JPH0527477A - Toner for developing electrostatic charge image - Google Patents

Abstract

PURPOSE:To provide a toner for developing an electrostatic charge image fixable at low temp., having excellent anti-offsetting property, vinyl chloride resistance and narrow particle size distribution and capable of forming a high quality image with high resolving power and excellent halftone reproducibility. CONSTITUTION:In this toner for developing an electrostatic charge image based on polymer particles and a colorant, the polymer particles are particles of a copolymer of methyl acrylate with other vinyl monomer such as styrene, a styrene deriv. or ester of acrylic acid or methacrylic acid with 2-4C alcohol. The copolymer particles are produced by dispersion polymn.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a high-quality electrostatic image developing toner having a narrow particle size distribution.

[0002]

2. Description of the Related Art Conventional toners have been manufactured by a pulverizing method. However, a toner having a small particle size has been required with the recent improvement in image quality. Therefore, the pulverizing method makes it difficult to efficiently manufacture a toner at a low cost. It's coming. Therefore, recently, many methods for producing toner by polymerization methods such as suspension polymerization method, two-step swelling method, and dispersion polymerization method have been reported, but considering the narrow particle size distribution and the ease of the process, dispersion Polymerization methods are suitable.

For toner, it is important not to cause offset at the time of fixing, and offset has been prevented by applying a releasing oil such as silicone oil to the fixing roller. However, in this method, the toner itself is desired to have offset resistance because it hinders downsizing and simplification of the copying machine. The toner can have offset resistance by increasing the degree of crosslinking of the particles, but on the other hand, the fixing temperature becomes high, and it is difficult to satisfy both offset resistance and low temperature fixing property. Furthermore, it is also important to have PVC mat resistance. JP-A-59-218459, JP-A-63-309968 and the like report methods which satisfy both offset resistance and low temperature fixing property. However, it is not a method that also satisfies vinyl chloride resistance.

As a method for imparting vinyl chloride resistance to the toner, JP-A-62-119551 and JP-A-63-280262 are known.
Has been reported. However, this method is not a toner having a uniform particle diameter because it does not have offset resistance and is not dispersion-polymerized.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a toner which satisfies all of low temperature fixing property, anti-offset property and vinyl chloride matting property in one step and has a narrow particle size distribution.

[0006]

According to the present invention, in an electrostatic charge image developing toner whose main components are polymer particles and a colorant, the polymer particles are styrene or a styrene derivative produced by dispersion polymerization. Provided is a toner for developing an electrostatic charge image, which is a copolymer particle of methyl acrylate and another vinyl monomer, and the other vinyl monomer is acrylic or methacrylic acid other than methyl ester. An electrostatic charge image developing toner according to claim 1, which is an acid ester, wherein the other vinyl monomer is acrylic or methacrylic acid and a carbon number of 2 to 2.
4. An electrostatic charge image developing toner according to claim 1, which is an ester with an alcohol of item 4.

The inventors of the present invention have conducted extensive studies in order to achieve the above-mentioned object, and as a result, carry out dispersion polymerization by using a specific vinyl monomer as polymer particles constituting a toner for developing an electrostatic image. It was found that it is effective to use the particles obtained by the above, and the present invention has been completed.

The present invention will be described in detail below. The polymer particles used for the electrostatic image developing toner of the present invention are particles having a narrow particle size distribution obtained by a dispersion polymerization method.
Narrow particle size distribution is the volume average of Coulter Multisizer (manufactured by Coulter Electronics Co., Ltd.), when using an aperture tube of 100 μm, the aperture current etc. is measured by a cartmatic (count value of 30,000 or more). This means a particle size distribution in which the ratio of the particle diameter (dv) to the number average particle diameter (dn) is 1.00 ≦ (dv / dn) ≦ 1.15. As the particle size distribution after completion of polymerization, dv / dn is preferably 1.10 or less. If the particle size distribution is broad, the particles are colored unevenly.
Further, the dv should be in the range of 1 to 20 μm. Particularly, toner having a particle size of 10 μm or less is most suitable for high-resolution image reproduction. The electrostatic image developing toner of the present invention is produced by a method including the dispersion polymerization step and the step of dyeing the polymer particles obtained in the step in a solvent.

The starting vinyl monomers constituting the polymer particles used in the toner of the present invention are styrene or its derivatives, methyl acrylate and other vinyl monomers. As the other vinyl monomer, for example, an acrylic or methacrylic acid ester other than methyl acrylate is suitable, and an ester of an alcohol having 2 to 4 carbon atoms is particularly preferable. Examples of styrene and its derivatives include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, p-ethylstyrene, 2,4.
-Dimethylstyrene, pn-butylstyrene, pt
ert-butyl styrene, pn-hexyl styrene,
pn-octyl styrene, pn-nonyl styrene,
pn-decylstyrene, pn-dodecylstyrene,
Examples thereof include p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, 3,4-dichlorostyrene and the like. Examples of esters with alcohols having 4 or less carbon atoms include ethyl acrylate, n-butyl acrylate, isobutyl acrylate, propyl acrylate, 2-acrylic acid acrylate.
Chlorethyl and the like.

Methyl acrylate has good resistance to vinyl chloride matting, but if it is too large, it will be difficult to suppress the occurrence of offset, so it is desirable not to exceed the amount of styrene. Acrylic acid other than methyl has a low Tg of its homopolymer, so even a small amount is effective for low-temperature fixability, but if it is too large, it will be easily fused to vinyl chloride mat, so that it does not exceed 10% by weight of the total amount of monomers. It is preferable. Although the amount of each monomer is arbitrary, in consideration of the above, the glass transition point is adjusted to 40 to 90 ° C, preferably 50 to 70 ° C.

The polymer of the present invention may be polymerized in the presence of a crosslinking agent. As a cross-linking agent preferably used, an aromatic divinyl compound which is divinylbenzene, divinylnaphthalene and their derivatives, other ethylene glycol dimethacrylate, diethylene glycol methacrylate, triethylene glycol methacrylate, trimethylolpropane triacrylate, allyl methacrylate, tert-butylamino Diethylenic carboxylic acid esters such as ethyl methacrylate, tetraethylene glycol methacrylate, 1,3-butanediol dimethacrylate, all divinyl compounds such as N, N-divinylaniline, divinyl ether, divinyl sulfide, divinyl sulfone and three or more A compound having a vinyl group is used alone or as a mixture.

In the dispersion polymerization method for polymerizing the vinyl monomer as the raw material, a polymer dispersion stabilizer which dissolves in the hydrophilic organic liquid is added to the hydrophilic organic liquid, and the polymer dispersion stabilizer is dissolved in the hydrophilic organic liquid. However, the resulting polymer is a method of forming particles by adding one or more vinyl monomers which are swollen or hardly dissolved in the hydrophilic liquid. It also includes a reaction in which a polymer having a smaller particle size than the intended particle size but a narrow particle size distribution is used in advance to grow in the above system. The monomer used for the growth reaction may be the same as that used to prepare the seed particles or a different monomer, but it should not be dissolved in the polymer hydrophilic organic liquid. The polymer dispersion obtained by such a method, in the dyeing step described below,
It can be used as it is and contributes to simplification of the manufacturing process.

In the present invention, the hydrophilic organic liquid is, for example, methyl alcohol, ethyl alcohol, denatured ethyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, tert-butyl alcohol, sec-butyl alcohol, tert-amyl alcohol. , 3-pentanol, octyl alcohol,
Alcohols such as benzyl alcohol, cyclohexanol, furfuryl alcohol, ethyl glycol, glycerin, and diethylene glycol, methyl cellosolve, cellosolve, isopropyl cellosolve, butyl cellosolve, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether. And other ether alcohols.

These organic liquids may be used alone or as a mixture of two or more. In addition, alcohols,
And an organic liquid other than ether alcohols in combination with the above-mentioned alcohols and ether alcohols to change various SP values under the condition that the polymer particles of the organic liquid are not soluble, It is possible to suppress the size of particles produced, the coalescence of particles and the generation of new particles by changing the polymerization conditions. Organic liquids used in combination with these include hexane, octane, petroleum ether,
Hydrocarbons such as cyclohexane, benzene, toluene, xylene, halogenated hydrocarbons such as carbon tetrachloride, trichloroethylene, tetrabromoethane, ethers such as ethyl ether, dimethyl glycol, trioxane, tetrahydrofuran, methylal, diethyl acetal, etc. Acetals, acetone, methyl ethyl ketone,
Methyl isobutyl ketone, ketones such as cyclohexanone, butyl formate, butyl acetate, ethyl propionate, esters such as cellosolve acetate, acids such as formic acid, acetic acid, propionic acid, sulfur such as nitropropene, nitrobenzene, dimethylamine, etc., The nitrogen-containing organic compounds also include water. SO ₄ ²⁻ , NO ₂ ⁻ , PO ₄ ³⁻ , Cl ⁻ , N are added to the above-mentioned solvent composed mainly of hydrophilic organic liquid.
Polymerization may be carried out in the presence of a +, K +, Mg ² +, Ca ² + and other inorganic ions. The average particle size, particle size distribution, and drying conditions of the polymer particles produced can be adjusted by changing the type and composition of the mixed solvent at the start of polymerization, during the polymerization, and at the end of the polymerization.

A dispersion stabilizer may be used in the production of the particles in the present invention. Suitable examples of the dispersion stabilizer include acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid and itaconic acid. , Acids such as crotonic acid, fumaric acid, maleic acid or maleic anhydride, or acrylic monomers containing a hydroxyl group, for example β-hydroxyethyl acrylate, β-methacrylic acid
-Hydroxyethyl, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate, γ-hydroxypropyl acrylate, γ-hydroxypropyl methacrylate, 3-chloro-2-hydroxypropyl acrylate, 3-chloro-2 methacrylate -Hydroxypropyl, diethylene glycol monoacrylic acid ester, diethylene glycol monomethacrylic acid ester, glycerin monoacrylic acid ester, glycerin monomethacrylic acid ester, N-methylol acrylamide, N-methylol methacrylamide, etc., vinyl alcohol or ethers with vinyl alcohol, for example Vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, etc., or esters of vinyl alcohol and a compound containing a carboxyl group For example, vinyl acetate, vinyl propionate, vinyl butyrate, etc., acrylamide, methacrylamide, diacetone acrylamide or their methylol compounds, acid chlorides such as acrylic acid chloride, methacrylic acid chloride, vinylpyridine, vinylpyrrolidone, vinylimidazole, ethyleneimine. Homopolymers or copolymers having a nitrogen atom such as or a hetero atom thereof, polyoxyethylene, polyoxypropylene, polyoxyethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene Alkyl amide, polyoxyethylene nonyl phenyl ether, polyoxyethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ether, polio Polyoxyethylenes such as xyethylene nonyl phenyl ether, celluloses such as methyl cellulose, hydroxyethyl cellulose and hydroxypropyl cellulose, or those having the above hydrophilic monomer and benzene nucleus such as styrene, α-methylstyrene and vinyltoluene or derivatives thereof. Alternatively, copolymers with acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile, acrylamide, etc., and further with crosslinkable monomers such as ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, allyl methacrylate, divinylbenzene, etc. It can be used.

These polymer compound dispersions are appropriately selected depending on the hydrophilic organic liquid to be used, the seed of the desired polymer particles and the production of seed particles or the production of grown particles. In order to prevent coalescence mainly in three dimensions, a polymer having a high affinity for the polymer particle surface and an adsorptive property and a high affinity for a hydrophilic organic liquid and a high solubility is selected. Also,
In order to increase the repulsion between particles in a three-dimensional manner, one having a molecular chain of a certain length, preferably one having a molecular weight of 10,000 or more is selected. However, when the molecular weight is too high, the viscosity of the liquid is remarkably increased, the operability and the stirring property are deteriorated, and the precipitation probability of the produced polymer on the surface of the particles is varied, so that caution is required. Further, it is also effective for stabilization to make the above-mentioned monomer of the polymer compound dispersant partially coexist with the monomer constituting the intended polymer particles.

Generally, the amount of the polymer dispersant used in the production of the seed particles varies depending on the kind of the polymerizable monomer for forming the intended polymer particles, but is 0.1 to 1 with respect to the hydrophilic organic liquid.
0 wt% is more preferable, and 1 to 5 wt% is more preferable. When the concentration of the polymer dispersion stabilizer is low, the resulting polymer particles have a relatively large diameter, and when the concentration is high, small particles are obtained. There is little effect on reducing the diameter.

Needless to say, the above-mentioned polymer dispersion stabilizer and, if necessary, the inorganic fine powder, pigment, and surfactant are necessary for the production of seed particles, but the particles may be mixed with each other during the growth reaction. The polymerization may be carried out by allowing it to be present in a vinyl monomer solution or seed particle dispersion liquid added for the purpose of preventing the coalescence, so that stabilization of polymer particles and improvement of particle size distribution can be further enhanced.

The particles initially formed are stabilized by the polymeric dispersant stabilizer distributed in equilibrium between the hydrophilic organic liquid and the polymer particle surface, but the unreacted vinyl monomer is hydrophilic. When it is considerably present in the organic liquid, it is swelled to some extent and has tackiness, and the steric repulsive force of the polymer dispersion stabilizer is overcome to agglomerate. Further, when the amount of the monomer is extremely large with respect to the hydrophilic organic liquid, the produced polymer is completely dissolved and does not precipitate unless the polymerization proceeds to some extent. The state of precipitation in this case takes the form of forming a highly sticky lump.

Therefore, the amount of the monomer with respect to the hydrophilic organic liquid at the time of producing the particles is naturally limited, and it may be slightly different depending on the kind of the hydrophilic organic liquid, but it is 100% by weight or less, preferably. 50% by weight or less is suitable.

Polymerization may be carried out in the presence of a compound having a large chain transfer constant for the purpose of adjusting the average molecular weight. For example, a low molecular weight compound having a mercapto group, carbon tetrachloride, bromine tetrachloride, etc. may be mentioned. The toner of the present invention has polymer particles having a weight average molecular weight of 0.5 to
It is preferable that 100,000 to 1,000,000 or more high molecular weight components or crosslinking components are contained in an amount of 5 to 50% by weight in order to secure fixability and offset resistance.

The polymerization initiator used in the present invention includes
The usual radical initiators which are soluble in the solvent used are used. For example, 2,2'-azobisbutyronitrile,
Azo polymerization initiators such as 2,2'-azobis (2,4-dimethylvaleronitrile), persulfate initiators such as lauryl peroxide, benzoyl peroxide, tert-butyl peroctoate and potassium persulfate Alternatively, a system in which sodium thiosulfate, amine or the like is used in combination with this is used. The concentration of the polymerization initiator is 10 vinyl monomers.
0.1 to 10 parts by weight is preferable with respect to 0 parts by weight. Polymerization is performed by completely dissolving the polymer dispersant in the hydrophilic organic liquid, then adding the raw material vinyl monomer, polymerization initiator, etc., and stirring at a speed such that the flow in the reaction vessel becomes uniform. The heating is performed at a temperature corresponding to the decomposition rate of the initiator. In addition,
Since the temperature at the initial stage of polymerization has a large influence on the particle size generated, the temperature is raised to the polymerization temperature after adding the monomer,
It is desirable that the initiator be dissolved in a small amount of solvent and then added.

At the time of polymerization, it is necessary to sufficiently expel oxygen in the air in the reaction vessel with an inert gas such as nitrogen gas or argon gas. If the oxygen purge is insufficient, fine particles are likely to be generated.

In order to carry out the polymerization in the high polymerization rate region, a polymerization time of 5 to 40 hours is required. However, the polymerization may be stopped in a state of desired particle size and particle size distribution, or a polymerization initiator may be added. The polymerization rate can be increased by sequentially adding or performing the reaction under high pressure.

After completion of the polymerization, it may be used in the dyeing step as it is, or after removing unnecessary fine particles, residual monomers, polymer dispersion stabilizer and the like by operations such as sedimentation, centrifugation and decantation, The polymer slurry may be recovered and dyed. However, the stability of the dyeing system is higher and the unnecessary aggregation is suppressed if the dispersion stabilizer is not removed. However, in the case of purification, there is also an advantage that it can be replaced with a solvent most suitable for dyeing.

The organic solvent used for dyeing the polymer particles with the dye is one in which the polymer particles used do not dissolve, or one which causes some swelling, specifically, a solubility parameter [SP value]. The polymer particles [S
P value] is 1.0 or more, preferably 2.0 or more. For example, with respect to styrene-acrylic resin, methanol, ethanol having a high [SP value],
Alcohol type such as n-propanol or [SP
N-hexane, n-heptane or the like having a low value] is used.
Of course, if the difference in [SP value] is large, the wetting of the polymer particles becomes poor, and good dispersion of the polymer particles cannot be obtained. Therefore, the optimum [SP value] difference is preferably 2 to 5.

As a dyeing method, a dye is dispersed and dissolved in an organic solvent, and then polymer particles are dispersed. The weight ratio of the dye to the polymer particles may be determined according to the degree of coloring, but is usually 1 per 100 parts by weight of the polymer particles.
~ 50 parts by weight are used. After dispersing the dye and the resin particles in the organic solvent, it is desirable to keep the liquid temperature at a temperature not higher than the glass transition temperature of the polymer particles and not lower than 20 ° C. lower than the glass transition temperature, and stirring for about 30 to 1 hour. . The stirring method is a commercially available stirrer, for example, a homomixer,
It may be stirred using a magnetic stirrer or the like.

Further, even if the dye is directly added to the slurry obtained after the completion of the polymerization by dispersion polymerization, that is, the solution in which the polymer particles are dispersed in the organic solvent, and the mixture is heated and stirred under the above conditions. Good.

The polymer particles are stabilized by a dispersion stabilizer, and even if the dyeing temperature is raised above the glass transition temperature of the resin, the particles do not aggregate or fuse with each other, and the dyeing efficiency (the dye used) Of these, the ratio taken into the resin) is also high.

As the dye used for dyeing, the ratio [D1] / [D] of the solubility [D1] in the solvent used for dyeing and the solubility [D2] in the organic solvent capable of dissolving the polymer particles is used.
2] needs to be 0.5 or less, but [D1]
It is particularly preferable that / [D2] is 0.2 or less. Solubility in organic solvent capable of dissolving the polymer particles [D2]
It is desirable to determine the solubility [D2] experimentally or from the SP value to determine the solvent in which the polymer particles are best dissolved. The high solubility of the dye in a solvent that dissolves the polymer well (it is desirable that the polymer has an SP value of ± 2) means that the polymer and the dye have high affinity. When [D1] / [D2] is 0.5 or more, dyeing is not performed at all, or coloring is insufficient because the interior is not colored.

The dye is not particularly limited as long as it satisfies the above-mentioned solubility characteristics. However, a water-soluble dye such as a cationic dye or an anionic dye may have a large environmental change, and the resistance of the toner may be lowered, resulting in a transfer. The rate may deteriorate. Therefore, vat dyes, disperse dyes, oil-soluble dyes are preferable,
Oil-soluble dyes are particularly preferable. Also, several kinds of dyes can be used together depending on the coloring. The ratio (weight) of the dye to be dyed and the polymer particles is arbitrarily selected according to the degree of coloring, but usually 1 to 100 parts by weight of the polymer particles are used for dye 1 to.
50 parts by weight is preferred.

The dye in the present invention can be appropriately selected depending on the polymer particles and the solvent used for dyeing. For example, an alcohol such as methanol or ethanol having a high SP value is used as the dyeing solvent, When a styrene-acrylic resin having an SP value of about 9 is used, the polymer does not dissolve in the dyeing solvent. However, acetone with SP value around 9,
It dissolves well in organic solvents such as toluenebenzene.

In this case, examples of dyes that can be used include C.I. I. SOLVENT YELLOW (6, 9, 17, 31, 35, 100, 102, 103, 105) C.I. I. SOLVENT ORANGE (2, 7, 13, 14, 66) C.I. I. SOLVENT RED (5, 16, 17, 18, 18, 19, 22, 23, 143, 145, 146, 149, 150, 151, 157, 158) C.I. I. SOLVENT VIOLET (31, 32, 33, 37) C.I. I. SOLVENT BLUE (22,63,78,83-86,191, 194,195,104) C.I. I. SOLVENT GREEN (24, 25) C.I. I. SOLVENT BROWN (3, 9) and the like are preferable. Commercially available dyes include, for example, Hodogaya Chemical's Aizen SOT dye Y.
ellow-1,3,4, Orange-1,2,3,
Scarlet-1, Red-1, 2, 3, Brown
-2, Blue-1, 2, Violet-1, Green
n-1,2,3, Black-1,4,6,8 and BASF Sudan dye Yellow-146,15
0, Orange-220, Red-290, 380,
460, Blue-670 and Mitsubishi Kasei dialresin Yellow-3G, F, H2
G, HG, HC, HL, Orange-HS, G, Re
d-GG, S, HS, A, K, h, H5B, Viole
t-D, Blue-J, G, N, K, P, H3G, 4
G, Green-C, Brown-A and oil color Yellow-3 of Orient Chemical Industry
G, GG-S, # 105, Orange-PS, Pr,
# 201, Scarlet- # 308, Red-5B,
Brown-GR, # 416, Green-BG, # 5
02, Blue-BOS, IIN, Black-HBB,
# 803, EB, EX, Sumitomo Chemical's Sumiplast Blue GP, OR, Red FB, 3B, Yellow FL7
G, GC, Nippon Kayaku Kayaron Polyester Black EX
-SF300, Kayaset Red-B, Blue A-2
R, etc. can be used. Of course, the dye is not limited to the above examples because it is appropriately selected depending on the combination of the polymer particles and the solvent used for dyeing.

After the dyeing step is completed, it is necessary to remove the dispersion stabilizer, residual monomer, ultrafine particles, and undyed dye. Filtration with a filter, centrifugal sedimentation, and liquid cyclone separation may be performed. The dispersion stabilizer is substantially removed by this treatment, and the triboelectric chargeability is hardly affected. If the obtained product is in the form of a moist cake, it is dried in a rotary kiln, a vibration fluidized dryer or the like, and if it is in the form of a slurry, a spray dryer, a fluidized bed dryer or the like can be used. By mixing the charge control agent, the releasability improving agent, and the fluidity improving agent with the slurry or the cake during drying, the particles can be uniformly attached to the surface of the particles.

The dry dyeing polymer particles obtained as described above are mechanically driven with a charge control agent, if necessary, on the surface thereof. As a method of driving, the colored polymer particles and the charge control agent are mixed in advance, and then mechanical energy is applied to fix the charge control agent on the surface of the colored polymer particles. Any mixing method such as a ball mill, a V blender, or a Henschel may be used. As a method of applying mechanical energy, a method of applying an impact force to the mixture by a blade rotating at a high speed, a method of injecting the mixture into a high-speed air stream to accelerate the particles and colliding the particles with each other or a suitable collision plate, etc. There is. Specifically, as a mounting, MechanoFusion (Hosokawa Micron Co., Ltd.), mill type (Nippon Pneumatic Mfg. Co., Ltd.)
Examples thereof include a device for reducing the crushing air pressure, a hybridization system (Nara Machinery Co., Ltd.), and an automatic mortar. Further, in addition to mechanical energy, auxiliary energy may be applied to provide thermal energy.

The charge control agent is preferably one which becomes a primary particle of 1 μm or less after the above treatment. In addition, if a part of the polymer and heat are fused on the surface, the charge control agent will separate from the toner surface during running, and will move to the drum or the carrier of the two-component developer, or the sleeve in the one-component development process. Therefore, a long-life toner with high durability can be expected. The ratio of the charge control agent to the colored polymer particles may ideally cover the surface monomolecularly, but is usually 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight (colored polymer. Used (for 100 parts of particles).

Examples of the charge control agent in the present invention include the following. Nigrosine, carbon number 2-16
Azine dyes containing alkyl groups (Japanese Patent Publication No. 42-162)
No. 7), basic dyes [eg C.I. I. Basic
Yellow 2 (C.I. 41000), C.I. I. B
asic Yellow 3, C.I. I. Basic R
ed 1 (C.I. 45160), C.I. I. Basic
Red9 (C.I. 42500), C.I. I. Basi
c Violet 1 (C.I. 42535), C.I.
I. Basic Violet 3 (C.I. 4255
5), C.I. I. Basic Violet 14 (C.
I. 42520), C.I. I. Basic Blue 1
(C.I. 42025), C.I. I. Basic Blu
e 3 (C.I. 51005), C.I. I. Basic
Blue 5 (C.I. 42140), C.I. I. Bas
ic Blue 7 (C.I. 42595), C.I. I.
Basic Blue 9 (CI.52015),
C. I. Basic Blue 24 (C.I. 5203
0), C.I. I. Basic Blue 25 (C.I.
52025), C.I. I. Basic Blue 26
(C.I.44045), C.I. I. Basic Gre
en 1 (C.I. 42040), C.I. I. Basic
Lake pigments of these basic dyes, such as Green 4 (C.I. 42000), (as a laker,
Phosphotungstic acid, phosphomolybdic acid, phosphotungstic molybdic acid, tannic acid, lauric acid, gallic acid, ferricyanide, ferrocyanide, etc., C.I. I. So
Vent Black 3 (C.I. 26150), Hansa Yellow G (C.I. 11680), C.I. I. Mor
drant Black 11, C.I. I. Pigmen
t Black1, benzolmethyl-hexadecyl ammonium chloride, decyl-trimethyl ammonium chloride, or dialkyltin compounds such as dibutyl or dioctyl, dialkyltin borate compounds,
Polyamine resins such as guanidine derivatives, amino group-containing vinyl polymers and amino group-containing condensation polymers, JP-B-41-20153 and 43-27596
Nos. 44-6397 and 45-26478, and metal complex salts of monoazo dyes. JP-B-55-42
752, Japanese Patent Publication No. 58-41508, Japanese Patent Publication No. 58-7
No. 384, Japanese Patent Publication No. 59-7385, salicylic acid, dialkyl salicylic acid, naphthoic acid, metal complexes of Zn, Al, Co, Cr, Fe and the like of dicarboxylic acids, sulfonated copper phthalocyanine pigments and the like.

In the present invention, it is also possible to further mix a fluidizing agent with the toner in which the charge control agent has been injected. In this case, as the fluidizing agent, known ones such as titanium oxide, hydrophobic silica, zinc stearate, magnesium stearate and the like are used. As a mixing method, V
A general mixing device such as a blender or a ball mill may be used.

If necessary, in order to prevent a phenomenon in which toner particles are aggregated and solidified during storage and to provide a protective film, fine resin particles having a relatively high Tg, such as PMMA (polymethyl methacrylate) and PTFE. (Polytetrafluoroethylene), PVDF (polyvinylidene fluoride) submicron fine particles, polyolefins, fatty acid esters, fatty acid metal salts, higher alcohols, paraffin waxes and the like as well as the charge control agent can be driven into the surface It is possible, but at that time, it is important to make the particles fine by means such as recrystallization, pulverization and emulsification.

[0040]

【Example】

1. Production of Polymer Particles Examples 1 to 3 and Comparative Example 1 A sealable reaction container equipped with a stirring blade, a cooling condenser, nitrogen gas, and an introduction pipe was installed in a constant temperature water tank, and 100 parts by weight of methanol and polyvinyl were added to the reaction container. Pyrrolidone (5 parts by weight) was squeezed in, and the stirring blade was rotated to completely dissolve polyvinylpyrrolidone. After that, the inside of the container was replaced with nitrogen gas, and the following materials were charged. Example 1: Styrene 22 parts by weight Methyl acrylate 14 parts by weight Ethyl acrylate 4 parts by weight Example 2: Styrene 20 parts by weight Methyl acrylate 18 parts by weight Ethyl acrylate 2 parts by weight Example 3: Styrene 26 parts by weight Acrylic acid Methyl 12 parts by weight n-butyl acrylate 2 parts by weight Examples 1-3 Divinylbenzene 0.4 parts by weight tert-dodecyl mercaptan 0.2 parts by weight Azobisisobutyronitrile 0.6 parts by weight Polymerization started. 18 from the start of polymerization
After an hour, it was cooled to room temperature to obtain a dispersion liquid. A part of the dispersion is sampled and Coulter Multisizer (100μ
The particle size distribution was measured with a m-aperture tube).

Examples 4 to 5 and Comparative Example 2 A sealable reaction container equipped with a stirring blade, a cooling condenser, nitrogen gas and an introduction pipe was installed in a constant temperature water tank, and 90 parts by weight of methanol and polyvinyl acetate were added to this reaction container. 4 parts by weight was squeezed in, and the stirring blade was rotated to completely dissolve polyvinyl acetate. Then, the inside of the container was replaced with nitrogen gas, and the following composition was charged. Example 4: Styrene 24 parts by weight Methyl acrylate 14 parts by weight n-Butyl acrylate 2 parts by weight Example 5: o-Methylstyrene 22 parts by weight Methyl acrylate 14 parts by weight Ethyl acrylate 4 parts by weight Comparative Example 1: Styrene 28 parts by weight 2-ethylhexyl acrylate 10 parts by weight n-butyl methacrylate 2 parts by weight Examples 4 to 5 and Comparative Example 2: 1,3-butanediol dimethacrylate 1.2 parts by weight tert-dodecyl mercaptan 0.2 parts by weight The temperature in the partial water tank was raised to 50 ° C., and 10 parts by weight of methanol and 0.6 parts by weight of azobisisobutyronitrile were added, whereby polymerization started immediately. Two hours after the initiation of polymerization, the temperature was raised to 65 ° C. to increase the reaction rate. After 6 hours, 0.2 part by weight of 1,3-butanediol dimethacrylate and 1 part by weight of methanol were added. After 24 hours from the start of the reaction, it was cooled to room temperature to obtain a dispersion liquid. A part of the dispersion was sampled and the particle size distribution was measured with a Coulter Multisizer (100 μm aperture tube). The results are shown in Table 1. Table 1
Where dv is the volume average particle diameter, dn is the number average particle diameter, and d
v / dn shows a particle size distribution.

2. Toner Production 130 parts by weight of each dispersion was placed in a flask, and 2.4 parts by weight of Oil Black HBB (manufactured by Orient Chemical Co., Ltd.) and 0.6 parts by weight of Oil Orange 201 (manufactured by Orient Chemical Co., Ltd.) were gradually added while stirring with a stirrer. Was added to. The stirring was continued for 24 hours at room temperature. The dyeing solution was passed through a 75 μm filter to remove aggregates of undissolved dye.
After that, the dyeing solution is subjected to centrifugal sedimentation, the supernatant is removed, and redispersion is carried out 3 times in a mixed solvent of 50 parts by weight of methanol and 50 parts by weight of distilled water, filtered, air-dried and dried under reduced pressure at 30 ° C. for 5 hours. Thus, polymer particles colored in black were obtained. After that, for Examples 1 to 3 and Comparative Example 1, the polymer and 1.3 parts by weight of zinc 3,5-tert-butylsalicylate were stirred in an Auster blender for 3 minutes and then converted into a hybridization system NHS-1 type. 7,000 rp
It was processed for 5 minutes.

3. Evaluation method 1) Fixing temperature 3 parts by weight of toner and 97 parts by weight of carrier are mixed with stirring to form a developer, and the fixing temperature (fixing roll surface temperature) of a copying machine (Ricoh Imagio 40) is changed to obtain a fixed image. It was The black solid portion of this fixed image was rubbed with a sand eraser 5 times (by a clock meter), and the temperature at which the reflection density was 0.8 or more was taken as the fixing temperature. 2) Offset resistance Using a copying machine in which silicone oil was removed from the fixing section, a fixed image was obtained in the same manner as in 1), and it was examined whether there was image stain due to offset. 3) Black solid part (2 cm x 3) of the image at the fixing temperature obtained in the vinyl chloride mat resistance 1)
(cm) was sandwiched between vinyl chloride mats and left at 30 ° C. for 3 hours under constant pressure. After that, the image was separated from the vinyl chloride mat and it was examined whether the toner was fused.

4. Evaluation results of Evaluation Examples 1 to 5 and Comparative Example 1 are shown in Table 1.
All the fixed images were images with good resolution and halftone reproducibility.

[Table 1]

[0045]

The toner for developing an electrostatic charge image of the present invention produced as described above can be fixed at a low temperature, is excellent in offset resistance and vinyl chloride resistance, and has a narrow particle size distribution, resolution and halftone. High quality images with good reproducibility can be obtained.

Claims (3)

[Claims] 1. A toner for developing an electrostatic charge image, which comprises polymer particles and a colorant as main components, wherein the polymer particles are styrene or styrene derivative methyl acrylate and other vinyl monomers produced by dispersion polymerization. A toner for developing an electrostatic charge image, which is a copolymer particle of 2. The toner for developing an electrostatic charge image according to claim 1, wherein the other vinyl monomer is an acrylic or methacrylic acid ester other than methyl ester. 3. The electrostatic image developing toner according to claim 1, wherein the other vinyl monomer is an ester of acrylic or methacrylic acid and an alcohol having 2 to 4 carbon atoms.