JPH07199527A - Electrostatic image developing color toner, developer, and image forming method - Google Patents

Abstract

PURPOSE:To enhance image quality with respect to image density and fog, etc., to prevent toner scattering, to improve its fixability and to extend its life by incorporating a specified vinyl resin, a nonmetallic quaternary ammonium salt, a quaternary ammonium salt containing a metal, and a colorant. CONSTITUTION:This color toner contains the vinyl resin having a Mw/Mn ratio of >=20 in a tetrahydrofuran-soluble fraction, where Mw and Mn are a weight average molecular weight and a number average molecular weight, respectively: the nonmetallic quaternary ammonium salt, the metal-containing quaternary ammonium salt comprising an anion part having a metal complex structure, and the colorant. Since a styrene-acrylic resin has good toner characteristics, it is preferable for this vinyl resin. A molybdenum metal is especially preferable for the metal-containing quaternary ammonium salt from the viewpoints of chargeability characteristics and color tone.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a color toner for developing an electrostatic charge image for developing an electrostatic charge image formed on the surface of a photoreceptor in electrophotography, electrostatic recording and the like, and development using the color toner. Agent and image manufacturing method.

[0002]

2. Description of the Related Art An electrophotographic system is disclosed in US Pat.
No. 7,691, British Patent Nos. 1,165,406 and 1,165,405, a photoconductive material is uniformly applied to a photoreceptor. A charging step for imparting an electrostatic charge, an exposure step for irradiating light to form an electrostatic latent image, a developing step for adhering toner to a latent image portion, a transfer step for transferring to a toner image support, a heat treatment for the toner image, It consists of a fixing process to fix it to the image support with pressure, flash light, etc., a cleaning process to remove the toner remaining on the photoconductor, and a static elimination process to remove the electrostatic charge on the photoconductor and return it to the initial state. Repeatedly produces several prints.

As a dry toner for developing an electrostatic image used in the field of electrophotography, a toner using a polystyrene resin (Japanese Patent Publication No. 44-16118) and a toner using a styrene-butyl methacrylate copolymer resin ( Japanese Examined Sho 56
No. 11143), a toner using a styrene-acrylic resin, a toner using a bisphenol-type epoxy resin obtained by reacting bisphenol with epichlorohydrin (JP-A-57-96354), and a glycol having a bisphenol skeleton. Toner using polyester resin obtained by reacting with polybasic acid (Japanese Patent Publication No.
No. 2-25420) is known, but styrene-acrylic resins can control a wide range of resin properties such as molecular weight, glass transition point, melt viscosity, etc., compared to other resins, and are extremely designed in terms of toner. Most of the toner is dominated by the toner using the styrene-acrylic resin because it is advantageous.

[0004]

In recent years, electrophotography and electrostatic photography have been required to have multicolor image quality in accordance with diversification of information and high density of information. In order to meet this demand, the hue of toner has been required to be a color other than black. Color toner (toner of colors other than black)
Since a precise color tone is required, the raw materials used are also limited in terms of color tone. In the case of the conventional black toner, since there is no such restriction, a wide variety of raw materials can be used, and the toner characteristics can be adjusted relatively easily.
However, it is difficult to develop a color toner having the same level of performance as the black toner, since only colorless or light-colored raw materials can be used for the color toner, excluding the pigment used. Further, in a printer or a copying machine which prints at a high speed, it is particularly serious, and it is the actual situation that a practical color toner cannot be obtained yet.
The present invention solves such a problem, and an object of the present invention is to provide a color toner excellent in image quality such as image density and fog. Furthermore, it is an object of the present invention to provide a long-life color toner that maintains image quality even after repeated use, does not cause toner scattering, and exhibits good fixing characteristics.

[0005]

DISCLOSURE OF THE INVENTION The present invention is a vinyl-based resin or non-metal having a ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of tetrahydrofuran (hereinafter abbreviated as THF) soluble content of 20 or more. A color toner for developing an electrostatic charge image containing a quaternary ammonium salt, a metal-containing quaternary ammonium salt having an anion part having a metal complex structure, and a colorant, and a developer comprising the color toner for developing an electrostatic charge image and a carrier. The present invention relates to an image manufacturing method using these.

A styrene-acrylic resin is preferably used as the vinyl resin which is a binder resin of the color toner for electrostatic image development of the present invention because of its good toner characteristics. Here, the styrene-acrylic resin is obtained by polymerizing a vinyl monomer containing styrene-based monomers and acrylic-based monomers (acrylic acid and methacrylic acid and their derivatives such as esters) as essential components. Is a copolymer. Examples of the styrene-based monomer here include styrene, α-methylstyrene, p-methylstyrene, pt-butylstyrene, p-chlorostyrene, hydroxystyrene, and divinylbenzene as a crosslinking agent. As a derivative.

As the acrylic monomer, methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, pentyl methacrylate, hexyl methacrylate, heptyl methacrylate, octyl methacrylate, nonyl methacrylate, Decyl methacrylate, undecyl methacrylate, dodecyl methacrylate, glycidyl methacrylate, methoxyethyl methacrylate, propoxyethyl methacrylate, butoxyethyl methacrylate, methoxydiethylene glycol methacrylate, ethoxydiethylene glycol methacrylate, methoxyethylene glycol methacrylate, butoxy methacrylate Triethylene glycol, methoxydipropylene glycol methacrylate, phenoxyethyl methacrylate, methac Phenoxydiethylene glycol methacrylate, phenoxytetraethylene glycol methacrylate, benzyl methacrylate, cyclohexyl methacrylate, tetrahydrofurfuryl methacrylate, dicyclopentenyl methacrylate, dicyclopentenyloxyethyl methacrylate, N-vinyl-2-pyrrolidone methacrylate, Methacrylonitrile, methacrylamide, N-
Methylol methacrylamide, phthalimidoethyl methacrylate, phthalimidopropyl methacrylate, morpholinoethyl methacrylate, morpholinopropyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, diacetone methacrylamide, acrylic acid, methyl acrylate, ethyl acrylate , Propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, butyl acrylate,
Octyl acrylate, nonyl acrylate, decyl acrylate, undecyl acrylate, dodecyl acrylate, glycidyl acrylate, methoxyethyl acrylate, propoxyethyl acrylate, butoxyethyl acrylate,
Methoxydiethylene glycol acrylate, ethoxydiethylene glycol acrylate, methoxyethylene glycol acrylate, butoxytriethylene glycol acrylate, methoxydipropylene glycol acrylate, phenoxyethyl acrylate, phenoxydiethylene glycol acrylate, phenoxytetraethylene glycol acrylate, benzyl acrylate , Cyclohexyl acrylate, tetrahydrofurfuryl acrylate,
Dicyclopentenyl acrylate, dicyclopentenyl oxyethyl acrylate, N-vinyl-2-pyrrolidone acrylate, glycidyl acrylate, acrylonitrile,
Acrylamide, N-methylol acrylamide, diacetone acrylamide, vinyl pyridine, phthalimidoethyl acrylate, phthalimidopropyl acrylate,
Reaction of methacrylic acid or acrylic acid with a monomer having one vinyl group in one molecule such as morpholinoethyl acrylate, morpholinopropyl acrylate, dimethylaminoethyl acrylate, diethylaminoethyl acrylate, etc. Products such as ethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, 1,5-pentanediol dimethacrylate,
1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate,
Tripropylene glycol dimethacrylate, hydroxypivalic acid neopentyl glycol ester dimethacrylate, trimethylolethane trimethacrylate,
Trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, trismethacryloxyethyl phosphate, bis (methacryloyloxyethyl) hydroxyethyl isocyanurate, tris (methacryloyloxyethyl) isocyanurate, ethylene glycol diacrylate, 1 , 3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,
5-pentanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, diethylene glycol diacrylate,
Triethylene glycol diacrylate, polyethylene glycol diacrylate, tripropylene diacrylate, hydroxypivalic acid neopentyl glycol diacrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, tris There are monomers having two or more vinyl groups in one molecule such as acryloxyethyl phosphate, bis (methacryloyloxyethyl) hydroxyethyl isocyanurate, and tris (methacryloyloxyethyl) isocyanurate.

Further, in order to prevent toner adhesion to the soft vinyl chloride sheet, it is preferable to use a vinyl monomer having a hydroxyl group. Corresponding monomers include 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxy-3-phenyloxypropyl methacrylate, 2-hydroxybutyl methacrylate, glycidyl methacrylate and methacrylic acid or acrylic acid. And half-esterified products of bisphenol type epoxy resin and methacrylic acid or acrylic acid, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxy-3-phenyloxypropyl acrylate, acrylic acid There are acrylic monomers such as 2-hydroxybutyl. In addition, when charging property under high humidity (about 60% RH or more) and blocking resistance are required, a vinyl monomer having a secondary hydroxyl group, for example, 2-hydroxypropyl methacrylate, methacrylic acid 2 -Hydroxy 3-phenyloxypropyl, 2-hydroxybutyl methacrylate, 3-hydroxybutyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxy-3 acrylate
-Phenyloxypropyl, 2-hydroxybutyl acrylate, 3-hydroxybutyl acrylate and the like can be preferably used. In particular, 2-hydroxypropyl methacrylate and 2-hydroxypropyl acrylate are preferable from the viewpoint of the characteristics of the resin. The vinyl monomer having a secondary hydroxyl group is particularly preferably used in an amount of 80 mol% or more of all the hydroxyl group-containing monomers. The hydroxyl group-containing monomer has a polymer hydroxyl value of 80.
It is preferable that it is blended so as to be ˜250.

In addition, vinyl monomers such as dialkyl maleates such as dibutyl maleate, dialkyl fumarates such as dibutyl fumarate, and dialkyl itaconates such as dibutyl itaconate can be used in combination. Of these monomers, preferred are those having one vinyl group in one molecule, such as styrene, styrene derivatives,
There are methacrylic acid ester, acrylic acid ester, dialkyl maleate, dialkyl fumarate, and dialkyl itaconate. As the monomer (crosslinking agent) having two or more vinyl groups in one molecule, divinylbenzene, dimethacrylate and diacrylate of alkylene glycol having 2 to 6 carbon atoms are preferable.

In particular, styrene and an alkyl ester of methacrylic acid or acrylic acid having 1 to 5 carbon atoms in the alkyl group as a main component, dialkyl maleate, dialkyl fumarate and / or dialkyl itaconic acid (particularly preferably maleic acid). A mixed system using dibutyl and / or dibutyl fumarate) and a cross-linking agent (particularly preferably divinylbenzene) is excellent in fixing strength and stability of offset resistance against changes in fixing temperature and image density. Even in a system using a small amount of the charge control agent, which is a feature of the present invention, the dispersibility of the charge control agent is excellent, which is preferable. The cross-linking agent is 0.05 to 1.0% by weight based on all monomers, dialkyl maleate, dialkyl fumarate and / or
Or dialkyl itaconate is 0.1 to 5.0 in all monomers.
It is particularly preferable to use the composition in an amount of wt% in terms of improvement in fixing strength and offset resistance.

The above-mentioned monomer mixture can be polymerized by various polymerization methods to obtain a vinyl resin, but it is preferable to polymerize by a suspension polymerization method. The reason for this is that it is easy and stable to manufacture, does not require desolvation treatment, has good toner storability, is less likely to cause toner filming on the photoreceptor, and is also economically advantageous. This is because there is an advantage in that the chargeability of the resin is high and the amount of the charge control agent mixed in the toner can be reduced. Upon polymerization, the polymerization initiator used is acetyl peroxide,
Decanoyl peroxide, lauroyl peroxide, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, diisopropyl percarbonate, di-2-ethyl-hexyl percarbonate, acetylcyclohexanesulfonyl peroxide, peroxide Tert-butyl acetate, perisobutyric acid
tert-butyl, azobisisobutyronitrile, 2,2 '
-Azobis-2,4-dimethylvaleronitrile, 2,
Known examples include 2'-azobis-4-methoxy-2,4-dimethylvaleronitrile, tert-butyl per-2-ethylhexanoate, tert-butyl perbenzoate and the like. These are preferably used in an amount of 0.1 to 15% by weight based on the total amount of monomers. Further, it is preferable that these are dissolved in a monomer before use.

In the present invention, the vinyl resin is THF
Weight-average molecular weight (Mw) and number-average molecular weight (M
The ratio of n) is adjusted to 20 or more, preferably 20 to 100. When the number average molecular weight (Mn) / number average molecular weight (Mn) is less than 20, the charge control agent is not uniformly dispersed in the binder resin and the charge control agent is not taken in a predetermined amount. Are generated, and they become high-charged toner or low-charged or reverse-charged toner, and they are hypersensitivity to potential defects of organic photoconductive substances and minute defects due to mechanical shock or discharge breakdown, and are expressed as image defects, Color toner is not faithfully developed on the latent image on the photoconductor, its developability is poor, or the color toner image on the latent image on the photoconductor is difficult to transfer to the image support during belt transfer. Further, since the latent image potential gradient is not normally sensed, the latent image potential is attached to a portion other than the image forming portion of the photoconductor, which causes deterioration of image quality and poor cleaning. Naturally, if the transfer residual color toner is recycled and used, the image quality becomes low. Further, toner scattering easily occurs, which causes problems in safety, hygiene, and economy. Such a phenomenon remarkably appears when the charge control agent is 0.1% by weight or less in the toner. Further, since the toner becomes finer due to the impact with the carrier and the friction with the container, it becomes impossible to maintain the set toner characteristics, which makes it difficult to repeatedly use the toner for a long time, which is one of the objects of the present invention. In the present invention, the average molecular weight of the resin is a value measured by a gel permeation chromatography method and converted using a standard polystyrene calibration curve.

The glass transition temperature of the vinyl resin is 35.
The temperature is preferably adjusted to -100 ° C, particularly 50-90.
It is preferably adjusted to ° C. Glass transition temperature is 35 ℃
When the amount is less than the range, the toner is apt to cause blocking (a phenomenon in which toner particles aggregate and agglomerate) during the storage period or in the developing machine. On the other hand, when the glass transition temperature exceeds 100 ° C., the fixing property tends to decrease, and the toner is melt-kneaded,
When it is manufactured by a crushing and classifying process, time is spent in the crushing process, and the production efficiency tends to decrease. In the color toner of the present invention, two or more of the above vinyl-based resins may be combined to form a binder resin, or one or more other resins may be used in combination in addition to the above-mentioned vinyl-based resin.

Other resins include KR-216, K
R-220, KR-152, KR-271, KR-25
5 (all manufactured by Shin-Etsu Chemical Co., Ltd.), SR-2400, S
Silicone resin such as R-2406, SH-840 (all manufactured by Toray Silicone Co., Ltd.), 1-Solex (Cd
F-Chemic) norbornene-based polymer, C-200
A, C-250A (all manufactured by Mitsubishi Kasei Co., Ltd.), polyester carbonate such as Iupilon P-1000 (manufactured by Mitsubishi Gas Chemical Co., Inc.), Lignol R-70, R-120,
Xylene resins such as R-140 and P-2 (all manufactured by Lignite Co., Ltd.), Epicoat 1004, 1007, 100
9, 1010, YL-903, 906, Epicoat 60
4 (above Ciel), Epomic R304, R30
7, epoxy resins such as R309 (all manufactured by Mitsui Petrochemical Industry Co., Ltd.), Nipol BR-1220, 1032, 1
441, Nipol IR2200, Nipol NBR,
Diene resin such as 2057S, 2007J (all manufactured by Nippon Zeon Co., Ltd.), PC / RESIN2H, 3H, 8H,
11A (above Hitachi Chemical Co., Ltd.), ATR200
5, 2009, 2010, HTR-1, HTR-2 (all manufactured by Kao Corporation), FC017, 034, 035, 03
Commercially available polyester resins such as 6 (all manufactured by Mitsubishi Rayon Co., Ltd.), phenol resins, terpene resins, coumarone resins, amide resins, amide imide resins, butyral resins,
Examples include amino resins, urethane resins, ethylene / vinyl acetate copolymers, ethylene / acrylic ester copolymers. As the binder resin in the present invention, the vinyl resin, particularly the styrene-acrylic resin is used as a main component (especially 100 to 70% by weight), and the other resin is used in an amount of 0 to 30% by weight. preferable.

The binder resin used in the present invention preferably has a residual monomer content of 0.15% by weight or less. If the content of the residual monomer exceeds 0.15% by weight, there is a tendency that the probability of occurrence of print defects such as print density drop and print density unevenness during mounting increases. The amount of residual monomer can be measured by a gas chromatography method or the like. For example, to create a calibration curve by gas chromatography of each monomer or solvent, dissolve the copolymer in a fixed amount of solvent, subjected to gas chromatography, using the calibration curve, each residual monomer or Residual solvent can be quantified. In addition, in the Example mentioned later, it quantified by this method. The binder resin is preferably blended in the color toner in an amount of 60 to 95% by weight. If this amount is less than 60% by weight, the toner binding force to the toner image support is weak, and when the toner image support is bent or rubbed, the toner image is lost, and print failure is likely to occur. On the other hand, when the binder resin content exceeds 95% by weight, poor print quality tends to result due to insufficient hiding power of the color toner image.

The toner of the present invention contains a non-metal quaternary ammonium salt and a metal-containing 4 in which the anion portion has a metal complex structure.
At least two types of charge control agents, that is, a quaternary ammonium salt (hereinafter simply referred to as a metal-containing quaternary ammonium salt), are added to the toner. As the metal atom of the metal-containing quaternary ammonium salt, molybdenum is particularly preferable in terms of charging characteristics and color tone. The non-metal quaternary ammonium salt and the metal-containing quaternary ammonium salt are added to the toner by 0.1 to 4 respectively.
It is preferably contained in an amount of% by weight, particularly preferably 0.5 to 3% by weight. When the amount of the non-metal quaternary ammonium salt is less than 0.1% by weight, the toner is difficult to be charged quickly and is likely to scatter in the initial stage of mixing the toner and the carrier, and the amount of the metal-containing quaternary ammonium salt is 0. If the amount is less than 1% by weight, the toner tends to scatter with the progress of printing. Further, even if each amount exceeds 4% by weight, no further improvement is observed.

The total amount of the charge control agent is preferably 1 to 5% by weight with respect to the toner. If it is less than 1% by weight, toner scattering is likely to occur, while if it exceeds 5% by weight, problems such as deterioration in fixing property and environmental resistance may occur. Further, the weight ratio of the non-metal quaternary ammonium salt and the metal-containing quaternary ammonium salt is 2: 1 to 1: 2.
It is preferable in terms of toner characteristics.

Preferred as the non-metal quaternary ammonium salt used in the present invention are those in which the anion portion A ⁻ in the following general formula (I) is a non-metal ion, and preferred as the metal-containing quaternary ammonium salt are: The anion part A ⁻ in the following general formula (I) has a metal complex structure.

[Chemical 1] (In the formula, R ¹ , R ² , R ³ and R ⁴ are each independently an optionally substituted alkyl group, aryl group, aralkyl group, alkenyl group or the like, and A ⁻ is an anion) Anion A ⁻ is a nonmetallic quaternary ammonium salt, and is a chloride ion, a bromine ion, an iodine ion, a sulfate ion, a nitrate ion, a perchlorate ion, a borate ion, a phosphate ion, an organic phosphate ion, a benzoate ion, There are organic sulfonate ions such as naphthol sulfonate ion and paratoluene sulfonate ion, and carboxylate ion. Particularly preferable are organic sulfonate ions such as naphthol sulfonate ion and paratoluene sulfonate ion, and metal-containing quaternary ammonium salt. Then, molybdic acid, tungstic acid, phosphomolybdic acid, silicomolybdic acid, phosphotungstic acid, silicic acid Tungsten acid, silicotungstic molybdate, phosphotungstic molybdic acid, chromic molybdate, there are chromic acid, a those containing molybdenum are preferred. R ¹ , R ² , R ³ and R ⁴ preferably have 1 to 30 carbon atoms.

The cation of the non-metal quaternary ammonium salt is
Specifically, the following are preferred.

[Chemical 2] Specific examples of preferable cations of the metal-containing quaternary ammonium salt include the following.

[Chemical 3]

Specific non-metallic quaternary ammonium salts include, for example, Bontron P-51 (produced by Orient Chemical Industry Co., Ltd.), which is a quaternary ammonium salt of naphtholsulfonic acid, and TP-4040 (Hodogaya Chemical Industry ( stock)
Commercial products), copy charge PSY UP2038 (manufactured by Hoechst), LRA-901 (manufactured by Nippon Carlit Co., Ltd.) and the like are preferable. Further, as the metal-containing quaternary ammonium salt, it is possible to use molybdic acid 4
TP-302, TP-415 which are primary ammonium salts
Commercial products such as those manufactured by Hodogaya Chemical Co., Ltd. are preferred. As other charge control agents, Bontron N-01, N-07, N-04 (all manufactured by Orient Chemical Industry Co., Ltd.), Copy Blue P
R (manufactured by Hoechst Co., Ltd.) and the like, which can be used in combination within a range that does not hinder the color tone, charging characteristics, and the like.

A colorant other than black is used in the color toner of the present invention. Specifically, yellow lead, cadmium yellow, yellow iron oxide, titanium yellow, chrome yellow, naphthol yellow, Hansa yellow, pigment yellow, benzidine yellow, permanent yellow, quinoline yellow lake,
Yellow colorants such as anthrapyrimidine yellow, orange colorants such as permanent orange, molybdenum orange, balkan first orange, benzine orange, indanthrene brilliant orange, brown colorants such as iron oxide, amber and permanent brown, red iron oxide, rose red iron oxide , Antimony, Permanent Red, Fire Red, Brilliant Carmine, Lightfast Red Toner, Permanent Carmine, Pyrazolone Red,
Bordeaux, Helio Bordeaux, Rhodamine Lake, DuPont Oil Red, Thioindigo Red, Thioindigo Maroon, Watching Red Strontium and other red colorants, cobalt purple, fast violet, dioxazine violet, methyl violet lake and other purple colorants, methylene blue, Blue colorants such as aniline blue, cobalt blue, cerulean blue, chalco oil blue, metal-free phthalocyanine blue, phthalocyanine blue, ultramarine blue, indanthrene blue, indigo, chrome green, cobalt green, pigment green B, green gold, Pigment or dye such as green colorant such as phthalocyanine green, malachite green oxalate, polychrome brom copper phthalocyanine, titanium oxide , Metal oxide powder such as zinc oxide is used. The amount of colorant is 0.1 to 15 relative to the total amount of toner.
It is preferably wt%.

The toner of the present invention preferably further contains a polyolefin. As the polyolefin, ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, 3-methyl-1-butene, 3-methyl-2-pentene, 3-propyl-5-
A polymer of an olefin monomer such as methyl-2-hexene or a copolymer of the above olefin monomer and acrylic acid, methacrylic acid, vinyl acetate or the like is applicable, and polypropylene is particularly preferable. These are 0.5 to 1 in the toner.
It is preferably blended in an amount of 0% by weight, particularly 1 to 5% by weight.
If it is less than 0.5% by weight, the fixing strength and the fixing characteristics such as offset in the heat roll fixing method tend to be poor. On the other hand, if it exceeds 10% by weight, the fluidity of the toner is inferior, so that problems such as poor image quality due to poor developer fluidity and material retention in the toner and developer container are likely to occur. .

If desired, the toner of the present invention may contain other compounds. Other compounds include lower alcohol esters of fatty acids such as butyl stearate and propyl stearate, Casta wax (made by Ito Oil Co., Ltd.), diamond wax (Shin Nippon Rika Co., Ltd.).
Polyhydric alcohol esters of fatty acids such as palm aceti (manufactured by NOF CORPORATION), Hoechst wax E, Hoechst wax-OP (manufactured by HEXA ACTEN GEZELSHAFT), higher alcohol esters of fatty acids such as carnauba wax, and bis. Amide Blast Flow (manufactured by Nitto Chemical Co., Ltd.), Amide 6L, 7S and 6H (manufactured by Kawaken Fine Chemicals Co., Ltd.), Hoechst Wax C (manufactured by Hoechst Actien Gelshaft), and other alkylene bis fatty acid amide compounds, Nipol NBR, 2057S,
2007J, BR1220 and other diene resins having a weight average molecular weight of 50,000 or more, hydroxyl group-containing vinyl resins,
Examples include vinyl resins containing carboxyl groups. These compounds play a role of finely adjusting the charging property and fixing property of the toner and improving the life of the photoconductor and the toner, and can be added to the toner in an amount of 0 to 10% by weight.

The above-mentioned binder resin, charge control agent, colorant, and other compounds added as necessary are homogenized to obtain a toner. For example, after dry-mixing the above components with a Henschel mixer, micro-mixing in a molten state is performed with a kneader, and then the cooled kneaded product is finely pulverized with a pin mill, jet mill or the like, preferably having an average particle size of 5 to 30 μm.
m, and particularly preferably a toner having an average particle size of 7 to 15 μm. In the color toner of the present invention, the above toner may be used as a toner base, and other additives may be externally added and mixed (externally added). For example, the surface layer may contain magnetic powder within a range that does not change the color tone. Such magnetic powders include metal powders of iron, manganese, nickel, cobalt, etc., iron ferrite, copper-zinc ferrite, barium-nickel ferrite, nickel-zinc ferrite, manganese-zinc ferrite, lithium-zinc ferrite,
Various ferrites such as magnesium-zinc-copper ferrite and barium-copper-zinc ferrite are preferable.

Further, fine silica powder can be used as another additive. When silica fine powder is used, 0.1 to 1% by weight, particularly 0.2 to
It is preferable to add and mix 0.8% by weight. If the silica fine powder is less than 0.1% by weight, the sharpness and fogging of the image tend to be inferior, and if it exceeds 1% by weight, the image density during repeated use tends to be low and the fixing strength tends to be low.
As the above-mentioned silica fine powder, hydrophobized silica fine powder is most suitable. Such silica fine powder is a fine powder of silicon dioxide in which surface silicon atoms are silanol groups,
For example, octyltrichlorosilane, decyltrichlorosilane, nonyltrichlorosilane, 4-isopropylphenylchlorosilane, 4-tert-butylphenylchlorosilane, dimethyldichlorosilane, dipentyldichlorosilane, dihexyldichlorosilane, dioctyldichlorosilane, dinonyldichlorosilane, didecyl. Dichlorosilane, didodecyldichlorosilane, 4-tert-butylphenyldichlorosilane, didecenyldichlorosilane, di-2-ethylhexyldichlorosilane, di-3,3-dimethylpentyldichlorosilane, trimethylchlorosilane, trihexylchlorosilane, tridecyl Reacts with compounds such as chlorosilane, dioctylchlorosilane, octyldimethylchlorosilane, 4-isopropylphenyldiethylchlorosilane By, it is obtained by binding a hydrophobic group through an oxygen atom to the surface silicon atoms of the silicon dioxide particles. These silica fine powders preferably have an average primary particle diameter of 30 mμ or less from the viewpoint of protecting the photoreceptor. Such silica fine powders include Aerosil R972, silica D-17, T-805, R-81.
2, RA200H, RX-C (all manufactured by Nippon Aerosil Co., Ltd.), Talanox 500 (manufactured by Tarco), Ca
b-O-Sil, M-5, MS-7, MS-75, HS
-5, EH-5, S-17, TS-720 (above, manufactured by Cabot Corporation) and the like are commercially available.

Further, as another additive, a fatty acid metal salt can be used in order to improve the characteristics such as the life of the photoreceptor and the developer. As the fatty acid metal salt, a metal salt of a saturated or unsaturated fatty acid, such as maleic acid, stearic acid, oleic acid, palmitic acid, renolic acid, ricinoleic acid or ricinoleic acid and zinc, magnesium, calcium, lead, iron, nickel, cobalt. , And salts with copper or aluminum, among others, zinc stearate,
Aluminum stearate, calcium stearate,
Magnesium stearate can be preferably used. The fatty acid metal salt is preferably added in an amount of 0.01 to 0.5% by weight, more preferably 0.01 to 0.2% by weight, based on the toner base. When the fatty acid metal salt is less than 0.01% by weight, the life may be particularly short when the photoconductor is an organic photoconductor. On the other hand, if it exceeds 0.5% by weight, the fluidity of the toner tends to decrease, and the toner tends to adhere to the photoconductor or the developing machine.

Further, other additives can be added to the toner of the present invention, if necessary. Such additives include aluminum oxide, zinc oxide, titanium oxide,
Examples include fine particles such as calcium carbonate and polymethylmethacrylate. Other additives added as necessary to the toner base are mixed and processed by a V-type mixer, a Henschel mixer, a Turbula mixer, a hybridizer, etc., and held in the toner base. The toner for developing an electrostatic image obtained as described above is used as a developer of the present invention in combination with a carrier.

The carrier is spherical in shape,
Pseudosphere, flat, sponge-like material, iron oxide powder, iron, copper, zinc, lead, magnesium, lithium,
Ferrite carriers such as manganese, cobalt, nickel, barium, etc. can be used, but the material of the carrier is such that the load on the developing machine is small and the image quality is good.
Ferrite or magnetite is preferable, and a spherical ferrite-based carrier is particularly preferable. Further, a material in which the above ferrite or magnetite is used as a core material and the surface of which is coated with a resin is preferably applied. This resin-coated carrier is preferable because it has an excellent charging rising property and does not cause the toner to be fused to the carrier surface during repeated use and can maintain an appropriate charging function. In addition, since the problem that the amount of carrier charge is accumulated due to use and the color toner held on the carrier side is less likely to be developed and the image density becomes thin, the resin to be coated may be a silicone resin, an acrylic resin, or a fluorine resin. A resin is preferable, and a fluorine resin is particularly preferable.

The developer of the present invention has an electric resistivity of 1 × 10 ^{8 to} 3 × 10 ¹⁰ Ω, which is measured by the apparatus shown in FIG.
.Cm, particularly preferably 5 × 10 ⁸ to 2 × 10 ¹⁰ Ω · cm. Thus, in order to adjust the electric resistivity, it is preferable that carbon black, various metal powders, an electric resistance adjusting agent such as a surfactant, and the like are mixed with the coating resin and the mixture is used for coating the material carrier. When the electric resistivity of the developer is less than 10 ⁸ Ω · cm, leakage of electric charge is large and stable chargeability is difficult to obtain, and halftone and fine line images are difficult to be produced well, and when it exceeds 3 × 10 ¹⁰ Ω · cm. The image density is likely to decrease and the edge effect is likely to occur. The mixing ratio of the toner in the developer is preferably 1 to 10% by weight, more preferably 1 to 7% by weight based on the total amount of the toner and the carrier. If it is less than 1% by weight, the density of the printed matter is low, or the carrier sticks to the photoreceptor, so-called carrier sticking is likely to occur. On the other hand, when it exceeds 10% by weight, the toner scattering is conspicuous, which tends to deteriorate the quality of the printed matter and tends to contaminate the working environment.

In the image producing method of the present invention, the electrostatic latent image formed on the photoconductor is visualized by the developer containing the color toner of the present invention, then transferred to a support such as paper, and then fixed. Therefore, a desired image can be manufactured. In the image producing method of the present invention, those containing an amorphous metal photoconductive substance as a photoreceptor, particularly those containing selenium, have good matching with a developer and can maintain image quality for a long period of time. preferable. Also,
In the high-speed development process in which the peripheral speed of the photoconductor rotates at a peripheral speed of 20 cm / s or more, the image producing method of the present invention shows a remarkable difference from the conventional method.

[0031]

The present invention will be described in detail below with reference to examples.
The present invention is not limited to this. Examples 1 to 6 and Comparative Examples 1 to 4 (1) Production of Copolymers R-1 to R-7 Apatite (Supertite 1) dispersed in 10% by weight of water.
0, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) 87 to 92 containing 3,000 parts by weight of an aqueous dispersion medium in which 100 parts by weight of micro dispersion are contained.
The monomers shown in Table 1 and the polymerization initiator were charged into a reaction vessel at ℃ under a nitrogen stream and held for about 6 hours. After that, once raise the temperature to 40
After cooling to 0 ° C, the monomers and polymerization initiators shown in Table 2 were charged and held at 87 to 92 ° C for about 4 hours, and further held at 96 ° C or higher for 10 hours. After cooling, it was washed with an aqueous solution of hydrochloric acid, filtered and dried with hot air to obtain a copolymer. The properties of the copolymer are shown in Table 3.

[0032]

[Table 1]

[0033]

[Table 2]

[0034]

[Table 3]

(2) Manufacture of Toner The toner materials shown in Table 4 were collectively preliminarily mixed with a Henschel mixer and then melt-kneaded with a biaxial kneader. Then, the cooled kneaded product was subjected to a pin mill and a jet mill to obtain a toner having an average particle size of 10 to 12 μm. (3) Evaluation (a) Evaluation method 4000 g of developer composed of toner and carrier shown in Table 4
An image was produced using a laser beam printer equipped with an amorphous selenium photoconductor and evaluated. After charging the photoreceptor to about 700 V with a corotron, information is written with a helium-neon laser, this is subjected to reversal development by a magnetic brush method, and then fixed with a heat roll. The peripheral speed of the photoconductor is 32 cm / s
ec, development gap 1.3mm for ferrite carrier,
The iron powder carrier was evaluated by mounting it on a printer having a size of 3.5 mm. Printing was performed in an environment of 20 ° C. and a relative humidity of 40%. The heat roll temperature during printing is 190 ° C.

(B) Fixing Strength The fixing strength of the initial image was calculated by the following formula.

[Equation 1] (C) Image density (OD), fog and halftone Image density (OD) and fog are Macbeth reflection densitometer RD
It was measured using a Model 514 (manufactured by A division kollmorgen Corp.). The degree of halftone reproduction was visually determined. The evaluation criteria of halftone reproducibility are as follows. ◯: A good halftone image can be obtained. Δ: Halftone is slightly thin. ×: Halftone does not appear. (D) Scattering The degree of scattering of toner was visually determined. The evaluation criteria for toner scattering are as follows. ◯: Almost no scattering Δ: A slight amount of scattering is recognized ×: Large amount of scattering (e) Electrical resistivity of developer The electrical resistivity of the developer was measured by using the measuring device shown in FIG.
In addition, (1) of FIG. 1 shows a configuration of the measuring apparatus, and (2) shows a circuit diagram. Charge the measuring cell 2 with 800 g of the developer 4,
The ears of the developer were formed on the magnet roll 1, the magnet roll and the counter electrode were connected to form a closed circuit, and a DC voltage was applied to the closed circuit to determine the electrical resistivity of the developer by the following equation.

[Equation 2]

[0037]

[Table 4]

[0038]

[Table 5]

Example 7 When the copolymer of Example 1 was replaced with R-4 and the same evaluation as in Example 1 was carried out, the fixing strength was 92%, the initial image density was 1.3, the initial fog was 0.1, and the initial fog was 0.1. Scattering ○, initial halftone ○, image density 1.1 after 400,000 pages, fog 0.1 after 400,000 pages, scattering after 400,000 pages ○, halftone after 400,000 pages ○ . Example 8 When the copolymer of Example 1 was replaced with R-6 and the same evaluation as in Example 1 was carried out, the fixing strength was 80%, the initial image density was 1.3, the initial fog was 0.1, and the initial scattering was ○. The initial halftone was good, the image density after 400,000 pages was 1.1, the fog after 400,000 pages was 0.1, the scattering after 400,000 pages was good, and the halftone after 400,000 pages was good. Example 9 When the copolymer of Example 1 was replaced with R-7 and the same evaluation as in Example 1 was carried out, the fixing strength was 90%, the initial image density was 1.3, the initial fog was 0.1, the initial scattering was ○. The initial halftone was good, the image density after 400,000 pages was 1.1, the fog after 400,000 pages was 0.1, the scattering after 400,000 pages was good, and the halftone after 400,000 pages was good.

Example 10 Evaluation was conducted in the same manner as in Example 1 except that an ultrahigh-speed laser beam printer having a selenium photoreceptor having a peripheral speed of about 80 cm / sec was used. The fixing strength was 90% and the initial image density was 1 .3,
Initial fog 0.1, initial scattering ○, initial halftone
The image density was 1.1, the image density after 600,000 pages was 1.1, the fog after 0.1 million pages was 0.1, the scattering after 600,000 pages was good, and the halftone after 600,000 pages was good. Comparative Example 5 When the copolymer of Example 1 was replaced with R-5 and the same evaluation as in Example 1 was carried out, the fixing strength was 90%, the initial image density was 1.3, the initial fog was 0.1, the initial scattering was ○. Initial halftone ○, image density after 400,000 pages 0.7, fog after 400,000 pages 0.2, scattering after 400,000 pages △, halftone after 400,000 pages ○ and running performance compared to Example 1 Inferior to

[0041]

As is clear from the above results, the color toner and developer of the present invention are excellent in image quality such as image density and fog and fixing characteristics, and are capable of high-speed printing of a color image in which toner scattering does not occur. It can be maintained even after repeated use for a long time.

[Brief description of drawings]

FIG. 1 (1) shows the structure of a measuring device for measuring the electrical resistivity of a developer, and FIG. 1 (2) shows its circuit diagram.

[Explanation of symbols]

 1 ... Magnet roll (diameter 60 mm, rotation speed 235 rpm) 2 ... Measuring cell 3 ... Counter electrode (aluminum) 4 ... Developer (800 g)

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location G03G 9/107 9/113 15/01 J 15/08 507 L 21/00 350 G03G 9/08 361 9/10 311 321 354 (72) Inventor Chiaki Okada 4-13-1, Higashimachi, Hitachi City, Ibaraki Prefecture Hitachi Chemical Co., Ltd. Yamazaki Factory

Claims (16)

[Claims] 1. A vinyl resin having a ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of a tetrahydrofuran-soluble component of 20 or more, a non-metal quaternary ammonium salt, and a metal containing an anion part having a metal complex structure. A color toner for developing an electrostatic charge image, which comprises a quaternary ammonium salt and a colorant. 2. The color toner for developing an electrostatic charge image according to claim 1, wherein the metal atom of the metal-containing quaternary ammonium salt having an anion portion having a metal complex structure is molybdenum. 3. The electrostatic image development according to claim 1, wherein the vinyl resin is a resin obtained by polymerizing a monomer mixture containing a dialkyl maleate, a dialkyl fumarate and / or a dialkyl itaconate. Color toner. 4. The color toner for electrostatic image development according to claim 1, 2 or 3, wherein the vinyl resin is a resin obtained by polymerizing a monomer mixture containing a crosslinking agent. 5. The vinyl resin is a resin obtained by polymerizing a monomer mixture containing dibutyl maleate and / or dibutyl fumarate and a crosslinking component.
2. A color toner for developing an electrostatic charge image according to 2, 3 or 4. 6. The color toner for developing an electrostatic image according to claim 1, 2, 3, 4 or 5, wherein the vinyl resin is a styrene-acrylic resin. 7. The color toner for developing an electrostatic charge image according to claim 1, wherein the vinyl resin is a resin obtained by suspension polymerization. 8. A developer comprising the electrostatic toner image developing color toner according to claim 1 and a carrier. 9. The developer according to claim 8, wherein the carrier is ferrite or magnetite. 10. The developer according to claim 8, wherein the carrier is resin-coated. 11. The developer according to claim 10, wherein the resin to be coated is a fluororesin. 12. A developer having an electric resistivity of 10 ^{8 to} 3 × 1.
The developer according to claim 8, 9, 10 or 11, which has a resistance of 0 ¹⁰ Ω · cm. 13. A method for producing an image using the color toner for developing an electrostatic charge image according to claim 1 or the developer according to claim 8, 9, 10 or 11. 14. The image manufacturing method according to claim 13, wherein a photoconductor containing an amorphous metal photoconductive substance is used as the photoconductor. 15. The image producing method according to claim 13, wherein the amorphous metal photoconductive substance is selenium. 16. The method for producing an image according to claim 13, 14 or 15, wherein a photosensitive member having a peripheral speed of 20 cm / s or more is used.