JPS6135454A - Toner - Google Patents

Abstract

PURPOSE:To improve fixability, offsettability and blocking resistance by making different the concn. of the cyclized rubber in the surface layer part and central part of toner components. CONSTITUTION:The system consisting of a polymerizable monomer into which a dye pigment, cyclized rubber and other additives according to need are incorporated is dispersed into a dispersion medium where a dispersant exists. The cyclized rubber has the property to migrate to a positive electrode by an electrophoresis method and is classified to an anionic polymer electrostatically charged negative. the cationic polymer electrostatically charged negative. The cationic dispersant prevents the coalescence of the particles with each other and stabilizes the particles by binding ionically with the cyclized rubber incorporated into the polymerizable monomer on the particle surface of the polymer. The toner paticles form a kind of pseudo capsule in the surface layer part of which the cyclized rubber exists much. The inside is so polymerized as to have a relatively low mol.wt. and excellent fixing characteristic. The cyclized rubber having good blocking resistance and excellent developability and wear resistance is usable for the surface layer part.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a toner used in a method for developing a latent image.

[Prior Art] Conventionally, as an electrophotographic method, US Pat. No. 2,297,8111
Although many methods are known, as described in Japanese Patent Publication No. 1, Japanese Patent Publication No. 42-23910, and Japanese Patent Publication No. 43-24748, etc., they generally utilize photoconductive substances and perform various methods. forming an electrical latent image on the photoreceptor by means;
Next, the latent image is developed using toner, and when the image is desired to be saved, an operation called "fixing" is performed. Such fixing methods include applying the latent image bearing surface as it is, or after transferring it to a transfer body.
A method of dissolving the toner in a heat chamber and embedding the toner at the same time, a method of dissolving the toner using a solvent and then removing the solvent, and a method of applying a resin solution called a fixer onto the image to fix it. Methods are known.

There are also developing methods for visualizing toner using an electrical latent image, such as the magnetic brush method described in U.S. Pat. No. 2,874,063 and the U.S. Pat. The cascade development method described and 2.22
1,778, such as the powder cloud method, the fur brush development method, and the liquid development method, it is constructed so as to satisfy the various development and fixing methods described above and to obtain sufficient performance.

Various types of toners used in this manner are known. These are constructed to be compatible with the above-mentioned developing method and fixing method. Although the toner is constructed in such a manner as to satisfy the development characteristics and fixing characteristics, it is generally difficult to balance the development characteristics and fixing characteristics. In order for the toner to fix, the wood must have adhesion and cohesion, and for development, each toner must move independently, which are fundamentally contradictory requirements. This is because there is. These conditions are becoming increasingly strict, especially when high-performance toners are required these days, toners that develop and fix at high speed, and toners that fix with little energy (for example, very little pressure). becomes. In other words, the more it is attempted to make a toner with better fixing properties, the more severe the development characteristics become.

Conventionally, toners used for electrostatic image phenomena are generally made by melt-mixing colorants and other additives in thermoplastic resin.
After uniform dispersion, the solidified product is finely pulverized and classified to produce colored fine particles of a desired particle size. Although this manufacturing method can produce fairly good toners, it does have certain limitations.

That is, the toner obtained using the pulverization method must have some brittleness so that the material is somewhat susceptible to pulverization. However, things that are too fragile
In order to obtain a toner with an appropriate particle size distribution after being too finely pulverized, it is necessary to cut the fine powder which is not worth it, which increases the cost. Furthermore, in the developing device of a copying machine, the toner is sometimes further pulverized. Furthermore, when a material with a low melting point is used to improve heat fixability, a fusion phenomenon occurs in a crushing device or a classification device, and continuous production may not be possible.

Other requirements for toners include having triboelectric properties suitable for development, forming good images, no change in performance when left unused, no solidification (blocking, etc.), and adequate heat fixing properties. Examples of such requirements are that the surface of the photoreceptor is not contaminated, etc. Especially when it comes to retention,
Offset printing, where toner adheres to the fuser roller and is retransferred onto the next sheet of copy paper, has always been a problem.
To prevent this, a release agent such as silicone oil has been applied to the fixing roller. However, in recent years, it has become common to include a polyolefin such as polypropylene or polyethylene in the toner to prevent offset without applying a release agent to the fixing roller. However, this method has problems in that the fixing roller itself does not have a sufficient effect in preventing offset, so an auxiliary fixing roller cleaning device is required, and it is not possible to make large quantities of copies without maintenance. Therefore, attempts were made to add a larger amount of polyolefin or to use a polyolefin with a lower melting point, but these efforts resulted in fusion in the crusher or classifier, or because the polyolefin with a lower melting point was exposed on the toner surface, blocking This resulted in problems such as lag and poor wave properties, resulting in a significant decrease in developability.

Furthermore, toner produced by the conventional pulverization method is
Since the grains have different shapes and are amorphous, it is thought that the triboelectric properties of each grain are different, and the fluidity is also poor, which is thought to cause variations in developability.

Spherical toners have been proposed to overcome the various drawbacks of these pulverized toners. For example, the spray method has been known for a long time. However, this method involves melting the resin or dissolving it in a solvent, spraying it out in a mist form from a nozzle, and then cooling or drying it to obtain toner. Therefore, it is difficult to obtain a toner that satisfies the above-mentioned drawback of fixing offset property.
Furthermore, polyolefins are woody; incompatible with resins, and tend to precipitate non-uniformly on the surface of the spheres during cooling or solvent evaporation.

On the other hand, in order to overcome the drawbacks of the pulverization method, a method for producing toner using a suspension polymerization method has been proposed.

That is, since it does not involve any pulverization process, it does not need to be brittle, and because it is spherical, it has excellent fluidity, and therefore triboelectric charging is uniform.

However, even with this method, it cannot be said that the toner is fully satisfactory. This is because the entire polymer is almost homogeneous, so if you lower the molecular weight and Tg to improve heat fixing properties, blocking properties will worsen, and this will contaminate the carrier particle surface and photoreceptor surface, making it difficult to develop. This also reflects the image quality and deteriorates the image quality. On the other hand, if polymerization or cross-linking is performed excessively in order to improve blocking properties, this will lead to a vicious cycle in which heat fixing properties deteriorate. It is difficult to satisfy the contradictory characteristics and quality of developability.

Furthermore, a method for producing toner using a microcapsule method has been proposed for the same purpose.

However, until now, the practical ones are:
It has not been announced yet. One reason for this is that materials that are suitable as toner materials are not necessarily suitable as microcapsule materials;
In particular, it is difficult to impart toner development suitability, particularly charge controllability, to the material constituting the wall.

Currently, a common encapsulation method involves dispersing a solid core material in a solution of a material that forms a wall and envelops the core material, and then removing the solvent using heat or other means to form a wall and enveloping the core material. Some materials precipitate a substance around a core material. This method has the advantage of being able to use materials with a clear origin, such as materials with excellent fixing properties and materials with excellent developability, while keeping the characteristics of the materials as they are. The combinations are limited. In addition, even within these limited combinations, the core material material is not completely insoluble, and it is difficult to completely prevent the elution of low molecular weight components, which are intentionally made to exist in order to improve fixing properties. That's funny. This eluted component may prevent the wall material from adhering to the surface of the core material, or the core material may be mixed into the wall material, which may adversely affect developability and durability. Therefore, there is a problem that sufficient functional separation cannot be achieved.

Furthermore, even with microcapsule toners that have overcome the above-mentioned difficulties, the impact caused by the impact during the developing operation
There are also problems such as peeling of wall materials, and in order to put microcapsule toner into practical use, there are issues such as the completeness of the coating and the durability of the coating.
At present, there are still many issues that need to be resolved.

[Problems to be Solved by the Invention] Therefore, an object of the present invention is to provide a new toner that solves these problems.

A further object of the present invention is to provide a toner that has good fixing properties, good offset properties, and good anti-blocking properties.

A further object of the present invention is to provide a toner with good fluidity and good developability.

[Means and effects for solving the problems] According to the present invention, a toner containing cyclized rubber is characterized in that the concentration of the cyclized rubber in the surface layer portion and the center portion of the toner particles is different. Toner is provided.

The present invention will be explained in detail below.

In the toner of the present invention, a system containing a polymerizable monomer, dye and pigment, cyclized rubber, or other additives as necessary is dispersed in a dispersion medium in which a dispersant is present. Preferably, it is obtained by suspending and polymerizing in a highly polar dispersion medium (for example, water) in which a dispersant having a weak electric charge opposite to that of the cyclized rubber is dispersed. The cyclized rubber used here has the property of moving to ten electrodes by electrophoresis, and is classified as a negatively charged polymer, that is, an anionic polymer. Here, the cationic dispersant j± each ionically bonds with the cyclized rubber contained in the polymerizable monomer on the surface of the polymer particles to prevent coalescence of particles and stabilize the particles. That is, since the cyclized rubber gathers on the surface of the suspended particles, it takes on a kind of shell-like form, and the resulting particles become pseudo-capsules.

That is, the toner particles obtained according to the present invention are a kind of pseudo-capsule in which cyclized rubber is present in a large amount in the surface layer in the component composition from the surface layer to the center.

In other words, regardless of the initial polymerization of the polymerizable heavy body,
The cyclized rubber for the surface layer portion may have a desired degree of polymerization. Therefore, the inner part is polymerized to have a relatively low molecular weight and excellent fixing properties, and the surface layer part can be made of a cyclized rubber having good blocking properties, developability, and abrasion resistance.

Furthermore, a release agent can be added to the toner of the present invention in order to further improve the fixing properties. The mold release agent is hydrophobic;
Because it has a low molecular weight, it has polar groups and is difficult to mix with polar polymers that have a large molecular weight, so it does not come out on the surface where the cyclized rubber gathers but is pushed into the toner. During fixing, it comes out from inside, significantly improving fixing properties and offset properties. At this time, the mold release agent is thought to function as a plasticizer, a lubricant, and an oil effect.

The mold release agent used in the present invention is a substance that comes into contact with the fixing roller during fixing and functions to reduce friction, improve mold release properties, or improve fluidity when melted, and includes, for example, polyfluorinated ethylene, Examples include fluororesins, fluorinated hydrocarbon oils, silicone oils, polyethylene, polypropylene, and long-chain compounds having carbon chains.

The release agent is preferably used in an amount of 0.5 to 15 parts by weight per 100 parts by weight. If it is less than 0.5 parts by weight, the effect will be small, and if it is more than 15 parts by weight, it will be excessive.

Long-chain compounds with carbon chains include hydrocarbons, fatty acids,
and their esters, metal soaps, fatty alcohols, polyhydric alcohols, and their metal salts, their chlorides, fluorides, amides, bisamides, etc.

Examples of long-chain compounds having carbon chains include the following.

(1) Normal and isoparaffins represented by CnH2n+2 (n=12-50) or compounds having some unsaturated bonds therein.

Examples include: C,zn-Dodecane 012 (-28) 1-Dode
ceneC13n-Tridecane C13(-2H) 1-Tridecane
eC14n-Tetradecane C,4(-28) 1-Tetradecane
eneC,5n-Pentadecane (:Br, (-2H) 1-Pe
ntadeceneCH(, n-Hexadecane Cab (-2H) 1-Hexad
eceneC,g
n-0ctadecanec,?
(-2H) 1-Octadecene
C1q, n-Nona
decane(:Bq (-2H) 1
-NonadeceneC2o
n-EicosaneC2Q (2H)
1-EicoseneC22n-Docosa
ne C2+ n-Tetraca
saneCog n-0
ctacosane C32n-Dotriaconta
neC34n-Hexatriacontane, and also includes squalene C3o and squalane 2,8.10,15,19.23 hexamethyltetracosane (CC3o Htz).

(2) A fatty acid having a hydrocarbon chain as described above,
For example, there is something like the following table.

Table 1 Saturated straight chain fatty acids (3) Also, alcohols and esters thereof can be used, for example as shown in the following table.

Table 3: Saturated alcohols Examples of esters include:

Ethylene glycol monostearate HOCH2-(HzOO([1:+7 H Baglyceryl monostearate HOH2C-CHOH-CI2000C17H35 Sorbitan monostearate CG Ht (0) Chlorides such as chlorinated paraffin can also be used.

(5) Metal soaps which are metal salts of these metals can also be used.

Table 4 Metallic Soaps (6) Amides and bisamides with hydrocarbon chains can also be used.

For example, as shown in the table below.

Table 5 Fatty acid amides and N-methylenebisamides These are commercially available singly or in mixtures. Generally, they are known as paraffin wax, microcrystalline wax, montan wax, ceresin wax, osikelite, carnauba wax, rice wax, shellack wax, zazol wax, metal soap, amide wax, and lubricant. 'Manufacturers and product names include paraffin wax (Nippon Oil), paraffin wax (Nippon Oil), microwax (Nippon Oil), microcrystalline wax (Nippon Oil), Hoechst wax (Ha: gchst AG)
), Diamond Wax (New Japan Chemical), Suntite (Seiko Chemical), Panacet (Nippon Oil & Fats), etc.

Typical grades of paraffin wax include those shown in the table below.

Table 7 Paraffin wax (manufactured by Hiki Seiro) Others, such as Hoechst wax OP (partially saponified montanic acid ester wax, Hoechst AG), Hoechst wax E (montanic acid ester wax, Hoechst AC)
), Hoechst wax GL3 (partially saponified synthetic wax, Hoechst AC), Banase) S-218 (NOF), Sparmaceti (NOF), Nirasan caster wax A (NOF), Olimes H (Yoken Fine Chemicals), etc. There is.

In addition, amide waxes include behenic acid amide (Diaamide KN (Nippon Hydrogen)), stearic acid amide (Aamide HT (Lion Oil), Aamide S (Nitto Kagaku), Aamide T (Nitto Kagaku), and Diamid 200. (Japan Hydrogen), Diamond AP-1,
(Nippon Hydrogen)), Valmitic acid amide (Neutron 5
-18 (Japanese Camphor), Aamide P (Nitto Kagaku)), Lauric acid amide (Aamide C (Lion Armor),
(Nitto Chemical), Diamond (Nippon Hydrogen), etc.

In addition, erucic acid amide (
RAM (Fine 0reanics Inc.)
, =Neetron S (Japanese camphor), LUBROL
EA (1, C, L), Alflo P-1-0 (NOF), Diamond L-200 (Nippon Hydrogen)), Brizic acid amide, Oleic acid amide (Armoslip CP)
(Lion Oil), Neutron (Japanese Camphor), Amide O (Nitto Chemical), Diamond 0-200 (Japan Hydrogen), Diamond G-200 (Japan Hydrogen), Neutron E18 (Japanese Camphor)), Elaidic Acid Amide, As bis fatty acid amide type, methylene bisbehenic acid amide (Diamid NK Bis (Nippon Hydrogen)), methylene bis stearic acid amide (Diamid 200 Bis (Nippon Hydrogen)), Armowax (Lion Armor), Bisamide (Nitto Chemical) ), methylene bis oleic acid amide (Luburon O (Nippon Hydrogen)), ethylene bis stearic acid amide (Armowax EBS (Lion Armor)), ethylene bis oleic acid amide, hexamethylene bis stearic acid amide (Amide 65 (Yoken)) Fine Chemical)), hexamethylene bistearic acid amide (Amide 60 (Yoken Fine Chemical)), octamethylene bis-erucic acid amide, monoalkylolamide,
N-(2-hydroxyethyl)lauric acid amide (Tohol N130 (Toho Chemical), Amizol LME)
, N-(2-hydroxyethyl)erucic acid amide,
N-(2-hydroxyethyl) stearic acid amide (
Amizole (Yoken Fine Chemicals)), N-(
2-hydroxyethyl)oleic acid amide, N-(2-
There are aliphatic amides such as hydroxymethyl) stearamide (methylolamide (Nitto Chemical)).

As the mold release agent, those having a melting point of 150°C or lower are preferable, and those exemplified in Tables 6 and 7 having a melting point of 80°C or lower are more preferable.

In order to achieve the object of the present invention, toner particles have a weight average molecular weight (Mw) of 10,000 or more and a glass transition point (Tg) of 40°C.
It is preferable that it is above.

When My is 10,000 or less and tg is 40° C. or less, image quality deteriorates in continuous image output.

The toner of the present invention preferably has a nearly spherical shape, and preferably has a Wardell practical sphericity of 0.85 to 1.00.

Here, Wardell's practical sphericity is a value expressed as the ratio of the diameter of a circle with an area equal to the projected area of the target particle to the diameter of the smallest circle circumscribing the projected image of the target particle, and is more specifically Specifically, it was measured by the following method. That is, an appropriate amount of toner is placed on a glass slide and dispersed so that individual toner particles do not come into contact with each other or overlap. These toner particles were mixed with Luzex 450
(manufactured by Nippon Regulator) on the CR7 screen at a magnification of 500 times, here Luzex 450
If the individual particles exist separately, we can freely choose any particle and measure its projected area, so
From this we can calculate the diameter of a circle with equal area. On the other hand, this CR7 screen is photographed as it is, and the diameter of the smallest circle circumscribing the projected image of the particles is determined by drawing. Here, the above-mentioned ratio was calculated for 100 randomly selected toner particles, and the average value was determined, which was defined as [Wardell's practical sphericity].

The cyclized rubber used in the present invention is an isomer of rubber consisting of (C5Hg)n with a degree of unsaturation reduced to 1/2 to 1/4 of the original, and has a cyclic structure within the rubber molecule. It can be obtained by various methods such as the reaction of rubber with sulfuric acid or sulfone m, a method from hydrogenated halogenated rubber, a method by heating, and a reaction between rubber and a metal halide.
Furthermore, it refers to a graft or block polymer obtained by polymerizing a vinyl monomer in the presence of the above-mentioned rubber, or it refers to a polymer modified by a certain method. These cyclized rubbers are used in an amount of 1 to 30 parts by weight per 100 parts by weight of the monomer. If it is less than 1 part by weight, the effect of the present invention will be small, and if it is more than 30 parts by weight, it will be excessive.

Suitable dispersion media used in the present invention include, for example, any suitable stabilizer, such as polyvinyl alcohol,
Gelatin, methyl cellulose, methyl hydropropyl cellulose, ethyl cellulose, sodium salt of carboxymethyl cellulose, polyacrylic acid and their salts, starch, gum alginate, zein, casein,
Tricalcium phosphate, talc, barium sulfate, bentonite, aluminum hydroxide, ferric hydroxide, titanium hydroxide,
The stabilizer, such as thorium hydroxide, can be incorporated into the aqueous phase in a stabilizing amount in the continuous phase, preferably about 0.
．． It is used within the range of 1 to 10% by weight.

The cationic dispersant preferably used in the present invention is one that is highly charged in water, such as aluminum oxide,
Examples include aluminum hydroxide, magnesium oxide, magnesium hydroxide, and hydrophilic positively charged silica fine powder.

General surface treating agents can be used to obtain the hydrophilic positively chargeable silica fine powder used in the present invention. For example, there is one represented by the general formula X+*S iYn. Here, X is an alkoxy group or a chlorine atom. m: 1 or 2 or 3°Y is a hydrocarbon group having a primary to tertiary amino group. n: 3 or 2 or 1°) 12N-121; H2NH, H2LiH2, H2S1-LLII; H3;

Q H2N-CONH-(Hz CH2CH2-5r-(Q
C2H=;)3H2N-CH,0H2C)12Si(O
CR Yo CH,).

HzNCH2CI2NICH2CHa CH25t (
OCHJ)2H2NCH2CH2CH2Si(OCH
x) 3H, NCR2CH2NHCH2CH2NHGH
3CH,CH25i(OCH3)jH,020GOCI
, CH2NHCII, 0H2CH2Si(OCHj)J
H, C, 0111: OCH, Cl2NIIC) I2CH
2NHCH1CI2CH2S i (OCHj)jH
,Cyo0COGH2C)I2NIC)120H2NHC
H20H2NHCI2・CI, NHCH2Cl, C
H25i (OCHJ)aNH,C,Hto5i(OC
Hj)i C4H5N HCHz CH2CHz S i(OCH
J) i or polyaminoalkyltrialkoxysilane, etc., and these may be used alone or in a mixed system of two or more.

The silica fine powder may be treated by any general method, but for example, the silica fine powder may be stirred and a solution of the treating agent may be added little by little to the silica fine powder.

Another method is to vaporize and spray a treatment agent or a solution thereof onto fine silica powder in a gas phase. The following polymerizable monomers can be applied to the present invention by suspension polymerization in a dispersion medium in the presence of a cyclized rubber, an additive, a dispersant, etc.

Styrene, 0-methylstyrene, m-methylstyrene,
p-methylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, 3,4-dichlorostyrene, p-ethylstyrene, 2,4-dimethylstyrene, p-n-butylstyrene, p-tert -butylstyrene, p-n-hexylstyrene, p-n-octylstyrene, p-n-nonylstyrene, p-n-
Styrene and its derivatives such as decylstyrene and p-n-dodecylstyrene; ethylenically unsaturated monoolefins such as ethylene, propylene, butylene, and isobutylene; halogens such as vinyl chloride, donylidene chloride, vinyl bromide, and vinyl fluoride Vinyl esters such as vinyl acetate, vinyl propionate, vinyl benzoate: methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, methacrylic acid α-methylene aliphatic monocarboxylic acid esters such as dodecyl, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylamine ethyl methacrylate, diethylaminoethyl methacrylate, etc. methyl acrylate, ethyl acrylate, n-butyl acrylate , isobutyl acrylate, propyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, and other acrylic acid esters; vinyl methyl ether, vinyl Vinyl ethers such as ethyl ether and vinyl isobutyl ether; Vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone, and methyl isopropenyl ketone; Vinyl compounds; Vinylnaphthalenes: Examples include acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylaterile, and acrylamide.

During polymerization, polymerization is carried out in the presence of the following crosslinking agent,
It may also be a crosslinked polymer.

Divinylbenzene, divinylnaphthalene, divinyl ether, divinyl sulfone, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butylene glycol dimethacrylate , 1
, 6 hexane glycol dimethacrylate, neopentyl glycol dimethacrylate, dipropylene glycol dimethacrylate, polypropylene glycol dimethacrylate, 2,2'bis(4-methacryloxyjethoxyphenyl)propane, 2,2'bis(4-acryloxy) General crosslinking agents such as (jetoxyphenyl)propane, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, tetramethyl-tyrolmethane tetraacrylate, dibromneopentyl glycol dimethacrylate, and allyl phthalate can be used as appropriate.

The amount of these crosslinking agents used is 0.00% based on the total amount of
01 to 15% by weight (more preferably 0.1 to 10% by weight)
) is better to use.

The polymerization initiator may be any suitable polymerization initiator, such as azobisisobutyronitrile (AIBN), benzoyl peroxide, methyl ethyl ketone peroxide, isopropyl peroxycarbonate, cumene hydroperoxide, 2,4-dichlorylbenzoyl peroxide. Polymerization of monomers can be carried out using oxide, lauroyl peroxide, and the like. Generally, about 0.5 to 5% of initiator by weight is sufficient.

In addition, water-soluble polymers cause emulsion polymerization simultaneously in water and contaminate the resulting suspension polymer with small emulsion polymer particles, so water-soluble polymerization inhibitors, such as metal salts, are added to the water phase. It is also good to prevent emulsion polymerization of Furthermore, in order to increase the viscosity of the medium and prevent coalescence of particles, glycerin, glycol, etc. may be added to the water. In addition, NaCu, KCfL, Na
It is also possible to use salts such as 2SO4.

In the suspension method, a monomer system in which a polymerization initiator, colorant, monomer, and additives are uniformly dissolved or dispersed is added to an aqueous phase, that is, a continuous phase containing a suspension stabilizer, in a conventional manner. Disperse using a stirrer, homomixer, homogenizer, etc.

Preferably, the monomer droplets have the desired toner particle size,
In general, the stirring speed and time may be adjusted so that the particles have a size of 301 L or less, and thereafter, stirring may be carried out to the extent that sedimentation of the particles is prevented so that this state is substantially maintained by the action of the dispersion stabilizer. The polymerization temperature is set at 50°C or higher, generally from 70 to 90°C. After the reaction is completed, the produced toner particles are collected by a suitable method such as washing, filtration, decantation, centrifugation, etc., and dried.

In addition, in order to adjust the degree of polymerization, a molecular weight regulator can also be used as appropriate.

When the toner is used as a color toner, a coloring agent may be added as necessary, and known pigments or dyes can be used as the coloring agent.

Examples of dyes include c, r, direct red 1, and c.
,1, Direct Red 4, C,1, Acid Red 1
,C,1,Basic Red 1. C, 1, Modern Tread 30, C, R, Direct Blue 1. C, 1, Direct Blue 2, C, R, Acid Blue 9, C, 1,
Ay-15, G, 1. Hessy-7)) Blue 3, C, I.

Basic Blue 5, C, 1, Mordand Blue, c
,y,Direct Green 6,C,1,Basic Green 4,G,1. There is a basic green 6th grade.

Pigments include yellow lead, cadmium yellow, mineral fast yellow, navel yellow, naphthol yellow S, Hansa yellow G, permanent yellow NCG.
, tartrazine lake, red yellow lead, molybdenum orange, permanent orange GTR, pyrazolone orange, benzidine orange G, cadmium red, permanent red 4R, watching red calcium salt, eosin lake, brilliant carmine 3B, manganese purple, fast violet B, Methyl violet lake, dark blue, cobalt blue, alkali blue lake, Victoria blue lake, phthalocyanine blue, fast sky blue, indanthrenblue-BC, chrome green, chromium oxide, pigment green B, malachite green lake, final yellow green G, Carbon black, etc.

Contains magnetic powder to use the toner as a magnetic toner! (Based on "C'%j," as such magnetic powder,
Materials that are magnetized when placed in a magnetic field are used, including powders of ferromagnetic metals such as iron, cobalt, and nickel, or alloys and compounds such as magnetite, hematite, and ferrite. The content of this magnetic powder is 1% per toner weight.
0 to 70% by weight is good.

It may also be coated with a resin or a suitable treatment agent. Moreover, there are no special restrictions on the manufacturing method. Also, known additives for dispersing magnetic powder may be added. Particularly preferred is a resin or a magnetic material treated with an appropriate treatment agent.

If necessary, a charge control agent, a colorant, and a fluidity modifier may be added to the toner, and the charge control agent and fluidity modifier are mixed (externally added) with the toner particles and used. It's okay. Examples of the charge control agent include metal-containing dyes and nigrosine, and conventionally known dyes and pigments can be used as the colorant, and examples of the fluidity modifier include colloidal silica and fatty acid metal salts. There is. In addition, for the purpose of increasing the volume, fillers such as carbonate power) lesium, fine powdered silica, etc.
It can also be blended into the toner in a range of 0 wt%. Further, a fluidity improver such as fine Teflon powder may be added to prevent toner particles from coagulating with each other and improve fluidity.

All known methods can be used to develop this toner. For example, two-component development methods such as cascade method, magnetic brush method, microtoning method, conductive component development method, insulating component development method; -t, partial development method containing magnetic material such as jumping development method. ; Powder cloud method and fur brush method; Non-magnetic component development method in which toner is held on a toner carrier by electrostatic force and transported to a developing section for development; non-magnetic toner and magnetic particles are arranged, Examples include a developing method in which a magnetic brush of magnetic particles is formed under a magnetic field, non-magnetic toner is supplied onto a toner carrier, and the layer thickness of the non-magnetic toner on the toner carrier is controlled.

[Example] Next, the present invention will be explained with reference to Examples.

Example 1 Styrene IBOgn-butyl methacrylate 40g Alpex GK-450 cyclized rubber chill (manufactured by Hoechst) 20g Copper phthalonanine blue (manufactured by Dainichiseika) 120g Paraffin wax 155 (manufactured by Nippon Jiro Co., Ltd.) 2g at 70°C The mixture was heated to dissolve and disperse. This was mixed for about 5 minutes while being heated to about 70° C. in a container equipped with a high shear force mixing device such as TK Homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). Thereafter, 6 g of azobis-(2,4-dimethylvaleronitrile) was dissolved.

Separately, 4 g of Aerosil 11200 was dispersed in 1000 ml of water, heated to 55° C., and the above-mentioned 1000ml system was added to the mixture while stirring with a TK homomixer, followed by stirring at 8000 rpm for about 80 minutes. Then, stir this mixed system with a paddle blade stirrer,
Polymerization was completed. Thereafter, the dispersant was removed with sodium hydroxide, followed by filtration, washing with water, and drying to obtain a toner. Wardell's practical sphericity was in the range of 0.85 to 1.00. To 100 g of this toner, 0.2 g of hydrophobized silica R-1172 (manufactured by Nippon Aerosil ■) was added as a developer, and N
Developed using a P-5500 machine. Initial images are good;
Even when 50,000 images were printed continuously, there was little change in image quality and the image quality was good. Furthermore, the fixing properties and offset properties were also good.

Comparative Example 1 The toner obtained in Example was mixed with a hot roll, pulverized, and classified to obtain a toner having a similar number average diameter.

When image printing was carried out in the same manner as in Example 1, the image quality and density deteriorated significantly after 50,000 continuous images were printed.

Example 2 Styrene 160gn-butyl methacrylate 40g cyclized rubber (
ALPEX GK-514) 20g paraffin wax 155 8g magnetic powder BL-22
0 (manufactured by Titan Kogyo Co., Ltd.) 120g 2g of an α-olefin maleic acid adduct was heated to 70°C to dissolve and disperse. This was mixed in a container equipped with a high shear mixing device such as TK Homo Mixer (manufactured by Tokushu Kika Kogyo) for about 70 minutes.
The mixture was mixed for about 5 minutes while heating to 0°C. Thereafter, 6 g of azobisisobutyronitrile was dissolved.

Separately, Aerosil 112004 was treated with 1000 ml of water and 10% of γ-aminopropylethoxysilane treatment agent.
g was dispersed and heated to 70°C, and the above monomer system was added to the mixture under stirring using a TK homomixer, followed by stirring at 8000 rpm for about 60 minutes. Thereafter, this mixed system was stirred using paddle blade stirring to complete the polymerization. Thereafter, the dispersant was removed with sodium hydroxide, followed by filtration, washing with water, and drying to obtain a toner.

The obtained toner had a number average diameter of 8. ? It was p, ra. This toner is substantially spherical and has a Wardell practical sphericity of 0.
．． It was in the range of 85 to 1.00. This toner 10
0.4 g of Aeroseal R-972 (manufactured by Nippon Aeroseal Co., Ltd.) was added to 0g to prepare a developer. Commercially available copying machine MP-
When the image was printed using 270RE, the image was good.

Comparative Example 2 The toner obtained in Example 2 was mixed with a hot roll, pulverized,
The toners were classified to obtain toners having similar number average diameters.

When image printing was carried out in the same manner as in Example 2, the image quality and density were significantly lowered after printing 50,000 sheets.

Example 3 A toner was obtained in the same manner as in Example 1 except that 40 g of Alpex GK-450 was used. When images were produced in the same manner, the images were good, and the offset and fixing properties were also good.

Example 4 A toner was obtained in the same manner as in Example 2, except that 40 g of Fullpex 0K-514 was used. When images were produced in the same manner, the images were good, and the offset and fixing properties were also good.

Example 5 Paraffin wax 155 of Example 1 (manufactured by Nippon Seiro)
Mouth Micro Wax 180 (manufactured by Nippon Oil) instead of
A toner was obtained in the same manner except that 20 g of the following was used. When images were produced in the same manner, the images were good, and the offset and fixing properties were also good.

Example 6 A toner was obtained in the same manner as in Example 1 except that 8 g of zinc stearate was used instead of paraffin 155 (manufactured by Hiki Seiro). When images were produced in the same manner, the images were good, and there were no practical problems in offset properties and fixing properties.

Example 7 A toner was obtained in the same manner as in Example 1 except that 1.5 g of divinylbenzene was added and the polymerization temperature was 60°C. When image output was performed in the same manner, the image was good, and the offset property and
There were no practical problems with fixing properties.

Example 8 Example 2 (diethylene glycol dimethacrylate) 1
．． A toner was obtained in the same manner except that 5 g was added and the polymerization temperature was 75°C. When images were produced in the same manner, the images were good, and there were no practical problems in offset properties and fixing properties.

Example 9 A toner was obtained in the same manner as in Example 3 except that 1.5 g of divinylbenzene was added and the polymerization temperature was set at e o'c. When images were produced in the same manner, the images were good, and there were no practical problems in offset properties and fixing properties.

Example 10 The procedure of Example 1 was repeated except that paraffin wax 155 was removed, and 5 g of azobisisobutyronitrile was dissolved. Separately, water 1000 ran and Aeroseal 200 4
g was dispersed and heated to 85°C. Thereafter, a toner was obtained in the same manner as in Example 1. Image printing was performed in the same manner as in Example 1. Even when 50,000 images were printed continuously, there was little change in image quality and the image quality was good. Furthermore, the fixing properties were also good.

Example 11 A toner was obtained in the same manner as in Example 2 except that paraffin wax 155 was removed and azobisisobutyronitrile was changed to 5 g. When the image was produced in the same manner as in Example 2, a good image was obtained.

[Effects of the Invention] As described above, in the toner of the present invention, since the concentration of cyclized rubber in the surface layer and center of the toner particles changes continuously, a large amount of cyclized rubber exists inside the toner. The fixing properties are ensured by the components, and the cyclized rubber present in large amounts in the surface layer of the toner ensures blocking resistance, developability, and abrasion resistance, making it possible to form images of excellent image quality.

Claims (1)

[Claims] (1) A toner containing cyclized rubber, characterized in that the concentration of the cyclized rubber in the surface layer and the center of the toner particles is different.