JP2001092177A - Toner and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide toner having a fine particle diameter and sharp distribution of the grain size with which a high definition image can be stably obtained even under conditions of high humidity or low temperature and low humidity. SOLUTION: The toner contains at least a binder resin and a coloring agent, and has the following features. (i) The number average particle diameter ranges 0.5 to 6.0 μm. (ii) The coefficient of variation of the number distribution is <=20%. (iii) The toner contains a methanol-soluble resin component extracted with methanol by 0.01 to 10 wt.% based on the mass of the toner, and the methanol-soluble resin component contains a polymer composition containing a hydroxy group and has a hydroxy group value (OHv) of 300 to 450 mgKOH/g.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] 1. Field of the Invention [0002] The present invention relates to a toner for forming an electrostatic latent image and a toner for forming a toner image in a toner jet type image forming method, and a method for manufacturing the same.

[0002]

2. Description of the Related Art An electrophotographic method is disclosed in U.S. Pat.
Numerous methods are known as described in Japanese Patent Publication No. 7,691, Japanese Patent Publication No. 42-23910 and Japanese Patent Publication No. 43-24748. Generally, a photoconductive substance is used to form an electric latent image on a photoreceptor by various means, and then the latent image is developed using toner, and if necessary, using direct or indirect means. After transferring a toner image onto a transfer material such as paper, the toner image is fixed by heating, pressurizing, heating and pressurizing, or solvent vapor to obtain a copy or print. The toner remaining on the photosensitive member without being transferred is cleaned by various methods as necessary, and the above-described steps are repeated.

[0003] The toner as described above is generally a particle mainly composed of a binder resin and a colorant, and further contains a charge control agent, a fixing aid, and the like, if necessary. Usually, the particle size is in the range of several to several tens of μm. This toner is generally manufactured by a so-called pulverization method in which a colorant such as a dye, a pigment or a magnetic material is mixed and melted in a thermoplastic resin, and the colorant is uniformly dispersed in the thermoplastic resin, and then pulverized and classified. ing.

In recent years, an image forming apparatus using an electrophotographic method has
It has been widely used not only as a copy machine for office work for copying text documents, but also as a high-quality full-color output and a high-definition output of a computer. Furthermore, printers and personal computers have been used in general fields as computers have become more general-purpose, and accordingly, demands for high-quality output images have appeared in all environments.

As a result, the performance required of the toner becomes higher, and if the improvement of the image quality from the toner side, that is, the performance improvement of high quality under various environments cannot be achieved,
Excellent image formation is no longer feasible.

As one of means for achieving such high image quality, there is a method of reducing the particle size of the toner. Certainly, improvement in image quality and resolution has been achieved by reducing the particle diameter to several μm.

However, a conventional pulverization method of a toner has a problem that when a strong impact force is applied to reduce the particle diameter of the toner, the material to be pulverized may be fused to the pulverization apparatus. It is difficult to reduce the particle size to the following, and it is also difficult to sharpen the particle size distribution to a certain extent due to the cohesive force of the powder when the toner particle size is reduced even in the classification operation. As a result, it becomes difficult to control the charge amount of the toner, and problems such as scattering and fogging of an image occur.

In order to reduce the particle size of the toner and to improve the sharpness of the particle size distribution, a toner produced by a polymerization method has been proposed. For example, Japanese Patent Publication No. 6-52432 and Japanese Patent Application Laid-Open No. 5-93002 disclose a method for producing particles having a sharp particle size distribution of about 1 to 10 μm. Further, Japanese Patent Publication No. 6-58543 and Japanese Patent Publication
JP-A-58544 discloses a method for producing particles for forming an image having a stable charge property and improved functionality by coating a substance comprising a coloring agent or a conductive agent and a binder resin in addition to a sharp particle size distribution. A method is disclosed.

However, such particles having a sharp particle size distribution are excellent in fluidity, but on the other hand, when they are allowed to stand still, they are packed tightly, and the toner aggregates particularly when left in a high temperature environment. Occurs. In the particles coated with a coloring agent or a conductive agent for imparting the above-described functionality, there is a problem that the particles are more easily condensed when densely packed due to non-uniformity in fine portions on the toner surface. is there. When the toner or the developer aggregates, charging failure is likely to occur, and as a result, a problem that the resolution of the developed image is deteriorated is caused.

Further, when a conductive agent is coated, the toner particles have an appropriate charge in a normal temperature and normal humidity environment, but cannot retain the charge under a high humidity condition. Occurs.

[0011]

SUMMARY OF THE INVENTION An object of the present invention is to provide a toner which has solved the above problems and a method for producing the same.

That is, the present invention provides a toner capable of stably obtaining a high-definition image even under high humidity and low temperature and low humidity, and having a fine particle size and a sharp particle size distribution, and a method for producing the same. The purpose is to:

[0013]

The above objects can be achieved by the present invention described below.

That is, the present invention relates to a toner having at least a binder resin and a colorant.
(I) the number average particle size is 0.5 to 6.0 μm;
(Ii) the coefficient of variation of the number distribution is 20% or less;
ii) The amount of the methanol-soluble resin component extracted by methanol is 0.01 to 10% by mass based on the mass of the toner.
The methanol-soluble resin component contains a polymer composition having a hydroxyl group, and
The present invention relates to a toner having a hydroxyl value (OHv) of gKOH / g.

Further, the present invention provides a polymer which is soluble in a solvent for polymerization and which is formed by polymerization, and a polymerizable monomer which is insoluble in the solvent for polymerization, and a polymer which is soluble in the solvent for polymerization. Dissolving a polymer composition in the solvent for polymerization to prepare a polymerization reaction system; setting the amount of dissolved oxygen in the polymerization reaction system at the start of the polymerization reaction to 2.0 mg / liter or less, Polymerizing the polymerizable monomer in the presence of a polymerization initiator in a reaction system; obtaining polymer particles from the polymerization reaction system; and forming a toner from the obtained polymer particles. A method for producing a toner, wherein the obtained toner contains at least a binder resin and a colorant, (i) the number average particle size is 0.5 to 6.0 μm, and (ii) the number distribution Has a coefficient of variation of 20% or less,
(Iii) 0.01 to 10% by mass, based on the mass of the toner, of a methanol-soluble resin component extracted with methanol, wherein the methanol-soluble resin component contains a polymer composition having a hydroxyl group. And 300 to 45
The present invention relates to a method for producing a toner, which has a hydroxyl value (OHv) of 0 mgKOH / g.

One of the features of the present invention is that in the toner,
The number average particle diameter is in the range of 0.5 to 6.0 μm, the coefficient of variation of the number distribution is in the range of 20% or less, and the methanol-soluble resin component extracted by the methanol solvent, that is, the toner has a surface layer. And the methanol-soluble resin component, that is, the surface layer of the toner contains a polymer composition having a hydroxyl group, and is contained in an amount of 300 to 450 mgKOH /
g of hydroxyl value.

According to a detailed study by the present inventors, it has been found that a toner having a number average particle size of 0.5 to 6.0 μm can be developed faithfully with respect to a latent image. Was. Furthermore, it has been found that in the toner having such a fine particle diameter, the coefficient of variation of the number distribution is required to be in the range of 20% or less in order to suppress the variation in charging. Further, in order to prevent the packing and the coagulation of the toner when the toner having the fine particle size and the uniform particle size are settled in this way, 0.01 to 10% by mass of a surface resin component soluble in methanol is provided near the toner surface. The inclusion was found to be effective. Further, the resin component soluble in methanol contains a polymer composition having a hydroxyl group, and has a hydroxyl value (OHv) of 300 to 450 mg KOH.
/ G makes it possible to obtain a stable output image with good toner charging characteristics in various environments from a low humidity environment to a high humidity environment.

In the present invention, the hydroxyl value (OHv) is
According to the standard method for analyzing fats and oils (edited by the Japan Association of Fats and Chemicals), it refers to the number of milligrams of potassium hydroxide required to neutralize acetic acid bound to hydroxyl groups when acetylating 1 g of a sample.

Most of the methanol-soluble resin component extracted by methanol, that is, the component of the toner surface layer is considered to be mostly the polymer composition and the binder resin in the toner surface layer portion, but a small amount of residual resin is present. Monomers, initiators,
It is believed that other additives are also included.

Furthermore, in the present invention, it has also been found that when the resin component soluble in methanol contains a polymer composition having a hydroxyl group, the environmental stability becomes very good.

Further, in the present invention, the methanol-soluble resin component has at least repeating units (I) and (II) represented by the following structural formulas. ) And (I)
The total number of repeating units of (I) is at least 50% of the number of units constituting the entire methanol-soluble resin component, and the number of repeating units of the repeating unit (I) is at least one of the repeating units (I) and (II). 60 to 1 for the total number of
When the content is 00%, the affinity with the binder resin as the main component of the toner particles is good, and the environmental stability is more excellent.

[0022]

[Outside 3] (Wherein, R ₁ is (CH ₂ ) _n , n = 1 to 4, R ₂ is H,
Substituted or unsubstituted alkyl group, halogen atom, R ₃ -R
₇ represents a hydrogen atom, a substituted or unsubstituted alkyl group, a halogen atom, a nitrile group, a hydroxyl group, and a repeating unit (I)
And (II) may be plural types. )

Further, in the present invention, in the molecular weight distribution of the methanol-soluble resin component in terms of polystyrene by GPC, (i) a component having a maximum value in the range of 2,000 to 100,000, and (ii) a component having a molecular weight of 200 to 1,000. When the content is 3% by mass or less, aggregation of toner particles can be prevented, environmental stability can be improved, and high-quality output can be achieved.

The toner of the present invention is preferably a method of directly producing the toner by a polymerization method. Among them, a polymer that can be dissolved in a solvent for polymerization and is produced by polymerization is a polymerizable monomer that is insoluble in the solvent for polymerization, and
Dissolving a polymer composition soluble in the polymerization solvent in the polymerization solvent to prepare a polymerization reaction system; the amount of dissolved oxygen in the polymerization reaction system at the start of the polymerization reaction is 2.0 mg / liter. Setting the following, a step of polymerizing the polymerizable monomer in the presence of a polymerization initiator in the polymerization reaction system; a step of obtaining polymer particles from the polymerization reaction system; It is preferable that the toner is produced by a method for producing a toner having a step of producing a toner.

In the polymerization reaction system in which the polymer composition having a hydroxyl group is dissolved, the polymerization is started with the amount of dissolved oxygen at the start of the polymerization reaction being 2.0 mg / liter or less, whereby a uniform particle size is obtained. It can produce particles with a distribution.

Further, in the production method, methanol and / or ethanol or a mixture thereof is mixed with 3
Production having a washing step of washing polymer particles with a mixed solvent containing in the range of 0 to 99.9% by mass, and further with a mixed solvent for washing containing 30% by mass or more of a saturated alcohol represented by the following chemical formula-1. The method is preferred.

(Chemical Formula-1) C _n H _{2n + 1} OH n = 1 to 5

Further, it is preferable that the washing solvent used in the washing step contains water in the range of 0.1 to 70% by mass, preferably 0.5 to 65% by mass. Finally, it is more preferable to wash with water.
As described above, by using a washing medium containing methanol and / or ethanol or a mixture thereof in the range of 30 to 99.9% by mass and water of 0.1 to 70% by mass as a solvent, the weight is reduced. The effect that a desired amount of the coalescing composition can be left on the surface is obtained. Further, in the washing process, the polymer composition can be favorably made to exist on the toner surface by washing a plurality of times with a mixed solvent containing 30% by mass or more of the saturated alcohol represented by (Chemical Formula 1). Preferably, the mixed solvent used for washing is equivalent to or poorer than the mixed solvent used for polymerization. Further, it is preferable that water is used for the final cleaning in order to perform surface modification as described above.

[0029]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The configuration of the present invention will be described in detail.

The toner of the present invention has a number average particle diameter of 0.5.
It is important that the thickness is in the range of 1.0 to 6.0 μm, preferably 1.0 to 5.0 μm. This is necessary to obtain a high-definition image, and if it is smaller than 0.5 μm, it becomes difficult to handle as a dry powder. On the other hand, if the thickness exceeds 6 μm, it becomes impossible to faithfully develop the latent image of minute dots, so that the reproducibility of highlights becomes particularly poor.

Further, in the present invention, the coefficient of variation of the number distribution of the toner is preferably 20% or less, more preferably 18% or less.

The variation coefficient of the toner number distribution is calculated by the following equation.

[0033]

[Outside 4]

In the present invention, the spread of the particle size distribution in addition to the average particle size of the toner greatly contributes to the image reproducibility particularly in the transfer process. That is, when the coefficient of variation exceeds 20%, the development is performed favorably even if the average particle diameter is within the range of the present invention, but the toner is splattered at the time of transfer and there is a toner that is not transferred. Become like

In the present invention, a methanol-soluble resin component extracted with methanol as a surface layer is contained in an amount of 0.01 to 10% by mass relative to the total mass of the toner, and the methanol-soluble resin component has a hydroxyl group. Having a hydroxyl value (OHv) of 300 to 450 mg
It is preferably KOH / g.

0.01% by mass of methanol-soluble resin component
If it is less than 30, a significant difference suitable for the environmental stability of the toner does not appear. On the other hand, if the content exceeds 10% by mass, the amount of moisture adsorbed on the toner surface becomes too large, which causes a disadvantage that the charge amount in a high humidity environment is reduced. Preferably it is 0.2 to 8% by mass, more preferably 0.5 to 7.5% by mass.

In the present invention, what is required together with the resin component of the surface layer is that the resin component contains a polymer composition having a hydroxyl group and has a hydroxyl value (OHv) of 300 to 450.
mgKOH / g. When the resin component of the surface layer contains the polymer composition having a hydroxyl group and is localized on the surface, in the case of the toner of the present invention having a relatively high hydroxyl value, the above-mentioned moisturizing effect on the toner surface is preferred. It is considered that the environmental stability as described above is favorably achieved. At the same time, by producing particles in a state in which the polymer composition having a hydroxyl group is dissolved in the polymerization reaction system at the time of toner production, a particle having a very sharp particle size distribution can be obtained.

Preferably, the hydroxyl value (OHv) is 340
430 mgKOH / g, more preferably 36 mgKOH / g.
It is 0 to 400 mgKOH / g. Hydroxyl value (OH
If v) is less than 300 mgKOH / g, the production stability of the toner cannot be obtained. On the other hand, if it exceeds 450 mgKOH / g, the number of hydroxyl groups increases and the amount of charge in a high humidity environment is reduced.

In the present invention, the methanol-soluble resin component has at least repeating units (I) and (II) represented by the following structural formulas, and in the methanol-soluble resin component, the repeating units (I) and (II) ) Is 50% or more of the number of units constituting the entire methanol-soluble resin component, and the number of repeating units of the repeating unit (I) is equal to or less than that of the repeating units (I) and (II). Preferably, it is 60 to 100% of the total number.

[0040]

[Outside 5] (Wherein, R ₁ is (CH ₂ ) _n , n = 1 to 4, R ₂ is H,
Substituted or unsubstituted alkyl group, halogen atom, R ₃ -R
₇ represents a hydrogen atom, a substituted or unsubstituted alkyl group, a halogen atom, a nitrile group, a hydroxyl group, and a repeating unit (I)
And (II) may be plural types. )

If the total of the repeating units (I) and (II) is less than 50%, good environmental stability cannot be obtained, and if the repeating unit (I) is less than 50%, the toner in a low humidity environment will not be obtained. This tends to increase the charge amount, and involves instability in the toner manufacturing method.

In the present invention, when a polymer composition having at least the repeating units (I) and (II) represented by the above structural formula is used, a plurality of types of the repeating unit (I) may be present. Similarly, a plurality of types of the repeating unit (II) may be present. In the above structural formula, R ₁ is (CH ₂ ) _n , n = 1 to 4, R ₂ is H, a substituted or unsubstituted alkyl group, a halogen atom, R _{3 to} R ₇ are a hydrogen atom,
Represents a substituted or unsubstituted alkyl group, a halogen atom, a nitrile group, or a hydroxyl group.

Examples of the repeating unit (I) include polymers of hydroxymethyl methacrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, and 4-hydroxybutyl methacrylate.

Examples of the repeating unit (II) include a phenylethylene group, a 1-phenyl-1-methylethylene group, a 1-phenyl-1-fluoromethylethylene group,
-Phenyl-1-trifluoromethylethylene group, 1-
Phenyl-1-hydroxymethylethylene group, 1-phenyl-1-carboxymethylethylene group, 1-phenyl-1-ethylethylene group, 1-phenyl-1-n-propylethylene group, 1-phenyl-1-isopropylethylene Group, 1-phenyl-1-n-butylethylene group, 1
-Phenyl-1-isobutylethylene group, 1-phenyl-1-t-butylethylene group, 1-phenyl-1-n-
Pentylethylene group, 1-phenyl-1-isopentylethylene group, 1-phenyl-1-neopentylethylene group, 1-phenyl-1-t-pentylethylene group, 1-
Phenyl-1-n-hexylethylene group, 1-phenyl-1-isohexylethylene group, 1-phenyl-1-fluoroethylene group, o-tolylethylene group, 1- (o-
Tolyl) -1-methylethylene group, 2,3-xylylethylene group, 1- (2,3-xylyl) -1-methylethylene group, m-cumenylethylene group, 1- (m-cumenyl)
-1-methylethylene group, mesitylethylene group, 1-mesityl-1-methylethylene group, p-trifluoromethylphenylethylene group, 1- (p-trifluoromethylphenyl) -1-methylethylene group, p- Methoxymethylphenylethylene group, 1- (p-methoxymethylphenyl) -1-methylethylene group, p-hydroxymethylphenylethylene group, 1- (p-hydroxymethylphenyl) -1-methylethylene group, p-aminomethyl Phenylethylene group, 1- (p-aminomethylphenyl)-
1-methylethylene group, pentafluorophenylethylene group, 1-1 pentafluorophenyl-1-methylethylene group, p-nitrilephenylethylene group, 1- (p-
Nitrilephenyl) -1-methylethylene group, p-hydroxyphenylethylene group, 1- (o-hydroxyphenyl) -1-methylethylene group, p-carboxyphenylethylene group, 1- (p-carboxyphenyl) -1-
Methylethylene group, p-sulfophenylethylene group, 1
-(P-sulfophenyl) -1-methylethylene group, p
-Aminophenylethylene group, 1- (p-aminophenyl) -1-methylethylene group and the like.

The repeating units (I) and (I) of the present invention
Examples of the polymer composition having I) include styrene-hydroxymethyl methacrylate copolymer, α-methylstyrene-2-hydroxyethyl methacrylate copolymer, and styrene-α-methylstyrene-2-hydroxyethyl methacrylate copolymer Etc. can be given.

In the present invention, the polymer composition preferably has a repeating unit having a hydrocarbon substituent having 3 or more carbon atoms in a side chain. More preferably, it is a hydrocarbon substituent having 5 or more carbon atoms. Thereby, the compatibility between the toner particles and the polymer composition is improved, so that the production process of the toner particles can be stabilized, and the environmental stability is also improved.

Examples of the hydrocarbon group include an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an aryl group, an alkoxyl group, an aryloxyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyl group, an acyloxyl group, And a ring group.

For example, examples of the alkyl group include n-propyl, isopropyl, 3,3,3,2,2-pentafluoro-n-propyl, n-butyl, s-butyl and t-butyl. , 4-cyano-n-butyl group, 4-amino-n-butyl group, n-pentyl group, t-pentyl group, isopentyl group, neopentyl group, n-hexyl group, heptyl group, octyl group, nonyl group, decyl A cycloalkyl group such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group or a cyclooctyl group; an alkenyl group such as an allyl group, 1-propenyl group, isopropenyl group, Pentenyl group, 2-butenyl group, 3-methyl-
2-butenyl group or the like; cycloalkenyl group as cyclohexenyl group or the like; aryl group as phenyl group, o-toluyl group, m-toluyl group, p-toluyl group, p-ethylphenyl group, xylyl group, -N-butylphenyl group, -tert-butylphenyl group, pn
-Hexylphenyl group, pn-octylphenyl group,
pn-nonylphenyl group, pn-decylphenyl group, pn-dodecylphenyl group, benzyl group, p-hydroxyphenyl group, p-methoxyphenyl group, p-carboxyphenyl group, p-sulfophenyl group A biphenylyl group, a p-fluorophenyl group, an m, p-difluorophenyl group, a naphthyl group, an anthryl group and the like; the alkoxyl group includes a t-butoxyl group, an n-propoxyl group, an isopropoxyl group and an n-pentyloxy Aryloxyl group such as phenoxy group; alkoxycarbonyl group such as n-propoxycarbonyl group, isopropoxycarbonyl group, pentyloxycarbonyl group, 3-chloro-
2-acid phosphooxypropoxycarbonyl group and the like; aryloxycarbonyl group such as phenoxycarbonyl group; acyl group as valeryl group and benzoyl group; acyloxyl group as n-propylcarbonyloxy group and isopropylcarbonyl An oxy group, a pentylcarbonyloxy group, a benzoyloxy group, a benzylcarbonyloxy group and the like; examples of the heterocyclic group include a 2-pyrrolyl group, a 2-pyridyl group, a 2-quinolyl group, a morpholino group, an imidazolyl group, a 2-pyrrolidinonyl group, And N-carbazolyl group.

The toner of the present invention preferably has a molecular weight distribution of 2,000 to 100,000 in terms of polystyrene-equivalent molecular weight distribution of the methanol-soluble resin component by GPC.
And a molecular weight of 200 to 100
It is preferable to contain the 0 component at 3% by mass or less. This is necessary for the toner of the present invention to stabilize the charge amount in various environments and to improve the blocking resistance and the non-aggregation property under a high temperature environment.

As the method for producing the toner of the present invention, the following methods are mentioned as preferred embodiments.

The toner of the present invention is soluble in a polymerization solvent, and a polymer formed by polymerization is a polymerizable monomer that is insoluble in the polymerization solvent and a polymerizable monomer that is insoluble in the polymerization solvent. Dissolving a polymer composition in the solvent for polymerization to prepare a polymerization reaction system; setting the amount of dissolved oxygen in the polymerization reaction system at the start of the polymerization reaction to 2.0 mg / liter or less, Polymerizing the polymerizable monomer in the presence of a polymerization initiator in a reaction system; obtaining polymer particles from the polymerization reaction system; and forming a toner from the obtained polymer particles. It is preferable to use a method for producing a toner. Therefore, the solvent-soluble resin component soluble in methanol of the present invention mainly contains the above-described polymer composition. Specific examples of such a polymer composition include the compounds described above.

As the solvent preferably used in the present invention, specifically, any organic solvent or a mixed solvent of the organic solvent and water can be used. Preferably, an organic solvent that does not react with the polymerizable monomer composition or a mixed solvent of the organic solvent and water is used. The amount of water used is 0.1 to 50% by mass, preferably 0.1 to 50% by mass.
-40% by mass, more preferably 0.1-30% by mass, even more preferably 0.5-20% by mass.
When a large amount of water exceeding mass% is contained, there arises a problem that uniform toner particles cannot be obtained.

Specific examples of the solvent used in the present invention include, for example, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, 1-pen Tanol, 2-pentanol, 3-entanol, 2-methyl-1-butanol, isopentyl alcohol, tert-pentyl alcohol, 1-hexanol, 2-methyl 1-pentanol, 4-methyl-2
Alcohols such as pentanol 2-ethylbutanol, 1-heptanol, 2-heptanol, 3-heptanol, 2-octanol, 2-ethyl1-hexanol, benzyl alcohol, cyclohexanol; methyl cellosolve, cellosolve, isopropyl cellosolve, butyl cellosolve , Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; esters such as ethyl acetate, butyl acetate, ethyl propionate, cellosolve acetate; pentane, 2-methylbutane, n-hexane , Cyclohexane, 2-methylpentane, 2,2-dimethylbutane,
2,3-dimethylbutane, heptane, n-octane, isooctane, 2,2,3-trimethylpentane, decane, nonane, cyclopentane, methylcyclopentane,
Aliphatic or aromatic hydrocarbons such as methylcyclohexane, ethylcyclohexane, p-menthane, bicyclohexyl, benzene, toluene, xylene, and ethylbenzene; halogenated hydrocarbons such as carbon tetrachloride, trichloroethylene, chlorobenzene, and tetrabromoethane; Ethenols such as ethyl ether, dimethyl ether and trioxane tetrahydrofuran; acetals such as methylal and diethyl acetal; fatty acids such as formic acid, acetic acid and propionic acid; nitropropene, nitrobenzene,
Sulfur such as dimethylamine, monoethanolamine, pyridine, dimethylformamide, dimethylsulfoxide
Nitrogen-containing organic compounds; and water.

As the polymerizable monomer used in the present invention, specifically, for example, styrene, o-methylstyrene, m-
Styrene monomers such as methylstyrene, p-methoxystyrene, p-ethylstyrene, p-tert-butylstyrene; acrylic acid, methyl acrylate, ethyl acrylate, n-butyl acrylate, n-propyl acrylate; Acrylic esters such as isobutyl acrylate, octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, acrylic sanstearyl, 2-chloroethyl acrylate, phenyl acrylate; methacrylic acid, methyl methacrylate, ethyl methacrylate, methacrylic acid N-propyl acrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate,
Methacrylates such as stearyl methacrylate, phenyl methacrylate, dimethylaminomethyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, and benzine methacrylate; 2-
Hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, acrylonitrile, methacrylonitrile, acrylamide, etc., as well as alkyl vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, n-butyl ether, isobutyl ether; β-chloroethyl vinyl ether, phenyl vinyl ether , P-methylphenyl ether, p-
Diene compounds such as chlorophenyl ether, p-bromophenyl ether, p-nitrophenyl vinyl ether, p-methoxyphenyl vinyl ether and butadiene; acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, monobutyl itaconate, Monobutyl maleate, phosphoric acid-containing monomer, specifically, acid phosphooxyethyl methacrylate, acid phosphooxypropyl methacrylate, sulfonic acid group-containing monomer, dimethylaminoethyl acrylate, diethylaminoethyl methacrylate, acroylmorpholine , 2-vinylpyridine, 3-vinylpyridine, 4-
Vinylpyridine, N-vinylpyrrolidone, 2-vinylimidazole, N-methyl-2-vinylimidazole, N
-Vinyl imidazole.

These monomers can be used alone or in combination of two or more.
A suitable polymer composition can be selected so as to obtain preferable characteristics.

According to the present invention, a high molecular weight component or a gel component can be contained. The introduction of such a component is achieved by using a crosslinking agent having two or more polymerizable double bonds per molecule. Specific examples of the crosslinking agent include, for example, aromatic divinyl compounds such as divinylbenzene and divinylnaphthalene; ethylene glycol diacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate,
Tetraethylene glycol dimethacrylate, 1,3-
Butylene glycol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, 1,4-butanediol diacrylate, neopentyl glycol diacrylate, 1,6
-Hexanediol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol dimethacrylate,
Examples thereof include compounds such as pentaerythritol tetramethacrylate, glycerol acroxydimethacrylate, N, N-divinylaniline, divinyl ether, divinyl sulfide, and divinyl sulfone, and two or more of them may be appropriately mixed and used. Such crosslinkers are
It can be preliminarily mixed with the polymerizable mixture, or can be added as needed during the polymerization.

In the method for producing a toner of the present invention, a step of washing the toner after polymerization is also an important step. As the washing solvent used for washing, a solvent similar to the polymerization solvent used for the polymerization may be used, but preferably, a mixed solvent containing 30% by mass or more of a saturated alcohol represented by the following Chemical Formula 1 is used. Is more preferable.

(Chemical Formula 1) C _n H _{2n + 1} OH n = 1 to 5

More preferably, the mixed solvent used in the washing step contains water in the range of 0.1 to 70% by mass. At this time, it is preferable that the solvent is a poorer solvent than the solvent used at the time of polymerization. Further, it is more preferable to wash with water last in the washing step. In this way, it is important that the polymer composition is present on the surface in a desired amount in the washing process and at the same time, the above-mentioned steps are carried out to remove the extremely low molecular weight component. In addition, the number of washings is 1
By performing the process from about 10 times to about 10 times, a desired amount of the methanol-soluble resin component can be present even when the type of the material is different.

The washed toner is dried and used as a toner. The drying step is not particularly limited, and the toner can be obtained by a conventionally used drying method.

If necessary, the toner of the present invention may be subjected to a classification operation after drying.

In the present invention, any known coloring agents can be used. Regarding the method of adding the colorant, it can be dyed by any means such as a method of containing the polymerizable monomer composition in the toner at the same time as the polymerization or a method of obtaining particles and then dyeing with a dye in a warm solvent or the like. It is possible.

Specifically, carbon black or a known organic colorant such as C.I. I. Direct Red 1, C.I. I.
Basic Red 1, C.I. I. Modern Red 30,
C. I. Direct Blue 1, C.I. I. Direct Blue 2, C.I. I. Acid Blue 15, C.I. I. Basic Blue 3, C.I. I. Basic Blue 5, C.I. I. Modant Blue 7, C.I. I. Direct Green 6,
C. I. Basic Green 4, C.I. I. Dyes such as Basic Green 6; cadmium yellow, mineral first yellow, navel yellow, naphthol yellow S, Hanza yellow G, permanent yellow NC
G, tartrazine lake, molybdenum orange GTR,
Benzidine Orange G, Cadmium Red 4R, Watching Red Calcium Salt, Brilliant Carmine 3
Pigments such as B, Fast Violet B, Methyl Violet Lake, Cobalt Blue, Alkaline Blue Lake, Victoria Blue Lake, Quinacridone, Rhodamine Lake, Phthalocyanine Blue, Fast Sky Blue, Pigment Green B, Malachite Green Lake, Final Yellow Green G, etc .; . I. Solvent Yellow 6, C.I. I. Solvent Yellow 9, C.I. I. Solvent Yellow 17, C.I. I. Solvent Yellow 3
1, C.I. I. Solvent Yellow 35, C.I. I. Solvent Yellow 100, C.I. I. Solvent Yellow 10
2, C.I. I. Solvent Yellow 103, C.I. I. Solvent Yellow 105, C.I. I. Solvent Orange 2, C.I. I. Solvent Orange 7, C.I. I. Solvent Orange 13, C.I. I. Solvent orange 14,
C. I. Solvent Orange 66, C.I. I. Solvent Red 5, C.I. I. Solvent Red 16, C.I. I. Solvent Red 17, C.I. I. Solvent Red 18,
C. I. Solvent Red 19, C.I. I. Solvent Red 22, C.I. I. Solvent Red 23, C.I. I. Solvent Red 143, C.I. I. Solvent Red 14
5, C.I. I. Solvent Red 146, C.I. I. Solvent Red 149, C.I. I. Solvent Red 150,
C. I. Solvent Red 151, C.I. I. Solvent Red 157, C.I. I. Solvent Red 158, C.I.
I. Solvent Violet 31, C.I. I. Solvent Violet 32, C.I. I. Solvent violet 3
3, C.I. I. Solvent Violet 37, C.I. I. Solvent Blue 22, C.I. I. Solvent Blue 63,
C. I. Solvent Blue 78, C.I. I. Solvent Blue 83, C.I. I. Solvent Blue 84, C.I. I. Solvent Blue 85, C.I. I. Solvent Blue 86,
C. I. Solvent Blue 104, C.I. I. Solvent Blue 191, C.I. I. Solvent Blue 194, C.I.
I. Solvent Blue 195, C.I. I. Solvent Green 24, C.I. I. Solvent Green 25, C.I. I.
Solvent Brown 3, C.I. I. Solvent Brown 9
Etc. Commercially available dyes include, for example, Mitsubishi Kasei Diarange Yellow-3G, Yellow-F and Yellow.
w-H2G, Yellow-HG, Yellow-H
C, Yellow-HL, Orange-HS, Ora
nge-G, Red-GC, Red-S, Red-H
S, Red-A, Red-K, Red-H5B, Vio
let-D, Blue-J, Blue-G, Blue-
N, Blue-K, Blue-P, Blue-H3G,
Blue-4G, Green-C, Brown-A; Hodogaya Chemical's indigo dye SOT dye Yellow-1, Yellow
low-3, Yellow-4, Orange-1, O
range-2, Orange-3, Scarlet-
1, Red-1, Red-2, Red-3, Brown
-2, Blue-1, Blue-2, Violet-
1, Green-1, Green-2, Green-
3, Black-1, Black-4, Black-
6, Black-8; sudan dye Ye of BASF
llow-146, Yellow-150, Orange
e-220, Red-290, Red-380, Red
-460, Blue-670; from Orient Chemical Industries,
Oil black, oil color Yellow-3G,
Yellow-GG-S, Yellow- # 105, O
range-PS, Orange-PR, Orange
-# 201, Scarlet- # 308, Red-5
B, Brown-GR, Brown- # 416, Gre
en-BG, Green- # 502, Blue-BO
S, Blue-IIN, Black-HBB, Blac
k- # 803, Black-EB, Black-EX;
Sumitomo Chemical Sumiplast Blue GP, Blue O
R, Red-FB, Red-3B, Yellow FL7G,
Yellow GC; Nippon Kayaku Kayalon polyester black EX-SF300, Kayaset RedB, Blue A-2R, and the like.

Further, in the present invention, a magnetic toner can be obtained by using a magnetic substance as a coloring agent.

As the polymerization initiator used in the present invention, any conventionally known polymerization initiator can be used. Specific examples of such a polymerization initiator include, for example, 2,2′-azobis- (2,
4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 1,1'-azobis- (cyclohexane-1-carbonitrile), 2,2'-azobis-4
Azo or diazo polymerization initiators such as -methoxy 2,4-dimethylvaleronitrile; 2,2'-azobis (2
-Aminodipropane) dihydrochloride, 2,2'-azobis (N, N'-dimethyleneisobutylamidine),
Amidine compounds such as 2,2'-azobis (N, N'-dimethyleneisobutylamidine) dihydrochloride; benzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl peroxycarbonate, cumene hydroperoxide, 2,4-dichlorobenzoyl peroxide And peroxide-based polymerization initiators such as lauroyl peroxide; and persulfide-based initiators such as potassium persulfate and ammonium persulfate, and also mixtures of the above-mentioned initiators.

Specific examples of the anionic polymerizable initiator include, for example, SrR ₂ , CaR ₂ , K, KR, Na,
NaR, Li, LiR, ketyl, R-MgR, R-ON
a, R-OK, R-OLi, strong alkalis such as sodium hydroxide and potassium hydroxide; weak alkalis such as pyridine and ammonia; ROR (where R represents an alkyl group).

Examples of the cationically polymerizable initiator include, for example, SnCl ₄ , BF ₃ , AlCl ₃ , Ti
Cl ₃ or the like can also be used.

In the present invention, a known chain transfer agent may be added. Specifically, for example, halogenated hydrocarbons such as carbon tetrachloride, carbon tetrabromide, ethyl dibromide acetate, ethyl tribromide acetate, ethyl dibromide, ethane dibromide, ethane dichloride; diazothioether; Hydrocarbons such as benzene, ethylbenzene and isopropylbenzene; mercaptans such as tertiary decyl mercaptan and n-dodecyl mercaptan; and disulfides such as diisopropylzantogen disulfide can also be added.

In the toner of the present invention, a charge control agent can be added for the purpose of controlling chargeability. As the charge control agent, any of the well-known positive charge control agents and negative charge control agents commonly used for toners can be used. Specifically, for example, it has a nigrosine dye, a triphenylmethane dye, a quaternary ammonium salt, an amine or imine compound, a metal compound of salicylic acid or alkyl salicylic acid, a metal-containing monoazo dye, a carboxylyl group or a sulfoxyl group. Examples include compounds, humic acids such as nitrohumin, and humic salts. In the present invention, preferably, the use of a negative charge control agent improves environmental stability.

To the toner of the present invention, various external additives can be added for the purpose of improving fluidity and chargeability. As the external additive, any known external additive usually used for a toner can be used. Specifically, for example, there are fine powders of silica, titanium oxide, alumina and the like. The external additive preferably used has a BET specific surface area of 300 m ² / g.
That's all. Although it can be used at less than 300 m ² / g, it is necessary in order to maintain a uniform surface state of the toner having a sharp particle size distribution in addition to a fine particle size and to perform good charging.

The toner of the present invention can be mixed with carrier particles and used as a two-component developer.
Carriers include iron powder, magnetite, ferrite,
A conventionally used carrier such as a magnetic material-dispersed resin carrier can be used. Preferably, the number average particle size is 30.
It is necessary that the particle size be not more than μm in order to impart a sufficient charge to the toner.

The measuring method used in the present invention will be described.

The measurement of the methanol-soluble resin component soluble in methanol was performed by precisely weighing 10 g of the toner in a beaker (w1).
Then, 200 g of special grade methanol is added and stirred for 24 hours. After removing the solid content using a filter paper, the extract was dried to dryness and precisely weighed as a methanol-soluble resin component (w2).
And a methanol-soluble resin component (% by mass) = w2 / w1 ×
Calculate with 100.

[0074] Composition analysis of the polymer composition of the methanol-soluble resin component extracted by methanol is performed using a Perkin Elmer FT-IR ₁ 600 type by infrared absorption analysis. The measurement is performed by using a KBr tablet method, mixing the methanol-soluble resin component extracted and solidified with KBr, and observing infrared absorption from 4000 to several hundred cm-1. The composition analysis is performed based on the intensity ratio of the specific peak due to the hydroxyl group.

To measure the hydroxyl value of the methanol-soluble resin component, 0.5 g of a sample is precisely weighed (W), and the sample is placed in a 200 ml beaker, and 150 ml of a toluene / ethanol (7: 3) mixed solution is added and dissolved. .

Using an ethanol solution of 1 / 10N KOH, the solution in the beaker is titrated with a potentiometric titrator. The titrator used is AT-Kyoto of Kyoto Electronics Industry Co., Ltd.
APB using 400win workstation
Automatic titration with -410 electric burette. K at this time
The used amount of the OH solution is set to S (ml), blank measurement is performed at the same time, and the used amount of the KOH solution at this time is set to B (ml). Based on this, the hydroxyl value is determined from the following equation.

Hydroxyl value = (S−B) × f × 5.61 / W
f: KOH solution factor

The molecular weight distribution of the toner and the methanol-soluble resin component of the present invention can be measured by using a GPC measuring device (HLC-8120).
GPC (manufactured by Tosoh Corporation).

Measurement conditions Column: TSKgel HM-M (6.0 × 15 cm)
Temperature: 40 ° C. Solvent: THF Flow rate: 0.6 ml / min Detector: RI Sample concentration: 10 μl of 0.1% sample

In the sample preparation, the sample is put in THF,
After leaving it for several hours, shake it sufficiently (until the sample is no longer united) and let it stand for another 12 hours. What passed through the sample processing filter (pore size 0.45 μm) is used as a GPC sample.

As the calibration curve, a molecular weight calibration curve prepared from a monodisperse polystyrene standard sample is used. From the logarithmic curve (logM) obtained, the maximum molecular weight is determined. Further, an extremely low molecular weight component contained in the toner resin is calculated from a cumulative curve having a molecular weight of 200 to 1000.

The particle size of the toner particles used in the present invention is measured by using a laser scan type particle size distribution analyzer (CIS-100 GAL) for toner having an average particle size of 1 μm or more.
(Manufactured by AI Co., Ltd.) in the range of 0.4 μm to 60 μm. A sample was prepared by adding 0.5 to 2 mg of a toner to a solution of 0.2 ml of a surfactant (alkylbenzene sulfonate) in 100 ml of water, dispersing the mixture for 2 minutes with an ultrasonic disperser, and placing the mixture in a cubic cell containing a magnetic stirrer. About 80% of water is added, and one or two drops of a sample ultrasonically dispersed therein are added with a pipette. Dn obtained from this,
S. D. Based on the (standard deviation), the number average particle diameter and the variation coefficient are determined.

For a toner having an average particle diameter of 1 μm or less, a scanning electron microscope (FE-SEM S-
800 Hitachi, Ltd.) and take a 5000 × photograph, and based on the photograph, adjust the horizontal Feret diameter to 0.05 μm.
The above particles are measured to have a cumulative total of 300 or more. The average is defined as the number average particle size. In addition, the coefficient of variation is calculated from this numerical value by the same calculation formula as that of CIS-100.

The method for measuring the triboelectric charge used in the present invention will be described. When the toner and the carrier are converted into a developer, they are mixed so as to have an appropriate mixing amount (2 to 15% by mass), and mixed by a Turbula mixer for 180 seconds. This mixed powder (developer) is placed in a metal container equipped with a conductive screen having an opening of 20 μm (635 mesh) at the bottom, sucked by a suction machine, and the weight difference between before and after suction and the condenser connected to the container. The amount of triboelectrification is determined from the potential accumulated in. At this time, the suction pressure is set to 33.3 kPa (250 mmHg). With this method, the triboelectric charge amount is calculated using the following equation.

Q / M (μC / g) = (C × V) / (W1−W2) (W1 is the mass before suction, W2 is the mass after suction, C is the capacity of the condenser, V is the potential stored in the capacitor.)

[0086]

EXAMPLES The present invention will be described below with reference to examples. The present invention is not limited by the embodiments.

Example 1 274 parts by weight of methanol 26 parts by weight of styrene-2-hydroxyethyl methacrylate copolymer (copolymer composition ratio = 2: 8, Mw (weight average molecular weight) = 52,600) styrene 78 parts by mass ・ 22 parts by mass of n-butyl acrylate ・ 5 parts by mass of 2,2′-azobisisovaleronitrile ・ 6 parts by mass of copper phthalocyanine A mixture comprising:
The solution was mixed well for 30 minutes while bubbling at 1 / min. When the amount of dissolved oxygen at the start of polymerization was measured, it was 0.9.
mg / liter. Then, set the temperature of the oil bath to 5
The mixture was refluxed under a nitrogen atmosphere at 5 ° C. for 14 hours.

After cooling to room temperature, solid-liquid separation and washing of the dispersion were repeated. For the washing, a solvent prepared at a ratio of 80% by mass of methanol to 20% by mass of water was used. This operation was repeated four times, and finally, the resultant was washed with water. The obtained slurry was dried, and the number average particle diameter (Dn) was 5.13 μm.
m, toner particles having a number distribution variation coefficient of 11.4% were obtained.

As a result of performing extraction with a methanol solution for 24 hours, the ratio of the methanol-soluble resin component was 2.4% by mass.

The weight ratio of the polymer compound to the resin fine particles was calculated by qualitative analysis and quantitative analysis of the methanol-soluble resin component. The hydroxyl value (OH
V) was 355 mg KOH / g, and the weight average molecular weight (Mw) of the resin component was 49,800. The component having a molecular weight of 200 to 1,000 was 0.6% by mass in the toner. Was.

With respect to 100 parts by mass of the obtained toner particles,
Disintegrated BET specific surface area 380 m ² / g silica
Five parts by mass were mixed with a Henschel mixer and externally added. Table 1 shows the physical properties of the obtained toner particles.

With respect to 7 parts by mass of this toner, 93 parts by mass of a carrier obtained by coating a silicone resin on a ferrite core having an average particle size of 35 μm were put in a poly bottle, and mixed and stirred by a turbuler mixer to obtain a developer.

This developer was used at low temperature and low humidity (L / L: 15 ° C. /
10%), normal temperature and normal humidity (N / N: 23.5 ° C./60%),
The charge amount was measured under each environment of high temperature and high humidity (H / H: 30 ° C./80%). As a result, L / L: -35.
9 μC / g, N / N: −34.1 μC / g, H / H: −
It was 32.5 μC / g, which was excellent in environmental stability.

A full-color laser copier copier CLC-500 modified machine manufactured by Canon Inc. (The surface of the developer carrying member of the developing container was matted so that Rz = 10 μm. Further, in order to precisely evaluate the halftone reproducibility, , The normal laser spot diameter was reduced by 20%), and a solid image and a halftone image were formed by a minimum spot, and image evaluation was performed in three environments.

The evaluation of the reproducibility of the halftone formed by the minimum spot is performed by multi-value recording by pulse width modulation (PWM) of the laser in one pixel, and the reproducibility of the toner with respect to the minimum spot is determined on the surface of the photosensitive drum. Was observed with a microscope, and evaluated based on the following evaluation criteria.

(Evaluation Criteria) A: No disturbance of dots, very good reproduction even to very small dots B: No scattering, slight variation in dot shape, good C: Scattering, variation in dot shape No problem in practical use D: Scattering, variation in dot shape is remarkable E: Not developed where dots should be, or scattering is severe

The evaluation of fog is performed using a “reflectometer”.
The fog density (%) was calculated from the difference between the whiteness of the white portion of the printout image measured by (Tokyo Denshoku Co., Ltd.) and the whiteness of the transfer paper, and evaluated based on the following evaluation criteria.

(Evaluation criteria) A: less than 1.5% B: 1.5% or more, less than 2.5% C: 2.5% or more, less than 4.0% D: 4.0% or more

Table 2 shows the results. In any environment, the image density of the solid image was high, the occurrence of fog was sufficiently suppressed, and the reproducibility of halftone was good.

Example 2 280 parts by mass of methanol styrene-α-methylstyrene-2-hydroxyethyl methacrylate copolymer (copolymer composition ratio = 1: 1: 2, Mw (weight average molecular weight) = 52, 000) 20 parts by mass ・ Styrene 80 parts by mass ・ n-butyl acrylate 20 parts by mass ・ 2,2′-azobisisobutyronitrile 5.5 parts by mass ・ Copper phthalocyanine 5 parts by mass is charged into the reaction vessel. And nitrogen for 300m
The solution was mixed well for 30 minutes while bubbling at 1 / min. When the amount of dissolved oxygen at the start of polymerization was measured, it was 1.2
mg / liter. As in the case of Example 1, reflux was performed at an oil bath temperature of 63 ° C. for 14 hours under a nitrogen stream. Next, washing was repeated in the same manner as in Example 1 to obtain particles. The obtained slurry is dried to obtain a number average particle diameter (Dn).
5.87 μm and toner particles having a number distribution variation coefficient of 14.0% were obtained.

As a result of performing extraction with a methanol solution for 24 hours, the ratio of the methanol-soluble resin component was 2.1% by mass.

The hydroxyl value and GPC molecular weight distribution of the methanol-soluble resin component were measured in the same manner as in Example 1. As a result, the hydroxyl value was 341 mgKOH / g, and the weight average molecular weight of the resin component was 53,700. , Molecular weight 20
The components of 0 to 1000 were 1.0% by mass in the toner.

The external addition was carried out in the same manner as in Example 1. Table 1 shows the physical properties of the obtained toner particles.

A developer was prepared and evaluated in the same manner as in Example 1. As a result, L / L: -31.1 μC / g,
N / N: −28.9 μC / g, H / H: −27.9 μC
/ G.

Further, image evaluation was performed in three environments in the same manner as in Example 1.

Table 2 shows the results. The results were as good as in Example 1.

Example 3 Methanol 272 parts by mass Styrene-3-hydroxypropyl acrylate copolymer 28 parts by mass (copolymer composition ratio 1: 9, Mw (weight average molecular weight) = 66,100) Styrene 80 parts by mass ・ 20 parts by mass of n-butyl acrylate ・ 5 parts by mass of 2,2′-azobisisobutyronitrile ・ 5 parts by mass of copper phthalocyanine A mixture comprising:
The solution was mixed well for 30 minutes while bubbling at 1 / min. When the amount of dissolved oxygen at the start of polymerization was measured, it was 0.7
mg / liter. In the same manner as in Example 1, reflux was performed at an oil bath temperature of 63 ° C. for 14 hours under a nitrogen stream. Next, washing was repeated in the same manner as in Example 1 to obtain particles. The obtained slurry is dried to obtain a number average particle diameter (Dn).
Toner particles having a toner distribution of 4.72 μm and a coefficient of variation of the number distribution of 12.8% were obtained.

As a result of performing extraction with a methanol solution for 24 hours, the ratio of the methanol-soluble resin component was 2.3% by mass.

The hydroxyl value and GPC molecular weight distribution of the methanol-soluble resin component were measured in the same manner as in Example 1. As a result, the hydroxyl value was 391 mgKOH / g, and the weight average molecular weight of the resin component was 62,800. , Molecular weight 20
The components of 0 to 1000 were 1.5% by mass in the toner.

The external addition was carried out in the same manner as in Example 1. Table 1 shows the physical properties of the obtained toner particles.

A developer was prepared and evaluated in the same manner as in Example 1. As a result, L / L: -36.0 μC / g,
N / N: -34.4 μC / g, H / H: -33.9 μC
/ G.

Further, image evaluation was performed in three environments in the same manner as in Example 1.

Table 2 shows the results. The results were as good as in Example 1.

Example 4 275 parts by mass of methanol 25 parts by mass of poly-2-hydroxyethyl methacrylate (Mw (weight average molecular weight) = 67,000) 80 parts by mass of styrene 20 parts by mass of n-butyl acrylate A mixture consisting of 5 parts by mass of 2,2'-azobisisobutyronitrile and 5 parts by mass of copper phthalocyanine is charged into a reaction vessel, and nitrogen is fed for 300 m.
The solution was mixed well for 30 minutes while bubbling at 1 / min. When the amount of dissolved oxygen at the start of polymerization was measured, it was 1.2
mg / liter. As in Example 1, reflux was performed at an oil bath temperature of 72 ° C. for 14 hours under a nitrogen stream. Next, washing was repeated in the same manner as in Example 1 to obtain particles. The obtained slurry is dried to obtain a number average particle diameter (Dn).
3.99 μm and toner particles having a number distribution coefficient of variation of 11.4% were obtained.

As a result of performing extraction with a methanol solution for 24 hours, the ratio of the methanol-soluble resin component was 2.8% by mass.

The hydroxyl value and GPC molecular weight distribution of the methanol-soluble resin component were measured in the same manner as in Example 1. As a result, the hydroxyl value was 412 mgKOH / g, and the weight average molecular weight of the resin component was 648,000. , Molecular weight 2
The components of 00 to 1000 were 2.0% by mass in the toner.

External addition was carried out in the same manner as in Example 1. Table 1 shows the physical properties of the obtained toner particles.

A developer was prepared and evaluated in the same manner as in Example 1. As a result, L / L: −25.4 μC / g,
N / N: −23.9 μC / g, H / H: −22.2 μC
/ G.

Further, image evaluation was performed in three environments in the same manner as in Example 1.

Table 2 shows the results. The results were as good as in Example 1.

Comparative Example 1 Methanol 260 parts by mass Styrene-2-hydroxyethyl methacrylate copolymer 40 parts by mass (copolymer composition ratio = 4: 6, Mw (weight average molecular weight) = 51,000) Styrene 80 parts by mass n-butyl acrylate 20 parts by mass 2,2'-azobisisovaleronitrile 4.5 parts by mass Copper phthalocyanine 5 parts by mass A mixture comprising
The solution was mixed well for 20 minutes while bubbling at 1 / min. When the amount of dissolved oxygen at the start of polymerization was measured, it was 1.0
mg / liter. Next, particles were obtained in the same manner as in Example 1. The obtained slurry was dried to obtain a number average particle diameter (Dn) of 4.11 μm and a number distribution variation coefficient of 30.
9% of toner particles were obtained.

As a result of performing extraction with a methanol solution for 24 hours, the ratio of the methanol-soluble resin component was 1.2% by mass.

The hydroxyl value and the GPC molecular weight distribution of the methanol-soluble resin component were measured in the same manner as in Example 1. As a result, the hydroxyl value was 208 mgKOH / g, and the weight average molecular weight of the resin component was 49,500. , Molecular weight 20
The components of 0 to 1000 were 0.7% by mass in the toner.

External addition was carried out in the same manner as in Example 1. Table 1 shows the physical properties of the obtained toner particles.

A developer was prepared and evaluated in the same manner as in Example 1. As a result, L / L: -47.1 μC / g,
N / N: -40.7 µC / g, H / H: -37.3 µC
/ G, and the environmental difference of the charge amount widened.

Further, image evaluation was performed in three environments in the same manner as in Example 1.

Table 2 shows the results. As a result, the dispersion of minute dots was conspicuous because the particle size distribution was broad.

Comparative Example 2 • 270 parts by mass of methanol • 30 parts by mass of styrene-2-hydroxyethyl methacrylate copolymer (copolymer composition ratio = 2: 8, Mw (weight average molecular weight) = 8,100) • styrene 80 parts by mass n-butyl acrylate 20 parts by mass 2,2'-azobisisovaleronitrile 4.5 parts by mass Copper phthalocyanine 5 parts by mass A mixture comprising
The solution was mixed well for 30 minutes while bubbling at 1 / min. When the amount of dissolved oxygen at the start of polymerization was measured, it was 0.7
mg / liter. Next, particles were obtained in the same manner as in Example 1. The obtained slurry was dried to obtain a number average particle diameter (Dn) of 4.72 μm and a coefficient of variation of number distribution.
3% of toner particles were obtained.

As a result of performing extraction with a methanol solution for 24 hours, the ratio of the methanol-soluble resin component was 4.1% by mass.

The hydroxyl value and the GPC molecular weight distribution of the methanol-soluble resin component were measured in the same manner as in Example 1. As a result, the hydroxyl value was 375 mgKOH / g, and the weight average molecular weight of the resin component was 10,200. , Molecular weight 20
The components of 0 to 1000 were 11.1% by mass in the toner.

External addition was carried out in the same manner as in Example 1. Table 1 shows the physical properties of the obtained toner particles.

A developer was prepared and evaluated in the same manner as in Example 1. As a result, L / L: -21.0 μC / g,
N / N: −18.3 μC / g, H / H: −15.2 μC
/ G, and the environmental difference of the charge amount widened.

Further, image evaluation was performed in three environments in the same manner as in Example 1.

Table 2 shows the results. As a result, fogging occurred in all environments, and a decrease in image density was observed under low temperature and low humidity.

[0135]

[Table 1]

[0136]

[Table 2]

[0137]

As described above, in a toner having a fine particle size and a sharp particle size distribution, a surface resin component soluble in methanol is contained in a certain range on the toner surface, so that the toner can be used in a low-temperature low-humidity to high-temperature high-humidity environment. It is possible to provide a toner that achieves high image quality by being excellent in charge amount stability and developing / transferring properties.

Claims (13)

[Claims] 1. A toner having at least a binder resin and a colorant, wherein (i) the number average particle size is from 0.5 to 6.
0 μm, (ii) the coefficient of variation of the number distribution is not more than 20%, and (iii) the methanol-soluble resin component extracted by methanol is 0.01% to the toner mass.
And the methanol-soluble resin component contains a polymer composition having a hydroxyl group, and
A toner having a hydroxyl value (OHv) of 0 to 450 mgKOH / g. 2. The methanol-soluble resin component has at least repeating units (I) and (II) represented by the following structural formula, and the repeating units (I) and (II) in the methanol-soluble resin component Is at least 50% of the number of units constituting the entire methanol-soluble resin component, and the number of repeating units of the repeating unit (I) is the sum of the repeating units (I) and (II). 2. The toner according to claim 1, wherein the amount is 60 to 100% of the number. [Outside 1] (Wherein, R ₁ is (CH ₂ ) _n , n = 1 to 4, R ₂ is H,
Substituted or unsubstituted alkyl group, halogen atom, R ₃ -R
₇ represents a hydrogen atom, a substituted or unsubstituted alkyl group, a halogen atom, a nitrile group, a hydroxyl group, and a repeating unit (I)
And (II) may be plural types. ) 3. The method according to claim 1, wherein the methanol-soluble resin component contains at least 2-hydroxyethyl methacrylate as a repeating unit of (I) and styrene as a repeating unit of (II). The toner described in the above. 4. A polystyrene-equivalent molecular weight distribution of the methanol-soluble resin component determined by gel permeation chromatography (GPC), wherein (i) a molecular weight of 200
The toner according to any one of claims 1 to 3, wherein the toner has a weight average molecular weight (Mw) in the range of 0 to 100,000, and (ii) contains a component having a molecular weight of 200 to 1,000 in an amount of 3% by mass or less. 5. The toner according to claim 1, wherein a methanol-soluble resin component extracted with methanol is added to the toner in an amount of 0.
2. The composition according to claim 1, wherein the content is 2 to 8% by mass.
5. The toner according to any one of items 1 to 4. 6. A polymer which is soluble in a solvent for polymerization and which is produced by polymerization is a polymerizable monomer which is insoluble in the solvent for polymerization, and a polymer composition which is soluble in the solvent for polymerization. Dissolving the product in the polymerization solvent to prepare a polymerization reaction system; setting the amount of oxygen dissolved in the polymerization reaction system at the start of the polymerization reaction to 2.0 mg / L or less, A process for polymerizing the polymerizable monomer in the presence of a polymerization initiator; a process for obtaining polymer particles from the polymerization reaction system; and a process for forming a toner from the obtained polymer particles. Wherein the obtained toner contains at least a binder resin and a colorant, and (i) has a number average particle size of 0.5 to 6.0.
μm, (ii) the coefficient of variation of the number distribution is not more than 20%, and (iii) 0.01 to 10% by mass of a methanol-soluble resin component extracted with methanol, based on the mass of the toner. And the methanol-soluble resin component contains a polymer composition having a hydroxyl group, and
Having a hydroxyl value (OHv) of from about 450 mgKOH / g to about 450 mgKOH / g. 7. The amount of dissolved oxygen in the polymerization reaction system at the start of polymerization of the polymerizable monomer is reduced to 2.0 mg / liter or less by bubbling by blowing an inert gas in the polymerization reaction system. 7. The method according to claim 6, wherein the setting is performed. 8. The amount of dissolved oxygen in the polymerization reaction system at the start of polymerization of the polymerizable monomer may be 2.0 mg / liter by applying ultrasonic waves to the polymerization reaction system to remove oxygen. 7. The method according to claim 6, wherein the toner is set as follows. 9. The amount of dissolved oxygen in the polymerization reaction system at the time of initiation of polymerization of the polymerizable monomer is determined by blowing an inert gas into the polymerization reaction system and bubbling the same. The method for producing a toner according to claim 6, wherein the content is set to 2.0 mg / liter or less by applying oxygen and deoxidizing. 10. The method according to claim 1, wherein the polymerization solvent is methanol and / or methanol.
Or 30 to 9 parts of ethanol or their mixture
7. A mixed solvent containing 9.9% by mass, wherein the obtained polymer particles are washed with a solvent containing 30% by mass or more of a saturated alcohol represented by the following chemical formula-1. 10. The method for producing a toner according to any one of claims 1 to 9. (Formula _{-1) C n H 2n + 1} OH n = 1~5 11. The methanol-soluble resin component has at least repeating units (I) and (II) represented by the following structural formula, and the repeating units (I) and (II) in the methanol-soluble resin component Is 50% or more of the number of units constituting the entire methanol-soluble resin component, and the number of repeating units of the repeating unit (I) is the sum of the repeating units (I) and (II). The method according to any one of claims 6 to 10, wherein the amount is 60 to 100% of the number. [Outside 2] (Wherein, R ₁ is (CH ₂ ) _n , n = 1 to 4, R ₂ is H,
Substituted or unsubstituted alkyl group, halogen atom, R ₃ -R
₇ represents a hydrogen atom, a substituted or unsubstituted alkyl group, a halogen atom, a nitrile group, a hydroxyl group, and a repeating unit (I)
And (II) may be plural types. ) 12. A polystyrene-equivalent molecular weight distribution of the methanol-soluble resin component determined by gel permeation chromatography (GPC), wherein (i) a molecular weight of 20
Having a weight average molecular weight in the range of 00 to 100000,
The method according to any one of claims 6 to 11, wherein (ii) a component having a molecular weight of 200 to 1000 is contained in an amount of 3% by mass or less. 13. The toner according to claim 1, wherein a methanol-soluble resin component extracted by methanol is added to the toner mass.
The method for producing a toner according to any one of claims 6 to 12, wherein the content is 0.2 to 8% by mass.