JP3114039B2 - Polymerization toner - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polymerization toner used in a method for visualizing a latent image.

[0002]

2. Description of the Prior Art Electrophotography is disclosed in U.S. Pat. No. 2,297,6.
As described in, for example, US Pat. No. 91/91, a number of methods are known. Generally, a photoconductive substance is used to form an electric latent image on a photoreceptor by various means, and then the latent image is formed. The image is developed using toner, and if necessary, the toner image is transferred to a transfer material such as paper, and then fixed by heating, pressure, or solvent vapor to obtain a copy. As a method of developing using toner or a method of fixing a toner image, conventionally, various methods have been proposed, and a method suitable for each image forming process has been adopted.

Conventionally, toners used for these purposes are generally prepared by melt-mixing a coloring agent composed of a dye and a pigment in a thermoplastic resin, uniformly dispersing the same, and then using a pulverizer or a classifier to obtain a toner having a desired particle size. Has been manufactured.

[0004] Although this method can produce fairly good toners, it does have certain limitations, namely the choice of toner materials. For example, the resin colorant dispersion is brittle enough,
It must be able to be comminuted in an economically feasible production equipment. However, when the resin colorant dispersion is made brittle to satisfy these requirements, the particle size range of the particles formed when actually pulverized at a high speed tends to be widened, and in particular, a relatively large proportion of the fine particles The problem of inclusion occurs. Further, such a highly brittle material is liable to be further pulverized or powdered when used for development in a copying machine or the like. Further, in this method, it is difficult to completely and uniformly disperse solid fine particles such as a colorant in a resin,
Depending on the degree of the dispersion, fog may increase, the image density may decrease, or the color mixing / transparency may be poor. Further, exposure of the coloring agent to the fracture surface may cause fluctuations in development characteristics.

On the other hand, in order to overcome the problems of the toner caused by these pulverization methods, Japanese Patent Publication Nos.
Nos. 10799 and 51-14895 propose a method for producing a toner by a suspension polymerization method. In the suspension polymerization method, a polymerizable monomer, a colorant, a polymerization initiator, and, if necessary, a crosslinking agent, a charge control agent, and other additives are uniformly dissolved or dispersed to form a monomer composition. A continuous phase containing the monomer composition containing a dispersion stabilizer,
For example, the toner particles are dispersed in an aqueous phase using a suitable stirrer, and simultaneously undergo a polymerization reaction to obtain toner particles having a desired particle size.

This method does not require any pulverizing step, so that the toner does not need to be brittle, a soft material can be used, and the classifying step can be omitted. Large cost reduction effects such as reduction of time and improvement of process yield.

Further, there is an advantage that a colorant is not exposed to the particle surface and uniform triboelectricity is obtained.

[0008] Examples of the colorant used in the method for producing a toner by the suspension polymerization method include pigments and dyes. In the case of a toner production method by a pulverization method, a pigment or a dye having polymerization inhibition may be used as a colorant. Some of them are notable, and usable colorants are greatly limited. In particular, dyes have a remarkable tendency to exhibit polymerization inhibition properties, and in the case of a toner production method by a suspension polymerization method, it has been difficult to obtain a toner having a desired color and excellent development characteristics by the dye.

As a method for solving the above problems, Japanese Patent Application Laid-Open No. 2-275964 discloses a dye having polymerization inhibition properties.
A method for producing a polymerized toner in which a pigment is treated by a bulk polymerization method has been proposed. According to this method, it is possible to obtain a polymerization toner excellent in color tone, but there is a problem that the number of manufacturing steps is increased.

Japanese Patent Publication Nos. 1-217465, 2-51165, and 2-108068 disclose magenta color toners, and Japanese Patent Publication Nos. 1-227162, 2-51165 and 2-51165. JP-A-2-108068 discloses a yellow color toner, Japanese Patent Publication No. 1-237.
JP-A-667-67 and JP-A-3-87754 propose an anthraquinone dye as a colorant for a cyan color toner. When these dyes are used, a toner having good melt miscibility with a binder resin, light resistance, and the like, and excellent in charging characteristics, color tone, and the like can be obtained. However, in consideration of the improvement in chargeability, color tone and the like with the recent enhancement of the functions of color copiers, the dispersibility of the dye in the toner is not sufficient.

[0011]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems and to provide a polymerized toner having excellent dispersibility of a colorant in a toner, and excellent charging characteristics and light resistance. It is in.

Another object of the present invention is to provide a colorant having excellent color tone without polymerization inhibition and suitable for each of the polymerization toners of magenta toner, yellow toner and cyan toner.

Another object of the present invention is to provide a polymerized toner having excellent fixability.

[0014]

SUMMARY OF THE INVENTION An object of the present invention is to provide a polymerizable monomer system containing at least a polymerizable monomer and a colorant, and an aqueous system containing a dispersion stabilizer (excluding silica). A polymerized toner obtained by suspension polymerization in a medium, wherein 0.1 to 20 parts by weight of the following general formula (I) or (I) is used as the colorant based on 100 parts by weight of the polymerizable monomer.
This is achieved by using a pigment together with an anthraquinone dye selected from the group consisting of I), (III) and (IV).

[0015]

Embedded image j, k = 0~4 n = 1~4 R 1 = alkyl group, an alkoxyl group, alkoxyalkoxyl group, a halogen atom, an alkoxyalkyl group, an aralkyl group, an alkoxycarbonyl group, an alkyl carboxyl group, -H R ₂ = -H , -OH (however, there is no R ₁ = R ₂ = H) R ₃ = alkyl group, alkoxyl group. ]

[0016]

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[Wherein R ₄ = hydrogen atom, halogen atom,
Alkyl group, a cycloalkyl group, an alkoxyl group, an alkoxyalkyl group, alkoxyalkoxyl group, an aralkyl group, an alkoxycarbonyl group, an alkylcarboxyl group R ₅ = -OH, -NH _2, and -H. ]

[0018]

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[Wherein the benzene ring P is one or more alkyl groups, cycloalkyl groups, alkoxy groups, hydroxyl groups, trifluoromethyl groups, alkoxyalkoxy groups, hydroxyalkyl groups, alkylcarbonyl groups, alkoxycarbonyl groups, It represents a carboxy group or a phenyl group substituted with a halogen atom. ]

[0020]

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Wherein R _{6 to} R ₁₁ are a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, an aralkyl group, an alkoxy group, an alkoxyalkoxy group, an alkoxyalkyl group, an alkoxycarbonyl group. Or an acyloxy group. ]

Further, the object of the present invention is to provide C.I. I. Pigment Blue 16 and C.I. I. P
5 to 80 wt% with respect to the blue 16
C. I. Pigment Blue 15: 3.

As a result of intensive studies, the present inventors have obtained a polymerized toner obtained by subjecting a polymerizable monomer system containing a colorant to suspension polymerization in an aqueous medium. Anthraquinone dyes having the structures of general formulas (I) to (IV), or C.I. I. Pigment Blue 1
6 and C.I. I. By using Pigment Blue 15: 3, a polymerized magenta toner, yellow toner or cyan toner having no polymerization inhibition, good dispersibility of the colorant in the toner, and excellent in charging characteristics, color tone and the like can be obtained. I found something.

The details of the colorant according to the polymerized toner of the present invention are described below.

(1) Colorant for magenta toner of the general formula (I) R ₁ , R ₂ and R _{3 in the} general formula (I) are as described above. As a specific example,

Alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-octyl and 1,1,3,3-tetramethylbutyl Group;

Alkoxyl groups such as methoxy, ethoxy, n-propoxy, n-butoxy, t-butoxy and n-hexyloxy;

Alkoxyalkoxyl groups such as methoxymethoxy, ethoxyethoxy, methoxyethoxy and ethoxymethoxy;

An alkoxyalkyl group such as a methoxymethyl group, a methoxyethyl group, an ethoxyethyl group, an n-propoxyethyl group and an n-butoxyethyl group;

Aralkyl groups such as benzyl group, phenethyl group and γ-phenylpropyl group;

An alkoxycarbonyl group such as a methoxycarbonyl group, an ethoxycarbonyl group and an n-propoxycarbonyl group;

Acetyloxy group, ethyl carboxy group,
An alkylcarboxyl group such as an n-propylcarboxy group is exemplified.

The halogen in R ₁ includes a fluorine atom, a chlorine atom and a bromine atom.

The compound of the formula (I) can be prepared by a conventional method.
Starting from 1-amino-2-halogeno-4-hydroxyanthraquinone, in the presence of a base such as potassium carbonate,
It is easily obtained by reacting with phenols and thiophenols.

The anthraquinone dye of the formula (I) used in the present invention is added in an amount of 0.1 to 20 parts by weight based on 100 parts by weight of the polymerizable monomer. Further, these anthraquinone dyes must be used in combination with a generally known pigment. I. Quinacridone pigments such as C.I. Pigment Red 122; I. Pigment Red 5
Azo pigments such as C.7; I. Solvent Red 49
And a lake pigment of a rhodamine dye.

(2) Colorant for Yellow Toner of General Formula (II) R ₄ and R ₅ in the general formula (II) are as described above, and specific examples of the hydrocarbon substituent in R ₄ are as follows. Is

Methyl, ethyl, n-propyl, isopropyl, pentyl, isopentyl, heptyl, nonyl, hexyl, n-butyl, isobutyl, t-butyl, n-octyl, 1,1,3,3-
An alkyl group such as a tetramethylbutyl group;

Cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group and cycloheptyl group;

Methoxy, ethoxy, n-propoxy, n-butoxy, t-butoxy, n-hexyloxy, octyloxy, cyclohexyloxy,
Alkoxyl groups such as decyloxy, dodecyloxy and octadecyloxy;

Alkoxyalkoxyl groups such as methoxymethoxy, ethoxyethoxy, methoxyethoxy and ethoxymethoxy;

An alkoxyalkyl group such as a methoxymethyl group, a methoxyethyl group, an ethoxyethyl group, an n-propoxyethyl group and an n-butoxyethyl group;

An aralkyl group such as a benzyl group, a phenethyl group and a γ-phenylpropyl group, a methoxycarbonyl group,
Alkoxycarbonyl groups such as an ethoxycarbonyl group and an n-propoxycarbonyl group;

An acetyloxy group, an ethylcarboxy group,
An alkylcarboxyl group such as an n-propylcarboxy group is exemplified.

The halogen in R ₄ includes a fluorine atom, a chlorine atom and a bromine atom.

The compound of the general formula (II) is reacted with thiophenols using 1,8-dinitroanthraquinone or 1,8-dichloroanthraquinone as a starting material in the presence of a base such as potassium carbonate by a conventional method. Can be easily obtained.

The anthraquinone dye of the general formula (II) used in the present invention is added in an amount of 0.1 to 20 parts by weight based on 100 parts by weight of the polymerizable monomer. Further, these anthraquinone dyes must be used in combination with a generally known pigment. I. Pigment Yellow 15,1
It is used in combination with a disazo pigment such as 6,17.

(3) Colorant for cyan toner of general formulas (III) and (IV) Specific examples of the benzene ring P in the general formula (III) include:

Methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, 1,1,
3,3-tetramethylbutyl group, n-hexyl group, n-
An alkyl group such as an octyl group;

A cycloalkyl group such as a cyclopentyl group or a cyclohexyl group;

Alkoxy groups such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy and t-butoxy;

Alkoxyalkoxy groups such as methoxymethoxy, ethoxyethoxy, methoxyethoxy and ethoxymethoxy;

A hydroxyalkyl group such as a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, a hydroxy-2,2-dimethylpropyl group;

An alkylcarbonyl group such as a methylcarbonyl group or an ethylcarbonyl group;

An alkoxycarbonyl group such as a methoxycarbonyl group or an ethoxycarbonyl group;

An alkylcarboxy group such as an acetoxy group or a propionyloxy group;

A phenyl group substituted with one or more hydroxyl groups, trifluoromethyl groups and one or more halogen atoms such as fluorine, chlorine and bromine atoms.

Further, specific examples of R _{6 to} R _{11 in} the general formula (IV) include:

A hydrogen atom, a halogen atom, a fluorine atom, a chlorine atom, a bromine atom or the like, and an alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group or a butyl group;

A cycloalkyl group such as a cyclopentyl group, a cyclohexyl group or a cyclooctyl group;

An alkenyl group such as an allyl group, a 2-butenyl group or a 2-pentenyl group;

Phenyl group, p-methylphenyl group, m-
Aryl groups such as methylphenyl group, p-methoxyphenyl group, p-ethoxycarbonylphenyl group;

Aralkyl groups such as benzyl, phenethyl and 3-phenylpropyl;

An alkoxy group such as a methoxy group, an ethoxy group and an isopropoxy group;

An alkoxyalkoxy group such as a methoxymethoxy group, a methoxyethoxy group, an ethoxymethoxy group and an ethoxyethoxy group;

An alkoxyalkyl group such as a methoxymethyl group, a methoxyethyl group, an ethoxyethyl group and a propoxyethyl group;

An alkoxycarbonyl group such as a methoxycarbonyl group or an ethoxycarbonyl group;

An acyloxy group such as an acetyloxy group and an ethylcarbonyloxy group is exemplified.

The compound of the general formula (III) can be prepared by an ordinary method using 1,5-dihydroxy-4,8-dichloroanthraquinone as a starting material by an Ullmann condensation reaction.
It is easily obtained by reacting with anilines. In addition, the compound of the general formula (IV) can be easily obtained by reacting with 1,4-dichloroanthraquinone as a starting material and an aniline by a Ullmann condensation reaction using a conventional method.

The anthraquinone dye of the general formula (III) or (IV) used in the present invention is a polymerizable monomer 10
0.1 to 20 parts by weight is added to 0 parts by weight. These anthraquinone dyes are C.I. I. Pigment Blue 15 and other phthalocyanine pigments.

(4) Colorant for cyan toner C.I. I. Pigment Blue
16 is C.I. I. Pigment Blue 16 in an amount of 5 to 80% by weight of C.I. I. Pigment Bl
ue 15: 3. C.I. I. P
It is preferable that the addition amount of the immagentBlue 16 be 0.1 to 20 parts by weight based on 100 parts by weight of the polymerizable monomer.

The above-mentioned pigments have no inhibitory property at the time of the polymerization reaction and have very good granulation properties.

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

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

In the present invention, polymerization may be carried out by adding a resin to the monomer system. For example, the monomer contains a hydrophilic functional group such as an amino group, a carboxylic acid group, a hydroxyl group, a sulfonic acid group, a glycidyl group, and a nitrile group that cannot be used because it dissolves in an aqueous suspension to cause emulsion polymerization due to water solubility. When it is desired to introduce a monomer component into the toner, a random copolymer of these with a vinyl compound such as styrene or ethylene,
It can be used in the form of a copolymer such as a block copolymer or a graft copolymer, or in the form of a polycondensate such as polyester or polyamide, or a polyaddition polymer such as polyether or polyimine. When such a high molecular polymer containing a polar functional group is coexisted in the toner, the wax component described below is phase-separated, the encapsulation becomes stronger, and the performance of the toner of the present invention is improved. desirable. The amount used is preferably 1 to 20 wt%. The average molecular weight of the high molecular polymer containing these polar functional groups is preferably 5,000 or more. 5,0
If it is less than 00, especially 4,000 or less, since the present polymer tends to concentrate near the surface, adverse effects on developability, blocking resistance and the like are likely to occur, which is not preferable. Further, if a polymer having a molecular weight different from the molecular weight range of the toner obtained by polymerizing the monomer is dissolved in the monomer and polymerized, a toner having a wide molecular weight distribution and high offset resistance can be obtained. I can do it.

In the present invention, a charge control agent can be added to the toner material in order to control the chargeability of the toner. It is desired that the charge control agent has no polymerization inhibitory property or water phase transfer property.For example, as the positive charge control agent, a nigrosine dye, a triphenylmethane dye, a quaternary ammonium salt, an amine or imine-based dye is used. Compound,
Examples of the negative charge control agent include metal compounds of salicylic acid or alkyl salicylic acid, gold-containing monoazo dyes, polymers having a carboxylic acid or sulfonic acid functional group, and humic acids and salts such as nitrohumic acid. .

In the suspension polymerization method of the present invention, a plasticizer and a plasticizer are added to the toner in order to improve the low-temperature fixing property or to improve the releasability when combined with a hot roll fixing device.
Low-temperature fluidizing components such as liquid rubber, silicone oil, and wax, and low surface energy substances can be contained.

Examples of the wax include, for example, paraffin / polyolefin waxes and modified products thereof, for example, oxides and grafted products, higher fatty acids and metal salts thereof, higher aliphatic alcohols, higher aliphatic esters, and aliphatic amide waxes. And the like. These waxes have a softening point of 30 to 1 according to the ring and ball method (JIS K2531).
Those having a temperature of 30C, preferably 50-100C are desirable. Further, it is desirable to dissolve in the polymerizable monomer. If the softening point is lower than 30 ° C., it is difficult to keep the same in the toner. If the softening point is higher than 130 ° C., it is difficult to dissolve in the polymerizable monomer, and the dispersion of the wax tends to be nonuniform. In order to increase the viscosity of the composition, the particle size distribution during granulation is widened, which is not preferable. Generally, the amount of the wax to be added is preferably 5 to 30% by weight based on the toner.

A silicone oil can be used to further enhance the releasability. The silicone oil used in the present invention preferably has a viscosity at 25 ° C. of 100 to 100,000 centistokes. Outside this range, the releasing effect is reduced, and the same problems as in the case of the wax are caused in terms of the toner retention and the granulation. The amount of the silicone oil added is generally 0.1 to 1 per 100 parts by weight of the polymerizable monomer.
It is appropriate to use 0 parts by weight. Even if it is used in an amount of 10 parts by weight or more, the releasability is already sufficiently exhibited, and the image surface is merely sticky, so that further addition is meaningless.

The polymerization initiator used in the present invention, which has a half-life of 0.5 to 30 hours during the polymerization reaction, is subjected to the polymerization reaction in an amount of 0.5 to 20% by weight of the polymerizable monomer. And a polymer having a maximum molecular weight between 5,000 and 100,000, and can provide the toner with desirable strength and appropriate melting properties. 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 Or diazo polymerization initiators: benzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl peroxycarbonate, cumene hydroperoxide, 2,4-
Peroxide-based polymerization initiators such as dichlorobenzoyl peroxide and lauroyl peroxide are exemplified. In the present invention, a known chain transfer agent may be added to adjust the molecular weight.

In the present invention, a crosslinking agent may be added, and the preferable addition amount is 0.001 to 15% by weight.

In the suspension polymerization method of the present invention, known surfactants and organic / inorganic dispersants can be used as dispersion stabilizers (excluding silica). Among them, inorganic dispersants generate harmful ultrafine powder. The dispersion stability is obtained due to its steric hindrance. Therefore, even if the reaction temperature is changed, the stability is hardly lost, the washing is easy, and the toner is hardly affected. Examples of such inorganic dispersants include calcium phosphate, magnesium phosphate, aluminum phosphate,
Polyvalent metal salts of phosphoric acid such as zinc phosphate; carbonates such as calcium carbonate and magnesium carbonate; inorganic salts such as calcium metasilicate, calcium sulfate and barium sulfate;
Examples include inorganic oxides such as magnesium hydroxide, aluminum hydroxide, bentonite, and alumina.

These inorganic dispersants can be used as polymerizable monomers 10
It is desirable to use 0.2 to 20 parts by weight alone with respect to 0 parts by weight, but 0.001 to 0.1 parts by weight, since it is difficult to generate ultrafine particles but a little poor at atomizing the toner. May be used in combination.

Examples of the surfactant include sodium dodecylbenzene sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate,
Examples include 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 formed 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 can be achieved. At this time, a water-soluble sodium chloride salt is simultaneously produced as a by-product, but when the water-soluble salt is present in the aqueous medium, the dissolution of the polymerizable monomer in water is suppressed, and the ultrafine toner by emulsion polymerization is used. Is more convenient because it is difficult to generate. Since it becomes an obstacle when removing the residual polymerizable monomer at the end of the polymerization reaction, it is better to replace the aqueous medium or to desalinate with an ion exchange resin. The inorganic dispersant can be almost completely removed by dissolving with an acid or alkali after completion of the polymerization.

In the toner production method of the present invention, the above-mentioned toner composition, that is, a toner such as a colorant, a release agent, a plasticizer, a binder, a charge control agent, a crosslinking agent, etc., is required in the polymerizable monomer. Components and other additives, for example, an organic solvent to reduce the viscosity of the polymer formed in the polymerization reaction, a dispersant, etc., are added as appropriate, and a homogenizer, a ball mill, a colloid mill, a dispersing machine such as an ultrasonic dispersing machine, etc. The monomer system uniformly dissolved or dispersed according to the above 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 disperser such as a high-speed stirrer or an ultrasonic disperser to make the desired toner particle size at once. As for the timing of the addition of the polymerization initiator, it may be added at the same time as the other additives are added to the polymerizable monomer, or may be mixed immediately before being suspended in the aqueous medium. Immediately after the granulation and before the initiation of the polymerization reaction, a polymerization initiator dissolved in a polymerizable monomer or a solvent can be added.

After the granulation, stirring may be performed using a usual stirrer to such an extent that the particle state is maintained and the floating and settling of the particles are prevented.

In the polymerization step, the polymerization is carried out at a polymerization temperature of 40 ° C. or higher, generally 50 to 90 ° C. When the polymerization is carried out in 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 150 at the end of the polymerization reaction.
It is possible to increase to ° C.

In addition, as a method of consuming the polymerizable monomer by increasing the polymerization conversion, an organic solvent which is a solvent of the toner is added to the polymer system, and a plasticizer is used to such an extent that the blocking resistance of the toner is not deteriorated. There is a method of lowering the viscosity of the polymer system by putting the amount in the polymer system.

As a method for removing the unreacted polymerizable monomer and / or organic solvent, a highly volatile polymer is used in which the toner binder resin does not dissolve but the polymerizable monomer and / or organic solvent component dissolves. A method of washing with an organic solvent, a method of washing with an acid or alkali, a solvent component that does not dissolve a foaming agent or a polymer is put into a polymer system, and the resulting polymer is made porous to form a polymerizable monomer and / or Alternatively, there is a method of increasing the volatilization area of the organic solvent component. However, since it is difficult to select a solvent such as elution of toner components and persistence of the solvent, the polymerizable monomer and / or the organic solvent component are reduced under reduced pressure. Evaporation is most preferred.

Finally, at least 1000 ppm or less of polymerizable monomer and its reaction residue generated during fixing,
Alternatively, in order to eliminate the off-flavor due to the solvent, the content is more desirably 100 ppm or less.

Thereafter, the dispersion stabilizer is removed, and the generated toner particles are collected by washing, filtration and dried.

The additives used in the present invention for imparting various properties are selected from the viewpoint of durability when added to the toner.
The particle diameter is preferably 1/10 or less of the weight average diameter of the toner particles. The particle size of the additive means an average particle size obtained by observing the surface of the toner particles with an electron microscope. As additives for the purpose of imparting these properties, for example, the following are used.

1) Fluidity-imparting agents: metal oxides (silicon oxide, aluminum oxide, titanium oxide, etc.), carbon black, carbon fluoride, etc. Those subjected to a hydrophobic treatment are more preferable.

2) Abrasives: metal oxides (strontium titanate, cerium oxide, aluminum oxide, magnesium oxide, chromium oxide, etc.), nitrides (silicon nitride, etc.), carbides (silicon carbide, etc.), metal salts (calcium sulfate, etc.) , Barium sulfate, calcium carbonate, etc.).

3) Lubricants: fluororesin powder (vinylidene fluoride, polytetrafluoroethylene, etc.), fatty acid metal salt (zinc stearate, calcium stearate, etc.).

4) Charge controllable particles: metal oxides (such as tin oxide, titanium oxide, zinc oxide, silicon oxide, and aluminum oxide) and carbon black.

These additives are used in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the toner particles.
0.1 to 5 parts by weight are used. These additives may be used alone or in combination of two or more.

The particle size distribution measurement in the present invention will be described.

As a measuring device, Coulter Counter T
A-II type (manufactured by Coulter), number average distribution,
Interface to output volume average distribution (made by Nikkaki)
And CX-1 personal computer (manufactured by Canon)
And the electrolyte is 1% Na using primary grade sodium chloride.
Prepare a Cl aqueous solution.

The measuring method is as follows.
In 50 ml, 0.1 to 5 ml of a surfactant, preferably an alkylbenzene sulfonate, is added as a dispersant, and 0.5 to 50 mg of a measurement sample is further added.

The electrolytic solution in which the sample was suspended was subjected to a dispersion treatment for about 1 to 3 minutes using an ultrasonic disperser, and the particle size distribution of 2 to 40 μm particles was measured using the Coulter Counter TA-II using a 100 μm aperture as an aperture. Is measured to obtain a volume average distribution and a number average distribution. A weight average particle diameter is obtained from the obtained volume average distribution and number average distribution.

The light resistance was determined after irradiation with a fade meter (carbon arc lamp) at 63 ° C. for 60 hours.

Hereinafter, the present invention will be specifically described based on examples.

[0104]

EXAMPLES Example 1 is a magenta toner, Example 2 is a yellow toner, Example 3 is a cyan toner, Examples 4 and 5
Is C. I. An example of a cyan toner containing Pigment Blue 16 is shown.

Reference Example 1 0.1 M Na ₃ PO ₄ aqueous solution 4 in 710 g of ion-exchanged water
After charging 50 g and heating to 60 ° C., the mixture was stirred at 12,000 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo). 68 g of 1.0 M CaCl ₂ aqueous solution
Was gradually added to obtain an aqueous medium containing Ca ₃ (PO ₄ ).

Styrene 160 g n-butyl acrylate 40 g paraffin wax (mp 70 ° C.) 50 g styrene-methacrylic acid copolymer (95: 5, Mw 50,000) 10 g di-t-butylsalicylate metal compound 1 g

[0107]

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The above-mentioned formulation was heated to 60 ° C., and was subjected to 12,000 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo).
To dissolve and disperse uniformly. To this, a polymerization initiator, 2,
2'-azobis (2,4-dimethylvaleronitrile) 1
0 g was dissolved to prepare a polymerizable monomer system. The polymerizable monomer system is charged into the aqueous medium, and the mixture is subjected to 9,000 rpm with a TK homomixer at 60 ° C. in an N ₂ atmosphere.
Then, the mixture was stirred at m for 20 minutes to granulate the polymerizable monomer system. Thereafter, the mixture was reacted at 60 ° C. for 1 hour while stirring with a paddle stirring blade, and then the liquid temperature was set to 80 ° C., and the reaction was performed for 10 hours. Thereafter, the mixture is cooled, hydrochloric acid is added to dissolve Ca ₃ (PO ₄ ) ₂ ,
After filtration, washing and drying, a polymerized magenta toner was obtained. The particle size of the obtained toner was 8.2 μm in weight average particle size and had a sharp particle size distribution.

With respect to 100 parts by weight of the obtained toner, B
0.5 parts by weight of a hydrophobic silica having a specific surface area of 200 m ² / g by the ET method was externally added. To 5 parts by weight of this toner, 95 parts by weight of an acryl-coated ferrite carrier were mixed to prepare a developer. Using this developer and externally added toner, a full-color copier CLC-500 manufactured by Canon
When the image output was evaluated using a remodeling machine, a stable clear, good magenta color image was obtained without a decrease in the developability even after 20,000 sheets had been durable. In addition, the copy was excellent in fixability, and the light resistance of the copy was good, and it was grade 6.

Reference Example 2 The anthraquinone dye of Reference Example 1 was used.

[0111]

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[0112] Except for the change to
A polymerized magenta toner was obtained. The particle size of the obtained toner is
It had a weight average diameter of 8.3 μm and a sharp particle size distribution.

A developer was prepared according to the same formulation as in Reference Example 1, and image development was evaluated. As a result, a clear magenta color good image was obtained without deteriorating developability even after 20,000-sheet running. was gotten. In addition, the copy was excellent in fixability, and the light resistance of the copy was good, and it was grade 6.

[0114] The anthraquinone dye of Example 1 Reference Example 1

[0115]

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C. I. Pigment Red 122 was changed to 10 g to obtain a polymerized magenta toner in the same manner as in Reference Example 1. The obtained toner had a weight average particle diameter of 7.9 μm and a sharp particle size distribution.

A developer was prepared according to the same formulation as in Reference Example 1, and image out evaluation was performed. As a result, a clear image having a clear magenta color was obtained without deterioration in developability even after 20,000-sheet running. was gotten. Further, the copy was excellent in fixability, and the light resistance of the copy was also good, and it was grade 8.

Comparative Example 1 Anthraquinone dye used in Reference Example 10 10 g Styrene-acrylic copolymer (Mw = 40,000, Mw / Mn = 3.5) 200 g Paraffin wax (mp = 70 ° C.) 50 g -T-butylsalicylic acid metal compound 1g

After mixing the above formulation, the mixture was heated to 150 ° C.
When melt-mixing was performed to obtain pulverized toner,
Paraffin wax was separated, and a uniform melt-kneaded product could not be obtained.

Comparative Example 2 A specific surface area of 1,200 g of ion-exchanged water by the BET method was 2
10 g of amino-modified colloidal silica of 00 m ² / g
The mixture was heated to 60 ° C. and dispersed at 10,000 rpm for 10 minutes using a TK homomixer M type (manufactured by Tokushu Kika Kogyo Co., Ltd.). Further, hydrochloric acid was added to adjust the pH of the aqueous medium to 6
And

Styrene 160 g n-butyl acrylate 40 g paraffin wax (mp 70 ° C.) 50 g styrene-methacrylic acid copolymer (95: 5, Mw = 50,000) 10 g di-t-butylsalicylate metal compound 1 g anthraquinone Magenta dye 10g (Red Violet R, manufactured by Bayer AG)

When the same operation as in Reference Example 1 was carried out using the above formulation, the polymerization reaction did not sufficiently proceed, and polymer particles usable as toner particles were not obtained.

Comparative Example 3 In Comparative Example 1, melt kneading, coarse pulverization, fine pulverization, and classification were carried out using a formulation not using paraffin wax to obtain a pulverized magenta toner having a weight average diameter of 8.0 μm.

A developer was prepared according to the same formulation as in Reference Example 1, and the image formation was evaluated. As a result, fog occurred when the number of endurances reached 10,000. In addition, the fixability was poor.

Reference Example 3 The anthraquinone dye of Reference Example 1 was used.

[0126]

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A polymerized yellow toner was obtained in the same manner as in Reference Example 1 except that this was changed. The particle diameter of the obtained toner was 8.1 μm in weight average diameter and had a sharp particle size distribution.

A developer was prepared according to the same formulation as in Reference Example 1 and image out evaluation was carried out. As a result, a clear and excellent yellow image was obtained without deteriorating developability even after 20,000-sheet running. was gotten. Further, the copy was excellent in fixability, and the light resistance of the copy was good, and the copy was grade 7.

Reference Example 4 The anthraquinone dye of Reference Example 1 was used.

[0130]

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[0131] Except for the change to
A polymerized yellow toner was obtained. The particle size of the obtained toner is
It had a sharp particle size distribution with a weight average diameter of 8.2 μm.

A developer was prepared according to the same formulation as in Reference Example 1, and image out evaluation was performed. As a result, a clear image with a clear yellow color was obtained without deteriorating developability even after 20,000-sheet running. was gotten. Further, the copy was excellent in fixability, and the light resistance of the copy was good, and the copy was grade 7.

Example 2 The anthraquinone dye of Reference Example 1 was used

[0134]

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C. I. Pigment Yellow 17 was changed to 10 g to obtain a polymerized yellow toner in the same manner as in Reference Example 1. The obtained toner had a weight average particle diameter of 7.9 μm and a sharp particle size distribution.

A developer was prepared according to the same formulation as in Reference Example 1, and the image output was evaluated. As a result, a clear image having a clear yellow color was obtained without a decrease in developability even after 20,000 sheets had been durable. was gotten. Further, the copy was excellent in fixability, and the light resistance of the copy was also good, and it was grade 8.

Comparative Example 4 Anthraquinone dye used in Reference Example 10 10 g Styrene-acrylic copolymer (Mw = 40,000, Mw / Mn = 3.5) 200 g Paraffin wax (mp = 70 ° C.) 50 g -T-butylsalicylic acid metal compound 1g

After mixing the above formulation, the mixture was heated to 150 ° C.
When melt-mixing was performed to obtain pulverized toner,
Paraffin wax was separated, and a uniform melt-kneaded product could not be obtained.

Reference Example 5 The anthraquinone dye of Reference Example 1 was used.

[0140]

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A polymerized cyan toner was obtained in the same manner as in Reference Example 1, except for changing the above. The particle size of the obtained toner was 8.2 μm in weight average particle size and had a sharp particle size distribution.

A developer was prepared according to the same formulation as in Reference Example 1, and the image output was evaluated. As a result, a clear and excellent image of a stable cyan color was obtained without a decrease in developability even after 20,000 sheets had been durable. was gotten. Further, the copy was excellent in fixability, and the light resistance of the copy was good, and the copy was grade 7.

Reference Example 6 The anthraquinone dye of Reference Example 1 was used.

[0144]

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[0145] Except for the change to
A polymerized cyan toner was obtained. The obtained toner had a sharp particle size distribution with a weight average particle size of 8.0 μm.

A developer was prepared according to the same formulation as in Reference Example 1 and image out evaluation was performed. As a result, a clear image of a good cyan color was obtained without deterioration in developability even after 20,000 sheets of durability. was gotten. In addition, the copy was excellent in fixability, and the light resistance of the copy was good, and it was grade 6.

Example 3 The anthraquinone dye of Reference Example 1 was used

[0148]

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C. I. Pigment Blue 15 was replaced with 10 g to obtain a polymerized cyan toner in the same manner as in Reference Example 1. The obtained toner has a particle diameter of 7.
It had a sharp particle size distribution of 9 μm.

A developer was prepared according to the same formulation as in Reference Example 1, and image out evaluation was performed. As a result, a clear image of a good cyan color was obtained without deterioration in developability even after 20,000-sheet running. was gotten. Further, the copy was excellent in fixability, and the light resistance of the copy was also good, and it was grade 8.

Comparative Example 5 Anthraquinone dye used in Reference Example 10 10 g Styrene-acrylic copolymer (Mw = 40,000, Mw / Mn = 3.5) 200 g Paraffin wax (mp = 70 ° C.) 50 g -T-butylsalicylic acid metal compound 1g

After mixing the above formulation, the mixture was heated to 150 ° C. and melt-mixed to obtain a pulverized toner. However, the paraffin wax was separated and a uniform melt-kneaded product could not be obtained.

Comparative Example 6 In Comparative Example 5, melt kneading, coarse pulverization, fine pulverization and classification were carried out using no paraffin wax to obtain a pulverized cyan toner having a weight average diameter of 8.0 μm.

A developer was prepared according to the same formulation as in Reference Example 1, and the image formation was evaluated. As a result, fog occurred when the number of endurances reached 10,000. In addition, the fixability was poor.

REFERENCE EXAMPLE 7 The anthraquinone dye of Reference Example 1 was prepared using C.I. I. Pigme
A polymerized cyan toner was obtained in the same manner as in Reference Example 1 except that nt Blue 16 was changed. The particle size of the obtained toner was 8.2 μm in weight average particle size and had a sharp particle size distribution.

A developer was prepared according to the same formulation as in Reference Example 1, and image out evaluation was performed. As a result, a stable and good image was obtained without deterioration in developability even after 10,000 sheets of durability.

Embodiment 4 C.I. I. Pigment Blue 168 g C.I. I. Pigment Blue 15: 3 2g

A cyan toner was obtained in the same manner as in Reference Example 1, except that the anthraquinone dye was changed to the above. The particle size of the obtained toner was 8.0 μm in weight average diameter, and had a sharp particle size distribution.

When evaluation was performed in the same manner, a good cyan image was obtained even in the durability test of 10,000 sheets. Further, the hue of the fixed image of the present example was very excellent as compared with the hue of the fixed image of Reference Example 7.

Example 5 170 g of styrene 170 g of 2-ethylhexyl acrylate 30 g of paraffin wax (mp = 76 ° C.) 40 g of styrene-methacrylic acid copolymer (95: 5, Mw 50,000) 10 g of C.I. I. Pigment Blue 16 5 g Anthraquinone blue dye represented by the following general formula 5 g

[0161]

Embedded image

A cyan toner having a weight average diameter of 7.8 μm was obtained in the same manner as in Reference Example 1 with the above formulation.

When evaluated similarly, a good image was obtained and the cyan toner was excellent in vividness.

Comparative Example 7 Pigment used in Reference Example 10 10 g Styrene-acrylic copolymer (Mw = 40,000, Mw / Mn = 3.5) 200 g Paraffin wax (mp = 70 ° C.) 50 g Di-t -Butylsalicylic acid metal compound 1g

After mixing the above formulation, the mixture was heated to 150 ° C. and melt-mixed to obtain a pulverized toner. However, the paraffin wax was separated, and a uniform melt-kneaded product could not be obtained.

Comparative Example 8 A specific surface area determined by the BET method
10 g of amino-modified colloidal silica of 00 m ² / g
The mixture was heated to 60 ° C. and dispersed at 10,000 rpm for 10 minutes using a TK homomixer M type (manufactured by Tokushu Kika Kogyo Co., Ltd.). Further, hydrochloric acid was added to adjust the pH of the aqueous medium to 6
And

Styrene 160 g n-butyl acrylate 40 g paraffin wax (mp 70 ° C.) 50 g styrene-methacrylic acid copolymer (95: 5, Mw = 50,000) 10 g di-t-butylsalicylate metal compound 1 g Reference Example 10g of pigment used in 7

When the same operation as in Reference Example 1 was performed using the above formulation, the polymerization reaction did not proceed sufficiently, and polymer particles usable as toner particles were not obtained.
This is considered to be due to the use of amino-modified colloidal silica as the dispersion stabilizer.

Comparative Example 9 In Comparative Example 7, melt kneading, coarse pulverization, fine pulverization, and classification were carried out using no paraffin wax, to obtain a pulverized cyan toner having a weight average diameter of 8.0 μm.

A developer was prepared according to the same formulation as in Reference Example 1, and the image formation was evaluated. In addition, the fixability was poor.

[0171]

As described above, according to the present invention,
A polymerized toner having good charging characteristics and light resistance, no polymerization inhibition, and excellent fixability can be obtained.

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Kasutani Rare 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Inventor Makoto Shinbayashi 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inside (72) Inventor Kazuyuki Miyano 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (56) References JP-A-3-140968 (JP, A) JP-A-4-67045 (JP) JP-A-4-7301 (JP, A) JP-A-2-51165 (JP, A) JP-A-1-227162 (JP, A) JP-A-3-87754 (JP, A) JP-A-237667 (JP, A) JP-A-5-301909 (JP, A) JP-A-4-140757 (JP, A) JP-A-1-159666 (JP, A) JP-A-2-196247 (JP, A A) JP-A-5-222109 (JP, A) (58) Field (Int.Cl. ^7, DB name) G03G 9/09 G03G 9/087

Claims (7)

(57) [Claims] 1. A polymerization method obtained by suspension polymerization of a polymerizable monomer system containing at least a polymerizable monomer and a colorant in an aqueous medium containing a dispersion stabilizer (excluding silica). A toner, wherein the colorant is 100 parts by weight of a polymerizable monomer.
0.1 to 20 parts by weight of the following general formulas (I), (II),
A polymerized toner comprising a combination of an anthraquinone dye selected from the group consisting of (III) and (IV) and a pigment . Embedded image j, k = 0~4 n = 1~4 R 1 = alkyl group, an alkoxyl group, alkoxyalkoxyl group, a halogen atom, an alkoxyalkyl group, an aralkyl group, an alkoxycarbonyl group, an alkyl carboxyl group, -H R ₂ = -H , -OH (however, there is no R ₁ = R ₂ = H) R ₃ = alkyl group, alkoxyl group. ] [Wherein, R ₄ = hydrogen atom, halogen atom, alkyl group,
Shows a cycloalkyl group, an alkoxyl group, an alkoxyalkyl group, alkoxyalkoxyl group, an aralkyl group, an alkoxycarbonyl group, an alkylcarboxyl group R ₅ = -OH, -NH _2, and -H. ] [Wherein, the benzene ring P is one or more alkyl groups, cycloalkyl groups, alkoxy groups, hydroxyl groups, trifluoromethyl groups, alkoxyalkoxy groups, hydroxyalkyl groups, alkylcarbonyl groups, alkoxycarbonyl groups,
It represents an alkylcarboxy group or a phenyl group substituted with a halogen atom. ] [Wherein, R _{6 to} R ₁₁ represent a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, an aralkyl group, an alkoxy group, an alkoxyalkoxy group, an alkoxyalkyl group, an alkoxycarbonyl group, or Shows an acyloxy group. ] 2. The coloring agent represented by the general formula (I)
Anthraquinone dyes, quinacridone pigments, azo
Glue composed of lacquer based pigment and rhodamine dye
A combination of a pigment selected from
The polymerization method toner according to claim 1. 3. The coloring agent represented by the general formula (II):
Used anthraquinone dyes and disazo pigments
The polymerization method toner according to claim 1, wherein the polymerization is performed. 4. The coloring agent according to the general formula (III) or
An anthraquinone dye represented by (IV),
2. The method according to claim 1, wherein an anine pigment is used in combination.
Polymerization toner. 5. A polymerized toner obtained by suspension-polymerizing a polymerizable monomer system containing at least a colorant in an aqueous medium containing a dispersion stabilizer (excluding silica), As a coloring agent, C.I. I. Pigment Blue 1
6 and C.I. I. Pigment Blue 16 in an amount of 5 to 80% by weight of C.I. I. PigmentBlue
And 15: 3. 6. The polymerization toner according to claim 5 , wherein the dispersion stabilizer is contained in an amount of 0.2 to 20 parts by weight based on 100 parts by weight of the polymerizable monomer. 7. The method according to claim 1, wherein the dispersion stabilizer is selected from the group consisting of calcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, calcium carbonate, magnesium carbonate, calcium metasilicate, calcium sulfate and barium sulfate. 7. The polymerization toner according to 5 or 6 .