JP2003195569A - Black toner - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a black toner which has excellent blocking resistance, preservability under a high-temperature environment, low-temperature fixability, high-temperature offset resistance, glossiness, and transferability and can form high-definition and high grade images. <P>SOLUTION: The black toner contains at least a binder resin, a wax and a coloring agent and is characterized in that the modulus of elasticity in storage (G'<SB>80</SB>) at 80°C of the toner exists in the range from 1×10<SP>6</SP>to 1×10<SP>8</SP>[dN/m<SP>2</SP>]; the loss tangent (tanδ) at 140°C exists in the range from 0.2 to 1.5 and the toner contains at least an iron phthalocyanine compound at 2 to 20 parts by mass per 100 parts by mass the binder resin and the wax at 0.5 to 10 parts by mass per 100 parts by mass the binder resin. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a black toner of an electrostatic charge development or toner jet system, which does not use oil for preventing offset of the toner to a fixing device, or heats with a reduced oil usage. The present invention relates to a black toner that exhibits high definition even when a pressure fixing unit is used.

[0002]

2. Description of the Related Art In recent years, with the widespread use of image forming apparatuses such as copying machines and printers, their applications have expanded to a wide variety and the demands on their image quality have become strict. That is, when copying an image such as a general photograph, a catalog or a map, it is required to reproduce extremely fine and faithfully even a minute portion without being crushed or interrupted.

In addition, the frequency of full-color image formation is increasing, and under the present circumstances, black toner is often required to have a performance capable of being used for color.

Such a toner needs to have good meltability when heat is applied to it and color-mixing properties with other color toners, and has a low softening point and a sharp melt property with a low melt viscosity. It is preferable to use high toner. By using such a sharp melt toner, the color reproduction range of the copy can be widened and a copy faithful to the original image can be obtained. However, such a toner having a high sharp melt property has a high affinity with the fixing roller or the fixing film and tends to be offset to the fixing roller or the fixing film during fixing.

Conventionally, when a sharp melt toner is used, a releasing agent such as silicone oil is applied to the fixing roller in order to improve the releasing property of the toner from the fixing roller. However, in such an image forming method, the following problems have occurred. That is, in the current fixing system in which a releasing agent such as oil is applied to the roller, the structure of the main body becomes complicated and maintainability deteriorates, and this oil application promotes shortening of the life of the fixing roller. There is a problem.

On the other hand, in order to improve the fixing performance, a toner having a specific storage elastic modulus has hitherto been proposed.

For example, in JP-A-11-84716 and JP-A-8-54750, 180 ° C. or 17
Toners having a specific storage modulus at 0 ° C have been proposed.

However, both low-temperature fixing and high-temperature offset resistance are compatible, no oil is used to prevent high-temperature offset, or good fixing properties and sufficient color mixing are achieved by a heating / pressurizing fixing means using a small amount of oil. As a color toner that requires characteristics, the viscosity of the toner is too low, and the storability in a high temperature environment is not satisfactory.

Further, Japanese Patent Laid-Open No. 5-249735,
JP-A-7-92737, JP-A-7-234542
JP-A-7-295298, JP-A-8-2
No. 34480, JP-A-8-278662, and JP-A-10-171156 also propose a toner having a specific storage elastic modulus. However,
In order to obtain practical fixing characteristics and storability, it was necessary to improve.

Further, in order to obtain a good visible image, it is mainly necessary that the toner has good triboelectric chargeability.

If the charge amount of the toner is large, the adhesion between the toner particles is strong, the fluidity is lowered, and problems are likely to occur in the stability of toner replenishment and charge impartment to the replenishment toner.

Further, conventionally, a black conductive material such as a magnetic material or carbon black has been used as a coloring material for black toner, but when these materials are added in an amount sufficient to obtain a sufficient coloring power. Tends to leak charge, and tends to reduce the amount of charge. This tendency is more remarkable when a polyester binder having a high negative charging performance is used.

As a result, the phenomenon of so-called toner scattering or fogging in which toner having a low charge is scattered is likely to occur. Therefore, it is preferable that the amount of such a conductive substance be as small as possible.

It is known that the charge of the toner changes greatly depending on the degree of dispersibility of the colorant in the binder resin and the charging characteristics of the colorant itself as described above. This easily causes problems such as fog and toner scattering, and causes various problems such as toner spent on the carrier, toner filming on the drum, contamination of the fixing roller, and insufficient bending resistance of the fixed image after fixing. Therefore, improving the dispersibility of the colorant is an important technical issue in addition to the color reproducibility.

An example of using an inorganic pigment as a colorant for an electrostatic image developing toner is disclosed in JP-A-10-115949, but it is often used for special purposes such as pattern formation in ceramic products. Generally, carbon black and magnetite are widely used in electrophotography.

Conventionally, examples of using iron phthalocyanine pigments are disclosed in JP-A-3-111480 and JP-A-10-83.
No. 903, No. 208914, Japanese Patent Laid-Open No. 2000-
Although disclosed in JP-A-330326 and the like, JP-A-10-83903 and JP-A-208914 focus on the magnetism, and for processes designed on the assumption that non-magnetic toner is used. , Its magnetism becomes a problem. That is, problems such as poor stirring and poor developability occur.

Further, in Japanese Patent Laid-Open No. 3-111480, attention is paid to the near infrared ray absorbing function, and this alone is not sufficient for toner applications. Further, although Japanese Patent Application Laid-Open No. 2000-330326 focuses on the deodorizing function, it is still one of the objects of the present invention to obtain a long-life developer excellent in fixing characteristics and developing characteristics. Not enough.

Further, conventionally known colorants for black toner have various problems. For example, dye-based colorants are generally inferior in light resistance and have a problem in storage stability of images.

[0019]

SUMMARY OF THE INVENTION An object of the present invention is to provide a black toner which solves the above problems.

That is, 1) it has excellent low-temperature fixability / high-speed fixability, 2) it has excellent storage stability, heat resistance, and blocking resistance, and 3) it has a coloring power that makes it possible to stably obtain high concentrations. 4) Good dispersibility of the colorant and excellent toner covering power (hiding power) 5) High light resistance, 6)
It shows good fixing property and color mixing property, 7) has sufficient triboelectrification property, and 8) has an appropriate glossiness to enhance image quality,
9) The anti-offset performance is sufficiently prevented and the fixing temperature is wide. 10) There is no toner fusion to the developing device, that is, the parts such as the sleeve, the blade and the application roller.
1) Further good cleaning property, no filming on the photoconductor, 12) No toner scattering, no fog, excellent halftone reproducibility, excellent solid uniformity,
(13) It is to provide a black toner which is less likely to be spent as a carrier by repeated copying, 14) has excellent fixing properties such as adhesion of a fixed image and bending resistance of the fixed image, and 15) has excellent durability stability.

[0021]

According to the present invention, a black toner containing at least a binder resin, a wax and a colorant has a storage elastic modulus (G ′ ₈₀ ) of 1 × 10 ⁶ at 80 ° C. To 1 × 10 ⁸ [dN / m ² ] and a loss tangent (tan δ) at 140 ° C. of 0.2 to 1.5, and at least iron phthalocyanine represented by the formula (I) as a colorant. The toner contains a complex compound in an amount of 2 to 20 parts by mass based on 100 parts by mass of the binder resin, and the toner contains wax in an amount of 0.5 to 100 parts by mass of the binder resin.
To 10 parts by mass of the black toner.

[0022]

[Chemical 3] (In the formula, X represents an electron-withdrawing group, and n represents an integer of 1 to 16.)

X in the general formula (I) is a functional group exhibiting an electron-withdrawing property, and examples thereof include a halogen atom, a nitro group, a cyano group, a sulfone group, and the like. From the viewpoints of the above, a halogen atom such as a fluorine atom, a chlorine atom and a bromine atom or a nitro group is preferable, and a fluorine atom and a chlorine atom are particularly preferable.
In addition, n represents the number of X, and the number of n is
It is related to the transportability of electrons and is in the range of 1-16.

As a result of intensive studies by the present inventors, the present invention is excellent in high temperature offset resistance even in a heating and pressure fixing means in which oil is not used or the amount of oil used is small, and long-term storage in a high temperature environment. In order to achieve both stability and low temperature fixability, it has been found that it is effective for the toner to satisfy the above requirements, and in addition, it has high heat resistance, excellent light resistance, and good color tone. Of black toner can be obtained.

[0025]

DETAILED DESCRIPTION OF THE INVENTION The toner of the present invention will be described in detail.

First, the storage elastic modulus (G _'80 ) at a temperature of 80 ° C. is 1 × 10 in order to improve the storage stability, heat resistance and blocking resistance of the toner in a high temperature environment.
⁶ to 1 × 10 ⁸ [dN / m ² ] and preferably 1 × 1
It is 0 ^{6 to} 5 × 10 ⁷ [dN / m ² ]. When the storage elastic modulus (G ′ ₈₀ ) is smaller than 1 × 10 ⁶ [dN / m ² ], the storage stability in a high temperature environment, the heat resistance and the blocking resistance are poor, and the toner particles coalesce with each other. It is not preferable because a large toner aggregate is formed. In recent years, copiers,
Since the output speed of printers and miniaturization of the main body are advancing, the temperature inside the machine tends to rise, and in order to stably obtain high-definition and high-quality images, the toner is It is important to have sufficient storage stability, heat resistance, and blocking resistance in. When the storage elastic modulus (G ′ ₈₀ ) is larger than 1 × 10 ⁸ [dN / m ² ], the storage stability, heat resistance and blocking resistance are sufficient, but sufficient fixability at low temperature is obtained. Is not preferable because it cannot be obtained.

The loss tangent (t
an δ) is 0.2 to 1.5, preferably 0.3 to 1.5, in order to achieve both sufficient fixability and high temperature offset resistance, and further to obtain an image having uniform gloss.
It is 1.0. If the loss tangent (tan δ) is larger than 1.5, it is not preferable because sufficient high temperature offset resistance of the toner cannot be obtained. Also, the loss tangent (t
If an δ) is less than 0.2, the toner cannot be sufficiently fixed, and the image quality is significantly deteriorated.

Further, the binder resin used in the toner of the present invention is (a) a polyester resin, or (b) a hybrid resin having a polyester unit and a vinyl copolymer unit, or (c) a hybrid resin. A resin selected from either a mixture of a vinyl copolymer and a vinyl copolymer or a mixture of (d) a hybrid resin and a polyester resin is preferable, but the resin component is measured by gel permeation chromatography (GPC). The molecular weight distribution shows that the main peak has a molecular weight of 3,500 to 1
It has a molecular weight of 20,000, preferably a molecular weight of 4,000 to 9,000.
It is preferable that Mn is 5.0 or more. When the main peak is in the region where the molecular weight is less than 3,500, the hot offset resistance of the toner is insufficient. On the other hand, when the main peak is in the region where the molecular weight exceeds 10,000,
It is not preferable because sufficient low-temperature fixability of the toner cannot be obtained and the transparency of OHP becomes insufficient. Also, Mw /
When Mn is less than 5.0, it becomes impossible to obtain good offset resistance.

When a polyester resin is used as the binder resin, alcohol and carboxylic acid, carboxylic acid anhydride, carboxylic acid ester or the like can be used as a raw material monomer. Specifically, for example, as the dihydric alcohol component, polyoxypropylene (2.2) -2,2-
Bis (4-hydroxyphenyl) propane, polyoxypropylene (3.3) -2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene (2.0)-
2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (2.0) -polyoxyethylene (2.0) -2,2-bis (4-hydroxyphenyl)
Propylene, polyoxypropylene (6) -2,2-bis (4-hydroxyphenyl) propane and other bisphenol A alkylene oxide adducts, ethylene glycol, diethylene glycol, triethylene glycol,
1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, neopentyl glycol, 1,4-butenediol, 1,5-pentanediol, 1,6-hexanediol, 1,4- Examples thereof include cyclohexanedimethanol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, bisphenol A, hydrogenated bisphenol A and the like.

Examples of trihydric or higher alcohol components include 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-trihydroxymethylbenzene etc. are mentioned.

As the acid component, aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid or their anhydrides; alkyldicarboxylic acids such as succinic acid, adipic acid, sebacic acid and azelaic acid or their anhydrides;
Examples thereof include succinic acid substituted with an alkyl group having 6 to 12 carbon atoms or an anhydride thereof; unsaturated dicarboxylic acids such as fumaric acid, maleic acid and citraconic acid or an anhydride thereof.

Among them, particularly, the following general formula (3)
And a carboxylic acid component consisting of a carboxylic acid having a valence of 2 or more or a carboxylic acid thereof or an acid anhydride thereof or a lower alkyl ester thereof (for example, fumaric acid, maleic acid, maleic anhydride, phthalic acid, Polyester resins obtained by polycondensing terephthalic acid, trimellitic acid, pyromellitic acid, etc.) as acid components are preferable because they have good charging characteristics.

[0033]

[Chemical 4] (In the formula, R represents an ethylene or propylene group, and x, y
Are each an integer of 1 or more, and the average value of x + y is 2 to 10. )

Further, when a hybrid resin having a polyester unit and a vinyl-based copolymer unit is used as the binder resin, further excellent wax dispersibility and
It can be expected to improve low-temperature fixability and offset resistance. The “hybrid resin component” used in the present invention means a resin in which a vinyl polymer unit and a polyester unit are chemically bonded. Specifically, a polyester unit and a vinyl polymer unit obtained by polymerizing a monomer having a carboxylic acid ester group such as (meth) acrylic acid ester are formed by a transesterification reaction, preferably a vinyl polymer. To form a graft copolymer (or block copolymer) in which the main polymer is a trunk polymer and the polyester unit is a branch polymer.

Examples of the vinyl-based monomer for producing the vinyl-based resin include the following. Styrene: o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, p-phenylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p-tert- Butylstyrene, pn-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene, pn-dodecylstyrene, p-methoxystyrene, p-chlorostyrene, 3, Styrene and its derivatives such as 4-dichlorostyrene, m-nitrostyrene, o-nitrostyrene and p-nitrostyrene; styrene unsaturated monoolefins such as ethylene, propylene, butylene and isobutylene; unsaturated such as butadiene and isoprene Polyenes; vinyl chloride, vinylden chloride,
Vinyl halides such as vinyl bromide and vinyl fluoride;
Vinyl esters such as vinyl acetate, vinyl propionate, vinyl benzoate; methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-methacrylic acid
Α-methylene aliphatic monocarboxylic acids such as butyl, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate. Esters; methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-octyl acrylate,
Dodecyl acrylate, 2-ethylhexyl acrylate,
Stearyl acrylate, 2-chloroethyl acrylate,
Acrylic esters such as phenyl acrylate; Vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether; Vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone, methyl isopropenyl ketone; N-vinyl pyrrole, N
-N-vinyl compounds such as vinylcarbazole, N-vinylindole and N-vinylpyrrolidone; vinylnaphthalenes; acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile and acrylamide.

Further, unsaturated dibasic acids such as maleic acid, citraconic acid, itaconic acid, alkenylsuccinic acid, fumaric acid, mesaconic acid; maleic anhydride, citraconic anhydride, itaconic anhydride, alkenylsuccinic anhydride. Unsaturated dibasic acid anhydrides such as: maleic acid methyl half ester, maleic acid ethyl half ester, maleic acid butyl half ester, citraconic acid methyl half ester, citraconic acid ethyl half ester, citraconic acid butyl half ester, itaconic acid methyl ester Half ester of unsaturated dibasic acid such as half ester, methyl alkenyl succinic acid half ester, fumaric acid methyl half ester, mesaconic acid methyl half ester; unsaturated dibasic acid ester such as dimethyl maleic acid, dimethyl fumaric acid; Le acid, methacrylic acid, crotonic acid,
Α, β-unsaturated acids such as cinnamic acid; crotonic anhydride,
Α, β-unsaturated acid anhydrides such as cinnamic acid anhydride,
An anhydride of β-unsaturated acid and lower fatty acid; alkenylmalonic acid, alkenylglutaric acid, alkenyladipic acid,
Examples thereof include monomers having a carboxyl group such as acid anhydrides and monoesters thereof.

Further, acrylic acid or methacrylic acid esters such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate; 4- (1-hydroxy-1-methylbutyl) styrene, 4- (1- Mention may be made of monomers having a hydroxy group such as hydroxy-1-methylhexyl) styrene.

In the toner of the present invention, the vinyl polymer unit of the binder resin may have a crosslinked structure crosslinked with a crosslinking agent having two or more vinyl groups, but the crosslinking used in this case. Examples of the agent include aromatic divinyl compounds such as divinylbenzene and divinylnaphthalene; examples of diacrylate compounds linked by an alkyl chain include ethylene glycol diacrylate, 1,
3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6 hexanediol diacrylate, neopentyl glycol diacrylate and those obtained by replacing the acrylate of the above compounds with methacrylate. Examples of diacrylate compounds linked by an alkyl chain containing an ether bond include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 400 diacrylate, and the like.
Examples thereof include polyethylene glycol # 600 diacrylate, dipropylene glycol diacrylate, and those obtained by replacing the acrylate of the above compounds with methacrylates; examples of diacrylate compounds linked by a chain containing an aromatic group and an ether bond include polyoxy compounds. Ethylene (2) -2,2-bis (4-hydroxyphenyl) propane diacrylate, polyoxyethylene (4) -2,
2-bis (4-hydroxyphenyl) propane diacrylate and the compounds obtained by replacing the acrylates of the above compounds with methacrylates can be mentioned.

As the polyfunctional cross-linking agent, pentaerythritol triacrylate, trimethylol ethane triacrylate, trimethylol propane triacrylate, tetramethylol methane tetraacrylate, oligoester acrylate and the acrylates of the above compounds are replaced by methacrylates; Examples include triallyl cyanurate and triallyl trimellitate.

In the present invention, it is preferable that the vinyl copolymer component and / or the polyester resin component contain a monomer component capable of reacting with both resin components. Among the monomers constituting the polyester resin component, those capable of reacting with the vinyl-based copolymer include, for example, phthalic acid, maleic acid,
Examples thereof include unsaturated dicarboxylic acids such as citraconic acid and itaconic acid, or anhydrides thereof. Among the monomers constituting the vinyl-based copolymer component, those capable of reacting with the polyester resin component include those having a carboxyl group or a hydroxy group, and acrylic acid or methacrylic acid esters.

As a method for obtaining the reaction product of the vinyl resin and the polyester resin, either one of the above-mentioned polymers containing monomer components capable of reacting with the vinyl resin and the polyester resin is present. Alternatively, a method of obtaining by polymerizing both resins is preferable.

The polymerization initiator used when producing the vinyl copolymer of the present invention is, for example, 2,2′-
Azobisisobutyronitrile, 2,2'-azobis (4
-Methoxy-2,4-dimethylvaleronitrile), 2,
2'-azobis (-2,4-dimethylvaleronitrile), 2,2'-azobis (-2 methylbutyronitrile), dimethyl-2,2'-azobisisobutyrate,
1,1'-azobis (1-cyclohexanecarbonitrile), 2- (carbamoylazo) -isobutyronitrile, 2,2'-azobis (2,4,4-trimethylpentane), 2-phenylazo-2,4- Dimethyl-4-methoxyvaleronitrile, 2,2'-azobis (2-methyl-propane), methyl ethyl ketone peroxide,
Ketone peroxides such as acetylacetone peroxide and cyclohexanone peroxide, 2,2-
Bis (t-butylperoxy) butane, t-butyl hydroperoxide, cumene hydroperoxide,
1,1,3,3-tetramethylbutyl hydroperoxide, di-t-butyl peroxide, t-butyl cumyl peroxide, di-cumyl peroxide, α,
α′-bis (t-butylperoxyisopropyl) benzene, isobutyl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, benzoyl peroxide, m- Trioyl peroxide, di-isopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-n-propyl peroxydicarbonate,
Di-2-ethoxyethyl peroxycarbonate, di-
Methoxyisopropyl peroxydicarbonate, di (3-methyl-3-methoxybutyl) peroxycarbonate, acetylcyclohexylsulfonyl peroxide, t-butylperoxyacetate, t-butylperoxyisobutyrate, t-butylperoxyneo Decanoate, t-butylperoxy 2-ethylhexanoate, t-butylperoxylaurate, t-butylperoxybenzoate, t-butylperoxyisopropyl carbonate, di-t-butylperoxyisophthalate, t-butyl peroxyallyl carbonate,
t-amyl peroxy 2-ethylhexanoate, di-
t-butyl peroxyhexahydroterephthalate,
An example is di-t-butyl peroxyazelate.

Examples of the production method capable of preparing the hybrid resin used in the toner of the present invention include the production methods shown in the following (1) to (6).

(1) A method in which vinyl resin, polyester resin and hybrid resin components are blended after production, and the blend is produced by dissolving and swelling in an organic solvent (eg xylene) and then distilling off the organic solvent. It Incidentally, the hybrid resin component, after separately producing a vinyl polymer and a polyester resin, dissolved and swollen in a small amount of an organic solvent, added with an esterification catalyst and alcohol,
An ester compound synthesized by performing transesterification by heating can be used.

(2) After the vinyl polymer unit is manufactured,
It is a method of producing a polyester unit and a hybrid resin component in the presence of this. The hybrid resin component is produced by reacting a vinyl polymer unit (a vinyl monomer can be added if necessary) with a polyester monomer (alcohol, carboxylic acid) and / or polyester. Also in this case, an organic solvent can be appropriately used.

(3) A method for producing a vinyl polymer unit and a hybrid resin component in the presence of the polyester unit after the production. The hybrid resin component is produced by reacting a polyester unit (a polyester monomer can be added if necessary) with a vinyl-based monomer and / or a vinyl-based polymer unit.

(4) After the vinyl polymer unit and the polyester unit are produced, the vinyl resin and / or the polyester monomer (alcohol, carboxylic acid) are added in the presence of these polymer units to produce the hybrid resin component. It Also in this case, an organic solvent can be appropriately used.

(5) After the production of the hybrid resin component, a vinyl-based monomer and / or a polyester monomer (alcohol, carboxylic acid) is added to carry out addition polymerization and / or polycondensation reaction, and thereby a vinyl-based polymer unit and polyester. The unit is manufactured. In this case, as the hybrid resin component, those manufactured by the above-mentioned manufacturing methods (2) to (4) can be used, and those manufactured by a known manufacturing method can be used as necessary. Furthermore, an organic solvent can be appropriately used.

(6) A vinyl-based polymer unit, a polyester unit and a hybrid resin component are produced by mixing vinyl-based monomers and polyester monomers (alcohol, carboxylic acid, etc.) and continuously performing addition polymerization and polycondensation reaction. To be done. Furthermore, an organic solvent can be appropriately used.

In the above production methods (1) to (5), the vinyl polymer unit and / or the polyester unit may be a plurality of polymer units having different molecular weights and crosslinking degrees.

The binder resin contained in the toner of the present invention is a mixture of the above polyester and a vinyl copolymer, a mixture of the above hybrid resin and a vinyl copolymer, the above polyester resin and the above hybrid resin. In addition to this, a mixture of vinyl-based copolymers may be used.

Next, the wax used in the present invention will be described.

The toner of the present invention contains one kind or two or more kinds of wax.

Further, the toner of the present invention has a temperature of 30 at the endothermic curve in the differential thermal analysis (DSC) measurement from the viewpoint of achieving both low temperature fixing property and blocking resistance.
Have one or more endothermic peaks in the range of ~ 200 ° C,
The peak temperature of the maximum endothermic peak in the endothermic peak is 50 to
It is preferably in the range of 120 ° C. More preferably, the maximum endothermic curve peak is in the range of 60 to 100 ° C. When the peak temperature of the maximum endothermic peak is less than 50 ° C., the blocking resistance of the toner becomes poor,
Further, fogging is likely to occur in a high temperature environment. On the other hand, if the peak temperature of the maximum endothermic peak exceeds 120 ° C., the fixability will decrease.

Examples of the wax used in the present invention include the following. Aliphatic hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, microcrystalline wax, paraffin wax, oxides of aliphatic hydrocarbon waxes such as oxidized polyethylene wax, or block copolymers thereof; carnauba wax, Examples thereof include waxes containing a fatty acid ester as a main component such as sazole wax and montanic acid ester wax, and those obtained by partially or entirely deoxidizing fatty acid ester such as deoxidized carnauba wax. Further, saturated linear fatty acids such as palmitic acid, stearic acid, and montanic acid; unsaturated fatty acids such as brassic acid, eleostearic acid, and valinaric acid; stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnaubayl alcohol, ceryl alcohol. , Saturated alcohols such as melisyl alcohol; polyhydric alcohols such as sorbitol; linoleic acid amide,
Fatty acid amides such as oleic acid amide and lauric acid amide; saturated fatty acid bisamides such as methylenebisstearic acid amide, ethylenebiscapric acid amide, ethylenebislauric acid amide, hexamethylenebisstearic acid amide; ethylenebisoleic acid amide, Unsaturated fatty acid amides such as hexamethylene bisoleic acid amide, N, N'dioleyl adipamide, N, N'dioleyl sebacic acid amide; m-xylene bisstearic acid amide, N, N 'distearyl isophthalic acid Aromatic bisamides such as amides; Aliphatic metal salts such as calcium stearate, calcium laurate, zinc stearate, magnesium stearate (generally called metal soap); aliphatic hydrocarbon wax, styrene and acrylic Waxes grafted with vinyl monomers such as; partial esterification products of fatty acids such as behenic acid monoglyceride and polyhydric alcohols; methyl ester compounds having a hydroxyl group obtained by hydrogenation of vegetable oils and the like. To be

As the wax particularly preferably used in the present invention, an aliphatic hydrocarbon wax can be mentioned. For example, a low molecular weight alkylene polymer obtained by radically polymerizing alkylene under a high pressure or a Ziegler catalyst under a low pressure; an alkylene polymer obtained by thermally decomposing a high molecular weight alkylene polymer; a synthesis gas containing carbon monoxide and hydrogen; A synthetic hydrocarbon wax obtained from the distillation residue of hydrocarbon obtained by the method or obtained by hydrogenating these is preferable. Further, the one in which the hydrocarbon wax is fractionated by the use of press sweating method, solvent method, vacuum distillation or fractional crystallization method is more preferably used. Hydrocarbons as a base are those synthesized by the reaction of carbon monoxide and hydrogen using a metal oxide catalyst (often two or more multi-component catalysts) [eg, gintol method, hydrocoal method (fluid catalyst bed Hydrocarbon compounds synthesized by the use)]; Hydrocarbons having up to several hundred carbons obtained by the Arge method (using an identification catalyst bed) in which a lot of waxy hydrocarbons are obtained; Alkylene such as ethylene by Ziegler catalyst The polymerized hydrocarbon is preferable because it is a straight chain hydrocarbon having little branching, small size, and long saturation. A wax synthesized by a method that does not rely on the polymerization of alkylene is particularly preferable because of its molecular weight distribution.

In the molecular weight distribution of the wax, the main peak is preferably in the region of molecular weight 400 to 2400, and more preferably in the region of 430 to 2000. By having such a molecular weight distribution, preferable thermal characteristics can be imparted to the toner.

The melting point of the wax is preferably 60 to 110 ° C., more preferably 65 to 100 ° C., so that the wax functions more effectively during fixing of the toner.

The wax is used in an amount of 0.5 to 10 parts by mass, preferably 2 to 8 parts by mass, per 100 parts by mass of the binder resin.

The wax is usually contained in the binder resin by a method of dissolving the resin in a solvent, raising the temperature of the resin solution, and adding and mixing while stirring, or a method of mixing at the time of kneading.

Next, the pigment used in the present invention will be described.

The inventors of the present invention have made earnest studies on black toner, and as a result of using the iron phthalocyanine compound represented by the general formula (I) as the toner having the viscoelastic property of the present invention, the charging It has been found that a toner having a good charging property that rises quickly and can be maintained for a long period of time can be obtained. Further, a toner having a sufficient coloring power can be obtained, and a toner with less fog and toner scattering can be obtained.

Among them, the axially coordinated iron phthalocyanine compound represented by the general formula Fe (Cl) Pc is particularly preferable. In the formula, Pc represents a phthalocyanine residue, and chlorine in one molecule is 3.
It contains 0 to 5.9% by mass, preferably 4.5 to 5.9% by mass.

The combined use of the binder resin and the iron phthalocyanine colorant, which bring about the physical properties of the toner in the present invention, shows excellent dispersibility, no detachment from the toner surface is observed, and various problems such as fog, drum contamination and cleaning failure are observed. Does not cause the problem of. Further, even when the toner is used as a two-component developer, it does not cause a problem such as carrier contamination and exhibits stable charging characteristics in long-term durability.

The toner of the present invention also has excellent light resistance,
The image sample is a JIS K
Almost according to 7102, even when a long-term exposure test was performed, almost no color change was observed.

Magnetite and maghemite are suitable as black and brown pigment powders for coloring. However, when a magnetic iron oxide pigment powder such as magnetite or maghemite is used, unlike the non-magnetic inorganic coloring pigment powder, it tends to cause magnetic agglomeration because it has magnetism and tends to have poor dispersibility. Those that do not have magnetism are preferred.

In the present invention, it is particularly preferable to use an inorganic colorant together with the iron phthalocyanine pigment. Specific examples of the inorganic colorant include metal oxides as exemplified below.

For example, as a metal oxide, red iron oxide, chrome green, etc., as a solid solution of metal oxide, manganese pink, chrome alumina green, chrome titanium yellow,
Vanadium tin yellow, antimony tin grayish blue, lilac, vanadium zirconium yellow, etc. (Zn, Co) O.Al ₂ O ₃ , ZnO. (A
1, Cr) ₂ O ₃ , (Zn, Co) O · (Al, Cr) ₂
O ₃ , ZnO. (Al, Cr, Fe) ₂ O ₃ , (Mn, C
o) O. (Cr, Fe) ₂ O ₃ , CuO.Cr ₂ O _3, etc.,
As a solid solution of the complex oxide, antimony yellow and the like can be mentioned. In addition, cobalt olipin, nickel olipin, uvarovite, etc. as silicates, chromium tin pink, vanadium blue, turkish blue, as solid solution of silicate,
Examples thereof include praseodymium yellow and coral red, sulfides such as cadmium orange, and sulfur selenides such as cadmium red, selenium red, and mandarin.

By adding an inorganic pigment having a high true specific gravity to the iron phthalocyanine pigment, the coloring power is improved and the dispersibility of the colorant is improved. This also contributes to improving the dispersibility of the wax in the binder resin. Further, this is a phenomenon that cannot be brought about by the conventional black toner using only the inorganic pigment or dye or the black toner obtained by mixing a plurality of organic pigments or dyes. Further, the bending resistance of the fixed image can be maintained.

Further, when the average dispersed particle size of the iron phthalocyanine complex compound in the toner is smaller than the average dispersed particle size of the inorganic pigment in the toner, the effect of improving the dispersibility is large, and more preferably, the iron phthalocyanine The average dispersed particle diameter of the complex compound in the toner is preferably 2/3 or less of the average dispersed particle diameter of the inorganic pigment in the toner. It is considered that this is because the iron phthalocyanine complex compound mainly contributes to the hiding power, and the inorganic pigment mainly contributes to the tint control and the dispersibility improvement. The particle size of these pigments is determined by TEM observation.

The reason why good results can be obtained by using the inorganic pigment is that when the substances having different specific gravities are used as the pigment component, especially when the resin having the property of obtaining the toner viscoelasticity of the present invention is used, the dispersion is improved. Is improved,
It is possible to obtain a sufficient coloring power and an appropriate gloss value. Further, it has been found that the dispersibility of the wax is improved and the fixable temperature range is greatly expanded. The effect of improving the wax dispersibility is particularly large with respect to the wax having a relatively low melting point which can be preferably used in the present invention.

Examples of the inorganic pigment include carbon black, titania, zinc oxide, metatitanic acid compounds and the like. The inorganic pigment may be used alone,
Two or more kinds may be used in combination, and the total addition amount of the inorganic pigment is
2 to 6% by mass relative to the toner particles is preferred, 2.5 to
5 mass% is more preferable. It is also possible to contain resin powder or inorganic powder such as silica or alumina.

The inorganic pigment preferably has no magnetism, but when a magnetic material having a saturation magnetization of more than 60 Am ² / g is used, its content should be 5% by mass or less based on the mass of the toner. Is desirable. 5% by mass
When it exceeds, the developability is lowered and it becomes difficult to obtain a sufficient image density.

Further, in the present invention, other coloring agents may be used in combination with the iron phthalocyanine compound.

As the colorant used, pigments and / or dyes can be used.

For example, as the dye, C.I. I. Direct Red 1, C.I. I. Direct Red 4, C.I. I. Acid Red 1, C.I. I. Basic Red 1, C.I. I.
Mordant Red 30, C.I. I. Direct Blue 1,
C. I. Direct Blue 2, C.I. I. Acid Blue 9, C.I. I. Acid Blue 15, C.I. I. Basic Blue 3, C.I. I. Basic Blue 5, C.I. I. Mordant Blue 7, C.I. I. Direct Green 6, C.I.
I. Basic Green 4, C.I. I. Basic green 6 and the like can be mentioned.

As the pigment, mineral fast yellow, navel yellow, naphthol yellow S, Hansa yellow G, permanent yellow NCG, tartrazine lake, molybdenum orange, permanent orange GTR, pyrazolone orange, benzidine orange G,
Permanent Red 4R, Watching Red Calcium Salt, Eosin Lake, Brilliant Carmine 3B, Manganese Purple, Fast Violet B, Methyl Violet Lake, Cobalt Blue, Alkali Blue Lake, Victoria Blue Lake, Phthalocyanine Blue, Fast Sky Blue, Indanthrene Blue. BC, chrome green, pigment green B, malachite green rake, final yellow green G and the like.

As the magenta pigment, C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9,
10, 11, 12, 13, 14, 15, 16, 17, 1
8, 19, 21, 22, 23, 30, 31, 32, 3
7, 38, 39, 40, 41, 48, 49, 50, 5
1, 52, 53, 54, 55, 57, 58, 60, 6
3,64,68,81,83,87,88,89,9
0,112,114,122,123,163,20
2,206,207,209,238, C.I. I. Pigment violet 19, C.I. I. Bat red 1, 2,
10, 13, 15, 23, 29, 35 and the like.

Although such a pigment may be used, it is also possible to use a dye and a pigment together. Examples of magenta dyes include C.I. I. Solvent Red 1,3,8,23,2
4, 25, 27, 30, 49, 81, 82, 83, 8
4,100,109,121, C.I. I. Disperse Red 9, C.I. I. Solvent Violet 8,13,1
4, 21, 27, C.I. I. Disperse Violet 1
Oil-soluble dyes such as C.I. I. Basic red 1, 2,
9, 12, 13, 14, 15, 17, 18, 22, 2
3,24,27,29,32,34,35,36,3
7, 38, 39, 40, C.I. I. Basic Violet 1,3,7,10,14,15,21,25,26,
And basic dyes such as 27 and 28.

Cyan pigments include C.I. I. Pigment Blue 2, 3, 15, 16, 17; C.I. I. Acid Blue 6; C.I. I. Acid Blue 45 or a copper phthalocyanine pigment having 1 to 5 phthalimidomethyl groups substituted on the phthalocyanine skeleton.

As the yellow pigment, C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11,
12, 13, 14, 15, 16, 17, 23, 62, 6
5,73,74,83,93,97,147,155,
168, 180, 185, C.I. I. Bat yellow one
3, 20 and the like.

The amount of these colorants used is not particularly limited, but is preferably 20 parts by mass or less with respect to 100 parts by mass of the binder resin.

The toner of the present invention preferably contains a metal compound of an aromatic carboxylic acid derivative. This not only functions as a charge control agent,
It has a cross-linking action and also contributes to adjusting the viscoelasticity of the toner within the range of the present invention.

Although the reason why the metal compound of the aromatic carboxylic acid derivative improves the dispersibility of the pigment is not clear, a partial crosslinking reaction proceeds due to the interaction between the binder resin and the metal compound of the aromatic carboxylic acid derivative. It can be considered that the dispersibility of the hardly dispersible pigment of the formula (I) was increased by increasing the share of the colorant during kneading.

Examples of the aromatic carboxylic acid include the following three compounds (4) to (6).

[0086]

[Chemical 5] [In the formula, R ₁ to R ₇ are the same or different groups, a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon _{atoms, -OH, -NH 2, -NH (} CH 3 ), -N
_{(CH 3) 2, -OCH 3} , -O (C 2 H 5), - COOH
Or show a -CONH _2. ]

Preferred R ₁ is a hydroxyl group,
An amino group and a methoxy group are mentioned, and a hydroxyl group is preferable among them. As the aromatic carboxylic acid, a dialkyl salicylic acid such as di-tert-butyl salicylic acid is particularly preferable.

As the metal forming the organometallic compound,
Mg ²⁺ , Ca ²⁺ , Sr ²⁺ , Pb ²⁺ , Fe ²⁺ , Co ²⁺ , N
i ²⁺ , Zn ²⁺ , Cu ²⁺ , Al ³⁺ , Cr ³⁺ , Fe ³⁺ , Zr
⁴⁺ can be given. In the present invention, the organometallic compound is preferably an aluminum compound of di-tert-butylsalicylic acid.

The metal compound of aromatic carboxylic acid is, for example, an aromatic carboxylic acid dissolved in a sodium hydroxide aqueous solution, an aqueous solution in which metal atoms having a valence of 2 or more are melted is added dropwise to the sodium hydroxide aqueous solution, and the mixture is heated and stirred. Then, the pH of the aqueous solution is adjusted, cooled to room temperature, and then filtered and washed with water to synthesize a metal compound of an aromatic carboxylic acid.
However, the synthesis method is not limited to the above.

The organometallic compound is used in an amount of 0.5 to 10 parts by weight, preferably 1 to 9 parts by weight, and more preferably 1.5 to 8 parts by weight, based on 100 parts by weight of the binder resin. It is also preferable in terms of adjusting the triboelectric charging characteristics.

When the amount is less than 0.5 part by mass, not only does it not function as a charge control agent, but also good pigment dispersibility cannot be achieved. On the other hand, when the amount is more than 10 parts by mass, the crosslinking proceeds too much and the fixability as a toner is impaired.

In the toner of the present invention, a compound other than the above-mentioned organometallic compounds may be used as a charge control agent, if necessary, in order to further stabilize its chargeability.

In addition to the above, preferred examples of the charge control agent usable in the present invention include the compounds shown below.

[0094]

[Chemical 6]

By using this compound, the durability of the charge amount hardly changes and a long life can be achieved.

To prepare the toner particles used in the present invention, a binder resin, a pigment as a colorant, a wax, and if necessary, a charge control agent and other additives are sufficiently mixed with a mixer such as a ball mill. After mixing, heat roll,
The toner is melted, kneaded and kneaded using a kneader such as a kneader or an extruder to make the resins compatible with each other to disperse the pigment, and after cooling and solidification, pulverization and strict classification are carried out to obtain toner particles. Obtainable.

Examples of the kneading device include a heating kneader, a single-screw extruder, a twin-screw extruder, and a kneader.
A heating kneader is particularly preferable.

The toner of the present invention has a weight average particle diameter of 4 to 1.
It is preferably 0 μm. Further, the toner of the present invention has a number average particle size of 3.5 to 9.5 μm, 5 to 50% by number of particles having a particle size of 4 μm or less in the toner number distribution, and a particle size in the toner volume distribution. 12.70
It is preferable that the particles having a size of μm or more are 5 vol% or less.

In the toner of the present invention, the toner particles having a particle diameter of 4 μm or less are preferably 5 to 50% by number, and more preferably 5 to 25% by number based on the total number of particles. Furthermore, particle size 1
From the viewpoint of improving image quality, it is preferable that particles having a particle size of 2.70 μm or more be 7% by volume or less.

Further, it is preferable that the fluidity improver is externally added to the toner particles of the present invention from the viewpoints of image quality improvement and storability in a high temperature environment. As the fluidity improver, inorganic fine powder such as silica, titanium oxide, aluminum oxide is preferable. The inorganic fine powder is preferably hydrophobized with a hydrophobizing agent such as a silane coupling agent, silicone oil, or a mixture thereof.

Examples of the hydrophobizing agent include coupling agents such as silane coupling agents, titanate coupling agents, aluminum coupling agents and zircoaluminate coupling agents.

Specifically, for example, as a silane coupling agent, RmSiYn [wherein R represents an alkoxy group, m represents an integer of 1 to 3, Y represents an alkyl group, a vinyl group, a phenyl group, a meta group] An acryl group, an amino group, an epoxy group, a mercapto group or a derivative thereof is shown, and n is an integer of 1 to 3. ] What is represented by these is preferable. For example, vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, isobutyltrimethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, trimethylmethoxysilane, hydroxypropyl. Examples thereof include trimethoxysilane, phenyltrimethoxysilane, n-hexadecyltrimethoxysilane, and n-octadecyltrimethoxysilane.

The treatment amount is preferably 1 to 60 parts by mass, and more preferably 3 parts by mass with respect to 100 parts by mass of the inorganic fine powder.
˜50 parts by mass.

Particularly preferred in the present invention is a compound represented by the general formula (7):

[0105]

[Chemical 7] [In formula, n shows the integer of 4-12 and m shows the integer of 1-3. ] It is an alkyl alkoxy silane coupling agent shown by these. In the alkylalkoxysilane coupling agent, when n is less than 4, the treatment is easy, but the degree of hydrophobicity is low, which is not preferable. When n is greater than 12, the hydrophobicity is sufficient, but the titanium oxide fine particles are often coalesced with each other, so that the fluidity-imparting ability is likely to decrease. m is 3
When it is larger, the reactivity of the alkylalkoxysilane coupling agent is lowered, and it becomes difficult to favorably perform hydrophobicity. More preferably, the alkylalkoxysilane coupling agent has n of 4 to 8 and m of 1 to 2.

The treatment amount of the alkylalkoxysilane coupling agent is also preferably 1 to 60 parts by mass, more preferably 3 to 50 parts by mass with respect to 100 parts by mass of the inorganic fine powder.

The hydrophobizing treatment may be carried out by using one kind of hydrophobizing agent alone, or by using two or more kinds of hydrophobizing agents.
For example, one type of coupling agent may be used alone for hydrophobic treatment, or two types of coupling agents may be used for hydrophobic treatment at the same time, or after another type of coupling agent is used for hydrophobic treatment, another coupling agent may be used for further hydrophobic treatment. You may perform a conversion process.

The fluidizing agent is preferably added in an amount of 0.01 to 5 parts by mass with respect to 100 parts by mass of the toner particles,
It is more preferable to add 05 to 3 parts by mass.

The black toner of the present invention can be applied to a one-component developer and a two-component developer and is not particularly limited. When the black toner of the present invention is used in a two-component developer, examples of carriers used in combination include, for example, surface-oxidized or unoxidized iron, nickel, copper, zinc, cobalt, manganese, chromium, rare earth metals and the like. Alloys or oxides and ferrites can be used. Further, a resin carrier in which fine particles such as magnetite and hematite are bound and granulated with a resin can be used.

In particular, magnetic ferrite particles of three elements of Mn-Mg-Fe formed by using manganese, magnesium and iron components as main components are preferable as carrier particles. The magnetic carrier particles are preferably coated with a resin, and the resin is preferably a silicone resin. In particular, a nitrogen-containing silicone resin or a modified silicone resin produced by reacting a nitrogen-containing silane coupling agent with a silicone resin is used to impart a negative triboelectric charge to the color toner of the present invention, environmental stability, and carrier. It is preferable in terms of suppressing the contamination of the surface of the.

The magnetic carrier has an average particle size of 15 to 60.
μm (more preferably 25 to 50 μm) is preferable. As a method for preparing the magnetic particles so as to have the above-mentioned average particle size and specific particle size distribution, for example, classification can be performed by using a sieve. In particular,
In order to carry out classification with high accuracy, it is preferable to repeat the sieving a plurality of times using a sieve having an appropriate opening. It is also an effective means to use a mesh whose opening shape is controlled by plating or the like.

When a two-component developer is prepared, good results are usually obtained when the mixing ratio is 2 to 15% by mass, preferably 4 to 13% by mass as the toner concentration in the developer. If the toner density is less than 2%, the image density tends to be low, and if it exceeds 15% by mass, fog and in-machine scattering are likely to increase.

Next, methods for measuring each physical property will be described below.

Toner Viscoelasticity Measuring Method The toner is pressure-molded into a disk-shaped sample having a diameter of 8 mm and a thickness of about 2 to 3 mm. Next, set on the parallel plate and
The temperature is gradually raised in the temperature range of 0 to 200 ° C., and the temperature dispersion is measured. The temperature rising rate is 2 ° C./min, the angular frequency (ω) is fixed at 6.28 rad / sec, and the strain rate is automatic. The temperature is plotted on the horizontal axis and the storage elastic modulus (G ') is plotted on the vertical axis, and the value at each temperature is read.

Loss elastic modulus (G ″) / storage elastic modulus (G ′)
Then, the loss tangent (tan δ) is obtained. RDA-II (Rheometrics) is used for the measurement.

Method for measuring endothermic peak of toner ASTM D3418-8 using a differential scanning calorimeter (DSC measuring device), DSC-7 (manufactured by Perkin Elmer)
Measure according to 2. A measurement sample is precisely weighed in an amount of 2 to 10 mg, preferably 5 mg. This is put in an aluminum pan, and an empty aluminum pan is used as a reference, and a temperature rising rate is 10 ° C / min in a measurement temperature range of 30 to 200 ° C.
At room temperature and humidity. During this temperature raising process, the temperature 30
The endothermic peak of the main peak of the DSC curve in the range of ˜200 ° C. is obtained.

Molecular Weight (GPC) Measurement The molecular weight of the chromatogram by gel permeation chromatography (GPC) is measured under the following conditions.
The column was stabilized in a heat chamber at 40 ° C., and tetrahydrofuran (THF) as a solvent was caused to flow through the column at a temperature of 1 ml / min at a temperature of this column to prepare a resin having a sample concentration of 0.05 to 0.6% by mass. About 50 to 200 μl of the THF sample solution is injected and measured. In measuring the molecular weight of a sample, the molecular weight distribution of the sample is calculated from the relationship between the logarithmic value and the number of counts (retention time) of a calibration curve prepared using several kinds of monodisperse polystyrene standard samples. The standard polystyrene sample for preparing the calibration curve is, for example, manufactured by Tosoh Corporation or Pressure Ch
electrical Co. Made molecular weight 6 × 10 ² , 2.1
× 10 ³ , 4 × 10 ³ , 1.75 × 10 ⁴ , 5.1 × 1
0 ⁴ , 1.1 × 10 ⁵ , 3.9 × 10 ⁵ , 8.6 × 10 ⁵ ,
It is suitable to use 2 × 10 ⁶ , 4.48 × 10 ⁶ and use at least about 10 standard polystyrene samples. An RI (refractive index) detector is used as the detector.

As a column, a plurality of commercially available polystyrene gel columns may be combined in order to accurately measure the molecular weight region of 10 ³ to 2 × 10 ⁶ , and for example, Shodex GPC KF-801 manufactured by Showa Denko KK 80
2, 803, 804, 805, 806, 807 combinations and Waters μ-styragel 50
A combination of 0, 10 ³ , 10 ⁴ and 10 ⁵ can be mentioned.

Measurement of Toner Particle Size Distribution In the present invention, the average particle size and particle size distribution of the toner are measured using Coulter Counter TA-II type (manufactured by Coulter Co.), but Coulter Multisizer (manufactured by Coulter Co.) may also be used. It is possible. As the electrolytic solution, a 1% NaCl aqueous solution is prepared using first grade sodium chloride. For example, ISOTON R-II (manufactured by Coulter Scientific Japan Co.) can be used. As a measuring method, a surfactant, preferably 0.1 to 5 ml of an alkylbenzene sulfonate is added as a dispersant to 100 to 150 ml of the electrolytic aqueous solution, and a measurement sample is further added to 2 to 20 m.
Add g. The electrolytic solution in which the sample is suspended is about 1 with an ultrasonic disperser.
Dispersion treatment is performed for 3 minutes, and 2.00 is obtained by using the measuring device with an aperture of 100 μm.
The volume distribution and the number distribution were calculated by measuring the volume and the number of the toner having a particle size of μm or more. Then, the weight-based weight average particle diameter (D4) (the median value of each channel is used as a representative value for each channel) determined from the volume distribution according to the present invention was determined.

The channels are 2.00 to 2.52.
μm; 2.52 to 3.17 μm; 3.17 to 4.00 μm
m; 4.00 to 5.04 μm; 5.04 to 6.35 μ
m; 6.35 to 8.00 μm; 8.00 to 10.08 μm
m; 10.08-12.70 μm; 12.70-16.
00 μm; 16.0-20.20 μm; 20.20
25.40 μm; 25.40-32.00 μm; 32.
13 channels of 00-40.30 μm are used.

[0121]

EXAMPLES Hereinafter, specific examples of the present invention will be described, but the present invention is not limited to these examples.

Production Example of Iron Phthalocyanine A A reactor was charged with 113 parts by mass of phthalimide, 156 parts by mass of urea, 47 parts by mass of ferrous chloride (hydrous salt), 0.5 part by mass of ammonium molybdate, and 500 parts by mass of trichlorobenzene. 130-135 ° C, 1 hour, 185-195
After reacting at ℃ for 7 hours, the solvent is distilled off by vacuum distillation.
to recover.

The obtained crude product was wet pulverized and then 70 ° C.
After being treated with 2000 parts by mass of a 10% sulfuric acid solution for 3 hours, cooled, washed with water, dried and pulverized to obtain 100 parts by mass of Fe (Cl) Pc having a chlorine content of 5.69% by mass.

100 parts by mass of the obtained Fe (Cl) Pc was added to 850 parts by mass of anhydrous Glauber's salt and 200 parts of ethylene glycol.
It was put into a kneader kneader together with parts by mass, treated at 80 ° C. for 7 hours, discharged into 10,000 parts by mass of water, sufficiently dispersed, washed with water and dried (above, salt-milling (S
alt-milling)) to obtain an average particle size of 0.1
1 μm of iron phthalocyanine A was obtained.

Production Example of Iron Phthalocyanine B In the production example of iron phthalocyanine A, the salt-milling treatment conditions were changed, and 100 parts by mass of the obtained Fe (Cl) Pc was added to anhydrous Glauber's salt 85.
It was put into a kneader kneader together with 0 parts by mass and 200 parts by mass of ethylene glycol, and treated at 70 ° C. for 5 hours, and then 1
After discharging into 0000 parts by mass of water, sufficiently dispersing, washing with water and drying, iron phthalocyanine B having an average particle diameter of 0.26 μm was obtained.

(Hybrid Resin Production Example 1) As a vinyl-based copolymer, styrene 1.9 mol, 2-ethylhexyl acrylate 0.21 mol, fumaric acid 0.15 m
Ol, α-methylstyrene dimer 0.03 mol, and dicumyl peroxide 0.05 mol are placed in a dropping funnel. In addition, polyoxypropylene (2.2) -2,2
-Bis (4-hydroxyphenyl) propane 7.0mo
1, polyoxyethylene (2.2) -2,2-bis (4
-Hydroxyphenyl) propane 3.0 mol, terephthalic acid 3.0 mol, trimellitic anhydride 2.0 mo
1, fumaric acid 5.0 mol and dibutyl tin oxide 0.2 g
Was placed in a glass 4-liter four-necked flask, and a thermometer, a stirring rod, a condenser, and a nitrogen inlet tube were attached and placed in a mantle heater.

Next, after replacing the inside of the flask with nitrogen gas,
The temperature was gradually raised while stirring, and the vinyl resin monomer, the cross-linking agent and the polymerization initiator were dropped from the above dropping funnel over 4 hours while stirring at a temperature of 145 ° C. Then 200
The temperature was raised to ℃ and the reaction was carried out for 4 hours to obtain a hybrid resin (1). The results of molecular weight measurement by GPC are shown in Table 1.

(Hybrid Resin Production Example 2) Styrene 3.8 mol, α-methylstyrene dimer 0.07 m
except that 0.1 mol of diol and dicumyl peroxide were used, a reaction was performed in the same manner as in Hybrid Resin Production Example 1 to obtain a hybrid resin (2). The results of molecular weight measurement by GPC are shown in Table 1.

(Hybrid Resin Production Example 3) 4.0 mol of maleic acid and 3.5 mol of itaconic acid were used in place of 5.0 mol of fumaric acid, and 0.1 mol of isobutyl peroxide was used instead of 0.05 mol of dicumyl peroxide. A hybrid resin (3) was obtained by carrying out the reaction in the same manner as in Hybrid Resin Production Example 1 except that was used. The results of molecular weight measurement by GPC are shown in Table 1.

(Hybrid Resin Production Example 4) Instead of 3.0 mol of terephthalic acid and 2.0 mol of trimellitic anhydride, 5.2 mol of trimellitic anhydride was reacted and reacted in the same manner as in Hybrid Resin Production Example 1 to prepare a hybrid resin ( 4) was obtained. Table 1 shows the results of molecular weight measurement by GPC.
Shown in.

(Polyester Resin Production Example 1) Polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane 3.6 mol, polyoxyethylene (2.2) -2,2-bis ( 4-hydroxyphenyl)
Propane 1.6 mol, terephthalic acid 1.7 mol, trimellitic anhydride 1.1 mol, fumaric acid 2.4 mol
And 0.1 g of dibutyltin oxide in 4 liters of glass
The flask was placed in a one-necked flask, and a thermometer, a stirring rod, a condenser, and a nitrogen introducing tube were attached and placed in a mantle heater.
Under a nitrogen atmosphere, the reaction was carried out at 215 ° C. for 5 hours to obtain a polyester resin (5). The results of molecular weight measurement by GPC are shown in Table 1.

Polyester Resin Production Example 2 Polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane 1.6 mol, polyoxyethylene (2.2) -2,2-bis ( 4-hydroxyphenyl)
Propane 3.3 mol, terephthalic acid 1.6 mol, trimellitic anhydride 0.3 mol, fumaric acid 3.2 mol
With the above monomer composition, the reaction was performed in the same manner as above to obtain a polyester resin (6). The results of molecular weight measurement by GPC are shown in Table 1.

(Production Example 1 of vinyl resin) Styrene 2.
2 mol, 2-ethylhexyl acrylate 0.23 m
ol, 0.08 mol of dicumyl peroxide, and 3.2 g of dibutyltin oxide were placed in a 3-liter four-necked flask equipped with a thermometer, a stainless stir bar, a downflow condenser and a nitrogen inlet tube, and placed in a mantle heater. Then, the reaction was performed while stirring at a temperature of 225 ° C. in a nitrogen atmosphere to obtain a vinyl resin (7). The results of molecular weight measurement by GPC are shown in Table 1.

[0134]

[Table 1]

The waxes used in the present invention are listed in Table 2.

[0136]

[Table 2]

<Example 1> Black toner 1 was prepared by the following method.

Hybrid resin (1) 50 parts by mass Iron phthalocyanine A 50 parts by mass The above raw materials having the above formulation are first charged in a kneader type mixer, and the temperature is raised without pressure while mixing. 130 ° C
The mixture was heated to 50 ° C., and melted and kneaded for about 50 minutes to disperse the pigment, and then cooled, and the kneaded product was taken out to obtain a first kneaded product.

First kneaded product (content of pigment particles: 50% by mass) 10.0 parts by mass Hybrid resin (1) 100.0 parts by mass Wax (A) 5.0 parts by mass α-Fe ₂ O ₃ Hematite 2.0 parts by mass Aluminum compound of di-tertiarybutylsalicylic acid 4.0 parts by mass Preliminary mixing with the above-mentioned formulation was sufficiently performed with a Henschel mixer, and the temperature was set to 120 ° C. with a biaxial extrusion kneader The mixture was melt-kneaded, cooled, roughly crushed to about 1 to 2 mm using a hammer mill, and then finely crushed to a particle size of 20 μm or less by a fine pulverizer using an air jet system. Further, the obtained finely pulverized product was classified so that the volume average diameter in the particle size distribution was 6.
Black toner particles (classified product) selected to be 2 μm
Got

Hydrophobic aluminum oxide (BET 170 m ² / g) treated with i-C ₄ H ₉ Si (OCH ₃ ) ₃ : 25 parts by mass for the purpose of improving fluidity and imparting charging characteristics.
To 100 parts by weight of the black toner particles
By combining the parts by mass, a black toner 1 was obtained.

Further, the black toner 1 and magnetic ferrite carrier particles (average particle diameter 45 μm) surface-coated with a silicone resin were mixed so that the toner concentration would be 7 mass%, and the two-component black developer 1 was obtained. did. The results of measuring the physical properties of the toner are shown in Table 4.

With this black developer 1, a color copying machine CLC
-1130 (Canon) fixing unit with modified oil application mechanism removed (Process speed 295m
m / sec) in a single color mode at room temperature and low humidity (2
3 ° C / 5%), high temperature and high humidity environment (30 ° C / 80%), using an original document with an image area ratio of 20%, a 40,000-sheet printing durability test and normal temperature and normal humidity environment (23 ° C / 60%) %) Was used for the fixing test. Further, for the evaluation of the feasible area, a fixing unit modified so that the fixing temperature can be manually set was used.

Even after running 40,000 sheets, a black image that faithfully reproduces the original without fog was obtained, and the delicate image quality and the image density were almost unchanged. Conveyance in the copying machine and detection of developer concentration were also good, and stable image density was obtained. Even when the fixing temperature was set at 170 ° C. and repeated copying of 40,000 sheets, offset to the fixing roller did not occur at all. The occurrence of offset on the fixing roller is
It was performed by visually observing the surface of the fixing roller after repeated copying.

When the gloss (glossiness) of the image surface was measured, the image density at a contrast potential of 300 V was 1.7.
0 (Macbeth reflection density), and the gloss at that time is 21
%Met.

Evaluation Items / Methods: (1) Toner blocking resistance The toner was evaluated by leaving it in an oven at 50 ° C. for 2 weeks. As the evaluation, the level of cohesiveness was visually determined.

The evaluation criteria for toner cohesiveness are shown below. A: No aggregates are seen B: Some aggregates are seen but quickly disentangled C: Aggregates are disentangled with a developer stirring device (normal) D: Aggregates are not sufficiently dissociated with a developer stirring device (Somewhat bad)

(2) Image density Color reflection densitometer (X-RITE 404A; X-Ri
Based on the result of measurement by te), the worst evaluation value in the middle of the durability was set as the following evaluation standard numerical range. A: Density (D _max ) 1.6 or more B: Density (D _max ) 1.4 or more and less than 1.6 C: Density (D _max ) 1.2 or more and less than 1.4 D: Density (D _max ) Less than 1.2

(3) Fog The fog produced on the white image was measured with a "reflectometer" (manufactured by Tokyo Denshoku Co., Ltd.). Fog (%) was calculated from the relationship between the whiteness of the white background after passing through the fixing device and the whiteness of the transfer paper before passing through the fixing device, and the image stain was evaluated. Judgment was made based on the worst value during the durability including the initial stage and after 40,000 sheets. Worst value less than 0.7%; A, 0.7% or more and less than 1.5%; B, 1.5% or more and less than 2.3%; C, 2.3% or more; D

(4) Image Bending Property A solid image of 25 mm × 25 mm of toner was formed at a fixing temperature of 160 ° C., and was bent using a weight with a constant load, and the degree of image loss at the bent portion was qualitatively evaluated based on the following criteria. did. A: There was no image loss. B: A slight streak-like mark remained on the bent portion, but no image defect was observed. C: A streak-like mark remained on the bent portion, but no large image defect was observed. D: An image defect was recognized in the bent portion, and the base was exposed.

(5) After the endurance test of the fusing roller stain, the influence on the endurance of the fusing roller was evaluated based on how foreign matter adhered to the surface of the fusing roller. A: No deposit was observed, and there was almost no change on the image from the initial stage. B: Almost no deposits were seen, and the change in image quality was extremely small. C: The amount of adhered matter is extremely small, and the image has no problem. D: A level where there is an adhered substance and an image defect occurs.

Example 2 A black toner 2 was obtained in substantially the same manner as in Example 1 except that the following iron azo complex was used instead of the aluminum compound of di-tertiarybutylsalicylic acid. The toner measurement results are shown in Table 4.

[0152]

[Chemical 8]

<Examples 3 to 18> Black toners 3 to 18 were obtained in substantially the same manner as in Example 1 except that the materials shown in Tables 3 and 4 were used. The toner measurement results are shown in Table 4.

Comparative Example 1 A black toner 19 was obtained in substantially the same manner except that the hybrid resin (1) was replaced by the hybrid resin (4). The evaluation results are shown in Table 5.

Comparative Example 2 A black toner 20 was obtained in substantially the same manner except that the polyester resin (6) was used instead of the hybrid resin (1). The evaluation results are shown in Table 3. The black toner 20 is made of a resin having a small Mw / Mn, and as a result, G ′ at 120 to 180 ° C. also shows a small value, and the fixing test shows a low temperature (140 ° C.).
So I wound up on the upper roller.

Comparative Examples 3 to 6 Black toners 21 to 24 were obtained in substantially the same manner except that the colorants and charge control agents were changed as shown in Tables 3 and 4. The evaluation results are shown in Table 5.

[0157]

[Table 3]

[0158]

[Table 4]

[0159]

[Table 5]

[0160]

The black toner of the present invention has blocking resistance, storability in high temperature environment, low temperature fixing property, high speed fixing property,
It has excellent high-temperature offset resistance, glossiness, and transferability, and it is possible to stably obtain a high-definition, high-quality image that does not cause fog or toner scattering.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Yoshiyoshi Sugawara             3-30-2 Shimomaruko, Ota-ku, Tokyo             Non non corporation (72) Inventor Nozomi Komatsu             3-30-2 Shimomaruko, Ota-ku, Tokyo             Non non corporation (72) Inventor Kazuhiko Hayami             3-30-2 Shimomaruko, Ota-ku, Tokyo             Non non corporation (72) Inventor Takaaki Uetaki             3-30-2 Shimomaruko, Ota-ku, Tokyo             Non non corporation F-term (reference) 2H005 AA01 AA06 CA03 CA08 CA14                       CA18 CA22 CB03 DA02 EA03                       EA05

Claims (12)

[Claims] 1. A black toner containing at least a binder resin, a wax and a colorant, which has a storage elastic modulus (G ′ ₈₀ ) of 1 × at 80 ° C.
It is in the range of 10 ⁶ to 1 × 10 ⁸ [dN / m ² ] and 140
The loss tangent (tan δ) at 0 ° C. is in the range of 0.2 to 1.5, and the coloring agent contains at least the iron phthalocyanine complex compound represented by the formula (I) in an amount of 2 to 20 parts by mass per 100 parts by mass of the binder resin. A black toner characterized in that the toner contains wax in an amount of 0.5 to 10 parts by mass based on 100 parts by mass of the binder resin. [Chemical 1] (In the formula, X represents an electron-withdrawing group, and n represents an integer of 1 to 16.) 2. The black toner according to claim 1, wherein X in the general formula (I) of the iron phthalocyanine complex compound is a fluorine atom or a chlorine atom. 3. The black toner according to claim 1, wherein the black toner contains an inorganic pigment. 4. The black toner according to claim 3, wherein an average dispersed particle diameter of the iron phthalocyanine complex compound in the toner is smaller than an average dispersed particle diameter of the inorganic pigment in the toner. 5. The black according to claim 3, wherein an average dispersed particle diameter of the iron phthalocyanine complex compound in the toner is 2/3 or less of an average dispersed particle diameter of the inorganic pigment in the toner. toner. 6. The black toner according to claim 3, wherein the inorganic pigment is non-magnetic. 7. The black toner according to claim 1, wherein the toner contains a metal compound of an aromatic carboxylic acid derivative. 8. The black toner according to claim 7, wherein the metal compound of the aromatic carboxylic acid derivative is an aluminum compound of the aromatic carboxylic acid derivative. 9. The black toner according to claim 1, wherein the black toner contains a compound represented by the following general formula (II). [Chemical 2] 10. The black toner has a differential thermal analysis (DS).
C) In the endothermic curve in the measurement, a temperature of 30 to 200
It has one or more endothermic peaks in the range of ° C, and the peak temperature of the maximum endothermic peak in the endothermic peak is 50 to 120 ° C.
10. The black toner according to claim 1, wherein the black toner is in the range. 11. The black toner has a differential thermal analysis (DS).
C) In the endothermic curve in the measurement, a temperature of 30 to 200
It has one or more endothermic peaks in the range of ° C, and the peak temperature of the maximum endothermic peak in the endothermic peak is 60 to 100 ° C.
10. The black toner according to claim 1, wherein the black toner is in the range. 12. The binder resin is (a) a polyester resin, or (b) a hybrid resin having a polyester unit and a vinyl copolymer unit, or (c).
12. A resin selected from a mixture of a hybrid resin and a vinyl-based copolymer, or a mixture of (d) a hybrid resin and a polyester resin, according to any one of claims 1 to 11. Black toner.