JPH03243954A - Production of toner for developing electrostatic charge image - Google Patents

Abstract

PURPOSE:To produce toner particles having a sharp particle size distribution as well as satisfactory electrostatic chargeability by dispersing a colorant in a polymerizable monomer in the presence of a copolymer contg. specified sulfonic acid groups and carrying out suspension polymn. in a suspending medium. CONSTITUTION:A colorant is dispersed in a polymerizable monomer in the presence of a copolymer contg. sulfonic acid groups represented by formula I (where each of R1-R5 is H or methyl and the weight ratio of m:n is 98:2-80:20) and suspension polymn. is carried out in a suspending medium contg. an inorg. dispersant. A uniform toner having superior electrostatic chargeability, a sharp particle size distribution and superior resistance to moisture absorption can easily be produced.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention is a method for developing an electrostatic charge image formed on the surface of a photoconductive photoreceptor in electrophotography, electrostatic recording, electrostatic printing, etc. We will discuss the manufacturing method of toner used for this purpose.

[Conventional technology]

Conventionally, the toner manufacturing method used to develop electrostatic images involves premixing a binder resin, a colorant, a charge control agent, and in some cases magnetic powder and other additives, followed by melt-kneading. , pulverization, and classification to obtain a toner having a desired particle size range.

However, in this method, premixing, melt kneading,
Since many steps such as pulverization and classification and equipment for the same are required, there are problems such as an increase in toner production cost and low yield.
Components such as magnetic powder and other additives (hereinafter referred to as "toner characteristic imparting agents"), which are added in some cases, do not show good compatibility with the binder resin, so they are not sufficiently mixed in the melt mixing process. There are problems in that it is difficult to mix uniformly and it adversely affects the charging characteristics of the toner. Furthermore, since the obtained toner particles are produced by a pulverization method, their shape is amorphous, reducing the fluidity of the toner, and they are easily over-pulverized by stirring during charging in a copying machine, resulting in fine powder. However, there is also the problem that a fogging phenomenon occurs in the copied image.

As a method to improve the problems of the above conventional methods, a toner characteristic imparting agent is dispersed and contained in the polymerizable monomer constituting the binder resin, and this is carried out using suspension polymerization method or emulsion polymerization method. A method of directly producing toner for developing electrostatic images by polymerization has been proposed, for example, in JP-A-64-5006.
Publication No. 0 describes a method for uniformly dispersing a charge control agent in toner particles, in which the charge control agent is finely pulverized by wet grinding, and then mixed with a polymerizable monomer that is a constituent component of a binder resin. A method of directly manufacturing toner particles by dispersing the toner particles in the liquid and then carrying out suspension polymerization is disclosed, and also disclosed in Japanese Patent Publication No. 63-4
No. 5101 discloses a toner obtained by suspension polymerizing a polymerizable monomer in which a colorant is dispersed in an aqueous dispersion medium containing a dispersant made of orthophosphate and an anionic surfactant. A method of treating particles with dilute acid to remove dispersants that reduce the moisture absorption properties of the toner particles is disclosed.

[Problem that the invention seeks to solve]

The above-mentioned Japanese Patent Application Laid-Open No. 64-50080 and Japanese Patent Publication No. 63-
All of the methods disclosed in Publication No. 45101 involve directly producing toner for developing electrostatic images by suspension polymerization, so the resulting toner particles are spherical and have excellent fluidity, and the production cost is low. Although there are advantages, there are still some problems that require improvement.

For example, in the method disclosed in JP-A-64-50060, a fine azo dye is used as a charge control agent, so it is possible to disperse the charge control agent more uniformly in toner particles. However, since the charge control agent and the polymerizable monomer constituting the binder resin do not necessarily exhibit good compatibility, agglomeration may occur during suspension polymerization, resulting in the formation of polymer particles. It is difficult to uniformly incorporate the charge control agent into the toner particles, and as a result, there is a problem that the content, distribution state, etc. of the charge control agent between the toner particles becomes non-uniform, resulting in variations in the charging characteristics of the toner.

Furthermore, the method disclosed in Japanese Patent Publication No. 63-45101 not only requires a post-treatment step to remove the dispersant, but also allows the removal of orthophosphate through this post-treatment step; The surfactant is adsorbed on the surface of the toner particles, and it is difficult to completely remove it during the cleaning process, which reduces the moisture absorption properties of the toner. Fine particles having a diameter other than the desired particle size are likely to be generated, and these fine particles may have an adverse effect on toner properties, resulting in problems such as the necessity of a classification step in some cases.

Furthermore, in ordinary suspension polymerization methods other than those mentioned above,
Since a water-soluble polymer compound is generally used as a suspension stabilizer, in this case as well, the suspension stabilizer may remain in the polymer particles or on the particle surface and affect the moisture absorption resistance of the toner. It has also been pointed out that the polymer particles have an adverse effect, and that many fine particles are generated, making it difficult to obtain polymer particles with uniform particle diameters.

As a result of studies conducted to solve various problems in the conventional suspension polymerization method, the present invention has been developed to impart good charging characteristics to the resulting toner by using a copolymer with a specific structure. The present invention was completed based on the discovery that toner particles with a sharp particle size distribution can be easily produced using a stable suspension polymerization system.

[Means to solve the problem]

The method for producing the electrostatic image developing toner provided by the present invention is carried out using the following formula [wherein R1-R5 are hydrogen atoms or methyl groups,
m: The copolymerization ratio (wt%) of n is 98: 2 to 80:
20] In the presence of a copolymer containing a sulfonic acid group,
It is characterized in that a coloring agent is dispersed in a polymerizable monomer, and then suspension polymerization is carried out in a suspension medium containing a noodle-based dispersant.

Hereinafter, the method for producing the electrostatic image developing toner of the present invention will be explained in more detail.

8 Δ: The polymerizable monomer used in the method of the present invention is a component that constitutes the binder resin of the toner by polymerization, and specific examples thereof include styrene and 01m.

Styrenes and their derivatives such as p-styrene; α-methylene aliphatic monocarboxylic acid esters such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, and 2-ethylhexyl methacrylate; methyl acrylate, ethyl acrylate , butyl acrylate, acrylic esters such as 2-ethyl acrylate, etc., and these polymerizable monomers can be used alone or in combination of two or more types.

In addition, these polymerizable monomers contain a small proportion of other monomer units called crosslinking agents (preferably 3% by weight based on the polymerizable monomers).
(below) can also be mixed and used. Other monomer units that can be used include compounds having two or more copolymerizable unsaturated groups in one molecule, such as ethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate , butanediol di(
alkylene or di- or polyalkylene glycol di(meth)acrylates such as meth)acrylates;
Examples include poly(meth)acrylates of polyhydric alcohols such as trimethylolpropane tri(meth)acrylate; divinylbenzene, etc. By using these monomers, three-dimensional crosslinking can be achieved partially in the binder resin. By forming the structure, it is possible to improve toner properties such as high temperature offset properties and heat melting properties of the resulting toner.

B sulfone Δ = The sulfonic acid group-containing copolymer (hereinafter referred to as "copolymer (B)") that can be used in the method of the present invention is a polymer represented by the following formula, and the copolymer ( Since B) is extremely well compatible with the binder resin composed of the above polymerizable monomer, it is possible to impart good charging characteristics (negative charging characteristics) to the resulting toner. Polymer (B)
It also contributes to stabilizing the polymerization system during suspension polymerization, and has the effect of easily producing a toner with a sharp particle size distribution with almost no aggregates, and furthermore,
The copolymer also functions as a dispersant when uniformly dispersing the coloring agent and magnetic powder or other additives added as needed in the polymerizable monomer, so it can overcome the above-mentioned conventional concerns. It is not necessary to use water-soluble polymers or surfactants as in the turbidity polymerization method, and a toner with excellent moisture absorption resistance can be easily produced.

The copolymer (B) represented by the above formula includes a unit represented by the following formula (1) I [wherein R1 is a hydrogen atom or a methyl group] and a unit represented by the following formula (2) % formula % (2) [In the formula, R2-R5 are hydrogen atoms or methyl groups] It is a copolymer of units represented by the formula (1), and specific examples of the unit of formula (1) include styrene and/or α-methylstyrene. As a specific example of the sulfonic acid group-containing monomer represented by the unit of the above formula (2), tert-butyl (
meth)acrylamide sulfonic acid, N-methyl-ter
t-butyl (meth)acrylamide sulfonic acid and the like.

In the above copolymer (B), the unit represented by the above formula (1) is suitable as a component for making the copolymer (B) well compatible with the toner particles, and the copolymerization ratio of the unit is (m
) is more than 98% by weight, good compatibility is obtained, but in order to obtain the necessary charging characteristics as toner particles, the amount mixed with the polymerizable monomer (binder resin) must be increased. However, if the copolymerization ratio is 8.
If it is less than 0% by weight, the desired amount of charge cannot be obtained,
This is not preferable because the moisture resistance of the toner particles themselves also deteriorates.

Therefore, in the present invention, the preferred m: n copolymerization ratio (
weight%) ranges from 95:δ to B7:13.

In addition, in the above copolymer (B), a part of the units of the above formula (1), for example, (meth) within a range not exceeding 20% by weight.
Using acrylic acid alkyl esters as a copolymerization component is effective in improving compatibility with polymerizable monomers, and does not contradict the spirit of the present invention, but it may reduce transparency and charging characteristics. Since it tends to decrease, it is preferably within 10% by weight.

The polymerization method for producing the copolymer (B) may be any known solution polymerization method, suspension polymerization method, bulk polymerization method, etc., and is not particularly limited. A solution polymerization method is adopted in which the unit of the above formula (1) and the sulfonic acid group-containing monomer of the above formula (2) are copolymerized in an organic solvent containing a lower alcohol such as methanol, isopropanol, or butanol. Particularly preferred. In addition, the polymerization initiators that can be used during polymerization include peroxide-based initiators and azo-based initiators, but their decomposition products have carboxyl groups, which adds to the negative charging characteristics of the resulting toner particles. It is preferable to use a peroxide-based rWJ initiator that provides the following effects, and it is preferable to use the initiator in an amount of 0.5 to 5.0% by weight based on the polymerizable monomer.

The weight average molecule II (hereinafter referred to as r MW J) of the copolymer (B) used in the present invention is 2,0
00 to 15,000, and Mw is preferably 2.00 to 15.000.
If the Mw is smaller than 15°000, the environmental resistance will be poor, and the chargeability will be greatly reduced in a high humidity environment, and an offset phenomenon will easily occur during fixing.If the Mw is larger than 15°000, it will not be uniformly distributed in the polymerizable monomer. Because proper dispersion cannot be obtained, contamination of the photoreceptor becomes apparent.

In the present invention, the Mw of the particularly preferred copolymer (B) is 3
,000 to 8,000.

In the present invention, the copolymer (B) contains 100% of the polymerizable monomer
It is preferable to use the mixture in the range of 0.1 to 10 parts by weight. If the mixing amount is less than 0.1 part by weight, the required amount of charge will not be obtained, and at the same time, there will be problems between toner particles. Discrepancies occur in the amount of charge, which tends to make the fixed image unclear, and also causes drawbacks such as severe staining of the photoreceptor.On the other hand, if the amount of the mixture exceeds 10 parts by weight, the environmental resistance decreases and the compatibility deteriorates. Defects such as deterioration, occurrence of offset phenomenon, and staining of the photoreceptor are likely to occur.

αυ-IL1: The coloring agent used in the method of the present invention is not particularly limited and can be selected from a wide range, for example,
Carbon black, surface-treated grafted carbon black, calcoyl alcohol (C, I, Na a
zoee Blue 3), DuPont Oil Red (
C, I, NQ 26105), malachite green oxalay) (C, 1, positive 42000), quinoline yellow (C, I, Na 47005), rose bengal (C8■, positive 45435), nigrosine dye (C, I
, 504158), phthalocyanine blue (C, I
, Na 74160), ultramarine blue (C,
I, N1177103), lamp black (C, I
, N1177266) and mixtures thereof. These colorants are blended in a proportion necessary to form a visible image of sufficient density, and are usually 1 to 20 parts by weight, preferably 2 to 20 parts by weight, per 100 parts by weight of the polymerizable monomer.
It is used within the range of 7 parts by weight.

Kana JJL Gold: The method of the present invention uses the above-mentioned polymerizable monomer, copolymer (B)
, a colorant, and a suitable polymerization initiator in a high-speed stirring device (1
The mixed dispersion thus obtained was suspended under stirring in an aqueous dispersion medium containing a poorly water-soluble inorganic fine powder as a dispersant, using a conventional method. After the polymerization reaction is completed, appropriate post-treatment is performed, such as adding Brønsted acid to the system containing the produced polymer particles to remove the poorly water-soluble inorganic dispersant. After that, the polymer particles are collected by an appropriate method such as filtration, decantation, or centrifugation.
By drying, it can be made into a toner.

Polymerization initiators that can be used in the suspension polymerization include 2,2'-azobis-(2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, l,1'-azobis- -(cyclohexane-1-carbonitrile), 2,2'-azobis-4-methoxy-2,
Examples include azo polymerization initiators such as 4-dimethylvaleronitrile; peroxide polymerization initiators such as benzoyl peroxide, methyl ethyl ketone peroxide, and lauroyl peroxide; each of these polymerization initiators can be used alone, but In order to impart desired properties to the resulting toner, two or more types of polymerization initiators may be used in combination.

In addition, examples of poorly water-soluble and organic powders that can be used as a dispersant during suspension polymerization include tertiary calcium phosphate, magnesium phosphate, calcium sulfate, magnesium carbonate, calcium carbonate, and hydroxyapatite. I can do it. It is preferable to use these = S* powders with a primary particle size of 1 μm or less. After solubilizing by treating with nitric acid, the pH of the aqueous dispersion is adjusted under high-speed stirring, and the aqueous dispersion is reprecipitated as fine particles.The aqueous dispersion containing such fine particles can be suspended as is. It can be used as a dispersion medium during polymerization.

In addition, in the present invention, the above-mentioned polymerizable monomers,
In addition to the copolymer (B) and the colorant, various additives commonly used in the electrophotographic industry can be added as appropriate for the purpose of improving the properties of the resulting toner. For example, for the purpose of further improving anti-offset properties, substances with mold release properties may be used, such as higher fatty acids or metal salts of higher fatty acids, natural or synthetic waxes, higher fatty acid esters, or partially saponified products thereof. , alkylene bis fatty acid amides, fluororesins, silicone resins, etc. may also be blended. The amount of the polymerizable monomer is 10
Generally, the amount can be within the range of 1 to 10 parts by weight per 0 parts by weight, and in the case of a -component toner, a magnetic powder may be used in addition to each component including the above polymerizable monomer. I can do it. Examples of magnetic powders that can be used include ferrite, magnetite, iron, cobalt, nickel, and other ferromagnetic metals or alloys, or compounds containing these elements, or materials that do not contain ferromagnetic elements but undergo appropriate heat treatment. Examples of alloys that exhibit ferromagnetic properties when applied are alloys called Heusler alloys containing manganese and copper, such as manganese-copper-aluminum, manganese-copper-tin, or chromium dioxide. can. These magnetic materials have an average particle diameter of 0.1~
It is uniformly dispersed in the toner particles in the form of a fine powder within the range of 1 μm, and the amount thereof is generally 20 to 70 parts by weight, preferably 40 to 70 parts by weight, per 100 parts by weight of the polymerizable monomer.

In the toner obtained as described above, the dispersant in the suspending medium is completely removed from the toner particle surface, and therefore not only the surface of the toner particle but also the inside of the particle becomes hydrophilic. Since no components are present, a toner with excellent electrophotographic properties can be obtained.

〔Example〕

Hereinafter, the present invention will be explained in more detail based on Examples. In addition, the copolymerization ratio or mixing ratio of each component in the examples is expressed in parts by weight unless otherwise specified.

Synthesis example of heavy ΔB-1 2 with a stirrer, condenser, thermometer, and nitrogen inlet tube
In a reaction vessel, add 300 g of methanol, 100 g of toluene,
Styrene 570 g, tert-dimethylacrylamide sulfonic acid 30 g, lauroyl peroxide 12 g
The contents were solution-polymerized at 65°C for 10 hours under stirring and nitrogen introduction, and the contents were taken out from the flask, dried under reduced pressure, and ground in a jet mill to obtain a polymer (B) with Mw = 3,000.
) was manufactured.

Synthesis Examples 2 to 5 Various copolymers (B) were produced in the same manner as in Synthesis Example 1 above, except that styrene and tert-butylacrylamide sulfonic acid were used in the compositions shown in Table 1 below.

The Mw of the obtained copolymer (B) is also shown in Table-1.

Table 1 (Thursday) St in the column for the composition of copolymer (B): Styrene T-BAS: tert-butylacrylamide sulfonic acid initiator: lauroyl peroxide Example-1 Each component was added to an attritor according to the following recipe. A polymerizable monomer mixture was prepared.

Styrene 80 Butyl acrylate 202.2'-7 Zobisu(2
,4-dimethylvaleronitrile)
3 Copolymer (B) of Synthesis Example-1 0.5 Paraffin 155"F (Nippon Seirosha!) 4 Crosslinking agent (diethylene glycol dimethacrylate) 1 Carbon black (manufactured by Mitsubishi Kasei Corporation, MA-7) 5 Separately, 20 g of tertiary calcium phosphate was added to 1. kg of ion-exchanged water, and the mixture was stirred for 10 minutes at 110,000 rpm using a homomixer to prepare a dispersion medium.

The polymerizable monomer mixture of the above formulation is added to the above dispersion medium, and suspension polymerization is carried out at 60°C for 5 hours under stirring at 3500 rpm using a disperser type disperser to complete polymerization of the monomer mixture, After the polymerization reaction was completed, the reaction product was cooled and subjected to the following steps: dehydration, washing with nitric acid, washing with water, dehydration and drying to produce a toner.

The toner obtained as described above was evaluated by the following method, and the results are shown in Table 2 below.

LJi-1-U (1) Suspension polymerizability: In order to evaluate stability during polymerization, foaming during polymerization, agglomeration state of particles, dispersion state of carbon black in toner particles, washing, dehydration, and drying steps were performed. Comprehensive evaluation of ease of processing, etc.

(2) Particle size distribution: Measure the average particle diameter and degree of dispersion of toner particles using a Coulter counter (manufactured by Coulter Inc.).The degree of dispersion is calculated by the following formula.

(3) Charging stability: Toner particles and spherical iron oxide were mixed at a weight ratio of 3:97, and the mixture was heated for a certain period of time (10,6
After frictional charging (0,180 minutes), the amount of charge (μc/g) for each frictional charging time was measured using a blow-off powder charge amount measuring device manufactured by Toshiba Chemical Corporation, and the charging stability was determined by the variation in the amount of charge. Evaluate.

(4) High humidity characteristics (residual charge rate): Toner particles after 180 minutes of triboelectrification in the chargeability test in (3) above (the charge amount at this time is CI) were
After leaving it in a high humidity atmosphere of ℃ × 85% RH for 14 hours, the amount of charge (μc/g) was measured in the same manner as above (the amount of charge at this time was designated as CI), and the residual rate of charge amount was determined by the following formula. calculate.

Example 2 A polymerizable monomer mixture was prepared in the same manner as in Example 1 above according to the following recipe.

Styrene 80 Acrylic acid-
2-ethylhexyl 202.2'-azobis-(
2,4-dimethylvaleronitrile)
22.2'-Azobisisobutyronitrile 1 Copolymer (B) of Synthesis Example-2 2 Low molecular weight polypropylene (manufactured by Sanyo Chemical Industries, Ltd., Viscol 660P) 3 Kayasetsu Red 130 (manufactured by Nippon Kayaku Co., Ltd.) 2 The above The polymerizable monomer mixture was added to a dispersion medium prepared in the same manner as in Example 1, and suspension polymerization was carried out at 70°C for 5 hours with stirring at 3000 rpm, and the resulting reaction product was subjected to the same process. A toner was produced by the treatment and evaluated in the same manner, and the results are shown in Table 2 below.

Example 3 A polymerizable monomer mixture was prepared in the same manner as in Example 1 above according to the following recipe.

Styrene 80 Butyl acrylate 202.2'-azobis-(2
,4-dimethylvaleronitrile)
22. 2'-Azobisisobutyronitrile 1 Copolymer (B) of Synthesis Example-3 3 Low molecular weight polypropylene (manufactured by Sanyo Chemical Industries, Ltd., Viscoll 660P) 31. 3-Butylene gelicoldimetachloride crosslinking agent) 1
Carbon Black (manufactured by Mitsubishi Kasei Corporation, #40) 5 A toner was produced from the above polymerizable monomer mixture in the same manner as in Example 1, and evaluated in the same manner. The evaluation results are shown in Table 2 below.

Examples-4 and 5 In the formulation of the polymerizable monomer mixture of Example-1, copolymer (B) of Synthesis Example-4 and Synthesis Example were substituted for copolymer (B) of Synthesis Example-1. A toner was produced by suspension polymerization in the same manner as in Example-1, except that the copolymer (B) of No.-5 was used, and the obtained toner was evaluated in the same manner, and the evaluation results are shown in Table-2 below. It was shown to.

In addition, in this example, the copolymer (B
) was used as the copolymer of Example-4 and Synthesis Example-5 (
Example 5 was prepared using B).

Example-6 A toner was produced by suspension polymerization in the same manner except that in the formulation of the polymerizable monomer mixture of Example-1, the blending amount of the copolymer (B) of Synthesis Example-1 was changed to 13 parts. did. The obtained toner was evaluated in the same manner, and the results are shown in Table 2 below.

In the suspension polymerization of this example, a small amount of emulsion was produced as a by-product, and a very small amount of fine particles not containing carbon black were also produced, but the charging characteristics of the toner particles were relatively good.

Comparative Example 1 A polymerizable monomer mixture was prepared by mixing each component using an attritor according to the following recipe.

Styrene 8゜Butyl acrylate 2゜2.2'-azobis-(2
,4-dimethylvaleronitrile)
3 positron (Orient Chemical Needle Iri 3 Paraffin 155" F (manufactured by Nippon Gosei),...

Diethylene glycol dimethacrylate (crosslinking agent) 1 Carbon black (manufactured by Mitsubishi Kasei Corporation, MA-7) 5 Separately,
20g of tertiary calcium phosphate in 1kg of ion exchange water
and sodium dodecylbenzenesulfonate 0.5g
and stirred for 10 minutes using a homomixer at 10.00 rpm to prepare a dispersion medium.The polymerizable monomer mixture of the above formulation was added to this dispersion medium, and dispersion was carried out in the same manner as in Example-1. A toner was produced by carrying out suspension polymerization using a machine and evaluated. The evaluation results are shown in Table 2 below.

Comparative Example-2 A polymerizable monomer mixture was prepared by mixing each component using an attritor according to the following recipe.

Styrene 80 2-ethylhexyl acrylate 202.2'-azobis-
(2,4-dimethylvaleronitrile)
22.2'-Azobisisobutyronitrile 1
Copolymer (B) of Synthesis Example 2 2 Low molecular weight polypropylene (manufactured by Sanyo Chemical Industries, Ltd., Viscol 660P) 3 Kaya Set Red 130 (Nippon Kayaku Co., Ltd.) 3 Separately, add polyvinyl alcohol (Nippon Gosei) to 1 kg of ion exchange water. Dissolve 3 g of Gohsenol GH-23), add the polymerizable monomer mixture of the above formulation, and 3.
A toner was produced by carrying out suspension polymerization at 70'C for 5 hours under stirring at 500 rpm, and evaluated in the same manner as in Example-1. The evaluation results are shown in Table 2 below.

(The following is a blank space) [Effects of the Invention] The main feature of the method for producing an electrostatic image developing toner provided by the present invention is the use of the above-mentioned specific sulfonic acid group-containing copolymer. Due to its unique action, it is possible to easily produce a toner with excellent charging characteristics, no variation, and a sharp particle size distribution.Also, since it is necessary to use a surfactant, it has excellent moisture absorption resistance. This is an extremely excellent method for producing toner, such as the ability to obtain toner.

Claims (3)

[Claims] (1) The following formula ▲ There are mathematical formulas, chemical formulas, tables, etc.
0] In the presence of a copolymer containing a sulfonic acid group,
1. A method for producing a toner for developing electrostatic images, which comprises dispersing a colorant in a polymerizable monomer and then carrying out suspension polymerization in a suspension medium containing an inorganic dispersant. (2) The method for producing a toner for developing an electrostatic image according to claim 1, wherein the sulfonic acid group-containing copolymer has a weight average molecular weight in the range of 2,000 to 15,000. (3) The sulfonic acid group-containing copolymer is used in an amount ranging from 0.1 to 10 parts by weight per 100 parts by weight of the polymerizable monomer. Toner manufacturing method.