JP2003330225A - Method for manufacturing nonmagnetic toner - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To manufacture a toner which is excellent in electrification stability and durable for long-term use in a high temperature and high humidity environment. <P>SOLUTION: The toner is obtained by dispersing core particles containing a binder resin and a colorant in an aqueous medium, adding a sulfur-containing polymer and a polymerizable monomer to the medium, and carrying out seed polymerization to form obtain toner particles having a shell portion coating the surface of the core particles. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a non-magnetic toner for visualizing an electrostatic latent image in an image forming method such as an electrophotographic method, an electrostatic recording method, a magnetic recording method and a toner jet method. Regarding

[0002]

2. Description of the Related Art Conventionally, a number of methods are known as electrophotography, but generally, a photoconductive substance is used and an electric latent image is formed on an electrostatic charge image carrier (photoreceptor) by various means. An image is formed, then the latent image is developed with toner to form a visible image, and the toner image is transferred onto a transfer material such as paper as necessary, and then the toner image is transferred onto the transfer material by heat or pressure. It is fixed and a copy is obtained.

As a method of visualizing an electric latent image with toner, a cascade developing method, a pressure developing method, a magnetic brush developing method using a two-component developer composed of a carrier and a toner, and a toner carrier carrying a latent image carrier are used. The non-contact one-component developing method in which the toner flies from the toner carrier to the latent image carrier in a non-contact manner and the contact one-component developing method in which the toner carrier is brought into pressure contact with the latent image carrier to transfer the toner by the electric field are used. ing.

In addition, LED and LBP printers have recently become the mainstream of the market as a printer device, and the direction of technology is higher resolution, that is, 400, 600, 800, 1200 dpi instead of 240, 300 dpi.
Has become. At the same time, there is a strong demand for improvements in printing speed. Therefore, the developing system is also required to have higher definition. Further, the copiers are also becoming more sophisticated, and as a result, they are moving toward digitalization. In this direction, since the method of forming an electrostatic latent image with a laser is the main method, it is advancing toward the direction of high resolution, and here again, a high-resolution and high-definition developing method is required as in a printer. There is. As one means for satisfying this demand, the particle size of toner is being reduced, and it is disclosed in JP-A-1-1.
No. 12253, No. 1-191156, No. 2-2141
No. 56, No. 2-284158, No. 3-181952
No. 4,16,2048 and the like propose a toner having a specific particle size distribution and a small particle size.

On the other hand, the toner image formed on the photoconductor in the developing process is transferred to the transfer material in the transfer process, but the transfer residual toner in the image area and the fog toner in the non-image area remaining on the photoconductor are cleaned. It is cleaned in the process and stored in the waste toner container. Regarding this cleaning process, conventional blade cleaning, fur brush cleaning,
Roller cleaning was used. From the viewpoint of the apparatus, the apparatus inevitably becomes large in size because it is equipped with such a cleaning apparatus, which has been a bottleneck for making the apparatus compact. Further, from the viewpoint of ecology, a toner having excellent fixability is desired from the viewpoint of energy saving, and a system with less waste toner is desired from the viewpoint of effective use of the toner, so that transfer efficiency is high and fog is low. Toner is sought.

The developer used in such an image forming process is composed of a toner containing a binder resin and a colorant as main components, and in addition, other characteristics required as a toner such as a charge control agent and a release agent. It contains an additive to bring out.

Here, as described above, there is a demand for a higher resolution and higher definition developing system as a direction of recent technology, and in order to meet such demand, there is a direction of reducing the toner particle size. As described above, as the toner particle size becomes smaller, stable triboelectric charging of the toner powder becomes an important technology. That is, unless the individual fine toner particles have a uniform charge amount, the deterioration of image stability is more likely to occur. This is because the particle size of the toner is simply reduced, the charge amount of each toner is apt to become insufficient, and the adhesion force of the toner particles to the photoconductor is larger than the Coulomb force applied to the toner particles in the transfer process ( (Image force, van der Waals force, etc.) increase, and as a result, the amount of transfer residual toner increases, and in addition, the decrease in toner diameter leads to deterioration in fluidity, resulting in non-uniform charge amounts of individual toner particles. This is because there are many toner particles that are easily fogged and have poor transferability. From such a viewpoint, there is a strong demand for establishment of a technique for supplying a toner having a high charge amount and uniform.

Attempts have been made to solve the above problems by improving the manufacturing method.

In the conventional toner, a binder resin, a colorant, and the like are melt-mixed, uniformly dispersed, and then pulverized by a fine pulverizer,
Although a toner having a desired particle size has been classified (classified by a classifier) to be manufactured (pulverization method), there is a limitation in the selection range of materials for making the toner into a fine particle size. For example, the resin colorant dispersion must be sufficiently brittle to be finely pulverized in an economically available manufacturing apparatus. In order to make the resin colorant dispersion brittle from this requirement, when the resin colorant dispersion is actually pulverized at a high speed, particles in a wide particle size range are likely to be formed, and particularly a relatively large proportion of fine particles (excessive In addition, such highly brittle materials are often subjected to further pulverization or pulverization when used as a developing toner in a copying machine or the like.

Known charge control agents are mixed and dispersed in the toner for the purpose of charge stability. However, many charge control agents easily agglomerate, and it is extremely possible to uniformly disperse them in the toner binder. Have difficulty. This effect becomes larger as the toner particle size becomes smaller, and therefore the charge control agent is non-uniformly dispersed in each toner particle, so that the charge distribution of the toner becomes wider, causing problems such as fog and transferability. Therefore, it is possible to use an organic dye having good compatibility with the resin, for example, a nigrosine dye or an azo dye as a charge control agent, but these are mechanical shock,
It is liable to be decomposed or deteriorated due to friction, changes in temperature and humidity conditions, etc., and the phenomenon of deterioration in charge controllability is likely to occur. As a result, various characteristics required for the toner such as developing characteristics and durability are changed or deteriorated.

Of these, a polar polymer charge control agent has recently been attracting attention because of its excellent compatibility with other components and stability. For example, JP-A-3-56974 and 8-
179564, 11-184165, 11-2
88129, 11-327208, 2000
In each publication of JP-A-56518, a toner containing a sulfonic acid group or a similar functional group as an essential component is disclosed. However, even when these charge control agents are used, when the toner has a small particle size, the toner has a wider charge distribution than the case where other metal compound type charge control agents are added. Has come to be understood.

As a result of studies conducted by the inventors of the present invention, these charge control agents themselves have high performance to some extent in charging, but since they are polymers, they have high resistance and tend to be easily charged up. It has been found that this is because it is easily affected by poor dispersion and toner particle size distribution.

In order to overcome such problems, a method for producing a toner by a polymerization method has been proposed.

The toner (polymerized toner) obtained by the polymerization method has a uniform dispersion because the charge control agent is dissolved in the polymerizable monomer, and it is relatively easy to obtain a toner having a sharp particle size distribution. Is excellent at.

However, when the charge control agent is dissolved in the polymerizable monomer and then the polymerization is started, the rise of the charge amount of the toner is delayed, and the chargeability of the toner is poor especially under high humidity. The light and shade called so-called ghost as shown in FIG. This is the polymerization method
The highly polar charge control agent is unevenly distributed near the toner surface,
Since trying to obtain a small particle size toner increases the specific surface area,
It is considered that particles are easily generated in a form including water, and therefore the charging performance of the toner is deteriorated in a high temperature and high humidity environment.

In order to solve such a problem, an attempt has been made to form a resin layer containing a charge control agent on the outer shell of the toner by using seed polymerization or the like to uniformly increase the concentration of the charge control agent near the toner surface. There is. For example, JP-A-11-30
Japanese Patent No. 5482 discloses a technique for producing a toner in which a charge control agent is added to a polymerization reaction system together with an addition polymerizable monomer or a solvent after the initiation of an addition polymerization reaction of polymerized particles. However, as a result of the examination by the present inventors,
Among the charge control agents described in the specification, those having sufficient charge imparting ability to the toner are hardly soluble in the addition polymerizable monomer, and therefore, they are added in the state of suspension. For,
It has been found difficult to evenly distribute the charge control agent on the resin surface. Further, when the charge control agent is dissolved in a solvent and added, not only the process becomes complicated because the solvent must be removed later, but also the composition of the toner surface is swelled by the swelling of the resin particles in the solvent. May change. As a result, the obtained toner has a wide charge distribution, and phenomena such as ghost, fog, and transfer scattering on the image cannot be suppressed.

Further, JP-A-1-193748 and 6
JP-A-199957 discloses that a monomer having a charge controllable functional group is further added during the production of polymerized particles or after the completion of the polymerization to carry out the polymerization so that the charge controllable functional group is uniformly present on the particle surface. The method for producing the toner is disclosed. However, since the monomer having a charge controllable functional group has high polarity and low copolymerizability, if seed polymerization is carried out by directly adding the monomer, the concentration of the charge controllable functional group may be partially excessive. High parts are generated. As a result of studies conducted by the present inventors, it has been found that a toner having such a region having extremely high charge controllable functional group concentration unevenly has a low charge imparting ability. Therefore, the charge amount of the obtained toner is not sufficient enough, and the charge distribution is wide.

For such cases, attempts have been made to coat the toner surface with a resin containing a charge controllable functional group. For example, JP-A-6-332229 and JP-A-2000-258953 disclose toners in which core particles are coated with a charge control resin by mechanical impact force or heat. However, it is difficult to uniformly adhere to the toner surface by mechanical or thermal force, and because it is not adhered by a chemical bonding force, peeling from the surface may occur during long-term durability. It becomes a problem.

Further, Japanese Unexamined Patent Publication (Kokai) No. Hei 5-222109 discloses a technique relating to a method for producing a toner in which seed polymerization is carried out using potassium persulfate having a sulfonic acid residue as an initiator. With the toner obtained in this way, it is difficult to obtain the required sufficient charge amount.

[0020]

SUMMARY OF THE INVENTION An object of the present invention is to provide a toner manufacturing method which solves the above-mentioned problems of the prior art.

That is, an object of the present invention is to provide a method for producing a toner having high transfer efficiency and less fog.

Another object of the present invention is to provide a method for producing a ghost-free toner which is excellent in charge stability, has a high image density even in a long-term use under a high temperature and high humidity environment.

[0023]

According to the present invention, core particles composed of a resin composition containing at least a binder resin and a colorant are dispersed in an aqueous medium, and at least a polymerizable monomer and a polymerizable monomer are contained in the aqueous medium. The present invention relates to a method for producing a non-magnetic toner, which comprises at least a step of adding a sulfur-containing polymer and coating the surface of the core particle with a shell to form toner particles by seed polymerization.

[0024]

BEST MODE FOR CARRYING OUT THE INVENTION The present inventors have dispersed core particles composed of a resin composition containing a binder resin and a colorant in an aqueous medium, in which a polymerizable monomer and a charge controllable compound are contained. The concentration of the charge control agent in the vicinity of the surface of the toner particles can be increased uniformly by coating the shell portion on the surface of the core particles by adding a sulfur polymer and performing seed polymerization.
The present invention has been found out that it is possible to produce a ghost-free non-magnetic toner having a high image density even after long-term use under a high temperature and high humidity environment.

In the present invention, the core particles can be produced by a pulverization method, but the emulsion polymerization method, the aggregation method,
It is easier to produce by a polymerization method such as a suspension polymerization method or a dispersion polymerization method in that the step of redispersion is not necessary because the production step has a step in which the particles are dispersed in the dispersion medium. ,preferable. Among them, the sulfur-containing polymer according to the present invention can be stably produced in an aqueous system in which it is easy to disperse, particles having a sharp particle size distribution can be easily obtained, and particles having a uniform surface can be obtained. The suspension polymerization method is preferably used because it can be obtained.

When the core particles are prepared by a pulverization method, a known method can be used. For example, a binder resin, a colorant, and other additives necessary for toner, such as a release agent and a charge control agent, are thoroughly mixed in a mixer such as a Henschel mixer or a ball mill, and then heated roll, kneader, extruder. It is melt-kneaded using a heat kneader such as the above to uniformly disperse. Then, solidification by cooling, pulverization, classification, and if necessary, surface treatment are carried out to obtain core particles. The crushing process can be performed using a known crushing device such as a mechanical impact type or a jet type. Further, in the seed polymerization, the core particles are preferably spherical in terms of ensuring the uniformity of coating and wettability, and in order to obtain such resin particles, heat is further applied after the pulverization step. It is preferable to carry out a process of crushing or crushing, or auxiliary mechanical impact. Further, a hot water bath method in which finely pulverized (classified as necessary) particles are dispersed in hot water, a method of passing through a hot air stream, or the like may be used. The core particles thus obtained are dispersed in an aqueous medium to which a high molecular polymer, a dispersant, etc. are added, if necessary, and a polymerizable monomer and a sulfur-containing polymer are further added to the medium. Then, the non-magnetic toner can be manufactured by polymerizing.

In the present invention, when the core particles are produced by the suspension polymerization method, a colorant is added to the polymerizable monomer to be the binder resin, and if necessary, a release agent and a plasticizer are added. Agent, charge control agent, other additives such as a cross-linking agent, and a high-molecular polymer, a dispersant, etc. are appropriately added, and a homogenizer,
A polymerizable monomer composition that is uniformly dissolved or dispersed by a disperser such as a ball mill, a colloid mill, or an ultrasonic disperser is obtained. Next, the composition is suspended in an aqueous medium containing a dispersion stabilizer to carry out polymerization (formation of core particles). At this time, using a high-speed stirrer or a high-speed disperser such as an ultrasonic disperser to make the desired core particle size at a stretch,
The resulting toner particles have a sharp particle size. After the granulation, an ordinary stirrer may be used to stir the particles to the extent that the particle state is maintained and the particles are prevented from floating and settling.
Further, a polymerizable monomer and a sulfur-containing polymer are added to the core particle liquid and seed polymerization is carried out to form a shell portion on the surface of the core particle to produce toner particles.

In the production of core particles by the above suspension polymerization method, the following may be mentioned as the polymerizable monomer constituting the binder resin.

For example, styrene, o-methylstyrene,
Styrene-based monomers such as m-methylstyrene, p-methylstyrene, p-methoxystyrene, p-ethylstyrene, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, n-propyl acrylate. Acrylic acid esters such as n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate. , N-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethyl methacrylate. Methacrylic acid esters such as aminoethyl other acrylonitrile, methacrylonitrile, acrylamide, and the like. These monomers may be used alone or in combination. Among the above-mentioned monomers, it is preferable to use styrene or a styrene derivative alone or in combination with other monomers, from the viewpoint of developing characteristics and durability of the toner.

In the production of core particles, a resin may be added to the polymerizable monomer composition for polymerization. For example, a monomer is water-soluble and cannot be used because it dissolves in an aqueous suspension to cause emulsion polymerization and cannot be used as an amino group, a carboxylic acid group,
When it is desired to introduce a polymerizable monomer component having a hydrophilic functional group such as a hydroxyl group, a glycidyl group, or a nitrile group into the toner, a random copolymer, a block copolymer, or a graft of these and a vinyl compound such as styrene or ethylene. It can be used in the form of a copolymer such as a copolymer, or in the form of a polycondensate such as polyester or polyamide, or a polyaddition polymer such as polyether or polyimine. When a high molecular polymer containing such a polar functional group is allowed to coexist in the binder resin of the core particle, when a wax component is contained, the wax component is phase-separated, the encapsulation becomes stronger, and the blocking resistance is improved. It is possible to obtain a toner having good developability.

Further, a resin other than the above may be added to the monomer composition for the purpose of improving the dispersibility and fixing property of the material, the image characteristics, etc. Examples of the resin used include polystyrene, Homopolymers of styrene such as polyvinyltoluene and its substitution products; styrene-propylene copolymers, styrene-vinyltoluene copolymers, styrene-
Vinyl naphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-dimethylaminoethyl acrylate copolymer Polymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-dimethylaminoethyl methacrylate copolymer, styrene-vinyl methyl ether copolymer, Styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-maleic acid copolymer, styrene-maleic acid ester copolymer, etc. Styrene-based copolymer; polymethy Methacrylate, polybutyl methacrylate, polyvinyl acetate, polyethylene, polypropylene, polyvinyl butyral, silicone resin, polyester resin, polyamide resin, epoxy resin, polyacrylic acid resin, rosin, modified rosin, temper resin, phenol resin, aliphatic or alicyclic Group hydrocarbon resins, aromatic petroleum resins and the like can be used alone or in combination. The addition amount of these resins is preferably 1 to 20 parts by mass with respect to 100 parts by mass of the polymerizable monomer. If it is less than 1 part by mass, the effect of addition is small, while if it exceeds 20 parts by mass, it becomes difficult to design various physical properties of the polymerized toner.

Further, when a polymer having a molecular weight different from the molecular weight range of the polymer obtained by polymerizing the above-mentioned polymerizable monomer is dissolved in the monomer composition and polymerized, a wide molecular weight distribution can be obtained. It is possible to obtain a toner having a high offset property.

As the colorant used in the present invention, all known dyes and pigments used as conventional colorants for toner can be used, and examples thereof include carbon black, phthalocyanine blue, permanent brown FG, and the like. Brilliant First Scarlet, Pigment Green B, Rhodamine-B Base, Solvent Red 49, Solvent Red 146, Solvent Blue 3
5, quinacridone, carmine 6B, disazo yellow, and the like, which can be used alone or in combination of two or more. The amount of the colorant used is preferably about 2 to 25 parts by mass with respect to 100 parts by mass of the polymerizable monomer.

As the polymerization initiator used in the production of the core particles relating to the toner of the present invention, one having a half-life of 0.5 to 30 hours at the time of the polymerization reaction is added to 0.5 to the polymerizable monomer. It is preferable to carry out the polymerization reaction with an addition amount of 20 parts by mass.

The polymerization initiator may be added at the same time as other additives are added to the polymerizable monomer, or may be mixed immediately before being suspended in the aqueous medium. Also, a polymerization initiator dissolved in a polymerizable monomer or a solvent may be added immediately after granulation and before starting the polymerization reaction.

As the polymerization initiator used during the polymerization of the core particles, there are conventionally known azo type polymerization initiators, peroxide type polymerization initiators and the like.
2'-azobis- (2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 1,
1'-azobis (cyclohexane-1-carbonitrile), 2,2'-azobis-4-methoxy-2,4-dimethylvaleronitrile, azobisisobutyronitrile and the like are exemplified, and peroxide type polymerization initiators are exemplified. As tert-
Butyl peroxyacetate, tert-butyl peroxylaurate, tert-butyl peroxypivalate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxyisobutyrate,
tert-butyl peroxy neodecanoate, ter
t-hexylperoxyacetate, tert-hexylperoxylaurate, tert-hexylperoxypivalate, tert-hexylperoxy-2-ethylhexanoate, tert-hexylperoxyisobutyrate, tert-hexylperoxy Neodecanoate, tert-butyl peroxybenzoate,
α, α′-bis (neodecanoylperoxy) diisopropylbenzene, cumylperoxy neodecanoate,
1,1,3,3-tetramethylbutylperoxy-2-
Ethylhexanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, 1-cyclohexyl-1-methylethylperoxyneodecanoate,
2,5-Dimethyl-2,5-bis (2-ethylhexanoylperoxy) hexane, 1-cyclohexyl-1-
Methyl ethyl peroxy-2-ethyl hexanoate,
tert-hexyl peroxyisopropyl monocarbonate, tert-butyl peroxyisopropyl monocarbonate, tert-butyl peroxy 2-ethylhexyl monocarbonate, tert-hexyl peroxybenzoate, 2,5-dimethyl-2,5-bis (benzoylper) Oxy) hexane, tert-butylperoxy-m-toluoyl benzoate, bis (te
rt-butylperoxy) isophthalate, tert-
Butyl peroxy maleic acid, tert-butyl peroxy-3,5,5-trimethylhexanoate, peroxy ester such as 2,5-dimethyl-2,5-bis (m-toluoyl peroxy) hexane, Diacyl peroxides such as benzoyl peroxide, lauroyl peroxide, isobutyryl peroxide, diisopropyl peroxydicarbonate, peroxydicarbonates such as bis (4-tert-butylcyclohexyl) peroxydicarbonate, 1,1
-Di-tert-butylperoxycyclohexane,
1,1-di-tert-hexylperoxycyclohexane, 1,1-di-tert-butylperoxy-3,
3,5-trimethylcyclohexane, 2,2-di-te
Peroxyketals such as rt-butylperoxybutane, dialkyl peroxides such as di-tert-butyl peroxide, dicumyl peroxide, tert-butylcumyl peroxide, and ter
Examples thereof include t-butyl peroxyallyl monocarbonate, and if necessary, two or more kinds of these initiators can be used.

A crosslinking agent may be added when the core particles are produced. The preferred addition amount of the crosslinking agent is
It is 0.001 to 15 parts by mass with respect to 100 parts by mass of the polymerizable monomer.

As the cross-linking agent, a compound having two or more polymerizable double bonds is mainly used. For example, an aromatic divinyl compound such as divinylbenzene, divinylnaphthalene, etc .; for example, ethylene glycol diacrylate, Ethylene glycol dimethacrylate,
A carboxylic acid ester having two double bonds such as 1,3-butanediol dimethacrylate; a divinyl compound such as divinylaniline, divinyl ether, divinyl sulfide, divinyl sulfone; and a compound having three or more vinyl groups; Are used alone or as a mixture.

In the present invention, at least the polymerizable monomer and the sulfur-containing polymer are added to the aqueous medium in which the core particles produced as described above are dispersed, and seed polymerization is carried out to obtain the core particles. The surface is coated with a shell to form toner particles.

The sulfur-containing polymer used in the present invention is preferably a polymer having a sulfonic acid group, specifically, X (SO ₃ ⁻ ) _n · mY ^{k +} (X: the above-mentioned polymerizable monomer). A polymer moiety derived from a polymer, Y ^{k +} : a counter ion, k is a valence of the counter ion, m and n are integers, and n = k × m. Have. The counter ions are preferably hydrogen ions, sodium ions, potassium ions, calcium ions, ammonium ions, etc., and more preferably hydrogen ions.

Examples of the sulfur-containing monomer used for producing the sulfur-containing polymer used in the present invention include sulfonic acid group-containing vinyl monomers such as styrene sulfonic acid, vinyl sulfonic acid and methacryl sulfonic acid. Among these, (meth) acrylamide-based monomers having a sulfonic acid group such as 2-acrylamido-2-methylpropanesulfonic acid and 2-methacrylamido-2-methylpropanesulfonic acid are preferably used. Such a sulfur-containing polymer may be a homopolymer consisting only of these sulfur-containing monomers, or a copolymer of these sulfur-containing monomers and other monomers.

As a monomer forming a copolymer with the above-mentioned sulfur-containing monomer, there is a vinyl-based polymerizable monomer, and a monofunctional polymerizable monomer or a polyfunctional polymerizable monomer is used. can do.

Monofunctional polymerizable monomers include styrene; α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, p- n-butyl styrene, p-tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p-methoxy Styrene, styrene derivatives such as p-phenylstyrene; methyl acrylate, ethyl acrylate, n-propyl acrylate, iso-propyl acrylate, n-butyl acrylate, iso
-Butyl acrylate, tert-butyl acrylate, n-amyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, n-nonyl acrylate, cyclohexyl acrylate, benzyl acrylate, dimethyl phosphate ethyl acrylate, diethyl phosphate ethyl Acrylic polymerizable monomers such as acrylate, dibutyl phosphate ethyl acrylate, 2-benzoyloxyethyl acrylate; methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, iso-propyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, tert
-Butyl methacrylate, n-amyl methacrylate,
Methacrylic polymerizable monomers such as n-hexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, n-nonyl methacrylate, diethyl phosphate ethyl methacrylate, and dibutyl phosphate ethyl methacrylate; methylene aliphatic monocarboxylic acid ester; acetic acid Vinyl esters such as vinyl, vinyl propionate, vinyl butyrate, vinyl benzoate, vinyl formate; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone, vinyl isopropyl ketone Can be mentioned.

As the polyfunctional polymerizable monomer, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, 1,6
-Hexanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol diacrylate, polypropylene glycol diacrylate, 2,2'-bis (4- (acryloxydiethoxy) phenyl) propane, trimethylolpropane triacrylate, tetramethylolmethane Tetraacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate,
1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, polypropylene glycol dimethacrylate, 2,2′-bis (4- (methacryloxydiethoxy) phenyl) propane, 2,
2'-bis (4-methacryloxy polyethoxy) phenyl) propane, trimethylolpropane trimethacrylate, tetramethylolmethane tetramethacrylate, divinylbenzene, divinylnaphthalene, divinyl ether and the like can be mentioned.

Among them, a copolymer of a sulfonic acid group-containing (meth) acrylamide-based monomer and styrene or a (meth) acrylic acid ester is excellent in adhesion to core particles during seed polymerization, and has a toner chargeability. It is good and preferable.

Further, particularly in the case of a copolymer using methyl methacrylate as a comonomer, the dispersion of the sulfonic acid group-containing vinyl monomer in the sulfur-containing polymer is good, and the charge amount is uniform and the charge is uniform. It is preferable because a toner having excellent characteristics can be obtained.

Further, in this case, when the content of the sulfonic acid group-containing vinyl monomer in the copolymer is 0.1 to 10% by mass, the surface of the core particle can be uniformly covered, which is preferable. .

As the method for producing the sulfur-containing polymer used in the present invention, all known polymerization methods such as bulk polymerization, solution polymerization, emulsion polymerization, suspension polymerization, dispersion polymerization and ionic polymerization can be used. From the aspect, solution polymerization is preferable.

The sulfur-containing polymer preferably has a weight average molecular weight (Mw) of 2,000 to 100,000.
When the weight average molecular weight (Mw) is less than 2000, the fluidity of the toner is deteriorated and the transferability is deteriorated. 1000
If it exceeds 00, it takes time to dissolve it in the monomer, and it becomes difficult for the sulfur element to exist uniformly on the toner surface.

The glass transition point (Tg) of the sulfur-containing polymer is 5
0 ° C to 100 ° C is preferable. When the glass transition point is lower than 50 ° C., the fluidity and storability of the toner are poor, and the transferability is poor. When the glass transition point is higher than 100 ° C., the fixability of an image having a large toner printing rate is poor.

The acid value (mgKOH / g) of the sulfur-containing polymer is preferably 3 to 80, more preferably 5 to 40, and further preferably 5 to 30. When the acid value is less than 3, it is difficult to obtain a sufficient charge control action as mentioned in the present invention. On the other hand, when the acid value exceeds 50, the hygroscopicity increases, and it is difficult to obtain sufficient chargeability under high humidity.

The acid value is calculated as follows. The basic operation conforms to JIS-K0070.

The acid value means the mg number of potassium hydroxide required to neutralize free fatty acids, resin acids and the like contained in 1 g of the sample.

(1) Reagent (a) Solvent: Ethyl ether-ethyl alcohol mixed solution (1 + 1 or 2 + 1) or benzene-ethyl alcohol mixed solution (1 + 1 or 2 + 1). These solutions are mixed with phenolphthalein as an indicator immediately before use. / 10
Neutralize with potassium hydroxide ethyl alcohol solution.

(B) Phenolphthalein solution: 1 g of phenolphthalein was mixed with ethyl alcohol (95 v / v).
%) Dissolve in 100 ml.

(C) N / 10 potassium hydroxide-ethyl alcohol solution: Dissolve 7.0 g of potassium hydroxide in as little water as possible, add ethyl alcohol (95 v / v%) to make 1 liter, and leave for 2 to 3 days. After filtration. Standardization is performed according to JIS K 8006 (basic items regarding titration during reagent content test).

(2) Operation: 1 to 20 g of a sample is accurately weighed, 100 ml of a solvent and a few drops of a phenolphthalein solution as an indicator are added thereto, and the sample is shaken sufficiently until it is completely dissolved. For solid samples, heat on a water bath to dissolve. After cooling, this was titrated with a N / 10 potassium hydroxide ethyl alcohol solution, and the end point of neutralization was when the indicator was slightly reddish for 30 seconds.

(3) Calculation formula: The acid value is calculated by the following formula.

A = B × f × 5.661 / S A: Acid value B: Amount of N / 10 potassium hydroxide ethyl alcohol solution used (ml) f: Factor of N / 10 potassium hydroxide ethyl alcohol solution S: Sample (g)

Extraction of the sulfur-containing polymer from the toner is not particularly limited, and any method can be used.

The amount of the sulfur-containing polymer forming the shell part coated on the surface of the core particle is 100 parts by mass of the core particle.
0.05 to 20 parts by mass, preferably 0.1 to 10
Parts by mass.

Further, during the seed polymerization, the above-mentioned sulfur-containing polymer and the polymerizable monomer may be added separately or may be dissolved and added at the same time. It is preferable that the sulfur-containing polymer is dissolved in the volatile monomer, and this solution is added to the core particle liquid. The amount of the polymerizable monomer that dissolves the sulfur-containing polymer is not particularly limited as long as it dissolves the polymer, but from the viewpoint of ease of handling and uniformity of seeds, the solution The content of the sulfur-containing polymer therein is preferably 1 to 50% by mass, and more preferably 5 to 35% by mass. As a method for adding the solution, the solution may be added all at once, or may be added continuously or intermittently using a metering pump or the like. Further, the solution of the sulfur-containing polymer is added to an aqueous medium such as water, a fine dispersion treatment is performed using an ultrasonic emulsifier, etc., and the obtained dispersion is added to the aqueous medium in which the core particles are dispersed. Is also good.

When the core particles are produced by the suspension polymerization method, the timing for adding the solution of the sulfur-containing polymer is
From the viewpoint of the permeability of the monomer constituting the shell part and the stability of the dispersed core particles, when the conversion rate of the polymerizable monomer constituting the binder resin in the core particles is 10 to 95% Is preferable, and it is more preferable to add it at 20 to 90%.

When the solution of the sulfur-containing polymer is added when the polymerization conversion rate of the binder resin is low, a soft portion and a hard portion in which the reaction has not proceeded coexist, and aggregation easily occurs, which is not preferable. . On the other hand, when the polymerization conversion rate of the binder resin is 95% or more, the polymerizable monomer dissolving the sulfur-containing polymer is less likely to soak into the core particles,
It is not preferable because it increases the amount of fine powder and impairs the uniformity of charging.

The polymerization conversion rate can be measured by gas chromatography as follows.

As a specific measuring method, about 500 mg of the toner suspension is precisely weighed in a sample bottle, about 15 g of acetone precisely weighed is added to the sample bottle, and the resulting mixture is mixed well and ultrasonicated with an ultrasonic cleaner. For 30 minutes. Thereafter, filtration is performed using a membrane filter (for example, disposable membrane filter “25JP020AN” manufactured by Advantech Toyo Co., Ltd.), and 2 μl of the filtrate is analyzed by gas chromatography. Then, the polymerization conversion rate is calculated from a calibration curve prepared in advance using a monomer such as styrene. Specifically, the analysis is performed under the following conditions.

GC: HP company “6890GC” column: HP company “INNOWax” (200 μm × 0.
40 μm × 25 m) Carrier gas: He (constant pressure mode: 20 psi) Oven: Hold at 50 ° C. for 10 minutes, 20 at 10 ° C./minute
Raise to 0 ℃ and hold at 200 ℃ for 5 minutes. INJ: 200 ° C, pulsed splitless mode (2
0 → 40 psi, until 0.5 minutes split ratio: 5.0: 1.0 DET: 250 ° C. (FID)

As the polymerizable monomer capable of dissolving the sulfur-containing polymer during seed polymerization, styrene such as styrene, o-methylstyrene, p-methylstyrene, m-methylstyrene, p-methoxystyrene, p-ethylstyrene, etc. -Based monomers, acrylic acid, methacrylic acid, and methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, n-propyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-acrylic acid acrylate Ethylhexyl, stearyl acrylate, acrylic acid 2-
Acrylic esters such as chloroethyl and phenyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-methacrylic acid Ethylhexyl, stearyl methacrylate, phenyl methacrylate,
Examples thereof include methacrylic acid esters such as dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate, and other monomers such as acrylonitrile, methacrylonitrile and acrylamide.

These monomers may be used alone or as a mixture. Among the above-mentioned monomers, it is preferable to use styrene or a styrene derivative alone or in combination with other monomers, since the adsorbability to the core particles is enhanced and the durability is enhanced.

In the present invention, the polymerization initiator used during seed polymerization may be any known one such as a water-soluble initiator and an oil-soluble initiator, and may be used alone or in combination with 2
It is also possible to use two or more species together.

These polymerization initiators are added in an amount of 0.01 to 10 with respect to the polymerizable monomer usually used for forming the shell part.
It is used in an amount of 0.05% by mass, preferably 0.05 to 5% by mass. When the amount of the polymerization initiator added exceeds 10% by mass, not only is it uneconomical due to the increase in the amount used, but also the molecular weight does not increase and toner deterioration occurs. Further, if it is less than 0.01% by mass, a sufficient degree of polymerization cannot be obtained.

In the present invention, at the time of seed polymerization, 0.001 to 0.1% by mass of a surfactant is used relative to the polymerizable monomer in order to stabilize the emulsion of the dropped polymerizable monomer system. May be. This is for promoting the emulsification and dispersion of the polymerizable monomer system, and specific examples thereof include sodium dodecylbenzene sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium stearate, calcium oleate and the like. Can be mentioned.

The toner of the present invention may contain a releasing agent in order to improve the fixing property. The amount is 1 to 30 with respect to the binder resin.
It is preferable to contain mass%. More preferably 3
Is about 25% by mass. If the content of the release agent is less than 1% by mass, the effect of adding the release agent is not sufficient and the effect of suppressing the offset is also insufficient. On the other hand, if it exceeds 30% by mass, the long-term storage property is deteriorated, and the dispersibility of the toner material such as the release agent and the colorant is deteriorated, resulting in deterioration of the fluidity of the toner and deterioration of the image characteristics. . In addition, the release agent component also oozes out, resulting in poor durability under high temperature and high humidity. Furthermore, since a large amount of wax is included, the toner shape is likely to become distorted.

Generally, the toner image transferred onto the recording medium is then fixed on the transfer material by energy such as heat and pressure, and a semi-permanent image is obtained. At this time, hot roll type fixing is generally used. As described above, when a toner having a weight average particle diameter of 10 μm or less is used, a very high-definition image can be obtained. However, a toner particle having a small particle diameter is a fiber of paper when a recording medium such as paper is used. Of the heat fixing roller becomes insufficient to receive heat from the heat fixing roller, and a low temperature offset is likely to occur. However, in the toner according to the present invention, by containing an appropriate amount of the release agent, it becomes possible to achieve both high image quality and fixability.

Examples of the releasing agent that can be used in the present invention include petroleum waxes such as paraffin wax, microcrystalline wax and petrolactam and their derivatives, montan wax and its derivatives, hydrocarbon waxes and their derivatives by the Fischer-Tropsch method, Polyolefin wax represented by polyethylene and its derivatives,
Natural waxes such as carnauba wax and candelilla wax and their derivatives, which include oxides, block copolymers with vinyl monomers, and graft modified products. Further, higher aliphatic alcohols, fatty acids such as stearic acid and palmitic acid, or compounds thereof, acid amide wax, ester wax, ketone, hydrogenated castor oil and its derivatives, plant wax, animal wax and the like can be used.

Among these releasing agent components, those having an endothermic peak by differential thermal analysis of 40 to 110 ° C., that is, in the region of 40 to 110 ° C. at the time of heating in the DSC curve measured by a differential scanning calorimeter. Those having a maximum endothermic peak are preferable, and those having a maximum endothermic peak are more preferable. By having the maximum endothermic peak in the above temperature range, releasability is effectively exhibited while greatly contributing to low temperature fixing. If the maximum endothermic peak is less than 40 ° C, the self-aggregating force of the release agent component becomes weak, and as a result, the high temperature offset resistance deteriorates. Further, the release agent is more likely to seep out, the charge amount of the toner is reduced, and the durability under high temperature and high humidity is reduced. On the other hand, when the maximum endothermic peak exceeds 110 ° C., the fixing temperature becomes high and low-temperature offset easily occurs, which is not preferable. Further, when the toner is directly obtained by a polymerization method by performing granulation / polymerization in an aqueous medium, if the maximum endothermic peak temperature is high, problems such as precipitation of a release agent component mainly occur during granulation, and The dispersibility of the mold agent deteriorates, which is not preferable.

The maximum endothermic peak temperature of the release agent is measured by
It is carried out according to "ASTM D 3418-8". For the measurement, for example, "DSC-7" manufactured by Perkin Elmer is used. The melting point of indium and zinc is used to correct the temperature of the device detection unit, and the heat of fusion of indium is used to correct the amount of heat. An aluminum pan was used as a measurement sample, an empty pan was set as a control, the sample was heated to 200 ° C. once to remove the heat history, and then rapidly cooled, and the temperature rising rate was 10 ° C. again.
The DSC curve measured when the temperature is raised in the range of 30 to 200 ° C./min is used. The same measurement was carried out in Examples described later.

The toner obtained by the manufacturing method of the present invention is
In the molecular weight distribution measured by gel permeation chromatography (GPC) of the THF-soluble component of the toner, it is preferable that the main peak has a peak top in the molecular weight range of 5,000 to 50,000, and more preferably 8,000 to 40,000. . Peak top is 5
If it is less than 000, the storage stability of the toner may be problematic, or the toner may be significantly deteriorated when many sheets are printed out. Conversely, the peak top is 50
If it exceeds 000, there arises a problem in low temperature fixability.

The molecular weight of the resin component soluble in THF by GPC may be measured as follows.

A solution obtained by dissolving the toner in THF at room temperature for 24 hours is filtered through a solvent resistant membrane filter having a pore size of 0.2 μm to obtain a sample solution, and the sample solution is measured under the following conditions. In the sample preparation, the amount of THF is adjusted so that the concentration of the THF-soluble component is 0.4 to 0.6% by mass.

Device: High-speed GPC "HLC8120 GP
C "(manufactured by Tosoh Corporation) Column: Shodex KF-801, 802, 80
7, 804, 805, 806, and 807 (Showa Denko KK) Eluent: THF Flow rate: 1.0 ml / min Oven temperature: 40.0 ° C. Sample injection amount: 0.10 ml

In calculating the molecular weight of the sample,
Standard polystyrene resin (TSK standard polystyrene F-850, F-450, F-28 manufactured by Tosoh Corporation)
8, F-128, F-80, F-40, F-20, F-
10, F-4, F-2, F-1, A-5000, A-2
500, A-1000, A-500) is used.

The molecular weight of the toner can be arbitrarily changed depending on the combination of the type and amount of the initiator and crosslinking agent used. It can also be adjusted by using a chain transfer agent or the like.

In addition to the sulfur-containing polymer, the toner obtained according to the present invention may contain other charge control agent, if necessary. As the charge control agent, known charge control agents can be used, but when a toner is produced by a direct polymerization method as in the present invention, the polymerization inhibitory property is low, and a solubilized product in an aqueous dispersion medium is substantially present. Charge control agents not listed in are particularly preferred. Specific compounds include metal compounds of aromatic carboxylic acids such as salicylic acid, alkylsalicylic acid, dialkylsalicylic acid, naphthoic acid, and dicarboxylic acids as negative charge control agents, metal salts or metal complexes of azo dyes or azo pigments, and sulfones. Polymeric compounds having an acid or carboxylic acid group in the side chain, boron compounds, urea compounds, silicon compounds,
Examples include calix arenes. Examples of the positive charge control agent include a quaternary ammonium salt, a guanidine compound having the quaternary ammonium salt in its side chain, a nigrosine compound, and an imidazole compound.

The amount of these charge control agents used is determined by the type of binder resin, the presence or absence of other additives, and the toner production method including the dispersion method, and is not uniquely limited. However, it is preferably 0.1 to 10 parts by mass, and more preferably 0.1 to 100 parts by mass of the binder resin.
It is used in the range of 5 parts by mass.

The aqueous medium used in the present invention may contain, if necessary, a known surfactant as a dispersion stabilizer, an organic dispersant or an inorganic dispersant. Among them, the inorganic dispersant is less likely to produce harmful ultrafine powder, and because it has dispersion stability due to its steric hindrance, it is less likely to lose stability even when the reaction temperature is changed, and it is easy to wash and not adversely affect the toner. Therefore, it can be preferably used. Examples of such inorganic dispersants include polyvalent metal salts of phosphate such as calcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, carbonates such as calcium carbonate and magnesium carbonate, and inorganic salts such as calcium metasilicate, calcium sulfate, barium sulfate. Examples thereof include inorganic oxides such as salts, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, silica, bentonite, and alumina.

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

It is desirable that 0.2 to 20 parts by mass of these inorganic dispersants are used alone with respect to 100 parts by mass of the polymerizable monomer. Atomization is somewhat weak, so 0.001
You may use together 0.1 mass part surfactant.

Examples of the surfactant include sodium dodecylbenzenesulfate, sodium tetradecylsulfate, sodium pentadecylsulfate, sodium octylsulfate,
Examples thereof include sodium oleate, sodium laurate, sodium stearate, potassium stearate and the like.

In the step of polymerizing the core particles and the shell, the polymerization temperature is set to 40 ° C. or higher, generally 50 to 90 ° C. to carry out the polymerization. When the polymerization is carried out within this temperature range, the release agent and waxes to be sealed inside are precipitated by phase separation and the encapsulation becomes more complete. Further, in order to consume the remaining polymerizable monomer, it is possible to raise the reaction temperature to 90 to 150 ° C. at the end of the polymerization reaction.

The toner particles obtained by the polymerization of the shell portion are filtered, washed and dried by a known method after the completion of the polymerization, and if necessary, inorganic fine powder is mixed and adhered to the surface of the toner of the present invention. Obtainable. In addition, it is possible to cut a coarse powder or a fine powder by adding a classification process to the manufacturing process.

The toner according to the present invention preferably has a weight average particle diameter of 3 to 10 μm from the viewpoint of uniform coating of the shell portion. In a toner having a weight average particle diameter of less than 3 μm, the shell portion can uniformly cover the surface of the core particle, but the layer thickness tends to be insufficient, resulting in non-uniform charge amount of each toner particle. Ghost, fog, and transferability tend to deteriorate, which is not preferable. Further, when the weight average particle diameter of the toner exceeds 10 μm, the resin is likely to be segregated on the surface of the core particles, and characters or line images are easily scattered, and it is difficult to obtain high resolution. Further, as the resolution of the apparatus becomes higher, the reproduction of one dot tends to deteriorate with toner of 10 μm or more.

Here, the average particle size and particle size distribution of the toner can be measured by various methods such as "Coulter counter TA-II type" or "Coulter Multisizer" (manufactured by Beckman Coulter, Inc.). Coulter Multisizer "(manufactured by Coulter Co.)
Interface to output volume distribution (manufactured by Nikkaki) and "PC9801 Personal Computer" (NEC
1) is connected, and the electrolyte is 1
% NaCl aqueous solution is prepared. For example, "ISOTON
R-II ”(manufactured by Coulter Scientific Japan) can be used.

The measuring method is as follows:
0.1 to 5 ml of a surfactant, preferably an alkylbenzene sulfonate, is added as a dispersant to 150 ml,
Further, 2 to 20 mg of the measurement sample is added. The electrolytic solution in which the sample is suspended is dispersed by an ultrasonic disperser for about 1 to 3 minutes,
The volume distribution and the number distribution are calculated by measuring the volume and the number of the toner particles of 2 μm or more by using the 100 μm aperture as the aperture by the Coulter Multisizer. Then, the volume-based weight average particle diameter (D4) obtained from the volume distribution and the number-based length average particle diameter obtained from the number distribution, that is, the number average particle diameter (D1) are obtained. The same measurement was carried out in Examples described later.

It is also a preferable form to add an inorganic fine powder having a number average primary particle diameter of 4 to 80 nm as a fluidizing agent to the toner according to the present invention. The inorganic fine powder is added to improve the fluidity of the toner and make the toner particles evenly charged. However, the inorganic fine powder is subjected to a treatment such as a hydrophobic treatment to adjust the toner charge amount and environmental stability. It is also a preferable mode to add a function of improving

The number average primary particle diameter of the above inorganic fine powder is 80.
If it is larger than 80 nm or if the inorganic fine powder having a particle size of 80 nm or less is not added, the transfer residual toner easily adheres to the charging member when it adheres to the charging member, and stable and good charging characteristics are obtained. Is difficult. Further, good fluidity of the toner is not obtained, charge impartment to the toner particles is likely to be non-uniform, and problems such as increased fog, reduced image density, and toner scattering cannot be avoided. When the number average primary particle size of the inorganic fine powder is smaller than 4 nm, the inorganic fine powder has a strong cohesive property, and it has a wide particle size distribution with a strong cohesive property that is difficult to be broken by crushing treatment instead of the primary particles. It tends to act as an agglomerate, and image defects due to development of the agglomerate, damage to the image bearing member, the magnetic toner bearing member, and the like are likely to occur. In order to make the charge distribution of the toner particles more uniform, the number average primary particle size of the inorganic fine powder is more preferably 6 to 35 nm.

In the present invention, the number average primary particle size of the inorganic fine powder is measured by a photograph of the toner magnified by a scanning electron microscope, and XMA (X-ray spectroscopy) attached to the scanning electron microscope. While comparing the photograph of the toner mapped with the element contained in the inorganic fine powder by means of element analysis means such as analysis), 100 or more primary particles of the inorganic fine powder existing on the surface of the toner adhered or separated are present. It can be measured by measuring and determining the number-based average primary particle diameter and number-average primary particle diameter.

As the inorganic fine powder used in the present invention,
Silica, titanium oxide, alumina and the like can be used, and they may be used alone or in combination of two or more. As the silica, for example, both the so-called dry method produced by vapor phase oxidation of a silicon halide or the dry silica called fumed silica, and the so-called wet silica produced from water glass or the like can be used. Dry silica having less silanol groups on the surface and inside the fine silica powder and less production residues such as Na ₂ O and SO ₃ ^2- is preferable. Further, in the case of dry silica, it is also possible to obtain a composite fine powder of silica and other metal oxide by using other metal halogen compound such as aluminum chloride and titanium chloride together with the silicon halogen compound in the manufacturing process. Also includes.

The addition amount of the inorganic fine powder having a number average primary particle diameter of 4 to 80 nm is preferably 0.1 to 3.0% by mass, and 0.1% by mass to the toner particles. If it is less than 3.0%, the effect is not sufficient, and if it is 3.0% by mass or more, the fixing property becomes poor.

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

Further, in the present invention, it is preferable that the inorganic fine powder is a hydrophobized product in view of the characteristics in a high temperature and high humidity environment. When the inorganic fine powder added to the toner absorbs moisture, the charge amount of the toner particles is remarkably reduced, and the toner tends to scatter.

As the treating agent used for the hydrophobizing treatment, a treating agent such as silicone varnish, various modified silicone varnishes, silicone oils, various modified silicone oils, silane compounds, silane coupling agents, other organic silicon compounds and organic titanium compounds can be used. You may process it individually or in combination.

Among them, those treated with silicone oil are preferable, and more preferably, those treated with silicone oil at the same time as or after the inorganic fine powder is subjected to hydrophobic treatment with a silane compound are toner particles even in a high humidity environment. It is good for maintaining the high charge amount and preventing toner scattering.

As a method for treating such an inorganic fine powder, for example, a silylation reaction is carried out with a silane compound as a first step reaction to eliminate silanol groups by a chemical bond, and then a silicone oil is used as a second step reaction. A hydrophobic thin film can be formed on the surface.

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

As the silicone oil to be used, for example, dimethyl silicone oil, methylphenyl silicone oil, α-methylstyrene modified silicone oil, chlorophenyl silicone oil, fluorine modified silicone oil and the like are particularly preferable.

As a method for treating the inorganic fine powder with silicone oil, for example, the inorganic fine powder treated with the silane compound and the silicone oil may be directly mixed by using a mixer such as a Henschel mixer. You may use the method of spraying silicone oil on a fine powder. Alternatively, a method may be used in which after dissolving or dispersing silicone oil in a suitable solvent, inorganic fine powder is added and mixed, and the solvent is removed. The method using a sprayer is more preferable because the formation of aggregates of the inorganic fine powder is relatively small.

The amount of silicone oil to be treated is 1 to 40 parts by mass, preferably 3 to 3 parts by mass per 100 parts by mass of the inorganic fine powder.
5 parts by mass is good. If the amount of silicone oil is too small, good hydrophobicity cannot be obtained, and if it is too large, problems such as fog tend to occur.

The above inorganic fine powder is preferably silica, alumina or titanium oxide in order to impart good fluidity to the toner, and among them, silica is particularly preferable.
Further, the specific surface area of silica measured by the BET method by nitrogen adsorption is preferably in the range of ²⁰ to 350 m ² / g, more preferably 25 to 300 m ² / g.

The specific surface area is calculated according to the BET method by using a specific surface area measuring device Autosorb 1 (manufactured by Yuasa Ionics Co., Ltd.) to adsorb nitrogen gas on the sample surface and using the BET multipoint method.

Further, the toner obtained by the present invention includes
For the purpose of improving the cleaning property, it is also one of preferred forms to further add inorganic or organic spherical particles having a primary particle size of 30 nm or more, more preferably 50 nm or more. For example, spherical silica particles, spherical polymethylsilsesquioxane particles, spherical resin particles and the like are preferably used.

The toner obtained according to the present invention may further contain other additives within a range that does not have a substantial adverse effect, for example, lubricant powders such as Teflon (registered trademark) powder, zinc stearate powder and polyvinylidene fluoride powder. Alternatively, abrasives such as cerium oxide powder, silicon carbide powder, and strontium titanate powder, or fluidity-imparting agents such as titanium oxide powder and aluminum oxide powder, anti-caking agent, reverse polarity organic fine particles, and inorganic fine particles. Can also be used in a small amount as a developability improver. It is also possible to use these additives after the surface is hydrophobized.

Next, an example of an image forming apparatus that can suitably use the non-magnetic toner obtained by the manufacturing method of the present invention will be specifically described with reference to the drawings.

The image forming apparatus 60 shown in FIG.
0 dpi laser beam printer (Canon: LB
P-8Mark IV) was prepared. This device is modified so that the process speed is 80 mm / s. As shown in FIG. 2, this apparatus uniformly charges the photoconductor 16 using the charging roller 11 to which DC and AC components are applied. At this time, the DC component is controlled to a constant voltage and the AC component is controlled to a constant current. The electrically conductive layer of the charging roller 11 had a volume resistivity of 10 ² Ω · cm, and the resistive layer had a resistance of 10 ⁷ Ω · cm, and the contact pressure was set to 230 N / m. After charging, an electrostatic latent image is formed by exposing the image portion with a laser beam 20, and a toner image is formed as a visible image with a one-component non-magnetic toner, and then a transfer roller to which a voltage is applied (volume resistivity is 5 × 10 ⁹ Ω ・ c
m) The toner image is transferred onto the transfer material 18 by means of 17. The transfer material 18 bearing the toner image is fixed on the transfer material 18 by the fixing device 23. The photoconductor 16 and the transfer roller 1
The contact pressure with 7 was set to a linear pressure of 130 N / m. The toner partially left on the photoconductor 16 is cleaned by a blade made of urethane rubber used as the cleaning member 19.

As shown in FIG. 2, in the developing container 12, a toner carrier 14 as a toner supplier is in contact with the photoconductor 16. The moving direction and the rotational peripheral speed of the surface of the toner carrier 14 are the same in the contact portion with the surface of the photoconductor 16.

As a means for applying toner to the toner carrier 14, an application roller 15 is provided at the developing portion and is in contact with the toner carrier 14. At the contact portion, the toner is applied onto the toner carrier 14 by rotating so that the moving direction of the surface of the applying roller 15 moves in the direction opposite to the moving direction of the toner carrier 14. further,
To control the coat layer of the toner on the toner carrier 14,
A resin-coated stainless steel blade 13 is attached. In the developing area, the photoconductor 16 and the toner carrier 1
A DC developing bias is applied between the toner carrier 4 and the toner carrier 4, and the toner on the toner carrier 14 flies onto the photoconductor 16 in accordance with the electrostatic latent image to form a visible image.

Next, an example of an image forming method for forming a full color image will be described with reference to the drawings.

FIG. 3 shows an image forming apparatus in which a toner image of each color is formed in each of a plurality of image forming sections, and the toner images are sequentially superposed and transferred onto the same transfer material. Here, the first to fourth image forming portions 43a to 43d are arranged side by side, and each image forming portion includes a dedicated electrostatic latent image holding member, so-called photoconductor 34a to 34d. Photoconductor 34a
To 34d are latent image forming means 37a to 37d on the outer peripheral side,
Developing means 33a-33d, transfer discharge parts 38a-38
d and the cleaning units 33a to 33d are arranged. With such a configuration, first, the first image forming unit 4
The latent image forming means 37a forms a latent image of, for example, a yellow component color in the original image on the photoconductor 34a of 3a. The latent image is made into a visible image by the developer having a yellow toner of the developing means 33a, and at the transfer discharge part 38a,
It is transferred onto the recording material S as a transfer material. While the yellow image is being transferred to the transfer material S as described above, the latent image of the magenta component color is transferred to the photoconductor 34b in the second image forming section 43b.
A visible image is formed by the developer having magenta toner formed on the developing unit 32b. This visible image (magenta toner image) is superposed on a predetermined position of the transfer material S when the transfer material S, which has been transferred by the first image forming section 43a, is carried into the transfer discharge section 38b. Transcribed. After that, cyan and black images are formed by the third and fourth image forming units 43c and 43d by the same method as described above, and the same transfer material S is printed with cyan and
The black color is superimposed and transferred. When such an image forming process is completed, the transfer material S is fixed to the fixing device 36.
Then, the image on the transfer material S is fixed. As a result, a multicolor image can be obtained on the transfer material S. After the transfer, the photoconductors 34a to 34d are cleaned by the cleaning unit 33.
The residual toner is removed by a to 33d and is used for the subsequent latent image formation. In the image forming apparatus, the conveyor belt 39 is used to convey the recording material S as a transfer material. In FIG. 3, the transfer material S is conveyed from the right side to the left side. Each of the transfer discharge parts 38a to 38d in the image forming parts 43a to 43d
It passes through 38d and is transferred. In this image forming method, a transfer belt using a mesh of tetron fiber as a transfer means for transferring a transfer material and a thin dielectric such as polyethylene terephthalate resin, polyimide resin, urethane resin are used from the viewpoint of processing ease and durability. A conveyor belt using a body sheet is used. When the transfer material S passes through the fourth image forming unit 43d, an AC voltage is applied to the static eliminator 35, the transfer material S is neutralized and separated from the belt 39, and then enters the fixing device 36, where the image is fixed and discharged. It is discharged from the outlet 40.

In this image forming method, each image forming portion is provided with an independent electrostatic latent image holding member,
The transfer material may be configured to be sequentially conveyed to the transfer portion of each electrostatic latent image holding member by a belt type conveying means. Further, in this image forming method, an electrostatic latent image holding member common to the image forming portion is provided, and the transfer material is repeatedly fed to the transfer portion of the electrostatic latent image holding member by a drum type conveying means. Alternatively, each color may be transferred.

[0120]

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

(Production Example 1 of sulfur-containing polymer) Solvent: methanol 250 parts 2-butanone 150 in a pressurizable reaction vessel equipped with a reflux tube, a stirrer, a thermometer, a nitrogen introducing tube, a dropping device and a depressurizing device. Parts 2-propanol 100 parts monomer: styrene 83 parts butyl acrylate 12 parts 2-acrylamido-2-methylpropanesulfonic acid 3 parts (hereinafter referred to as "AMPS") and heated to reflux temperature with stirring. A solution prepared by diluting 0.28 parts of tert-butylperoxy-2-ethylhexanoate, which is a polymerization initiator, with 20 parts of 2-butanone was added dropwise over 30 minutes, followed by stirring for 5 hours to start polymerization.

The polymer obtained after distilling off the polymerization solvent under reduced pressure was roughly pulverized to 100 μm or less using a cutter mill equipped with a 150 mesh screen. The obtained polar polymer had a Tg of about 70 ° C. The obtained polar polymer is referred to as polar polymer 1. Table 1 shows the physical properties of the obtained sulfur-containing polymer.

(Production Example 2 of Sulfur-Containing Polymer) In Production Example 1 of polar polymer, the amount of butyl acrylate used was 9
Sulfur-containing polymer 2 was obtained in the same manner as sulfur-containing polymer 1 except that 3 parts of methyl methacrylate was added. Table 1 shows the composition and physical properties of the obtained sulfur-containing polymer.

(Production Example 3 of Sulfur-Containing Polymer) The same procedure as in Production Example 1 of polar polymer except that 3 parts of AMPS used was 1 part of styrenesulfonic acid,
Sulfur-containing polymer 3 was obtained. Table 1 shows the physical properties of the obtained sulfur-containing polymer.

[0125]

[Table 1]

(Production of Nonmagnetic Toner 1) Ion Exchange Water 7
Then, 451 parts of 0.1M-NaPO ₄ aqueous solution was added to 09 parts and the mixture was heated to 60 ° C., and then 1.0M-CaCl ₂ aqueous solution 6 was added.
7.7 parts was added to obtain an aqueous medium containing Ca ₃ (PO ₄ ) ₂ . Styrene 78 parts n-Butyl acrylate 22 parts Divinylbenzene 0.5 parts Saturated polyester resin 2 parts Carbon black 10 parts

The above formulation was uniformly dispersed and mixed using an attritor (Mitsui Miike Kakoki Co., Ltd.). Next, this mixture was heated to 60 ° C., 8 parts of ester wax (maximum value of endothermic peak in DSC 72 ° C.) was added and mixed therein, and the polymerization initiator tert-butyl-oxy-2-ethylhexano was added thereto. 4 parts by mass of the ate was dissolved to obtain a polymerizable monomer composition.

The above polymerizable monomer composition was added to the aqueous medium, and the mixture was mixed at 60 ° C. under N ₂ atmosphere with a TK homomixer (Tokushu Kika Kogyo Co., Ltd.) at 10,000 rpm at 1 rpm.
The mixture was stirred for 5 minutes and granulated. Then, the mixture was stirred at 80 ° C. for 1.5 hours while stirring with a paddle stirring blade. The polymerization conversion rate at this time was 70%.

On the other hand, the following mixture was uniformly dissolved and added dropwise to the above suspension at 80 ° C., and polymerization was further carried out for 4.5 hours. Styrene 10 parts Sulfur-containing polymer 1 3 parts 2,2′-azobis (2,4-dimethylvaleronitrile) 0.3 parts

After the completion of the reaction, distillation was further carried out at 80 ° C. for 2 hours, after which the suspension was cooled and hydrochloric acid was added to dissolve the dispersant, followed by filtration, washing with water and drying to obtain a weight average particle diameter of 7.1 μm. Black particles 1 were obtained.

100 parts of the black particles and a primary particle diameter of 12 n
The silica of m is treated with hexamethyldisilazane and then treated with silicone oil, and the BET value after treatment is 120 m.
1.0 part of ² / g of hydrophobic silica fine powder was mixed using a Henschel mixer (Mitsui Miike Kakoki Co., Ltd.) to prepare a non-magnetic toner 1.

(Production of Nonmagnetic Toner 2) Sulfur-Containing Polymer 1
Same as the production example of the non-magnetic toner 1 except that the sulfur-containing polymer 2 was used instead of.

(Production of Nonmagnetic Toner 3) Sulfur-Containing Polymer 1
Same as the production example of the non-magnetic toner 1 except that the sulfur-containing polymer 3 was used instead of.

(Production of Non-Magnetic Toner 4) After granulation, 80 ° C.
The reaction was performed for 3 hours, and the same procedure as in the production example of the non-magnetic toner 1 was performed except that the sulfur-containing polymer 1 was added at the time when the polymerization conversion rate was 93%.

(Production of Non-Magnetic Toner 5) After granulation, 80 ° C.
The reaction was performed for 5 hours, and the same procedure as in the production example of the non-magnetic toner 1 was performed except that the sulfur-containing polymer 1 was added at the time when the polymerization conversion rate was about 100%.

(Production of Nonmagnetic Toner 6) Ion Exchange Water 7
0.1M-NaPO in 09 parts_FourInput 22.6 parts of aqueous solution
Then, after heating to 60 ° C, 1.0M-CaCl₂Aqueous solution 3
Add 3.9 parts Ca₃(PO _Four)₂Aqueous medium containing
Except for the fact that it was obtained, it was the same as the production example of the non-magnetic toner 1.

[0137]   (Production of non-magnetic toner 7) Styrene / n-butyl acrylate copolymer (mass ratio 78/22) 100 parts Saturated polyester resin 2 parts Sulfur-containing polymer 1 10 parts Carbon black 10 parts Ester wax used in the production example of the non-magnetic toner 1 8 parts

The above materials were mixed in a blender to obtain 110
Melted and kneaded with a twin-screw extruder heated to ℃, cooled and kneaded the coarsely crushed product with a hammer mill, finely pulverize the coarsely crushed product with a jet mill, and classify the obtained finely pulverized product by air classification Resin particles (core particles) having a diameter of 7.6 μm were obtained.

Add 709 parts of ion-exchanged water to the flask, and add 0.1
Was charged M-NaPO ₄ aqueous solution 451 parts, followed by heating to 60 ° C., to obtain an aqueous medium containing Ca ₃ (PO _{4) 2} was added to 1.0 M-CaCl ₂ aqueous solution 67.7 parts.

The core particles were put into the aqueous medium so that the solid content was about 30%, and the core particles were primarily dispersed by stirring with a high-speed stirrer at 60 ° C. under N ₂ atmosphere. A part of this core particle dispersion liquid was sampled and it was confirmed that the weight average particle diameter was 7.6 μm. Then, it heated up at 80 degreeC, stirring with a paddle stirring blade.

On the other hand, the following mixture was uniformly dissolved and added dropwise to the above dispersion liquid at 80 ° C., and polymerization was carried out for 4.5 hours. Styrene 10 parts Sulfur-containing polymer 1 3 parts 2,2′-azobis (2,4-dimethylvaleronitrile) 0.3 parts After completion of the reaction, distillation is further carried out at 80 ° C. for 2 hours, and then the suspension is cooled. Then, hydrochloric acid was added to dissolve the dispersant, followed by filtration, washing with water and drying to obtain a toner having a weight average particle diameter of 7.7 μm.

To 100 parts of this toner, 1.0 part of the silica used in Production Example 1 of non-magnetic toner was added and mixed using a Henschel mixer to prepare non-magnetic toner 6.

(Production of Nonmagnetic Toner 8) Sulfur-Containing Polymer 1
Non-magnetic toner 1 except that AMPS was used instead of
The same as the manufacturing example of.

(Production of Nonmagnetic Toner 9) Sulfur-Containing Polymer 1
Was the same as the production example of the non-magnetic toner 1 except that T-77 (azo iron complex compound, Hodogaya Chemical Co., Ltd.) was used instead of.

(Production of Non-Magnetic Toner 10) n-Butyl acrylate was used in place of the sulfur-containing polymer 1, and 2,2-
Same as the production example of the non-magnetic toner 1 except that 0.5 part of potassium persulfate was used in place of azobis (2,4-dimethylvaleronitrile).

(Example 1) As an image forming apparatus, "LBP-8Mark IV" manufactured by Canon Inc. was modified to have a structure shown in FIG.

The potential of the electrostatic image carrier is the dark part potential V _d =
It was set to −580V and the light portion potential _VL = −150V. Also,
As a toner carrier, a medium resistance rubber roller (diameter 16 mm, hardness ASKERC 45 °, resistance 10 ⁵⁾ made of silicone rubber in which carbon black is dispersed to adjust resistance.
Ω · cm) and brought into contact with the photoconductor. The developing contact width at this time was set to about 3 mm. The peripheral speed of the toner carrier was set to 150% (120 mm / sec) in the forward direction with respect to the peripheral speed of the photoconductor (80 mm / sec).
An application roller made of urethane foam rubber was provided as a toner application member and brought into contact with the toner carrier. A voltage of about -550V was applied to the application roller. Further, a resin-coated stainless steel blade as a toner regulating member was contacted with a linear pressure of 39.2 N / m (40 g / cm). In addition, the applied voltage during development is the DC component (-450V)
Only tried.

The applied voltage at the time of charging is the DC component (-1.2 k
V), and the applied voltage at the time of transfer was set to the direct current component (-1.5 kV).

First, 100 g of the non-magnetic toner 1 was filled in a cartridge, and under high temperature and high humidity conditions (30 ° C., 80% RH), an image pattern test consisting of only horizontal lines with a printing rate of 2% was performed on 1,000 sheets. I went. As the transfer material, 90 g / m ² paper was used.

As a result, the non-magnetic toner 1 is initially and
A high transferability was exhibited after 1000 sheets of images were printed, and a good image without fog on the non-image area was obtained. Moreover, no ghost was generated.

The evaluation items described in the examples of the present invention and the comparative examples and their criteria will be described.

<Image Density> Regarding the image density, a solid image portion was formed, and this solid image was measured by a Macbeth reflection densitometer (manufactured by Macbeth Co.).

<Transfer Efficiency> The transfer efficiency is as follows. The transfer residual toner on the photosensitive member after the transfer of the solid black image is taped off with a Mylar tape and stripped off, and the value of the Macbeth density of the one adhered on the paper is C, after transfer and before fixing. When the Macbeth density of the Mylar tape stuck on the paper on which the toner is placed is D and the Macbeth density of the Mylar tape stuck on the unused paper is E, it was approximately calculated by the following formula.

Transfer efficiency (%) = {(D−C) / (D−E)} × 100 The transfer efficiency obtained from the above calculation results was judged according to the following criteria. A: Transfer efficiency is 96% or more. B: Transfer efficiency is 92% or more and less than 96%. C: Transfer efficiency is 89% or more and less than 92%. D: Transfer efficiency is less than 89%.

<Fog> Fog is measured by REFLECTMETER MODEL TC-6D manufactured by Tokyo Denshoku Co., Ltd.
It was measured using S. A green filter was used as a filter, and fog was calculated from the following formula.

Fog (reflectance) (%) = reflectance (%) on standard paper-reflectance (%) of non-image portion of sample Incidentally, the criterion for judging fog is as follows. A: Very good (less than 1.5%) B: Good (1.5% or more and less than 2.5%) C: Normal (2.5% or more and less than 4.0%) D: Poor (4% that's all)

<Ghost> Ghost judgment criteria are shown in FIG.
The image shown in is output and visually judged according to the following criteria. A: No ghost has occurred. B: A good image although a slight ghost is generated. C: Although the ghost is generated, the image quality is practically no problem. D: Image having bad ghost and not preferable for practical use.

(Examples 2 to 7) Non-magnetic toners 2 to 7 were used as toners, and an image forming test and durability evaluation were conducted under the same conditions as in Example 1. As a result, the non-magnetic toner 7
Regarding, regarding the transferability deterioration was observed after the durability test,
As a whole, the results were obtained with no major problems.
The results are shown in Table 2.

(Comparative Examples 1 to 3) Non-magnetic toners 8 to 10 were used as toners, and an image forming test and durability evaluation were conducted under the same conditions as in Example 1. As a result, with respect to the non-magnetic toners 8 and 9, the fog was significantly deteriorated after the durability test, and the ghost was generated.

The transferability of the non-magnetic toner 10 was poor. The results are shown in Table 2.

[0161]

[Table 2]

[0162]

According to the method for producing a non-magnetic toner of the present invention, a toner having high transfer efficiency and less fog can be produced.

Further, it is possible to produce a ghost-free toner which is excellent in charge stability, has a high image density even after long-term use in a high temperature and high humidity environment.

[Brief description of drawings]

FIG. 1 is a conceptual diagram of a ghost that occurs on an image.

FIG. 2 is a diagram showing a structure of an example of an image forming apparatus using a toner obtained by the manufacturing method of the present invention.

FIG. 3 is a diagram illustrating a structure of an example of an image forming apparatus including a plurality of image forming units.

[Paragraph number]

11 charging roller 12 Development container 13 blades 14 Toner carrier 15 Application roller 16 photoconductor 17 Transfer roller 18 Transfer material 19 Cleaning member 20 laser light 23 Fixer 33a-33d Cleaning unit 34a-34d photoconductor 35 Static eliminator 36 Fixer 37a-37d latent image forming means 38a to 38d Transfer discharging unit 39 Conveyor belt 40 outlet 43a to 43d Image forming unit

Continued front page    (72) Inventor Takehiko Chiba             3-30-2 Shimomaruko, Ota-ku, Tokyo             Non non corporation (72) Inventor Keiji Kawamoto             3-30-2 Shimomaruko, Ota-ku, Tokyo             Non non corporation F-term (reference) 2H005 AA11 AB06 AB07 CA02 EA05                       FA07

Claims (8)

[Claims] 1. A core particle composed of a resin composition containing at least a binder resin and a colorant is dispersed in an aqueous medium,
A non-magnetic material comprising at least a step of forming a toner particle by coating a shell part on the surface of the core particle by seed polymerization by adding at least a polymerizable monomer and a sulfur-containing polymer to the aqueous medium. Toner manufacturing method. 2. The method for producing a non-magnetic toner according to claim 1, wherein the sulfur-containing polymer contains at least a sulfonic acid group-containing vinyl monomer as a monomer component. 3. The method for producing a non-magnetic toner according to claim 2, wherein the sulfur-containing polymer contains at least a sulfonic acid group-containing (meth) acrylamide-based monomer as a monomer component. 4. The sulfur-containing polymer according to claim 2, wherein the sulfur-containing polymer is a copolymer containing at least a sulfonic acid group-containing vinyl monomer and methyl methacrylate as monomer components. Manufacturing method of non-magnetic toner. 5. The core particles are produced by subjecting a polymerizable monomer composition containing at least a polymerizable monomer constituting a binder resin and a colorant to suspension polymerization in an aqueous medium. The method for producing a non-magnetic toner according to any one of claims 1 to 4, wherein the non-magnetic toner is a toner. 6. In the suspension polymerization of the core particles, the polymerization conversion ratio of the polymerizable monomer constituting the binder resin is 10 to 95.
The method for producing a non-magnetic toner according to claim 5, wherein the polymerizable monomer and the sulfur-containing polymer are added at the time of%, and seed polymerization is started. 7. In the suspension polymerization of the core particles, the polymerization conversion rate of the polymerizable monomer constituting the binder resin is 20 to 90.
The method for producing a non-magnetic toner according to claim 5, wherein the polymerizable monomer and the sulfur-containing polymer are added at the time of%, and seed polymerization is started. 8. The non-magnetic toner has a weight average particle diameter of 3 to 10.
The method for producing a non-magnetic toner according to claim 1, wherein the non-magnetic toner has a thickness of μm.