JP2001109200A - Dry toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a dry toner with which high image quality can be stably obtained even when the toner is used in a low humidity or high humidity environment and image defects are not produced with time or when the toner is left to stand. SOLUTION: The toner contains at least a binder resin, a coloring agent, a release agent and an organic metal compound. The mol.wt. distribution of the toner measured by GPC shows at least one peak in the region of 3×103 to 3×104 mol.wt. and moreover, at least one peak in the region of 1×105 to 5×106. The organic metal compound is an aluminum compound of benzilic acid expressed by formula (1) without substituted or having substituents. In the formula, R1 and R2 may be same or different and each represents a substituent selected from a group of straight-chain or branched alkyl groups, alkenyl groups, alkoxy groups, halogen atoms, nitro groups, cyano groups, amino groups, carboxyl groups and hydroxyl groups, and each of m and n is an integer 0 to 5.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] 1. Field of the Invention [0002] The present invention relates to an electrophotographic method, an image forming method for visualizing an electrostatic image, and a dry toner used for a toner jet.

[0002]

2. Description of the Related Art Conventionally, electrophotography has been disclosed in U.S. Pat. No. 2,297,691, Japanese Patent Publication No. 42-23910.
Many methods are known as described in Japanese Patent Application Laid-Open Publication No. Sho. 43-24748, and the like. Generally, a photoconductive substance is used to form an electric latent image on a photoreceptor by various means. After forming the latent image with toner, the latent image is developed into a visible image, and if necessary, the toner is transferred to a transfer material such as paper. The toner is fixed to obtain a copy, and the toner remaining on the photoreceptor without being transferred is cleaned by various methods, and the above steps are repeated.

In recent years, such copying apparatuses have become smaller and smaller.
Lighter weight, higher speed, and higher reliability have been strictly pursued. In addition, it has begun to be used not only as a copy machine for office work for simply copying an original manuscript, but also for copying a high-resolution image such as a digital printer or graphic design as a computer output. For this reason, higher definition and higher image quality have been demanded as image quality, and as a result, the performance required for toner has also become higher.

Incidentally, the toner needs to have a positive or negative charge depending on the polarity of the electrostatic latent image to be developed. In order to cause the toner to retain electric charge, it is possible to use the frictional charging property of the resin which is a component of the toner. However, in this method, since the charging of the toner is not stable, the rise of the density is slow and fogging is easy to occur. 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 such as hydroxycarboxylic acid, dicarboxylic acid and aromatic diol; Resins containing components are known. Nigrosine dyes, azine dyes, triphenylmethane dyes and pigments, quaternary ammonium salts, polymers having a quaternary ammonium salt in the side chain, and the like are also known as positive friction charge control agents.

However, 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,
It has 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
JP-A-9073, JP-A-61-73693, 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, those proposed in these publications are all excellent from the viewpoint of imparting triboelectric charging, but have a simple developing device configuration and provide stable developing properties irrespective of environmental fluctuations, aging, and use conditions. Is rarely obtained.

Further, Japanese Patent Application Laid-Open No. 10-312089 discloses a toner in which a boron complex salt of benzylic acid and a metal salt of a salicylic acid derivative are used in combination. According to the study of the present inventors, although the use of a boron complex salt of benzylic acid and a metal salt of a salicylic acid derivative improves the triboelectric charge amount and charging speed of the toner, the charge control agent exhibits a different charging series. , There is still room for improvement in the triboelectric distribution of the toner.

[0009]

SUMMARY OF THE INVENTION An object of the present invention is to provide a dry toner which has solved the above-mentioned problems.

[0010] An object of the present invention is to provide a dry toner which can stably obtain high image quality even when used under low humidity or under high humidity and does not cause image defects even with aging or standing. It is in.

[0011]

SUMMARY OF THE INVENTION The present invention relates to a toner having at least a binder resin, a colorant, a release agent, and an organometallic compound, wherein the toner has a molecular weight of 3,000 in a molecular weight distribution measured by GPC. At least one peak in the region of 30,000 and a molecular weight of 10
The organometallic compound has at least one peak in the range of 000 to 5,000,000, and the organometallic compound is unsubstituted or substituted benzylic acid (benzilic acid) represented by the following formula (1). A dry toner comprising the aluminum compound of formula (1).

[0012]

Embedded image (In the formula, R ₁ and R ₂ may be the same or different and each represents a linear or branched alkyl group, alkenyl group, alkoxy group, halogen atom, nitro group, cyano group, amino group, carboxyl group, A substituent selected from the group consisting of a group and a hydroxyl group, and m and n each represent an integer of 0 to 5.)

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The present inventors have proposed unsubstituted or substituted benzylic acid (b) represented by the above formula (1).
benzylic acid), has at least one peak in a molecular weight range of 3,000 to 30,000 in a molecular weight distribution measured by GPC, and further has a molecular weight of 100,000 to 5,000.
The toner having at least one peak in the region of 0000 does not become excessively charged even in a low humidity environment while maintaining good startup without adversely affecting the fixing property. It has been found that a high charge amount can be obtained also in the above method.

The aluminum compound of benzylic acid used in the present invention has at least one peak in a molecular weight region of 5,000 to 20,000, and further has a molecular weight of 100,0.
By using in combination with a binder resin having at least one peak in the range of 00 to 3,000,000,
The performance as the compound can be exhibited extremely efficiently.
This is because the binder resin as described above has an appropriate elasticity, so that the kneading share can be applied at the time of melt kneading at the time of toner production, and the dispersion of raw materials such as an aluminum compound of benzylic acid can be improved. This is because
As a result, a toner having a stable charge can be obtained without adversely affecting the fixing property, which has been a conventional problem.

Further, the aluminum compound of benzylic acid of the present invention easily coordinates with oxygen such as carboxyl group and hydroxyl group, so that the carboxyl group and hydroxyl group are often coordinated to the aluminum atom. Therefore, when a styrene-based resin having a carboxyl group or an acid anhydride group as a functional group, a polyester resin, or the like is used as the binder resin, the aluminum compound of benzylic acid is well blended into the binder resin and has excellent dispersibility. In addition, it is possible to prevent the toner particles from dropping out of the toner particles, and to obtain uniform charging and stable charging durability.

Further, 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.

Specific examples of the unsubstituted or substituted benzyl acid used in the aluminum compound of benzyl acid according to the present invention are shown below, but the present invention is not limited to these benzyl acids.

[0018]

Embedded image

The aluminum compound of benzylic acid preferably used in the toner of the present invention is, for example, a mixture of unsubstituted or substituted benzylic acid and aluminum sulfate Al ₂ (SO ₄ ) ₃ at a desired molar ratio as described above. The reaction was heated under an alkaline atmosphere, and the resulting precipitate was collected by filtration.
Further, it can be obtained by washing with water and drying.
However, the method for producing the aluminum compound of benzylic acid according to the present invention is not limited to this.

The representative structural formula (I-) of the aluminum compound of benzylic acid preferably used in the toner of the present invention:
1) and (I-2) are listed below, but the present invention is not limited to these aluminum compounds of benzylic acid.

[0021]

Embedded image (Wherein X ⁺ is a monovalent cation and is selected from hydrogen, lithium, sodium, potassium, ammonium and alkylammonium.)

[0022]

Embedded image

Next, specific examples of the aluminum compound of benzylic acid preferably used in the toner of the present invention are shown below, but the present invention is not limited to these aluminum compounds of benzylic acid.

[0024]

Embedded image

[0025]

Embedded image

As a method for incorporating the aluminum compound of benzylic acid according to the present invention into a toner, there are a method in which the aluminum compound is contained in the toner particles and a method in which the aluminum compound is contained in the surface and / or outside of the toner particles. The preferable addition amount in the former case is 0.1 to 10 parts by mass of the aluminum compound of benzylic acid with respect to 100 parts by mass of the binder resin, and the preferable addition amount in the latter case is 100 parts by mass of the binder resin. The aluminum compound of benzyl acid is 0.01 to 5 parts by mass, and it is particularly preferable that the aluminum compound is mechanochemically fixed to the surface of the toner particles.

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 complexes of aromatic compounds. Further, phenol derivatives such as bisphenols and calixarenes are also used.

On the other hand, the following substances control the toner to be positively charged.

Modified products such as nigrosine and fatty acid metal salts, quaternary ammonium salts such as tributylbenzylammonium-1-hydroxy-4-naphthosulfonate and tetrabutylammonium tetrafluoroborate;
And onium salts such as phosphonium salts, which are analogs thereof, and their lake pigments, triphenylmethane dyes, and these lake pigments (as the lake-forming agent, phosphotungstic acid, phosphomolybdic acid, phosphotungsten molybdic acid, tannic acid) , Lauric acid, gallic acid, ferricyanide, ferrocyanide), metal salts of higher fatty acids; diorganotin oxides such as dibutyltin oxide, dioctyltin oxide, dicyclohexyltin oxide; dibutyltin borate, dioctyltin borate, dicyclohexyltin borate Diorganotin borates; these can be used alone or in combination of two or more.

The toner containing an aluminum compound of benzylic acid used in the present invention has little change in charging characteristics even under a high humidity or low humidity environment, can maintain stable development characteristics, and has a molecular weight distribution of the toner by GPC. Has at least one peak in a molecular weight range of 3,000 to 30,000, and a molecular weight of 100,000 to 5,
In the case of having at least one peak in the area of 1,000,000, the dispersibility is very good, and since the loss of the aluminum compound of benzylic acid from the toner is small, the durability is excellent without deteriorating the fixing property.

The toner of the present invention has a THF-soluble GPC
Has at least one peak in the molecular weight range of 3,000 to 30,000, and a molecular weight of 100,000.
It is characterized by having at least one peak in the region of 000 to 5,000,000, preferably having at least one peak in the region of molecular weight of 5,000 to 20,000, and having a molecular weight of 100,000 to 1,000,0
It is preferable that at least one peak exists in the region of 00. The THF-soluble component has a molecular weight of 100,000.
A toner in which the following components are 50 to 90% is also preferable.

In the molecular weight distribution, the toner having such peaks has a good balance of fixing property, anti-offset property and storage property.

The binder resin of the present invention has a molecular weight of 5,
000 to 20,000, and has at least one peak, and further has a molecular weight of 100,000 to 3,000,000.
It is desirable to have at least one peak in the region of 0.

In the case where such a peak is not present in the molecular weight distribution, the resin cannot have appropriate elasticity, so that the kneading shear cannot be applied during the melt kneading in the production of the toner, and the raw material such as aluminum compound of benzylic acid and the like cannot be obtained. Dispersibility deteriorates, and both fixability and durability stability deteriorate.

In the present invention, the T of the toner and the binder resin
The molecular weight distribution by GPC using HF (tetrahydrofuran) as a solvent is measured under the following conditions.

The column was stabilized in a heat chamber at 40 ° C., and THF was added to the column at this temperature as a solvent.
At a flow rate of 1 ml per minute, and the THF sample solution is
Inject μl and measure. In measuring the molecular weight of the sample, the molecular weight distribution of the sample was calculated from the relationship between the logarithmic value of a calibration curve prepared from several types of monodisperse polystyrene standard samples and the count value. As a standard polystyrene sample for preparing a calibration curve, for example, one having a molecular weight of about 10 ² to 10 ⁷ manufactured by Tosoh Corporation or Showa Denko KK, and it is appropriate to use at least about 10 standard polystyrene samples. The detector uses an RI (refractive index) detector.

It is preferable to combine a plurality of commercially available polystyrene gel columns. For example, Shodex GPC KF-801, 802, manufactured by Showa Denko KK
803, 804, 805, 806, 807, 800P or TSKgel G1000H manufactured by Tosoh Corporation
(H _XL ), G2000H (H _XL ), G3000H
(H _XL ), G4000H (H _XL ), G5000H
(H _XL ), G6000H (H _XL ), G7000H
(H _XL ) and a combination of TSKguard column.

A sample is prepared as follows.

After placing the sample in THF and leaving it to stand for several hours, it is shaken sufficiently, mixed well with THF (until the sample is no longer united), and allowed to stand for 12 hours or more. Then TH
The time of leaving in F is set to 24 hours or more. After that, sample processing filter (pore size 0.2 ~
0.5 μm, for example, Mysholi Disc H-25-2
(Made by Tosoh Corporation). ) Is used as a GPC sample. Further, the sample concentration is adjusted so that the resin component is 0.5 to 5 mg / ml.

The acid value of the binder resin used in the present invention is 1
-100 mgKOH / g, preferably 1-50 mgKOH / g, more preferably 2-100 mgKOH / g.
Preferably it is 40 mg KOH / g.

When the acid value of the binder resin is less than 1 mgKOH / g, the development stability and the durability stabilizing effect due to the interaction of benzylic acid with the aluminum compound cannot be sufficiently exhibited. On the other hand, if it exceeds 100 mgKOH / g, the binder resin has a high hygroscopicity, the image density tends to decrease, and the fog tends to increase.

In the present invention, the acid value of the binder resin is determined by the following method.

<Measurement of acid value> The basic operation is JIS K-0.
070.

1) Pulverized binder resin 0.5 to 2.0
(G) is precisely weighed to obtain a binder resin weight 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) Titration using a 0.1 N KOH methanol solution using a potentiometric titrator (for example, a potentiometric titrator AT-400 manufactured by Kyoto Electronics Co., Ltd. (winwork)
station) and automatic titration using an ABP-410 motorized burette. 4) At this time, the used amount of the KOH solution was defined as S (ml), and at the same time, a blank was measured.
(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

The constituents of the resin in the present invention include:
Various resins such as a vinyl polymer and a polyester resin which are generally used as a resin for a toner and have a carboxyl group or an acid anhydride group can be used.

In order to obtain a binder resin characteristic of the present invention, the following monomers can be used as monomers of the vinyl polymer.

For example, unsaturated dibasic acids and anhydride monomers such as maleic acid, citraconic acid, dimethyl maleic acid, itaconic acid, alkenyl succinic acid and anhydrides thereof; fumaric acid, metaconic acid, dimethyl fumaric acid; Further, monoesters of the above unsaturated dibasic acids. Α, β-unsaturated acids such as acrylic acid, methacrylic acid, crotonic acid, cinnamic acid and anhydrides thereof; anhydrides between the α, β-unsaturated acids and anhydrides with lower fatty acids; These anhydride monomers. Alkenyl malonic acid, alkenyl glutaric acid, alkenyl adipic acid and anhydrides and monoesters thereof. Among these, maleic acid, maleic acid half ester and maleic anhydride are particularly preferably used as monomers for obtaining the binder resin of the present invention.

Further, comonomer of the vinyl polymer includes
Examples 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 such as p-tert-butylstyrene, pn-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene, pn-dodecylstyrene and derivatives thereof; ethylene, Ethylene unsaturated monoolefins such as propylene, butylene and isobutylene; unsaturated polyenes such as butadiene; vinyl halides such as vinyl chloride, vinylidene chloride, vinyl bromide, and vinyl fluoride; vinyl acetate, vinyl propionate, and benzoate Vinyl esters such as vinyl acrylate; methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate , METAK Α-Methyl aliphatic monocarboxylic esters such as phenyl acrylate, 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, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate and phenyl acrylate; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl isobutyl ether Vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone, methyl isopropenyl ketone; N-vinyl pyrrole, N-vinyl carbazole, N
N- such as vinylindole and N-vinylpyrrolidone
Vinyl compounds such as vinyl compounds; vinyl naphthalenes; acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile, and acrylamide; esters of α, β-unsaturated acids and diesters of dibasic acids; One or more are used.

Of these, a combination of monomers that results in a styrene copolymer or a styrene-acrylic copolymer is preferred.

The reason that the styrenic copolymer is preferable is that a carboxyl group present at some places in the polymer chain of the styrenic copolymer effectively interacts with the aluminum compound of benzylic acid, so that a releasing agent, a magnetic material, etc. This is for improving the dispersibility with the raw material.

As the crosslinkable monomer, mainly 2
A monomer having two or more polymerizable double bonds is used.

The binder resin used in the present invention may be, if necessary, a polymer cross-linked with a cross-linkable monomer as exemplified below.

Aromatic divinyl compounds such as divinylbenzene and divinylnaphthalene; diacrylate compounds linked by an alkyl chain such as ethylene glycol diacrylate, 1,3-butylene glycol diacrylate and 1,4-butanediol Diacrylate,
1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate and methacrylates instead of the above compounds; diacrylate compounds linked by an alkyl chain containing an ether bond , For example, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 400 diacrylate,
Polyethylene glycol # 600 diacrylate, dipropylene glycol diacrylate and acrylates of the above compounds replaced with methacrylate; diacrylate compounds linked by a chain containing an aromatic group and an ether bond, for example, polyoxyethylene ( 2) -2,2
-Bis (4-hydroxydiphenyl) propane diacrylate, polyoxyethylene (4) -2,2-bis (4-
Hydroxydiphenyl) propane diacrylate and those obtained by replacing the acrylates of the above compounds with methacrylates; and further, polyester-type diacrylate compounds, for example, trade name MANDA (Nippon Kayaku). Examples of the polyfunctional crosslinking agent include pentaerythritol triacrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, tetramethylolmethanetetraacrylate, oligoester acrylate, and those obtained by replacing the acrylate of the above compound with methacrylate; Lucyanurate, triallyl trimellitate; and the like.

These cross-linking agents may be used in combination with other monomer components 10
It is preferable to use about 0.01 to 5 parts by mass (more preferably about 0.03 to 3 parts by mass) with respect to 0 parts by mass.

The selection of the initiator, the type of solvent and the reaction conditions when producing the resin of the present invention are important factors for obtaining the resin intended for the present invention. Examples of the initiator include 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-butylperoxide Organic peroxides such as oxides; azo and diazo compounds such as azobisisobutyronitrile and diazoaminoazobenzene can be used.

As a method for synthesizing the binder resin according to the present invention, a bulk polymerization method, a solution polymerization method, a suspension polymerization method, an emulsion polymerization method and the like can be used.

The aluminum compound of benzylic acid of the present invention has an excellent triboelectric charging ability and a high charge amount.
It is a suitable charge control agent for magnetic toners that require a high charge amount. Furthermore, in addition to the good dispersibility of the aluminum compound of benzylic acid itself, if a binder resin having an acid value is used, it works to improve the dispersibility of the magnetic material, so that durability and uniformity of charging can be obtained. .

The magnetic material used in the present invention includes iron oxides such as magnetite, maghemite, and ferrite;
Metals such as cobalt and nickel or alloys of these metals with metals such as aluminum, cobalt, copper, lead, magnesium, manganese, selenium, titanium, tungsten and vanadium and mixtures thereof are used, and the magnetic material surface or inside That contains a non-ferrous element is preferred.

As the magnetic substance 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 the fourth transition metal element are preferred elements. These elements may be taken into the iron oxide crystal lattice, may be taken into the iron oxide as an oxide, or may be present as an oxide or hydroxide on the surface. It is a preferred embodiment that it is contained as an oxide.

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 dispersion of the aluminum compound of benzylic acid used in the present invention, and the effect of the aluminum compound of benzylic acid of the present invention can be sufficiently exhibited.

Further, 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 when the weight average particle diameter is 10 μm or less, the uniformity of charging is promoted, the cohesion of the toner is reduced, and the image density and fog are improved. Developability is improved. In particular, the effect is remarkable in a toner having a weight average particle diameter of 6.0 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, as the particle size of the toner is reduced, the release of the aluminum compound of benzylic acid is apt to occur. However, the toner of the present invention is excellent in charge uniformity, so that even if a small amount of the aluminum compound of benzylic acid is present, the sleeve is not damaged. Less susceptible to contamination.

The content of these different elements is preferably 0.05 to 10% by mass based on the iron element of the magnetic iron oxide. The content is more preferably 0.1 to 7% by mass, particularly preferably 0.2 to 5% by mass, and further preferably 0.3 to 4% by mass. If the content is less than 0.05% by mass, the effect of containing these elements cannot be obtained, and good dispersibility and uniform charging cannot be obtained. On the other hand, when the content is more than 10% by mass, the discharge of electric charge is increased and insufficient charging is caused, so that the image density may be lowered or fog may increase.

In the content distribution of these different elements, it is preferable that the one that is present more in the vicinity of the surface of the magnetic body. For example, the ratio (B / A) × 100 of the content B of the foreign element existing when the iron element dissolution rate of the iron oxide is up to 20% by mass and the total content A of the foreign element of the magnetic iron oxide is 40% or more. It is preferred that Further, it is preferably from 40 to 80%, particularly preferably from 60 to 80%. By increasing the surface abundance, the dispersion effect and the electric diffusion effect can be further improved. The amount contained in the toner is preferably from 20 to 200 parts by mass, more preferably from 4 to 100 parts by mass, per 100 parts by mass of the resin component.
0 to 150 parts by mass is good.

Further, the sphericity (Ψ) of the magnetic iron oxide used in the present invention is preferably 0.8 or more. When the sphericity (Ψ) is smaller than 0.8, the individual particles of the magnetic iron oxide come into surface-to-surface contact with each other and have a particle size of 0.1 to
With a small magnetic iron oxide particle of about 1.0 μm, the magnetic iron oxide cannot be easily separated from each other even with a mechanical shearing force, so that the magnetic iron oxide may not be sufficiently dispersed in the toner. .

In some cases, the magnetic iron oxide used in the toner of the present invention may be treated with a silane coupling agent, a titanium coupling agent, titanate, aminosilane, or the like.

The amount of the element in the magnetic iron oxide of the present invention is determined by the fluorescence X
The measurement was carried out by performing a fluorescent X-ray analysis using a X-ray analyzer SYSTEM3080 (manufactured by Rigaku Denki Kogyo Co., Ltd.) in accordance with JIS K0119 general rules for fluorescent X-ray analysis. Regarding the element distribution, the amount of the element while dissolving hydrochloric acid was measured and quantified by plasma emission spectroscopy (ICP), and the dissolution rate was determined from the concentration of each element at the time of each dissolution with respect to the concentration of each element at the time of total dissolution.

The sphericity (Ψ) of the magnetic iron oxide was measured by using an iron oxide sample treated on a copper mesh of a collodion film with an electron microscope (H-700H, Hitachi, Ltd.) and applying an applied voltage of 100 k
The image is photographed at 10,000 × at V and the printing magnification is 3 ×, and the final magnification is 30,000 ×. by this,
The shape is observed, the maximum length (μm) and the minimum length (μm) of each particle are measured, 100 are randomly selected, calculated according to the following equation, and the calculated values are averaged.

Sphericity = minimum length of magnetic iron oxide (μm) / maximum length of magnetic iron oxide (μm)

Other colorants that can be used in the toner include any suitable pigments or dyes.

For example, pigments include carbon black, aniline black, acetylene black, naphthol yellow, hansa yellow, rhodamine lake, alizarin lake, bengara, phthalocyanine blue, indanthrene blue and the like. These are used in an amount sufficient to maintain the optical density of the fixed image. It is preferable to use 0.1 to 20 parts by mass, preferably 1 to 10 parts by mass of the pigment based on 100 parts by mass of the resin. A dye is further used for the same purpose. For example, there are azo dyes, anthraquinone dyes, xanthene dyes, methine dyes,
It is preferable to use 0.1 to 20 parts by mass, preferably 0.3 to 10 parts by mass of the dye based on 100 parts by mass of the resin.

The following waxes are used as the release agent in the present invention. For example, oxidation of aliphatic hydrocarbon wax such as low molecular weight polyethylene, low molecular weight polypropylene, polyolefin copolymer, polyolefin wax, microcrystalline wax, paraffin wax, Fischer-Tropsch wax; and aliphatic hydrocarbon wax such as polyethylene oxide wax. Or a block copolymer thereof; plant wax such as candelilla wax, carnauba wax, wood wax, jojoba wax; animal wax such as beeswax, lanolin, whale wax; minerals such as ozokerite, ceresin, petrolactam Waxes mainly containing fatty acid esters such as montanic acid ester wax and caster wax; and those obtained by partially or completely deoxidizing fatty acid esters such as deoxidized carnauba wax. That.
Further, unsaturated 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; stearyl alcohol; Saturated alcohols such as eicosyl alcohol, behenyl alcohol, carnaubayl alcohol, seryl alcohol, melisyl alcohol, or long-chain alkyl alcohols having a longer-chain alkyl group; polyhydric alcohols such as sorbitol; linoleic acid amide, oleic acid amide Aliphatic amides such as amide, lauric amide; saturated fatty acid bisamides such as methylenebisstearic acid amide, ethylenebiscapramide, ethylenebislauric amide, hexamethylenebisstearic acid amide; Unsaturated fatty acid amides such as oleic acid amide, hexamethylene bisoleic acid amide, N, N'-dioleyl adipamide, N, N'-dioleyl sebacic acid amide; m-xylene bis stearic acid amide; Aromatic bisamides such as N'-distearyl isophthalic acid amide; fatty acid metal salts such as calcium stearate, calcium laurate, zinc stearate and magnesium stearate (commonly referred to as metal soaps); aliphatic hydrocarbon waxes Wax grafted with a vinyl monomer such as styrene or acrylic acid; partially esterified product of a fatty acid such as behenic acid monoglyceride and a polyhydric alcohol;
Examples include a methyl ester compound having a hydroxyl group obtained by hydrogenating a vegetable oil or fat.

Preferred waxes include polyolefins obtained by radical polymerization of olefins 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 under low pressure using a catalyst such as a Ziegler catalyst or a metallocene catalyst; a polyolefin polymerized by using radiation, electromagnetic waves or light; Low molecular weight polyolefin obtained by pyrolysis of polyolefin; paraffin wax, microcrystalline wax, Fischer-Tropsch wax; synthetic hydrocarbon wax synthesized by the gindol method, hydrocoll method, Aage method, etc .; A synthetic wax, a hydrocarbon wax having a functional group such as a hydroxyl group or a carboxyl group;
A mixture of a hydrocarbon wax and a wax having a functional group; a wax obtained by graft-modifying a vinyl monomer such as styrene, maleic ester, acrylate, methacrylate, or maleic anhydride using these waxes as a base.

Further, these waxes are used in a press sweating method,
Solvent method, recrystallization method, vacuum distillation method, supercritical gas extraction method or liquid crystal method using sharpened molecular weight distribution,
Those from which low molecular weight solid fatty acids, low molecular weight solid alcohols, low molecular weight solid compounds, and other impurities have been removed are also preferably used.

The wax used in the present invention has a melting point of 65 to 16 in order to balance the fixing property and the offset resistance.
The temperature is preferably 0 ° C, more preferably 65 to 130 ° C, and particularly preferably 70 to 120 ° C. If the temperature is lower than 65 ° C., the blocking resistance decreases, and if the temperature exceeds 160 ° C., the offset resistance effect is hardly exhibited.

In the toner of the present invention, the total content of these waxes is 0.2 to 100 parts by mass of the binder resin.
It is effective to use at 20 to 20 parts by mass, preferably 0.5 to 10 parts by mass. Further, other waxes may be used in combination as long as they do not adversely affect.

In the present invention, the melting point of the wax is determined by 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 or a toner by a differential scanning calorimeter, it is preferable that the measurement is performed by a high-precision internal heating 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 taking a pre-history by raising the temperature once, and then measuring the temperature by 10 ° C./min.
After the temperature is lowered in the range of 0 to 200 ° C., a DSC curve measured when the temperature is raised is used.

As the coloring material that can be added to the toner of the present invention, conventionally known pigments or dyes such as carbon black and copper phthalocyanine can be used.

The toner of the present invention is preferably mixed with an inorganic fine powder or a hydrophobic inorganic fine powder. For example, it is preferable to add silica fine powder for use.

The silica fine powder used in the present invention may be either a dry method produced by vapor phase oxidation of a silicon halide compound or a dry method called fumed silica, and a so-called wet method produced from water glass or the like. Can be used, but dry silica which has few silanol groups on the surface and inside and has no production residue is preferable.

The silica fine powder used in the present invention is preferably subjected to a hydrophobic treatment. The hydrophobizing treatment is applied by chemically treating with an organic silicon compound or the like which reacts or physically adsorbs with the silica fine powder. A preferred method is to treat the dry silica fine powder produced by the vapor phase oxidation of the silicon halide compound with a silane coupling agent or simultaneously with the silane coupling agent and an organic silicon compound such as silicone oil. Is mentioned.

Examples of the silane coupling agent used in the hydrophobizing treatment include hexamethyldisilazane, trimethylsilane, trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, and allylphenyl. Dichlorosilane, benzyldimethylchlorosilane, bromomethyldimethylchlorosilane, α-chloroethyltrichlorosilane, β-chloroethyltrichlorosilane,
Chloromethyldimethylchlorosilane, triorganosilane mercaptan, trimethylsilyl mercaptan, triorganosilyl acrylate, vinyldimethylacetoxysilane, dimethylethoxysilane, dimethyldimethoxysilane, diphenyldiethoxysilane, hexamethyldisiloxane, 1,3-divinyltetramethyldi Siloxane and 1,3-diphenyltetramethyldisiloxane.

Examples of the organosilicon compound include silicone oil. Preferred silicone oils have a viscosity at 25 ° C. of about 3 × 10 ⁻⁵ to 1 × 10 ^5
-3 m ² / s, for example, dimethyl silicone oil, methylphenyl silicone oil, α-methylstyrene-modified silicone oil, chlorophenyl silicone oil, and fluorine-modified silicone oil are preferred.

For the method of treating silicone oil, for example, silica fine powder treated with a silane coupling agent and silicone oil may be directly mixed using a mixer such as a Henschel mixer, or the silica may be used as a base. A method of injecting silicone oil may be used. Alternatively, the silicone oil may be dissolved or dispersed in an appropriate solvent, mixed with a base silica fine powder, and the solvent may be removed.

An external additive other than the silica fine powder may be added to the magnetic toner of the present invention, if necessary.

For example, a charging auxiliary, a conductivity-imparting agent, a fluidity-imparting agent, an anti-caking agent, a release agent for fixing with a hot roll,
These are resin fine particles and inorganic fine particles that function as a lubricant, an abrasive and the like.

Lubricants such as, for example, Teflon (registered trademark), zinc stearate, and polyvinylidene fluoride, among which polyvinylidene fluoride is preferred. Alternatively, a polishing agent such as cerium oxide, silicon carbide, and strontium titanate, among which strontium titanate is preferable. Alternatively, for example, a fluidity-imparting agent such as titanium oxide or aluminum oxide, particularly a hydrophobic agent is preferable. A small amount of a caking preventing agent, a conductivity imparting agent such as carbon black, zinc oxide, antimony oxide, tin oxide and the like, and white and black fine particles of opposite polarity can also be used as a developing improver.

The inorganic fine powder or the hydrophobic inorganic fine powder mixed with the magnetic toner is used in an amount of 0.1 to 5 parts by mass (preferably 0.1 to 3 parts by mass) based on 100 parts by mass of the magnetic toner. good.

To produce 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 kneaded well using a hot kneader such as a hot roll, kneader or extruder. Then, after cooling and solidifying, it is preferable to obtain a toner by mechanical pulverization and classification.Otherwise, or after mixing a predetermined material with a monomer to constitute a binder resin to form an emulsified suspension, A method of producing a polymerized toner by polymerizing to obtain a toner, or a method of including a predetermined material in a core material, a shell material, or both in a so-called microcapsule toner composed of a core material and a shell material. After dispersing the constituent materials, a method of obtaining a toner by spray drying can be applied. Further, if necessary, desired additives are sufficiently mixed by a mixer such as a Henschel mixer to produce the toner according to the present invention.

For example, as a mixer, Henschel mixer (manufactured by Mitsui Mining); super mixer (manufactured by Kawata); ribocorn (manufactured by Okawara Seisakusho); Nauta mixer, turbulizer, cyclomix (manufactured by Hosokawa Micron); Spiral pin mixers (manufactured by Taiheiyo Kiko Co., Ltd.); Reedige mixers (manufactured by Matsubo Co., Ltd.); kneading machines include KRC kneader (manufactured by Kurimoto Tekkosho); bus co-kneader (manufactured by Buss); TEM Mold extruder (manufactured by Toshiba Machine Co., Ltd.); TEX twin-screw kneader (manufactured by Nippon Steel Works); PCM kneader (manufactured by Ikegai Iron Works); three roll mill, mixing roll mill, kneader (manufactured by Inoue Seisakusho); knee Decks (manufactured by Mitsui Mining Co., Ltd.); MS type pressure kneader, Nidder Ruder (manufactured by Moriyama Seisakusho); Banbury Mixer (manufactured by Kobe) Tokorosha, Ltd.) and the like. Examples of the pulverizer include a counter jet mill, a micron jet, an inomizer (manufactured by Hosokawa Micron); an IDS-type mill, a PJM jet pulverizer (manufactured by Nippon Pneumatic), a cross jet mill (manufactured by Kurimoto Iron Works), and ulmax ( SK Jet ・
Oh Mill (manufactured by Seishin Enterprise Co., Ltd.); Kryptron (manufactured by Kawasaki Heavy Industries, Ltd.); and Turbo Mill (manufactured by Turbo Kogyo). Classifiers include Classile, Micron Classifier, Spedd Classifier (Seishin Enterprise); Turbo Classifier (Nissin Engineering); Micron separator, Turboflex (ATP), TSP separator (Hosokawa Micron) Elbow jet (manufactured by Nippon Steel Mining), dispersion separator (manufactured by Nippon Pneumatic), and YM microcut (manufactured by Yasukawa Shoji). Ultrasonic (Koei Sangyo Co., Ltd.); Resona Sieve, Gyro Shifter (Tokuju Kosakusho Mori); Vibrasonic System (Dalton); Sonic Clean (Shinto) Turbo Screener (manufactured by Turbo Industries); Microshifter (manufactured by Makino Sangyo); circular vibrating sieve.

[0095]

Although the basic configuration and features of the present invention have been described above, the present invention will be specifically described below based on embodiments. However, this does not limit the embodiment of the present invention at all. Parts in the examples are parts by mass.

Table 1 shows the resins used in the examples, Table 2 shows the waxes, and Table 3 shows the magnetic substances. Styrene resin is
It was synthesized by suspension polymerization or by blending a solution-polymerized resin or a solution-polymerized resin with a solution-polymerized resin. As the magnetic material, magnetite particles were generated while adjusting the pH by adding a salt of an element present inside when magnetite was generated, and magnetic materials 1 to 5 were obtained. The magnetic substances 1 and 3 were made of silicate, the magnetic substance 2 was made of phosphate, and the magnetic substance 4 was made of magnesium salt to produce magnetite particles. In particular, magnetite particles were generated without adding a salt, and then a zirconium salt was added to adjust the pH and zirconia was precipitated on the surface of the magnetite particles to obtain a magnetic material 5.

Example 1-100 parts of binder resin B-90 parts of magnetic substance 1-4 parts of wax c-2 parts of compound (B-1) composed of benzylic acid (2 mol) and Al atom (1 mol) After pre-mixing with a mixer, 130
The mixture was melt-kneaded by a twin-screw kneading extruder set at a temperature of ° 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 subjected to a multi-part classifier utilizing the Coanda effect. To obtain toner particles having a weight average particle size of 6.5 μm. Hexamethylsilazane 15 wt% and dimethyl silicone 15 w
Methanol wettability 80 hydrophobized at t%
%, A hydrophobic silica fine powder having a BET specific surface area of 120 m ² / g, 1.2 parts of strontium titanate and 1.0 part of strontium titanate were externally added and mixed. 1 was prepared.

Table 4 shows the toner internal additives and physical properties.

This toner No. 1 is a commercially available LBP printer (LBP-) using a fixing device comprising a pressing member for bringing a recording material into close contact with the heating member via a film.
430 (manufactured by Canon Inc.) modified to three times the print speed to evaluate the fixability and the anti-offset property, and to use a commercially available LBP printer (LBP-930, LBP-930).
Using a modified version of 2.5 times the printing speed of Canon Inc., an environment of 15 ° C., 10% RH and 30 ° C., 8%
A print test of 15,000 sheets was performed in an environment of 0% RH.
As a result, a high-definition image with high image density and no fog was obtained in both environments. The evaluation results are shown in Tables 5, 6 and 7.

The fixing property was determined by applying a load of 50 g / cm ² ,
The fixed image was rubbed with a soft thin paper, and the reduction in image density before and after rubbing (%) was evaluated. ：: less than 10% △: 10% or more, less than 20% ×: 20% or more

The offset resistance was evaluated by printing out a sample image having an image area ratio of about 5% and evaluating the degree of stain on the image after 3000 sheets. ：: Offset has not occurred. △: Slight offset has occurred. ×: Offset has occurred severely.

The image density was measured by measuring reflection density using a Macbeth densitometer (manufactured by Macbeth) using an SPI filter to measure an image of 5 mm square. 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.

These evaluations were initially performed at 15,000 sheets.
I went after leaving it outside the machine for a day.

Examples 2 to 5 In the same manner as in Example 1, toner Nos. Two
5 were prepared, and the results of similar tests are shown in Tables 5, 6, and 7.

Comparative Examples 1 to 3 In the same manner as in Example 1, the toner Nos.
6, 7, and 8 were prepared, and the results of the same test are shown in Table 5,
6 and 7. In addition, as the organometallic compound, toner N
o. 8, benzylic acid (2 mol) and B atom (1 mol
The compound consisting of l) was used.

[0107]

[Table 1]

[0108]

[Table 2]

[0109]

[Table 3]

[0110]

[Table 4]

[0111]

[Table 5]

[0112]

[Table 6]

[0113]

[Table 7]

[0114]

According to the present invention, it has the above-mentioned aluminum compound of benzylic acid and has at least one peak in a molecular weight range of 3,000 to 30,000 in a molecular weight distribution measured by GPC. Molecular weight 100,
The toner having at least one peak in the region of 000 to 5,000,000 does not deteriorate the fixability, does not cause image defects even with lapse of time or is left, and has high image quality even when used under low humidity. Even when used under wet conditions, high image quality can be stably obtained.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Tsutomu Onuma 3-30-2 Shimomaruko, Ota-ku, Tokyo Inside Canon Inc. (72) Yoshihiro Ogawa 3-30-2 Shimomaruko, Ota-ku, Tokyo Kia Inside Non-corporation (72) Inventor Tsuneo Nakanishi 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Inventor Kaori 3-30-2 Shimomaruko, Ota-ku, Tokyo Inside Canon Inc. F term (reference) 2H005 AA01 AA02 AA06 AA08 CA04 CA13 CA14 CA25 CB03 DA02 EA03 EA06 EA07 EA10 FA06

Claims (12)

[Claims] At least a binder resin, a colorant, a release agent,
In a toner having an organometallic compound, the toner has at least one peak in a molecular weight region of 3,000 to 30,000 in a molecular weight distribution measured by GPC, and further has a molecular weight of 100,000 to 30,000.
At least one peak in the region of 5,000,000, and the organometallic compound is an unsubstituted or substituted benzylic acid (benzilic acid) represented by the following formula (1):
A dry toner comprising an aluminum compound (acid). Embedded image (In the formula, R ₁ and R ₂ may be the same or different and each represents a linear or branched alkyl group, alkenyl group, alkoxy group, halogen atom, nitro group, cyano group, amino group, carboxyl group, A substituent selected from the group consisting of a group and a hydroxyl group, and m and n each represent an integer of 0 to 5.) 2. The dry toner according to claim 1, wherein the aluminum compound of benzylic acid is added in an amount of 0.1 to 10 parts by mass based on 100 parts by mass of the binder resin. 3. The dry toner according to claim 1, wherein the aluminum compound of benzylic acid is externally added to the toner particles in an amount of 0.01 to 5 parts by mass based on 100 parts by mass of the binder resin. 4. The dry toner according to claim 1, wherein the binder resin has a carboxyl group or an acid anhydride group, and has an acid value of 1 to 100 mgKOH / g. . 5. The method according to claim 1, wherein the carboxyl group or the acid anhydride group of the binder resin is formed from an acid monomer selected from at least one of maleic acid, maleic acid half ester, and maleic anhydride. The dry toner according to claim 4, wherein: 6. The dry toner according to claim 1, wherein the binder resin is a styrene copolymer. 7. The dry toner according to claim 1, wherein the colorant is magnetic iron oxide, and is contained in an amount of 20 to 200 parts by mass based on 100 parts by mass of the binder resin. 8. The dry toner according to claim 7, wherein the magnetic iron oxide is magnetic iron oxide fine particles containing 0.05 to 10% by mass of a different element based on the iron element. 9. The ratio (B / A) × the content B of the foreign element present when the dissolution rate of the iron element in the magnetic iron oxide is up to 20% by mass and the total content A of the foreign element in the magnetic iron oxide. 100 is 40
%. The dry toner according to claim 7 or 8, wherein 10. The magnetic iron oxide has a sphericity (Ψ) of 0.8.
The dry toner according to any one of claims 7 to 9, having the above. 11. The dry toner according to claim 1, wherein the release agent is contained in an amount of 0.2 to 20 parts by mass based on 100 parts by mass of the binder resin. 12. The dry toner according to claim 1, wherein the releasing agent has a melting point of 65 to 160 ° C.