invention, carbon black, magnetic substance, dye, pigment and the like can be arbitrarily used. As the carbon black, channel black, furnace black, acetylene black, and the like can be used.
Thermal black, lamp black and the like are used. Ferromagnetic metals such as iron, nickel, and cobalt as magnetic materials,
Alloys containing these metals, compounds of ferromagnetic metals such as ferrite and magnetite, alloys that do not contain ferromagnetic metals but exhibit ferromagnetism by heat treatment, for example, Heusler such as manganese-copper-aluminum and manganese-copper-tin An alloy of a type called an alloy, chromium dioxide, or the like can be used.

As the dye, C.I. I. Solvent Red 1, 49, 52, 58, 63, 111, 1
22, C.I. I. Solvent Yellow 19, 44, 7
7, 79, 81, 82, 93, 98, 10
3, 104, 112, 162, C.I. I. Solvent Blue 25, 36, 60, 70, 93, 9
5 and the like, and a mixture thereof can also be used. Examples of the pigment include C.I. I. Pigment Red 5, 48: 1, 53: 1, 57: 1, 122,
139, 144, 149, 166, 177,
178, 222, C.I. I. Pigment Orange 3
1, 43, C.I. I. Pigment Yellow 14, 1
7, 93, 94, 138, 156, 158,
180, 185, C.I. I. Pigment Green 7,
C. I. Pigment Blue 15: 3, 60 and the like, and mixtures thereof can also be used. The number average primary particle size varies depending on the type, but
About 200 nm is preferable.

As a method of adding a colorant, a method of adding polymer particles prepared by an emulsion polymerization method at the stage of coagulation by adding a coagulant to color the polymer, or a process of polymerizing monomers. And a method of adding a colorant, polymerizing, and forming colored particles can be used. When the colorant is added at the stage of preparing the polymer, it is preferable to use the colorant after treating the surface with a coupling agent or the like so as not to inhibit the radical polymerizability.

Further, a releasing agent can be added as a fixing offset improving agent. The release agent is not particularly limited. Low molecular weight polypropylene (number average molecular weight = 1500
9000), low molecular weight polyolefin wax such as low molecular weight polyethylene, paraffin wax, Fischer-Tropsch wax, ester wax and the like. An ester wax represented by the following general formula can be suitably used.

R _1- (OCO-R ₂ ) _n n is an integer of 1 to 4, preferably 2 to 4, more preferably 3 or 4, and particularly preferably 4. R ₁ and R ₂ represent a hydrocarbon group which may have a substituent, and R ₁ has 1 to 40 carbon atoms, preferably 1 to 20 carbon atoms, more preferably 2 to 5 carbon atoms.
It is. Or, R ₂ has 1 to 40 carbon atoms, preferably 16 carbon atoms.
-30, more preferably 18-26.

Next, specific examples of the compounds will be described.

[0075]

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[0076]

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The amount of addition is 1 to 3 with respect to the whole toner.
0 mass%, preferably 2 to 20 mass%, more preferably 3 to 15 mass%.

The toner of the present invention is obtained by dissolving a release agent in a monomer, dispersing in water, polymerizing the resin, forming particles having electrol in the resin particles, and salting out with the colorant particles. / It is preferable to form colored particles by fusing to obtain a toner.

The charge control agents are also various known ones.
What can be dispersed in water can also be used. Specifically, nigrosine dyes, metal salts of naphthenic acid or higher fatty acids, alkoxylated amines,
Quaternary ammonium salt compounds, azo-based metal complexes, salicylic acid metal salts or metal complexes thereof.

The particles of the charge control agent and the fixability improving agent have a number average primary particle diameter of 10 to 500 in a dispersed state.
It is preferable to set it to about nm.

In a suspension polymerization method toner in which a toner component such as a colorant is dispersed or dissolved in a so-called polymerizable monomer is suspended in an aqueous medium and then polymerized to obtain a toner. By controlling the flow of the medium in the reaction vessel, the shape of the toner particles can be controlled. That is, the shape coefficient described later is 0.930 to
When the toner particles are 0.980, the flow of the medium in the reaction vessel is turbulent, and the polymerization proceeds, and the oil droplets existing in the aqueous medium in a suspended state gradually become polymerized. By doing so, when the oil droplets become soft particles, the coalescence of the particles is promoted by colliding the particles, the shape can be made irregular, and the shape coefficient can be adjusted within this range .

In the suspension polymerization method, by using a specific stirring blade, a turbulent flow can be formed, and the shape can be easily controlled. Although the reason for this is not clear, the flow of the medium formed in the stirring tank is generally in the case of a single-stage stirring tank (perspective view) as shown in FIG. Flows only along the wall from the lower part of the stirring tank to the upper part. Therefore, conventionally, a turbulent flow is generally formed by disposing a baffle plate 9 such as a wall surface of a stirring tank, and the efficiency of stirring is increased.
However, in such a device configuration, although a turbulent flow is partially formed, the turbulent flow acts in a direction in which the flow of the fluid stagnates, and as a result, the slip with respect to the particles is reduced. Sometimes you can't control it.

A stirring tank having a stirring blade which can be preferably used will be described with reference to the drawings. FIG. 2 is an example of a perspective view of a stirring tank provided with two-stage stirring blades (however, it will be described in detail later, the shape of the stirring blades should be changed, and a turbulence forming member (baffle plate) is also provided). Is better). FIG. 3 is a sectional view thereof. A rotating shaft 3 is suspended from the center of a vertical cylindrical stirring tank 2 having a heat exchange jacket 1 attached to the outer periphery of the stirring tank, and the rotating shaft 3 is brought close to the bottom surface of the stirring tank 2. There is a lower stirring blade 4 disposed therein and a stirring blade 5 disposed higher in the stage. The upper-stage stirring blade 5 is disposed at a crossing angle α that precedes the rotation direction with respect to the lower-stage stirring blade 4. In the present invention, the intersection angle α is less than 90 degrees (°). The lower limit of the intersection angle is not particularly limited, but may be about 5 ° or more, preferably 10 ° or more. FIG. 3 shows this in a top sectional view. If there are three or more stages, the intersection angle α between the adjacent stirring blades may be less than 90 degrees.

With this configuration, the medium is first stirred by the stirring blades arranged in the upper stage, and a flow to the lower side is formed. Then, by the stirring blade arranged in the lower stage,
It is presumed that the flow formed by the upper stirring blade is further accelerated downward, and a downward flow is separately formed by the stirring blade itself, so that the flow is accelerated as a whole and proceeds. As a result, it is presumed that a basin having a large shear stress formed as a turbulent flow is formed, so that the shape of the toner can be controlled.

In FIG. 2, the arrow indicates the rotation direction, 7 indicates the upper material inlet, and 8 indicates the lower material inlet. Also, FIG.
Is a turbulence forming member for making the stirring effective.

Here, the shape of the stirring blade is not particularly limited, but it has a rectangular plate shape, a notch in a part of the blade, and one or more middle holes, so-called slits, in the center. Things and the like can be used.

FIG. 4 shows these examples. (A) in the figure
(A) has a large central hole 6 in the center, (c) has a horizontal intermediate hole 6, and (d) has a vertical intermediate hole. There is something. In addition, even if these have different middle hole portions 6 in the upper stage and the lower stage,
The same thing may be used.

FIGS. 5 to 9 show examples of preferable structures which can be used as the structure of the stirring blade. FIG. 5 shows a configuration having a projection at the end of the stirring blade and / or a bent portion at the end, FIG. 6 shows a configuration having a slit at the lower stage of the stirring blade and bending and a projection at the end, and FIG. FIG. 8 shows a configuration in which an upper stirring blade has a slit and a lower stirring blade has a bent portion and a projection at an end thereof, and FIG. 9 shows a configuration in which the stirring blade has three stages. Are respectively shown. The angle of the bent portion at the end of the stirring blade is preferably about 5 to 45 °.

The agitating blade having the bent portion (4 "or 5") and the projections (4 'or 5') on the upper or lower portion effectively generates turbulence.

The gap between the upper and lower stirring blades having the above configuration is not particularly limited, but it is preferable that at least a gap is provided between the stirring blades. Although the reason is not clear, it is considered that the flow of the medium is formed through the gap, so that the stirring efficiency is improved. However, the gap has a width of 0.5 to 50%, preferably 1 to 30% with respect to the liquid level in the stationary state.

Further, the size of the stirring blade is not particularly limited, but the sum of the heights of all the stirring blades is 50% to 100%, preferably 60% to 100% of the liquid level in the stationary state. 95
%.

FIG. 7 shows an example of a stirring blade and a stirring tank used for forming a laminar flow in the suspension polymerization method. It is characterized in that no obstacle such as a baffle plate which forms a turbulent flow is provided in the stirring tank. Regarding the configuration of the stirring blade, similarly to the stirring blade used for forming the above-described turbulent flow, the upper stirring blade is arranged with the intersection angle α preceding the lower stirring blade in the rotation direction. It is preferable to provide a multi-stage configuration.

The shape of the stirring blade is not particularly limited as long as it does not form a turbulent flow.
It is preferably formed by a continuous surface, such as a square plate, and may have a curved surface.

On the other hand, in the case of a polymerization toner in which resin particles are associated or fused in an aqueous medium, the flow and temperature distribution of the medium in the reaction vessel at the fusion stage are controlled to further improve the shape after fusion. By controlling the heating temperature, the number of rotations for stirring, and the time in the control step, the shape distribution and shape of the entire toner can be arbitrarily changed.

That is, in the case of the polymerization toner in which the resin particles are associated or fused, the flow in the reactor is made laminar and the stirring blade and the stirring tank which can make the internal temperature distribution uniform are used. Temperature in the deposition process and the shape control process,
By controlling the number of rotations and time, it is possible to form a toner having the shape factor and uniform shape distribution of the present invention. The reason for this is that when fusion is performed in a place where a laminar flow is formed, strong stress is not applied to the particles that are undergoing aggregation and fusion (association or aggregated particles) and the flow is accelerated in a laminar flow. It is estimated that the shape distribution of the fused particles becomes uniform as a result of the uniform temperature distribution in the stirring tank.
Further, the fused particles gradually become spherical by heating and stirring in the subsequent shape control step, and the shape of the toner particles can be arbitrarily controlled.

As a stirring blade and a stirring tank used for a polymerization toner for associating or fusing resin particles, the same stirring blades and a stirring tank as in the case of forming a laminar flow in the above-mentioned suspension polymerization method can be used. The following can be used. It is characterized in that no obstacle such as a baffle plate which forms a turbulent flow is provided in the stirring tank. Regarding the configuration of the stirring blade,
Similar to the stirring blade used in the suspension polymerization method described above, the upper stirring blade is arranged with a crossing angle α that precedes the lower stirring blade in the rotation direction with respect to the lower stirring blade. Is preferred.

The shape of the stirring blade can be the same as that in the case of forming a laminar flow in the above-mentioned suspension polymerization method, and is not particularly limited as long as it does not form a turbulent flow. ) Are preferably formed by continuous surfaces such as a rectangular plate, and may have a curved surface.

The shape of the toner obtained by fusing is determined by the average value (average circularity) of the shape factor represented by the following equation.
Is 0.930 to 0.980, preferably 0.940 to
It is preferably 0.975.

Shape factor = (circumferential length obtained from equivalent circle diameter) / (perimeter of particle projected image) It is preferable that the shape factor distribution is sharp.
The standard deviation of the circularity is preferably 0.10 or less, and the CV value calculated by the following equation is preferably less than 20%, more preferably less than 10%.

CV value = {(standard deviation of circularity) / (average circularity)} × 100 By setting the average circularity to 0.930 to 0.980, the shape of the toner can be made somewhat irregular. The heat transfer can be made more efficient, and the fixability can be further improved. That is, an average circularity of 0.9
When the ratio is 80 or less, the fixing property can be improved.
Further, by setting the average circularity to 0.930 or more, the degree of irregularity of the particles can be suppressed, and the friability of the particles due to stress during long-term use can be suppressed.

Further, it is preferable that the distribution of the shape coefficient is sharp, and the standard deviation of the circularity is 0.10 or less, so that a toner having a uniform shape can be obtained. Since it can be reduced, the effect of preventing the fixing device from being contaminated by improving the fixing rate and reducing the offset property is further exhibited. When the CV value is also less than 20%, a sharp shape distribution can be similarly obtained, and the effect of improving the fixing property can be more remarkably exhibited.

The method of measuring the shape factor is not limited.
Take a photo magnified 0 times, use an image analyzer,
The average circularity can be calculated by measuring the circularity of 500 toners and calculating the arithmetic average value. In addition, as a simple measurement method, FPIA-200
0 (manufactured by Toa Medical Electronics Co., Ltd.).

To control the shape, an appropriate process end time may be determined while monitoring the characteristics of toner particles (colored particles) whose shape is being controlled in a process such as association.

The term “monitoring” means that a measuring device is incorporated in-line and the process conditions are controlled based on the measurement result. That is, for example, in the case of a polymerization toner formed by incorporating measurement of shape and the like in-line and associating or fusing resin particles in an aqueous medium, the shape and particle size are sequentially sampled in steps such as fusing. Is measured, and the reaction is stopped when the desired shape is obtained.

The monitoring method is not particularly limited, but a flow type particle image analyzer FPIA-
2000 (manufactured by Toa Medical Electronics Co., Ltd.) can be used. This apparatus is suitable because the shape can be monitored by performing image processing in real time while passing the sample liquid. That is, a pump or the like is used from the reaction field to constantly monitor and measure the shape and the like, and stop the reaction when the desired shape and the like are obtained.

The volume average particle diameter of the toner of the present invention is measured with a Coulter Counter TA-II or a Coulter Multisizer (manufactured by Coulter Inc.). In the present invention, a Coulter Multisizer was used, connected to an interface (manufactured by Nikkaki) for outputting a particle size distribution and a personal computer. The aperture used in the Coulter Multisizer is 1
The particle size distribution and the average particle size were calculated by measuring the volume distribution of toner having a particle size of 2 μm or more using a particle having a size of 00 μm.

The toner of the present invention has a volume average particle diameter of 3 to 8 μm. When toner particles are formed by a polymerization method, the particle diameter can be controlled by the concentration of the coagulant, the amount of the organic solvent added, the fusing time, and the composition of the polymer itself.

When the volume average particle diameter is 3 to 8 μm, in the fixing step, toner particles having a large adhesive force which fly and adhere to the heating member to cause offset are reduced, and the transfer efficiency is increased. The halftone image quality is improved, and the image quality of fine lines and dots is improved.

Measurement conditions (1) Aperture: 100 μm (2) Sample preparation method: Electrolyte [ISOTON R-1
1 (manufactured by Coulter Scientific Japan)
An appropriate amount of a surfactant (neutral detergent) is added to 50 to 100 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.

Further, in the toner of the present invention, more effects can be exhibited by adding and using fine particles such as inorganic fine particles and organic fine particles as external additives. The reason for this is presumed that the embedding and detachment of the external additive can be effectively suppressed, so that the effect is remarkable.

As the inorganic fine particles, it is preferable to use inorganic oxide particles such as silica, titania and alumina. Further, it is preferable that these inorganic fine particles have been subjected to a hydrophobic treatment with a silane coupling agent, a titanium coupling agent or the like. preferable. The degree of the hydrophobizing treatment is not particularly limited, but a methanol wettability of 40 to 95 is preferable. Methanol wettability is to evaluate the wettability to methanol.

In this method, 0.2 g of the inorganic fine particles to be measured is weighed and added to 50 ml of distilled water placed in a beaker having a content of 200 ml. Methanol is slowly dropped from a burette whose tip is immersed in the liquid until the whole of the inorganic fine particles is wet with stirring slowly.
When the amount of methanol required to completely wet the inorganic fine particles is a (ml), the degree of hydrophobicity is calculated by the following equation.

Degree of hydrophobicity = {a / (a + 50)} × 100 The amount of the external additive to be added is 0.1 to 5.
0 mass%, preferably 0.5 to 4.0 mass%. Various external additives may be used in combination.

The toner of the present invention is used as a one-component magnetic toner containing a magnetic material, for example, when used as a two-component developer by mixing with a so-called carrier, or when a non-magnetic toner is used alone. Although any of them can be suitably used, the toner of the present invention is preferably used as a two-component developer used by being mixed with a carrier.

As the carrier constituting the two-component developer, conventionally known materials such as metals such as iron, ferrite, and magnetite, and alloys of these metals with metals such as aluminum and lead are used as the magnetic particles. be able to.
Particularly, ferrite particles are preferable. The magnetic particles preferably have a volume average particle size of 15 to 100 μm, more preferably 25 to 60 μm. The volume average particle diameter of the carrier can be typically measured by a laser diffraction type particle size distribution analyzer “HELOS” (manufactured by SYMPATEC) equipped with a wet disperser.

The carrier is preferably a carrier further coated with a resin, or a so-called resin-dispersed carrier in which magnetic particles are dispersed in a resin. Although there is no particular limitation on the resin composition for coating, for example, an olefin resin, a styrene resin, a styrene / acrylic resin, a silicone resin, an ester resin, a fluorine-containing polymer resin, or the like is used. The resin for forming the resin dispersion type carrier is not particularly limited, and known resins can be used.For example, styrene acrylic resin, polyester resin, fluorine resin, phenol resin, and the like can be used. it can.

Next, a sectional configuration diagram of a color image forming apparatus as an example of the image forming apparatus according to the present invention is shown. In FIG. 10, reference numeral 21 denotes a photosensitive drum as a latent image carrier,
A photosensitive member (organic photosensitive member) is formed by coating on a drum base, and is grounded and driven to rotate clockwise as shown. Reference numeral 22 denotes a scorotron charger, which is a charging means, and applies uniform charging of a high potential VH to the peripheral surface of the photosensitive drum 21 by corona discharge using a grid maintained at a grid potential VG and a corona discharge wire. Prior to charging by the scorotron charger, PCL using a light emitting diode etc. to eliminate the history of the photoconductor until the previous print
It is preferable that the peripheral surface of the photoconductor is neutralized by performing exposure with a (pre-charging static eliminator).

After the photosensitive drum 21 is uniformly charged, the exposure means 23 performs image exposure based on the image signal.
The exposure means 23 includes a rotating polygon mirror 131 and an fθ lens 13 using a laser diode (not shown) as a light source.
2. Reflection mirror 13 through cylindrical lens 133
The optical path is bent by 4 to perform main scanning.

Image exposure is performed in synchronization with the rotation (sub-scan) of the photosensitive drum 21 to form a latent image. In this example, a character portion is exposed to form a reversal latent image such that the character portion has a lower potential VL.

Around the periphery of the photosensitive drum 21, developing means 24Y each containing a two-component developer comprising a toner such as yellow (Y), magenta (M), cyan (C), and black (K) and a carrier. , 24M, 24C, and 24K are provided.

The image forming process will be described. First, for example, yellow is developed as the first color. Usually, the developer is composed of a carrier having a ferrite core as a core and an insulating resin coated around the core, and a toner containing polyester as a main material and a pigment corresponding to a color, a charge control agent, silica, titanium oxide and the like. The developer is conveyed to the developing area while being regulated to a developer layer thickness of 100 to 600 μm on the developing sleeve by the layer forming means.

The gap between the developing sleeve and the photosensitive drum 21 in the developing zone is larger than the thickness of the developer layer.
0mm, during which the VAC AC bias and VDC
Are applied in a superimposed manner. VDC and VH,
Since the charge of the toner is of the same polarity, the toner triggered to separate from the carrier by the VAC is VDC
It does not adhere to the VH portion having a higher potential, but adheres to the VL portion having a lower potential than VDC, thereby performing visualization (reversal development).

After the visualization of the first color is completed, the image forming process for the magenta of the second color is started, and uniform charging is again performed by the scorotron charger, and a latent image based on the image data of the second color is formed by the exposure unit 23. Is done.

Again, a portion of the photoreceptor, which has a potential of VH over the entire surface of the photoreceptor drum 21 and has no image of the first color, forms a latent image similar to that of the first color and is developed. However, in the portion where the first color image is developed again, the latent image of VM ′ is formed by the light attached to the toner of the first color and the electric charge of the toner itself.
Development according to the potential difference between DC and VM 'is performed. This one
When the first color is developed by forming a VL latent image in the overlapping portion of the images of the first color and the second color, the balance between the first color and the second color is lost, so that the exposure amount of the first color is reduced and VH> V
There may be a case where the intermediate potential VM is such that M> VL.

The same image forming process as that for the second color magenta is performed for the third color cyan and the fourth color black, and a visible image of four colors is formed on the peripheral surface of the photosensitive drum 21.

On the other hand, one sheet of recording material (recording paper or the like) P conveyed from the paper supply cassette via the half-moon roller is temporarily stopped near the registration roller pair (paper supply roller) via the feed roller pair, and is transferred. When the timing of (1) is adjusted, the sheet is fed to the transfer area by rotating the registration roller.

In the transfer area, a transfer means is pressed against the peripheral surface of the photosensitive drum 21 in synchronization with the transfer timing, and the fed recording material P is sandwiched to transfer the multicolor image at once. .

Next, the recording material P is neutralized by the separating means, separated from the peripheral surface of the photosensitive drum 21, conveyed to the fixing device (fixing means) 40, and heated by the heating roller (upper roller).
After the toner is welded by heating and pressing of the pressure roller 41 and the pressure roller (lower roller) 42, the toner is discharged onto a paper discharge tray outside the apparatus via a paper discharge roller. The transfer unit is retracted from the peripheral surface of the photosensitive drum 21 after the recording material P has passed, and is ready for the formation of the next toner image.

On the other hand, the photosensitive drum 2 from which the recording material P has been separated
In the case of 1, after being subjected to static elimination by the static eliminator, the residual toner is removed and pressed by the pressure contact of the blade of the cleaning means 25, and is again subjected to static elimination by the PCL and electrification by the scorotron charger to enter the next image forming process. .
The blade moves immediately after the cleaning of the photoreceptor surface and retreats from the peripheral surface of the photoreceptor drum 21. The waste toner scraped into the cleaning means 25 by the blade is discharged by a screw and then stored in a waste toner collecting container (not shown).

As a preferred fixing method used in the present invention, a so-called contact heating method can be used. In particular, examples of the contact heating method include a heat and 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 disposed heating element.

In the heat roller fixing method, a heat source is often provided inside a metal cylinder made of iron, aluminum, or the like whose surface is coated with tetrafluoroethylene or polytetrafluoroethylene-perfluoroalkoxyvinyl ether copolymer or the like. It is formed of an upper roller 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. The nip width is 1 to 10 mm, preferably 1.
5-7 mm. The fixing linear velocity is 40 mm / sec to 60
0 mm / sec is preferable. When the nip is narrow, heat cannot be uniformly applied to the toner, causing uneven fixing. On the other hand, if the nip width is wide, the melting of the resin is promoted, and a problem occurs in that the fixing offset becomes excessive.

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.

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.

[0135]

EXAMPLES Next, typical embodiments of the present invention will be described as examples, but of course, the present invention is not limited thereto.

(Latex Preparation Example 1) 7.08 g of an anionic activator (sodium dodecylbenzenesulfonate: SDS) was previously placed in a 5000 ml separable flask equipped with a stirrer, a temperature sensor, a condenser, and a nitrogen introducing device.
Is dissolved in ion-exchanged water (2760 g). The internal temperature was raised to 80 ° C. while stirring at a stirring speed of 230 rpm under a nitrogen stream. On the other hand, the exemplary compound (2
0) 72.0 g was added to a monomer composed of 115.1 g of styrene, 42.0 g of n-butyl acrylate, and 10.9 g of methacrylic acid, and the mixture was heated to 80 ° C. and dissolved to prepare a monomer solution. The heated solution was mixed and dispersed by a mechanical disperser having a circulation path to prepare emulsified particles having a uniform dispersed particle diameter. Then, a solution in which 0.84 g of a polymerization initiator (potassium persulfate: KPS) was dissolved in 200 g of ion-exchanged water was added, and the mixture was heated and stirred at 80 ° C. for 3 hours to produce latex particles. Subsequently, a solution obtained by dissolving 7.73 g of a polymerization initiator (KPS) in 240 ml of ion-exchanged water was added.
At 0 ° C., a mixed solution of 383.6 g of styrene, 140.0 g of n-butyl acrylate, 36.4 g of methacrylic acid, and 13.7 g of polyoxyethylene glycol-di-2-mercaptoethyl ether was added dropwise over 120 minutes. After completion of the dropwise addition, the mixture was heated and stirred for 60 minutes and then cooled to 40 ° C. to obtain latex particles. This latex particle is referred to as Latex 1.

(Latex Preparation Example 2) In the latex preparation example 1, polyoxyethylene glycol-di-2-
15.0 g of polyoxypropylene glycol-di-2-mercaptoethyl ether was used in place of mercaptoethyl ether, and (1) was used in place of the exemplary compound (20).
Latex particles were obtained in the same manner except that 120.0 g of 9) was used. This is designated as latex 2.

(Latex Preparation Example 3) In the latex preparation example 1, the polyoxyethylene glycol-di-2-
Latex particles were obtained in the same manner except that 15.0 g of pentaerythritol ethylene oxide adduct tetra-2-mercaptoethyl ether was used instead of mercaptoethyl ether. This is designated as Latex 3.

(Latex Preparation Example 4) In the latex preparation example 1, the polyoxyethylene glycol-di-2-
Latex particles were obtained in the same manner except that 16.0 g of ethylene glycol di-2-mercaptoethyl ether was used instead of mercaptoethyl ether. This is designated as Latex 4.

(Latex Preparation Example 5) In the latex preparation example 1, the polyoxyethylene glycol-di-2-
Instead of mercaptoethyl ether, trimethylolpropane-tri-2-mercaptoethylether was used for 15.0.
Latex particles were obtained in the same manner except that g was used. This is designated as Latex 5.

(Latex Preparation Example 6) In the latex preparation example 1, the polyoxyethylene glycol-di-2-
Maleic acid-di-in place of mercaptoethyl ether
Latex particles were obtained in the same manner except that 15.0 g of 2-mercaptoethyl ester was used. This is designated as latex 6.

(Latex Preparation Example 7) In latex preparation example 1, polyoxyethylene glycol di-2-
Fumaric acid-di-2 instead of mercaptoethyl ether
-Latex particles were obtained in the same manner except that 18.0 g of mercaptoethyl ester was used. This is latex 7
And

(Latex Preparation Example 8) In the latex preparation example 1, polyoxyethylene glycol-di-2-
Latex particles were obtained in the same manner except that 15.0 g of t-dodecyl mercaptan was used instead of mercaptoethyl ether. This is designated as Latex 8.

(Example of Toner Preparation) Production of Colored Particles 1Bk 9.2 g of sodium n-dodecyl sulfate is dissolved in 160 ml of ion-exchanged water with stirring. 20 g of Regal 330R (carbon black manufactured by Cabot Corporation) is added to this solution with stirring.
Was gradually added, and then dispersed using CLEARMIX. Otsuka Electronics ELS-80 Electrophoretic Light Scattering Photometer
As a result of measuring the particle size of the dispersion using 0, the weight average particle size was 112 nm. This dispersion is referred to as “colorant dispersion 1”.

1250 g of the above-mentioned "latex 1", 2000 ml of ion-exchanged water and "colorant dispersion liquid 1" were combined with a temperature sensor, a cooling pipe, a nitrogen introducing device, and a stirring device.
Stir into a 4 liter four-necked flask. After adjusting to 30 ° C., a 5 mol / L aqueous sodium hydroxide solution was added to the solution to adjust the pH to 10.0. Then, 52.6 g of magnesium chloride hexahydrate was added to deionized water 72.
The aqueous solution dissolved in ml was added under stirring at 30 ° C. for 10 minutes. Thereafter, after standing for 3 minutes, heating is started and the temperature is raised to 90 ° C. in 6 minutes (heating rate = 10 ° C.).
° C / min). In that state, the particle size is measured using a coulter counter TA.
When measured by II, when the volume average particle diameter became 6.5 μm, an aqueous solution in which 115 g of sodium chloride was dissolved in 700 ml of ion-exchanged water was added to stop the particle growth, and the liquid temperature was further continued at 90 ° C. ± 2. The mixture was heated and stirred at 6 ° C. for 6 hours to cause salting out / fusion. Thereafter, 30 ° C. under the condition of 6 ° C./min.
Then, hydrochloric acid was added to adjust the pH to 2.0, and the stirring was stopped. The resulting colored particles are filtered, washed repeatedly with ion-exchanged water, and then dried with warm air at 40 ° C.
Colored particles were obtained. The colored particles obtained as described above are referred to as “colored particles 1Bk”. Production of Colored Particle 1Y Instead of carbon black, C.I. I. Pigment Yellow 185 was used to obtain colored particles in the same manner as in the production of colored particles 1Bk. This is referred to as “colored particle 1Y”. Production of colored particles 1M Instead of carbon black, C.I. I. Pigment Red 122 was used to obtain colored particles in the same manner as in the production of colored particles 1Bk. This is referred to as “colored particles 1M”. Production of Colored Particle 1C Instead of carbon black, C.I. I. Pigment Blue 15: 3 was used, except that Pigment Blue 15: 3 was used. This is referred to as “colored particle 1C”.

Production of Colored Particles 2Bk to 8C As shown in Table 1, "Latex 2" to "Latex 8" were used in place of Latex 1, and the colorant was changed to carbon black and colorant shown in Table 1. Except for the change, "colored particles 2Bk" to "colored particles 8C" were obtained in the same manner as in the manufacture of colored particles 1Bk.

[0147]

[Table 1]

(Production of colored particles 9Bk): Example of suspension polymerization method In a four-necked flask equipped with a high-speed stirrer (TK homomixer), 710 parts by mass of ion-exchanged water and 0.1 mol / L of trisodium phosphate were added. Add 450 parts by mass of aqueous solution, and add
C. and 68 parts by mass of a 1.0 mol / l aqueous solution of calcium chloride was gradually added under stirring conditions at a rotation speed of 12000 rpm to prepare an aqueous dispersion medium containing a dispersion containing colloidal tricalcium phosphate. Then, 165 parts by mass of a styrene monomer and 35 parts by mass of n-butyl acrylate, 14 parts by mass of carbon black (Legal 330R) were added, and 30 parts by mass of an ester wax (19) was added to a dispersion liquid dispersed by a sand grinder. Dissolved. Then, polyoxyethylene glycol-di-2
-2 parts by weight of mercaptoethyl ether and 10 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator were added to the aqueous dispersion medium under stirring conditions at a rotation speed of 12,000 rpm. And a solution containing the monomer was dispersed in water. Then
The polymerization reaction was performed for 10 hours under the stirring conditions of 65 ° C. and 200 rpm in a nitrogen stream using a reaction apparatus having the configuration of the stirring blade shown in FIG. 4B. At the end of the polymerization reaction, hydrochloric acid was added to remove tricalcium phosphate as a dispersion stabilizer, followed by filtration, washing and drying to prepare colored particles. This is referred to as “colored particles 9B
k ”. In addition, monitoring is performed during the polymerization,
By controlling the liquid temperature, the number of rotations of the stirring, and the heating time, the variation coefficient of the shape and the shape coefficient were controlled, and the variation coefficient of the particle diameter and the particle size distribution were arbitrarily adjusted by submerged classification.

(Production of colored particles 10Bk): Example of suspension polymerization method In the production of colored particles 9Bk, polyoxypropylene glycol-di-2-mercaptoethyl was used instead of polyoxyethylene glycol-di-2-mercaptoethyl ether. Colored particles were obtained in the same manner except that 3 parts by mass of ether was used. This is referred to as colored particles 10Bk.

(Production of colored particles 11Bk): Example of suspension polymerization method In the production of colored particles 9Bk, pentaerythritol ethylene oxide adduct tetra-2-mercapto was used in place of polyoxyethylene glycol-di-2-mercaptoethyl ether. Colored particles were obtained in the same manner except that 3 parts by mass of ethyl ether was used. This is colored particles 11B
k.

(Production of Colored Particles 12Bk): Example of Suspension Polymerization In the production of colored particles 9Bk, instead of polyoxyethylene glycol-di-2-mercaptoethyl ether, ethylene glycol-di-2-mercaptoethyl ether was used.
Colored particles were obtained in the same manner except that 16.0 g of tellurium was used. This is referred to as colored particles 12Bk.

(Production of Colored Particles 13Bk): Example of Suspension Polymerization In the production of colored particles 9Bk, trimethylolpropane-tri-2-mercaptoethyl ether was used instead of polyoxyethylene glycol-di-2-mercaptoethyl ether. Colored particles were obtained in the same manner except that 3 parts by mass were used. This is referred to as colored particles 13Bk.

(Production of colored particles 14Bk): Example of suspension polymerization method In the production of colored particles 9Bk, maleic acid-di-2-mercaptoethyl ester was used instead of polyoxyethylene glycol-di-2-mercaptoethyl ether. 3
Colored particles were obtained in the same manner except that parts by mass were used. This is referred to as colored particles 14Bk.

(Production of Colored Particles 15Bk): Example of Suspension Polymerization In the production of colored particles 9Bk, fumaric acid-di-2-mercaptoethyl ester was used instead of polyoxyethylene glycol-di-2-mercaptoethyl ether. Except for using, colored particles were obtained in the same manner. This is colored particles 1
5Bk.

(Production of colored particles 16Bk): Example of suspension polymerization method In the production of colored particles 9Bk, the procedure was the same except that t-dodecyl mercaptan was used in place of polyoxyethylene glycol-di-2-mercaptoethyl ether. Thus, colored particles were obtained. This is referred to as colored particles 16Bk.

The particle size properties such as the average circularity of the colored particles 1Bk to 16Bk were measured, and the results are shown in Tables 2 and 3.

[0157]

[Table 2]

[0158]

[Table 3]

The circularity was measured using FPIA-1000, the amount of sample analyzed = 0.3 μL, the number of detected particles = 1500-150.
It was measured under 5000 conditions.

Next, the molecular weight distribution of the resin of the colored particles 1 to 8 and the colored particles 9Bk to 16Bk was measured, and the results are shown in Table 4.

Here, the colored particle 1 group is the colored particle 1Bk / 1Y / 1M / 1C using the same latex resin, and the colored particle 2 group is the colored particle 2Bk / 2Y / 2M / 2C.
Are shown. Hereinafter, the same applies to the group of three colored particles to the group of eight colored particles.

The colored particles 8 and the colored particles 16Bk are comparative examples.

[0163]

[Table 4]

Then, the above-mentioned “colored particles 1Bk / 1Y / 1M
/ 1C "to" colored particles 8Bk / 8Y / 8M / 8C ",
1% by mass of hydrophobic silica (number-average primary particle diameter = 12 nm, hydrophobicity = 68) and hydrophobic titanium oxide (number-average primary particle size = 20 nm, hydrophobic) 1% by mass) and mixed with a Henschel mixer to obtain a toner.
These are referred to as “toner 1Bk / 1Y / 1M / 1C” to “toner 8Bk / 8Y / 8M / 8C”, “toner 9Bk” to
“Toner 16Bk”.

Incidentally, "toner 1Bk / 1Y / 1M / 1C"
Is a toner 1 group, and the toner 2 group “toner 2Bk /
2Y / 2M / 2C ”to 8 toner groups“ toner 8Bk / 8Y ”
/ 8M / 8C ".

Note that there is no difference between the colored particles and the toner in physical properties such as shape and particle diameter.

A ferrite carrier coated with a silicone resin and having a volume average particle diameter of 60 μm was mixed with each of the above toners to prepare a developer having a toner concentration of 6%. These are used in association with the toner, and the developer 1 group “developer 1Bk / 1”
Y / 1M / 1C ”to developer 8 group“ developer 8Bk / 8Y /
8M / 8C "," Developer 9Bk "to" Developer 16Bk "
And

Using the developer prepared here, a digital color printer Kon having substantially the same configuration as in FIG.
By using ica3015, the actual configuration was evaluated by changing the configuration of the fixing device to the configuration shown below.

As the fixing device, a pressure fixing type heat fixing device as shown in FIG. 11 was used. The specific configuration is as follows.

The surface was treated with PFA (tetrafluoroethylene-
A perforated aluminum alloy pipe 11 having a coating layer (perfluoroalkyl vinyl ether copolymer) 12 (thickness: 120 μm) 12 having an inner diameter of 40 mm and a total width of 310 mm, and having a built-in heater 13 at the center and having a thickness of 1.0 mm is heated. Roller (upper roller) 41, the surface of which is also a sponge-like silicone rubber (Asker C hardness = 48: thickness 2)
mm) A thickness of 2.0 mm with an inner diameter of 40 mm composed of 17
Roller (lower roller) 4 having an iron pipe 16
Two. The nip width was 5.8 mm. Using this fixing device, the printing linear velocity was set to 250 mm / sec.

Note that polydiphenyl silicone (viscosity at 20 ° C. is 10 Pa ·
s) was used.

The fixing temperature was controlled by the surface temperature of the upper roller, and was set to 175 ° C. The amount of silicone oil applied was 0.6 mg / A4.

Evaluation of Characteristics The evaluation of the fixability is based on the relative reflection density when the image density is set to “0” for the A4 halftone image (Y = M / C / Bk) printed in a single color. 1.0), and the fixing ratio was measured. The fixing rate is a value obtained by rubbing a fixed image with a 1 kg weight of “rolled cloth” and calculating a percentage change in image density before and after the rubbing.

Fixing rate (%) = ｛(image density after rubbing) /
(Image density before rubbing) Δ × 100 The surface temperature of the heating roller was 175 ° C. as a center value.

In a closed room having a floor of 5 m × 5 m and a height of 2 m, a pixel rate of 50% was obtained at a set temperature of 175 ° C.
Was printed on 1,000 sheets continuously, and the presence or absence of odor was evaluated by sensory evaluation. For the presence or absence of odor, 10 evaluators were used to evaluate the number of persons who felt odor. Table 5 shows the evaluation results.

[0176]

[Table 5]

In the examples of the present invention, none of the persons felt odor and showed good results. There is no problem with the fixing rate. On the other hand, in Comparative Examples outside the present invention, 7 to 8 out of 10 persons felt odor.

[0178]

According to the present invention, in a toner for developing an electrostatic latent image of a so-called polymerization method, the generation of odor during heat fixing is suppressed, the odor problem does not occur, and the small particle size excellent in fixability is obtained. And a method for producing the same.

[Brief description of the drawings]

FIG. 1 is a perspective view of an example of a stirring tank provided with a conventional stirring blade.

FIG. 2 is a perspective view of an example of a stirring tank provided with stirring blades.

FIG. 3 is a top sectional view of FIG. 2;

FIG. 4 is a schematic diagram of a shape of a stirring blade.

FIG. 5 is a perspective view of an example of a stirring tank provided with stirring blades.

FIG. 6 is a perspective view of an example of a stirring tank provided with stirring blades.

FIG. 7 is a perspective view of an example of a stirring tank provided with stirring blades.

FIG. 8 is a perspective view of an example of a stirring tank provided with stirring blades.

FIG. 9 is a perspective view of an example of a stirring tank provided with stirring blades.

FIG. 10 is a cross-sectional configuration diagram of a color image forming apparatus according to the present invention.

FIG. 11 is a schematic diagram of a heat fixing device according to the present invention.

[Explanation of symbols]

Reference Signs List 2 stirring tank 3 rotating shaft 4 lower stirring blade 5 upper stirring blade 6 middle hole portion 20Y, 20M, 20C, 20K image forming unit 21, 21Y, 21M, 21C, 21K photoconductor drum (latent image carrier) 22, 22Y, 22M, 22C, 22K Charging means 23, 23Y, 23M, 23C, 23K Exposure means 24, 24Y, 24M, 24C, 24K Developing means 25, 25Y, 25M, 25C, 25K Cleaning means P Recording material (recording paper)

 ──────────────────────────────────────────────────の Continuing on the front page (72) Inventor Kenji Hayashi 1st Konica Corporation, Sakuracho, Hino-shi, Tokyo In-house (72) Mikio Kamiyama 1st Konica Corporation, Sakuracho, Hino-shi, Tokyo F-term (reference) 2H005 AA01 AB03 AB06 CA04 CA30

Claims (14)

[Claims] 1. A resin particle prepared by polymerizing a radically polymerizable monomer composition containing a chain transfer agent represented by the following general formula (1) in an aqueous medium is subjected to salting out / fusion in an aqueous medium. A toner for developing an electrostatic latent image, which is obtained by performing Embedded image In the formula, Q is a polyvalent organic group, X ₁ is a carbonyl group or —CO
NH-, A ₁ and A ₂ are an alkylene group having 1 to 8 carbon atoms, X
₂ is an oxygen atom, a sulfur atom or -NH-, Z is a chain transfer group, p, q, r, and x are each 0 or 1, and m is 1 to 50.
And n represents an integer of 2 to 100, and when n is 2 or more, the contents in [] and () may be the same or different. 2. A resin particle prepared by polymerizing a radical polymerizable monomer composition containing a chain transfer agent represented by the following general formula (2) in an aqueous medium is subjected to salting-out / fusion in an aqueous medium. A toner for developing an electrostatic latent image, which is obtained by performing Embedded image In the formula, Q is a polyvalent organic group, A ₂ is an alkylene group having 1 to 8 carbon atoms, Z is a chain transfer group, p and q are each 0 or 1, and p and q do not become 1 at the same time. , M is 2 to 20
When n is 2 or more, the contents in [] may be the same or different. 3. Salting-out / fusing resin particles prepared by polymerizing a radically polymerizable monomer composition containing a chain transfer agent represented by the general formula (1) in an aqueous medium in an aqueous medium. A method for producing a toner for developing an electrostatic latent image. 4. A resin particle prepared by polymerizing a radically polymerizable monomer composition containing a chain transfer agent represented by the general formula (2) in an aqueous medium, is subjected to salting out / fusion in an aqueous medium. A method for producing a toner for developing an electrostatic latent image. 5. A composition in which a colorant is dispersed in a radically polymerizable monomer composition containing the chain transfer agent represented by the general formula (1), and the composition is obtained by suspension polymerization in an aqueous medium. A toner for developing an electrostatic latent image. 6. A composition in which a colorant is dispersed in a radically polymerizable monomer composition containing a chain transfer agent represented by the general formula (2), and the composition is obtained by suspension polymerization in an aqueous medium. A toner for developing an electrostatic latent image. 7. A composition in which a colorant is dispersed in a radical polymerizable monomer composition containing the chain transfer agent represented by the general formula (1) is subjected to suspension polymerization in an aqueous medium. A method for producing an electrostatic latent image developing toner. 8. A composition in which a colorant is dispersed in a radically polymerizable monomer composition containing the chain transfer agent represented by the general formula (2) is subjected to suspension polymerization in an aqueous medium. A method for producing an electrostatic latent image developing toner. 9. A resin obtained by polymerizing a radically polymerizable monomer composition containing a chain transfer agent represented by the general formula (1) in an aqueous medium and colorant particles, and obtained by coagulation. A toner for developing an electrostatic latent image, obtained by fusing the secondary particles obtained. 10. A resin obtained by polymerizing a radically polymerizable monomer composition containing the chain transfer agent represented by the general formula (2) in an aqueous medium and colorant particles, and obtained by coagulation. A toner for developing an electrostatic latent image, obtained by fusing the secondary particles obtained. 11. A resin obtained by polymerizing a radically polymerizable monomer composition containing the chain transfer agent represented by the general formula (1) in an aqueous medium and colorant particles, and obtained by coagulation. A method for producing a toner for developing an electrostatic latent image, comprising fusing the secondary particles obtained. 12. A resin obtained by polymerizing a radically polymerizable monomer composition containing the chain transfer agent represented by the general formula (2) in an aqueous medium and a colorant particle, and obtained by coagulation. A method for producing a toner for developing an electrostatic latent image, comprising fusing the secondary particles obtained. 13. An image which is visualized using the toner for developing an electrostatic latent image according to any one of claims 1, 2, 5, 6, 9 and 10, and an image transferred on a recording material is thermally treated. An image forming method comprising fixing. 14. An image which is visualized using the electrostatic latent image developing toner according to claim 1, and is transferred to a recording material by heat. An image forming apparatus characterized by fixing.