JPH03119364A - Toner for developing electrostatic charge image - Google Patents

Abstract

PURPOSE:To obtain a positively chargeable toner having superior stability, color reproducibility and transparency by incorporating a specified imidazole- metal complex compd. CONSTITUTION:An imidazole-metal complex compd. represented by formula I or II is incorporated. In the formulae I, II each R1-R6 is H, alkyl, etc., M is a metal such as Fe or Co, X is halogen or a monovalent ionic residue and n is an integer such as 2 or 4. The imidazole-metal complex compd. is used as an electric charge controlling agent, is applicable to a pulverized toner, a suspension-polymerized toner, etc., and may be incorporated into the toner or fixed on the surface of the toner. A positively chargeable color toner ensuring a stable uniform quantity of electric charges and having superior color reproducibility and transparency can be obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a new toner for developing electrostatic images in electrophotography, electrostatic recording, electrostatic printing, etc., more specifically, a toner with excellent positive chargeability. Regarding.

PRIOR ART AND ITS PROBLEMS Development of electrostatic latent images involves electrostatically applying negatively or positively triboelectrically charged toner to an electrostatic latent image having a positive or negative charge formed on a photoreceptor using various methods. The developed image is then fixed by transferring and fixing the toner image onto the transfer paper. This toner is first required to have an appropriate amount of charge in order to obtain a clear developed image without fogging or the like. Furthermore, it is also required that the amount of charge does not change over time, and that changes such as significant attenuation or solidification of the amount of charge do not occur due to environmental changes, such as changes in humidity. This is because when the amount of charge attenuates from the initially set value and becomes smaller, toner scattering increases, causing problems such as background fog, toner scattering on blank areas, and toner stains around the developing device. It is.

In order to meet the above requirements, a charge control agent is usually added during toner production, but in recent years color toners have become more popular, and a white or pale yellow charge control agent with excellent color reproducibility is required.

Colorless, white, or pale yellow negative charge control agents that impart a negative charge are commercially available and are highly effective, and there are no practical restrictions on the use of these control agents. However, positive charge control agents that impart a positive charge, especially those that can be used in color toners, are colored nigrosine dyes, white quaternary ammonium salts, or imidazole compounds (Japanese Patent Laid-Open No. 6
2-287262, JP-A No. 61-259265, JP-A No. 59-187350, etc.), but the types thereof are very small.

Nigrosine dyes do not consist of a single pure compound, but are a mixture of several compounds, and their exact composition is unknown, which poses a problem as they cannot always be expected to have the same level of functionality.

In addition, nigrosine dyes function effectively in imparting a stable charge to toner used in copiers that use medium-to-low copying speeds; Even if it is applied directly to toner for machines, the above function cannot be obtained. Regarding color toners, there are also problems in applying nigrosine dyes because they are colored.

Quaternary ammonium salts have problems such as unstable charging performance and environmental stability, large particle size and inability to dissolve during fixing, and odor. Also, quaternary ammonium salts, like nigrosine dyes, have insufficient charging performance.

Examples of imidazole compounds include diorganotinbisimidazole (JP-A-62-28726) represented by the following formula;
2), 2-aminobenzimidazoles represented by the following formula (Japanese Unexamined Patent Publication No. 61-217055), the charge control agent disclosed in this order is also an imidazole compound, It is completely different from the above compounds.

Problems to be Solved by the Invention As described above, there are only a few positive charge control agents that impart a positive charge, and colorless or light-colored ones that are particularly suitable for color toners are desired.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a positively charged toner having excellent charge build-up, stability, and environmental resistance.

Another object of the present invention is to provide a positively charged toner that has excellent color reproducibility and excellent translucency.

Means for Solving the Problems The present invention is based on vinyl imidazoles represented by the following general formula [I] (JP-A-59-18
7350) etc. are known.

R.

[In the formula, R8, R7 and R1 represent a hydrogen atom, an alkyl group, an aralkyl group or an aryl group, and may be the same or different; M is Fe, Co, N
i, Cu or H, represents a metal; M
When M is Cu5CO, it is 2.4 or 6, and when M is Hg, it is 2. ] or the following general formula [■]; R1 [wherein R3 and R1 are a hydrogen atom, an alkyl group,
Aralkyl group or I; represents an aryl group, which may be the same or different, and M is Fe, Co,
Represents the metal Ni5Cu or H. The present invention relates to an electrostatic charge developing toner characterized by containing an imidazole metal complex compound represented by J.

One-stitch margin II] O, l: bi [11] Medium, R,, R,, R1
, R4vR6 and R6 are a hydrogen atom, a C3 to C3S alkyl group (which may be branched), an aralkyl group such as benzyl or phenethyl, or an aryl group such as a phenyl group, and may be the same or different. Good too.

X represents a halogen atom or a monovalent ionic residue such as nitric acid or acetic acid.

n represents an integer of 2.4 or 6; when M is Fe5Ni, n is 2 or 4; when M is Cu or Go, n is 2.4
or 6, when M is Hg, n is 2.

The imidazole metal complex compound of the present invention is useful as a charge control agent for toners, and is particularly used as a charge control agent for positively chargeable toners.

Of course, the imidazole metal complex compound represented by the general formula [I] and the imidazole metal complex compound represented by Itsuzushiro III] may be used simultaneously.

The imidazole metal complex compound represented by the general formula [I] is represented by the following general formula [■]; R.

An imidazole compound represented by [formula, R1, R2 and R1 are the same as above] and MX, a metal salt represented by [M, X are the same as above] are dissolved and mixed in a solution such as ethanol or acetone, It can be synthesized by concentrating the reaction system. ] The imidazole metal complex compound represented by the general formula [II] can be obtained by superheating the imidazole metal complex represented by the general formula [I], or by combining the imidazole compound represented by the general formula [111] with MX. It can also be synthesized by dissolving the expressed metal salt in a solution such as ethanol or acetone and heating under reflux for a long period of time.

The imidazole metal complex compounds represented by the general formulas [I] and [II] of the present invention are exemplified below, but are not limited thereto.

In addition to the above-mentioned imidazole metal complex compounds of the present invention, known compounds may be used, such as those described in Journal of the Chemical Society of Japan (2), pages 216 to 22
It is also possible to use compounds described in, for example, P. 0, 1981.

The imidazole metal complex represented by the general formula [1] or [11] can be applied as a charge control agent to known toners such as pulverization toners, suspension polymerization toners, capsule toners, and the like. The imidazole metal complex represented by the general formula [I] or [111] may be contained inside the toner, or may be attached and fixed on the surface of the toner.

When contained inside, in addition to additives such as colorants, the imidazole metal complex charge control agent of the present invention is added,
Pulverized toner, suspension polymerized toner, capsule toner, etc. may be prepared by a conventional method.

In the case of a capsule toner, it is desirable to prepare the toner so that the outer shell layer contains the charge control agent.

In addition, in the embodiment in which the charge control agent is attached to the surface of the outer shell layer, the charge control agent may be attached to the above-mentioned toner surface by the action of van der Waals force and electrostatic force, and then fixed by mechanical impact force or the like. good.

Examples of devices that can be suitably used in such a method include a hybridization system that applies a high-speed air impact method (manufactured by Nara Kikai Seisakusho Co., Ltd.), Ong Mill (manufactured by Honkawa Micron Co., Ltd.), Mechanomill (manufactured by Kaida Seiko Co., Ltd.), etc. There is. However, it is of course not limited to this method.

Content of imidazole metal complex represented by general formula [I] or [111 (total amount if used simultaneously)
depends on the type of toner, toner additives, type of binder resin, etc., and the toner development method (two-component or one-component).
Should it be selected appropriately based on etc.? When it is contained inside the toner by pulverization method, suspension method, etc., toner constituent resin 1
0.1 to 20 parts by weight, preferably 1-
It has a 10-layer lid. If the amount is less than 0.1 part by weight, the desired amount of charge cannot be obtained, and if it is more than 20 parts by weight, the amount of charge becomes unstable and the fixing performance deteriorates.

When using the imidazole metal complex by adhering and fixing it to the toner surface, o, o
It is used in an amount of ot-to parts by weight, preferably 0.05 to 2 parts by weight, more preferably 0.1 to 1 parts by weight. If it is less than 0.001 part by weight, the amount of charge control agent present on the surface of the toner particles is small, resulting in insufficient charging, and if it is more than 10 parts by weight, the adhesion of the charge control agent to the toner surface will be insufficient. Peeling of the charge control agent from the toner surface becomes a problem during use. When a charge control agent is attached and fixed on the toner surface, a stable charge amount can be imparted by using a very small amount as described above.

When the imidazole metal complex represented by the general formula [I] or [I[] is contained inside the toner, 5 μI
Hereinafter, the particle size is preferably 3 μm or less, more preferably 1 μm or less. If a particle size larger than 5 μm is used, the dispersion state becomes non-uniform, and the characteristics of the amount of charge become non-uniform. When the imidazole metal complex is attached to the toner surface, it is used in a particle size of 1 μm or less, more preferably 0.5 μm or less. If a particle size larger than 1 μm is used, it is disadvantageous in terms of uniform adhesion and fixation to the toner surface.

The charge control agent imidazole metal complex of the present invention may be used in combination with other positive charge control agents. Further, in order to stabilize the charging property, a very small amount of a negative charge control agent may be added. When the charge control agent of the present invention is used in combination with other charge control agents as described above, the total amount thereof should be within the above-mentioned usage range.

As the positive charge control agent, for example, Nigrosinbase EX
(manufactured by Orient Chemical Industry Co., Ltd.), quaternary ammonium salt P
-51 (manufactured by Orient Chemical Industry Co., Ltd.), Nigrosine, Bontron N-01 (manufactured by Orient Chemical Industry Co., Ltd.), Sudan Chief Schwarz BB (Solvent Black 3: Co
for Index 26150), 7 Etschwarz HBN (C, I, No, 26150), Brilliant Spirits Schwarz TN (Farben, manufactured by Fabricken-Beyer), Zabon Schwarz X (manufactured by Farperke-Hoechst), and further alkoxylated amines, Alkylamide, molybdate chelate pigments, etc. are mentioned, and examples of negative charge control agents include Oil Black (Color Index 26150), Oil Black BY (manufactured by Orient Chemical Industry Co., Ltd.), Bontron S-
22 (manufactured by Orient Chemical Industry Co., Ltd.), salicylic acid metal rust E-81 (manufactured by Orient Chemical Industry Co., Ltd.), thioindigo pigment, sulfonylamine derivative of copper phthalocyanine, Spiron Black TRH (manufactured by Hodogaya Chemical Industry Co., Ltd.), Bontron S -34 (manufactured by Orient Chemical Industry Co., Ltd.), Nigrosine SO (manufactured by Orient Chemical Industry Co., Ltd.), Ceres Schwarz (manufactured by Orient Chemical Industry Co., Ltd.)
R) G (manufactured by Falpen-7 Abriken Haiya), Chromogenschwarz ETOO (C.

1, No. 14645), Azo Oil Black (R) (
(manufactured by National Aniline), etc.

The resin constituting the toner is not particularly limited as long as it is commonly used as a binder in toners, such as styrene obtained by polymerizing the monomers shown below. based resin, (
Thermoplastic resins such as meth)acrylic resins, olefin resins, amide resins, carbonate resins, polyethers, polysulfones, polyester resins, epoxy resins, or urea resins, urethane resins, epoxy resins, etc. Thermosetting resins, copolymers and polymer blends thereof, and the like are used. The synthetic resin used in the toner for developing electrostatic latent images of the present invention is not limited to one in a complete polymer state, such as a thermoplastic resin, but also an oligomer or a prepolymer, such as a thermosetting resin. It is also possible to use polymers containing a prebolimer, a crosslinking agent, etc. in a part of the polymer.

Specifically, the seven polymers constituting the resin used in the present invention are listed below. That is, examples of vinyl styrene include styrene, 0-methylstyrene, m-methylstyrene, p-methylstyrene, p-ethylstyrene, 2,4-dimethylstyrene,
p-n-butylstyrene, p-tart-butylstyrene, p-n-hexylstyrene, p-n-octylstyrene, p-n-nonylstyrene, p-n-decylstyrene, p-n-dodecylstyrene, p-n- Methoxystyrene, p-7 enylstyrene, p-chlorostyrene, 3.4
-': Examples include styrene and its derivatives such as chlorstyrene, among which styrene is most preferred. Examples of other vinyl monomers include ethylene, ethylenically unsaturated monoolefins such as propylene, butylene, and isobutylene, vinyl halides such as vinyl chloride, vinylidene chloride, vinyl bromide, and vinyl fluoride, vinyl acetate, Vinyl esters such as vinyl propionate, vinyl benzoate, vinyl butyrate, 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, methyl a-chloroacrylate, methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, propylene methacrylate, n-octinomethacrylate, dodecyl methacrylate, methacrylic acid 2 - σ-methylene aliphatic monocarboxylic acid esters such as ethylhexyl, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, (meth)acrylic acids such as acrylonitrile, methacrylonitrile, acrylamide, etc. Derivatives, vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether, vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone, methyl isopropenyl ketone, N-vinylvirol, N-vinylcarbazole, N-vinylindole, N Examples include N-vinyl compounds such as -vinylpyrrolidone and vinylnaphthalenes.

Monomers for obtaining amide resins include caprolactam; dibasic acids include terephthalic acid, isophthalic acid, adipic acid, maleic acid, succinic acid, cepatic acid, thioglycolic acid, and diamines. is ethylenediamine, diaminoethyl ether,! , 4-diaminobenzene, 1,4-diaminobutane, and the like.

Examples of diisocyanates for obtaining a urethane resin include p-fluorinated diisocyanate, p-xylene diisocyanate, and 1,4-tetramethylene diisocyanate, and examples of glycols include ethylene glycol and diethylene glycol. ,
Examples include propylene glycol and polyethylene glycol.

Examples of diisocyanates used to obtain a urea resin include p-7 22 diisocyanate, p-xylene diisocyanate, and 1,4-tetramethylene diisocyanate, and examples of diamines include ethylene diamine and diaminoethyl. ether, l, 4
-diaminobenzene, 1,4-diaminobutane, and the like.

In addition, examples of amines for obtaining epoxy resins include ethylamine, butylamine, ethylenediamine, l,4-diaminobenzene% 114-diaminobutane, and monoethanolamine, and examples of epoxies include diglycidyl Examples include ether, ethylene glycol diglycidyl ether, bisphenol A diglycidyl ether, and hydroquinone diglycidyl ether.

In addition, as a seven-mer for obtaining a polyester resin, polyol components include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, l,
4-butanediol, 1.3-butanediol, 2.3
-butanediol, 1,5-bentanediol, l, 6
-hexanediol, neopentyl glycol, 2-ethyl l.

3-hexanediol, 2.2.4-trimethyl-1,
3-pentanediono 1,4-bis(2-hydroxymethyl)cyclohexane, 2,2-bis(4-hydroxypropoxyphenyl)propane, bisphenol A
, hydrogenated bisphenol A1, polyoxyethylated bisphenol A, etc., and polybasic acid components include maleic acid, fumaric acid, mesaconic acid, citraconic acid,
Unsaturated carboxylic acids such as itaconic acid, glutaconic acid, 1.2.4-benzenetricarboxylic acid, 1,2.5-benzenetricarboxylic acid, phthalic acid, terephthalic acid, isophthalic acid, succinic acid, adipic acid, malonic acid, Sebacic acid, 1.2.4-cyclohexanetricarboxylic acid L 1
, 2.5-cyclohexanetricarboxylic acid, 1,2.4
-butanetricarboxylic acid, ■, 3-dicarboxy 2-
Examples include saturated carboxylic acids such as methyl-2-methylcarboxyprodone and tetra(methylcarboxy)methane, and acid anhydrides thereof and esters with lower alcohols may also be used. Specifically, for example, , maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, endomethylenetetrahydroheptalic anhydride, tetrachlorophthalic anhydride, tetrabromoheptalic anhydride, dimethyl terephthalate, and the like. In addition, the polyester resin used in the present invention is not limited to the one obtained by polymerizing a combination of one type each of the polyol component and other basic acid component as described above, but it may be one obtained by polymerizing using multiple types of each. In particular, as polybasic acid components, unsaturated carboxylic acids and saturated carboxylic acids, or polycarboxylic acids and polycarboxylic acid anhydrides are often combined.

It is desirable to further add a low molecular weight polyolefin wax to the thermoplastic resin, and the amount thereof is 1 to 10 parts by weight, preferably 2 to 10 parts by weight, per 100 parts by weight of the thermoplastic resin.
It is 6 parts by weight. For these compositions, the general formula of the present invention [
The compound represented by I] exhibits good ability to control positive chargeability and can provide practically sufficient chargeability.

Recently, there has been a demand for technology that allows for even faster copying.
Toners used for such high-speed development need to be improved in their ability to be fixed to transfer paper or the like in a short time and their separability from the fixing roller. Therefore, the homopolymer or copolymer synthesized from the above-mentioned styrene 7thmer (meth)acrylic monomer (meth)acrylate system, or the above-mentioned polyester resin used in high-speed development, has a number average molecular weight. Molecular weight (
Mn), weight average molecular weight (M w ), 2 average molecular weight (
The relationship with Mz) is 1.000≦Mn≦7,000 40≦Mw/Mn≦70 200≦Mz/Mn≦500, and the number average molecular weight (Mn) is further 2.0
It is preferable to use one in which 00≦Mn≦7.000.

In addition, polyester resin is attracting attention as a toner constituent resin due to its PVC resistance, translucency as a translucent color toner, and adhesiveness with OHP sheets, but normally polyester resin has its own characteristics. It exhibits negative chargeability as a toner resin, making it difficult to use as a positively chargeable toner resin. These polyester resins have a glass transition temperature of 55 to 70'C when used in translucent toners! It is desirable to use a linear polyester having a softening point of 80 to 150°C. When used as an oil-less fixing toner, the glass transition temperature is 55 to 80°C and the softening point is 80 to 1.
It is desirable that the gelling component be contained at 50° C. and 5 to 20 wt%. However, the imidazole zinc complex represented by the general formula [11] of the present invention exhibits good positive charge control ability even for such polyester resins, and can impart practically sufficient chargeability.

Further, the imidazole metal complex represented by the general formula [I] or [II] of the present invention is a linear polyester resin (A).
A toner composed of a resin whose main component is a linear urethane-modified polyester (C) obtained by reacting diisocyanate (B) with diisocyanate (B) can also be imparted with a practically good positive charge control ability. Note that the linear urethane-modified polyester referred to herein is a linear polyester resin (A) 1 consisting of dicarboxylic acid and diol, having a number average molecular weight of 1000 to 20000, an acid value of 5 or less, and whose terminal groups are essentially hydroxyl groups. A linear urethane-modified polyester resin obtained by reacting 0.3 to 0.95 mol per mol of diisocyanate (B), and the resin (C)
The main component is one having a glass transition temperature of 40 to 80°C and an acid value of 5 or less. As the dicarboxylic acid, diol and diisocyanate, those mentioned above can be used.

As the colorant contained in the toner for developing electrostatic latent images of the present invention, various organic and inorganic pigments and dyes of various colors as shown below can be used.

That is, examples of black pigments include carbon black, copper oxide, manganese dioxide, aniline black, and activated carbon.

Yellow pigments include yellow lead, zinc yellow, cadmium yellow, yellow iron oxide, mineral fast yellow, nickel titanium yellow, navel yellow naphthol yellow S1 Banzer yellow G, banzer yellow 10G, benzidine yellow 01 benzidine yellow GR, quinoline yellow lake. , permanent NCG, tartrazine lake, etc.

Orange pigments include red yellow lead, molybdenum orange, permanent orange GTR, pyrazolone orange, palkan orange, and industhrene brilliant orange RK.
, Benzidine Orange G.

Examples include Indus Lem Brilliant Orange GK.

Red pigments include red pigment, cadmium red, red lead, mercury sulfide, cadmium, permanent red 4R, resol red, pyrazolone red, watching red, calcium salt, lake red D1 brilliant carmine 6B, eosin lake, rhodamine lake B1 alizarin lake, Examples include Brilliant Carmine 3B.

Examples of violet pigments include manganese violet, 7 asto violet B1 methyl violet lake, and the like.

Examples of blue pigments include navy blue, cobalt blue, alkali blue lake, Victoria blue lake, phthalocyanine blue, metal-free phthalocyanine blue, partially chlorinated phthalocyanine blue, fast sky blue, and industhrene blue BC.

Examples of green pigments include chrome green, chromium oxide, pigment green B1 malachite green lake, and final yellow green G.

Examples of white pigments include zinc white, titanium oxide, antimony white, and zinc sulfide.

Extender pigments include pallite powder, barium carbonate, clay, silica, white carbon, talc, and alumina white.

In addition, various dyes such as basic, acidic, dispersed, and direct dyes include nigrosine, methylene blue, rose bengal,
They include quinoline yellow and ultramarine blue.

These colorants can be used singly or in combination, but in amounts of 1 to 20 parts by weight per 100 parts by weight of the synthetic resin contained in the core particles and the synthetic resin contained in the outer shell layer.
It is desirable to use parts by weight, more preferably 2 to 10 parts by weight. That is, if the amount is more than 20 parts by weight, the fixing properties of the toner will deteriorate, while if it is less than 1 part by weight, the desired image density cannot be obtained. Various pigments and dyes of various colors can be used as shown in the following.

Yellow pigments include C,1,10316 (S7 Tall Yellow S), C,1,1 l710 (Hansa Yellow 10
G), C, 1, l l 660 (Hansa Yellow 5G),
C,1,l l 670 (Banzaero-3G), C,1
, 11680 (Panza Yellow G), C, 1, 11730
() Hansa Yellow GR), C, 1, 11735 (Hansa Yellow A), c, r-11740 (Hansa Yellow RN)
,c,■,12710 (Hansa Yellow R),C,1,1
2720 (pigment yellow), C, 1, 21090
(Benzidine Yellow), c, 1.21095 (Pendidine Yellow G), C, 1,21100 (Benzidine Yellow GR), C-1,2OO40 (Permanent Yellow NC
G), C, 1, 21220 (Vulcan Fast Yellow 5), C, 1, 21135 (Parkan Fast Yellow R
)and so on.

Red pigments include C, 1, 12055 (Stalin ■), e, i, 12075 (permanent orange),
c, r, 12175 (Resol Fast Orange 3GL
), c, r, 12305 (permanent orange GTR
), C, 1, l l 725 (Hansa Yellow 3R), C
,1,21165 (Palcan Fast Orange GG),
C,1,21110 (Benzidine Orange G), C,1
, 12120 (Permanent Red 4R), C, l-1
270 (para red), C, 1,12085 (fire red), C, 1,12315 (brilliant fast scarlet), C, 1,12310 (permanent l/rad F2R), C, il 2335 (permanent red F4R), C , l-12440 (Permanent Red FRL), C, L, 12460 (Permanent Orange FRLL), C, 1, 12420 (Permanent Red F4RII), C, 1° 12450 (Light Fast Red Toner B), C, 1, 12490 (Bermanent Carmine FB), C, 1,15850 (Brilliant Carmine 6B), etc.

Examples of blue pigments include C, 1,74100 (metal-free phthalocyanine blue), C, 1,74160 (phthalocyanine blue), and C,I. 74180 (First Sky Blue) etc.

These colorants can be used alone or in combination. 1 to 10 parts by weight, more preferably 2 to 5 parts by weight, based on 100 parts by weight of the resin contained in the toner particles.
It is preferable to use parts by weight. In other words, 10! This is because if the amount is more than 1 part by weight, the fixing properties and light transmittance of the toner will deteriorate, while if it is less than 1 part by weight, the desired image density may not be obtained.

The toner of the present invention may contain an anti-offset agent in order to improve fixing properties. Various waxes, especially low molecular weight polypropylene, polyethylene,
Alternatively, polyolefin waxes such as oxidized polypropylene and polyethylene are preferably used. Furthermore, these waxes have a number average molecular weight (Mn) of 1000.
-20,000C, and those with a softening point (Ta11) of 80 to 150C are preferred. If the number average molecular weight Mn is too low or the softening point Tm is 80°C or lower, uniform dispersion with the synthetic resin component in the synthetic resin coating layer will not be possible, and only wax will be eluted onto the toner surface, causing the toner to deteriorate. This may not only cause undesirable results during storage or development, but also may cause contamination of the photoreceptor such as filming. In addition, the number average molecular weight exceeds 20,000,
Alternatively, if Tm exceeds 150°C, not only the compatibility with the resin deteriorates, but also the effects of containing wax such as high temperature offset resistance cannot be obtained. Further, from the viewpoint of compatibility, waxes having polar groups are desirable when used together with synthetic resins having polar groups.

A fluidizing agent may be added to the toner of the present invention to improve fluidity. Examples of the fluidizing agent include silica, aluminum oxide, titanium oxide, a mixture of silica and aluminum oxide, and a mixture of silica and titanium oxide. These substances may be added internally.

The toner of the present invention can be applied to both two-component developers and -component developers (magnetic and non-magnetic).

When used as a two-component developer, carrier powders such as ferrite carriers, coating carriers, iron powder carriers, gear carriers having a composite charging surface, and other known carrier powders can be used.

To prepare the toner for developing electrostatic images according to the present invention, the charge control agent according to the present invention is mixed with a thermoplastic resin, a pigment or dye as a coloring agent, and if necessary, a magnetic material, other additives, etc. - Thoroughly mix using a Lumil or other mixer, then melt, mix, and knead using a heat kneader such as a heated roll or kneader to make the resin doors compatible with each other, and disperse or dissolve the pigment or dye in the mixture. After cooling and solidifying, the toner can be crushed and classified to obtain a toner having a desired average particle size.

Alternatively, the material can be obtained by dispersing the material in a binder resin solution and then spray-drying it, or by mixing the specified material with the monomers that should constitute the binder resin to form a suspension and then polymerizing it. A polymerization toner manufacturing method for obtaining a toner, a so-called microcapsule toner consisting of a core material and a shell material, and a method in which the toner is contained in the core material, the shell material, or both can be applied.

Furthermore, it can also be effectively used in a method in which the charge control agent is attached to the surface layer by the action of van der Waals force and electrostatic force, and then fixed by mechanical impact force or the like.

Toners prepared by these methods can be used for developing to visualize electrostatic images in electrophotography, electrostatic recording, electrostatic printing, etc. by any conventionally known means.

[Example 1] (Toner A) Ingredients Parts by weight Styrene-n
-Butyl 100 methacrylate resin (softening point 132°C, glass transition point 60°C) Carbon black 8 (manufactured by Mitsubishi Chemical Corporation: MA#8) Viscoel 550P 5 (manufactured by Sanyo Chemical Industries, Ltd.) After thoroughly mixing the above materials in a ball mill, The mixture was kneaded on three rolls heated to 140°C. After cooling the kneaded material,
It was coarsely ground using a feather mill and further finely ground using a jet mill. Thereafter, air classification was performed to obtain a fine powder with an average particle size of 10 μm. The particles obtained here are referred to as (i).

Furthermore, 0.3 parts by weight of compound (5) as a charge control agent was added to 100 parts by weight of the fine particles obtained here in a Henschel mixer, mixed and stirred at a rotation speed of 1.500 rpm for 2 minutes, and the colorant-containing Fine particles of compound (5) were electrostatically adhered to the surface of the resin particles using a Van der 7 Aarska. Next, treatment was performed for 3 minutes at 6000 rpm using Nara Kikai Hypuridize Simin System NH3-1 model to fix compound (5) on the surface of the colorant-containing resin particles, thereby obtaining toner A.

[Example 2j (Toner B) Ingredients □ Polyester resin 100 (manufactured by Kako Co., Ltd.: Yo7ton NE-382) Brilliant Carmine 6B 3 (C1
15850) Compound (7) (yellow green, fine powder) 4 The above materials were thoroughly mixed in a ball mill, and then kneaded on three rolls heated to 140°C. After the kneaded material was left to cool, it was coarsely ground using a feather mill and further finely ground using a jet mill. Thereafter, air classification was performed to obtain a fine powder with an average particle size of 11 μm.

This obtained fine powder is referred to as toner B.

[Example 3] (Toner C) Ingredients □ Polyester resin 100 (manufactured by Kako Co., Ltd.: NE-1110) Carbon black 8 (manufactured by Mitsubishi Chemical Industries, Ltd.: MA#8) Low molecular weight oxidized polypropylene 3 Viscoll TS-200 (manufactured by Sanyo Chemical Co., Ltd.) Manufactured by Kogyosha) Compound (45)
(White, fine powder) 5 Example 2 (Toner B)
A fine powder with an average particle size of 11 pm was obtained in the same manner as above. This obtained fine powder is referred to as Toner C.

[Example 4] (Toner D) Ingredients Part by weight Polyester resin 100 (manufactured by Kako Co., Ltd.: NE-
382) Phthalocyanine pigment 3 Example 2
Colorant-containing resin particles having an average particle size of 8 μm were obtained in the same manner as above.

Furthermore, 0.3 parts by weight of compound (31) as a charge control agent was added to 100 parts by weight of the fine particles obtained here in a Henschel mixer, and mixed and stirred for 2 minutes at a rotational speed of 1.50 Orpm. The compound (31
) microparticles were deposited electrostatically with Van der 7 Aarska. Next, processing was performed for 3 minutes at 6000 rpm using Nara Machinery Hybridization System NH3-1 model to fix the compound (31) on the surface of the colorant-containing resin particles to obtain toner D.

[Example 51 (1.S.-E) T-monodisperse spherical copolymer of styrene and Loebdell methacrylate obtained by seed weight method (average particle size 6 μm = μm Nigarasity 54°C: Softening point 128
'C, 15% gelling component (toluene insoluble component) 1
00 parts by weight and carbon black (HM made by Mitsubishi Chemical Industries, Ltd.)
A#8) Put 8 parts by weight in a 10Q Hensielmi Giza 1
Mixing and stirring for 2 minutes at a rotation speed of 50 rpm1. Carbon black was attached to the surface of the polymer particles (4).Next, treatment was performed at 6,000 rpm for 3 minutes using a Nara Kikai Hybridization System NH31 model to immobilize carbon black on the surface of the polymer particles.

Furthermore, the above carbon black fully treated polymer particles 1
00 parts by weight and Wi M, A/i B M A (
1: 9) The above except that 10 parts by weight of particles Mp-4951 (manufactured by Soken Kagaku Co., Ltd.: average particle diameter 0°2 μm; glass transition temperature 85°C) were used in the hybridization system at a rotation speed of 800 rpm for 5 minutes. A resin coating layer was formed by the same treatment as (P-I-0) and 1.2 parts by weight of 100 parts by weight of the polymer particles obtained here, and 0.0 parts by weight of fine particles of a positive charge control agent compound (52X blue, fine powder).
5 parts by weight were used to form a carbon black layer, and the same treatment as described above was carried out to fix the fine particles of compound (52) on the surface of C4, resulting in an average particle size of 6-5 i.
' Obtained toner E with ms sphericity of 132 and coefficient of variation of 8%.
-0 [Comparative Example 11 (Toner F) In Example 3 (Toner C), the charge control agent was replaced with compound (45) by 1 degree, and nigrosine-based Bontron N-0R (
Fine particles with an average particle size of 11 μm were obtained in the same manner except that 5 parts by weight (manufactured by Orient Kagaku Kogyo Co., Ltd.) were changed to λ. The obtained fine particles are referred to as toner F.

[Comparative Example 2] (Toner G) In Example 3 (Toner C), the charge control agent and 1. Particles with an average particle size of 11 were obtained in the same manner except that 5 parts by weight of a 2-aminobenzimidazole compound having the following structural formula was used instead of compound (45). The fine particles obtained here are referred to as toner G.

[Example 6] 0ner H) Ingredients Parts by weight Thermoplastic styrene acrylic resin 100Mn: 4.200
My: 210.900Mz:
1.323,000 MvI/Mn= 50.2Mz
/Mn: 315 Tg: 62°C Softening point: 11
5℃ Acid value: 25.8・Carbon blank
8 (manufactured by Mitsubishi Chemical Industries, Ltd.: MA#8) - Low molecular weight polypropylene 4 (manufactured by Sanyo Chemical Industries, Ltd.: Viscole 605 P) - Compound (59)
3 A fine powder having an average particle size of 1111 m was obtained in the same manner as in Example 2 (toner B). The fine powder whole toner H obtained here is referred to as.

[Example 7J (Toner I) Ingredients Parts by weight: Thermoplastic polyester 41M fat 100Mn: 3.400
My: 213.400Mz: 1.183.200
My/Mn: 62.8Mz/Mn: 348
Acid value: 16.7 Softening point: 109°C Tg: 64
°C ・Lake Red C5 (manufactured by Dainichiseika Industries, Ltd.) ・Low molecular weight oxidized polypropylene 5 (manufactured by Sanyo Chemical Industries, Ltd.: Viscol TS-200) ・Compound (80)
3 A fine powder having an average particle size of 1 ham was obtained in the same manner as in Example 2 (toner B). The fine powder obtained here is referred to as Toner I.

[Example 8] (1-ner J) - Linear urethane modified polyester resin 100Mn:
4,000Mv: 35,400Mw/Mn:
8.9 Tg: 56°C Acid value: 0.8 - Copper phthalocyanine 5 (manufactured by Dainichiseika Kagyo Co., Ltd.) - Low molecular weight polypropylene 4 (manufactured by Sanyo Chemical Industries, Ltd.: Viscol 605P) - Compound (61)
3 A fine powder having an average particle size of 11 μm was obtained in the same manner as in Example 2 (Toner B). The fine powder obtained here is referred to as Toner J.

Comparative Example 3 A powder with an average particle size of 11 μm was obtained in the same manner as in Example 7, except that 3 parts by weight of Nigrosympers EX (manufactured by Orient Chemical Industries, Ltd.) was used instead of the compound of the present invention. The fine powder obtained here is referred to as toner (K).

[Comparative Example 4] A powder having an average particle size of 11 μm was obtained in the same manner as in Example 8 except that 5 parts by weight of quaternary ammonium salt P-51 (manufactured by Orient Chemical Industry Co., Ltd.) was used instead of the compound in the present invention. . The fine powder obtained here is referred to as toner (L).

[Example 9] Ingredients Parts by weight/Polyester resin 100Mn: 3,400
MW: 213,400Mz: 1.183.2
00 My/Mn: 62.8Mz/lJn: 34
8 Acid value: 16.7 Softening point: 109℃ Tg
: 64℃ ・Oxidized low molecular weight polypropylene 5 (thermal decomposition product of polypropylene, viscosity 140 cps at 160℃, acid value 5) ・Carbon black MA#8 8 (manufactured by Mitsubishi Chemical Industries, Ltd.) The above materials were used to prepare particles (i) Particles with an average particle size of 1002 μm were obtained in the same manner as in the above.

Furthermore, 0.3 parts by weight of compound (66) as a charge control agent was added to 100 parts by weight of the fine particles obtained here in a Henschel mixer, mixed and stirred at a rotation speed of 1,500 rpm for 2 minutes, and the colorant-containing A compound (66
) microparticles were attached by van der Waals forces and electrostatically. Next, treatment was performed at 6000 rpm for 3 minutes using Nara Kikai Hybridizer 3 System NHS-1 model to fix the compound (66) on the surface of the colorant-containing resin particles to obtain toner M.

[Comparative Example 51 In Example 9, the charge control agent treated on the particle surface was replaced with compound (66), and nigrosine dye Pontron N-
01 (manufactured by Orient Chemical Industry Co., Ltd.) A toner N having an average particle size of 1003 μm was obtained using the same composition and method except that the amount was 0.3 parts by weight.

[Example 10] 100 parts by weight of colorant-containing resin particles with an average particle size of 8 μm similar to Example 4 and MMA/iBMA (1:9) particles M
15 parts by weight of P-4951 (manufactured by Soken Kagaku Co., Ltd.; average particle size 0°2 μm, glass transition temperature 85°C) and 1 part by weight of the compound (71) according to the present invention were placed in a Nara Kikai 0, M, dizer and heated at 1200 rpm. After mixing and stirring at the rotational speed for 2 minutes,
Processing was performed for 5 minutes at a rotation speed of 8000 rpm using Nara Machinery Hybridization System NH3-1 type to form a resin coat layer containing a charge control agent compound (71), which was designated as toner O.

[Example 11 and Example 12] The thermoplastic resin used in Example 6 was
In, Thermoplastic styrene/acrylic resin Mn: 12,800 1h: 178
．． 900Mz: 957,600 My/Mn:
14. OMz/Mn: 75 Tg: 62.3
°C softening point = 127 °C In Example 12, thermoplastic styrene/acrylic resin Mn: 4.800 My: 374,400M
z: 3.321,600 My/Mn: 78Mz
/Mn: 692 Tg: 66.2°C Softening point =
The same composition except that the temperature was changed to 138°C: i.
・Toner P and Toner Q were obtained.

[Manufacture of Carrier] In order to subject the toner to the evaluation described below, a binder type carrier was manufactured as follows.

Ingredients Parts by weight: Polyester resin 100 (manufactured by Kakosha: NEi)
llO) ・Inorganic magnetic powder 500 (manufactured by Toda Kogyo Co., Ltd., EFT-1000) ・Carbon black 2 (manufactured by Mitsubishi Kasei Co., Ltd., MA#8) The above materials were thoroughly mixed with a Henschel mixer and pulverized 1
/, then cylinder part 180℃, cylinder head part 1
The mixture was melted and kneaded using an extrusion kneader set at 70°C. After cooling, the kneaded material was finely pulverized using a diene l-mill and then classified using a classifier to obtain a magnetic carrier having an average particle size of 55 μm.

E Particle Size Measurement] The particle sizes of toner and carrier were measured as follows.

(1) Carrier particle size The carrier particle size is Microtrack model 7995-1.
0sRA (manufactured by Nikkiso Co., Ltd.) was used to measure the average particle size.

(2) Toner Particle Size The average particle size of the toner was determined by measuring the relative weight distribution by particle size with a 100 μm aperture tube using a Coulter Counter (manufactured by Coulter Counter).

Examples 1 to 12 and Comparative Example 1 thus obtained
Toners A-Q of No. 5 to No. 5 were evaluated for their properties as described below. In addition, colloidal silica R-972 (manufactured by Nippon Aerosil Co., Ltd.) is added to each toner ioo weight part.
:O, 1 part by weight was post-treated and used for evaluation of the properties of the material.

Charge amount (Q/M) and scattering amount Here, 2 g of surface-treated toner and the above carrier 2
Put it in an 8g and 50cc plastic bottle and put it on a rotating stand for 120
In order to investigate the rise in the charge amount of the toner when rotated at Orpm, the charge amount was measured after stirring for 10 minutes.
We also investigated the amount of scattering at that time. In the same way, put the toner and carrier in a plastic bottle, and store it at 35°C and 85% relative humidity.
After storage for 4 hours, the amount of charge and the amount of scattering were measured, and the moisture resistance was also investigated.

The amount of scattering was measured using a digital dust meter model P5H2 (manufactured by Shibata Chemical Co., Ltd.). The dust meter and the magnet roll are
After setting 2g of developer on this magnet roll, set the magnet at a distance of 2000cm.
The dust meter reads the toner particles generated when rotating at rpm as dust, and calculates the number of counts per minute ep.
Display in m.

If the amount of scattering obtained here is 300epm or less, ○, 500
If it is less than 500 cpm, it is △, if it is more than 500 cpm, it is 3.
A graded evaluation was performed. A rank of △ or higher is practically usable, but a rank of O is desirable. Table I shows the measurement results of the amount of charge and the amount of scattering.

A two-component developer was prepared by mixing a predetermined toner shown in Image Output Evaluation Table 1 and the above carrier at a toner/carrier ratio of 7/93. Using this developer, Examples 1 to 12 and Comparative Example 1
~5, EP-4702 (system speed 18c
m/sec; manufactured by Minolta Camera Co., Ltd.) to perform various image evaluations shown in Table 1 (However, Examples 2.4 and 1
For 0, the fixing device of EP-4702 (manufactured by Minolta Camera Co., Ltd.) was improved to an oil coating method.1. ).

(2) Fog on images As described above, images were printed using the above-mentioned copying machine using various toner and carrier combinations.

Regarding the fog on the image, the toner fog on a white background image was evaluated and ranked. A rank of Δ or higher is practically usable, but a rank of 0 or higher is desirable.

2) Printing life test Using a chart with a B/W ratio of 6%, a printing durability test of 10,000 sheets was conducted to evaluate the image and fog.

The results are shown in Table 1. In the table, ◯ indicates a practically usable range, and X indicates a range that poses a practical problem.

3) Light Transmission A light transmission test was also conducted for Examples 2.4 and 1O.

Translucency was evaluated by visually observing the vividness of the color in the projected image when the fixed image on the OHP sheet was projected using an OHP projector. The results are shown in Table 1. In the table, ○ means a practically usable range in terms of color reproduction.

Humidity Test After storing the EP-4702 device at 35° C. and high humidity of 85% (relative humidity) for 24 hours, image evaluation, charge amount and scattering amount measurement were performed.

The results are shown in Table 1. The symbols in the table have the same meanings as explained in each evaluation above.

High-speed fixing properties Examples 6.7.9.118 and 12 were evaluated for high-speed fixing properties as follows.

Temperatures at which high-temperature offset and low-temperature offset occur when toner is fixed at a speed of 45c++I/see using a fixing device consisting of a 60mm fixing roller coated with Teflon-based resin and an LTV rubber roller pressed under it with a pressure of 100 kg. The fixing strength of 101.28 and ID0.6 when fixed at 175° C. was determined.

High-temperature offset is a phenomenon in which the toner in contact with the hot roll melts and softens, and the toner adhering to the roller is transferred to the copy paper during the second rotation.On the other hand, low-temperature offset is a phenomenon in which the toner is not sufficiently melted by the hot roll. Since only the surface was melted, there was almost no fixation on the paper and the toner adhering to the hot roll was
This is a phenomenon in which the image is transferred to the copy paper as it rotates.

ID is a value of image density measured with a Sakura reflection densitometer.

A strength of 80% or more is required for ID1.2 and 70% or more for ID0.6. Further, the non-offset width needs to be 100°C or more.

To measure the fixing strength, the toner image is erased by rubbing the copied image with a device with a load of 1 kg placed on sand and poppy rubber.

At this time, the ratio of the reflected temperature before and after rubbing with sand poppy rubber is 10
Expressed as a percentage of 0.

In the above evaluation O What cannot be used × It was expressed as

(Hereinafter, blank space) Effects of the Invention The toner containing the imidazole metal complex of the present invention shows a stable and uniform charge amount, and even when used continuously for a long time, it does not cause toner aggregation, fogging on images, toner scattering, etc. Does not occur.

By using the imidazole metal complex of the present invention, even a toner composed of a negatively chargeable resin can be used with a positive charge without impairing the above-mentioned effects.

According to the present invention, it is possible to obtain a color toner that maintains the above characteristics and has excellent brown color reproducibility or translucency.

The imidazole metal complex of the present invention can also be applied to toners for high-speed development.

Claims (1)

[Claims] 1. The following general formula [I]; ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [I] [In the formula, R_1, R_2 and R_3 represent a hydrogen atom, an alkyl group, an aralkyl group, or an aryl group. and may be the same or different; M is Fe, C
o, represents a metal such as Ni, Cu, or Hg; X represents a halogen atom or a monovalent ionic residue; n represents an integer of 2, 4, or 6, and when M is Fe or Ni,
, M is Cu, Co, 2, 4 or 6, M is Hg
In this case, it is 2. ] Or the following general formula [II]; ▲ Numerical formulas, chemical formulas, tables, etc. ▼ [II] may be different, and M is Fe,
Represents a metal such as Co, Ni, Cu or Hg. ] An electrostatic charge developing toner characterized by containing an imidazole metal complex compound represented by the following.