JP2003262980A - Toner, image forming method and process cartridge - Google Patents

Abstract

(57) [Problem] To provide a toner which is excellent in fog suppression, density stability and transferability, has less contamination on a toner carrier and a toner regulating portion, and gives a high quality image. SOLUTION: In the toner having toner particles containing at least a binder resin, a colorant and a vinyl copolymer and inorganic fine powder mixed with the toner particles, i) the toner has an average circularity of 0. Ii) the vinyl copolymer is at least the following general formula (1): (Wherein, R ₁ is a hydrogen atom or a methyl group, R ₂ and R ₃ are a hydrogen atom, an alkyl group which can be substituted with a substituent excluding an acid group,
Or a copolymer obtained by copolymerization of an amide group-containing vinyl monomer and a carboxyl group-containing vinyl monomer represented by the formula (1), wherein R ₂ and R ₃ are combined to form a heterocyclic ring together with a nitrogen atom). I do.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a toner used in a recording method using an electrophotographic method, an electrostatic recording method, an electrostatic printing method, a toner jet recording method, an image forming method using the toner, and Regarding process cartridge.

[0002]

2. Description of the Related Art The electrophotographic method generally utilizes a photoconductive material, forms an electrostatic charge image on a photosensitive member by various means, and then develops the electrostatic charge image with a toner, and if necessary, After transferring the toner image to a transfer material such as paper, heat,
The toner image is obtained by fixing with pressure, heat and pressure, or solvent vapor.

The developing methods applied to these electrophotographic methods and the like are roughly classified into a dry developing method and a wet developing method. The former is further divided into a method using a two-component developer and a method using a one-component developer.

As the toner applied to these dry developing methods, for example, a toner in which a colorant is dispersed in a binder resin is used.
Particles finely pulverized to about 15 μm are used as toner. As a toner that is a one-component developer, a toner containing magnetic fine particles as a colorant is used. Further, in the two-component developer, a toner containing carbon black, a pigment or the like as a colorant and carrier particles such as iron powder or magnetic ferrite particles are mixed and used.

In any of the developing type toners, it is necessary to charge the toner particles positively or negatively depending on the polarity of the electrostatically charged image to be developed.

In order to impart an electric charge to the toner particles, the triboelectrification property of the binder resin of the toner can be used.
In this case, the charge amount of the toner particles is small, the developed image has a low image density, is easily fogged, and becomes unclear.

Therefore, in order to impart a desired triboelectric chargeability to the toner, a dye, a pigment or a polymer compound is added as a charge control agent, and the positive charge control agent is, for example, a nigrosine dye or an azine type charge control agent. Dyes, copper phthalocyanine pigments, quaternary ammonium salts, etc. are used. As the negatively chargeable charge control agents, monoazo dye organometallic compounds, salicylic acid, naphthoic acid, dicarboxylic acid organometallic compounds, etc. are used. Since the above-mentioned charge control agents are often colored and may cause problems in color reproducibility when used for color toners, charge control resins that are polymer compounds that are almost colorless or have little coloring are Attention has been paid.

In Japanese Patent Application Laid-Open No. 63-184762, the binder resin is composed of a copolymer of styrene and / or α-methylstyrene and an alkyl (meth) acrylate, and styrene and / or α-methylstyrene and 2 A toner containing a copolymer with acrylamido-2-methylpropanesulfonic acid is disclosed.

Japanese Unexamined Patent Publication No. 2-167565 discloses a toner containing a charge control resin composed of a sulfonic acid group-containing acrylamide monomer and a vinyl monomer, and a charge control agent other than this.

JP-A-8-123096 discloses a toner containing a copolymer of a charge control agent containing an iron element, a styrene / acrylic monomer and a sulfonic acid-containing acrylamide monomer. There is.

In Japanese Patent Laid-Open No. 2000-305318,
A toner containing a polymer having a sulfonic acid group such as 2-acrylamido-2-methylpropanesulfonic acid is disclosed.

When the above polymer compound is used as a charge control agent, the sulfonic acid group-containing monomer component such as 2-acrylamido-2-methylpropanesulfonic acid contained in the polymer compound has high hydrophilicity. In addition, the affinity of the toner having hydrophobicity with the binder resin becomes lower than that. Therefore, when the material forming the toner particles, such as the binder resin, the polymer compound or the release agent, is released from the toner, the toner carrier and the toner regulating portion are contaminated, which causes an image defect.

JP-A-9-166887 and JP-A-20
No. 01-305793 discloses a specific carboxylic acid monomer (succinic acid monohydroxyethyl methacrylate).
A toner containing a copolymer with a styrene / acrylic monomer having the above is disclosed.

When the above copolymer is contained, the charge imparting property is insufficient and it is difficult to use it as a toner. Therefore, it is necessary to use a conventionally known charge control agent together as described in JP-A-2001-305793.

On the other hand, the toner image formed on the photoconductor in the developing step is transferred to the recording material in the transfer step, but the transfer residual toner in the image area and the fog toner in the non-image area remaining on the photoconductor are cleaned. The toner is stored in the waste toner container after being cleaned in the process. For this cleaning step, conventionally blade cleaning, fur brush cleaning, roller cleaning, etc. have been used. From the viewpoint of the apparatus, the size of the apparatus is inevitably increased due to the provision of such a cleaning apparatus, which has been a bottleneck when aiming to make the apparatus compact. Further, from the viewpoint of ecology, a system with less waste toner is desired in terms of effective utilization of toner, and a toner with high transfer efficiency and less fog is required.

Regarding the transfer efficiency, when the circularity (or sphericity) of the toner is low, the area where the toner comes into contact with the drum becomes large, and the unevenness becomes large, and the electric charge is concentrated at the edge portion, which corresponds to that portion. It is widely known that the deterioration of the releasability from the drum due to the increase of the image force generated as a result deteriorates. That is, in order to improve the transfer efficiency, it is necessary to increase the circularity of the toner.

In order to increase the circularity of the toner, the method of achieving it depends on the method of manufacturing the toner. The commercially available toner production methods are roughly classified into a pulverization method and a polymerization method. In the pulverization method, a binder resin, a colorant and the like are melt mixed, uniformly dispersed, pulverized by a fine pulverizer and classified by a classifier to produce a toner having a desired particle size. The toner obtained by the pulverization method has irregularities because the surface of the toner is a fracture surface caused by the pulverization due to the manufacturing method. Therefore, it is not possible to sufficiently increase the circularity only by pulverizing, and it becomes possible to make the particles spherical by a surface modification treatment such as mechanical impact or heat treatment as a post-treatment step. Further, the polymerization method is a method in which the resin particles and an associative aggregation toner for associating and aggregating the resin particles and the colorant, the release agent and the like into a desired particle diameter in an aqueous medium containing the emulsion-polymerized resin particles as the binder resin component are combined. Droplets having a desired particle size due to shearing force in a water-based medium of a polymerizable monomer composition in which a colorant, a release agent, a polymerization initiator, etc. are dispersed and dissolved in a polymerizable monomer serving as a resin component. 2 of the suspension polymerization toner that undergoes suspension polymerization after
There are different manufacturing methods. The associative aggregation toner also has unevenness on the surface due to its manufacturing method, but the toner after aggregation is heated as a post-treatment step, or seed polymerization is performed by newly adding a polymerizable monomer composition. Sphericalization is possible by the surface modification treatment in the subsequent process such as. Since the suspension polymerized toner is polymerized in droplets, its shape is closer to a true sphere than other manufacturing methods, and there are few irregularities, so a toner with high circularity can be obtained without requiring a post-treatment step. .

Therefore, the suspension polymerization method requires a smaller number of steps in order to obtain a toner having a high circularity.

[0019]

SUMMARY OF THE INVENTION An object of the present invention is to provide a toner which solves the above problems.

More specifically, an object of the present invention is to provide a toner which is excellent in fog suppression and density stability.
Further, the present invention provides a toner, an image forming method, and a process cartridge which are excellent in transferability, have less contamination on a toner carrier and a toner regulating portion, and give a high-quality image.

[0021]

The present invention provides a toner having toner particles containing at least a binder resin, a colorant and a vinyl copolymer, and a toner having an inorganic fine powder mixed with the toner particles. ) The toner has an average circularity of 0.940 or more, and ii) the vinyl-based copolymer has at least the following general formula (1):

[0022]

[Chemical 4] (In the formula, R ₁ is a hydrogen atom or a methyl group, R ₂ and R ₃ are a hydrogen atom, an alkyl group substitutable with a substituent excluding an acid group,
Or a copolymer obtained by copolymerizing an amide group-containing vinyl monomer represented by (an organic group in which R ₂ and R ₃ are bonded to form a heterocycle with a nitrogen atom) and a carboxyl group-containing vinyl monomer. Regarding toner.

The present invention also includes a developing step of developing an electrostatic charge image carried on an image carrier for carrying an electrostatic charge image with toner to form a toner image; forming on the image carrier. An image forming method including a transfer step of transferring the formed toner image onto a recording material with or without an intermediate transfer member; and a fixing step of heating and fixing the toner image transferred onto the recording material onto the recording material. In the above, the toner is the toner having the above configuration, and relates to an image forming method.

Further, according to the present invention, an electrostatic latent image formed on a photoreceptor is transferred to visualize a toner to form a toner image, and the toner image is transferred to a transfer material to form an image. A process cartridge used in an apparatus and configured to be detachable from the apparatus, comprising a photoconductor, a charging unit for charging the photoconductor, and a latent image formation for forming an electrostatic latent image on the photoconductor. At least one unit selected from a means, a transfer unit that transfers the toner image to the recording material, and a cleaning unit that removes the toner remaining on the photoconductor after the toner image is transferred to the transfer material, A process cartridge, which is integrally supported with a developing unit that develops an electrostatic latent image formed on the photoconductor with toner to form a toner image, and the toner is the toner having the above configuration. On di.

According to the present invention, the electrostatic latent image formed on the photoconductor is transferred to visualize the toner to form a toner image, and the toner image is transferred to a transfer material to form an image. A process cartridge used in an apparatus and configured to be detachable from the apparatus, comprising a photoconductor, a charging unit for charging the photoconductor, and a latent image formation for forming an electrostatic latent image on the photoconductor. Means and a transfer means for transferring the toner image to the recording material, and at least one means for developing the electrostatic latent image formed on the photoconductor with toner to form a toner image. A process cartridge, which is integrally supported, collects the toner remaining on the photoconductor after the toner image is transferred to the transfer material by the developing means, and the toner is the toner having the above-mentioned configuration. To.

[0026]

BEST MODE FOR CARRYING OUT THE INVENTION
As a result of diligent research on a toner that has excellent density stability and transferability, has little contamination on the toner carrier and the toner regulating member, and can obtain a high-quality image, a vinyl-based copolymer containing a monomer having a specific structure In the toner containing coalescence,
Further, it has been found that by satisfying a certain degree of circularity, good image quality can be obtained without causing the above-mentioned problems, and the present invention has been completed.

That is, the amide group-containing vinyl monomer represented by the general formula (1) and the carboxyl group-containing vinyl monomer which contribute to at least the charge controllability in the vinyl-based copolymer are simultaneously contained in the structure, and By adjusting the polymerization ratio and adjusting the acid value, glass transition temperature, and molecular weight of the vinyl-based copolymer to a specific range and setting the toner shape to a certain value or more, a high-quality image can be stably obtained. I found that

The toner of the present invention will be described in detail below.

(Vinyl-based Copolymer) In the toner of the present invention, the vinyl-based copolymer has at least the following general formula (1).

[0030]

[Chemical 5] (In the formula, R ₁ is a hydrogen atom or a methyl group, R ₂ and R ₃ are a hydrogen atom, an alkyl group substitutable with a substituent excluding an acid group,
Alternatively, it is a copolymer obtained by copolymerizing an amide group-containing vinyl monomer and an carboxyl group-containing vinyl monomer represented by (an organic group in which R ₂ and R ₃ are combined to form a heterocycle with a nitrogen atom).

Examples of the amide group-containing vinyl monomer represented by the general formula (1) include (meth) acrylamide;
N-substituted (meth) acrylamides such as N, N-dimethyl (meth) acrylamide, N-methyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-methylol (meth) acrylamide; N- (meth)
Acryloylmorpholine, N- (meth) acryloylpyrrolidone, N- (meth) acryloylpiperidine, N-
Contains a (meth) acryloylpyrrolidine, N- (meth) acryloyl-4-piperidone and other cyclic structures (meth)
Examples include acrylamide. One of these may be used, or two or more may be used in combination.

As the carboxyl group-containing vinyl monomer, for example, maleic acid, maleic acid half-esterified product, fumaric acid, fumaric acid half-esterified product, itaconic acid, itaconic acid half-esterified product, crotonic acid, cinnamon bark Acids and the like can be used, but a carboxyl group-containing vinyl monomer represented by the general formula (2) or (3) is preferable because the dispersed state in the binder resin can be easily adjusted.

[0033]

[Chemical 6] (In the formula, R ₄ is a hydrogen atom or a methyl group, R ₅ is a carbon atom of 2
~ 6 alkylene group, n is an integer of 0-10, X is a hydrogen atom, an alkali metal, an alkaline earth metal or a quaternary ammonium group)

[0034]

[Chemical 7] (In the formula, R₆Is a hydrogen atom or a methyl group, R₇Has 2 carbon atoms
~ 4 alkylene groups, R ₈Is an ethylene group, a vinylene group,
1,2-cyclohexylene group, phenylene group, X is hydrogen
Atom, alkali metal, alkaline earth metal or quaternary amine
Monium group)

Examples of the monomer of the general formula (2) include (meth) acrylic acid, (meth) acrylic acid dimer, and ω-carboxy-polycaprolactone mono (meth).
Examples of the monomer of the general formula (3) include monohydroxyethyl succinate (meth) acrylate, monohydroxyethyl maleate acrylate, monohydroxyethyl fumarate acrylate, and phthalate. Examples thereof include acid monohydroxyethyl (meth) acrylate and 1,2-dicarboxycyclohexane monohydroxyethyl (meth) acrylate.

One of these may be used, or 2
You may use together 1 or more types.

In the toner of the present invention, the copolymer obtained by copolymerizing the amide group-containing vinyl monomer represented by the general formula (1) and the carboxyl group-containing vinyl monomer is the monomer and the monomer copolymerizable with the monomer. The copolymerizable monomer may be styrene; α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene,
p-methylstyrene, 2,4-dimethylstyrene, p-
n-butyl styrene, p-tert-butyl styrene,
Styrene derivatives such as pn-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene, pn-dodecylstyrene, p-methoxystyrene and p-phenylstyrene; methyl. Acrylate, ethyl acrylate, n-propyl acrylate, iso-propyl acrylate, n-butyl acrylate, iso-butyl acrylate, ter
t-butyl acrylate, n-amyl acrylate, n
-Hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, n-nonyl acrylate, cyclohexyl acrylate, benzyl acrylate, dimethyl phosphate ethyl acrylate,
Acrylic monomers such as diethyl phosphate ethyl acrylate, dibutyl phosphate ethyl acrylate, 2-benzoyloxyethyl acrylate; methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, iso-propyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, tert-butyl methacrylate, n-amyl methacrylate, n-hexyl methacrylate, 2-
Methacrylic monomers such as ethylhexyl methacrylate, n-octyl methacrylate, n-nonyl methacrylate, diethyl phosphate ethyl methacrylate, dibutyl phosphate ethyl methacrylate; methylene aliphatic monocarboxylic acid ester; vinyl acetate, vinyl propionate, vinyl butyrate, benzoic acid Vinyl, vinyl esters such as vinyl formate; vinyl methyl ether,
Examples thereof include vinyl ethers such as vinyl ethyl ether and vinyl isobutyl ether; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and vinyl isopropyl ketone. One of these may be used, or two or more of them may be used in combination. Among them, styrene is inexpensive, has good copolymerizability with other vinyl monomers, and has a Tg of the copolymer. Is preferable because it can be easily adjusted.

In the toner of the present invention, when a copolymer of an amide group-containing vinyl monomer represented by the general formula (1) and a carboxyl group-containing vinyl monomer and the above-mentioned monomer is used as the vinyl-based copolymer, Formula (1)
The copolymerization amount of the amide group-containing vinyl monomer and the carboxyl group-containing vinyl monomer represented by
It may be 0% by mass, but is preferably 2 to 15% by mass.
If the copolymerization amount of each monomer is less than 0.2% by mass, the image density in a high humidity environment may decrease, and if it exceeds 20% by mass. Fogging tends to increase, which is not preferable. Also,
If the amide group-containing vinyl monomer and the carboxyl group-containing vinyl monomer represented by the general formula (1) do not exist at the same time, it is impossible to maintain a suitable charge amount of the toner in each environment.

The toner of the present invention is charged by the interaction between the amide group-containing vinyl monomer represented by the general formula (1) and the carboxyl group-containing vinyl monomer in the vinyl-based copolymer, and thus the copolymerization thereof is carried out. The chargeability changes depending on the ratio. The mass ratio of the vinyl monomer containing an amide group to the vinyl monomer containing a carboxyl group is 1: 5 to 3: 1.
However, it is preferably 1: 4 to 2:
1, more preferably 1: 3 to 1: 1. In both cases where the copolymerization ratio exceeds 1: 5 and a large amount of carboxyl group-containing vinyl monomers are copolymerized, and when the copolymerization ratio exceeds 3: 1 and a large amount of amide group-containing vinyl monomers are copolymerized, The chargeability of the toner tends to decrease and the distribution of charge amount tends to spread.

In the toner of the present invention, the vinyl-based copolymer has an acid value of 5 to 50 mgKOH / g, preferably 10 to 40 mgKOH / g. When the acid value of the vinyl-based copolymer is less than 5 mgKOH / g, the rise of charging of the toner may be poor, and when the acid value is more than 50 mgKOH / g, even at room temperature and low humidity environment. There is a case where the charge becomes low and the image quality is deteriorated, which is not preferable.

In the toner of the present invention, the vinyl copolymer may have a weight average molecular weight (Mw) of 2,000 to 100,000, preferably 5,000 to 50,000.
More preferably, Mw is 10,000 to 50,000. If M
In any case where w is less than 2000 and Mw is more than 100,000, it is difficult and unfavorable to make the state of the vinyl copolymer in the binder resin suitable for the present invention.

In the toner of the present invention, the glass transition temperature (Tg) of the vinyl-based copolymer may be 50 to 120 ° C, preferably 60 to 100 ° C. Tg
Is less than 50 ° C., the vinyl copolymer is apt to be fused to the toner carrier, and if it is more than 120 ° C., the interaction with the binder resin is small, and the vinyl resin is easily released from the toner particles. It becomes easy to contaminate the toner carrier and the toner regulation portion.

In the toner of the present invention, the vinyl-based copolymer can be produced by various polymerization methods, but a preferable polymerization method is to use no bulk solvent or use a small amount of bulk solvent. In the case of manufacturing by a legal method or a solution polymerization method, methanol as a reaction solvent,
Known solvents such as ethanol, propanol, 2-propanol, propanone, 2-butanone, dioxane, toluene and xylene can be used alone or in combination.

In the toner of the present invention, various polymerization initiators can be used in the production of the vinyl-based copolymer. For example, 2,2'-azobis (4-methoxy-2) can be used. , 4-dimethylvaleronitrile),
2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2-methylpropionitrile), 2,2'-azobis (2-butyronitrile),
1,1'-azobis (cyclohexane-1-carbonitrile), dimethyl 2,2'-azobis (methylpropionate), 4,4'-azobis (4-cyanopentanoic acid), 2,2'- Azobis (2,2,4 pentane), 1,1′-azobis (1-acetoxy-1-
Phenyl ethane) and other azo polymerization initiators such as benzoyl peroxide, lauroyl peroxide, dicumyl peroxide, tert-butyl peroxycumene, di-tert-butyl peroxide Agents, especially 2,2'-
Azobis (2-butyronitrile), 4,4′-azobis (4-cyanopentanoic acid) and 1,1′-azobis (1-acetoxy-1-phenylethane) are preferably used.

The toner of the present invention contains the vinyl-based copolymer in an amount of 0.1 to 20 parts by weight, preferably 0.2 to 10 parts by weight, based on 100 parts by weight of the binder resin. is there. If the content is less than 0.1 parts by mass, the charge amount is insufficient, and if it is more than 20 parts by mass, the charge amount becomes uneven, and in any case, especially in a high humidity environment. It is not preferable because it causes deterioration of image quality after being left underneath.

(Average Circularity) In the toner of the present invention,
The average circularity is 0.940 to obtain high quality images.
The above and the presence of the vinyl copolymer are indispensable.

The reason will be described below. Many general charge control agents are compounds having a complex or salt structure, and highly polar sites contribute to the charging property. However, since the vinyl-based copolymer, which is an essential component of the toner of the present invention, has a structure having a low-polarity charging site composed of an amide bond and a carboxyl group in the main skeleton of the vinyl-based resin, conventional charge control It shows a higher resistance than the agent. Therefore, it is hardly affected by moisture, and the environmental dependence of the charge amount is small.

Since the vinyl-based copolymer has a high compatibility with the binder resin of the toner, it does not exist in the toner particles as fine particles like a general charge control agent, and molecules are present on the surface of the toner particles. It is thought to exist at or near the level. Therefore, the release from the toner is suppressed, and the members involved in the charging of the toner are not contaminated. As a result, the triboelectric charging between the toner carrier and the toner regulating member is efficiently performed, the distribution of the charge amount is narrowed, and a high-quality image is obtained.

If the toner has a distorted shape with an average circularity of less than 0.940, not only the protrusions are overcharged due to friction, but also stress concentration on the protrusions causes the toner carrier and the toner regulating portion to be damaged. Accelerates pollution and deteriorates image quality with long-term use.

As described above, due to the characteristics peculiar to the vinyl copolymer and the toner shape having the average circularity of 0.940 or more,
It is possible to suppress the spread of the charge amount distribution and maintain high image quality for a long period of time.

The toner of the present invention preferably has an average circularity of 0.950 or more and a mode circularity of 0.95 or more described later, and an average circularity of 0.970 or more, in order to obtain the above effects. It is more preferable that the mode circularity is 0.99 or more.

(Average Particle Size) The toner of the present invention has a weight average particle size of 3 to 10 μm in order to further improve the image quality and faithfully develop finer latent image dots.
Is preferable, and more preferably 4 to 8 μm. In the case of a toner having a weight average particle diameter of less than 3 μm, the surface area of the entire toner increases, and the distribution of the amount of charge after leaving in a high humidity environment tends to widen. Is decreased, and it becomes difficult to uniformly charge individual toner particles, resulting in fog and transferability tending to deteriorate, and is likely to cause uneven unevenness of the image in addition to scraping and fusing. It is not preferable for the toner used. Further, when the weight average particle diameter of the toner exceeds 10 μm, scatter easily occurs in characters and line images, and it is difficult to obtain high resolution. Furthermore, as the resolution of the apparatus becomes higher, the reproduction of one dot tends to deteriorate with toner of 8 μm or more.

(Charge Control Agent) In the toner of the present invention,
The vinyl copolymer can also be used in combination with other known charge control agents as described in the prior art. For example, other charge control agents include organic metal complexes, metal salts or chelate compounds. Specific examples include a monoazo metal complex, an acetylacetone metal complex, a hydroxycarboxylic acid metal complex, a polycarboxylic acid metal complex, and a polyol metal complex. Other examples include carboxylic acid metal salts, carboxylic acid anhydrides, carboxylic acid derivatives such as carboxylic acid esters, condensation products of aromatic compounds, bisphenols, and phenol derivatives such as calixarene.

In the toner of the present invention, an organoaluminum compound is preferably used as a charge control agent together with the vinyl copolymer, and includes aromatic diols, aromatic hydroxycarboxylic acids, aromatic monocarboxylic acids and aromatic polycarboxylic acids. A compound obtained by reacting an aluminum compound with an aluminum compound (for example, an organoaluminum complex compound (complex, complex salt))
Or an organoaluminum salt), preferably an organoaluminum compound consisting of 2 mol of 3,5-di-tert-butylsalicylic acid and 1 mol of an aluminum atom. The organoaluminum compound is contained in the toner as an aluminum element in an amount of 0.0 to 100 parts by mass of the binder resin.
The content is 2 to 2 parts by mass, preferably 0.
The amount is 05 to 1.5 parts by mass, more preferably 0.1 to 1 part by mass. When the content of the organoaluminum compound contained in the toner is less than 0.02 part by mass as the aluminum element, not only the high temperature offset resistance of the toner is deteriorated but also the adhesion of the toner to the fixing member is deteriorated. When the amount is more than 2 parts by mass, the low temperature fixing property of the toner may be deteriorated, which is not preferable.

In the toner of the present invention, when the binder resin has an acid value, the organoaluminum compound is a kind of presumed to be an exchange reaction between the carboxyl group of the binder resin and the ligand during the toner manufacturing process. A complexing reaction (hereinafter referred to as "complexing reaction with aluminum") is preferable,
The dispersion state of the vinyl copolymer and the dispersion state of the wax suitable for the toner of the present invention can be achieved. In this case, the organoaluminum compound is an aromatic diol,
It is presumed that it does not exist as an aluminum complex or complex salt in which aromatic hydroxycarboxylic acid or aromatic carboxylic acid is coordinated.

In the toner of the present invention, an organic iron compound can be added as a charge control agent other than the organic aluminum compound which is preferably used.

The organic iron compound is a compound obtained by reacting a monoazo compound represented by the following formulas (4) to (7) with an iron compound, and the organic iron compound is used as iron element in the toner and 100 mass% of the binder resin. It is contained in an amount of 0.02 to 2 parts by mass, preferably 0.05 to 1.
5 parts by mass, more preferably 0.1 to 1 part by mass.
The organic iron compound contained in the toner is 0.0 as an iron element.
If it is less than 2 parts by mass, the stability of the image density of the toner in a high temperature and high humidity environment may occur, and if it is more than 2 parts by mass, the toner in a room temperature and low humidity environment may be present. However, there is a case where a problem occurs in the image density stability of 1.

[0058]

[Chemical 8]

(Wax) The toner of the present invention preferably contains a release agent in an amount of 0.5 to 50 parts by mass based on 100 parts by mass of the binder resin. Examples of the binder resin include various waxes, which will be described later.

The toner image transferred onto the transfer material is then transferred to
It is fixed on the transfer material by heat, pressure, or other energy, and a semi-permanent image is obtained. At this time, heat roll type fixing and film type fixing are commonly used.

As described above, an extremely high-definition image can be obtained by using toner particles having a weight average particle diameter of 10 μm or less, but toner particles having a small particle diameter are obtained when a transfer material such as paper is used. Then, it gets into the gaps between the fibers of the paper, the heat is not sufficiently received from the heat fixing roller, and the low temperature offset is likely to occur. However, in the toner according to the present invention, by containing an appropriate amount of the releasing agent, it becomes possible to achieve both high resolution and offset resistance.

Examples of the releasing agent that can be used in the toner according to the present invention include petroleum waxes such as paraffin wax, microcrystalline wax, petrolactam and derivatives thereof, montan wax and derivatives thereof, hydrocarbon wax by the Fischer-Tropsch method, and Derivatives thereof, polyolefin waxes represented by polyethylene and derivatives thereof, natural waxes such as carnauba wax and candelilla wax and derivatives thereof, and the like. These derivatives include oxides, block copolymers with vinyl monomers, and graft modified products. Further, higher aliphatic alcohols, fatty acids such as stearic acid and palmitic acid, or compounds thereof, acid amide wax, ester wax, ketone, hydrogenated castor oil and its derivatives, vegetable wax, animal wax and the like can be mentioned. Among these waxes, the endothermic peak in differential thermal analysis is 4
It is preferably from 0 to 110 ° C, more preferably from 45 to 90
What is ° C is preferred.

The content of the release agent used is preferably in the range of 0.5 to 50 parts by mass with respect to 100 parts by mass of the binder resin. If the content is less than 0.5 parts by mass, the effect of suppressing low-temperature offset is poor, and if it exceeds 50 parts by mass, long-term storability is deteriorated and dispersibility of other toner materials is deteriorated, resulting in toner fluidity. And deterioration of image characteristics.

The maximum endothermic peak temperature of the wax component is measured according to "ASTM D 3418-8". For the measurement, for example, Perkin Elmer DSC-7 is used. The melting point of indium and zinc is used to correct the temperature of the device detection unit, and the heat of fusion of indium is used to correct the amount of heat. An aluminum pan is used as a measurement sample, an empty pan is set as a control, and measurement is performed at a temperature rising rate of 10 ° C./min.

Further, the glass transition temperature (T
g) was taken as the Tg from the intersection of the baseline before the endothermic peak and the midline of the baseline after the endothermic peak and the rising curve from the DSC curve during the second temperature rise.

(Glass Transition Temperature) The toner of the present invention has a glass transition temperature (Tg) from the viewpoint of the storability of the toner.
Is 45 to 75 ° C, preferably 50 to 70 ° C. Tg
Is less than 45 ° C., the toner is likely to deteriorate in a high temperature atmosphere, and offset is likely to occur during fixing. Tg
Is more than 75 ° C., the fixing property tends to decrease, which is not preferable.

(Colorant) The toner of the present invention contains a colorant as an essential component for imparting coloring power.

The organic pigments or dyes preferably used in the present invention include the following.

As the organic pigment or organic dye as a cyan colorant, a copper phthalocyanine compound and its derivative, an anthraquinone compound, a basic dye lake compound and the like can be used. Specifically, C.I. I. Pigment Blue 1, C.I. I. Pigment Blue 7, C.I. I. Pigment Blue 15, C.I. I. Pigment Blue 15: 1, C.I.
I. Pigment Blue 15: 2, C.I. I. Pigment Blue 15: 3, C.I. I. Pigment Blue 15: 4
C. I. Pigment Blue 60, C.I. I. Pigment Blue 62, C.I. I. Pigment Blue 66 and the like.

Examples of organic pigments or organic dyes as magenta colorants include condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, perylene compounds. Is used. Specifically, C.I. I. Pigment Red 2,
C. I. Pigment Red 3, C.I. I. Pigment Red 5, C.I. I. Pigment Red 6, C.I. I. Pigment Red 7, C.I. I. Pigment Violet 19,
C. I. Pigment Red 23, C.I. I. Pigment Red 48: 2, C.I. I. Pigment Red 48: 3
C. I. Pigment Red 48: 4, C.I. I. Pigment Red 57: 1, C.I. I. Pigment Red 81:
1, C.I. I. Pigment Red 122, C.I. I. Pigment Red 144, C.I. I. Pigment Red 146,
C. I. Pigment Red 166, C.I. I. Pigment Red 169, C.I. I. Pigment Red 177, C.I.
I. Pigment Red 184, C.I. I. Pigment Red 185, C.I. I. Pigment Red 202, C.I. I.
Pigment Red 206, C.I. I. Pigment Red 2
20, C.I. I. Pigment Red 221, C.I. I. Pigment Red 254 and the like.

As the organic pigment or organic dye as the yellow colorant, compounds represented by condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds and allylamide compounds are used. Specifically, C.I. I. Pigment Yellow 12,
C. 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 62, C.I. I. Pigment Yellow 74, C.I. I.
Pigment Yellow 83, C.I. I. Pigment Yellow 93, C.I. I. Pigment Yellow 94, C.I. I. Pigment Yellow 95, C.I. I. Pigment Yellow 9
7, C.I. I. Pigment Yellow 109, C.I. I. Pigment Yellow 110, C.I. I. Pigment Yellow 1
11, C.I. I. Pigment Yellow 120, C.I. I. Pigment Yellow 127, C.I. I. Pigment Yellow 128, C.I. I. Pigment Yellow 129, C.I. I.
Pigment Yellow 147, C.I. I. Pigment Yellow 151, C.I. I. Pigment Yellow 154, C.I.
I. Pigment Yellow 168, C.I. I. Pigment Yellow 174, C.I. I. Pigment Yellow 175,
C. I. Pigment Yellow 176, C.I. I. Pigment Yellow 180, C.I. I. Pigment Yellow 18
1, C.I. I. Pigment Yellow 191, C.I. I. Pigment Yellow 194 and the like.

These colorants can be used alone or in the form of a mixture, or in the state of a solid solution. The colorant used in the toner of the present invention includes hue angle, saturation, lightness, light resistance,
It is selected from the viewpoints of OHP transparency and dispersibility in toner.

The colorant is added in an amount of 1 to 20 parts by mass based on 100 parts by mass of the binder resin.

As the black colorant, carbon black,
A magnetic material that is toned in black using the above yellow / magenta / cyan colorant is used.

In the present invention, when a toner is obtained by using a polymerization method, it is necessary to pay attention to the polymerization inhibitory property and the water phase transfer property of the colorant, and preferably surface modification such as polymerization inhibitory property is carried out. It is better to give a hydrophobic treatment with a substance that has no In particular, since many dyes and carbon black have a polymerization inhibitory property, caution is required when using them. As a preferred method of surface-treating a dye system,
A method of polymerizing a polymerizable monomer in the presence of these dyes in advance is mentioned, and the obtained colored polymer is added to the monomer system.

The carbon black may be treated in the same manner as the above-mentioned dye, or may be treated with a substance that reacts with the surface functional groups of the carbon black, such as polyorganosiloxane.

(Magnetic Material) When a magnetic material is used as the black colorant, unlike other colorants, it is used by adding 30 to 200 parts by mass to 100 parts by mass of the resin.

Examples of the magnetic substance include metal oxides containing elements such as iron, cobalt, nickel, copper, magnesium, manganese, aluminum and silicon. Of these, those containing iron oxide as a main component, such as ferrosoferric oxide and γ-iron oxide, are preferable. Further, from the viewpoint of controlling the toner chargeability, other metal elements such as silicon element or aluminum element may be contained. These magnetic particles are B-based by the nitrogen adsorption method.
ET specific surface area of ² to 30 m ² / g, especially 3 to 28 m ² / g
Is preferable, and magnetic powder having a Mohs hardness of 5 to 7 is more preferable.

The amount of magnetic material is 3 with respect to 100 parts by mass of the binder resin.
0 to 200 parts by mass, preferably 40 to 200 parts by mass, and more preferably 50 to 150 parts by mass. If the amount is less than 30 parts by mass, the coloring power may be insufficient, or in a developing device that uses magnetic force for toner transportation, the transportability may be insufficient and unevenness may occur in the developer layer on the toner carrier, resulting in image unevenness. Further, the image density tends to decrease due to the increase in the developer tribo. On the other hand, if the amount exceeds 200 parts by mass, the fixing property tends to be problematic.

The magnetic characteristics of the magnetic toner according to the present invention include a magnetic field of 79.6 kA / m (1000 Oersted).
Strength of 10 to 50 Am ² / kg (emu
/ G) is essential. 10 Am ² / kg (e
If it is less than mu / g), it is difficult to sufficiently improve the fog property even if the triboelectric charging property can be improved by adding the toner shape and the polar polymer, and further, 50 Am ² / kg (em
If it exceeds u / g), the developability also tends to decrease.

The magnetic properties of the magnetic powder and the magnetic toner are as shown in the vibration type magnetometer (VSM-3S-1 manufactured by Toei Industry Co., Ltd.).
5) was used.

The preferable particle size of the magnetic powder (iron oxide) used in the magnetic toner of the present invention is 0.1 to 0.3 μm in volume average particle size, and 0.03 μm or more to 0.
The number% of particles less than 1 μm is preferably 40% or less.

When an image is obtained from a magnetic toner using a magnetic powder having an average particle size of less than 0.1 μm, the tint of the image shifts to reddish, the blackness of the image becomes insufficient, and in a halftone image, Generally, it is not preferable because the tendency to feel reddish color becomes stronger. Further, when such a toner is used for a color image, it is not preferable because it is difficult to obtain color reproducibility and the shape of the color space tends to be distorted. Further, since the surface area of the magnetic powder is increased, the dispersibility is deteriorated and the energy required for manufacturing is increased, which is not efficient. Further, the density of the image to be obtained from the added amount of the magnetic powder may be insufficient, which is not preferable.

On the other hand, if the average particle diameter of the magnetic powder exceeds 0.3 μm, the mass per particle becomes large, so that the probability of exposure on the toner surface increases due to the difference in specific gravity with the binder during production, It is not preferable because the abrasion of the manufacturing apparatus may increase significantly and the sedimentation stability of the dispersion may decrease.

Further, in the toner, 0.
If the number% of particles having a size of 03 μm or more and less than 0.1 μm exceeds 40%, the surface area of the magnetic powder increases and the dispersibility decreases, and agglomerates easily occur in the toner, impairing the chargeability of the toner. However, it is preferably 40% or less because the possibility of lowering the coloring power increases. Further, if it is 30% or less, the tendency becomes smaller, and therefore it is more preferable.

Since the magnetic powder having a particle size of less than 0.03 μm receives a small stress due to the small particle size during the toner production, the probability of the powder appearing on the surface of the toner particles becomes low. Further, even if it is exposed on the surface of the particles, it hardly acts as a leak site and has substantially no effect. Therefore, in the present invention, attention is paid to particles having a size of 0.03 μm or more and less than 0.1 μm, and the number% thereof is defined.

Further, if the number of particles of more than 0.3 μm in the magnetic powder exceeds 10% by number, the coloring power tends to decrease and the image density tends to decrease, which is not preferable. More preferably, it is 5% by number or less.

In the present invention, it is preferable to use those in which the production conditions of the magnetic material are set so that the above-mentioned particle size distribution condition is satisfied, or the particle size distribution such as pulverization and classification is adjusted beforehand. As a classification method, for example,
A means using sedimentation separation such as centrifugation or thickener, or a means such as a wet classification device using a cyclone is suitable.

As a method for determining the particle size of the magnetic powder, the magnetic powder or the toner particles to be observed are sufficiently dispersed in the epoxy resin, and then cured in an atmosphere at a temperature of 40 ° C. for 2 days to obtain a cured product. As a sample on a thin piece by a microtome, a transmission electron microscope (TEM) at a magnifying power of 10,000 to 40,000 times shows 1 in the visual field.
It is preferable to observe 00 magnetic particles, determine the projected area thereof, and calculate the equivalent circle diameter of the obtained area to determine the volume average particle diameter. Furthermore, based on the result, 0.03 μm
The number% of particles above 0.1 μm and above 0.3 μm is calculated.

Such a magnetic powder may contain elements such as cobalt, nickel, copper, magnesium, manganese, and aluminum, and has iron oxide as a main component such as ferric tetroxide and γ-iron oxide. Yes, these may be used alone or in combination of two or more.

In the case of a magnetic toner, the toner of the present invention is preferably particles obtained by a polymerization method in order to achieve B / A and D / C described later.

Examples of the toner polymerization method include a direct polymerization method, a suspension polymerization method, an emulsion polymerization method, an emulsion association polymerization method, and a seed polymerization method. From the viewpoint of ease of taking, it is particularly preferable to manufacture by the suspension polymerization method. In this suspension polymerization method, a polymerizable monomer and a colorant (and optionally a polymerization initiator, a crosslinking agent, a charge control agent, and other additives) are uniformly dissolved or dispersed to form a monomer composition. After that, this monomer composition is added to a continuous layer (for example, an aqueous phase) containing a dispersion stabilizer.
The toner is dispersed in a suitable stirrer and simultaneously polymerized to obtain a toner having a desired particle size. The toner obtained by this suspension polymerization method (hereinafter, polymerized toner) is
Since the individual toner particle shapes are uniform, the distribution of the charge amount is relatively uniform, and thus high transferability is achieved.

Further, the core / shell structure in which the surface layer is formed by adding the polymerizable monomer and the polymerization initiator again to the fine particles obtained by suspension polymerization can be designed as necessary. .

However, even if the polymerized toner contains an ordinary magnetic substance, it is difficult to suppress the exposure of the magnetic substance from the particle surface. This is because the magnetic particles are generally hydrophilic and therefore tend to exist on the toner surface.The magnetic particles move randomly during stirring in a water solvent, and the surface of the suspended particles composed of the monomer is dragged to cause the shape of the particles. It is thought that this is due to the fact that is not easily distorted into a circular shape. In order to solve these problems, it is important to modify the surface characteristics of magnetic particles. Many proposals have been made for surface modification of magnetic materials used in polymerized toners. For example, JP-A-59
-200254, JP-A-59-200256, JP-A-59-200257, JP-A-59-2
Various silane coupling agent treatment techniques for magnetic materials have been proposed in Japanese Unexamined Patent Publication No. 24102 and the like.
No. 0 discloses a technique of treating magnetic particles containing elemental silicon with a silane coupling agent.

However, although the exposure of the magnetic substance from the surface of the toner particles is suppressed to some extent by these treatments, there is a problem that it is difficult to uniformly hydrophobize the magnetic substance surface. And the generation of non-hydrophobicized magnetic material particles cannot be avoided, and it is insufficient to completely suppress the exposure of the magnetic material.
In addition, as an example of using hydrophobized magnetic iron oxide, Japanese Patent Publication No. 60-
Japanese Patent No. 3181 proposes a toner containing magnetic iron oxide treated with alkyltrialkoxysilane. Although the addition of this magnetic iron oxide has certainly improved various electrophotographic characteristics of the toner, the surface activity of the magnetic iron oxide is originally small, and coalesced particles are generated at the treatment stage and the hydrophobicity is nonuniform. However, it is not always satisfactory, and further improvement is required for application to the image forming method of the present invention. Furthermore, use a large amount of processing agents,
When a highly viscous treatment agent or the like is used, the degree of hydrophobicity is certainly increased, but particles are coalesced with each other and the dispersibility is deteriorated. A toner manufactured using such a magnetic material has non-uniform triboelectrification, which causes fog and poor transferability.

Therefore, in the magnetic material used in the toner of the present invention, when the particle surface is made hydrophobic, the magnetic material particles are dispersed in the aqueous medium so as to have a primary particle diameter, and the coupling agent is added. It is particularly preferable to use a method of treating the surface while decomposing. In this hydrophobic treatment method, coalescence between magnetic particles is less likely to occur than in the gas phase, and the electrostatic repulsion action between the magnetic particles due to the hydrophobic treatment works so that the magnetic particles are almost in the state of primary particles. The surface is treated.

The method of treating the surface of the magnetic substance while hydrolyzing the coupling agent in an aqueous medium does not require the use of a coupling agent such as chlorosilanes or silazanes that generate a gas. Up to now, magnetic particles can easily be united with each other in the gas phase, and a highly viscous coupling agent, which has been difficult to perform good treatment, can be used, and the effect of hydrophobizing is very large.

Examples of the coupling agent that can be used in the surface treatment of the magnetic material according to the present invention include silane coupling agents and titanium coupling agents.
A silane coupling agent is more preferably used and is represented by the following general formula (I). During _{R m -Si-Y n (I} ) [ wherein, R represents a Arukookishi group, m represents an integer of 1 to 3, Y is an alkyl group, vinyl group, glycidoxy group,
A hydrocarbon group such as a methacryl group is shown, and n is an integer of 1 to 3. ]

Specifically, vinyltrimethoxysilane,
Vinyltriethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, vinyltriacetoxysilane, methyltrimethoxysilane, methyltriethoxysilane, isobutyltrimethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, trimethylmethoxysilane, hydroxypropyritri Examples thereof include methoxysilane, phenyltrimethoxysilane, n-hexadecyltrimethoxysilane, and n-octadecyltrimethoxysilane.

In particular, the magnetic particles are preferably hydrophobized in an aqueous medium by using an alkyltrialkoxysilane coupling agent represented by the following general formula (II). During _{C p H 2p + 1 -Si- (} OC q H 2q + 1) 3 (II) [ wherein, p represents an integer of 2 to 20, q is an integer of 1-3. ]

When p in the above formula (II) is smaller than 2, the hydrophobic treatment becomes easy, but it is difficult to impart sufficient hydrophobicity, and the exposure of the magnetic particles from the toner particles is suppressed. Becomes difficult. If p is greater than 20, the hydrophobicity will be sufficient, but the coalescence of magnetic particles will increase, and it will be difficult to disperse the magnetic particles sufficiently in the toner, resulting in fogging and transferability. It becomes worse.

When q is larger than 3, the reactivity of the silane coupling agent is lowered and it becomes difficult to sufficiently hydrophobize the silane coupling agent.

Particularly, an alkyltrialkoxy in which p in the formula represents an integer of 2 to 20 (more preferably an integer of 3 to 15) and q represents an integer of 1 to 3 (more preferably an integer of 1 or 2). It is preferable to use a silane coupling agent.

The treatment amount is 0.05 to 20 parts by mass, preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the magnetic material.

Here, the aqueous medium is a medium containing water as a main component. Specifically, water itself as an aqueous medium, water with a small amount of a surfactant added, and water pH
Examples include those to which a regulator is added and those to which an organic solvent is added to water. The surfactant is not particularly limited, but it is preferable to use a nonionic surfactant such as polyvinyl alcohol. The surfactant is preferably added in an amount of 0.1 to 5 mass% with respect to water. Examples of pH adjusters include inorganic acids such as hydrochloric acid. Examples of the organic solvent include methanol and the like, and it is preferably added in an amount of 0 to 500 mass% with respect to water.

Stirring is carried out, for example, by a mixer having stirring blades (specifically, a high shearing force mixing device such as an attritor or a TK homomixer) so that the magnetic particles become primary particles in an aqueous medium. It is good to do enough.

(B / A) Next, the ratio (B / A) of the content (B) of the iron element to the content (A) of the carbon element existing on the surface of the magnetic toner particles will be described. When the toner of the present invention is magnetic toner particles, it contains at least magnetic iron oxide as a magnetic material. The magnetic toner has a ratio (B / A) of the iron element content (B) to the carbon element content (A) present on the surface of the magnetic toner particles measured by X-ray photoelectron spectroscopy. , Less than 0.001 is preferable. This ratio (B / A) is 0.0
It is more preferably less than 005, and even more preferably less than 0.0003.

In the toner of the present invention, it is preferable that the toner particles have a high charge amount, and for that purpose, it is preferable that the magnetic material that is a charge leak site is not exposed on the surface.

Normally, when a magnetic toner in which a magnetic material is exposed on the surface of toner particles is used, electric charge is released by the exposed magnetic material. If the charge is released before development, that is, if the charge amount is remarkably low, the non-image area is developed and image fog occurs. On the other hand, if the charge is released after development, it is not transferred from the image carrier to the transfer member and remains on the image carrier, which leads to deterioration of image quality such as voids in transfer, which is not preferable. However, as described above, (B / A) is 0.0
If the magnetic toner is less than 01, that is, the amount of exposed magnetic material on the surface of the toner particles is extremely low, low image fog,
It is possible to obtain a high-quality image that is faithful to the latent image.

Ratio (B / A) of iron element content (B) to carbon element content (A) present on the toner particle surface
Can be measured by performing surface composition analysis by ESCA (X-ray photoelectron spectroscopy) as follows.

(D / C) A special toner in which magnetic particles are contained only in a specific portion inside the particles is disclosed in JP-A-7-
It has already been disclosed in Japanese Patent Publication No. 209904. However, JP-A-7-209904 does not mention the disclosed average circularity of the toner. Further, when printing is performed with such a magnetic toner for a long period of time, particles containing a large amount of a magnetic substance and hard to develop, that is, toner particles having a large particle size, tend to remain, resulting in deterioration of image density and image quality, and further deterioration of fixability. Such a magnetic toner is not preferable because it is also connected.

As can be derived from the above description, the preferable dispersed state of the magnetic substance in the toner particles is a state in which the magnetic substance particles are present in the entire toner particles as uniformly as possible without aggregation. That is, the projected circle equivalent diameter of the magnetic toner
In a cross-sectional observation of the magnetic toner using a transmission electron microscope (TEM), a toner satisfying the relationship of D / C ≦ 0.02, where D is the minimum value of the distance between the magnetic substance and the toner particle surface. The fact that the number of particles is 50% or more is also one of the preferable embodiments for the magnetic toner of the present invention.

In the present invention, the projected area circle equivalent diameter of the magnetic toner is defined as C, and the minimum value of the distance between the magnetic particle surface and the toner particle surface in the cross-sectional observation of the magnetic toner using a transmission electron microscope (TEM). Where D is D / C
The number of toner particles satisfying the relationship of ≦ 0.02 or less is preferably 50% or more, more preferably 65% or more,
75% or more is more preferable.

The reason is as follows.

When the condition of the present invention is not satisfied, the toner particles have no magnetic particles at least outside the boundary line D / C = 0.02. If the particles as described above are assumed to be spherical, at least 11.5% of the space where the magnetic material does not exist is present on the surface of the toner particle when one toner particle is the entire space. In reality, the magnetic particles are not uniformly arranged at the closest position to form an inner wall inside the toner particles, and thus it is clear that the amount is 12% or more.

If the magnetic particles do not exist in such a space per one particle, the magnetic substance is biased inside the toner particles, and the possibility of aggregation of the magnetic substance is extremely increased. As a result, the coloring power is lowered. Although the specific gravity of the toner particles increases according to the content of the magnetic powder, the binder resin and the wax component are unevenly distributed on the surface of the toner particles. Therefore, even if a surface layer is provided on the outermost surface of the toner particles by some means, if stress is applied to the toner particles or the toner particles at the time of manufacturing the toner, fusion or deformation is likely to occur, and the handling at the time of manufacturing However, there is a possibility that the toner becomes complicated, the powder characteristics of the toner obtained by the deformation are distributed, the electrophotographic characteristics are adversely affected, and the blocking resistance during storage of the toner is deteriorated. In the particle structure where the toner particle surface is only the binder resin and wax, and the magnetic particles are unevenly distributed inside, the toner particles have a soft outside and a hard inside, so it is very easy to embed external additives, and toner durability is improved. Sex deteriorates.
The risk of causing such adverse effects increases.

If the number of particles satisfying D / C ≦ 0.02 is less than 50%, the above-mentioned adverse effects such as a decrease in coloring power, a deterioration in blocking resistance and a deterioration in durability tend to be remarkable. .

Therefore, in the present invention, the number of particles satisfying D / C ≦ 0.02 is preferably 50% or more.

(Manufacturing Method) As an example of a method for manufacturing the toner of the present invention, a manufacturing method by a suspension polymerization method will be described.

When the toner of the present invention is produced by the suspension polymerization method, the following are examples of the polymerizable monomer constituting the polymerizable monomer system used.

Examples of the polymerizable monomer include styrene-based monomers such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, p-ethylstyrene, methyl acrylate, and acrylic acid. Ethyl acetate, n-butyl acrylate, isobutyl acrylate, n-propyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, etc. Acrylic esters, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate,
Examples thereof include methacrylic acid esters such as 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, and other monomers such as acrylonitrile, methacrylonitrile, and acrylamide.

These monomers may be used alone or in combination. Among the above-mentioned monomers, it is preferable to use styrene or a styrene derivative alone or in combination with other monomers, from the viewpoint of developing characteristics and durability of the toner.

In the production of the polymerized toner according to the present invention, a resin may be added to the monomer system for polymerization.

For example, since the monomer is water-soluble, it cannot be used because it dissolves in an aqueous suspension to cause emulsion polymerization and thus cannot be used. A hydrophilic functional group such as an amino group, a carboxylic acid group, a hydroxyl group, a glycidyl group or a nitrile group is contained. When it is desired to introduce the monomer component of the above into the toner, a random copolymer of these and a vinyl compound such as styrene or ethylene, a block copolymer or a graft copolymer, etc., in the form of a copolymer, or a polyester, It can be used in the form of a polycondensate such as polyamide, a polyaddition polymer such as polyether, polyimine and the like. When such a high molecular weight polymer containing a polar functional group is coexisted in the toner, the wax component is phase-separated, the inclusion becomes stronger, and the toner having good offset resistance, blocking resistance, and low temperature fixing property is obtained. Obtainable.

Further, a resin other than the above may be added to the monomer system for the purpose of improving the dispersibility and fixing property of the material, the image characteristics and the like. Examples of the resin used include polystyrene and polyvinyltoluene. Homopolymers of styrene and its substitutes; styrene-propylene copolymers, styrene-vinyltoluene copolymers, styrene-
Vinyl naphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-dimethylaminoethyl acrylate copolymer Polymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-dimethylaminoethyl methacrylate copolymer, styrene-vinyl methyl ether copolymer, Styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-maleic acid copolymer, styrene-maleic acid ester copolymer, etc. Styrene-based copolymer; polymethy Methacrylate, polybutyl methacrylate, polyvinyl acetate, polyethylene, polypropylene, polyvinyl butyral, silicone resin, polyester resin, polyamide resin, epoxy resin, polyacrylic acid resin, rosin, modified rosin, terpene resin, phenol resin, aliphatic or alicyclic Group hydrocarbon resins, aromatic petroleum resins and the like can be used alone or in combination.

The amount of addition of these resins is 10
1 to 20 parts by mass is preferable with respect to 0 parts by mass. If it is less than 1 part by mass, the effect of addition is small, while if it exceeds 20 parts by mass, it becomes difficult to design various physical properties of the polymerized toner.

Further, when a polymer having a molecular weight different from the molecular weight range of the toner obtained by polymerizing the monomer is dissolved and polymerized in the monomer, a toner having a wide molecular weight distribution and high offset resistance can be obtained. Obtainable.

As the polymerization initiator used in the production of the polymerized toner according to the present invention, a polymerization initiator having a half-life of 0.5 to 30 hours at the time of the polymerization reaction is 0.5 to 100 parts by mass of the polymerizable monomer. When the polymerization reaction is carried out with an addition amount of ˜20 parts by mass, a polymer having a maximum in the molecular weight of 10,000 to 100,000 can be obtained, and the toner can have desired strength and proper melting characteristics. Examples of the polymerization initiator include 2,2′-azobis- (2,4-dimethylvaleronitrile) and 2,2′-
Azo such as azobisisobutyronitrile, 1,1′-azobis (cyclohexane-1-carbonitrile), 2,2′-azobis-4-methoxy-2,4-dimethylvaleronitrile, azobisisobutyronitrile -Based or diazo-based polymerization initiators; benzoyl peroxide, t-butyl peroxy 2-ethylhexanoate, t-butyl peroxypivalate, t-butyl peroxyisobutyrate, t-butyl peroxy neodecanoate , Methyl ethyl ketone peroxide, diisopropyl peroxycarbonate, cumene hydroperoxide, 2,4
Examples thereof include peroxide type polymerization initiators such as dichlorobenzoyl peroxide and lauroyl peroxide.

When the polymerized toner according to the present invention is produced, a crosslinking agent may be added, and the preferable addition amount is 0.001 to 15 with respect to 100 parts by mass of the polymerizable monomer.
Parts by mass.

When producing the polymerized toner of the present invention, a molecular weight modifier may be used. Examples of the molecular weight modifier include t-dodecyl mercaptan, n-
Examples thereof include mercaptans such as dodecyl mercaptan and n-octyl mercaptan; halogenated hydrocarbons such as carbon tetrachloride and carbon tetrabromide; and α-methylstyrene dimer. These molecular weight modifiers can be added before the start of polymerization or during the polymerization. The molecular weight adjusting agent is usually 100 parts by mass of the polymerizable monomer,
It is used in a proportion of 0.01 to 10 parts by mass, preferably 0.1 to 5 parts by mass.

In the method for producing a polymerized toner according to the present invention, generally, a vinyl-based copolymer, a colorant, a release agent, a plasticizer, a charge control agent, and A cross-linking agent, optionally a component necessary as a toner such as magnetic powder, and other additives, such as an organic solvent, a high-molecular polymer, and a dispersant, which are added to reduce the viscosity of the polymer produced by the polymerization reaction, are appropriately added. Then, the monomer system uniformly dissolved or dispersed by a disperser such as a homogenizer, a ball mill, a colloid mill or an ultrasonic disperser is suspended in an aqueous medium containing a dispersion stabilizer. At this time, the particle size of the obtained toner particles becomes sharper by using a high-speed stirrer or a high-speed disperser such as an ultrasonic disperser to immediately make the desired toner particle size. Regarding the timing of addition of the polymerization initiator, it may be added at the same time when other additives are added to the polymerizable monomer, or may be mixed immediately before being suspended in the aqueous medium. Also, a polymerization initiator dissolved in a polymerizable monomer or a solvent may be added immediately after granulation and before starting the polymerization reaction.

After granulation, stirring may be carried out using an ordinary stirrer to such an extent that the particle state is maintained and the particles are prevented from floating and settling.

In the case of producing the polymerized toner according to the present invention, a known surface active agent or organic or inorganic dispersant can be used as a dispersion stabilizer. Among them, the inorganic dispersant hardly produces harmful ultrafine powder, and its steric Dispersion stability is obtained due to obstacles, so stability is unlikely to collapse even if the reaction temperature is changed,
It can be preferably used because it is easy to wash and hardly adversely affects the toner. Examples of such inorganic dispersants include calcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, and other polyvalent metal salts of phosphates, calcium carbonate, carbonates such as magnesium carbonate, calcium meta silicate, calcium sulfate, and barium sulfate. Examples thereof include inorganic salts, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, silica, bentonite, and inorganic oxides such as alumina.

These inorganic dispersants are used as the polymerizable monomer 10
0.2 to 20 parts by mass may be used alone with respect to 0 parts by mass, and 0.001 to 0.1 may be used for the purpose of adjusting the particle size distribution.
You may use together a mass part surfactant. Examples of the surfactant include sodium dodecylbenzene sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate,
Examples thereof include sodium octyl sulfate, sodium oleate, sodium laurate, sodium stearate, potassium stearate and the like.

When these inorganic dispersants are used, they may be used as they are, but in order to obtain finer particles, the inorganic dispersant particles can be generated in an aqueous medium. For example, in the case of calcium phosphate, a water-insoluble calcium phosphate can be produced by mixing an aqueous solution of sodium phosphate and an aqueous solution of calcium chloride under high-speed stirring, and more uniform and fine dispersion is possible. At this time, a water-soluble sodium chloride salt is by-produced at the same time, but if the water-soluble salt is present in the aqueous medium, the dissolution of the polymerizable monomer in water is suppressed, and ultrafine toner particles are generated by emulsion polymerization. It is more convenient because it is difficult to do. Since it becomes an obstacle when removing the remaining polymerizable monomer at the end of the polymerization reaction, it is better to replace the aqueous medium or desalt with an ion exchange resin. The inorganic dispersant can be almost completely removed by dissolving it with an acid or an alkali after completion of the polymerization.

In the polymerization step, the polymerization temperature is 40
Polymerization is carried out at a temperature of not less than 0 ° C, generally 50 to 90 ° C. When the polymerization is carried out within this temperature range, the release agent and waxes to be sealed inside are precipitated by phase separation and the encapsulation becomes more complete. In order to consume the remaining polymerizable monomer, the reaction temperature is 90 to 15 at the end of the polymerization reaction.
It is possible to raise it to 0 ° C. After the completion of polymerization, the polymerized toner particles are filtered, washed and dried by a known method, and the inorganic fine powder is mixed and adhered to the surface to obtain a toner. In addition, it is also one of the desirable modes to include a classification process in the manufacturing process and cut coarse powder and fine powder.

When the toner of the present invention is produced by a pulverization method, a known method may be used. For example, a binder resin,
The vinyl polymer, colorant, release agent, charge control agent, and other components necessary for toner and other additives and the like are thoroughly mixed with a mixer such as a Henschel mixer or a ball mill, and then heated roll, kneader, or extruder. Melt and knead using a heat kneader such as a ruder to make the resins compatible with each other and disperse or dissolve other toner materials such as colorants, cool and solidify, grind, classify, and if necessary. The toner of the present invention can be obtained by performing surface treatment to obtain toner particles and, if necessary, adding and mixing fine powder and the like. Either the classification or the surface treatment may be performed first. In the classification step, it is preferable to use a multi-division classifier in terms of production efficiency. The crushing process can be performed by a method using a known crushing device such as a mechanical impact type and a jet type. In order to obtain a toner having a specific circularity according to the present invention, it is preferable to further apply heat to pulverize or to additionally perform a mechanical impact treatment. Further, there may be used a hot water bath method in which finely pulverized toner particles (classified according to need) are dispersed in hot water, a method of passing through a hot air stream, or the like.

As a means for applying a mechanical impact force, for example, a method using a mechanical impact type crusher such as a Kryptron system manufactured by Kawasaki Heavy Industries Ltd. or a turbo mill manufactured by Turbo Kogyo Co., Ltd., or a mechanofusion system manufactured by Hosokawa Micron Co. As in the case of Nara Machinery's hybridization system and other devices, a method of pressing toner by the centrifugal force with the blades that rotate at high speed by centrifugal force and applying mechanical impact force to the toner by force such as compression force and friction force Can be mentioned.

When the mechanical impact method is used, the processing temperature is set to a temperature (Tg ± Tg) around the glass transition point Tg of the toner.
Thermo-mechanical impact of (10 ° C.) is preferable from the viewpoint of preventing aggregation and productivity. More preferably, it is particularly effective to improve the transfer efficiency by carrying out at a temperature within the range of the glass transition point Tg ± 5 ° C. of the toner.

Furthermore, the toner of the present invention is disclosed in
A method of atomizing a molten mixture in the air using a disk or a multi-fluid nozzle described in JP-A-6-13945 to obtain a spherical toner, or an aqueous organic solvent in which a monomer is soluble and the obtained polymer is insoluble The emulsion polymerization method represented by a dispersion polymerization method for directly producing a toner or a soap-free polymerization method for directly producing a toner by directly polymerizing in the presence of a water-soluble polar polymerization initiator, particles in a dispersion liquid containing a binder resin particle are used. The toner can also be produced by a method of producing a toner by using an association aggregation method in which the aggregated particles are aggregated to obtain aggregated particles and then the aggregated particles are heated and fused.

The binder resin used when the toner of the present invention is manufactured by a pulverization method is a homopolymer of styrene such as polystyrene and polyvinyltoluene, or a substitution product thereof; styrene-propylene copolymer, styrene-vinyltoluene copolymer. Coal, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-acrylic acid Dimethylaminoethyl copolymer, styrene-methylmethacrylate copolymer, styrene-ethylmethacrylate copolymer, styrene-butylmethacrylate copolymer, styrene-dimethylaminoethylmethacrylate copolymer, styrene-vinylmethylether Copolymer, styrene-vinyl ethylene Styrene-based copolymers such as ether copolymers, styrene-vinyl methyl ketone copolymers, styrene-butadiene copolymers, styrene-isoprene copolymers, styrene-maleic acid copolymers, styrene-maleic acid ester copolymers Combined; polymethyl methacrylate, polybutyl methacrylate, polyvinyl acetate, polyethylene, polypropylene, polyvinyl butyral, silicone resin, polyester resin, polyamide resin, epoxy resin, polyacrylic acid resin, rosin, modified rosin, terpene resin, phenol resin, fat Group or alicyclic hydrocarbon resins, aromatic petroleum resins, paraffin wax, carnauba wax and the like can be used alone or in combination. In particular, styrene-based copolymers and polyester resins are preferable in terms of developing characteristics and fixing properties.

(External Additive) In the toner of the present invention, 0.1 to 4 parts by mass of an inorganic fine powder having an average primary particle diameter of 4 to 80 nm is added as a fluidizing agent to 100 parts by mass of the entire toner. Is also a very preferable use form. The inorganic fine powder is added to improve the fluidity of the toner and make the toner base particles evenly charged, but the inorganic fine powder is subjected to a treatment such as a hydrophobic treatment to adjust the toner charge amount and improve the environmental stability. It is also preferable to impart functions such as.

When the average primary particle size of the inorganic fine powder is larger than 80 nm, good toner fluidity cannot be obtained, charge impartment to the toner particles is likely to be non-uniform, and the triboelectric chargeability under low humidity is reduced. Increased fog, as it leads to unevenness,
Problems such as a decrease in image density and a decrease in durability cannot be avoided. When the average primary particle diameter of the inorganic fine powder is smaller than 4 nm, the agglomeration of the inorganic fine particles is strengthened, and not as primary particles but as an agglomerate with a wide particle size distribution having a strong agglomeration that is hard to be broken by crushing treatment. It easily behaves, and image defects due to development of the aggregate, damage to the image bearing member or the toner bearing member, and the like are likely to occur. In order to make the charge distribution of the toner particles more uniform, the average primary particle size of the inorganic fine powder is more preferably 6 to 35 nm.

The average primary particle size of the inorganic fine powder is a photograph of the toner magnified by a scanning electron microscope, and further shows the elements contained in the inorganic fine powder by an element analysis means such as XMA attached to the scanning electron microscope. It can be measured by comparing the photograph of the mapped toner and measuring 100 or more primary particles of the inorganic fine powder present adhering or free on the toner surface and determining the number average diameter.

The content of the inorganic fine powder can be quantified by fluorescent X-ray analysis using a calibration curve prepared from a standard sample.

As the inorganic fine powder added to the toner of the present invention, silica, alumina, titania and the like can be used.

For example, as the silica, both a so-called dry method produced by vapor phase oxidation of a silicon halide or a dry silica called fumed silica and a so-called wet silica produced from water glass can be used. However, dry silica having less silanol groups on the surface and inside the fine silica powder and less production residues such as Na ₂ O and SO ₃ ²⁻ is preferable. Further, in the case of dry silica, it is also possible to obtain a composite fine powder of silica and another metal oxide by using another metal halogen compound such as aluminum chloride and titanium chloride together with a silicon halogen compound in the production process. Also includes.

The inorganic fine powder having an average primary particle size of 4 to 80 nm is preferably added in an amount of 0.1 to 4.0 parts by mass with respect to 100 parts by mass of the toner mother particles. If the amount is less than 0.1 part by mass, the effect is not sufficient,
If it exceeds 4.0 parts by mass, the fixability will be poor.

The inorganic fine powder is preferably hydrophobized from the viewpoint of improving the characteristics in a high humidity environment. When the inorganic fine powder added to the toner absorbs moisture, the charge amount of the toner is remarkably reduced, and the developability and transferability are likely to be degraded.

As the treatment agent for the hydrophobic treatment, a treatment agent such as silicone varnish, various modified silicone varnishes, silicone oil, various modified silicone oil, silane compounds, silane coupling agents, other organic silicon compounds and organic titanium compounds are used alone. Alternatively, it may be used in combination.

Among them, the one treated with silicone oil is preferable, and more preferably, the one treated with silicone oil at the same time as or after the hydrophobic treatment of the inorganic fine powder is treated with silicone oil even in a high humidity environment. Is high and the selective developability is reduced.

The conditions for treating the inorganic fine powder include, for example, a silylation reaction as a first step reaction to eliminate active hydrogen groups on the surface by chemical bonding, and then a second step reaction with silicone oil to make the surface hydrophobic. A thin film can be formed. The amount of silylating agent used is 10% inorganic fine powder.
5 to 50 parts by mass is preferable with respect to 0 parts by mass. If it is less than 5 parts by mass, it is not enough to eliminate the active hydrogen groups on the surface of the inorganic fine particles, and if it exceeds 50 parts by mass, the siloxane compound generated by the reaction between the excess silylating agents acts as a paste and acts as an adhesive between the inorganic fine particles. Agglomeration occurs and image defects are likely to occur.

The above silicone oil preferably has a viscosity at 25 ° C. of 10 to 200,000 mm ² / s, more preferably 3,000 to 80,000 mm ² / s. If it is less than 10 mm ² / s, the inorganic fine powder is not stable, and the image quality tends to deteriorate due to heat and mechanical stress. If it exceeds 200,000 mm ² / s,
Uniform treatment tends to be difficult.

As a method for treating the silicone oil, for example, the inorganic fine powder treated with the silane compound and the silicone oil may be directly mixed using a mixer such as a Henschel mixer, or the inorganic fine powder may be mixed with the silicone oil. A spraying method may be used. Alternatively, a method may be used in which silicone oil is dissolved or dispersed in a suitable solvent, and then inorganic fine powder is added and mixed to remove the solvent. The method using a sprayer is more preferable in that the formation of aggregates of the inorganic fine powder is relatively small.

The amount of silicone oil to be treated is 1 for inorganic fine powder.
1 to 23 parts by weight, preferably 5 to 20 parts by weight with respect to 00 parts by weight
Good mass parts. If the amount of silicone oil is too small, good hydrophobicity cannot be obtained, and if it is too large, the aggregation of inorganic fine particles is likely to occur.

The toner of the present invention exhibits more excellent image characteristics and durability by using, in addition to the above inorganic fine powder, conductive fine powder having a volume average particle size smaller than that of the toner.

The reason for the addition effect is considered to be that it is due to the function of sharpening the triboelectric charge amount distribution of the toner. Depending on the image forming system used, the toner of the present invention may need to further improve charge transfer under low humidity. At that time, if conductive fine powder is added to the toner of the present invention, an entropy-preferred homogenization reaction of charge transfer from a toner having a high charge amount to a toner having a low charge amount is likely to occur, and the triboelectric chargeability becomes more uniform.

The content of the conductive fine powder with respect to the entire toner is preferably 0.05 to 10 parts by mass per 100 parts by mass of the toner. When the content of the conductive fine powder in the whole toner is less than 0.05 parts by mass, the homogenization reaction rate under low humidity is insufficient. On the other hand, when the amount is more than 10 parts by mass, it becomes difficult to maintain a sufficient amount of charge under high humidity, fog and transferability are deteriorated, and durability is easily deteriorated. It is preferably 0.05 to 5 parts by mass.

The preferable resistance of the conductive fine powder is 1
It is not more than ⁰⁹ Ω · cm. Resistance of conductive fine powder is 10 ⁹ Ω
・ If it is larger than cm, the homogenization reaction rate is still insufficient. Further, if it is set to 10 ⁶ Ω · cm or less, the distribution of the charge amount becomes extremely sharp even under low humidity. On the other hand, if the resistance of the electroconductive fine powder is too low, the triboelectric charge amount may become low at high humidity. Therefore, it is preferably 10 ⁻¹ Ω · cm or more.

The volume average particle diameter of the conductive fine powder is 0.05.
It is preferably ˜5 μm. Average particle size is 0.05
If it is less than μm, the effect of promoting the homogenization reaction rate is low. It is speculated that this is because the probability of the presence of the conductive fine powder in the contact portion between the toner particles is reduced, so that the charge transfer from the high charge amount toner to the low charge amount toner is not promoted so much. More preferably, the number of particles of less than 0.5 μm in the particle size distribution is 70% by volume or less.

The average particle diameter of the conductive fine powder is 5 μm.
If it is larger than the above value, the van der Waals force with the toner particles is lowered, and the toner particles are easily detached from the toner particles and adhered to the toner carrier, which hinders triboelectric charging of the toner. More preferably, the number of particles having a particle size distribution of more than 5 μm is 7 number% or less.

From these viewpoints, the volume average particle diameter of the conductive fine powder is preferably 0.1 to 4 μm, and a non-magnetic material is preferable in order to suppress the adhesion to the toner carrier.

The conductive fine powder is preferably transparent, white or light-colored conductive fine powder because it is not noticeable as fog when the conductive fine powder is transferred onto the transfer material. The conductive fine powder is preferably transparent, white or light-colored conductive fine powder even in the sense that it does not interfere with the exposure light in the latent image forming step, and more preferably the conductive fine powder has a transmittance of 30 to the exposure light. % Or more is preferable.

In the present invention, the light transmittance of particles was measured by the following procedure. The transmittance is measured in a state where one layer of conductive fine powder of a transparent film having an adhesive layer on one side is fixed. The light was irradiated from the vertical direction of the sheet, and the light transmitted to the back surface of the film was condensed to measure the light amount. The transmittance of the particles was calculated as the net amount of light from the amount of light when only the film was attached to the particles. Actually X-Rite 3
It was measured using a 10T transmission densitometer.

As the conductive fine powder in the present invention, for example, carbon fine powder such as carbon black and graphite; metal fine powder such as copper, gold, silver, aluminum and nickel; zinc oxide, titanium oxide, tin oxide, aluminum oxide. , Indium oxide, silicon oxide, magnesium oxide,
Metal oxides such as barium oxide, molybdenum oxide, iron oxide and tungsten oxide; metal compounds such as molybdenum sulfide, cadmium sulfide and potassium titanate, or composite oxides of these, adjust the particle size and particle size distribution as necessary. It can be used. Among these, inorganic oxide fine particles such as zinc oxide, tin oxide and titanium oxide are particularly preferable.

Further, for the purpose of controlling the resistance value of the conductive inorganic oxide, a metal oxide doped with an element such as antimony or aluminum, or fine particles having a conductive material on the surface can be used. For example, titanium oxide fine particles surface-treated with tin oxide / antimony, stannic oxide fine particles doped with antimony, or stannic oxide fine particles are used.

Commercially available tin oxide / antimony treated conductive titanium oxide fine particles are, for example, EC-300.
(Titanium Industry Co., Ltd.), ET-300, HJ-1, H
I-2 (above, Ishihara Sangyo Co., Ltd.), WP (Mitsubishi Materials Co., Ltd.), etc. are mentioned.

Commercially available antimony-doped conductive tin oxides include, for example, T-1 (Mitsubishi Materials Co., Ltd.) and SN-100P (Ishihara Sangyo Co., Ltd.), and commercially available stannic oxide, SH-. S (Japan Chemical Industry Co., Ltd.) and the like can be mentioned.

The average particle size of the conductive fine powder in the present invention can be measured as follows.

A liquid module was attached to a LS-230 type laser diffraction type particle size distribution measuring apparatus manufactured by Coulter Co., Ltd., and a liquid module was attached to measure the particle size distribution in the range of 0.04 to 2000 μm. The average particle diameter (D1) is calculated from the average particle diameter (D4) and the specific gravity. As a measuring method, a trace amount of a surfactant was added to 10 cc of pure water, 10 mg of a conductive fine powder sample was added thereto, and the mixture was dispersed for 10 minutes with an ultrasonic disperser (ultrasonic homogenizer), and then a measurement time of 90 The measurement is performed once per second.

In the present invention, as a method for adjusting the particle size and particle size distribution of the conductive fine powder, the manufacturing method and the manufacturing conditions are set so that the primary particles of the conductive fine powder can obtain a desired particle size and particle size distribution at the time of manufacturing. In addition to the setting method, a method of aggregating small primary particles, a method of crushing large primary particles, a method of classification, and the like are possible. Furthermore, a method of adhering or immobilizing conductive particles on a part or all of the surface of base particles having a desired particle size and particle size distribution, and a form in which a conductive component is dispersed in particles having a desired particle size and particle size distribution. It is also possible to use a method of using the conductive fine particles that it has, and it is also possible to adjust the particle size and particle size distribution of the conductive fine powder by combining these methods.

The particle diameter when the particles of the conductive fine powder are formed as an agglomerate is defined as the average particle diameter as the agglomerate. There is no problem that the conductive fine powder exists not only in the state of primary particles but also in the state of agglomeration of secondary particles.

In the present invention, the resistance of the conductive fine powder was measured by the tablet method and normalized. That is, about 0.5 g of a powder sample was put in a cylinder with a bottom area of 2.26 cm ² , 147 N (15 kg) was applied to the upper and lower electrodes, and at the same time a voltage of 100 V was applied to measure the resistance value. Then, the specific resistance was calculated.

The toner of the present invention has a primary particle size of more than 30 nm (preferably a specific surface area of less than 50 m ² / g), more preferably a primary particle size of 50 nm or more (preferably a specific surface area) for the purpose of improving cleaning properties. Is less than 30 m ² / g), it is also one of the preferable modes to further add inorganic or organic particles having a nearly spherical shape. For example, spherical silica particles, spherical polymethylsilsesquioxane particles, spherical resin particles and the like are preferably used.

The developer used in the present invention may further contain other additives within a range that does not have a substantial adverse effect, for example, lubricant powders such as polyfluorinated ethylene powder, zinc stearate powder and polyvinylidene fluoride powder; or Abrasives such as cerium oxide powder, silicon carbide powder, and strontium titanate powder; or flowability-imparting agents such as titanium oxide powder and aluminum oxide powder; anti-caking agent;
Further, organic fine particles and inorganic fine particles having opposite polarities can be used in a small amount as a developing property improver. It is also possible to use these additives after the surface is hydrophobized.

The toner of the present invention is a non-magnetic toner,
It may be mixed with a carrier and used as a two-component developer. The resistance value of the carrier is the degree of unevenness of the carrier surface,
It is preferable to adjust the amount of resin to be coated to 10 ⁶ to 10 ¹⁰ Ω · cm.

As the resin for coating the surface of the carrier, a styrene-acrylic acid ester copolymer, a styrene-methacrylic acid ester copolymer, an acrylic acid ester copolymer, a methacrylic acid ester copolymer, a silicone resin,
Fluorine-containing resin, polyamide resin, ionomer resin,
Polyphenylene sulfide resin or a mixture thereof can be used.

As the magnetic material of the carrier core, oxides such as ferrite, iron-excessive ferrite, magnetite and γ-iron oxide, metals such as iron, cobalt and nickel, or alloys thereof can be used. The elements contained in these magnetic materials include iron, cobalt, nickel, aluminum, copper, lead, magnesium, tin,
Examples thereof include zinc, antimony, beryllium, bismuth, calcium, manganese, selenium, titanium, tungsten and vanadium.

As the additives used in the present invention for the purpose of imparting various characteristics other than those mentioned above, for example, the following ones are used.

(1) Abrasive: Metal oxide (strontium titanate, cerium oxide, aluminum oxide, magnesium oxide, chromium oxide, etc.), nitride (silicon nitride, etc.) / Carbide (silicon carbide, etc.), metal salt (sulfuric acid) Calcium, barium sulfate, calcium carbonate), etc.

(2) Lubricants: Fluorine-based resin powders (polyvinylidene fluoride, polytetrafluoroethylene, etc.), fatty acid metal salts (zinc stearate, calcium stearate, etc.), etc.

(3) Charge controllable particles: metal oxides (tin oxide, titanium oxide, zinc oxide, silicon oxide, aluminum oxide, etc.), carbon black, resin fine particles and the like.

These additives are used in an amount of 0.05 to 10 parts by mass, preferably 0.1 to 5 parts by mass, based on 100 parts by mass of the toner particles. These additives may be used alone or in combination.

In the case of a magnetic toner, it is preferable to use fine powders of two or more kinds of inorganic oxides or metal oxides in order to obtain durability stability of development and development stability after standing. In the case of the non-magnetic one-component developing method, it is preferable to use titanium oxide or alumina in order to improve fluidity and obtain image uniformity.

An image forming method to which the toner of the present invention is applicable will be described below with reference to the accompanying drawings.

First, the two-component developing method will be described.

The toner of the present invention can be applied to an image forming method by mixing it with a magnetic carrier and using a developing means 37 as shown in FIG. 1, for example. Specifically, while applying an alternating electric field, the magnetic brush moves the electrostatic charge image carrier (for example,
It is preferable that the development is performed in a state of being in contact with the photoconductor drum 33. The distance (SD distance) B between the developer bearing member (developing sleeve) 31 and the photosensitive drum 33 is 100 to 1.
The thickness of 000 μm is good for preventing carrier adhesion and improving dot reproducibility. If it is narrower than 100 μm, the supply of the developer tends to be insufficient and the image density becomes low, and if it exceeds 1000 μm, the magnetic force lines from the magnet S1 spread and the density of the magnetic brush becomes low, resulting in poor dot reproducibility and restraining the carrier. The force to do so weakens and carrier adhesion easily occurs. The toner 41 is sequentially supplied to the developing device,
The mixture is mixed with the carrier by the stirring means 35 and 36, and is conveyed to the developing sleeve 42 containing the fixed magnet 34.

The voltage between the peaks of the alternating electric field is 500 to 50.
00V is preferable, the frequency is 500 to 10000 Hz,
The frequency is preferably 500 to 3000 Hz, and can be appropriately selected and used for each process. In this case, the waveform may be triangular wave, rectangular wave, sine wave, or duty.
Various waveforms with different ratios can be selected and used. If the applied voltage is lower than 500 V, it may be difficult to obtain a sufficient image density, and the fog toner in the non-image area may not be collected well. If the voltage exceeds 5000 V, the electrostatic image may be disturbed via the magnetic brush, and the image quality may be degraded.

By using a two-component type developer having a well-charged toner, the fog removal voltage (Vback)
Can be lowered, and the primary charging of the photoconductor can be reduced, so that the life of the photoconductor can be extended. Vbac
The value k depends on the developing system, but is preferably 150 V or less, more preferably 100 V or less.

As the contrast potential, 200 to 500 V is preferably used so that a sufficient image density can be obtained.

When the frequency is lower than 500 Hz, although it is related to the process speed, charge injection into carriers may occur, which may deteriorate the image quality due to carrier adhesion or disturbing the latent image. If it exceeds 10000 Hz, the toner cannot follow the electric field and the image quality is likely to deteriorate.

The contact width (developing nip C) of the magnetic brush on the developing sleeve 31 with the photosensitive drum 33 is preferably in order to obtain sufficient image density, excellent dot reproducibility, and development without carrier adhesion. It is to be 3 to 8 mm. If the developing nip C is narrower than 3 mm, it is difficult to satisfactorily satisfy sufficient image density and dot reproducibility.
If the width is larger than mm, the packing of the developer occurs, the operation of the machine is stopped, and it becomes difficult to sufficiently suppress the carrier adhesion. As a method of adjusting the developing nip, the nip width is appropriately adjusted by adjusting the distance A between the developer regulating member 32 and the developing sleeve 31 or the distance B between the developing sleeve 31 and the photosensitive drum 33.

Particularly in outputting a full-color image in which halftone is emphasized, three or more developing devices for magenta, cyan, and yellow are used, and a toner of the present invention is used to form a digital latent image. By combining with the developing system described above, there is no influence of the magnetic brush, and since the latent image is not disturbed, it is possible to develop the dot latent image faithfully. Even in the transfer step, a high transfer rate can be achieved by using the toner of the present invention, and therefore high image quality can be achieved in both the halftone portion and the solid portion.

Further, in addition to the improvement of the initial image quality, the use of the toner of the present invention suppresses the deterioration of the image quality even when copying a large number of sheets, and the effects of the present invention can be sufficiently exhibited.

The toner image on the electrostatic image carrier 33 is transferred onto a transfer material by a transfer means 43 such as a corona charger,
The toner image on the transfer material is fixed by a heat and pressure fixing unit having a heating roller 46 and a pressure roller 45, and a fixed image is formed on the transfer material.

The transfer residual toner on the electrostatic image carrier 33 is removed from the electrostatic image carrier 33 by a cleaning means 44 such as a cleaning blade. The toner of the present invention has high transfer efficiency in the transfer step, less transfer residual toner, and
Since it has excellent cleaning properties, filming is unlikely to occur on the electrostatic image carrier. Further, even when a multi-sheet durability test is performed, the toner of the present invention has less burial of the external additive on the toner surface than the conventional toner, so that good image quality can be maintained for a long period of time.

In order to obtain a good full-color image, it is preferable to use an image forming apparatus having developing units for magenta, cyan, yellow, and black, and arranged so that black development is performed last. A tight image can be obtained by using it.

FIG. 2 shows an example of an image forming apparatus capable of favorably carrying out the multi-color or full-color image forming method.

The color electrophotographic apparatus shown in FIG. 2 has a transfer material conveying system I provided from the right side of the apparatus main body to substantially the center of the apparatus main body, and the transfer material conveying system I at the substantially center of the apparatus main body. The latent image forming section II provided near the transfer drum 415 and the developing means (that is, the rotary developing device) III provided near the latent image forming section II. Broadly divided.

The transfer material carrying system I has the following structure. Removable transfer material supply trays 402 and 403 are arranged so as to partially project out of the machine at the opening of the apparatus. Paper feed rollers 404 and 405 are arranged substantially directly above the trays 402 and 403.
04 and 405 are provided with a sheet feeding roller 406 and sheet feeding guides 407 and 408 so as to link the transfer drum 405 arranged on the left side and rotatable in the arrow A direction. In the vicinity of the outer peripheral surface of the transfer drum 415, a contact roller 409, a gripper 410, a transfer material separating charger 411, and a separating claw 412 are sequentially arranged from the upstream side to the upstream side in the rotation direction.

A transfer charger 413 and a transfer material separating charger 414 are provided on the inner peripheral side of the transfer drum 415. A transfer sheet (not shown) made of a polymer such as polyvinylidene fluoride is attached to a portion of the transfer drum 415 around which the transfer material is wound, and the transfer material is electrostatically attached on the transfer sheet. It is attached closely to. A conveyor belt means 416 is disposed on the upper right side of the transfer drum 415 close to the separation claw 412, and a fixing device 418 is disposed at the end (right side) of the conveyor belt means 416 in the transfer material conveying direction. There is. A discharge tray 417 that extends to the outside of the apparatus main body 401 and is detachable from the apparatus main body 401 is disposed further downstream than the fixing device 418 in the transport direction.

Next, the structure of the latent image forming section II will be described. A photosensitive drum (for example, an OPC photosensitive drum) 419, which is a latent image carrier rotatably in the direction of the arrow in FIG. 2, is arranged with its outer peripheral surface in contact with the outer peripheral surface of the transfer drum 415. Above the photosensitive drum 419 and in the vicinity of the outer peripheral surface thereof, a charge removing charger 420 and a cleaning unit 421 from the upstream side to the downstream side in the rotation direction of the photosensitive drum 419.
And a primary charger 423 are sequentially arranged, and an image exposure unit 424 such as a laser beam scanner for forming an electrostatic latent image on the outer peripheral surface of the photosensitive drum 419, and an image exposure reflection unit 425 such as a mirror. It is arranged.

The structure of the rotary developing device III is as follows. A rotatable housing (hereinafter referred to as "rotating body") 4 is provided at a position facing the outer peripheral surface of the photosensitive drum 419.
26, and four types of developing devices are mounted in four positions in the circumferential direction in the rotating body 426.
The electrostatic latent image formed on the outer peripheral surface of 9 is visualized (that is, developed). The above-mentioned four types of developing devices respectively include a yellow developing device 427Y, a magenta developing device 427M, a cyan developing device 427C, and a black developing device 427BK.

The sequence of the entire image forming apparatus having the above configuration will be described by taking the case of the full color mode as an example. When the photosensitive drum 419 described above rotates in the direction of the arrow in FIG.
Is charged by. In the apparatus of FIG. 2, the peripheral speed of the photosensitive drum 419 (hereinafter referred to as process speed) is 1
00 mm / sec or more (for example, 130 to 250 mm /
sec). When the photosensitive drum 419 is charged by the primary charger 423, image exposure is performed by the laser beam E modulated by the yellow image signal of the original 428, and an electrostatic latent image is formed on the photosensitive drum 419.
The electrostatic latent image is developed by the yellow developing device 427Y which is fixed in advance at the developing position by the rotation of the rotating body 426, and a yellow toner image is formed.

The transfer material conveyed through the paper feed guide 407, the paper feed roller 406, and the paper feed guide 408 is held by the gripper 410 at a predetermined timing, and the contact roller 409 and the contact roller concerned. 409 is electrostatically wound around the transfer drum 415 by the electrodes facing each other. The transfer drum 415 rotates in the direction of the arrow in FIG.
The yellow toner image formed by 27Y is transferred onto the transfer material by the transfer charger 413 at a portion where the outer peripheral surface of the photosensitive drum 419 and the outer peripheral surface of the transfer drum 415 are in contact with each other. The transfer drum 415 continues to rotate and prepares for transfer of the next color (magenta in FIG. 2).

The photosensitive drum 419 is the charger 4 for static elimination.
After the charge is removed by 20 and the cleaning means 421 by the cleaning blade cleans it, it is charged again by the primary charger 423, and image exposure is performed by the next magenta image signal to form an electrostatic latent image. The rotary developing device rotates while an electrostatic latent image is formed on the photosensitive drum 419 by imagewise exposure with a magenta image signal to position the magenta developing device 427M at the above-described predetermined developing position and to perform a predetermined operation. Develop with magenta toner. Subsequently, the above-described process is performed for cyan and black, respectively, and when the transfer of the four-color toner images is completed, the three-color visible image formed on the transfer material is charged by the chargers 422 and 414, respectively. The gripping of the transfer material by the gripper 410 is released, the transfer material is separated from the transfer drum 415 by the separation claw 412, and the transfer belt 416 is used to fix the transfer material.
Then, it is sent to 18 and fixed by heat and pressure to complete a series of full-color printing sequence, and a required full-color printing image is formed on one surface of the transfer material.

Next, the image forming method in the case of the magnetic toner of the present invention will be specifically described with reference to the drawings.

In the image forming apparatus of FIG. 3, reference numeral 100 denotes a photosensitive drum, around which a primary charging roller 117, a developing device 140, a transfer charging roller 114, a cleaner 116,
A register roller 124 and the like are provided. Then, the photoconductor 100 is charged to, for example, −700 V by the primary charging roller 117 (applied voltage is AC voltage −2.0).
k Vpp, DC voltage -700 Vdc). Then, the laser generator 123 irradiates the photosensitive member 100 with laser light 123 to expose the photosensitive member 100. Photoconductor 10
The electrostatic latent image on 0 is developed with a one-component magnetic developer by the developing device 140, and transferred onto the transfer material P by the transfer roller 114 that is in contact with the photoconductor via the transfer material P. The transfer material P on which the toner image is placed is conveyed to the fixing device 126 by the conveyor belt 125 or the like and fixed on the transfer material P. Further, the toner left on the photosensitive member is partially cleaned by the cleaning unit 116.
To be cleaned. As shown in FIG. 4, the developing device 140 is arranged in the vicinity of the photoconductor 100 and is a cylindrical toner carrier 1 made of a non-magnetic metal such as aluminum or stainless steel.
02 (hereinafter referred to as a developing sleeve) is provided, and the photoconductor 1
00 and the developing sleeve 102 are maintained at about 300 μm by a sleeve / photoconductor gap holding member (not shown). Magnet roller 1 in the developing sleeve
04 is fixed and arranged concentrically with the developing sleeve 102. However, the developing sleeve 102 is rotatable. The magnet roller 104 is provided with a plurality of magnetic poles as shown in the drawing. S1 influences development, N1 regulates toner coat amount, S2 influences toner intake / conveyance, and N2 influences toner blowout prevention. The toner is applied to the developing sleeve 102 by the toner applying roller 141, attached and conveyed. The elastic blade 103 is provided as a member for controlling the amount of toner to be conveyed.
The contact pressure of 03 with the developing sleeve 102 controls the amount of toner conveyed to the developing area. In the development area,
A DC and AC developing bias is applied between the photoconductor 100 and the developing sleeve 102, and the developer on the developing sleeve flies on the photoconductor 100 according to the electrostatic latent image to form a visible image.

Next, another image forming method will be described with reference to FIG.

In the apparatus system shown in FIG. 6, the developing units 54-1, 54-2, 54-3, and 54-4 respectively have a developer having a cyan toner, a developer having a magenta toner, and a developer having a yellow toner. A developer having a developing agent and black toner is introduced, and the electrostatic charge image formed on the photoconductor 51 is developed by the magnetic brush development system or the non-magnetic one-component development system, and the negatively chargeable toner image of each color is formed on the photoconductor 5.
1 is formed on. Photoreceptor 51 is a-Se, CdS, Z
It is a photosensitive drum or photosensitive belt having a photoconductive insulating material layer such as nO ₂ , OPC and a-Si. The photoconductor 51 is rotated in the arrow direction by a driving device (not shown).

As the photosensitive member 51, a photosensitive member having an amorphous silicon photosensitive layer or an organic photosensitive layer is preferably used.

As the organic photosensitive layer, the photosensitive layer contains a charge generating substance and a substance having a charge transporting property in the same layer.
It may be a single layer type or a function-separated type photosensitive layer in which the charge transport layer comprises a charge generation layer as a component. A laminated photosensitive layer having a structure in which a charge generation layer and then a charge transport layer are laminated in this order on a conductive substrate is one of preferred examples.

Polycarbonate resin, polyester resin, and acrylic resin are particularly preferable as the binder resin of the organic photosensitive layer because of good transferability and cleaning property, poor cleaning, fusing of negatively chargeable toner to the photoreceptor, and external additive. Filming is unlikely to occur.

In the charging step, there are a method of non-contact with the photoconductor 51 using a corona charger, and a contact type method using a roller or the like, any of which is used. A contact type as shown in FIG. 3 is preferably used for efficient uniform charging, simplification and low ozone generation.

The charging roller 52 basically has a cored bar 52b at the center and a conductive elastic layer 52a forming the outer periphery thereof. The charging roller 52 is pressed against the surface of the photoconductor 51 with a pressing force, and is rotated by the rotation of the photoconductor 51.

A preferable process condition when the charging roller is used is that the contact pressure of the roller is 5 to 500 g / cm.
When an AC voltage superimposed on a DC voltage is used, AC voltage = 0.5 to 5 kVpp, AC frequency = 50
Hz to 5 kHz, DC voltage = ± 0.2 to ± 1.5 kV, and when DC voltage is used, DC voltage = ± 0.2 to
± 5 kV.

As another charging means, there are a method using a charging blade and a method using a conductive brush. These contact charging means are effective in that high voltage becomes unnecessary and ozone generation is reduced.

As the material of the charging roller and the charging blade as the contact charging means, conductive rubber is preferable, and a releasing film may be provided on the surface thereof. As the releasable coating, nylon resin, PVDF (polyvinylidene fluoride), PVDC (polyvinylidene chloride), etc. can be applied.

The toner image on the photosensitive member has a voltage (for example, ±
It is transferred to the intermediate transfer member 5 to which 0.1 to ± 5 kV) is applied. The surface of the photoconductor after the transfer is cleaned by a cleaning unit 59 having a cleaning blade 58.

The intermediate transfer member 55 comprises a pipe-shaped conductive core 55b and an elastic layer 55 of medium resistance formed on the outer peripheral surface thereof.
It consists of a. The core metal 55b may be a plastic pipe coated with conductive plating.

The medium-resistance elastic layer 55a is made of an elastic material such as silicone rubber, polyfluorinated ethylene rubber, chloroprene rubber, urethane rubber, EPDM (ethylene propylene diene terpolymer), carbon black, zinc oxide, An electrical resistance value (volume resistivity) of 10 ⁵ to 10 ¹¹ Ω is obtained by mixing and dispersing a conductivity-imparting material such as tin oxide or silicon carbide.
・ Solid or foamed meat layer adjusted to a medium resistance of cm.

The intermediate transfer member 55 is disposed in parallel with the photosensitive member 51 so as to be in contact with the lower surface of the photosensitive member 51, and rotates in the counterclockwise direction indicated by an arrow at the same peripheral speed as the photosensitive member 51. To do.

[0223] The negatively chargeable toner image of the first color formed and carried on the surface of the photoconductor 51 is applied and transferred to the intermediate transfer body 55 while passing through the transfer nip portion where the photoconductor 51 and the intermediate transfer body 55 are in contact with each other. The intermediate transfer is sequentially performed on the outer surface of the intermediate transfer body 55 by the electric field formed in the transfer nip region by the bias.

If necessary, the detachable cleaning means 500 cleans the surface of the intermediate transfer body 55 after the transfer of the toner image to the transfer material. If the toner image is present on the intermediate transfer body, the toner image is not disturbed. Thus, the cleaning means 500 is separated from the surface of the intermediate transfer member.

A transfer means is disposed in parallel with the intermediate transfer body 55 so as to be in contact with the lower surface of the intermediate transfer body 55, and the transfer means 57 is, for example, a transfer roller or a transfer belt. Rotates clockwise at the same peripheral speed as the arrow. The transfer means 57 may be arranged so as to be in direct contact with the intermediate transfer body 55, or a belt or the like may be arranged so as to be in contact between the intermediate transfer body 55 and the transfer means 57.

In the case of the transfer roller, the core metal 57b at the center and the conductive elastic layer 57a having the outer periphery thereof are used as a basic structure.

For the intermediate transfer member and the transfer roller, general materials can be used. By setting the volume resistivity of the elastic layer of the transfer roller to be smaller than the volume resistivity of the elastic layer of the intermediate transfer member, the voltage applied to the transfer roller can be reduced and a good negative charging toner on the transfer material can be obtained. It is possible to form an image and prevent the transfer material from being wound around the intermediate transfer member. Particularly, it is particularly preferable that the volume resistivity of the elastic layer of the intermediate transfer body is 10 times or more than the volume resistivity of the elastic layer of the transfer roller.

The hardness of the intermediate transfer member and the transfer roller is JI.
It is measured according to SK-6301. The intermediate transfer member used in the present invention is preferably composed of an elastic layer belonging to the range of 10 to 40 degrees, while the hardness of the elastic layer of the transfer roller is higher than that of the elastic layer of the intermediate transfer member.
Those having a value of -80 degrees are preferable in order to prevent the transfer material from being wound around the intermediate transfer member. When the hardness of the intermediate transfer body and that of the transfer roller are opposite, a recess is formed on the transfer roller side, and the transfer material is likely to be wound around the intermediate transfer body.

The transfer means 57 is rotated at a constant speed or a peripheral speed different from that of the intermediate transfer body 55. The transfer material 6 is conveyed between the intermediate transfer body 5 and the transfer means 57, and at the same time, a bias having a polarity opposite to the triboelectric charge of the negatively charged toner is applied to the transfer means 57 from the transfer bias means. The negatively charged toner image on 55 is transferred to the surface side of the transfer material 56.

The material of the transfer rotary member may be the same as that of the charging roller, and the preferable transfer process condition is that the contact pressure of the roller is 5 to 500 g / c.
m, the DC voltage is ± 0.2 to ± 10 kV.

For example, the conductive elastic layer 57b of the transfer roller
Is a polyurethane in which a conductive material such as carbon is dispersed, an ethylene-propylene-diene terpolymer (EPDM)
It is made of an elastic body having a volume resistance of about 10 ⁶ to 10 ¹⁰ Ωcm. A bias is applied to the core metal 57a by a constant voltage power source. The bias condition is ± 0.2 to
± 10 kV is preferable.

Next, the transfer material 56 is conveyed to the fixing device 50 which is basically composed of a heating roller containing a heating element such as a halogen heater and an elastic pressure roller pressed against the heating roller by a pressing force, and heated. By passing between the roller and the pressure roller, the negatively charged toner image is heated and pressure-fixed on the transfer material. A method of fixing with a heater through a film may be used.

Next, an example of the developing method in the case of performing the non-magnetic one-component developing will be described with reference to FIG. Reference numeral 85 is a latent image holder, latent image formation is performed by an electrophotographic process means or electrostatic recording means (not shown), and 84 is a developing sleeve made of a non-magnetic sleeve such as aluminum or stainless steel. As the developing sleeve 84, a rough tube made of aluminum or stainless steel may be used as it is, but preferably, the surface thereof is uniformly roughened by blowing spherical particles such as glass beads, a mirror-finished one, or a resin coating. Things are good. Toner T is hopper 81
And is supplied onto the developing sleeve (toner carrier) 82 by the toner application roller 82. As the toner applying roller 82, a roller made of a foam material such as a porous elastic body (for example, soft polyurethane foam) is preferably used. The roller is rotated with respect to the developing sleeve 84 in a forward or reverse direction at a relative speed which is not 0, and the toner is supplied onto the developing sleeve 84 and the toner (undeveloped toner) after development on the developing sleeve 84 is peeled off. Also do. At this time, the contact width (nip width) of the toner applying roller 82 to the developing sleeve 84 is 2.0 to 10 in consideration of the balance of toner supply and stripping.
0 mm is preferable, and 4.0-6.0 mm is more preferable. Although stress is applied to the toner to increase aggregation due to toner deterioration, or the toner is likely to be fused and fixed to the developing sleeve 84 and the toner application roller 82, the toner of the present invention has fluidity and releasability. Since it has excellent durability and durability stability, it is also preferably used in the developing device shown in FIG. Further, instead of the toner applying roller 82, a brush roller made of resin fiber such as nylon or rayon may be used. The developing method shown in FIG. 5 is extremely effective in a one-component developing method using a non-magnetic one-component toner.

The toner supplied onto the developing sleeve 84 is applied in a thin layer and uniformly by the regulating member 83. As the toner regulating member 83, it is particularly preferable to apply the toner by pressure contact with the surface of the developing sleeve 84 with an elastic blade or elastic roller. As the elastic blade or elastic roller, it is preferable to use a material of triboelectrification series suitable for charging the toner to a desired polarity. The regulating member 83 is preferably silicone rubber, urethane rubber, styrene-butadiene rubber, or the like. Furthermore, polyamide, polyimide, nylon, melamine, melamine crosslinked nylon, phenol resin, fluororesin, silicone resin, polyester resin,
An organic resin layer such as urethane resin, styrene resin, and acrylic resin may be provided on the regulation member 83.

The contact pressure between the elastic blade or elastic roller and the developing sleeve 84 is 0.1 to 25 kg / m, preferably 0.5 to 12 kg as a linear pressure in the sleeve generatrix direction.
/ M is effective, and by adjusting the contact pressure to 0.1 to 25 kg / m, it becomes possible to effectively loosen the aggregation of toner, and instantly increase the triboelectric charge amount of toner. Will be possible. Development sleeve 84 by blade
In a system in which a thin layer is coated with toner, particularly in the non-magnetic one-component developing method, in order to obtain a sufficient image density, the developing sleeve 84 is 100% less than the latent image holding member 85.
It is rotated at a peripheral speed of ~ 300%. Preferably 120-2
It is rotated at a peripheral speed of 50%.

It is preferable that the thickness of the negatively chargeable toner layer on the developing sleeve 84 is made smaller than the opposing gap length between the developing sleeve 84 and the latent image holding member 85, and an alternating electric field is formed in this gap. Development sleeve 8 by bias power supply 100
By applying an alternating electric field or a developing bias in which a direct current electric field is superimposed on the alternating electric field to 4, it is possible to facilitate the movement of the toner from the developing sleeve 84 onto the latent image holding member 85, and to obtain a higher quality image. .

[0237]

EXAMPLES The present invention will be specifically described below with reference to production examples and examples, but the present invention is not limited thereto. All parts in the following formulations are parts by mass.

The methods for measuring the physical properties of the toner of the present invention are described below.

(1) Average Circularity and Mode Circularity The average circularity in the present invention is used as a simple method for quantitatively expressing the shape of particles, and in the present invention, flow particles made by Toa Medical Electronics are used. Image analyzer "FPIA-1"
The particle diameter of each particle measured for a group of particles having a circle equivalent diameter of 3 μm or more (ai) is determined by the following equation (1), and is expressed by the following equation (2). The average circularity (a) is defined as the value obtained by dividing the sum of the circularity of all the particles measured in 1. by the total number of particles (m).

[0240]

[Equation 1]

The mode circularity is 0.4%.
It is the circularity of the peak at which the frequency value becomes maximum in the circularity frequency distribution by dividing the measured circularity of each particle into 61 by 0.01 from 0 to 1.00 and allocating the measured circularity of each particle.

[0242] The measuring apparatus "FPIA-1000" used in the present invention calculates the circularity of each particle and
In calculating the average circularity and the modal circularity, the particles have a circularity of 0.40 to 1.00 depending on the circularity obtained.
Is divided into 61 classes, and a calculation method for calculating the average circularity and the mode circularity using the center value and frequency of the division points is used. However, the error between each value of the average circularity and the mode circularity calculated by this calculation formula is very small and can be substantially ignored, and in the present invention, the calculation time is shortened and For reasons of data handling such as simplification of the calculation formula, the concept of the calculation formula that directly uses the circularity of each particle described above may be used, and such a calculation formula partially modified may be used.

The measuring means is as follows. A dispersion liquid was prepared by dispersing 5 mg of the developer in 10 ml of water in which about 0.1 mg of the surfactant was dissolved, and ultrasonic waves (20 kH
z, 50 W) to the dispersion for 5 minutes to adjust the dispersion concentration to 5
The measurement is carried out by the above apparatus at 000 to 20,000 particles / μl, and the average circularity and the mode circularity of a particle group having an equivalent circle diameter of 3 μm or more are obtained.

The average circularity in the present invention is an index of the degree of unevenness of the developer, and it is 1.000 when the developer is a perfect spherical shape, and the circularity becomes smaller as the surface shape becomes more complicated. .

The reason why the circularity is measured only for the particle group having an equivalent circle diameter of 3 μm or more in this measurement is 3 μm.
This is because the particle group having an equivalent circle diameter of less than m includes a large number of particles of the external additive that exist independently of the toner particles, and the circularity of the toner particle group cannot be accurately estimated due to the influence thereof. .

(2) Average Particle Diameter The weight average particle diameter and number average particle diameter of the toner of the present invention can be measured by various methods such as Coulter Counter TA-II type or Coulter Multisizer (manufactured by Coulter). Specifically, it can be measured as follows. Interface (manufactured by Nikkaki) that outputs number distribution and volume distribution using Coulter Multisizer (manufactured by Coulter)
And PC9801 personal computer (NEC
1) is connected, and the electrolyte is 1
% NaCl aqueous solution is prepared. For example, ISOTON
R-II (manufactured by Coulter Scientific Japan) can be used. The measurement procedure is as follows. 100-150 ml of the electrolytic aqueous solution is added, and 2-20 mg of a measurement sample is further added. The electrolytic solution in which the sample is suspended is subjected to a dispersion treatment for about 1 to 3 minutes by an ultrasonic disperser, and the volume and number of toner particles of 2 μm or more are measured by using an aperture by the Coulter Multisizer to measure the volume distribution and the number distribution. And calculate. Then, the volume-based weight average particle diameter (D4) obtained from the volume distribution and the number-based average particle diameter obtained from the number distribution, that is, the number average particle diameter (D1) are obtained.

(3) Gel permeation chromatograph
Measurement of Molecular Weight Distribution by Fee In the present invention, the molecular weight of the resin in the toner was determined as a polystyrene-equivalent molecular weight from the molecular weight distribution in gel permeation chromatography (GPC). G
The measuring method of PC is as follows.

First, as a sample preparation, the toner was dissolved in tetrahydrofuran (THF) at room temperature so that the resin component in the sample was 0.4 to 0.6 mg / ml, and the resulting solution had a pore size of Filter with a 0.2 μm solvent resistant membrane filter.

Next, the column is stabilized in a heat chamber at 40 ° C., THF as a solvent is caused to flow at a flow rate of 1 ml / min, and about 100 μl of a THF sample solution is injected for measurement. In measuring the molecular weight of the sample, the molecular weight distribution of the sample was calculated from the relationship between the logarithmic value and the count number of the calibration curve prepared from several kinds of monodisperse polystyrene standard samples. As a standard polystyrene sample for preparing a calibration curve, TSK standard polystyrene F-8 manufactured by Tosoh Corporation
50, F-450, F-288, F-128, F-8
0, F-40, F-20, F-10, F-4, F-2,
F-1, A-5000, A-2500, A-1000,
A calibration curve was prepared using A-500. As the detector, an RI (refractive index) detector and a UV (ultraviolet) detector were arranged in series and used. As a column, it is better to combine multiple commercially available polystyrene gel columns.
In the present invention, the Shodex GPC K manufactured by Showa Denko KK
F-801, 802, 803, 804, 805, 80
It was measured with a combination of 6,807,800P. As the apparatus, a high speed GPC HPLC8120 GPC (manufactured by Tosoh Corporation) was used.

(4) Measurement of DSC (of vinyl-based copolymer
(Measurement of glass transition temperature and melting point of wax ) The maximum endothermic peak temperature of the wax component is measured by "AST
MD 3418-8 ". For the measurement, for example, Perkin Elmer DSC-7 is used. The melting point of indium and zinc is used to correct the temperature of the device detection unit, and the heat of fusion of indium is used to correct the amount of heat. An aluminum pan is used as a measurement sample, an empty pan is set as a control, and measurement is performed at a temperature rising rate of 10 ° C./min.

Further, the glass transition temperature (Tg) of the vinyl-based copolymer was measured by the DSC curve at the time of the second temperature increase, the baseline before the endothermic peak, the midline of the baseline after the endothermic peak, and the rising curve. The intersection was taken as Tg.

(5) Vinyl Copolymer and Binder of the Present Invention
Measurement of acid value of resin Measurement device, calibration of device, measurement temperature, sample adjustment are the same as those of toner measurement.

Measurement procedure: 1) 0.5 g of the vinyl copolymer or binder resin of the present invention
Weigh accurately. 2) Put the above toner in a 300 (ml) beaker, and mix 150 (ml) of toluene / ethanol (4/1) mixture.
Add and dissolve. 3) Titration using a potentiometric titrator using 0.1 mol / l KOH ethanol solution (for example, potentiometric titrator AT-400 (win manufactured by Kyoto Electronics Co., Ltd.).
(workstations) and automatic titration with ABP-410 electric burette is available). 4) The amount of KOH solution used at this time is S (ml), the blank is measured at the same time, and the amount of KOH solution used at this time is B (ml). 5) The acid value of the toner is calculated by the following formula. f is a factor of KOH. Acid value (mgKOH / g) = {(S−B) × f × 5.6
1} / W

(6) Method for measuring B / A The ratio (B / A) of the content (B) of the iron element to the content (A) of the carbon element present on the surface of the toner particles is as follows. It can be measured by performing surface composition analysis by (X-ray photoelectron spectroscopy analysis).

In the present invention, the ESCA device and measurement conditions are as follows. Equipment used: PHI 1600S type X-ray photoelectron spectrometer Measurement conditions: X-ray source MgKα (400 W) Spectral range 800 μmφ

In the present invention, the surface atomic concentration was calculated from the measured peak intensity of each element using the relative sensitivity factor provided by PHI.

In this measurement, the toner is ultrasonically washed in a solvent such as water or isopropanol in which the toner is not dissolved, the external additive adhering to the toner particle surface is removed, and then the toner is separated by magnetic force and dried. It is preferable to measure.

(7) Method of Measuring D / C In the present invention, a specific method of measuring D / C by TEM is as follows: after sufficiently dispersing particles to be observed in a room temperature curable epoxy resin, 2 in an atmosphere of 40 ° C
A method of observing the cured product obtained by curing for a day as it is or by freezing it as a flaky sample by a microtome equipped with diamond teeth is preferable.

The specific method for determining the ratio of the number of particles is as follows. For the particles for determining D / C by TEM, the equivalent circle diameter is obtained from the cross-sectional area in the micrograph, and the value is ± 10% of the number average particle diameter (D1) measured by the Coulter counter described above. The particles included in the width are the applicable particles, and for the applicable particles,
Measure the minimum value (D) of the distance from the magnetic particle surface and
To calculate. The D / C value calculated in this way is 0.
The ratio of particles of 02 or less is defined to be obtained by the following formula. The micrograph at this time is preferably 10,000 to 20,000 times in magnification in order to perform highly accurate measurement. In the present invention, a transmission electron microscope (H-600 manufactured by Hitachi) is used as an apparatus and observed at an accelerating voltage of 100 kV, and the magnification is 1
Observation and measurement were carried out using a microscope image of 10,000 times.

[0260]

[Equation 2]

Production of Vinyl Copolymer of the Present Invention: (Production Example 1 of Vinyl Copolymer) Styrene 75 was added to a 4-neck separable flask equipped with a stirrer, a cooler, a thermometer and a nitrogen introducing tube. Parts by mass, n-butyl acrylate 10
Parts by mass, N-methylmethacrylamide 5 parts by mass, monohydroxyethyl methacrylate succinate 10 parts by mass, toluene 250 parts by mass, methyl ethyl ketone 100 parts by mass, ethanol 50 parts by mass and 2,2'-azobis (2-methylbutyronitrile). ) 3 parts by mass were charged, stirred, and solution polymerized at 65 ° C. for 8 hours under nitrogen introduction. afterwards,
The polymer obtained after distilling off the polymerization solvent under reduced pressure was subjected to 1 using a cutter mill equipped with a 150 mesh screen.
Coarse pulverization to less than 00 μm, the vinyl copolymer of the present invention (V
1) was obtained.

Glass transition temperature (Tg) is 81.9 ° C., weight average molecular weight (Mw) is 23000, and acid value is 20.5 m.
It was gKOH / g.

(Production Examples 2 to 14 of Vinyl Copolymer) In Production Example 1, except that the monomer composition shown in Table 1 is changed, the vinyl copolymers 2 to 14 (V
2 to V14) were obtained. Table 1 also shows the glass transition temperature, the weight average molecular weight and the acid value.

(Comparative Production Examples 1 and 2 of Vinyl Copolymer) Comparative Production Example 1 was repeated except that the monomer composition shown in Table 1 was changed.
1) and 2 (W2) were obtained. Table 1 shows the glass transition temperature,
The weight average molecular weight and acid value are also shown.

[0265]

[Table 1]

Production of Binder Resin: (Resin Production Example 1) 200 parts by mass of xylene was placed in a reaction vessel equipped with a reflux tube, a stirrer, a thermometer, a nitrogen introducing tube, a dropping device and a decompression device, and then styrene was added. 79 parts by mass, 17 parts by mass of butyl acrylate, 4 parts by mass of monobutyl maleate and 4 parts by mass of di-t-butyl peroxide as a polymerization initiator were added, and the mixture was heated to the reflux temperature while aeration with nitrogen and kept for 12 hours. After that, xylene was distilled off under reduced pressure to obtain a low molecular weight polymer (L-1) having Mw of 7,000, Tg of 57.4 ° C. and an acid value of 12 mgKOH / g.

(Resin Production Example 2) 72 parts by mass of styrene, 26 parts by mass of butyl acrylate, 2 parts by mass of monobutyl maleate and a polymerization initiator (2,2'-bis (4,4-di-t).
-Butylperoxycyclohexyl) propane) 0.3
1 part by weight of a monomer mixture is placed in a reaction vessel equipped with a reflux tube containing 2 parts by weight of polyvinyl alcohol and 200 parts by weight of degassed ion-exchanged water, a stirrer, a thermometer and a nitrogen introducing tube, and suspended. To do. 75 ° C with aeration of nitrogen
The mixture is heated to that temperature for 20 hours, then 0.5 part by weight of benzoyl peroxide is added and kept for another 4 hours, heated to 95 ° C. and kept at that temperature for 2 hours to carry out the polymerization reaction. After the completion, the suspension is separated by filtration, washed with water and dried to obtain Mw of 1230000 and Tg of 59.5 ° C.
Thus, a high molecular weight polymer (H-1) having an acid value of 3 mgKOH / g was obtained.

(Resin Production Example 3) In a mixing vessel equipped with a reflux pipe, a stirrer, a thermometer and a pressure reducing device, 25 parts by mass of the polymer (L-1) and 25 parts by mass of the polymer (H-1) were added to 200 parts of xylene.
It has a main peak at a molecular weight of 7900 by adding to a mass part, heating and dissolving, and distilling off xylene under reduced pressure.
It has a sub-peak at a molecular weight of 890000 and an Mw of 230.
And a acid value of 10 mgKOH / g was obtained as a binder resin (B-1).

(Production Example 1 of hydrophobic iron oxide) 1.0 to 1.1 equivalents of caustic soda solution with respect to iron ions were mixed with an aqueous ferrous sulfate solution to prepare an aqueous solution containing ferrous hydroxide. Prepared.

While maintaining the pH of the aqueous solution at around 9,
Blow in air and oxidize at 80-90 ℃
A slurry liquid of the child was obtained. After washing and filtering, this water-containing slurry
The Lee solution was once taken out. At this time, a small amount of water-containing sample
It was collected and the water content was measured. Next, this hydrous sump
Re-dispersed in another aqueous medium without drying and then re-dispersed
Adjust the pH of the sprinkling liquid to about 6 and use sufficient silane
Pulling agent (n-C ₆H₁₃Si (OCH₃)₃) Magnetic
2.0 parts by mass per 100 parts by mass of iron oxide (amount of magnetic particles
Is calculated as the value obtained by subtracting the water content from the water sample)
Added and subjected to coupling treatment. Generated hydrophobic porcelain
The active particles are washed, filtered and dried by a conventional method, and then slightly coagulated.
Hydrophobic iron oxide 1 is obtained by disintegrating the collected particles.
It was

(Production Example 2 of Hydrophobic Iron Oxide) Except that 2.5 parts by mass of a silane coupling agent (nC ₁₀ H ₂₁ Si (OCH ₃ ) ₃ ) is added to 100 parts by mass of magnetic iron oxide. Hydrophobic iron oxide 2 was obtained in the same manner as hydrophobic iron oxide 1.

Production Example 3 of Hydrophobic Iron Oxide Except that 0.8 part by mass of the silane coupling agent (n-C ₆ H ₁₃ Si (OCH ₃ ) ₃ ) is added to 100 parts by mass of the magnetic iron oxide. Hydrophobic iron oxide 3 was obtained in the same manner as hydrophobic iron oxide 1.

Production Example 4 of Hydrophobic Iron Oxide Except that 3.0 parts by mass of the silane coupling agent (n-C ₂ H ₅ Si (OCH ₃ ) ₃ ) is added to 100 parts by mass of magnetic iron oxide. Hydrophobic iron oxide 4 was obtained in the same manner as hydrophobic iron oxide 1.

Production Example 5 of Hydrophobic Iron Oxide Except that 0.2 part by mass of the silane coupling agent (n-C ₄ H ₉ Si (OCH ₃ ) ₃ ) is added to 100 parts by mass of the magnetic iron oxide. Hydrophobic iron oxide 5 was obtained in the same manner as hydrophobic iron oxide 1.

(Production Example 1 of Magnetic Toner) Ion-exchanged water 7
After adding 451 parts by mass of 0.1 mol / liter-Na ₃ PO ₄ aqueous solution to 09 parts by mass and heating to 60 ° C., 1.0 m
67.7 parts by mass of an ol / liter-CaCl ₂ aqueous solution was gradually added to obtain an aqueous medium containing a calcium phosphate salt. -Styrene 80 parts by mass-n-butyl acrylate 20 parts by mass-P. O. And E. O. Saturated polyester resin obtained by condensation reaction of adduct and terephthalic acid 5 parts by mass, divinylbenzene 0.3 parts by mass, vinyl copolymer 1 (V1) 2 parts by mass, hydrophobic iron oxide 1 90 parts by mass An attritor (Mitsui Miike Kakoki Co., Ltd.) was used to uniformly disperse and mix.

This monomer composition was heated to 60 ° C., and 6 parts by mass of an ester wax containing behenyl behenate as a main component (maximum value of endothermic peak in DSC of 72 ° C.) was added and mixed therein. Polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) [t _1/2 = 140
Min, 60 ° C.] 5 parts by mass were dissolved.

The above polymerizable monomer system was put into the above aqueous medium, and the mixture was mixed with a TK homomixer (Tokushu Kika Kogyo Co., Ltd.) at 60 ° C. and N ₂ atmosphere at 10,000 rpm for 1 minute.
The mixture was stirred for 5 minutes and granulated. Then, the mixture was reacted at 60 ° C. for 6 hours while stirring with a paddle stirring blade. After that, adjust the liquid temperature to 80 ° C.
The stirring was continued for another 5 hours. After the completion of the reaction, the suspension was cooled and hydrochloric acid was added to dissolve the calcium phosphate salt, followed by filtration, washing with water and drying to obtain magnetic toner particles.

Next, 100 parts by mass of the obtained magnetic toner particles were treated with hexamethyldisilazane on silica having a primary particle diameter of 12 nm and then treated with silicone oil to obtain a hydrophobic resin having a BET value of 120 m ² / g after the treatment. Henschel mixer (Mitsui Miike Kakoki Co., Ltd.)
And mixed to prepare Magnetic Toner 1.

The formulation of the magnetic toner 1 is shown in Table 2 together with those of the magnetic toners obtained in the magnetic toner production examples and comparative production examples shown below.

(Production Examples 2 to 14 of Magnetic Toner) Instead of the vinyl copolymer 1 (V1), the vinyl copolymer 2 to
Magnetic toners 2 to 14 were obtained in the same manner as the magnetic toner 1 except that 14 (V2 to 14) was used.

(Magnetic Toner Production Example 15) A magnetic toner 15 was obtained in the same manner as the magnetic toner 1 except that the addition amount of the vinyl copolymer 1 (V1) was changed from 2 parts by mass to 0.05 part by mass. It was

(Production Example 16 of magnetic toner) Magnetic toner 16 was prepared in the same manner as magnetic toner 1 except that the addition amount of vinyl copolymer 1 (V1) was changed from 2 parts by mass to 22 parts by mass.
Got

(Magnetic Toner Production Example 17) A magnetic toner 17 was obtained in the same manner as the magnetic toner 1 except that the addition amount of the vinyl copolymer 1 (V1) was changed from 2 parts by mass to 0.15 parts by mass. It was

(Production Example 18 of magnetic toner) Magnetic toner 18 was prepared in the same manner as magnetic toner 1 except that the addition amount of vinyl copolymer 1 (V1) was changed from 2 parts by mass to 17 parts by mass.
Got

(Production Example 19 of magnetic toner) Black particles 10
0 parts by mass of silica having a primary particle diameter of 12 nm was treated with silicone oil, and the BET value after the treatment was 120 m ² / g.
A magnetic toner 19 was obtained in the same manner as the magnetic toner 1 except that 1 part by mass of the hydrophobic silica fine powder of was used.

(Production Example 20 of Magnetic Toner) A magnetic toner 20 was obtained in the same manner as the magnetic toner 1 except that the addition amount of the ester wax was changed from 6 parts by mass to 0.3 part by mass.

(Production Example 21 of magnetic toner) A magnetic toner 21 was obtained in the same manner as the magnetic toner 1 except that the addition amount of the ester wax was changed from 6 parts by mass to 55 parts by mass.

(Production Example 22 of Magnetic Toner) A magnetic toner 22 was obtained in the same manner as the magnetic toner 1 except that the ester wax was changed to polyethylene wax having a maximum endothermic peak of 120 ° C.

(Production Example 23 of Magnetic Toner) A magnetic toner 23 was obtained in the same manner as the magnetic toner 1 except that the hydrophobic iron oxide 1 was replaced with the hydrophobic iron oxide 2.

(Production Example 24 of Magnetic Toner) A magnetic toner 24 was obtained in the same manner as the magnetic toner 1 except that the hydrophobic iron oxide 1 was changed to the hydrophobic iron oxide 3.

(Production Example 25 of Magnetic Toner) A magnetic toner 25 was obtained in the same manner as the magnetic toner 1 except that the hydrophobic iron oxide 1 was changed to the hydrophobic iron oxide 4.

(Production Example 26 of Magnetic Toner) Hydrophobic iron oxide 4 was used in place of the addition amount of the hydrophobic iron oxide 1 of 90 parts by mass.
The amount added was changed to 120 parts by mass. A magnetic toner 26 was obtained in the same manner as the magnetic toner 1 except for the above.

(Production Example 27 of Magnetic Toner) In Production Example 1 of magnetic toner, a TK homomixer (Tokushu Kika Kogyo Co., Ltd.) was used in the presence of 0.05% by mass of sodium dodecylbenzenesulfonate in an aqueous medium. A magnetic toner 27 was obtained in the same manner as the magnetic toner 1 except that the mixture was stirred at 8,000 rpm for 15 minutes and granulated.

(Production Example 28 of Magnetic Toner) Preparation of Resin Microparticle Dispersion Liquid 1: styrene 320 parts by mass n-butyl acrylate 80 parts by mass divinylbenzene 3 parts by mass dodecanethiol 6 parts by mass carbon tetrabromide 4 By mass, the above components are mixed and dissolved to prepare a solution, while 6 parts by mass of a nonionic surfactant (Nonipol 400, manufactured by Kao Corporation) and an anionic surfactant (Neogen SC, manufactured by Dai-ichi Kogyo Yakuhin Co., Ltd.) 10 parts by mass is dissolved in 550 parts by mass of ion-exchanged water, and the above solution is added and dispersed in a flask to emulsify to 10
While slowly stirring and mixing for 5 minutes, 50 parts by mass of ion-exchanged water in which 5 parts by mass of ammonium persulfate was dissolved was added. Then, after thoroughly replacing the inside of the system with nitrogen, the flask was heated to 70 ° C. in an oil bath while stirring, and emulsion polymerization was continued for 5 hours as it was to obtain a center diameter of 224 nm, a glass transition temperature of 59 ° C., and a Mw of 70,500. Anionic resin fine particle dispersion liquid 1 containing the resin fine particles of was obtained.

Preparation of Magnetic Material Dispersion Liquid 1: 150 parts by mass of hydrophobic iron oxide 5 10 parts by mass of nonionic surfactant (Nonipol 400 manufactured by Kao Corporation) 400 parts by mass of ion-exchanged water The above components were mixed and dissolved. A homogenizer (manufactured by IKA,
Ultra Turrax) for 10 minutes to obtain a magnetic substance dispersion liquid 1 having a central particle diameter of 0.23 μm.

Preparation of Release Agent Dispersion Liquid 1: Paraffin wax (melting point peak temperature 90 ° C.) 50 parts by mass Cationic surfactant (Sanizol B50 manufactured by Kao Corporation) 5.5 parts by mass Ion-exchanged water 200 parts by mass Parts After heating the above components to 98 ° C. under pressure and sufficiently dispersing them with IKA's Ultra Turrax T50, they are subjected to a dispersion treatment with a pressure discharge type homogenizer to contain release agent particles having a center diameter of 0.16 μm. A release agent dispersion liquid 1 was obtained.

Preparation of Dispersion of Vinyl Copolymer 1 (V1): 20% by mass methyl ethyl ketone solution of vinyl copolymer (V1) 100 parts by mass 5 parts by mass of the anionic surfactant described above Ion exchange 400 parts by mass of water The above components are mixed and dissolved, and a homogenizer (made by IKA,
Ultra Turrax) for 10 minutes to obtain a dispersion 1 of a vinyl-based copolymer (V1) having a central particle diameter of 160 nm.

Resin fine particle dispersion liquid 1 258 parts by mass Magnetic substance dispersion liquid 1 336 parts by mass Release agent dispersion liquid 1 32 parts by mass Polyaluminum chloride 1.6 parts by mass In a round stainless steel flask, After thoroughly mixing and dispersing with a homogenizer (Ultra Turrax T50 manufactured by IKA Co., Ltd.), the flask was heated to an aggregation temperature of 63 ° C. while stirring the flask in a heating oil bath. Then 63 ° C
After holding for 60 minutes at 60 ° C, vinyl-based copolymer 1 (V
50.5 parts by mass of the dispersion liquid of 1) was added and gently stirred.

Then, the pH of the system was adjusted to 7.0 with a 0.5 mol / L sodium hydroxide aqueous solution, the stainless steel flask was closed, and the mixture was heated to 80 ° C. while continuing stirring with a magnetic seal. did. After that, adjust the pH to 5.0
It was kept for 6 hours while distilling off methyl ethyl ketone. After completion of the reaction, the mixture was cooled, filtered, and sufficiently washed with ion-exchanged water, and then solid-liquid separation was performed by Nutsche suction filtration. Furthermore, 3L of ion-exchanged water at 40 ° C
Was dispersed again in, and stirred and washed at 300 rpm for 15 minutes.

After repeating this washing operation 5 times, solid-liquid separation was carried out by Nutsche suction filtration. Then, vacuum drying was continued for 12 hours, and then 1.2 parts by mass of hydrophobic silica (hexamethyldisilazane treatment, BET 200 m ² / g) was externally added to obtain a toner 28. The toner particle size was measured with a Coulter counter to find that the weight average particle size was 7.5 μm.
The average circularity was 0.948. Further, the ratio of the iron element content (B) to the carbon element content (A) present on the toner surface measured by X-ray photoelectron spectroscopy (B)
/ A) is 0.0009, and the transmission electron microscope (TE
D / C ≦ 0.02 by observing the cross section of the toner using M)
The number of particles satisfying the condition was 70% or more.

(Production Example 29 of magnetic toner) 100 parts by mass of binder resin (B-1) 6 parts by mass of wax (maximum point of hydrocarbon wax and endothermic peak: 102 ° C.) Vinyl copolymer 1 (V1) 2 parts by mass Hydrophobic magnetic iron oxide 1 90 parts by mass The above mixture was melt-kneaded in a twin-screw extruder heated to 120 ° C., and the cooled mixture was roughly crushed with a cutter mill, and then a counter jet mill. (Hosokawa Micron Co., Ltd.) is used for fine pulverization, and the Coanda effect is used to classify into three types of particle sizes, coarse powder, medium powder, and fine powder, and then classified by a multi-split airflow classifier, and then impact type Surface treatment equipment (treatment temperature 47 ℃, rotary treatment blade peripheral speed 90m / s
ec. 2) was used to obtain magnetic toner particles.

Magnetic toner 29 was obtained by mixing 100 parts by mass of the magnetic toner particles with 1.2 parts by mass of the silica used in Production Example 1 of the magnetic toner with a Henschel mixer.

(Comparative Production Examples 1-2 of Magnetic Toner) Magnetic toner except that comparative vinyl copolymers 1 to 2 (W1 to W2) were used in place of vinyl copolymer 1 (V1). Comparative magnetic toners 1 and 2 were obtained in the same manner as in 1.

(Comparative Production Example 3 of Magnetic Toner) Except that (organic zinc compound consisting of 3,5-di-t-butylsalicylic acid and zinc atom) was used in place of the vinyl copolymer 1 (V1), Comparative magnetic toner 3 was obtained in the same manner as magnetic toner 1.

(Comparative Production Example 4 of Magnetic Toner) Binder Resin (B-1) 100 parts by mass Wax 6 parts by mass (hydrocarbon wax, maximum point of endothermic peak: 102 ° C.) Vinyl copolymer 1 (V1) 2 parts by mass Hydrophobic iron oxide 1 90 parts by mass The above mixture was melt-kneaded by a twin-screw extruder heated to 120 ° C., and the cooled mixture was coarsely crushed by a cutter mill, and then a counter jet mill. (Hosokawa Micron Co., Ltd.) is used for fine pulverization, and the Coanda effect is used for classification into a coarse powder, medium powder, and fine powder into three particle sizes, which are classified by a multi-division airflow classifier to obtain a weight average diameter. Is 7.0 μm
Magnetic toner particles of

To 100 parts by mass of the magnetic toner particles, 1.2 parts by mass of the silica used in Production Example 1 of magnetic toner was mixed with a Henschel mixer to obtain a comparative magnetic toner 4.

(Production Example 1 of non-magnetic toner) Instead of the hydrophobic iron oxide 1, a yellow colorant (CI PY17) was added.
A non-magnetic toner 1 was obtained in the same manner as the magnetic toner 1 except that 0 part by mass was used.

(Production Example 2 of non-magnetic toner) Non-magnetic toner 2 was obtained in the same manner as non-magnetic toner 1 except that a magenta colorant (CI PR122) was used instead of the yellow colorant.

(Production Example 3 of non-magnetic toner) A non-magnetic toner 3 was obtained in the same manner as the non-magnetic toner 1 except that a cyan colorant (CI PB15: 3) was used instead of the yellow colorant.

(Production Example 4 of non-magnetic toner) Instead of the yellow colorant, carbon black (BET specific surface area = 6) was used.
Non-magnetic toner 4 was obtained in the same manner as non-magnetic toner 1 except that 5 m ² / g) was used.

(Comparative Production Examples 1-2 of Non-Magnetic Toner) In place of the vinyl-based copolymer 1 (V1), comparative vinyl-based copolymers 1-2 (W1 and W2) were used, except that Nonmagnetic toners 1 and 2 for comparison were obtained in the same manner as the magnetic toner 3.

(Comparative Production Example 3 of Non-Magnetic Toner) Comparative Production Example 3 of magnetic toner was compared with Comparative Production Example 3 except that 10 parts by mass of a cyan colorant (CI PB15: 3) was used in place of the hydrophobic iron oxide 1. Comparative non-magnetic toner 3 was obtained in the same manner as magnetic toner 3 for toner.

(Comparative Production Example 4 of non-magnetic toner) Comparative Production Example 4 of magnetic toner was compared with Comparative Example 4 except that 10 parts by mass of a cyan colorant (CI PB15: 3) was used in place of the hydrophobic iron oxide 1. Comparative non-magnetic toner 4 was obtained in the same manner as magnetic toner 4 for toner.

The materials and characteristic values used for the magnetic toner of the present invention and the comparative magnetic toner are shown in Table 2, and the materials and characteristic values used for the non-magnetic toner of the present invention and the comparative non-magnetic toner are shown in Table 3. Show.

[0315]

[Table 2]

[0316]

[Table 3]

(Photoreceptor Production Example 1) 30φ as a photoreceptor
Was used as the base. The following layers were sequentially laminated by dip coating to prepare a photoconductor. (1) Conductive coating layer: Mainly composed of a powder of tin oxide and titanium oxide dispersed in a phenol resin. Film thickness 15μ
m. (2) Undercoat layer: Mainly composed of modified nylon and copolymer nylon. The film thickness is 0.6 μm. (3) Charge generation layer: Mainly composed of an azo pigment having absorption in a long wavelength region dispersed in butyral resin. Film thickness 0.6
μm. (4) Charge transport layer: Mainly composed of a hole-transporting triphenylamine compound dissolved in a polycarbonate resin (molecular weight of 20,000 according to Ostwald viscosity method) at a mass ratio of 8:10, and a polytetrafluoroethylene powder ( Particle size 0.2
(μm) was added in an amount of 10% by mass based on the total solid content, and uniformly dispersed. The film thickness is 25 μm. The contact angle with water was 95 degrees.

The contact angle was measured using pure water, and the apparatus used was a contact angle meter CA-X type manufactured by Kyowa Interface Science Co., Ltd.

Example 1 As an image forming apparatus, LBP is used.
-1760 (manufactured by Canon Inc.) was modified and the one roughly shown in FIG. 3 was used.

The organic photoconductor (OPC) drum of Photoconductor Production Example 1 was used as the electrostatic image carrier. In this photoconductor,
As a primary charging member, a rubber roller charging device in which conductive carbon is dispersed and coated with nylon resin is used.
Contact at a linear pressure of (60 g / cm), DC voltage -700
A bias in which an alternating voltage of 1.2 kVpp is superimposed on Vdc is applied to uniformly charge the photoconductor. Following the primary charging, an electrostatic latent image is formed by exposing the image portion with laser light. At this time, the dark portion potential Vd = −700V and the light portion potential VL = −180V.

The gap between the photosensitive drum and the developing sleeve is 28
The thickness of the toner carrier is 0 μm and the layer thickness of the toner carrier is about 7 as shown below.
μm, JIS center line average roughness (Ra) 1.0 μm resin layer was formed on an aluminum cylinder with a diameter of 16φ whose surface was blasted.
T (950 gauss), thickness 1.0 as a toner regulating member
3 mm urethane blade with a free length of 1.0 mm
They were brought into contact with each other with a linear pressure of 9.2 N / m (40 g / cm). Phenolic resin 100 parts by weight Graphite (particle size: about 7 μm) 90 parts by weight Carbon black 10 parts by weight

Next, as a developing bias, a DC bias component Vdc = -500V and an AC bias component V to be superimposed.
pp = 1250V and f = 2000Hz were used. Also,
The peripheral speed of the developing sleeve is the peripheral speed of the photoconductor (94 mm / sec).
110% speed in the forward direction (103 mm / s
ec).

A transfer roller (made of ethylene-propylene rubber in which conductive carbon is dispersed, volume resistance value of conductive elastic layer 10 ⁸ Ωcm, surface rubber hardness 24 °, diameter 20)
mm, contact pressure 59 N / m (60 g / cm)) in the forward direction with respect to the peripheral speed of the photoconductor (94 mm / sec) by 105%.
(99 mm / sec), transfer bias is DC 1.4
It was set to kV.

As a fixing method, a fixing apparatus of the type which does not have an oil coating function of LBP-1760 and which is heated and pressure-fixed by a heater through a film is used. At this time, use a pressure roller having a surface layer of fluororesin,
The diameter of the roller was 30 mm. The fixing temperature was set to 170 ° C. and the nip width was set to 7 mm.

First, the magnetic toner 1 was used as the magnetic toner, and the horizontal line image with the print area ratio of 4% was used in the normal temperature and normal humidity (23 ° C., 50% RH) environment in the intermittent mode (that is, every time one sheet is printed out). The image development test and the durability test were performed on 3,000 sheets in a mode in which the developing device was paused for 10 seconds and the toner deterioration was promoted by the preliminary operation at the time of restart, and the image density, image fog and transferability were evaluated. As the transfer material, 75 g / m ² paper was used. The image was evaluated according to the following evaluation criteria.

Further, under the high temperature and high humidity (30.degree. C., 80% RH) environment and the low temperature and low humidity (15.degree. C., 10% RH) environment, the image forming test of 3000 sheets was similarly conducted, and
(3) was evaluated under all environments, and (4) was evaluated under high temperature and high humidity.

In all the environments, the image density was high and the fog was small throughout, and the developing sleeve and the toner regulating member were also well contaminated under high temperature and high humidity.

The results are shown in Table 4.

Image evaluation was carried out as follows.

(1) Image Density By using a transfer material of a normal copying machine plain paper (75 g / m ² ), a solid black image is output after 3000 sheets of the image output test and the density is measured. evaluated. The image density was measured by using a "Macbeth reflection densitometer RD918" (manufactured by Macbeth Co., Ltd.) to measure the relative density with respect to the image of the white background portion having a document density of 0.00. A: Very good 1.40 or more B: Good 1.35 or more, less than 1.40 C: No problem 1.20 or more, less than 1.35 D: No problem in practical use 1.00 or more, less than 1.20 E : Slightly less than 1.00

(2) Image fog "REFLECTMETER MODEL TC-6D"
The fog density (%) was calculated from the difference between the whiteness of the white background portion of the printout image measured by "S" (manufactured by Tokyo Denshoku Co., Ltd.) and the whiteness of the transfer paper to evaluate the image fog. A green filter was used as the filter. A: Very good less than 0.5% B: Very good less than 1.0% C: Good 1.0% or more and less than 2.0% D: No problem in practical use 2.0% or more and less than 3.0% E: Somewhat difficult 3.0% or more

(3) Transferability The transfer efficiency is as follows: The transfer residual toner on the photosensitive member after the transfer of the solid black image is taped off with a Mylar tape and peeled off, and the value of the Macbeth density of the one stuck on the paper is C, after transfer and before fixing. When the Macbeth density of the Mylar tape stuck on the toner-laden paper was set to D and the Macbeth density of the Mylar tape stuck to the unused paper was set to E, it was approximately calculated by the following formula.

[0333]

[Equation 3]

If the transfer efficiency is 90% or more, the image has no problem. A: Very good (97% or more) B: Very good (95 to less than 97%) C: Good (92 to less than 95%) D: Practical (90 to less than 92%) E: Not practical (less than 90%) )

(4) Contamination state of the developer carrying member and the developer regulating member After the printing out, the adhering toner is removed by air blow and the surface of the developer carrying member and the developer regulating member are contaminated or adhered. The situation and the effect on the printout image were visually evaluated. A: Very good (not generated) B: Very good (slightly contaminated, but does not affect the image) C: Good (stains or adheres but hardly affects the image) D: Practical use (contamination and sticking, but little effect on image) E: Practical use (contamination and sticking are large, causing image defects)

<Examples 2 to 29> Magnetic toners 2 to 29 were used as the magnetic toner, and the image forming test and the durability evaluation were performed by the same image forming method as in Example 1. as a result,
There was no problem with the initial image characteristics, and a result with no problem was obtained up to a durability of 3000 sheets. In Example 20, when the durability was exceeded 2500 sheets at low temperature and low humidity, the back stain of the image was slightly generated.

The results are shown in Table 4.

<Comparative Examples 1 to 4> Comparative magnetic toners 1 to 4 were used as the magnetic toners, and the image forming test and the durability evaluation were performed by the same image forming method as in Example 1. As a result, the image characteristics were not good from the beginning, and an image defect occurred along with the durability test.

[0339]

[Table 4]

<Examples 30 to 33> Nonmagnetic toners 1 to 4 were used as the nonmagnetic toner, and the nonmagnetic toners 1 to 4 commercially available as shown in FIG. 6 using the nonmagnetic one-component developing device as shown in FIG. Table 5 shows the results of evaluation performed in the same manner as in Example 1 using a modified full-color printer.

<Comparative Examples 5 to 8> Comparative non-magnetic toners 1 to 4 were used as non-magnetic toners, and an image forming test and durability evaluation were performed by the same image forming method as in Example 30. As a result, the image characteristics were not good from the beginning, and an image defect occurred along with the durability test. The results are shown in Table 5.

[0342]

[Table 5]

[0343]

EFFECT OF THE INVENTION The toner of the present invention having the above-mentioned structure can obtain a high-quality image under any environment. Further, the toner of the present invention has a small amount of residual toner on the photoconductor after the transfer step, and can be used efficiently.

Further, the developer carrier and the developer regulating member are less contaminated, and a high-definition image can be stably provided for a long period of time.

[Brief description of drawings]

FIG. 1 is a schematic view of a developing device to which the toner of the present invention can be applied.

FIG. 2 is a schematic diagram for explaining a full-color or multi-color image forming method.

FIG. 3 is a diagram showing an example of an image forming apparatus used in an embodiment of the present invention.

FIG. 4 is a diagram showing an example of a developing unit for one-component development.

FIG. 5 is a schematic view showing a non-magnetic one-component developing device.

FIG. 6 is a schematic diagram of an image forming method using an intermediate transfer member.

[Explanation of symbols]

34a core metal 34b elastic layer 35 Transfer bias power supply 100 photosensitive drum 102 Development sleeve 103 elastic blade 104 magnet roller 114 transfer roller 116 Cleaning means 117 Primary charging roller 121 Laser generator 123 laser light 124 register roller 125 conveyor belt 126 Fixer 140 developer 141 developer stirring member

Front page continuation (51) Int.Cl. ⁷ Identification code FI theme code (reference) G03G 9/083 G03G 9/08 325 15/08 507 331 101 15/08 507B (72) Inventor Eriko Yanase Ota Ward, Tokyo 3-30-2 Shimomaruko Canon Inc. (72) Inventor Tatsuya Nakamura 3-30-2 Shimomaruko Ota-ku, Tokyo Canon Inc. F-term (reference) 2H005 AA01 AA06 AA08 AA15 CA02 CA04 CA08 CA12 CA14 CA18 CA26 CB07 CB13 DA02 EA03 EA05 EA06 EA07 EA10 FA06 2H077 AA37 AC16 AD06 AD13 AD17 AD18 AD36 EA03 EA13 EA14 EA16 GA13

Claims (35)

[Claims] 1. A toner having toner particles containing at least a binder resin, a colorant and a vinyl-based copolymer, and an inorganic fine powder mixed with the toner particles, wherein: i) the average circularity of the toner is 0.940 or more, ii) the vinyl-based copolymer is at least represented by the following general formula (1): (In the formula, R ₁ is a hydrogen atom or a methyl group, R ₂ and R ₃ are a hydrogen atom, an alkyl group substitutable with a substituent excluding an acid group,
Or a copolymer obtained by copolymerizing an amide group-containing vinyl monomer represented by (an organic group in which R ₂ and R ₃ are bonded to form a heterocycle with a nitrogen atom) and a carboxyl group-containing vinyl monomer. Toner. 2. The toner according to claim 1, wherein the toner has a negative charging property. 3. The toner according to claim 1, wherein the toner has an average circularity of 0.950 or more and a modal circularity of 0.95 or more. 4. The toner according to claim 1, wherein the average circularity of the toner is 0.970 or more and the mode circularity is 0.99 or more. 5. The toner according to claim 1, wherein 20% by number or less of particles having a circularity of less than 0.950 are included in the toner. 6. The toner according to claim 1, wherein the number of particles having a circularity of less than 0.950 is 15% or less in the toner. 7. The vinyl-based copolymer is a copolymer obtained by copolymerization with an amide group-containing vinyl monomer represented by the general formula (1), a carboxyl group-containing vinyl monomer and a styrene monomer. 7. The toner according to any one of claims 1 to 6. 8. The vinyl-based copolymer contains 0.2 to 20% by mass of an amide group-containing vinyl monomer represented by the general formula (1) and a carboxyl group-containing vinyl monomer, respectively. 8. The toner according to any one of 1 to 7. 9. The vinyl copolymer contains 2 to 15 mass% each of an amide group-containing vinyl monomer represented by the general formula (1) and a carboxyl group-containing vinyl monomer represented by the general formula (1). 7. The toner according to any one of 7. 10. The vinyl monomer containing a carboxyl group
Is the following general formula (2) or (3) [Chemical 2] (In the formula, R_FourIs a hydrogen atom or a methyl group, R_FiveHas 2 carbon atoms
~ 6 alkylene group, n is an integer of 0-10, X is hydrogen source
Child, alkali metal, alkaline earth metal or quaternary ammonium
(Nium group) [Chemical 3] (In the formula, R₆Is a hydrogen atom or a methyl group, R₇Has 2 carbon atoms
~ 4 alkylene groups, R ₈Is an ethylene group, a vinylene group,
1,2-cyclohexylene group, phenylene group, X is hydrogen
Atom, alkali metal, alkaline earth metal or quaternary amine
Monomer containing a carboxyl group represented by
Mar. 1 to 9, characterized in that it is a mer.
The toner according to. 11. The toner according to claim 1, wherein the vinyl-based copolymer has a weight average molecular weight (Mw) of 2000 to 100,000. 12. The toner according to claim 1, wherein the vinyl-based copolymer has a weight average molecular weight (Mw) of 5,000 to 50,000. 13. The toner according to claim 1, wherein the vinyl-based copolymer has a glass transition temperature (Tg) of 50 to 120 ° C. 14. The toner according to claim 1, wherein the glass transition temperature (Tg) of the vinyl-based copolymer is 60 to 100 ° C. 15. The vinyl-based copolymer is 5 to 50 m
An acid value of gKOH / g.
15. The toner according to any one of 14 to 14. 16. The vinyl-based copolymer is 10 to 40.
The toner according to any one of claims 1 to 14, which has an acid value of mgKOH / g. 17. The toner according to claim 1, wherein the toner contains the vinyl-based copolymer in an amount of 0.1 to 20 parts by mass with respect to 100 parts by mass of a binder resin. The toner described. 18. The toner according to claim 1, wherein the toner contains the vinyl copolymer in an amount of 0.2 to 10 parts by mass with respect to 100 parts by mass of a binder resin. The toner described. 19. The inorganic fine powder having an average primary particle diameter of 4 to 80 nm is contained in an amount of 0.1 to 4 parts by mass with respect to 100 parts by mass of the toner as a whole. toner. 20. The inorganic fine powder is at least silica,
20. The toner according to claim 19, wherein the toner is one selected from titanium oxide, alumina, and complex oxides thereof. 21. The toner according to claim 19, wherein the inorganic fine powder is hydrophobized. 22. The toner according to claim 19, wherein the inorganic fine powder is at least hydrophobized with silicone oil. 23. The toner according to claim 19, wherein the inorganic fine powder is hydrophobized with at least a silane compound and silicone oil. 24. The toner according to claim 1, wherein the toner contains 0.5 to 50 parts by mass of wax with respect to 100 parts by mass of a binder resin. 25. The wax has a DSC curve measured by a differential scanning calorimeter of 40 to 110 at a temperature rise.
The toner according to claim 24, which has a maximum endothermic peak in a region of ° C. 26. The wax has a DSC curve measured by a differential scanning calorimeter at 45 to 90 ° C. when heated.
25. The toner according to claim 24, which has a maximum endothermic peak in the region. 27. The toner contains 10 to 10 parts of the binder resin.
27. The toner according to claim 1, which contains 150 parts by mass of iron oxide. 28. The ratio (B / A) of the content (B) of the iron element to the content (A) of the carbon element present on the toner surface measured by X-ray photoelectron spectroscopy analysis is less than 0.001. , C is the projected area circle equivalent diameter of the toner, and D is the minimum value of the distance between the iron oxide and the toner surface in the cross-section observation of the toner using a transmission electron microscope (TEM).
50 toner% satisfying the relationship of D / C ≦ 0.02
28. The toner according to claim 27, which is the above. 29. The toner according to claim 27, wherein the ratio (B / A) is less than 0.0005. 30. The magnetic toner according to claim 27, wherein the ratio (B / A) is less than 0.0003. 31. 65% by number or more of toner satisfying the relationship of D / C ≦ 0.02.
31. The magnetic toner according to any one of 30 to 30. 32. The toner satisfying the relationship of D / C ≦ 0.02 is 75% by number or more.
31. The magnetic toner according to any one of 30 to 30. 33. A developing step of developing an electrostatic charge image carried on an image carrier for carrying an electrostatic charge image with a toner to form a toner image; the toner formed on the image carrier An image forming method, comprising: a transfer step of transferring an image onto a recording material with or without an intermediate transfer member; and a fixing step of heating and fixing the toner image transferred onto the recording material onto the recording material. Is a toner according to any one of claims 1 to 32. 34. An image forming apparatus for forming an image by transferring a toner to an electrostatic latent image formed on a photoreceptor to visualize the toner, and transferring the toner image to a transfer material to form an image. A process cartridge configured to be detachable from the apparatus, including a photoconductor, a charging unit that charges the photoconductor, and a latent image forming unit that forms an electrostatic latent image on the photoconductor. At least one unit selected from a transfer unit that transfers the toner image to the recording material and a cleaning unit that removes the toner remaining on the photosensitive member after the toner image is transferred to the transfer member is the photosensitive member. 33. The toner according to claim 1, which is integrally supported with a developing unit that develops the electrostatic latent image formed above with toner to form a toner image. Professional Scan cartridge. 35. An image forming apparatus for forming an image by transferring an electrostatic latent image formed on a photoconductor to a toner to visualize the electrostatic latent image and transferring the toner image to a transfer material. A process cartridge configured to be detachable from the apparatus, including a photoconductor, a charging unit that charges the photoconductor, and a latent image forming unit that forms an electrostatic latent image on the photoconductor. At least one unit selected from a transfer unit that transfers the toner image to the recording material is integrally supported with a developing unit that develops the electrostatic latent image formed on the photoconductor with toner to form a toner image. The toner remaining on the photoconductor after the toner image is transferred to the transfer material is collected by the developing means,
33. A process cartridge, wherein the toner is the toner according to any one of claims 1 to 32.