JPH10239899A - Production of polymer particles, and toner for developing electrostatic charge image using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve the dispersion stability of colorant-contg. composite polymer particles when a quinacridone pigment is used as the colorant by emulsion- polymerizing a vinyl monomer, adding the quinacridone pigment and heating them. SOLUTION: A vinyl monomer is emulsion-polymerized, a quinacridone pigment as a colorant is added and they are heated at a certain temp. to produce the objective polymer particles. These processes may be repeated. When the colorant is a phthalocyanine pigment, polymer particles are previously added to the polymerizing process and similar processes are carried out. In the case of the quinacridone pigment, the dispersion stability of the resultant colorant- contg. composite polymer particles is improved. In the case of the phthalocyanine pigment, the control of mol.wt. is improved.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a toner for developing an electrostatic image in electrophotography, electrostatic recording, electrostatic printing, and the like, and a method for producing polymer particles used for producing the toner.

[0002]

2. Description of the Related Art Conventionally, generally used toners are obtained by appropriately dry-mixing a polymer obtained by various polymerization methods with a colorant such as carbon black, a charge controlling agent and / or a magnetic material, and then extruder or the like. Melt kneading, then pulverization,
It is manufactured by classification.

As another method, a method of directly manufacturing a toner by a suspension polymerization method or the like has been proposed. A method using particles produced by an emulsion polymerization method has also been proposed (Japanese Unexamined Patent Publication No.
220358, JP-A-4-284461)
Have been.

However, the toner obtained by the above-described melt-kneading and pulverizing method has a limitation in controlling the toner particle size, and it is difficult to produce a toner having a small particle size with high yield. In addition, there is a disadvantage that the components forming the toner are not uniformly dispersed and the charge amount distribution tends to be broad.

Further, the direct production method by the suspension polymerization method also has a disadvantage that not only is it difficult to reduce the particle size, but also the particle size distribution becomes wide. Furthermore, the toner produced by this method has a drawback that it is basically spherical and is difficult to clean in an electrophotographic process.

On the other hand, the methods disclosed in JP-A-60-220358 and JP-A-4-284461 are disclosed in
Although it is possible to obtain non-spherical particles having irregularities on the surface instead of a true spherical toner as described above, it is difficult to control the particle size and particle size distribution, and the desired particle size after the reaction is completed.
Classification is required to obtain a particle size distribution.

Further, in the method disclosed in JP-A-4-284461, it is necessary to finely adjust the zeta potential of the colorant and the polymer particles. This not only makes it difficult to improve the productivity, but also causes the colorant and the like to be easily localized in the generated toner particles, and as a result, the generated toner particles cannot have sufficient mechanical strength. have.

In order to solve the above-mentioned drawbacks, the present inventors have proposed a method disclosed in Japanese Patent Application Laid-Open No. Hei 6-329947. This method performs polymerization in the presence of a colorant and other desired additives during the emulsion polymerization, for example, a fixability improving agent,
The produced composite polymer particles such as a colorant are aggregated to produce a non-spherical toner. According to this method, it is easy to control the particle size and particle size distribution of the toner particles, and since the additives such as the colorant do not localize in the toner particles, sufficient mechanical strength can be obtained.

However, this method still has a problem. That is, when a quinacridone-based pigment is used as a colorant, the dispersion stability of the composite polymer particles such as the colorant is reduced, so that there is a disadvantage that the production yield is reduced. Further, when a phthalocyanine-based pigment is used as a coloring agent, it is difficult to control the molecular weight of the polymer particles, and may form an oligomer.

[0010]

SUMMARY OF THE INVENTION A first object of the present invention is to improve the dispersion stability of a composite polymer particle component such as a colorant when a quinacridone pigment is used as a colorant. The purpose of is to improve the polymer molecular weight controllability when using a phthalocyanine pigment as a colorant,
An object of the present invention is to provide a non-spherical toner having a narrow particle size distribution by solving these problems.

[0011]

The object of the present invention has been attained by employing the following constitution.

(1) A polymer comprising a first polymerization step of emulsion-polymerizing a vinyl monomer, a step of adding a quinacridone pigment after the emulsion polymerization step, and a step of performing a heat treatment after the addition of the pigment. Method for producing particles.

(2) A polymer comprising a first polymerization step of emulsion-polymerizing a vinyl monomer, a step of adding a phthalocyanine-based pigment after the emulsion polymerization step, and a step of performing a heat treatment after the addition of the pigment. Method for producing particles.

(3) The method for producing polymer particles according to (1), wherein a vinyl monomer is further added and emulsion polymerization is carried out.
A process of adding a quinacridone pigment thereafter, and a heat treatment after adding the quinacridone pigment.

(4) A toner for developing an electrostatic charge image, which is produced by associating a plurality of polymer particles produced by the method for producing polymer particles according to (1), (2) or (3). .

The present inventors have conducted various studies, and as a result,
We have found that the following method can be used to achieve the first purpose.

That is, the method comprises a first polymerization step of emulsion-polymerizing a vinyl monomer, a step of adding a quinacridone pigment after the emulsion polymerization step, and a step of performing a heat treatment at a constant temperature after the addition of the pigment. Of producing polymer particles.

A polymer particle comprising a step of adding a quinacridone pigment after a second polymerization step of adding a vinyl monomer and emulsion-polymerizing, and a step of heat-treating the pigment at a constant temperature after adding the pigment. Manufacturing method.

As a result of various studies, the present inventors have found that the following method is employed in order to achieve the second object.

That is, the method comprises a first polymerization step of emulsion-polymerizing a vinyl monomer, a step of adding a phthalocyanine pigment after the emulsion polymerization step, and a step of performing a heat treatment at a constant temperature after the addition of the pigment. Of producing polymer particles.

Further, the intended toner can be obtained by using the above polymer particles.

Next, the raw materials according to the present invention, the polymerization method,
A method of producing the toner for developing an electrostatic image by associating the obtained polymer particles will be described.

(Colorant) Examples of the quinacridone colorant include C.I. I. Pigment Red 122, C.I. I.
Pigment Red 207, C.I. I. Pigment Red 2
09, C.I. I. Pigment Red 202, C.I. I. Pigment Red 206, C.I. I. Pigment Violet 19. Particularly, as the colorant for the magenta toner, C.I. I. Pigment Red 122 is preferably used.

The phthalocyanine pigments include C.I. I.
Pigment Blue 15, C.I. I. Pigment Blue 1
5: 1, C.I. I. Pigment Blue 15: 2, C.I. I.
Pigment Blue 15: 3, C.I. I. Pigment Blue 15: 4, C.I. I. Pigment Blue 15: 5, C.I.
I. Pigment Blue 15: 6, C.I. I. Pigment Blue 16, C.I. I. Pigment Blue 17: 1, C.I.
I. Pigment Green 7, C.I. I. Pigment Green 36, C.I. I. Pigment Green 37. As the cyan toner, C.I. I. Pigment Blue 15: 3 is preferably used.

(Colorant Dispersion) The colorant is finely dispersed in an aqueous phase in the presence of a surfactant and used in the form of an aqueous dispersion. For preparing the dispersion, an ultrasonic disperser, a pressure disperser, and a medium disperser are used.

The surfactant is selected depending on the type of the copolymer component in the polymer particles, particularly the ionic monomer.
When the ionic monomer is anionic, the surfactant is selected from an anionic surfactant and / or a nonionic surfactant. When the ionic monomer is cationic, a cationic surfactant and / or a nonionic surfactant are selected.

As a preferred surfactant, it is preferable to use the same type of ionic surfactant as the ionic monomer of the polymer particles. Further, as the surfactant used for preparing the colorant dispersion, it is preferable to use the same surfactant as the surfactant used when performing emulsion polymerization.

(Vinyl Monomer) As the vinyl monomer constituting the polymer particles, a combination of a hydrophobic monomer and an ionic monomer is used. The ionic monomer is used in a copolymerization ratio of 0.1 to 15% by weight.

Examples of the hydrophobic monomer include styrene derivatives such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, and o-methylstyrene.
-Ethoxystyrene, m-ethoxystyrene, p-ethoxystyrene, o-butoxystyrene, m-butoxystyrene, p-butoxystyrene, o-chlorostyrene,
m-chlorostyrene, p-chlorostyrene, 2,4-dimethylstyrene, 2,4-dichlorostyrene, 2,4-
Examples include dibromostyrene, p-hydroxystyrene, o-hydroxystyrene and the like.

Examples of (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, and (meth) acrylate.
Sec-butyl acrylate, ter (meth) acrylate
t-butyl, 2-ethylhexyl (meth) acrylate,
Examples thereof include cyclohexyl (meth) acrylate and dodecyl (meth) acrylate.

Further, tolyl monomers such as acrylonitrile and methacrylonitrile, vinyl ether monomers such as vinyl methyl ether and vinyl ethyl ether, vinyl ester monomers such as vinyl acetate and vinyl butyrate,
Examples include olefin-based monomers such as ethylene, propylene, and isobutylene, and conjugated diene-based monomers such as butadiene, isoprene, chloroprene, and dimethylbutadiene.

The monomer having an ionic group of the present invention is
It is selected from monomers having a cationic group or monomers having an anionic group. These are selected depending on the charge polarity of the toner. When the chargeability of the toner is positive, a monomer having a cationic group is copolymerized, and when the chargeability of the toner is negative, a monomer having an anionic group is copolymerized.

As the cationic group of the monomer having a cationic group, a monomer having at least one group selected from an amino group, an amide group and a quaternary ammonium base is used. The monomer is represented by the following general formulas (I) to (VII).

[0034]

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[0035]

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(However, R ¹ is a hydrogen atom or a carbon atom having 1
And R ² represents an alkylene group having 1 to 8 carbon atoms, an alkyleneoxyalkylene group having 1 to 8 carbon atoms, a phenylene group, a naphthylene group, a phenylene alkylene group, or a combination of two or more of these groups. R ³ and R ⁴ may be the same or different and each represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a phenyl group, a naphthyl group, or a phenylalkyl group. M represents a simple bonding group or -CONR-, -COO-. A represents a benzyl group or a phenethyl group (provided that R is
Represents a hydrogen atom or a methyl group). B represents a pyridyl group or an imidazolyl group. Examples of the monomer represented by the general formula (I) include the following compounds.

N, N-dimethylaminoethyl methacrylate, N, N-diethylaminoethyl methacrylate,
N-methylaminoethyl methacrylate, N, N-dimethylaminomethyl methacrylate, p-N, N-dimethylaminophenyl methacrylate, N, N-dimethylaminoethyl acrylate, N, N-diethylaminoethyl acrylate, N-methylaminoethyl acrylate , N, N-diethylaminomethyl acrylate, p-
N, N-dimethylaminophenyl acrylate.

Examples of the monomer represented by the general formula (II) include the following compounds.

N, N-dimethylaminoethyl methacrylamide, N, N-diethylaminoethyl methacrylamide, N-methylaminoethyl methacrylamide, N, N
-Dimethylaminomethyl methacrylamide, p-N, N
-Dimethylaminophenyl methacrylamide, N, N-
Dimethylaminoethylacrylamide, N, N-diethylaminoethylacrylamide, N-methylaminoethylacrylamide, N, N-diethylaminomethylacrylamide, p-N, N-dimethylaminophenylacrylamide.

Examples of the monomer represented by the general formula (III) include the following compounds.

N, N-dimethylmethacrylylamide,
N, N-diethylmethacrylamide, N-propylmethacrylamide, N, N-dimethylacrylamide,
N-diethylacrylamide, N-propylacrylamide.

Examples of the monomer represented by the general formula (IV) include the following compounds.

P-N, N-dimethylaminostyrene, p
-N, N-diethylaminostyrene, pN, N-dipropylaminostyrene, p-N-methylaminostyrene.

As examples of the monomer represented by the general formula (V), the following compounds can be given. For example,
N-vinyldimethylamine, N-vinyldiethylamine, N-vinyldipropylamine, N-vinylpropylamine.

Examples of the vinyl monomer represented by the general formula (VI) include the following compounds.

For example, vinylbenzyldialkylamines each having an amino group at the meta or para position (the alkyl group is a substituted or unsubstituted alkyl group having n = 1 to 6 carbon atoms);
Vinylphenethyl dialkylamine (the alkyl group is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms).

Examples of the vinyl monomer represented by the general formula (VII) include the following compounds.

4-vinylpyridine, 2-vinylpyridine, N-vinylimidazole.

Further, quaternary ammonium salts of the above general formulas (I) to (VII) can also be used. For example, an alkyl group having 1 to 6 carbon atoms, a benzyl group,
Those having a cycloalkyl group or the like can be mentioned.

Examples of the monomer having an anionic group include:
A vinyl monomer having a carboxyl group, a sulfone group, and a phosphate group is used. Examples of monomers having a carboxyl group include acrylic acid, methacrylic acid, itaconic acid,
Maleic acid, fumaric acid, crotonic acid, tetrahydroterephthalic acid, α-alkyl-substituted acrylic acid (substituted alkyl has 1 to 4 carbon atoms), monoalkylitaconic acid (alkyl has 1 to 4 carbon atoms), monoalkyl maleic acid (alkyl Is a group having 1 to 4 carbon atoms.

Examples of the monomer having a sulfonic acid group include:
Examples thereof include styrene sulfonic acid and 2-acrylamido-2-methylpropane sulfonic acid.

Examples of the monomer having a phosphate group include 2-
Azide phosphooxyethyl methacrylate, 2-azido phosphooxypropyl methacrylate, and 3-chloro-2-azid phosphopropyl methacrylate are exemplified.

(Copolymer Composition) The polymer of the present invention is used as a copolymer of a hydrophobic monomer and an ionic monomer. Since the ionic monomer is mainly used for controlling the particle size distribution at the time of synthesizing the toner and for imparting chargeability to the toner, in the case of a positively chargeable toner, at least one kind of monomer selected from the group of cationic monomers is used. In the case of a negatively chargeable toner, at least one monomer selected from the group of anionic monomers is copolymerized. If the copolymerization ratio of the ionic monomer is too small, a sufficient charge amount cannot be exhibited.If the copolymerization ratio is too large, not only the hydrophilicity of the particles increases and the environmental difference in the charge amount becomes large, but also the polymerization in emulsion polymerization becomes heavy. It becomes difficult to form coalesced particles.

For this reason, the ionic monomer is used in a copolymerization ratio of 0.1 to 15% by weight depending on the desired charge amount. More preferably, the copolymerization ratio is selected in the range of 0.5 to 10% by weight.

The polymer particles of the present invention have a glass transition temperature (hereinafter abbreviated as Tg) in the range of 40 to 70 ° C. Within the range of the copolymerization ratio of the ionic monomer, one or more hydrophobic monomers are selected from the group, and the monomer type and the copolymerization ratio are selected so as to satisfy the Tg.

(Emulsion Polymerization Method) As a method for synthesizing the polymer particles of the present invention, a method generally called an emulsion polymerization method is used. In the emulsion polymerization method, a required amount of a surfactant is dissolved in an aqueous phase, a monomer is added, a water-soluble radical polymerization initiator is added under heating and stirring, and polymerization is performed to a desired polymerization addition rate. The surfactant is generally added at a concentration higher than the critical micelle forming concentration (hereinafter abbreviated as CMC), preferably at a concentration of 2 to 3 times the CMC, but a stable polymer particle is prepared even at a concentration lower than the CMC. Some can be done. Further, a so-called soap-free emulsion polymerization method without using a surfactant can also be applied to the present invention.

In the present invention, a polymerization step of adding a monomer to an aqueous phase to carry out polymerization when forming a composite with the colorant of the present invention comprises a step of adding a colorant dispersion and heating. When the colorant is a quinacridone pigment,
This step can be repeated as needed. Further, when the colorant is a phthalocyanine pigment, a plurality of polymerization steps can be combined similarly to the quinacridone pigment by adding polymer particles in advance to the polymerization step and performing the same step.

In the case of a quinacridone pigment, as described above, in addition to the method in which polymer particles are dispersed in an aqueous phase in advance, as another method, the first emulsion polymerization is performed, and then the second emulsion polymerization is performed. Further, it is also possible to add a pigment and perform a heat treatment.

Between the first polymerization step and the second polymerization step,
Although it is possible to carry out the polymerization at the same temperature, it is preferable to lower the temperature and once stop the polymerization reaction completely, add a monomer or the like, raise the temperature and heat to carry out the polymerization reaction. The temperature for stopping the polymerization reaction after the first polymerization reaction needs to be at least equal to or lower than the radical generation temperature of the radical polymerization initiator. Generally, it is lowered to 50 ° C. or lower, preferably 30 ° C. or lower.

When a cationic monomer is used as the copolymerizable monomer, at least one surfactant selected from a cationic surfactant and / or a nonionic surfactant is used as the surfactant. When used, it is desirable to use at least one surfactant selected from an anionic surfactant and / or a nonionic surfactant.

Similarly, when a cationic monomer is used as the copolymerization monomer for the radical polymerization initiator, at least one water-soluble radical polymerization initiator selected from a cationic water-soluble radical polymerization initiator and / or a nonionic water-soluble radical polymerization initiator is used. When an anionic monomer is used as the ionic radical polymerization initiator, it is desirable to use at least one surfactant selected from an anionic water-soluble radical polymerization initiator and / or a nonionic water-soluble radical polymerization initiator.

It is preferable that the same surfactant is used as the surfactant used in the emulsion polymerization and the surfactant used for dispersing the colorant. This is because the dispersibility of the colorant particles and the dispersibility of the polymer particles are greatly separated by using different surfactants, and the dispersibility of the toner is greatly different. This is because the distribution may be large.

Further, if necessary, a chain transfer agent can be added as a molecular weight regulator.

(Radical polymerization initiator) Examples of the water-soluble anionic radical polymerization initiator include, for example, potassium persulfate, ammonium persulfate, 4,4'-azobis (4-cyanovaleric acid) and the like.

Examples of the water-soluble cationic radical polymerization initiator include, for example, 2,2'-azobis (2-methylpropionamidine) dihydrochloride, 2,2'-azobis [2-
(2-imidazolin-2-yl) propane] dihydrochloride,
2,2'-azobis [2- (5-methyl-2-imidazolin-2-yl) propane] dihydrochloride, 2,2'-azobis [2- (4,5,6,7-tetrahydro-1- 1,
3-diazepin-2-yl) propane] dihydrochloride, 2,
2'-azobis [2- (5-hydroxy-3,4,5,
6-tetrahydropyrimidin-2-yl)] dihydrochloride,
2,2'-azobis (2-methyl-N-phenylpropionamide) dihydrochloride, 2,2'-azobis [N- (4
-Chlorophenyl) -2-methylpropionamide] dihydrochloride, 2,2'-azobis [N- (4-hydroxyphenyl) -2-methylpropionamide] dihydrochloride,
2,2'-azobis [2-methyl-N- (phenylmethyl) propionamide] dihydrochloride, 2,2-azobis [2-methyl-N- (2-propenyl) propionamide] dihydrochloride, 2'-azobis (2-methylpropionamide) dihydrochloride, 2,2'-azobis [N- (2
-Hydroxyethyl) -2-methylpropionamide]
Dihydrochloride and the like.

Examples of the water-soluble nonionic radical polymerization initiator include, for example, 2,2'-azobis {2-methyl-N
-[1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide}, 2,2'-azobis {2-methyl-N- [1,1-bis (hydroxyethyl) -2-hydroxyethyl] Propionamide｝,
2,2'-azobis {2-methyl-N- (2-hydroxyethyl) propionamide], 2,2'-azobis (2-methylpropionamide) dihydrate, 2,2'-
Azobis [2- (hydroxymethyl) propionitrile] and the like.

These water-soluble radical polymerization initiators can be used by selecting at least one initiator from the group of anionic, cationic and nonionic. Further, if necessary, a combination of an anionic polymerization initiator and a nonionic polymerization initiator and a combination of a cationic polymerization initiator and a nonionic polymerization initiator can be appropriately selected in combination.

(Molecular Weight and Molecular Weight Distribution) The molecular weight of the polymer particles of the present invention can be selected according to the purpose, but a preferred range is 5,000 to 1,000,000 in weight average molecular weight (hereinafter abbreviated as Mw). , Preferably in the range of 8,000 to 500,000. Further, the molecular weight distribution (index obtained by dividing the weight average molecular weight by the number average molecular weight, abbreviated as Mw / Mn) is in the range of 2 to 50, preferably 2.1.
To 30.

Further, the molecular weight distribution may be a single-modal molecular weight distribution or a multi-modal molecular weight distribution. When synthesizing polymer particles having a multi-modal molecular weight distribution, as described above,
By combining the polymerization steps a plurality of times, it is possible to obtain polymer particles having a desired multimodal molecular weight distribution.

(Fixability improver) If necessary, a fixability improver such as low molecular weight polyolefin (low molecular weight polyethylene, low molecular weight polypropylene and a mixture thereof), paraffin, natural wax (carnauba wax,
Beeswax, montan wax), carboxylic acids having a long hydrocarbon chain having 12 or more carbon atoms, and esters thereof. These are preferably added to the colorant dispersion during polymerization in the form of an aqueous dispersion, and then polymerized. The aqueous dispersion of the fixability improving agent can be obtained by emulsifying and dispersing the fixability improver in water heated to a temperature higher than the softening temperature of the fixability improver. Softening temperature of fixability improver is 100 ° C
In the case of exceeding, the dispersion can be easily prepared by pressurized emulsification.

The fixing property improver preferably used in the present invention is a low-molecular-weight polyolefin (low-molecular-weight polyethylene, low-molecular-weight polypropylene and a mixture thereof), and a modified polyolefin obtained by modifying the low-molecular-weight polyolefin with an ionic monomer. is there. As the ionic monomer, the aforementioned ionic monomer is used. The ionic monomer is 1 × 10 ^-2 mmol / g-Poly
It is preferable that denaturation be performed in the range of 1 mmol / g-Polymer to mer.

The low molecular weight polyolefin has a number average molecular weight (hereinafter abbreviated as Mn) of 50 as a preferable molecular weight.
It is 0-10000, more preferably 800-5000.

When the ionic monomer of the polymer particles is anionic, a fixing property modifier modified with an anionic monomer is used. When the ionic monomer of the polymer particles is cationic, the cationic monomer is used. It is preferred to use a fixing property improving agent modified by the above.

Further, the fixing property improving agent is preferably added to the toner of the present invention in a range of 0.5 to 15% by weight. More preferably, it is added in the range of 1 to 10% by weight.

The fixability improver according to the present invention is prepared by adding a desired weight to the aqueous phase in the emulsion polymerization as the above-mentioned aqueous dispersion, mixing with the monomer according to the present invention, and stirring to obtain a water-soluble radical polymerization initiator. A water-soluble radical polymerization initiator is added at a temperature raised to or lower than the radical generation temperature, and the temperature is raised to the radical generation temperature to carry out emulsion polymerization to form a complex.

(Heat Treatment Step of Pigment Dispersion) After the emulsion polymerization step, the dispersion of the phthalocyanine pigment or the quinacridone pigment is added to the emulsion polymerization liquid, that is, the polymer particle dispersion, and subjected to heat treatment. At this point, the emulsion polymerization of the present invention is substantially complete and the polymerization conversion is at least 99% or more.

That is, the above-mentioned pigment dispersion is added after the emulsion polymerization of the present invention is substantially completed. When the pigment dispersion is added after the completion of the emulsion polymerization without performing the heat treatment, for example, after cooling the polymerization liquid, a large difference occurs between the dispersion stability of the polymer particles and the dispersion stability of the pigment dispersion, and a toner-forming reaction occurs. In the step (1), either one of the polymer particles or the pigment-dispersed particles is liable to be selectively aggregated, and it is difficult to generate desired toner particles.

If the temperature in the treatment step is too low, the effect is small, and if it is too high, undesired aggregation occurs. Also, if the time is short, the effect is small, and if the stirring speed is too fast, it may cause aggregation,
Should be set appropriately.

In the heat treatment step, heating is performed at least at room temperature or higher, preferably at a temperature higher than the Tg of the polymer particles, more preferably at the same temperature as the emulsion polymerization reaction, and the stirring speed is the same as that at the time of the emulsion polymerization reaction. It is preferred to stir at a stirring speed. The time of the heat treatment step is 1/10 of the polymerization time.
The above is performed within the same time range. Preferably, the heat treatment is performed at 1/6 or more and 1/2 or less.

(Tonerization treatment) Emulsion polymerization particle dispersion in which quinacridone-based pigment or phthalocyanine-based pigment, which is a colorant formed as described above, is compounded, is used to improve the fixability of these polymer particles and colorant particles and, if desired, improvement of fixability. A plurality of agent particles can be associated and grown to a desired particle size, and at the same time, heated above the glass transition temperature to fuse the associated particles to form strong toner particles.

The heating temperature at this time is preferably in the range of + 5 ° C. to + 50 ° C., the glass transition temperature of the resin. More preferably, the glass transition temperature is from + 10 ° C to + 40 ° C.

When associating the aqueous polymer dispersion containing a colorant with the emulsion polymerization according to the present invention, the ionic groups present on the particle surfaces of the resin fine particles in the aqueous dispersion before or during the associating reaction are used. Is preferably used in a state where ions are partially dissociated. That is, in the case of an anionic group, it is preferable to make it partially dissociated by an alkali. In the case of a cationic group, on the contrary, it is partially dissociated by an acid, or preferably has a quaternary ammonium salt structure. By making the ionic group at least partially in an ion dissociated state, the generation of so-called coarse particles outside the desired particle size range is significantly suppressed, and as a result, toner particles having a narrow particle size distribution can be generated.

In the production of the toner particles of the present invention, at least a part of the ionic dissociating groups present on the particle surfaces of the resin fine particles in the aqueous polymer dispersion containing a colorant is converted to an ion dissociated state by emulsion polymerization. A coagulant is added to the aqueous polymer dispersion while stirring, and an organic solvent that is infinitely soluble in water is added, and then heated to a temperature equal to or higher than the glass transition temperature of the resin to form the polymer aqueous dispersion.

Examples of the coagulant include salts selected from monovalent, divalent and trivalent metal salts, organic and inorganic acids, and organic and inorganic alkalis. For example, sodium chloride, potassium chloride, lithium chloride, magnesium chloride, calcium chloride, aluminum chloride and the like. Examples of the acid include hydrochloric acid, sulfuric acid, acetic acid, and a water-insoluble carboxylic acid. Examples of the alkali include inorganic alkalis such as sodium hydroxide, potassium hydroxide, and lithium hydroxide, and organic amine compounds such as trimethylamine and triethylamine. Preferably, monovalent metal salts, that is, sodium chloride, potassium chloride and lithium chloride are used.

Further, if necessary, an organic solvent and a surfactant which are infinitely soluble in water can be added. They are,
It is used for adjusting the shape of the toner to be generated and sharpening the particle size distribution. The organic solvent infinitely soluble in water is selected from alcohols and ketones that do not dissolve the polymer. Particularly preferred is isopropyl alcohol. The surfactant includes a nonionic surfactant.

(Method for Producing Polymer Particles) The polymer particles of the present invention are produced by the following steps.

[Production Method 1] A hydrophobic monomer and an ionic monomer and, if necessary, an aqueous dispersion of a fixability improver are added to an aqueous phase, and the mixture is stirred while stirring at a temperature lower than the radical generation temperature of a water-soluble radical polymerization initiator. Or a first emulsion polymerization step in which a water-soluble radical polymer initiator or an aqueous solution thereof is added at a temperature higher than that, and polymerization is performed while maintaining the temperature at or above the radical generation temperature of the radical polymerization initiator.

After completion of the emulsion polymerization step, a quinacridone-based pigment dispersion or a phthalocyanine-based pigment dispersion, which is a colorant dispersion, is added, and heat treatment is performed.

[Production Method 2] A hydrophobic monomer and an ionic monomer, and if necessary, an aqueous dispersion of a fixing property improver are added to an aqueous phase, and the mixture is stirred while stirring at or below the radical generation temperature of a water-soluble radical polymerization initiator. Or a first emulsion polymerization step in which a water-soluble radical polymer initiator or an aqueous solution thereof is added at a temperature higher than that, and the polymerization is maintained at a temperature not lower than the radical generation temperature of the radical polymerization initiator.

After completion of the emulsion polymerization step, a quinacridone-based pigment dispersion, which is a colorant dispersion, is added, and heat treatment is performed.

Further, a hydrophobic monomer and an ionic monomer, and if necessary, water and an aqueous dispersion of a fixability improver are added to the first emulsion polymerization particle dispersion, and the mixture is stirred while stirring a water-soluble radical polymerization initiator. A second emulsion polymerization step of adding a water-soluble radical polymer initiator or an aqueous solution thereof at a temperature not higher than or equal to the radical generation temperature of the above and maintaining the temperature at or above the radical generation temperature of the radical polymerization initiator to carry out polymerization. .

After completion of the second emulsion polymerization step, a step of adding a quinacridone pigment dispersion which is a colorant dispersion and performing a heat treatment.

[Production Method 3] A hydrophobic monomer and an ionic monomer and, if necessary, an aqueous dispersion of a fixability improver are added to an aqueous phase, and the mixture is stirred while stirring at a temperature below the radical generation temperature of a water-soluble radical polymerization initiator. Or a first emulsion polymerization step in which a water-soluble radical polymer initiator or an aqueous solution thereof is added at a temperature higher than that, and the polymerization is maintained at a temperature not lower than the radical generation temperature of the radical polymerization initiator.

After the completion of the emulsion polymerization step, a quinacridone-based pigment dispersion, which is a colorant dispersion, is added, and heat treatment is performed.

A step of cooling the polymer particle dispersion, which has been subjected to the first emulsion polymerization step and the heat treatment step, to a temperature below the radical generation temperature of the water-soluble radical polymerization initiator.

Further, a hydrophobic monomer and an ionic monomer, and if necessary, water and an aqueous dispersion of a fixability improver are added to the first emulsion polymerization particle dispersion, and the water-soluble radical polymerization initiator is added while stirring. A second emulsion polymerization step in which a water-soluble radical polymer initiator or an aqueous solution thereof is added at a temperature equal to or lower than the radical generation temperature or higher and the polymerization is maintained at a temperature equal to or higher than the radical generation temperature of the radical polymerization initiator.

After completion of the second emulsion polymerization step, a step of adding a quinacridone pigment dispersion which is a colorant dispersion and performing a heat treatment.

[Production Method 4] In Production Method 3, a similar step is repeated for the desired number of times from the second heat treatment step to the n-th emulsion polymerization step and the n-th heat treatment step.

[Production Method 5] A polymer particle dispersion containing a fixability improving agent dispersion, if necessary, in a water phase, a hydrophobic monomer, an ionic monomer,
Further, if necessary, a fixability improver dispersion is added, and a water-soluble radical polymer initiator or an aqueous solution thereof is added at a temperature equal to or lower than the radical generation temperature of the water-soluble radical polymerization initiator while stirring, A first emulsion polymerization step in which polymerization is performed while maintaining a temperature equal to or higher than the radical generation temperature of the radical polymerization initiator.

After completion of the emulsion polymerization step, a step of adding a quinacridone-based pigment dispersion or a phthalocyanine-based pigment dispersion, which is a colorant dispersion, and performing a heat treatment.

[Production Method 6] A dispersion of two or more polymer particles having different physical properties, including a dispersion of a fixability improving agent, if necessary, in a water phase, a hydrophobic monomer, an ionic monomer, and Accordingly, a fixability improving agent dispersion is added, and while stirring, a water-soluble radical polymer initiator or an aqueous solution thereof is added at a temperature not higher than or equal to the radical generation temperature of the water-soluble radical polymerization initiator, and the radical polymerization is performed. A first emulsion polymerization step in which polymerization is performed while maintaining the temperature equal to or higher than the radical generation temperature of the initiator.

After completion of the emulsion polymerization step, a step of adding a quinacridone-based pigment dispersion or a phthalocyanine-based pigment dispersion, which is a colorant dispersion, and performing a heat treatment.

[Production Method 7] A hydrophobic monomer and an ionic monomer and, if necessary, an aqueous dispersion of a fixability improver are added to an aqueous phase, and the mixture is stirred while stirring at or below the radical generation temperature of a water-soluble radical polymerization initiator. Or a first emulsion polymerization step in which a water-soluble radical polymer initiator or an aqueous solution thereof is added at a temperature higher than that, and the polymerization is maintained at a temperature not lower than the radical generation temperature of the radical polymerization initiator.

Further, a hydrophobic monomer and an ionic monomer, and if necessary, water and an aqueous dispersion of a fixability improver are added to the first emulsion polymerization particle dispersion, and the water-soluble radical polymerization initiator is added while stirring. A second emulsion polymerization step in which a water-soluble radical polymer initiator or an aqueous solution thereof is added at a temperature equal to or lower than the radical generation temperature or higher and the polymerization is maintained at a temperature equal to or higher than the radical generation temperature of the radical polymerization initiator.

After completion of the second emulsion polymerization step, a step of adding a quinacridone-based pigment dispersion or a phthalocyanine-based pigment dispersion, which is a colorant dispersion, and performing a heat treatment.

[Production Method 8] A hydrophobic monomer and an ionic monomer, and if necessary, an aqueous dispersion of a fixability improver are added to an aqueous phase, and the mixture is stirred while stirring at a temperature not higher than the radical generation temperature of a water-soluble radical polymerization initiator. Or a first emulsion polymerization step in which a water-soluble radical polymer initiator or an aqueous solution thereof is added at a temperature higher than that, and the polymerization is maintained at a temperature not lower than the radical generation temperature of the radical polymerization initiator.

Further, a hydrophobic monomer and an ionic monomer, and if necessary, water and an aqueous dispersion of a fixability improver are added to the first emulsion polymerization particle dispersion, and while stirring, the water-soluble radical polymerization initiator is added. A water-soluble radical polymer initiator or an aqueous solution thereof is added at a temperature equal to or lower than the radical generation temperature, and the polymerization is performed a desired number of times while maintaining the temperature equal to or higher than the radical generation temperature of the radical polymerization initiator, n times. n emulsion polymerization steps.

After the completion of the n-th emulsion polymerization step, a quinacridone-based pigment dispersion or a phthalocyanine-based pigment dispersion, which is a colorant dispersion, is added, and a heat treatment is performed.

[Production Method 9] A hydrophobic monomer and an ionic monomer and, if necessary, an aqueous dispersion of a fixability improver are added to an aqueous phase, and the mixture is stirred while stirring at a temperature lower than the radical generation temperature of a water-soluble radical polymerization initiator. Or a first emulsion polymerization step in which a water-soluble radical polymer initiator or an aqueous solution thereof is added at a temperature higher than that, and the polymerization is maintained at a temperature not lower than the radical generation temperature of the radical polymerization initiator.

A step of cooling the polymer particle dispersion having undergone the first emulsion polymerization step and the heat treatment step to a temperature equal to or lower than the radical generation temperature of the water-soluble radical polymerization initiator.

Further, a hydrophobic monomer and an ionic monomer, and if necessary, water and an aqueous dispersion of a fixability improver are added to the first emulsion polymerization particle dispersion, and the water-soluble radical polymerization initiator is added while stirring. A second emulsion polymerization step in which a water-soluble radical polymer initiator or an aqueous solution thereof is added at a temperature equal to or lower than the radical generation temperature or higher and the polymerization is maintained at a temperature equal to or higher than the radical generation temperature of the radical polymerization initiator.

After completion of the second emulsion polymerization step, a quinacridone-based pigment dispersion or a phthalocyanine-based pigment dispersion, which is a colorant dispersion, is added, and a heat treatment is performed.

[Production Method 10] A hydrophobic monomer and an ionic monomer and, if necessary, an aqueous dispersion of a fixability improving agent are added to an aqueous phase, and the mixture is stirred while stirring at a temperature lower than the radical generation temperature of a water-soluble radical polymerization initiator. Or a first emulsion polymerization step in which a water-soluble radical polymer initiator or an aqueous solution thereof is added at a temperature higher than that, and the polymerization is maintained at a temperature not lower than the radical generation temperature of the radical polymerization initiator.

A step of cooling the polymer particle dispersion having undergone the first emulsion polymerization step and the heat treatment step to a temperature not higher than the radical generation temperature of the water-soluble radical polymerization initiator.

Further, a step of repeating the above steps (n) times a desired number of times, n times.

Next, the n-th emulsion polymerization step is performed.

After the completion of the n-th emulsion polymerization step, a quinacridone-based pigment dispersion or a phthalocyanine-based pigment dispersion, which is a colorant dispersion, is added, and heat treatment is performed.

The polymer particles of the present invention can be produced by using any one of the above production methods.

(Production Method of Toner) In the production method of the toner of the present invention, the pH of the polymer dispersion polymerized according to the above-mentioned production method of polymer particles is adjusted from neutral to alkaline in the case of the polymer particles having an anionic monomer. If a cationic monomer is used in the region, adjust the region from neutral to acidic, then add a flocculant, etc., and heat from the glass transition temperature of the polymer to the glass transition temperature + 50 ° C to grow to the desired particle size. Let it.

It is preferable to add a surfactant in order to further maintain the stability of aggregation, that is, to suppress excessive aggregation that causes unnecessary particle growth. As the surfactant, a nonionic surfactant can be preferably used. Further, for the purpose of controlling the shape of the toner particles, an organic solvent which is infinitely soluble in water can be added.

The order of addition is as follows: (I) a coagulant or an aqueous solution thereof is added to the polymer particle dispersion of the present invention in which part or all of the ionic monomer component is dissociated;
An organic solvent which is infinitely soluble in water, a nonionic surfactant or an aqueous solution thereof is sequentially added, and the mixture is heated to a temperature ranging from the glass transition temperature of the polymer to the glass transition temperature + 50 ° C., and maintained at this temperature for a predetermined time to carry out the reaction. Do.

(II) A nonionic surfactant or an aqueous solution thereof, a coagulant or an aqueous solution thereof, or an organic solvent which is infinitely soluble in water is added to the polymer particle dispersion of the present invention in which part or all of the ionic monomer component is dissociated. The polymer is sequentially added, heated to a temperature range from the glass transition temperature of the polymer to the glass transition temperature + 50 ° C., and maintained at this temperature for a predetermined time to carry out the reaction.

(III) An organic solvent, a nonionic surfactant or an aqueous solution thereof, a coagulant or an aqueous solution thereof which is infinitely soluble in water is dissolved in the polymer particle dispersion of the present invention in which a part or all of the ionic monomer component is dissociated. The polymer is sequentially added, heated to a temperature range from the glass transition temperature of the polymer to the glass transition temperature + 50 ° C., and maintained at this temperature for a predetermined time to carry out the reaction.

(IV) An aggregating agent or an aqueous solution thereof, and a nonionic surfactant dissolved in an organic solvent infinitely soluble in water are sequentially added to the polymer particle dispersion of the present invention in which part or all of the ionic monomer component is dissociated. After the addition, the mixture is heated to a temperature in the range from the glass transition temperature of the polymer to the glass transition temperature + 50 ° C., and maintained at this temperature for a predetermined time to carry out the reaction.

(V) An aqueous solution in which both a nonionic surfactant and a coagulant are dissolved in the polymer particle dispersion of the present invention in which a part or all of the ionic monomer component is dissociated, and an organic solvent which is infinitely soluble in water are sequentially added. After the addition, the mixture is heated to a temperature in the range from the glass transition temperature of the polymer to the glass transition temperature + 50 ° C., and maintained at this temperature for a predetermined time to carry out the reaction.

(VI) An aggregating agent or an aqueous solution of an aggregating agent, an organic solvent which is infinitely soluble in water, a nonionic surfactant or an aqueous solution thereof, in the polymer particle dispersion of the present invention in which part or all of the ionic monomer component is dissociated. Is added at the same time, the mixture is heated to a temperature range from the glass transition temperature of the polymer to the glass transition temperature + 50 ° C., and the temperature is maintained for a predetermined time to carry out the reaction.

Further, after the polymer particle dispersion of the present invention in which a part or all of the ionic monomer component is in a dissociated state is heated to a temperature equal to or higher than the room temperature of the polymer and at a temperature of Tg + 50 ° C. of the polymer particles,
It is also possible to add the additives according to the above-mentioned order of addition, and to further carry out a heating reaction at a predetermined temperature in a range of from Tg of the polymer particles to Tg + 50 ° C. for a predetermined time.

As a method for growing primary particles to a desired toner particle size, it is also possible to use two types of primary particles having different charges and grow them using a heteroaggregation method.

The toner particles thus produced are repeatedly washed and filtered to remove contaminants such as a coagulant, a surfactant and an organic solvent, and then dried, and further added with necessary external additives to form a toner. . Further, in the case of a two-component developer, a carrier is mixed with the above-mentioned toner and used as a developer.

The toner thus produced is 3-1
A toner having an average particle size of 5 μm, a controlled molecular weight and a molecular weight distribution, and a narrow particle size distribution is provided.

[0131]

EXAMPLES The present invention will be described below in detail with reference to examples, but embodiments of the present invention are not limited thereto.

(Synthesis Example 1) 2250 ml of distilled water, 5.20 g of sodium dodecyl sulfate, 249.9 g of styrene were placed in a 5,000 ml four-head separable flask equipped with a stirrer, a nitrogen inlet tube, a cooling tube and a temperature sensor. n-
46.0 g of butyl acrylate, 10.7 methacrylic acid
g was added and the internal temperature was raised to 75 ° C. while stirring under a nitrogen stream.

After raising the temperature, an aqueous solution of a polymerization initiator obtained by dissolving 8.25 g of potassium persulfate in 309 ml of distilled water was added, and the polymerization reaction was carried out for 3 hours while maintaining the internal temperature at 75 ° C.
I. Pigment Red 122 (trade name: KET Red)
309, obtained from Dainippon Ink and Chemicals, Inc.)
A dispersion of 8.40 g in an aqueous solution in which 8.50 g of sodium dodecyl sulfate was dissolved in 200 ml of distilled water was added, and the mixture was stirred at 75 ° C. for 1 hour and then cooled to room temperature. After cooling the magenta pigment composite polymer solution, a portion was taken out and dried, and the molecular weight was measured using gel permeation chromatography (manufactured by Tosoh Corporation), and Mw = 3.5 × 10 in terms of styrene.
⁴ , Mw / Mn = 2.6. Further, the polymerization residue was separated and the production rate was examined. The result was 0.1 wt%. No formation of a viscous oligomer-like substance was observed.

(Synthesis Example 2) C.I. I. Pigment Red 122 is C.I. I. Pigment Blue 15: 3
(Product name: KET Blue 104, obtained from Dainippon Ink and Chemicals, Inc.) The same operation was performed except that the molecular weight was Mw = 3.6 × 10 ⁵ , and Mw / Mn was 2.
5 was obtained.

Further, when the polymerization residue was separated and the production rate was examined, it was 0.2 wt%. No formation of a viscous oligomer-like substance was observed.

(Synthesis Example 3) 450 ml of distilled water, 1.41 g of sodium dodecyl sulfate, 49.98 g of styrene were placed in a 5,000 ml four-head separable flask equipped with a stirrer, a nitrogen inlet tube, a cooling tube and a temperature sensor. 9.19 g of n-butyl acrylate, 2.15 of methacrylic acid
g, tert-dodecyl mercaptan 0.029 g, aqueous polypropylene wax dispersion (Mn = 3.6 × 10
³ , acid value 20 mg KOH / g, solid content 20%) 18.4
g was added and the internal temperature was raised to 75 ° C. while stirring under a nitrogen stream.

After the temperature was raised, an aqueous solution of a polymerization initiator in which 0.78 g of potassium persulfate was dissolved in 40 ml of distilled water was added.
After conducting the polymerization reaction for 3 hours while maintaining the temperature at 5 ° C, C.I. I.
Pigment Red 122 (trade name: KET Red 3)
09, obtained from Dainippon Ink and Chemicals, Inc.) 3.68
g of sodium dodecyl sulfate in 40 ml of distilled water.
Was added to an aqueous solution in which was dissolved, and the mixture was stirred at 75 ° C. for 1 hour and then cooled to room temperature. After cooling the magenta pigment composite polymer solution, 1800 ml of distilled water, 5.65 g of sodium dodecyl sulfate, 199.90 g of styrene, n
36.79 g of butyl acrylate, methacrylic acid 8.
58 g, tert-dodecyl mercaptan 6.07 g,
Aqueous dispersion of polypropylene wax (Mn = 3.6 × 1
0 ³ , acid value 20 mg KOH / g, solid content 20%) 73.
58 g was added and the internal temperature was increased to 75 while stirring under a nitrogen stream.
The temperature was raised to ° C.

After the temperature was raised, an aqueous solution of a polymerization initiator prepared by dissolving 3.12 g of potassium persulfate in 160 ml of distilled water was added. The polymerization reaction was carried out for 3 hours while maintaining the internal temperature at 75 ° C.
I. Pigment Red 122 (trade name: KET Red)
309, obtained from Dainippon Ink and Chemicals, Inc.)
A dispersion obtained by dispersing 4.72 g in an aqueous solution in which 6.8 g of sodium dodecyl sulfate was dissolved in 160 ml of distilled water was added, and the mixture was stirred at 75 ° C. for 1 hour, and then cooled to room temperature. After cooling the magenta pigment composite polymer solution, a part thereof was taken out and dried, and the molecular weight was measured using gel permeation chromatography (manufactured by Tosoh Corporation). Mw = 5.13 × 1 in terms of styrene.
0 ^4, was Mw / Mn = 4.95.

Further, when this molecular weight is separated into two peaks according to the distribution, Mw ₁ = 2.81 × 10 ⁵ and Mw ₂ = 1.57 ×
10 ⁴ , and the area ratio was 13/87. When the polymerization residue was separated and the production rate was examined, it was 0.13 wt%. No formation of a viscous oligomer-like substance was observed.

(Synthesis Example 4) C.I. I. Pigment Red 122 is C.I. I. Pigment Blue 15: 3, except that the polymerization was carried out in the same manner as described above to obtain a cyan pigment composite polymerization solution. The molecular weight is Mw = 5.25 in terms of styrene.
× 10 ⁴ , Mw / Mn = 5.02.

Further, when this molecular weight is separated into two peaks according to the distribution, Mw ₁ = 2.92 × 10 ⁵ and Mw ₂ = 1.58 ×
10 ⁴ , and the area ratio was 14/86. When the polymerization residue was separated and the production rate was examined, it was 0.21% by weight. No formation of a viscous oligomer-like substance was observed.

(Synthesis Example 5) Styrene / n-butyl acrylate / methacrylic acid = 81.5 / 15 / 3.5 (weight ratio, Mw = 2.6 × 10 ⁵ , Mw / Mn = 2.6) and Aqueous polypropylene dispersion (Mn = 3.6 × 10 ³ ,
570 g of a polymer fine particle dispersion (solid content: 10 wt%) containing 6 wt% of the above copolymer as an polypropylene (acid value: 20 mg KOH / g, solid content: 20%) was equipped with a stirrer, nitrogen introduction tube, cooling tube and temperature sensor. And added to the 5,000 ml separable flask
Further, 1800 ml of distilled water and sodium dodecyl sulfate 5.
65 g, styrene 199.90 g, n-butyl acrylate 36.79 g, methacrylic acid 8.58 g, tert
-6.07 g of dodecyl mercaptan, aqueous dispersion of polypropylene wax (Mn = 3.6 × 10 ³ , acid value 20 m)
(gKOH / g, solid content: 20%) 73.58 g was added, and the internal temperature was raised to 75 ° C. while stirring under a nitrogen stream. After raising the temperature, 3.12 g of potassium persulfate was added to 160 m of distilled water.
After the polymerization reaction was carried out for 3 hours while maintaining the internal temperature at 75 ° C., the polymerization reaction solution dissolved in C.I. I. Pigment Blue 15: 3 (Product name: KET Blue 10
4. Obtained from Dainippon Ink and Chemicals, Inc.) 18.4 g
Of sodium dodecyl sulfate in 200 ml of distilled water
Was added to an aqueous solution in which was dissolved, and the mixture was stirred at 75 ° C. for 1 hour and then cooled to room temperature. After cooling the cyan pigment composite polymerization solution, a part thereof is taken out and dried, and the molecular weight is measured using gel permeation chromatography (manufactured by Tosoh Corporation). Mw = 5.12 × 10 ⁴ , Mw / M in terms of styrene
n = 4.89. Further, when this molecular weight is separated into two peaks according to the distribution, Mw ₁ = 2.73 × 10 ⁵ , Mw ₂ =
1.38 × 10 ⁴ and the area ratio was 13/87. The polymerization residue was separated and the production rate was examined.
t%. No formation of a viscous oligomer-like substance was observed.

(Comparative Synthesis Example 1) A stirring device, a nitrogen introducing tube,
5,000 ml 4 with cooling tube and temperature sensor
C. in the separable flask on the head. I. Pigment Red 1
22 (trade name: KETRED 309, obtained from Dainippon Ink and Chemicals, Inc.) was added a dispersion of 3.68 g of an aqueous solution of 1.7 g of sodium dodecyl sulfate dissolved in 40 ml of distilled water, and 450 ml of distilled water was further added. , Styrene 49.98 g, n-butyl acrylate 9.19 g,
2.15 g of methacrylic acid, 0.029 g of tert-dodecyl mercaptan, and 18.4 g of an aqueous dispersion of polypropylene wax (Mn = 3.6 × 10 ³ , acid value 20 mgKOH / g, solid content 20%) were added, and the mixture was stirred under a nitrogen stream. , The internal temperature was raised to 75 ° C.

After the temperature was raised, an aqueous solution of a polymerization initiator in which 0.78 g of potassium persulfate was dissolved in 40 ml of distilled water was added.
After the polymerization reaction was performed for 3 hours while maintaining the temperature at 5 ° C., the mixture was cooled to room temperature. Further, the above C.I. I. 181.52 g of Pigmentlet 122 dispersion, 1800 ml of distilled water, styrene 1
99.90 g, n-butyl acrylate 36.79 g,
8.58 g of methacrylic acid, 6.67 g of tert-dodecyl mercaptan, 73.58 g of an aqueous dispersion of polypropylene wax (Mn = 3.6 × 10 ³ , acid value 20 mgKOH / g, solid content 20%) were added, and the mixture was stirred under a nitrogen stream. , The internal temperature was raised to 75 ° C.

After the temperature was raised, an aqueous solution of a polymerization initiator in which 3.12 g of potassium persulfate was dissolved in 160 ml of distilled water was added. The polymerization reaction was carried out for 3 hours while maintaining the internal temperature at 75 ° C., followed by cooling to room temperature. After cooling the magenta pigment composite polymer solution, a part thereof is taken out and dried, and the molecular weight is measured by gel permeation chromatography (Tosoh). Mw = 5.48 × 10 ^{4 in} terms of styrene, Mw / Mn = 5. 79.

Further, when this molecular weight is separated into two peaks according to the distribution, Mw ₁ = 2.61 × 10 ⁵ and Mw ₂ = 1.47 ×
10 ⁴ , and the area ratio was 11/89. Further, the polymerization residue of this polymerization solution was separated and the formation rate of the residue was determined. As a result, it was 12 wt%. No formation of a viscous oligomer-like substance was observed.

(Comparative Synthesis Example 2) C.I. I.
Pigment Red 122 is C.I. I. Pigment Blue 1
Polymerization was carried out with the same formulation except that the ratio was changed to 5: 3. After cooling the pigment composite polymerization solution, a part thereof is taken out and dried, and the molecular weight is measured using gel permeation chromatography (manufactured by Tosoh Corporation). Mw = 3.43 × 10 ⁴ , M
w / Mn = 3.2. Furthermore, when this molecular weight is separated into two peaks according to the distribution, Mw ₁ = 2.28 × 10 ⁵ , Mw
₂ = 1.65 × 10 ⁴ and the area ratio was 8/92.

Further, the polymerization residue of this polymerization solution was separated and the formation rate of the residue was examined. As a result, it was 0.1% by weight. Also, generation of 6 wt% of the viscous oligomer-like substance was recognized.

Those prepared according to the above Synthesis Examples 1 to 5 were designated as pigment composite polymer liquids 1 to 5 of the present invention, and those prepared according to Comparative Synthesis Examples 1 and 2 were referred to as comparative pigment composite polymer liquids 1 and 2.

(Preparation of Toner) A toner was prepared by using the above-described pigment composite polymer solutions 1 to 5 of the present invention and comparative pigment composite polymer solutions 1 and 2. The fabrication method is described below.

To 500 ml of the pigment composite polymerization solution was added 5N-sodium hydroxide to adjust the pH to 9.5. This polymerization solution was mixed with a stirrer, a cooling pipe, and a temperature sensor.
The mixture was placed in a 00 ml separable flask and stirred. Further, 39.08 g of sodium chloride was added to 136.6 m of distilled water.
aqueous solution, isopropyl alcohol 87.8
2. octylphenoxypolyethoxyethanol
After sequentially adding an aqueous solution in which 34 g was dissolved in 30 ml of distilled water, the internal temperature was raised to 85 ° C., and the mixture was heated and stirred as it was for 6 hours. After the content was cooled to room temperature, filtration and washing with water were repeated for purification, followed by drying.

(Evaluation of Performance) Toners prepared from the pigment composite polymerization liquids 1 to 5 of the present invention and the comparative pigment composite polymerization liquids 1 and 2 which have been subjected to the above-mentioned treatments were used as toners 1 to 5 and comparative toners 1 and 2 of the present invention, respectively. And

The toner that had been dried was sieved using a 330-mesh sieve (mesh size: 45 μm). At this time, the residue generation rate was calculated from the sum of the residue remaining on the sieve and the residue remaining in the reactor and the charged amount.

After the toner under the sieve was dispersed in an aqueous system, the average particle size (d ₅₀ ) and the particle size distribution (CV = σ / d ₅₀ ) were measured by using a laser diffraction particle size analyzer SALD-1100. . Also, the state of the toner surface was observed using a scanning electron microscope, and from the results, ◎,
△, で, × were evaluated in four stages.

Further, the toner under the sieve was mixed with a carrier coated with styrene / methyl methacrylate = 1/1 and having an average particle diameter of 40 μm so that the toner concentration became 4%, and the mixture was shaken. One minute after the shake and 60 minutes after the shake The subsequent charge amount was measured using a blow-off method.

The results are shown in Table 1 below.

[0157]

[Table 1]

From the above results, the toner produced by the method of the present invention has a narrow particle size distribution, has little residue, and has good toner surface smoothness. Further, the charge rises quickly and the charge amount is stabilized in a short time. On the other hand, the comparative toner has a poor particle size distribution and a large residue generation rate. In addition, the rising of charging is poor and unstable. Further, in the polymerization, the generation rate of aggregation residue is high, and generation of oligomer is also recognized.

[0159]

According to the present invention, firstly, it is possible to improve the dispersion stability of composite polymer particles such as a colorant when a quinacridone pigment is used as a colorant, and secondly, as a colorant. Control of molecular weight can be improved when a phthalocyanine pigment is used. By solving these problems, a non-spherical toner having a narrow particle size distribution can be provided.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI G03G 9/08 381 (72) Inventor Tomoe Kikuchi 1st Sakuracho, Hino-shi, Tokyo In-house Konica Corporation (72) Inventor Yoshiki Nishimori Tokyo 1 Konica Stock Company, Sakuracho, Hino-shi

Claims (4)

[Claims] 1. A polymer particle comprising: a first polymerization step of emulsion-polymerizing a vinyl monomer; a step of adding a quinacridone pigment after the emulsion polymerization step; and a step of performing a heat treatment after the addition of the pigment. Manufacturing method. 2. A polymer particle comprising a first polymerization step of emulsion-polymerizing a vinyl monomer, a step of adding a phthalocyanine pigment after the emulsion polymerization step, and a step of performing a heat treatment after the addition of the pigment. Manufacturing method. 3. The method for producing polymer particles according to claim 1, further comprising adding a vinyl monomer to carry out emulsion polymerization, followed by adding a quinacridone pigment.
And a step of heat-treating after adding the quinacridone-based pigment. 4. A toner for developing an electrostatic charge image, wherein a plurality of polymer particles produced by the method for producing polymer particles according to claim 1, 2 or 3 are associated with each other.