JP2000131889A - Toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner capable of stably obtaining high quality image even in the case of using the toner under low humidity and not causing any image defect with lapse of time by using a titanium aromatic polycarboxylic acid complex compound. SOLUTION: This toner contains a binder resin and a colorant and an organic metal compound, and this organic metal complex compound is a titanium complex or titanium complex salt containing titanium as a metal atom and as a ligand the aromatic polycarboxylic acid. It is preferred that the binder resin to be used has an acid value of 1-100 mg KOH/g. When the acid value is <1 mg KOH/g, development stability and time lapse stability due to an interaction of the binder resin and the organic titanium compound cannot be fully exhibited and a cross-linking effect is made less probable to occur, and on the other hand, when it exceeds 100 mg KOH/g, the hygroscopicity of the binder resin tends to rise and image density tends to lower, and fog tends to increase.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for forming a toner for visualizing an electrostatic latent image in an image forming method such as electrophotography and electrostatic recording or a toner image in a toner jet type image forming method. For toner.

[0002]

2. Description of the Related Art Toner must have a positive or negative charge, depending on the polarity of the electrostatic latent image to be developed.

In order to make the toner retain electric charge, it is possible to use the frictional charging property of a resin which is a component of the toner. However, in this method, the charging of the toner is not stable.
Density rises slowly and fog is easy. Therefore, a charge control agent is added to impart a desired triboelectric charge to the toner.

At present, as charge control agents known in the art, as triboelectric charge control agents, metal complex salts of monoazo dyes, metal complex salts of hydroxycarboxylic acids, dicarboxylic acids, aromatic diols and the like; Resins containing components are known. Nigrosine dyes, azine dyes, triphenylmethane dyes and pigments, quaternary ammonium salts, and polymers having quaternary ammonium salts in the side chain are known as positive friction charge control agents.

However, most of these charge control agents are colored and many cannot be used for color toners. Most of the colorless, white, or light-colored toners applicable to color toners have insufficient performance. They have drawbacks such as lack of uniformity of highlights and large fluctuations in image density in a durability test.

In addition, some charge control agents have the following disadvantages. It is difficult to balance image density and fog, it is difficult to obtain sufficient image density in a high-humidity environment, poor dispersibility in resin, adversely affects storage stability, fixability, and offset resistance.

Conventionally, metal complexes and metal salts of aromatic carboxylic acids have been disclosed in JP-A-53-127726 and JP-A-57-127726.
JP-A-111541, JP-A-57-124357, JP-A-57-104940, JP-A-61-6
No. 9073, JP-A-61-73963, JP-A-61-267058, JP-A-62-10515
No. 6, JP-A-62-145255, JP-A-62-145255
JP-A-2-163601, JP-A-63-208865, JP-A-3-276166, JP-A-4-84
Some proposals have been made, such as Japanese Patent Application Laid-Open No. 141 and JP-A-8-160668. However,
These publications are all excellent in terms of imparting triboelectric charging.However, with a simple developing device configuration, stable developability can be obtained regardless of environmental changes, aging, and use conditions. There are few things that can be done. Also, there are few high-speed machines that can provide stable developability even during long-term durability. Further, there are many cases in which there is an influence of other raw materials and restrictions on other raw materials occur. At present, none of the above items are satisfactory.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to provide a toner which can stably obtain high image quality even when used under low humidity or under high humidity and does not cause image defects over time. To provide.

SUMMARY OF THE INVENTION It is an object of the present invention to provide a toner which is less likely to generate deteriorated toner even in a simple developing device configuration such as a cartridge type, and which can obtain excellent developability.

[0010]

According to the present invention, there is provided a toner containing at least a binder resin, a colorant and an organometallic compound, wherein the organometallic compound has titanium as a metal element and has a ligand as a ligand. The present invention relates to a toner which is a titanium complex or a titanium complex salt coordinated with an aromatic polycarboxylic acid.

The present inventors have found that by using an aromatic polycarboxylic acid complex compound of titanium, a high charge amount can be obtained even in a high-humidity environment while maintaining a good start-up, and the charge becomes excessive even in a low-humidity environment. Has been found to be able to obtain a toner without any problems.

Furthermore, it has been found that by combining this feature with a magnetic toner containing a magnetic material or by applying it to a one-component developing method, excellent developability can be obtained. That is, the organic titanium compound of the present invention is a suitable negative charge control agent that satisfies these requirements for a magnetic toner or a toner for one-component development that requires a rapid rise of charge at a small frictional charge opportunity and a high charge amount. It is. As described above, it is suitably used for the toner used in the one-component developing method, and is most suitable for the toner used in the non-magnetic one-component developing method. Of course, it can be used for a two-component developer.

Furthermore, in the present invention, when used together with a binder resin having an acid value, the polarity of water molecules can be used to greatly increase the effect of enhancing the charge. Further, by using two or more kinds of waxes having different melting points or different compositions, the dispersibility can be made very good, and the durability and charge uniformity can be improved.

As described above, not only the amount of charge in a low-humidity and high-humidity environment becomes sufficient, but also a decrease in density during long-term durability can be suppressed. The present invention is particularly suitable for a magnetic toner containing a magnetic iron oxide having various different elements. Oxides and hydroxides of different elements, iron oxides incorporating different elements,
Iron oxide in which different elements are mixed crystal adsorbs water molecules, and can effectively enhance charging using the polarity of water molecules. When used together with a binder resin having an acid value, charge enhancement can be performed more effectively.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION In the organic titanium compound of the present invention, oxygen such as a carboxyl group or a hydroxyl group is easily coordinated, and therefore, a carboxyl group or the like is frequently coordinated with a titanium ion. When a binder resin having an acid value such as a styrene-based resin having a carboxyl group as a functional group or a polyester-based resin is used as the binder resin, it can be easily blended into the binder resin, has excellent dispersibility, and falls off from the toner particles. And uniform charging and stable charging durability can be obtained. Further, the influence on the transparency of the toner is reduced, which is preferable for expressing a vivid color for the color toner.

The organotitanium compound of the present invention is excellent in triboelectric charging ability and can obtain a high charge amount, so that it is a suitable charge control agent for a magnetic toner requiring a high charge amount. Furthermore, in addition to the good dispersibility of the organic titanium compound itself, when a binder resin having an acid value is used, the dispersibility of the magnetic material is improved, so that durability and charge uniformity can be obtained. .

Further, it has been found that the organotitanium compound of the present invention has excellent releasability when used with a plurality of kinds of waxes. This makes it possible to obtain a toner that has excellent offset resistance and is effective in preventing contamination of the fixing member. This effect is particularly great when used together with a binder resin having an acid value.

The present invention achieves the object of the present invention by a toner containing a titanium complex or a titanium complex salt of an aromatic polycarboxylic acid. Preferred are titanium complexes or complex salts represented by the general formula (1) or (2).

[0019]

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In the general formulas (1) and (2), R ₁ and R ₂
Is hydrogen, alkyl, aryl, aralkyl, cycloalkyl, alkenyl, alkoxy, aryloxy, hydroxyl, acyloxy, alkoxycarbonyl, aryloxycarbonyl, acyl, carboxyl, halogen, nitro Group, an amino group, or a carbamoyl group, which may be linked to each other to form an aliphatic ring, an aromatic ring, or a heterocyclic ring (that is, the formula (1),
In (2), an aromatic residue is represented by a benzene ring, but the aromatic residue has a naphthalene ring, an anthracene ring, a phenanthrene ring, or the like. ), This case may have a substituent group R _1, R ₂ in the ring, the substituents R _1,
R ₂ may have from 1 to 4 (or more depending on the aromatic residue), and may be the same or different, and L is a neutral ligand, water, alcohol,
Ammonia, alkylamine, pyridine, C
Represents a monovalent cation, hydrogen, an alkali metal, ammonium, or alkylammonium; z represents an integer of 1 to 4 (which may be more depending on the aromatic residue);
The aromatic polycarboxylic acids serving as ligands in each complex or complex salt may be the same or different. From the viewpoint of improving the dispersibility of the complex or complex salt in the binder resin or improving the chargeability, the substituents R ₁ and R ₂ are preferably an alkyl group, an alkenyl group, a carboxyl group, or a hydroxyl group, and L is water. Preferably, C is hydrogen, sodium, potassium, ammonium, or alkylammonium. Particularly preferred is a neutral complex having no tetravalent titanium and having a tetravalent titanium in the case of the general formula (2), which has excellent environmental stability and has good dispersibility in a binder resin. And excellent durability can be obtained.

The organic titanium compound of the present invention is obtained by dissolving titanium trichloride in the case of a trivalent titanium complex compound and titanium isopropoxide in the case of a tetravalent titanium complex compound in water, an alcohol, or an aqueous alcohol solution, It is synthesized by adding an aromatic polycarboxylic acid and an alkali metal salt thereof, or by adding an aromatic polycarboxylic acid and an alkali agent. These organic titanium compounds are recrystallized with an aqueous alcohol solution or the like, and purified by washing with alcohol.
In the case of a complex salt of trivalent titanium, a complex salt having various counter ions can be obtained by treating the product with a mineral acid, an alkali agent, or an amine agent. In the present invention,
Titanium complex salts include those having a plurality of counter ions such as hydrogen ions, alkali metal ions, and ammonium ions.

The following are specific examples of the organic titanium compound used in the present invention. Although the case where two water molecules are coordinated is also included, the description of the water molecules is omitted here. In addition, although the counter ions include those having a plurality of types, only the most common counter ions are described here.

[0023]

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[0024]

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[0025]

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[0026]

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[0027]

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[0028]

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[0029]

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[0030]

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As a method for incorporating the organic titanium compound of the present invention into the toner, there are a method of adding the compound to the inside of the toner and a method of adding the compound externally. As a preferable addition amount in the case of internal addition, 0.1 to 10 parts by weight,
More preferably, it is used in the range of 0.5 to 5 parts by weight. In the case of external addition, the amount is preferably 0.01 to 5 parts by weight, and particularly preferably mechanochemically fixed to the toner surface.

The compounds of the present invention can also be used in combination with known charge control agents as described in the prior art. For example, other organic metal complexes, metal salts, and chelate compounds include monoazo metal complexes, acetylacetone metal complexes, hydroxycarboxylic acid metal complexes, polycarboxylic acid metal complexes, and polyol metal complexes. Other examples include metal salts of carboxylic acids, carboxylic acid derivatives such as carboxylic acid anhydrides and esters, and condensates of aromatic compounds. Further, phenol derivatives such as bisphenols and calixarenes are also used.

Examples of the type of the binder resin used in the present invention include styrene resins, styrene copolymer resins,
Polyester resin, polyol resin, polyvinyl chloride resin, phenol resin, natural modified phenol resin, natural resin modified maleic acid resin, acrylic resin, methacrylic resin, polyvinyl acetate, silicone resin, polyurethane resin, polyamide resin, furan resin, epoxy resin , Xylene resin, polyvinyl butyral, terpene resin, coumarone indene resin, petroleum resin and the like can be used.

Examples of comonomers for the styrene monomer of the styrene copolymer include styrene derivatives such as vinyltoluene; for example, acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, dodecyl acrylate, octyl acrylate, Acrylates such as 2-ethylhexyl acrylate and phenyl acrylate; methacrylates such as methacrylic acid, methyl methacrylate, ethyl methacrylate, butyl methacrylate and octyl methacrylate; for example, maleic acid and maleic acid Dicarboxylic acids having a double bond such as butyl, methyl maleate, dimethyl maleate, etc .; for example, acrylamide, acrylonitrile, methacrylonitrile, butadiene; for example, vinyl chloride, vinyl acetate, benzoate Vinyl esters such as Le;
For example, ethylene-based olefins such as ethylene, propylene, butylene and the like;
Vinyl ketones such as vinyl hexyl ketone; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether and the like;
And the like, alone or in combination of two or more.

As the cross-linking agent, compounds having two or more polymerizable double bonds are mainly used, for example, aromatic divinyl compounds such as divinylbenzene, divinylnaphthalene and the like; for example, ethylene glycol diacrylate, ethylene glycol Dimethacrylate, 1,3-
Carboxylic acid esters having two double bonds such as butanediol dimethacrylate; divinyl compounds such as divinyl aniline, divinyl ether, divinyl sulfide and divinyl sulfone; and compounds having three or more vinyl groups, alone or as a mixture Used as

When the binder resin is styrene-acrylic,
The molecular weight distribution of the toner is a molecular weight distribution of the THF-soluble component by GPC, and at least one peak exists in a region having a molecular weight of 3,000 to 50,000, and at least one peak exists in a region having a molecular weight of 100,000 or more. 5 components with a distribution of 100,000 or less
A binder resin having a content of 0 to 90% is preferable.

In the case where the binder resin is a polyester resin, at least one peak exists in a region having a molecular weight of 3,000 to 50,000 in a similar molecular weight distribution of the toner, and a component having a molecular weight of 100,000 or less has a peak of 60 to 100. % Is preferable. More preferably, at least one peak exists in a region having a molecular weight of 5,000 to 20,000.

The toner containing the organic titanium compound used in the present invention has a small variation in charging characteristics even under a high or low humidity environment, can maintain stable developing characteristics, and uses a binder resin having an acid value. In this case, the dispersibility is very good, and the organic titanium compound is less missing from the toner, so that the durability is excellent.

Further, it has been found that the toner used in the present invention exhibits excellent charging ability in a frictional charging process with a developer carrying member. That is, regarding the charging ability of the toner containing the binder resin having an acid value and the organic titanium compound with the material of the developer carrier, a large amount of charge can be generated even with a small contact with the surface of the developer carrier. all right.

The acid value of the binder resin used in the present invention is 1
mgKOH / g to 100 mgKOH / g, preferably 1 mgKOH / g to 70 mgKOH / g, and more preferably 1 mgKOH / g to 50 mgKOH / g.
mgKOH / g is good, especially 2 mgKOH / g to 4 mgKOH / g.
It is preferably 0 mgKOH / g. When the acid value of the binder resin is less than 1 mgKOH / g, the development stability and the durability stabilization effect due to the interaction with the organic titanium compound cannot be sufficiently exhibited, and the crosslinking effect is hardly exhibited. on the other hand,
If it exceeds 100 mgKOH / g, the binder resin has a high hygroscopicity, and the image density tends to decrease and the fog tends to increase.

In the present invention, the acid value of the entire polymer component of the toner composition is determined by the following method.

<Measurement of acid value> The basic operation is JIS K-0.
070. 1) The sample is used after removing additives other than the polymer component in advance, or the acid value and the content of the component other than the polymer are obtained in advance. 0.5 to 2.0 (g) of the crushed sample is precisely weighed, and the weight of the polymer component is defined as W (g). 2) The sample is placed in a 300 (ml) beaker, and 150 (ml) of a mixed solution of toluene / ethanol (4/1) is added and dissolved. 3) Using an ethanol solution of 0.1 mol / l KOH, titrate with a potentiometric titrator (for example, a potentiometric titrator AT-400 manufactured by Kyoto Electronics Co., Ltd. (win)
workstation) and automatic titration using an ABP-410 motorized burette is available). 4) The amount of the KOH solution used at this time is defined as S (ml), a blank is measured at the same time, and the amount of the KOH solution used at this time is defined as B (ml). 5) Calculate the acid value by the following equation. f is a factor of KOH.

Acid value (mgKOH / g) = ｛(S−B) ×
f × 5.61｝ / W

Examples of the monomer for adjusting the acid value of the polymer component include acrylic acid such as acrylic acid, methacrylic acid, α-ethylacrylic acid, crotonic acid, cinnamic acid, vinyl acetic acid, isocrotonic acid, angelic acid and the like. α
-Or β-alkyl derivatives, fumaric acid, maleic acid,
Citraconic acid, alkenyl succinic acid, itaconic acid, mesaconic acid, dimethyl maleic acid, unsaturated dicarboxylic acids such as dimethyl fumaric acid and monoester derivatives or anhydrides, and such monomers alone or in combination, A desired polymer can be produced by copolymerizing with another monomer. Among them, it is particularly preferable to use a monoester derivative of an unsaturated dicarboxylic acid for controlling the acid value.

More specifically, for example, monomethyl maleate, monoethyl maleate, monobutyl maleate, monooctyl maleate, monoallyl maleate,
Monoesters of α, β-unsaturated dicarboxylic acids such as monophenyl maleate, monomethyl fumarate, monoethyl fumarate, monobutyl fumarate, monophenyl fumarate, etc .; monobutyl n-butenylsuccinate, monomethyl n-octenylsuccinate, Monoesters of alkenyldicarboxylic acids such as monoethyl n-butenylmalonate, monomethyl n-dodecenylglutarate, monobutyl n-butenyladipate, and the like are included.

The above-mentioned carboxyl group-containing monomer may be added in an amount of 0.1 to 20 parts by weight, preferably 0.2 to 15 parts by weight, based on 100 parts by weight of all the monomers constituting the binder resin.

The reason why the monoester monomer of dicarboxylic acid as described above is selected is that it is used in the form of an ester having a low solubility in an aqueous suspension and a high solubility in an organic solvent or another monomer. Is preferred.

In the present invention, the carboxylic acid groups and carboxylic acid ester sites in the copolymer obtained by the above method can be saponified by alkali treatment. That is, a carboxylic acid group or a carboxylic acid ester site may be changed to a polar functional group by reacting with a cation component of an alkali.

This alkali treatment may be carried out after the production of the binder resin, by introducing it as an aqueous solution into the solvent used during the polymerization and stirring. Examples of the alkali that can be used in the present invention include Na, K, Ca, Li, Mg, and Ba.
Hydroxides of alkali metals and alkaline earth metals such as;
There are hydroxides of transition metals such as Zn, Ag, Pb, and Ni; hydroxides of quaternary ammonium salts such as ammonium salts, alkylammonium salts, and pyridium salts. Particularly preferred examples include NaOH and KOH. .

In the present invention, the saponification reaction does not need to be carried out over all of the carboxylic acid groups and carboxylic acid ester sites in the copolymer. I just need to change.

The amount of the alkali used in the saponification reaction is difficult to determine unconditionally depending on the type of the polar group in the binder resin, the dispersion method, the type of the constituent monomers, and the like. What is necessary is just 02-5 times equivalent. When the amount is less than 0.02 equivalent, the saponification reaction is not sufficient, and the number of polar functional groups generated by the reaction decreases, and as a result, the crosslinking reaction by the subsequent saponification becomes insufficient. On the other hand, when the amount exceeds 5 times equivalent, the functional group such as a carboxylic acid ester site is adversely affected by hydrolysis of the ester, generation of a salt by a saponification reaction, and the like.

When the alkali treatment is carried out at an equivalent of 0.02 to 5 times the acid value, the residual cation concentration after the treatment is 5 to 1%.
It is contained between 000 ppm and can be preferably used to regulate the amount of alkali.

From the viewpoint of storage stability, the resin composition according to the present invention has a glass transition temperature (Tg) of 45 to 75 ° C., preferably 50 to 70 ° C .; The toner is liable to be deteriorated, and offset is likely to occur during fixing. On the other hand, when Tg exceeds 75 ° C., the fixability tends to decrease.

As a polymerization method that can be used in the present invention as a method for synthesizing the binder resin of the present invention, there are a solution polymerization method, an emulsion polymerization method and a suspension polymerization method.

Among them, the emulsion polymerization method is a method in which a monomer (monomer) almost insoluble in water is dispersed in an aqueous phase as small particles with an emulsifier, and polymerization is carried out using a water-soluble polymerization initiator. . In this method, the reaction heat can be easily adjusted, and the phase in which the polymerization is performed (oil phase composed of a polymer and a monomer)
And the aqueous phase are separate, so that the termination reaction rate is low, resulting in a high polymerization rate and a high degree of polymerization. Further, due to the relatively simple polymerization process and the fact that the polymerization product is fine particles, in the production of toner,
There is an advantage as a method for producing a binder resin for a toner because it is easy to mix with a colorant, a charge control agent and other additives.

However, the resulting polymer tends to be impure due to the added emulsifier, and an operation such as salting out is required to remove the polymer. To avoid this inconvenience, suspension polymerization is advantageous.

In the suspension polymerization, 100 parts by weight or less of the monomer (preferably 1 part by weight) is added to 100 parts by weight of the aqueous solvent.
(0 to 90 parts by weight). Examples of usable dispersants include polyvinyl alcohol, partially saponified polyvinyl alcohol, and calcium phosphate, and are generally used in an amount of 0.05 to 1 part by weight based on 100 parts by weight of the aqueous solvent. The polymerization temperature is suitably from 50 to 95 ° C., but is appropriately selected depending on the initiator used and the intended polymer.

The binder resin used in the present invention is preferably formed by using a polyfunctional polymerization initiator alone or in combination with a monofunctional polymerization initiator as exemplified below.

Specific examples of the polyfunctional polymerization initiator having a polyfunctional structure include 1,1-di-t-butylperoxy-
3,3,5-trimethylcyclohexane, 1,3-bis- (t-butylperoxyisopropyl) benzene,
2,5-dimethyl-2,5- (t-butylperoxy)
Hexane, 2,5-dimethyl-2,5-di- (t-butylperoxy) hexane, tris- (t-butylperoxy) triazine, 1,1-di-t-butylperoxycyclohexane, 2,2 -Di-t-butylperoxybutane, 4,4-di-t-butylperoxyvaleric acid-n-butyl ester, di-t-butylperoxyhexahydroterephthalate, di-t-butylperoxyazelate , Di-t-butylperoxytrimethyladipate, 2,2-bis- (4,4-di-t-butylperoxycyclohexyl) propane, 2,2-t-
Polyfunctional polymerization initiator having a functional group having a polymerization initiation function such as two or more peroxide groups in one molecule such as butylperoxyoctane and various polymer oxides,
And a functional group having a polymerization initiating function such as a peroxide group in one molecule such as diallyl peroxydicarbonate, t-butyl peroxymaleic acid, t-butyl peroxyallyl carbonate and t-butyl peroxyisopropyl fumarate And a polyfunctional polymerization initiator having both a polymerizable unsaturated group.

Of these, more preferred are 1,1
-Di-tert-butylperoxy-3,3,5-trimethylcyclohexane, 1,1-di-tert-butylperoxycyclohexane, di-tert-butylperoxyhexahydroterephthalate, di-tert-butylperoxyase And 2,2-bis- (4,4-di-t-butylperoxycyclohexyl) propane, and t-butylperoxyallyl carbonate.

These polyfunctional polymerization initiators are preferably used in combination with a monofunctional polymerization initiator in order to satisfy various performances required as a binder for a toner.
In particular, it is preferable to use the polyfunctional polymerization initiator together with a polymerization initiator having a half life of 10 hours lower than the decomposition temperature for obtaining a half life of 10 hours.

Specifically, benzoyl peroxide,
1,1-di (t-butylperoxy) -3,3,5-trimethylcyclohexane, n-butyl-4,4-di (t
-Butylperoxy) valerate, dicumyl peroxide, α, α'-bis (t-butylperoxydiisopropyl) benzene, t-butylperoxycumene, di-t
Organic peroxides such as -butyl peroxide; and azo and diazo compounds such as azobisisobutyronitrile and diazoaminoazobenzene.

These monofunctional polymerization initiators may be added to the monomer at the same time as the polyfunctional polymerization initiator. However, in order to keep the efficiency of the polyfunctional polymerization initiator properly,
It is preferable to add the compound after the half-life of the polyfunctional polymerization initiator has passed in the polymerization step.

These initiators are preferably used in an amount of 0.05 to 2 parts by weight based on 100 parts by weight of the monomer from the viewpoint of efficiency.

In order to achieve the object of the present invention, it is also preferable that the polymer is cross-linked with a cross-linkable monomer as exemplified below.

As the crosslinkable monomer, a monomer having two or more polymerizable double bonds is mainly used. Specific examples include aromatic divinyl compounds (eg, divinylbenzene, divinylnaphthalene, etc.); diacrylate compounds linked by an alkyl chain (eg, ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4 -Butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6
Hexanediol diacrylate, neopentyl glycol diacrylate, and acrylates of the above compounds replaced with methacrylate); diacrylate compounds linked by an alkyl chain containing an ether bond (for example, diethylene glycol diacrylate, triethylene glycol) Diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 400 diacrylate, polyethylene glycol # 600 diacrylate, dipropylene glycol diacrylate, and those obtained by replacing the acrylate of the above compound with methacrylate); Diacrylate compounds linked by a chain containing, for example, polyoxyethylene (2) -2,2-bis (4-hydroxyphenyl) propanediacryle DOO, polyoxyethylene (4) -
2,2-bis (4-hydroxyphenyl) propane diacrylate and those obtained by replacing the acrylates of the above compounds with methacrylates; further, polyester-type diacrylate compounds (for example, trade name MANDA (Nippon Kayaku)) ). As multifunctional crosslinking agents, pentaerythritol acrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, tetramethylolpropane triacrylate, tetramethylolmethanetetraacrylate, oligoester acrylate, and acrylates of the above compounds to methacrylate Alternatives; triallyl cyanurate, triallyl trimellitate; and the like.

These cross-linking agents are used in combination with other monomer components 10
It is preferably used in the range of 0.0001 to 1 part by weight, preferably 0.001 to 0.5 part by weight with respect to 0 part by weight.

Among these crosslinkable monomers, those which are preferably used from the viewpoints of toner fixability and anti-offset properties include aromatic divinyl compounds (particularly divinylbenzene), and a chain containing an aromatic group and an ether bond. Diacrylate compounds.

As other synthesis methods, a bulk polymerization method and a solution polymerization method can be used. However, in the bulk polymerization method, any polymer can be obtained by increasing the termination reaction rate by polymerizing at a high temperature, but there is a problem that the reaction is difficult to control. In this regard, in the solution polymerization method, a low molecular weight polymer can be easily obtained under mild conditions by utilizing the difference in chain transfer of radicals depending on the solvent, and by adjusting the amount of the initiator and the reaction temperature, It is preferable to obtain a low molecular weight compound in the resin composition used in the present invention. In particular, a solution polymerization method under a pressurized condition is also preferable from the viewpoint of minimizing the amount of the initiator used and minimizing the influence of the residual initiator.

The comonomers for obtaining the binder resin of the present invention include the following.

For example, styrene; o-methylstyrene, m
-Methylstyrene, p-methylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, 3,4-dichlorostyrene, p-ethylstyrene,
2,4-dimethylstyrene, pn-butylstyrene,
Styrene derivatives such as p-tert-butylstyrene, p-n-hexylstyrene, p-n-octylstyrene, p-n-nonylstyrene, p-n-decylstyrene, p-n-dodecylstyrene; ethylene, propylene , Butylene, ethylenically unsaturated monoolefins such as isobutylene; unsaturated polyenes such as butadiene and isoprene; vinyl halides such as vinyl chloride, vinylidene chloride, vinyl bromide, and vinyl fluoride; vinyl acetate, vinyl propionate, Vinyl esters such as vinyl benzoate; methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, (2-ethylhexyl) methacrylate, methacryl Stearyl acid Α-methylene aliphatic monocarboxylic esters such as phenyl methacrylate, dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate; methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, propyl acrylate, acryl Acrylic esters such as n-octyl acid, dodecyl acrylate, acrylic acid (2-ethylhexyl), stearyl acrylate, acrylic acid (2-chloroethyl), phenyl acrylate; vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether Vinyl ethers such as; vinyl methyl ketone;
Vinyl ketones such as vinyl hexyl ketone and methyl isopropenyl ketone; N-vinyl compounds such as N-vinyl pyrrole, N-vinyl carbazole, N-vinyl indole, N-vinyl pyrrolidone; vinyl naphthalenes;
Acrylic acid derivatives such as acrylonitrile, methacrylonitrile, and acrylamide or methacrylic acid derivatives are exemplified. These vinyl monomers are used alone or as a mixture of two or more monomers.

Of these, a combination of monomers that will result in a styrene copolymer and a styrene acrylic copolymer is preferred.

Further, the binder resin of the present invention contains at least 65% of a styrene-based polymer component or a styrene-based copolymer component.
It is preferred that the content be at least part by weight from the viewpoint of mixing properties.

As a method for producing a binder resin, a high molecular weight polymer and a low molecular weight polymer are separately synthesized by a solution polymerization method, then they are mixed in a solution state, and then a solvent blending method is performed. A low-molecular-weight polymer obtained by melt-kneading with a mixer or the like, or a low-molecular-weight polymer obtained by a solution polymerization method or the like is dissolved in a monomer constituting a high-molecular-weight polymer, subjected to suspension polymerization, washed with water and dried, and subjected to resin composition. And a two-stage polymerization method for obtaining a product. However, the dry blending method has problems in terms of uniform dispersion and compatibility, and the two-stage polymerization method has many advantages in uniform dispersibility, but increases the amount of low molecular weight components to higher molecular weight components. In the presence of a low molecular weight polymer component, it is difficult to synthesize a high molecular weight polymer having a large molecular weight, and there is a problem that an unnecessary low molecular weight polymer is produced as a by-product. Therefore, the solution blending method is most preferable. Further, as a method for introducing a predetermined acid value into the low molecular weight polymer component, a solution polymerization in which the acid value can be easily set as compared with an aqueous polymerization method is preferable.

An acid value can be obtained by using a polyester resin. The composition of the polyester resin will be described.

Examples of the dihydric alcohol component include ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol and 1,5-pentanediol. , 1,6-hexanediol, neopentyl glycol, 2-ethyl-1,3-
Hexanediol, hydrogenated bisphenol A, bisphenol represented by the formula (A) and derivatives thereof;

[0077]

Embedded image (Wherein R is an ethylene or propylene group, x,
y is an integer of 0 or more, and the average value of x + y is 0 to 10. ).

Diols represented by the formula (B):

[0079]

Embedded image Where x 'and y' are integers of 0 or more, and x '
The average value of + y 'is 0 to 10. ).

As the divalent acid component, for example, phthalic acid,
Benzenedicarboxylic acids such as terephthalic acid, isophthalic acid and phthalic anhydride or their anhydrides and lower alkyl esters; alkyl dicarboxylic acids such as succinic acid, adipic acid, sebacic acid and azelaic acid or their anhydrides and lower alkyl esters; n- Alkenyl succinic acids or alkyl succinic acids such as dodecenyl succinic acid, n-dodecyl succinic acid, or anhydrides and lower alkyl esters thereof; fumaric acid, maleic acid, citraconic acid, unsaturated dicarboxylic acids such as itaconic acid or anhydrides, lower acids And dicarboxylic acids such as alkyl esters; and derivatives thereof.

Further, it is preferable to use a trivalent or higher valent alcohol component and a trivalent or higher valent acid component which also function as a crosslinking component.

The trihydric or higher polyhydric alcohol component includes
For example, sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol,
1,2,4-butanetriol, 1,2,5-pentanetriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,
3,5-trihydroxybenzene and the like.

The trivalent or higher polycarboxylic acid component in the present invention includes, for example, trimellitic acid, pyromellitic acid, 1,2,4-benzenetricarboxylic acid,
2,5-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,4-butanetricarboxylic acid, 1,2,2
5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methyl-2-methylenecarboxypropane, tetra (methylenecarboxyl) methane, 1,2,7,8-
Octanetetracarboxylic acid, empol trimer acid, and anhydrides and lower alkyl esters thereof;

[0084]

Embedded image (Wherein X is an alkylene group or alkenylene group having 1 to 30 carbon atoms having at least one side chain having 1 or more carbon atoms), such as tetracarboxylic acids, and anhydrides and lower alkyl esters thereof. And polyvalent carboxylic acids and derivatives thereof.

The alcohol component used in the present invention is 40 to 60 mol%, preferably 45 to 55 mol%.
%, 60 to 40 mol% as an acid component, preferably 5%
It is preferably from 5 to 45 mol%.

It is also preferable that the content of the trivalent or higher polyvalent component is 1 to 60 mol% of all the components.

The polyester resin can also be obtained by generally known condensation polymerization.

The magnetic material used in the present invention includes iron oxides such as magnetite, maghemite, and ferrite;
Metals such as cobalt and nickel or these metals and aluminum, cobalt, copper, lead, magnesium, tin,
Alloys of metals such as zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten, and vanadium and mixtures thereof are used, and those containing a non-ferrous element on the surface or inside the magnetic material are preferable.

As the magnetic material used in the present invention, magnetic iron oxides such as magnetite, maghemite, and ferrite containing different elements and mixtures thereof are preferably used.

Among them, lithium, beryllium, boron, magnesium, aluminum, silicon, phosphorus, germanium, titanium, zirconium, tin, lead, zinc, calcium, barium, scandium, vanadium, chromium, manganese, cobalt, copper, nickel, gallium, Cadmium, indium, silver, palladium, gold, mercury, platinum, tungsten, molybdenum, niobium, osmium, strontium, yttrium, technetium, ruthenium,
A magnetic iron oxide containing at least one element selected from rhodium and bismuth is preferable. In particular, lithium, beryllium, boron, magnesium, aluminum, silicon, phosphorus, germanium, zirconium, tin, and a transition metal element of the fourth period are preferable elements. These elements may be taken into the iron oxide crystal lattice, may be taken into the iron oxide as an oxide, or may exist as oxides or hydroxides on the surface. It is a preferred embodiment that it is contained as an oxide.

These elements can be incorporated into the particles by adjusting the pH by mixing the salts of the respective elements when the magnetic material is formed. In addition, precipitation can be performed on the particle surface by adjusting the pH after the formation of the magnetic particles or adjusting the pH by adding a salt of each element.

The magnetic material containing these elements is well compatible with the binder resin and has very good dispersibility. Furthermore, this good dispersibility can improve the dispersibility of the organic titanium compound used in the present invention, and the effect of the organic titanium compound of the present invention can be sufficiently exhibited. That is, the magnetic material functions as a dispersion medium, and the dispersion of the organic titanium compound is assisted by the good dispersibility of the magnetic material, and the dispersibility of the organic titanium compound is improved. In addition, these magnetic substances have an effect of adsorbing water molecules and making the organic titanium compound easily exert an emphasis on charging by the water molecules. This effect can be exhibited more effectively when used together with a binder resin having an acid value.

These magnetic materials have a uniform particle size distribution.
In combination with the dispersibility in the binder resin, the chargeability of the toner can be stabilized. In recent years, the toner particle diameter has been reduced, and even in the case where the weight average particle diameter is 10 μm or less, charging uniformity is promoted, toner cohesion is reduced, image density is improved, and fog is improved. Equal developability is improved. In particular, the effect is remarkable in a toner having a weight average particle diameter of 8.0 μm or less, and an extremely high-definition image can be obtained. It is preferable that the weight average particle size is 2.5 μm or more, since sufficient image density can be obtained. On the other hand, when the particle size of the toner is reduced, the release of the titanium compound is also likely to occur.However, the toner of the present invention is excellent in charging uniformity, so that even if a certain amount of the titanium compound is present, the toner is less susceptible to sleeve contamination. Become.

The content of these different elements is preferably 0.05 to 10% by weight based on the iron element of the magnetic iron oxide. More preferably 0.1 to 7% by weight,
Particularly preferably, it is 0.2 to 6% by weight, more preferably 0.3 to 5% by weight. If it is less than 0.05% by weight, the effect of containing these elements cannot be obtained, and good dispersibility and uniform charging cannot be obtained. When the content is more than 10% by weight, the discharge of electric charge is increased to cause insufficient charging, which may lower the image density or increase fog.

[0095] In the content distribution of these different elements, it is preferable that the one that is more present near the surface of the magnetic material is used. For example, when the dissolution rate of the iron element in the iron oxide is 20%, the dissolution rate of the different element is 20% of the total amount of the different element.
% To 100% is preferred. Further, it is preferably from 25% to 100%, particularly preferably from 30% to 100%. By increasing the surface abundance, the dispersion effect and the electric diffusion effect can be further improved.

These magnetic materials have an average particle size of 0.05 to 1.
It is preferably 0 μm, more preferably 0.1 to 0.5 μm. Those having a BET specific surface area of ² to 40 mm ² / g are used. The shape is not particularly limited, and an arbitrary shape is used. As the magnetic characteristics, the magnetic field 795.
A saturation magnetization of 10 to 200 Am ² / kg under 8 kA / m,
Residual magnetization is 1 to 100 Am ² / kg, coercive force is 1 to 30
What is kA / m is used. These magnetic materials are used in an amount of 20 to 200 parts by weight based on 100 parts by weight of the binder resin.

The amount of the element in the magnetic iron oxide of the present invention is determined by the fluorescence X
Ray analyzer SYSTEM3080 (Rigaku Denki Kogyo Co., Ltd.)
And X-ray fluorescence analysis in accordance with JIS K0119 General rules for X-ray fluorescence analysis.
The element distribution is obtained by measuring and quantifying the amount of the element while dissolving hydrochloric acid by plasma emission spectroscopy (ICP), and calculating the dissolution rate from the concentration of each element at the time of each dissolution with respect to the concentration of each element at the time of dissolution. .

The number average diameter can be determined by measuring a photograph enlarged by a transmission electron microscope with a digitizer or the like. The magnetic properties of the magnetic material are values measured using an “oscillating sample magnetometer VSM-3S-15” (manufactured by Toei Kogyo Co., Ltd.) under an external magnetic field of 795.8 kA / m. The specific surface area is obtained by adsorbing nitrogen gas on the sample surface using a specific surface area measuring device Autosoap 1 (manufactured by Yuasa Ionics) according to the BET method, and calculating the specific surface area using the BET multipoint method.

The waxes used in the present invention include the following. For example, aliphatic hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, polyolefin copolymer, polyolefin wax, microcrystalline wax, paraffin wax and sasol wax; oxides of aliphatic hydrocarbon wax such as polyethylene oxide wax Or a block copolymer thereof; candelilla wax, carnauba wax,
Plant waxes such as wood wax and jojoba wax;
Animal waxes such as lanolin and whale wax; mineral waxes such as ozokerite, ceresin and petrolatum; waxes mainly containing fatty acid esters such as montanic acid ester wax and caster wax; fatty acid esters such as deoxidized carnauba wax. A partially or entirely deoxidized product may be used. Further, saturated linear fatty acids such as palmitic acid, stearic acid, montanic acid, or long-chain alkyl carboxylic acids having a longer-chain alkyl group; unsaturated fatty acids such as brassic acid, eleostearic acid, and barinaric acid; Saturated alcohols such as stearyl alcohol, eicosyl alcohol, behenyl alcohol, carnaubyl alcohol, seryl alcohol, melisyl alcohol, and long-chain alkyl alcohols having a longer-chain alkyl group; polyhydric alcohols such as sorbitol; linole Fatty acid amides such as acid amide, oleic acid amide and lauric acid amide; saturated fatty acid amides such as methylenebisstearic acid amide, ethylenebiscapric acid amide, ethylenebislauric acid amide and hexamethylenebisstearic acid amide Amides; unsaturated fatty acid amides such as ethylene bisoleic acid amide, hexamethylene bis oleic acid amide, N, N'-dioleyl adipamide, N, N'-dioleyl sebacic acid amide; m-xylene bis stearin Aromatic bisamides such as acid amide and N, N'-distearyl isophthalamide; fatty acid metal salts such as calcium stearate, calcium laurate, zinc stearate and magnesium stearate (commonly referred to as metal soaps); Waxes obtained by grafting aliphatic hydrocarbon waxes with vinyl monomers such as styrene and acrylic acid; partially esterified products of fatty acids such as behenic acid monoglyceride and polyhydric alcohols; obtained by hydrogenation of vegetable oils and fats Having a hydroxyl group Glycol ester compounds and the like.

The wax preferably used is a polyolefin obtained by radical polymerization of an olefin under high pressure;
A polyolefin obtained by purifying a low-molecular-weight by-product obtained during polymerization of a high-molecular-weight polyolefin; a polyolefin polymerized using a catalyst such as a Ziegler catalyst or a metallocene catalyst under a low pressure; a polyolefin polymerized using radiation, electromagnetic waves, light, or the like; A low molecular weight polyolefin obtained by thermally decomposing a high molecular weight polyolefin; a paraffin wax, a microcrystalline wax, a Fischer-Tropsch wax; a synthetic hydrocarbon wax synthesized by a Zintall method, a hydrocoll method, an Age method, etc .; Synthetic wax as a monomer, a hydrocarbon wax having a functional group such as a hydroxyl group, a carboxyl group, etc .; a mixture of a hydrocarbon wax and a hydrocarbon wax having a functional group; Ester, acrylate, methacrylate, and the like wax graft-modified with a vinyl monomer such as maleic anhydride.

These waxes may be obtained by sharpening the molecular weight distribution using a press sweating method, a solvent method, a recrystallization method, a vacuum distillation method, a supercritical gas extraction method, a molten liquid crystal precipitation method, or a low molecular weight solid. Fatty acids, low molecular weight solid alcohols,
Low molecular weight solid compounds and those from which other impurities have been removed are also preferably used.

In the toner of the present invention, the total content of these waxes is 0.2 to 100 parts by weight of the binder resin.
It is effective to use at 20 to 20 parts by weight, preferably 0.5 to 10 parts by weight.

In the present invention, the melting point of the wax is DSC
The temperature at the peak top of the maximum endothermic peak of the wax measured in the above is defined as the melting point of the wax.

In the present invention, in the DSC measurement of a wax with a differential scanning calorimeter, it is preferable to measure the wax with a high-precision internal heating type input compensation type differential scanning calorimeter. For example, DSC-7 manufactured by PerkinElmer can be used.

The measuring method is as described in ASTM D3418-82.
Perform according to. The DSC curve used in the present invention is obtained by raising and lowering the temperature once, taking a pre-history, and then setting the temperature rate to 10 ° C./m.
In, a DSC curve measured when the temperature is raised is used.

When the organotitanium compound of the present invention is used with two or more different waxes, more excellent effects can be obtained. The wax exerts a plasticizing action and a releasing action on the toner, and when used at the same time, one of the actions is emphasized. When the organic titanium compound of the present invention is present, these effects are remarkably exhibited,
The effect works more effectively than when each wax is used alone. When plasticized by the wax, the dispersion of the organotitanium compound is improved, and accordingly, the releasability of another wax appears more clearly. At this time, it is even more effective when used together with a binder resin having an acid value.

Here, two kinds of waxes are selected.
In the case of a wax having the same structure, a wax having a relatively low melting point exhibits a plasticizing effect, and a wax having a relatively high melting point exhibits a releasing effect. At this time, the difference in melting point is 10 ° C to 100 ° C.
At ℃, this functional separation appears effectively. When the temperature is lower than 10 ° C., the function separation effect is hardly exhibited, and when the temperature is higher than 100 ° C., the function is hardly emphasized by the interaction.

Further, those having a branched structure, those having a polar group such as a functional group, and those modified with a component different from the main component relatively exert a plasticizing action, and have a more linear structure. A non-polar or unmodified straight product having no or a functional group or the like exhibits a releasing effect. Preferred combinations include, for example, a combination of a polyethylene homopolymer copolymer containing ethylene as a main component and a polyolefin homopolymer copolymer containing an olefin other than ethylene as a main component, a combination of a polyolefin and a graft-modified polyolefin, an alcohol wax, a fatty acid wax, Combination of ester wax and hydrocarbon wax, combination of Fischer Tropsch wax, polyolefin wax and paraffin wax, microcrystalline wax, combination of Fischer Tropsch wax and polyolefin wax, combination of paraffin wax and microcrystalline wax, carnauba wax, candelilla wax·
Examples include a combination of rice wax / montan wax and a hydrocarbon wax.

As the colorant that can be used in the toner of the present invention, any suitable pigment or dye can be used. For example, as pigments, carbon black, aniline black, acetylene black, naphthol yellow, hansa yellow, rhodamine lake, alizarin lake, bengara,
Examples include phthalocyanine blue and indanthrene blue. These are used in an amount necessary to maintain the optical density of the fixed image, and are used in an amount of 0.1 to 100 parts by weight of the binder resin.
An addition amount of 20 parts by weight, preferably 0.2 to 10 parts by weight is good. A dye is further used for the same purpose. For example, there are azo dyes, anthraquinone dyes, xanthene dyes, and methine dyes, and 0.1 to 20 parts by weight, preferably 0.3 to 10 parts by weight, per 100 parts by weight of the binder resin is good. .

In the present invention, it is preferable to add an inorganic oxide such as silica, alumina or titanium oxide, or an inorganic fine powder of fine particles such as carbon black or carbon fluoride.

It is preferable that silica, alumina, and titanium oxide be fine particles when dispersed on the surface of the toner because the fluidity-imparting property becomes higher. The average particle size is 5 to 10
The thickness is preferably 0 nm, more preferably 5 to 50 n.
m is good. Preferably as maternal fine powder in the range of 30 m ² / g or more in specific surface area according to the measured nitrogen adsorption (especially 60~400m ² / g) by the BET method, the surface-treated fine powder, 20 m ² / g or more (Especially 40-300
m ² / g).

The application amount of these fine powders becomes an appropriate surface coverage when added in an amount of 0.03 to 5% by weight based on the weight of the toner base.

The degree of hydrophobicity of the inorganic fine powder used in the present invention is preferably 30% or more in methanol wettability, more preferably 50% or more. As the hydrophobizing agent, a silane compound which is a silicon-containing surface treating agent and silicone oil are preferable.

For example, alkylalkoxysilanes such as dimethyldimethoxysilane, trimethylethoxysilane and butyltrimethoxysilane, dimethyldichlorosilane, trimethylchlorosilane, allyldimethylchlorosilane, hexamethyldisilazane, allylphenyldichlorosilane And silane coupling agents such as benzyldimethylchlorosilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, divinylchlorosilane, and dimethylvinylchlorosilane.

Further, the following positively chargeable materials may be used for adjusting the charge amount. Silane coupling agents such as aminopropyltrimethoxysilane, aminopropyltriethoxysilane, dimethylaminopropyltrimethoxysilane, diethylaminopropyltrimethoxysilane, dipropylaminopropyltrimethoxysilashi, dibutylaminopropyltrimethoxysilane, and amino-modified Silicone oil or the like can be used.

The toner of the present invention can be used as a two-component toner by mixing with a carrier. The current value of the carrier is preferably adjusted to 20 to 200 μA by adjusting the degree of unevenness of the carrier surface and the amount of resin to be coated.

Examples of the resin for coating the carrier surface include styrene-acrylate copolymer, styrene-methacrylate copolymer, acrylate copolymer, methacrylate copolymer, silicone resin, and the like.
Fluorine-containing resin, polyamide resin, ionomer resin,
Polyphenylene sulfide resin or the like, or a mixture thereof can be used.

As the magnetic material of the carrier core, oxides such as ferrite, iron-rich ferrite, magnetite and γ-iron oxide, metals such as iron, cobalt and nickel or alloys thereof can be used. The elements contained in these magnetic materials include iron, cobalt, nickel, aluminum, copper, lead, magnesium, tin,
Examples include zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten, and vanadium.

As the additives for imparting various properties used in the present invention, for example, the following are used.

(1) Abrasives: metal oxides (strontium titanate, cerium oxide, aluminum oxide, magnesium oxide, chromium oxide, etc.), nitrides (silicon nitride, etc.), carbides (silicon carbide, etc.), metal salts (sulfuric acid, etc.) Calcium, barium sulfate, calcium carbonate).

(2) Lubricants: fluororesin powder (polyvinylidene fluoride, polytetrafluoroethylene, etc.), fatty acid metal salts (zinc stearate, calcium stearate, etc.).

(3) Charge controllable particles: metal oxides (tin oxide, titanium oxide, zinc oxide, silicon oxide, aluminum oxide, etc.), carbon black, resin fine particles and the like.

These additives are used in an amount of 0.05 to 10 parts by weight, preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the toner particles. These additives are
They may be used alone or in combination.

In the case of a magnetic toner, it is preferable to use fine powders of two or more kinds of inorganic oxides or metal oxides in order to obtain the durability stability of development and the development stability after standing. In the case of the non-magnetic one-component developing method, it is preferable to use titanium oxide and alumina in order to improve the fluidity and obtain the image uniformity.

In producing the toner according to the present invention, the above-mentioned toner constituent materials are sufficiently mixed by a ball mill or other mixer, and then sufficiently kneaded using a hot kneader such as a hot roll kneader or an extruder. After cooling and solidifying, a method of obtaining a toner by mechanical pulverization and classification is preferable.Otherwise, a predetermined material is mixed with a monomer to constitute a binder resin to form an emulsified suspension, followed by polymerization. A method of producing a toner by allowing the toner to be obtained by a method of producing a toner; or a method of including a predetermined material in a core material and / or a shell material in a so-called microcapsule toner comprising a core material and a shell material; A method in which the toner is obtained by dispersing the constituent materials and then spray-drying the same is applicable. Further, if necessary, the desired additive is sufficiently mixed with a mixer such as a Henschel mixer to produce the toner according to the present invention.

[0126]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto.

Table 1 shows the resins used in the examples, Table 2 shows the waxes, and Table 3 shows the magnetic substances. The styrene resin was synthesized by a solution polymerization method, and the polyester resin was synthesized by a dehydration condensation method. The magnetic material was prepared by adding a salt of an element present therein at the time of magnetite generation and adjusting the pH to generate magnetite particles, thereby obtaining magnetic materials α to ε. Magnetic substance α
Is a silicate, a magnetic substance β is a silicate and an aluminum salt, a magnetic substance γ is a phosphate, and a magnetic substance δ is a magnesium salt to produce magnetite particles. For the magnetic material ε, a zinc salt was added to generate magnetite particles, and a silicate was added to adjust the pH to obtain a magnetic material. As for the magnetic material 燐, a phosphate was added to generate magnetite particles, and a silicate was added to adjust the pH to obtain a magnetic material. In particular, magnetite particles were generated without adding a salt, and a magnetic material θ was obtained. After the formation of the magnetic material θ, the pH is adjusted by adding a zirconium salt, and zirconia is precipitated on the surface of the magnetite particles to form a magnetic material η.
I got

[0128]

[Table 1]

[0129]

[Table 2]

[0130]

[Table 3]

Example 1 100 parts by weight of binder resin B 100 parts by weight of magnetic substance α 2 parts by weight of titanium compound 21 3 parts by weight of wax c 4 parts by weight of wax e

After the above materials were premixed by a Henschel mixer, they were melted and kneaded by a twin screw extruder set at 130 ° C. The obtained kneaded material was cooled, coarsely pulverized by a cutter mill, pulverized by a fine pulverizer using a jet stream, and the obtained finely pulverized powder was classified using a multi-part classifier utilizing Coanda effect. , Weight average particle size 5.8 μm
Was obtained. For 100 parts by weight of toner particles,
BET specific surface area of 120 m which has been hydrophobized with 10 wt% of hexamethyldisilazane and 10 wt% of dimethyl silicone
1.0 parts by weight of ² / g of silica were externally added and mixed to form a toner N
o. 1 was prepared.

This toner no. 1 at 15 ° C., 1 using a commercially available printer LBP-930 (manufactured by Canon Inc.).
4,000 in an environment of 0% RH and an environment of 30 ° C. and 80% RH
A print test of 0 sheets was performed. As a result, a high-definition image with high image density and no fog was obtained in both environments. Details are shown in Tables 5 and 6.

The image density was measured by measuring the reflection density using a Macbeth densitometer (manufactured by Macbeth) using an SPI filter, and measuring a 5 mm square image. The fog was measured using a reflection densitometer (reflectometer model TC-6DS, manufactured by Tokyo Denshoku Co., Ltd.), and the worst value of the reflection density on the white background after image formation was Ds, and the average reflection density of the transfer material before image formation was Dr.
The fog was evaluated using Ds-Dr as the fog amount. The smaller the value, the better the fog suppression. The image quality is evaluated by forming an image of 100 isolated dots and determining how many of the 100 dots can be represented. The higher the number of reproduced dots, the higher the image quality. The fouling of the fixing member was evaluated based on the following criteria. A: There is no stain on the fixing member. B: There is a little stain on the fixing member. C: The fixing member is stained, but there is no effect on the image. D: The fixing member is stained, and offset occurs in the image.

Examples 2 to 10 In the same manner as in Example 1, toner Nos. Two
Table 10 shows the results of the same test.

Comparative Examples 1 to 4 In the same manner as in Example 1, toner No. 11
14 were prepared, and the results of similar tests are shown in Tables 5 and 6. The following compounds 46 to 49 which are zinc compounds, iron compounds, aluminum compounds and chromium compounds as the compounds
It was used.

[0137]

Embedded image

Example 11 Binder resin H 100 parts by weight Copper phthalocyanine 4 parts by weight Titanium compound 11 2 parts by weight

After the above materials were preliminarily mixed with a Henschel mixer, they were kneaded with a twin-screw kneading extruder set at 100 ° C. The obtained kneaded material was cooled, coarsely pulverized with a cutter mill, finely pulverized using a pulverizer using a jet stream, and classified using a multi-partition classifier utilizing the Coanda effect, to obtain a weight average particle size. 7.8 μm toner particles were obtained. To 100 parts by weight of the obtained toner particles, 10 parts by weight of isobutyltrimethoxysilane and 10 parts by weight of dimethyl silicone
Hydrophobic titania fine powder treated in parts by weight (methanol wettability 65%, BET specific surface area 75 m ² / g)
1.5 parts by weight of toner No. 15 were prepared.

The resulting toner No. 15 were subjected to the following evaluation tests.

<Image Evaluation Test> A commercially available color printer (LBP-2030, manufactured by Canon Inc.) was used at 15 ° C.
In each environment of 10% RH, 30 ° C. and 80% RH, 3,000 sheets were printed, and the image density and fog were evaluated.

The image density was measured using a "Macbeth reflection densitometer" (manufactured by Macbeth). The fog is measured using a “reflection densitometer” (manufactured by Tokyo Denshoku Technology Center Co., Ltd.) to measure the reflection density of the transfer paper and the reflection density of the transfer paper after copying the solid white, and calculate the difference between the reflection density and the fog value. The smaller the value, the better the fog suppression. The fog is measured by measuring the reflection density of a transfer material before image formation and a white background portion after image formation using a reflection densitometer (reflectometer model TC-6DS manufactured by Tokyo Denshoku Co., Ltd.), and calculating an average value. . The difference between the reflection densities before and after image formation is evaluated as fog.

The image quality is evaluated by forming an image of 100 isolated dots and expressing how many of the 100 dots can be represented. The higher the number of reproduced dots, the higher the image quality.

Tables 7 and 8 summarize the evaluation results of the image evaluation test.

Example 12 Binder resin H 100 parts by weight Dimethylquinacridone 5 parts by weight Titanium compound 15 2 parts by weight

After the above materials were preliminarily mixed with a Henschel mixer, they were kneaded with a biaxial kneading extruder set at 100 ° C. The obtained kneaded material was cooled, coarsely pulverized by a cutter mill, finely pulverized using a pulverizer using a jet stream, and classified using a multi-partition classifier utilizing the Coanda effect to obtain a weight average particle diameter of 7%. 0.8 μm toner particles were obtained. 100 parts by weight of γ-type alumina fine powder produced by the pyrolysis method
Hydrophobic alumina fine powder treated with 10 parts by weight of butyltrimethoxysilane and 5 parts by weight of dimethyl silicone (methanol wettability 70%, BET specific surface area 82 m)
^/ G) (1.5 parts by weight) was added to 100 parts by weight of the toner particles, and externally added and mixed. 16 were prepared.

This toner no. Example 11 using 16
The same running test was performed. Image density, fog,
Tables 7 and 8 show the evaluation results of developability such as image quality.

Example 13 Binder resin 100 parts by weight Disazo pigment (CI Pig. Yellow 17) 3 parts by weight Titanium compound 29 2 parts by weight

After the above materials were preliminarily mixed with a Henschel mixer, they were kneaded with a twin-screw kneading extruder set at 100 ° C. The obtained kneaded material was cooled, coarsely pulverized by a cutter mill, finely pulverized using a pulverizer using a jet stream, and classified using a multi-partition classifier utilizing the Coanda effect to obtain a weight average particle diameter of 7%. 0.8 μm toner particles were obtained. Hydrophobic alumina fine powder (methanol wettability: 75%, BET specific surface area: 77 parts) treated with 10 parts by weight of n-butyltrimethoxysilane and 5 parts by weight of dimethyl silicone to 100 parts by weight of δ-type alumina fine powder produced by a flame decomposition method
m ² / g) was added to 100 parts by weight of toner particles, and externally added and mixed. 17 was prepared.

This toner no. Example 11 using No. 17
The same running test was performed. Image density, fog,
Tables 7 and 8 show the evaluation results of developability such as image quality.

Example 14 Binder resin 100 parts by weight Carbon black 4 parts by weight Titanium compound 34 2 parts by weight

After the above materials were preliminarily mixed with a Henschel mixer, they were kneaded with a biaxial kneading extruder set at 100 ° C. The obtained kneaded material was cooled, coarsely pulverized by a cutter mill, finely pulverized using a pulverizer using a jet stream, and classified using a multi-partition classifier utilizing the Coanda effect to obtain a weight average particle diameter of 7%. 0.8 μm toner particles were obtained.

100 parts by weight of the obtained toner particles were added to 100 parts by weight of rutile-type titania fine powder produced by the sulfuric acid method, and 10 parts by weight of isobutyltrimethoxysilane and 10 parts by weight of dimethyl silicone were treated with hydrophobic titania fine powder ( Methanol wettability 70%, BET specific surface area 59 m ² / g) 1.5 parts by weight were externally added and mixed to form toner N.
o. 18 was prepared.

This toner No. Example 11 using No. 18
The same running test was performed. Image density, fog,
Tables 7 and 8 show the evaluation results of developability such as image quality.

[0155]

[Table 4]

[0156]

[Table 5]

[0157]

[Table 6]

[0158]

[Table 7]

[0159]

[Table 8]

[0160]

The present invention is a toner which can provide excellent developability even in a simple developing device configuration such as a single-use cartridge type such as a copying machine or a printer. Further, the present invention is a toner that suppresses generation of image stains from a fixing member in any electrophotographic output device. Further, the present invention is a toner that can obtain high image quality regardless of the use environment, and does not change even with the lapse of time, and can obtain an image faithful to a latent image for a long period of time.

Claims (5)

[Claims] 1. A toner containing at least a binder resin, a colorant and an organometallic compound, wherein the organometallic compound has titanium as a metal element and an aromatic polycarboxylic acid is coordinated as a ligand. A titanium complex or a titanium complex salt. 2. The toner according to claim 1, wherein the binder resin has an acid value of 1 mgKOH / g to 100 mgKOH / g. 3. The coloring agent according to claim 1, wherein said coloring agent contains a heterogeneous element on the basis of iron element.
3. The toner according to claim 1, wherein the magnetic iron oxide is contained in an amount of from 0.05% by weight to 10% by weight. 4. The toner according to claim 1, wherein the toner contains at least two kinds of waxes having different melting points with a difference of 10 ° C. to 100 ° C. 5. The toner according to claim 1, comprising at least two kinds of waxes having different compositions.