JP2003005448A - Dry electrophotographic color toner and method for manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a dry electrophotographic color toner and a method for manufacturing the toner which does not cause filming on a photoreceptor, a regulating member for the thickness of a developer layer, a developing sleeve or the like even after the toner is used for continuous printing for a long time with a single-component or two-components color developing method, and which has excellent electrification characteristics and which can stably form images excellent in transparency, image density, picture quality or the like. SOLUTION: In the dry electrophotographic color toner containing at least a binder resin, an electrification controlling agent and a coloring agent, the binder resin is a polyester resin and/or a polyol resin containing no THF insoluble content, having <=4 wt.% of the component with <=500 molecular weight in the molecular weight distribution by gel permeation chromatography(GPC) by 4 wt.%, having one peak in the region from 3,000 to 9,000 molecular weight and having the weight average particle size Dr satisfying 0.1 mm<=Dr<=0.7 mm. The weight average particle diameter Dc of the electrification controlling agent satisfies 0.001<=Dc/Dr<=1.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a dry electrophotographic color toner used as a developer for developing an electrostatic image in electrophotography, electrostatic recording, electrostatic printing and the like, and a method for producing the same.

[0002]

2. Description of the Related Art A developer used in electrophotography, electrostatic recording, electrostatic printing or the like is once attached to a latent image carrier such as a photoconductor on which an electrostatic charge image is formed in the developing process. Next, after being transferred from the photoreceptor to a transfer medium such as transfer paper in the transfer step, it is fixed on the paper surface in the fixing step. At that time, as a developer for developing the electrostatic charge image formed on the latent image holding surface, a two-component developer composed of a carrier and a toner and a one-component developer not requiring a carrier (magnetic toner, Non-magnetic toner) is known.
In the two-component development method, the toner particles adhere to the surface of the carrier to deteriorate the developer, and since only the toner is consumed, the toner concentration in the developer decreases. Therefore, there is a drawback that the developing device becomes large in size. On the other hand, the one-component developing system is becoming the mainstream of the developing system because it does not have the above-mentioned drawbacks and has an advantage of downsizing of the apparatus.

In recent years, OA and colorization in offices have progressed further, and not only the conventional copying of originals consisting only of characters, but also originals including graphs and the like created by a personal computer are output by a printer, presentation materials, etc. As a result, the chances of making many copies are increasing. Many of the printer output images are solid images, line images, and halftone images, and the market demands for image quality are changing accordingly, and the demand for high reliability is further increasing.

Conventionally, electrophotographic processes using a one-component developer are classified into a magnetic one-component developing system using a magnetic toner and a non-magnetic one-component developing system using a non-magnetic toner. The magnetic one-component developing method is a method of holding a magnetic toner containing a magnetic substance such as magnetite by using a developer carrying member provided with a magnetic field generating means such as a magnet inside, and developing a thin layer by a layer thickness regulating member. Recently, many have been put to practical use in small printers. On the other hand, in the non-magnetic one-component developing method, since the toner does not have a magnetic force, a toner replenishing roller or the like is pressed against the developer carrier to supply the toner onto the developer carrier and electrostatically hold it to form a layer. The layer is developed by thinning it with a thickness regulating member. Since it does not contain a colored magnetic material, it has the advantage of being compatible with colorization.
Further, since a magnet is not used for the developer bearing member, it is possible to reduce the weight and cost, and it has been put to practical use in small full-color printers and the like in recent years.

However, the current situation is that the one-component developing system still has many problems to be improved. In the two-component developing method, a carrier is used as a toner charging and conveying means, and the toner and the carrier are sufficiently stirred and mixed inside the developing device and then conveyed to the developer carrying member for development, so that the toner and carrier are used for a relatively long time. It is possible to maintain stable charging and conveyance, and it is also easy to support high-speed developing devices.

On the other hand, in the one-component developing system, since there is no stable charging and conveying means like a carrier, charging and conveyance defects are likely to occur due to long-term use and speeding up. That is, in the one-component developing method, after the toner is conveyed onto the developer carrier,
Although the toner is made thin by the layer thickness regulating member to develop, the carrier was used because the contact / friction charging time between the toner and the friction carrying member such as the developer carrying member and the layer thickness regulating member is very short. Compared to the two-component development method, the amount of low-charged and reverse-charged toner tends to increase. In particular, in the non-magnetic one-component developing method, usually, a means for carrying toner (developer) by at least one toner carrying member and developing the electrostatic charge image formed on the latent image carrier by the carried toner is adopted. However, at that time, it is said that the layer thickness of the toner on the surface of the toner conveying member must be made as thin as possible. This also applies when using a two-component developer having a very small carrier diameter, and especially when a one-component developer is used and its toner has a high electric resistance. Since it is necessary to charge this toner by the developing device, the layer thickness of the toner must be remarkably thin. This is because if the toner layer is thick, only the vicinity of the surface of the toner layer is charged, and it becomes difficult to uniformly charge the entire toner layer. For this reason, the one-component type developing system exerts a large load on the developer because of its charging ability, and although the one-component toner can obtain good images and developing characteristics at the initial stage, these restrictions are not observed in long-term use. Due to the force and the pressing force, image deterioration and development characteristics are likely to occur due to toner filming on the developing sleeve and toner adhesion on the blade.

Particularly in the case of full-color toners, a method of lowering the molecular weight of the resin and the softening temperature has been conventionally used in order to impart the sharp melt property and the fixability.
Since such a binder resin impairs the resin strength, there is a problem that toner fusion and filming are likely to occur. In order to prevent such blade fusion and filming of toner, methods such as introducing a cross-linking agent into the binder resin and increasing the glass transition temperature of the resin have been adopted. However, even with such a binder resin, sufficient strength cannot be imparted, and the fusion of the toner to the regulating member and the occurrence of filming cannot be sufficiently solved.

On the other hand, a charge control agent is added to stabilize the charge of the toner. The charge control agent controls the triboelectric charge amount of the toner and maintains the triboelectric charge amount. Typical charge control agents having negative chargeability include monoazo dyes, salicylic acid, naphthoic acid, metal salts and metal complex salts of dicarboxylic acids, diazo compounds, complex compounds with boron, and the like. Examples of the charge control agent include quaternary ammonium salt compounds, imidazole compounds, nigrosine, and azine dyes. However, some of these charge control agents have a color, and many cannot be used for color toners. In addition, since these charge control agents have poor compatibility with the binder resin, those existing on the toner surface, which are greatly involved in charging, are likely to be detached, resulting in uneven charging of the toner, development sleeve, and photosensitivity. It has a drawback that it is easily polluted such as body filming. Therefore, in the past, a good image was obtained in the initial stage, but there was a phenomenon that the image quality gradually changed and scumming and blurring occurred, especially when applied to color copying and continuously used while supplying toner. , The toner charge amount has decreased and the color tone of the initial copy image is markedly different, and it cannot withstand long-term use, and after a few thousand sheets, an image forming unit called a process cartridge is replaced early. It had an inevitable drawback. Therefore, the load on the environment is large and the user's time and effort are required. Further, since many of these contain heavy metals such as chromium, they are becoming a problem in terms of safety in recent years.

In order to solve the above problems, Japanese Patent Laid-Open Nos. 63-88564, 63-184762, 3-56974, and 6-2306 have been proposed.
Japanese Patent Publication No. 09 discloses a resin charge control agent having improved compatibility with a binder resin, transparency of a toner fixed image, and safety. Since these resin charge control agents have good compatibility with the binder resin, they are excellent in stable chargeability and transparency. However, these resin charge control agents have the drawback of being inferior in charge amount and charge rate as compared with toners using metal salts or metal complex salts of monoazo dye, salicylic acid, naphthoic acid, and dicarboxylic acid. Further, although the chargeability is improved by increasing the addition amount of the resin charge control agent, it adversely affects the toner fixability (low temperature fixability, offset resistance). Further, since these compounds have a large environmental stability of the charge amount (moisture resistance), they also have a problem that they are likely to cause scumming (fog). Further, in JP-A-8-30017, JP-A-9-171271, JP-A-9-212896, and JP-A-11-218965, an organic acid group such as a sulfonate group is used as a resin charge control agent. A copolymer of a monomer containing an aromatic monomer having an electron-withdrawing group has been proposed. However, due to hygroscopicity and adhesiveness that are thought to be due to monomers containing organic acid groups such as sulfonate groups, a sufficient amount of charge is secured, but the dispersion in the binder resin is not sufficient, and the toner is charged for a long time. The effect of suppressing the variation of the above and preventing the developing sleeve and the photoconductor filming are not sufficient. Further, in order to improve the compatibility with the styrene-based resin or polyester-based resin which is the binder resin, as the resin charge control agent, a monomer containing an organic acid group such as a sulfonate group, an aromatic monomer having an electron-withdrawing group, and a styrene-based resin are used. Although a copolymer with a monomer or a polyester-based monomer has been proposed, the effects of maintaining the charge amount for a long period of time and preventing the developing sleeve and the photoconductor filming are not sufficient. In particular, as a binder resin for a full-color toner, it is insufficient for a polyester resin and a polyol resin which are suitable in terms of color developability and image strength.

Further, due to miniaturization and high speed, a process for developing in a short time with a small amount of developer has been adopted.
There is a demand for a developer having a better charge rising property.

On the other hand, for the electrophotographic toner, for example, raw materials including a binder resin, a charge control agent, a colorant, etc. are blended, the blend is premixed and stirred, then melt-kneaded, and the obtained kneaded product is cooled. After that, the resulting pulverized product is classified, and the obtained classified product and additives are mixed to obtain an electrophotographic toner. In the manufacture of electrophotographic toner, it is important that the charge control agent, pigment (coloring agent), etc. are uniformly dispersed. If the toner is not uniformly dispersed, the translucency of the full-color toner is insufficient and the chargeability varies depending on the color, and the charge control agent causes the toner to scatter inside the apparatus. In order to improve these drawbacks, in Japanese Patent No. 2859633, by defining the weight average particle diameter of the binder resin (binder resin), the knitting phenomenon is eliminated during premixing and the shearing force of the kneader is easily applied. It is described that the lack of coloring power and instability of charging characteristics can be eliminated by doing so. However, at present, it is not possible to obtain sufficient dispersibility by simply mixing a colorant and a binder resin. As a toner, in addition to mechanical and electrical stability against external factors such as impact and humidity, an overhead projector (OHP) There was a problem that the light transmittance (transparency) when used for was not sufficient.

Further, particularly in a system in which a load is apt to be applied to the toner at the time of development by the one-component developing system, the charge control agent as described above has a poor compatibility with the binder resin, so that the toner surface which is greatly involved in charging is However, there is a drawback that the substances existing in the toner are easily detached, and the toner is easily contaminated due to variations in the charging of the toner, the developing sleeve and the filming of the photoconductor. Therefore, even when such a charge control agent is conventionally used, a good image can be obtained in the initial stage, but the phenomenon that the image quality is gradually changed and scumming or blurring occurs occurs, especially in color copying. When applied and continuously used while replenishing the toner, the toner charge amount decreases and the color tone of the copied image is markedly different from that of the initial copy image, and it cannot withstand long-term use. It has a drawback that the image forming unit, called “image forming unit”, must be replaced at an early stage. Therefore, the load on the environment is large and the user's time and effort are required.

In recent years, the demand for printers has expanded, and the downsizing, speeding up and cost reduction of devices have progressed, and higher reliability and longer life have begun to be demanded for the devices, and toners also maintain various characteristics for a long period of time. Although it is required that these resin charge control agents cannot maintain their charge control effect, the development sleeve and layer thickness regulating members (blades and rollers)
However, there is a problem in that the charging performance of the toner is deteriorated due to the contamination of the toner and the filming of the photosensitive member occurs.

[0014]

DISCLOSURE OF THE INVENTION The object of the present invention is that the binder resin, the charge control agent, the colorant, etc. are excellent in dispersibility, the charge amount and the transport amount of the toner are stable, and the background stain is high. High image quality can be obtained, and even during long-term use, contamination of the developer carrier and developer layer thickness control member (blade and roller) and photoconductor filming can be prevented for a long time (tens of thousands or more). And a method for producing the same. Another object of the present invention is to obtain a stable charge amount without impairing the advantages of a resin charge control agent having excellent compatibility with a binder resin, transparency of a toner-fixed image, and safety, and to provide a high image density at a high image density. The present invention provides a color toner for electrophotography that can obtain high image quality with less stains, and a method for manufacturing the same. Still another object of the present invention is to provide an overhead projector (O
(EN) Provided are a color toner for electrophotography having excellent light transmittance (transparency) when used for HP), and a method for producing the same.

[0015]

In order to solve the above problems, the inventors of the present invention have made intensive studies by paying attention to the constituent components of the binder resin and the particle size of the raw material when the toner is mixed, and as a result, as a binder resin for full-color toner. When a polyester resin having a specific molecular weight distribution suitable from the viewpoint of color developability image strength, a polyol resin, and a charge control agent having a specific particle size ratio to the particle size are used, excellent dispersibility is obtained. It can prevent contamination of the developer carrier (developing roller, sleeve) and development layer thickness control member (blade or roller) and photoconductor filming for a long time of tens of thousands of sheets or more, and has higher charging amount and sharp charging. The present inventors have found that a color toner for electrophotography, which can obtain a quantity distribution, has a good charge rise, and is excellent in scumming, can be obtained, and has completed the present invention.

That is, according to the present invention, (1) in a dry electrophotographic color toner containing at least a binder resin, a charge control agent, and a colorant, the binder resin does not contain a THF insoluble component, and gel permeation chromatography is used. In the molecular weight distribution in the graph (GPC), the content ratio of the component having a molecular weight of 500 or less is 4% by weight or less, and one peak is present in the region of the molecular weight of 3000 to 9000, and the weight average particle diameter Dr is 0.1 mm.
A polyester resin and / or a polyol resin having ≦ Dr ≦ 0.7 mm, and further, a weight average particle diameter Dc of the charge control agent is 0.001 ≦ Dc / Dr ≦ 1 for dry electrophotography. Color toner, (2) at least a binder resin, a charge control agent, and a colorant are mixed and stirred, the resulting mixture is melt-kneaded, and the resulting kneaded product is cooled and then pulverized. The obtained pulverized product is classified. In the method for producing a dry electrophotographic color toner in which the classified product and the additive are further mixed to obtain a toner, a THF insoluble component is not included as the binder resin and gel permeation chromatography (GPC) In the molecular weight distribution, the content of components having a molecular weight of 500 or less is 4% by weight or less, and a molecular weight of 3000 to 900.
A polyester resin and / or a polyol resin having one peak in the region of 0 and having a weight average particle diameter Dr of 0.1 mm ≦ Dr ≦ 0.7 mm is used, and the weight average particle diameter Dc is used as the charge control agent. Is 0.001 ≦ Dc /
A method for producing a dry electrophotographic color toner, characterized in that Dr ≦ 1 is used, (3) the charge control agent is (a) a sulfonate group-containing monomer, and (b) an aromatic group-containing aromatic group. (1) or a resin charge control agent comprising a monomer, and (c) an acrylic acid ester monomer and / or a methacrylic acid ester monomer, and / or (d) an aromatic vinyl monomer as a constituent unit. (2) Dry electrophotographic color toner and method for producing the same, (4) Dispersion particle size of the charge control agent in the toner is 0.05 μm to 1.5 μm in major axis and 0.02 to 1 in minor axis. The color toner for dry electrophotography according to any one of (1) to (3) above, and the method for producing the same, and (5) the weight average particle diameter Dc of the charge control agent is 0. .1 Dc / Dr ≦ 1, wherein the color toner for dry electrophotography according to any one of the above (1) to (4) and a method for producing the same, and (6) the colorant is mixed with the binder resin in advance. The color toner for dry electrophotography according to any one of (1) to (5) above and a method for producing the same, (7) the pretreatment product of the colorant has a weight average particle size of The dry electrophotographic color toner according to (6) above and a method for producing the same are provided.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. First, the dry electrophotographic color toner of the present invention will be described. The dry electrophotographic color of the present invention contains at least a binder resin, a charge control agent, and a colorant.

As the binder resin used in the present invention, a polyester resin or a polyol resin suitable as a binder resin for a full-color toner in terms of color developability and image strength is used.
In a color image, since several types of toner layers are stacked in layers, the toner layer becomes thick, and the image has cracks and defects due to insufficient strength of the toner layer, and proper gloss is lost. For this reason, polyester resin and polyol resin are used in order to maintain appropriate gloss and excellent strength.

The polyester resin can be generally obtained by an esterification reaction of a polyhydric alcohol and a polycarboxylic acid. Among the monomers constituting the polyester resin in the present invention, as the polyhydric alcohol monomer,
Including trifunctional or higher polyfunctional monomers, for example, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butadieneol, neopentyl glycol, 1,4- Butenediol, 1,5-
Pentanediol, diols such as 1,6-hexanediol, bisphenol A, hydrogenated bisphenol A, bisphenol A alkylene oxide adducts such as polyoxypropyleneized bisphenol A, other dihydric alcohols, or sorbitol, 1,2 , 3, 6
-Hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,
2,5-pentanetriol, glycerol, diglycerol, 2-methylpropanetriol, 2-methyl-
Examples include 1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxybenzene, and other polyhydric alcohols having 3 or more valences.

Among these monomers, those using bisphenol A alkylene oxide adduct as a main component monomer are preferably used. Bisphenol A
When an alkylene oxide adduct is used as a constituent monomer, a polyester having a relatively high glass transition point is obtained due to the properties of the bisphenol A skeleton, and the copy blocking resistance and heat resistant storage stability are good. Further, the presence of the alkyl groups on both sides of the bisphenol A skeleton functions as a soft segment in the polymer, and the color developability and the image strength at the time of fixing the toner are improved. Of the bisphenol A alkylene oxide adducts, as the alkylene group, ethylene group and propylene group are preferably used.

Among the monomers constituting the polyester resin in the present invention, examples of the polyvalent carboxylic acid monomer include polyfunctional monomers having a valence of 3 or more, such as maleic acid, fumaric acid, citraconic acid, itaconic acid and glutaconic acid. , Phthalic acid, isophthalic acid, terephthalic acid, cyclohexanedicarboxylic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, malonic acid, or alkenylsuccinic acid or alkylsuccinic acid such as n-dodecenylsuccinic acid, n-dodecylsuccinic acid, Anhydrides of these acids, alkyl esters, other divalent carboxylic acids,
And 1,2,4-benzenetricarboxylic acid, 2,
5,7-naphthalene tricarboxylic acid, 1,2,4-naphthalene tricarboxylic acid, 1,2,4-naphthalene tricarboxylic acid, 1,2,4-butane tricarboxylic acid, 1,
2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methyl-methylenecarboxypropane, tetra (methylenecarboxyl) methane, 1,2,7,8-
Examples thereof include octane tetracarboxylic acid, enpole trimer acid, anhydrides thereof, alkyl esters, alkenyl esters, aryl esters, and other trivalent or higher carboxylic acids.

Specific examples of the above-mentioned alkyl group, alkenyl group or aryl ester include trimethyl 1,2,4-benzenetricarboxylic acid, trimethyl 1,2,4-benzenetricarboxylic acid and 1,2,4-benzenetricarboxylic acid. Acid triethyl, tri-n-butyl 1,2,4-benzene tricarboxylate, triisobutyl 1,2,4-benzene tricarboxylate, tri-n-octyl 1,2,4-benzene tricarboxylate, 1,2,4-benzene Tricarboxylic acid tri-2-ethylhexyl, 1,2,4-benzenetricarboxylic acid tribenzyl, 1,2,4-benzenetricarboxylic acid tris (4-isopropylbenzyl)
Etc.

It is known that the chargeability of a polyester resin and the acid value are in a substantially proportional relationship, and that the higher the acid value, the greater the negative chargeability of the resin. Also affects. That is, if the acid value is high, the charge amount will be high under low temperature and low humidity, and the charge amount will be low under high temperature and high humidity, and background stains, image density, and color reproducibility will be large, making it difficult to maintain high image quality. . Therefore, the acid value of the polyester resin is preferably 20 KOH mg / g or less,
Further, 5 KOH mg / g or less is preferable.

As the polyol resin used in the present invention, from the viewpoints of environmental stability of charging, fixing stability, color reproducibility, gloss stability, curl prevention after fixing, etc., the end of the epoxy resin is capped, Further, those having a polyoxyalkylene portion in the main chain are preferable. For example, epoxy resin with glycidyl groups at both ends and 2 with glycidyl groups at both ends
It can be obtained by reacting an alkylene oxide adduct of a dihydric phenol with a dihalide, an isocyanate, a diamine, a diol, a polyhydric phenol, or a dicarboxylic acid. Of these, it is most preferable to react a dihydric phenol from the viewpoint of reaction stability. In addition, it is also preferable to use polyhydric phenols and polyhydric carboxylic acids in combination with dihydric phenol within the range where gelation does not occur.

Examples of the alkylene oxide adduct of dihydric phenol having glycidyl groups at both ends used in the present invention include the following. Examples thereof include reaction products of ethylene oxide, propylene oxide, butylene oxide, and mixtures thereof with bisphenols such as bisphenol A and bisphenol F. The obtained adduct may be glycidylated with epichlorohydrin or β-methylepichlorohydrin before use.

Particularly, a glycidyl ether of an alkylene oxide adduct of bisphenol A represented by the following general formula (1) is preferable.

[Chemical 1]

The binder resin of the present invention does not have a THF insoluble content, and has a molecular weight of 500 in gel permeation chromatography (GPC) distribution.
The content ratio of the following components is 4% by weight or less, and the molecular weight is 3
It is characterized by having one peak in the region of 000 to 9000. When the THF-insoluble matter is contained, the gloss is lowered and the transparency is lowered, so that a high-quality image cannot be obtained when an OHP sheet is used. On the other hand, if the content of the component having a molecular weight of 500 or less exceeds 4% by weight, the blade or sleeve is contaminated due to long-term use and filming easily occurs.

The molecular weight distribution of the present invention is measured by GPC as follows. The column was stabilized in a heat chamber at 40 ° C., and THF as a solvent was flowed through the column at this temperature at a flow rate of 1 ml per minute to adjust the sample concentration to 0.05 to 0.6 wt% THF of the toner base.
Inject 200 μl of the sample solution for measurement. The THF sample solution is a 0.45 μm liquid chromatograph filter before injection.
HF insoluble components are removed. In measuring the molecular weight of the toner sample, the molecular weight distribution of the sample is calculated from the relationship between the logarithmic value of the calibration curve prepared using several kinds of monodisperse polystyrene standard samples and the count number. As a standard polystyrene sample for preparing a calibration curve, for example, Pressure
Chemical Co. Alternatively, the molecular weight manufactured by Toyo Soda Kogyo Co., Ltd. is 6 × 10 ² , 2.1 × 10 ³ , 4 × 1.
0 ³ , 1.75 × 10 ⁴ , 5.1 × 10 ⁴ , 1.1 × 1
0 ⁵ , 3.9 × 10 ⁵ , 8.6 × 10 ⁵ , 2 × 10 ⁶ , 4.
It is suitable to use a standard polystyrene sample of at least 10 points by using a sample of 48 × 10 ⁶ . An RI (refractive index) detector is used as the detector. Whether or not the binder resin is insoluble in THF is determined when the THF sample solution for molecular weight distribution measurement is prepared. That is, when the 0.45 μm filter unit is attached to the tip of the syringe and the liquid is pushed out from the inside of the syringe, it is determined that there is no THF insoluble content unless the filter is clogged.

The binder resin of the present invention preferably has an endothermic peak in DSC in the range of 60 to 70 ° C. If the temperature is lower than 60 ° C., there is a problem in toner storage stability.
On the other hand, when the temperature exceeds 70 ° C., the toner productivity is lowered and it is difficult to obtain a highly transparent toner. D of the present invention
The endothermic peak in SC is Rigak manufactured by Rigaku Denki Co., Ltd.
u THRMOFLEX TG8110 is measured at a temperature rising rate of 10 ° C./min, and the main maximum peak of the endothermic curve is read.

The binder resin of the present invention has a ratio Mw / of the weight average molecular weight (Mw) and the number average molecular weight (Mn).
It is preferable that Mn is 2 to 10. Mw / Mn is 1
If it exceeds 0, no gloss is obtained when the toner is fixed as a toner, and a glossy high-quality image cannot be obtained.
Further, when Mw / Mn is less than 2, the productivity is lowered in the pulverizing step at the time of toner production, the blade or sleeve is contaminated by long-term use, and filming easily occurs.

Further, the binder resin of the present invention is preferably at a temperature of 95 to 120 ° C. at which the apparent viscosity by the flow tester becomes 10 ⁴ Pa · s. If it is less than 95 ° C, there is no room for hot offset at the time of fixing, while if it is 120 ° C or more, sufficient gloss cannot be obtained. To measure the temperature at which the apparent viscosity is 10 ⁴ Pa · s, a Shimadzu CFT-500 type was used as a flow tester, a load of 10 kg / cm ² , an orifice diameter of 1 mm x a length of 1 mm,
Viscosity was measured at a heating rate of 5 ° C / min, and apparent viscosity was 10 ⁴ P.
The temperature at which a · s is reached is read.

Furthermore, the binder resin of the present invention is
The weight average particle diameter Dr is 0.1 mm ≦ Dr ≦ 0.7 mm. When Dr is less than 0.1 mm, air is likely to be included between the binder resin powders in mixing the toner components during toner production, and shearing force and compression force are not applied in the kneading machine when kneading the toner components. Therefore, sufficient dispersion cannot be obtained, and microscopic dispersion cannot be obtained.
On the other hand, if Dr is larger than 0.7 mm, the history of the particle size of the resin or the charge control agent is likely to remain even if shearing force is applied during kneading, and the charge control agent and the colorant are sufficiently dispersed in the resin particles. Since it becomes impossible, the transparency is likely to be deteriorated, and the charge amount distribution is further widened, so that toner scattering is likely to occur.

As the charge control agent used in the present invention, all known charge control agents can be used, and one or more charge control agents may be mixed and used. Nigrosine dyes,
Triphenylmethane dye, chromium-containing metal complex dye,
Molybdic acid chelate pigment, rhodamine dye, alkoxy amine, quaternary ammonium salt, fluorine-modified quaternary ammonium salt, alkylamide, phosphorus simple substance or compound, tungsten simple substance or compound, salicylic acid derivative metal salt compound, fluorine-based interface Both positive and negative polarities such as activators can be mentioned.

However, salts of heavy metals (nickel, copper, zinc, mercury, chromium, etc.) are not preferable from the viewpoint of safety, and from the viewpoint of transparency and compatibility with the binder resin, the following monomers are polymerized. The resin charge control agent obtained as described above is preferable. Constituting resin charge control agent (a)
Examples of the sulfonate group-containing monomer include an aliphatic sulfonate group-containing monomer and an aromatic sulfonate group-containing monomer. Examples of the aliphatic sulfonate group-containing monomer include vinyl sulfonic acid, allyl vinyl sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, methacryloyloxyethyl sulfonic acid, and other alkali metal salts, alkaline earth metal salts, amine salts, and Examples thereof include quaternary ammonium salts. Examples of the aromatic sulfonate group-containing monomer include styrene sulfonic acid, sulfophenyl acrylamide, sulfophenyl maleimide, sulfophenyl itaconimide, and other alkali metal salts, alkaline earth metal salts, amine salts, and quaternary ammonium salts. .

(B) Examples of the aromatic monomer having an electron-withdrawing group include chlorostyrene, dichlorostyrene, bromostyrene, fluorostyrene, nitrostyrene, styrene substitution products such as cyanstyrene, and chlorophenyl (meth).
Acrylate, bromophenyl (meth) acrylate,
Phenyl (meth) acrylate substitution products such as nitrophenyl (meth) acrylate and chlorophenyloxyethyl (meth) acrylate, chlorophenyl (meth) acrylamide, bromophenyl (meth) acrylamide,
Phenyl (meth) acrylamide substitution products such as nitrophenyl (meth) acrylamide, chlorophenylmaleimide, dichlorophenylmaleimide, nitrophenylmaleimide, phenylmaleimide substitution products such as nitrochlorophenylmaleimide, chlorophenylitaconimide,
Examples thereof include phenylitaconimide substitution products such as dichlorophenylitaconimide, nitrophenylitaconimide and nitrochlorophenylitaconimide, and phenyl vinyl ether substitution products such as chlorophenyl vinyl ether and nitrophenyl vinyl ether. Particularly, a phenylmaleimide-substituted product and a phenylitaconimide-substituted product substituted with a chlorine atom or a nitro group are preferable in terms of charging property and filming resistance.

Examples of the (c) acrylic acid ester and methacrylic acid ester monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, and (meth) ) Isobutyl acrylate, stearyl (meth) acrylate,
Dodecyl (meth) acrylate, (meth) acrylic acid 2-
Examples include ethylhexyl and the like.

Examples of the aromatic vinyl monomer (d) include styrene, vinyltoluene and α-methylstyrene.

By adding (a) a sulfonic acid group-containing monomer as a monomer constituting the resin charge control agent, the negative charge imparting effect of the resin charge control agent is improved, but the environmental stability of the toner is improved due to its hygroscopicity. (Temperature and humidity stability)
It is generally known to be used as a copolymer with an aromatic monomer having an electron-withdrawing group, etc.
Although it is sufficient to use several thousand sheets, if used for tens of thousands or more for a long period of time, the developing sleeve and layer thickness regulating members (blades and rollers) will be contaminated and the photoconductor filming will occur, and the toner will be charged. There is a problem that stability and high image quality are not sufficiently maintained, and productivity is reduced. In order to make up for such drawbacks, color developability as a binder resin for full-color toner,
For polyester resin and polyol resin suitable from the viewpoint of image strength, (a) a sulfonate group-containing monomer, (b) an aromatic monomer having an electron-withdrawing group, and (c) an acrylic acid ester and / or a methacrylic acid ester. By using a copolymer obtained by polymerizing at least three kinds of monomers as a resin charge control agent,
Excellent long-term charging and environmental stability, good development of thin layers without contamination of developing sleeves and layer thickness control members (blades and rollers), photoconductor filming prevention, high image quality maintained, productivity Thus, a high color toner for electrophotography can be obtained.

It is presumed that these effects are due to the following reasons. That is, by using (a) a sulfonate group-containing monomer and (b) an aromatic monomer having an electron-withdrawing group in combination, the negative charge imparting effect is enhanced, and (c) an acrylic acid ester and / or a methacrylic acid ester monomer is used. By doing so, the environmental stability of charging is further increased, the resin hardness is increased, the pulverizability is improved, and the developing sleeve and layer thickness regulating member (blade and roller) are not contaminated, and the effect of preventing photoreceptor filming is achieved. In addition, when combined with a polyester resin suitable as a binder resin for a full-color toner in terms of color developability and image strength, an appropriate dispersibility can be obtained, and a color toner for electrophotography with a sharp charge distribution can be obtained. .

The composition ratio of the monomers in the resin charge control agent of the present invention is such that (a) the sulfonic acid group-containing monomer is 1 to 3
0 wt% is preferable, more preferably 2 to 20 wt%
Is. When the amount of the (a) sulfonic acid group-containing monomer is less than 1% by weight, the rise of charge and the amount of charge are insufficient, and the image is likely to be affected. On the other hand, if it exceeds 30% by weight, the environmental stability of charging is deteriorated, the charging amount at high temperature and high humidity is low, and the charging amount at low temperature and low humidity is high, so that the charging stability of the toner and the maintenance of high image quality are not sufficient. Further, there is a problem that the developing sleeve and the layer thickness regulating member (blade and roller) are apt to be contaminated and the filming of the photoconductor is caused, and the productivity at the time of toner production by the kneading / pulverizing method is also lowered.

(B) The aromatic monomer having an electron-withdrawing group is preferably 1 to 80% by weight, more preferably 20 to
It is 70% by weight. (B) When the amount of the aromatic monomer having an electron-withdrawing group is less than 1% by weight, the charge amount is insufficient,
Soil and toner scatter easily occur. On the other hand, if it exceeds 80% by weight, the dispersion in the toner is poor, the charge amount distribution of the toner is widened, and scumming and toner scattering easily occur, and the maintenance of high image quality is not sufficient.

The amount of the (c) acrylic acid ester and / or methacrylic acid ester monomer is preferably 10 to 80% by weight, more preferably 20 to 70% by weight. (C) When the acrylic acid ester and / or methacrylic acid ester monomer is less than 10% by weight, sufficient environmental stability of charging cannot be obtained, and the pulverizability at the time of toner production by the kneading / pulverization method is sufficient. In addition, it is not possible to sufficiently prevent contamination of the developing sleeve, the layer thickness regulating member (blade or roller), and filming of the photoconductor. If it exceeds 80% by weight, the rise of electrification and the electrification amount are not sufficient and the image is likely to be affected.

Further, the aromatic vinyl monomer (d) is preferably 0 to 30% by weight, more preferably 3 to 20.
% By weight. If the amount of the aromatic vinyl monomer (d) exceeds 30% by weight, the resin becomes hard, the dispersibility in the toner is lowered, the charge distribution is widened, and scumming and toner scattering in the machine are likely to occur. Further, the fixability of the toner, especially the color developability when the color toners are mixed, becomes poor.

The resin charge control agent obtained by combining these monomers can obtain a proper dispersibility by further combining with a polyester resin or polyol resin which is suitable as a binder resin for a full-color toner from the viewpoint of color developability and image strength. In addition, a color toner for electrophotography having a sharp charge amount distribution can be obtained, and long-term charge stability and high image quality can be obtained.

The charge control agent of the present invention is preferably added in an amount of 0.1 to 20% by weight, more preferably 0.5 to 10% by weight, and still more preferably 1.0.
~ 5% by weight. If it is less than 0.1% by weight, the rise of electrification and the electrification amount are not sufficient, and the image is likely to be affected by scumming and scatter. When it exceeds 20% by weight, the dispersion is poor, the charge amount distribution is widened, and scumming and toner scattering in the machine are likely to occur.

As the colorant, all known dyes and pigments can be used. For example, carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (1
0G, 5G, G), cadmium yellow, yellow iron oxide,
Loess, Yellow lead, Titanium yellow, Polyazo yellow, Oil yellow, Hansa yellow (GR, A, RN, R), Pigment yellow L, Benzidine yellow (G, GR), Permanent yellow (NCG), Balkan fast yellow (5G) , R), tartrazine lake, quinoline yellow lake, anthrazan yellow BGL, isoindolinone yellow, red iron oxide, red lead, lead vermilion, cadmium red, cadmium mercury red, antimon verm, permanent red 4R, para red, Faise Red, Parachlor Ortho Nitroaniline Red, Resor Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carnmin BS, Permanent Red (F2R, F4R, FRL, FRLL, F4R)
H), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Resor Rubin G
X, Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Toluidine Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamin Lake B, Rhodamine Lake. Y, Alizarin Rake,
Thioindigo Red B, Thioindigo Maroon, Oil Red, Quinacridone Red, Pyrazolone Red, Polyazo Red, Chrome Vermillion, Benzidine Orange, Perinone Orange, Oil Orange, Cobalt Blue, Cerulean Blue, Alkali Blue Lake, Peacock Blue Lake, Victoria Blue Rake, metal-free phthalocyanine blue, phthalocyanine blue, fast sky blue, indanthrene blue (RS, BC),
Indigo, Ultramarine, Navy Blue, Anthraquinone Blue, Fast Violet B, Methyl Violet Lake, Cobalt Purple, Manganese Purple, Dioxane Violet, Anthraquinone Violet, Chrome Green, Zinc Green, Chromium Oxide, Pyridian, Emerald Green, Pigment Green B, Naphthol Green B , Green gold, acid green lake, malachite green lake, phthalocyanine green, anthraquinone green, titanium oxide, zinc white, lithobon and mixtures thereof can be used. The amount of the colorant used is generally 0.1 to 50 parts by weight based on 100 parts by weight of the binder resin.

In particular, the colorant is pre-treated with the above binder resin to enhance the dispersibility of the pigment (colorant) in the binder resin, and the above content provides sufficient coloring power to improve the transparency and color development of the toner. The chargeability can be improved and the charge can be easily controlled. The pretreatment with the resin is performed by melt-kneading the binder resin and the colorant at a constant ratio and coarsely pulverizing them. Generally, the mixing ratio is 1 to 1 part by weight of the colorant of the resin.
5 parts by weight is desirable. 1 part resin for 1 part by weight of colorant
If it is less than part by weight, the colorant cannot be sufficiently dispersed. If the amount of the resin is more than 5 parts by weight with respect to 1 part by weight of the colorant, the dispersive force does not act on the colorant and sufficient dispersion cannot be achieved. Two
When using more than one colorant, even if treated individually,
Alternatively, the pigment may be mixed in advance before the treatment.

In order to impart a releasing property to the manufactured toner, it is preferable to add wax to the manufactured toner. The wax has a melting point of 40 to 120.
C., preferably 50 to 110.degree. If the melting point of the wax is too high, the fixability at low temperatures may be insufficient, while if the melting point is too low, the offset resistance and durability may be reduced. The melting point of the wax is the differential scanning calorimetry (DSC).
Can be sought by. That is, the melting peak value when a few mg of sample is aged at a constant temperature rising rate, for example (10 ° C./min), is taken as the melting point.

Examples of the wax that can be used in the present invention include solid paraffin wax, micro wax, rice wax, fatty acid amide wax, fatty acid wax, aliphatic monoketones, fatty acid metal salt wax, fatty acid ester wax. , Partially saponified fatty acid ester wax, silicone varnish, higher alcohol, carnauba wax, and the like. Further, low molecular weight polyolefins such as low molecular weight polyethylene and polypropylene can also be used. In particular, a polyolefin having a softening point of 70 to 150 ° C. by the ring and ball method is preferable, and a polyolefin having a softening point of 120 to 150 ° C. is more preferable.

Examples of the cleaning property improver for removing the toner remaining on the photoconductor or the primary transfer medium after the transfer include, for example, fatty acid metal salts such as zinc stearate, calcium stearate and stearic acid, for example, polymethylmethacrylate fine particles and polystyrene. Examples thereof include polymer particles produced by soap-free emulsion polymerization of particles and the like. The fine polymer particles have a relatively narrow particle size distribution and a volume average particle diameter of 0.01 to 1 μm.
Are preferred.

The toner of the present invention contains, as other additives,
For example, colloidal silica, hydrophobic silica, Teflon (registered trademark), fluoropolymer, low molecular weight polyolefin, fatty acid metal salt (zinc stearate, aluminum stearate, calcium stearate, etc.), metal oxide (titanium oxide, aluminum oxide, oxidation) It is also possible to include tin, antimony oxide, etc.), a conductivity-imparting agent (carbon black, tin oxide, etc.), a magnetic material, and those obtained by surface-treating these additives. These additives may be used alone or in combination of two or more, and the content thereof is generally 0.1 to 10 parts by weight with respect to 100 parts by weight of the toner.

The toner of the present invention may be a magnetic toner containing a magnetic material. Examples of magnetic materials include iron oxide (magnetite, ferrite, hematite, etc.), metal (iron, cobalt, nickel, etc.), the metal and aluminum, cobalt, copper, lead, magnesium, tin, zinc, antimony, beryllium, bismuth, calcium, cadmium,
Examples include alloys or mixtures of manganese, selenium, titanium, tungsten, vanadium, and the like. These magnetic materials preferably have a volume average particle diameter of about 0.1 to 2 μm, and the amount contained in the toner is 5 to 150 parts by weight with respect to 100 parts by weight of the binder resin content.

The toner of the present invention may be used as a two-component developer using a carrier. The carrier used here may be any conventional carrier such as iron powder, ferrite, magnetite, or glass beads. Further, these carriers may be resin-coated. The resin used in this case is a known one such as polyfluorocarbon, polyvinyl chloride, polyvinylidene chloride, phenol resin, polyvinyl acetal, acrylic resin, silicone resin,
Silicone coated carriers are excellent from the viewpoint of developer life. If necessary, conductive powder or the like may be contained in the coating resin. As the conductive powder, metal powder, carbon black, titanium oxide, tin oxide, zinc oxide or the like can be used.
It is preferable that these conductive powders have an average particle diameter of 1 μm or less. When the average particle diameter is larger than 1 μm, it becomes difficult to control the electric resistance. The mixing ratio of the toner and the carrier of the two-component developer is generally 0.5 to 20.0 parts by weight of the toner with respect to 100 parts by weight of the carrier.

Next, the method for producing the dry electrophotographic color toner of the present invention will be described. The method for producing the toner of the present invention may be any conventionally known method, including a step of mechanically mixing toner components containing at least a binder resin, a charge control agent and a colorant, a step of melt-kneading, and a step of pulverizing. A method of manufacturing a toner having a step of classifying can be applied. Further, in the mechanical mixing step and the melt-kneading step, a manufacturing method of returning powders other than particles to be the product obtained in the pulverizing or classifying step and reusing them is also included. After the step of melting and kneading with the powder other than the particles to be the product here (by-product), the fine particles and coarse particles other than the components to be the product of the desired particle size obtained in the crushing step and the classification step to be performed subsequently. It refers to fine particles or coarse particles other than the components that generate the product having a desired particle size. It is preferable to mix 1 to 20 parts by weight of the by-product with 100 parts by weight of the raw material and preferably 100 parts by weight of the main raw material in the step of mixing or melt-kneading such by-product.

The method for producing the toner of the present invention will be described in more detail. In the method for producing a toner of the present invention, the step of mixing and agitating at least the binder resin, the charge control agent and the colorant may be carried out under ordinary conditions using an ordinary mixer having rotating blades. The weight average particle diameter Dr of the binder resin is 0.1 mm ≦ Dr ≦ 0.7
mm, and the weight average particle diameter Dc of the charge control agent is 0.001 ≦ Dc / Dr with respect to the weight average particle diameter Dr of the binder resin.
It is necessary that ≦ 1. As described above, when Dr is less than 0.1 mm, air is likely to be included between the binder resin powders in the mixing of the toner components during the production of the toner, and the shearing force is applied by the kneader during the kneading of the toner components during the production of the toner. Since the share of the compressive force is not applied, sufficient dispersion cannot be obtained, and microscopic dispersion cannot be obtained. On the other hand, if Dr is 0.7 mm or more or Dc / Dr is larger than 1, the particle size history of the resin or the charge control agent is likely to remain even if shearing force or the like is applied during kneading, and the charge control agent and the colorant are Since the particles cannot be sufficiently dispersed into the resin particle size, the transparency is likely to be deteriorated, and the charge amount distribution is widened, so that toner scattering is likely to occur. On the other hand, when Dc / Dr is less than 0.001, the shearing force to the binder resin can be obtained, but the dispersing force to the charge control agent becomes difficult to work, so that the dispersion diameter in the resin becomes large,
Those existing on the surface of the toner are likely to be detached, so that the toner is unevenly charged, and the developing sleeve and the photoconductor filming are contaminated.

Further, when the above resin charge control agent is used, since the specific gravity of the resin charge control agent is relatively close to that of the binder resin, Dc / Dr
Is more preferably 0.1 ≦ Dc / Dr ≦ 1,
Further, it is preferable that 0.5 ≦ Dc / Dr ≦ 0.9 because mixing is further improved. Further, the weight average particle diameter of the pretreated colorant during coarse pulverization in order to increase the dispersibility in the toner is 0.1 to 1 mm, which is almost the same as that of the binder resin, so that mixing and stirring during toner formation can be performed. It is preferable because a sufficient mixing force is applied, segregation can be eliminated, and the dispersing force can be increased.

Upon completion of the above mixing steps, the mixture is then placed in a kneader and melt-kneaded. As the melt kneader, a uniaxial or biaxial continuous kneader or a batch type kneader using a roll mill can be used. For example, KTK type twin screw extruder manufactured by Kobe Steel, TEM type extruder manufactured by Toshiba Machine Co., Ltd., twin screw extruder manufactured by KCK, PCM twin screw extruder manufactured by Ikegai Iron Works, Buss manufactured by Bus Co. A co-kneader or the like is preferably used. It is important to carry out this melt-kneading under appropriate conditions so that the molecular chain of the binder resin is not broken. Specifically, the melt-kneading temperature should be determined with reference to the softening point of the binder resin. If the temperature is lower than the softening point, the cutting will be severe, and if it is too high, the dispersion will not proceed.

After the above melt-kneading process is completed, the kneaded product is then pulverized. In this pulverizing step, it is preferable to first coarsely pulverize and then finely pulverize. At this time, a method of colliding with a collision plate in a jet stream to pulverize, colliding particles in a jet stream to pulverize, or pulverizing with a narrow gap between a rotor and a stator rotating mechanically is preferably used.

After the completion of this pulverizing step, the pulverized product is classified in an air stream by centrifugal force or the like to produce a toner having a predetermined particle size, for example, an average particle size of 5 to 20 μm. In addition, when preparing a toner, in order to improve the fluidity, storability, developability and transferability of the toner, the hydrophobic silica fine powder and the like listed above are added to the toner manufactured as described above. Inorganic particles may be added and mixed. A general powder mixer is used for mixing the external additives, but it is preferable to equip a jacket or the like to control the internal temperature. To change the history of the load applied to the external additive, the external additive may be added midway or gradually. Of course, the rotation speed of the mixer, rolling speed, time,
The temperature and the like may be changed. A strong load may be applied first, and then a relatively weak load may be applied, or vice versa.
Examples of the mixing equipment that can be used include a V-type mixer, a rocking mixer, a Loedige mixer, a Nauta mixer, and a Henschel mixer.

[0060]

EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to these examples. In the following examples, parts and% are based on weight unless otherwise specified.

(Synthesis Example of Binder Resin) Synthesis Example 1 Stirrer, thermometer, nitrogen inlet, flow-down condenser,
In a 4-neck separable flask equipped with a cooling tube, 740 g of polyoxypropylene (2,2) -2,2-bis (4-hydroxyphenyl) propane and polyoxyethylene (2
2) -2.2-bis (4-hydroxyphenyl) propane 300 g, dimethyl terephthalate 466 g, isododecenyl succinic anhydride 80 g, and tri-n-butyl 1,2,4-benzenetricarboxylate 114 g were added together with the esterification catalyst. It was Under a nitrogen atmosphere, the atmospheric pressure was raised up to 210 ° C in the first half, and the reaction was performed while stirring at 210 ° C in the latter half under reduced pressure. As a result, a polyester resin having a molecular weight of 500 or less and a content of 3.5%, a molecular weight peak of 7500, and a Tg of 62 degrees was obtained. The polyester resin was pulverized with a simple pulverizer and the weight average particle diameter of the polyester resin (A) was 0.25 mm. Three types of particle size binder resins, a 91 mm polyester resin (B) and a 0.08 mm polyester resin (C), were obtained. At this time, the average particle size was measured by a vibrating screener.

Synthesis Example 2 Polyoxypropylene (2,2) -2,2-bis (4-)
Hydroxyphenyl) propane 1225g, polyoxyethylene (2,2) -2,2-bis (4-hydroxyphenyl) propane 165g, terephthalic acid 500g, isododecenyl succinic anhydride 130g, 1,2,4-benzenetricarboxylic acid triisopropyl 170 g was added to the thruster with the esterification catalyst. These were reacted under the same apparatus and conditions as in Synthesis Example 1 to obtain a polyester resin having a molecular weight of 500 or less and a content of 3.7%, a molecular weight peak of 4000, and a Tg of 62 ° C. A polyester resin (D) of 0.63 mm was obtained.

Synthesis Example 3 Polyoxypropylene (2,2) -2,2-bis (4-)
Ester of 714 g of hydroxyphenyl) propane, 663 g of polyoxyethylene (2,2) -2,2-bis (4-hydroxyphenyl) propane, 648 g of isophthalic acid, 150 g of isooctenylsuccinic acid and 120 g of 1,2,4-benzenetricarboxylic acid It was added to the flask together with the oxidization catalyst. These were reacted under the same apparatus and conditions as in Synthesis Example 1 to give a molecular weight of not more than 500, content: 3.0%, molecular weight peak: 8000, Tg: 64 ° C., weight average particle diameter: 0.15 m.
m polyester resin (E) was obtained.

Synthesis Example 4 In a separable flask equipped with a stirrer, a thermometer, a nitrogen inlet and a cooling tube, 378.4 g of an epoxy resin having a low molecular weight bisphenol A (number average molecular weight: about 360), a high molecular weight bisphenol A type propylene Glycidylated oxide adduct (n + m in the general formula (1): about 2.1)
191.0 g, bisphenol F274.5g, p-cumylphenol 70.1g, and xylene 200g were added. In a nitrogen atmosphere, the temperature is raised to 70 to 100 ° C., 0.1839 g of lithium chloride is added, the temperature is further raised to 160 ° C., and xylene is removed under reduced pressure.
Polymerized for hours. Thus, a polyol resin having a molecular weight of 500 or less and a content of 4.5% and a molecular weight peak of 8000 was obtained, which was pulverized with a simple pulverizer to obtain a weight average particle diameter of 0.51.
mm polyol resin (F) was obtained.

Synthetic Example 5 The same as in Synthetic Example 4 except that the polymerization was carried out at a reaction temperature of 180 ° C. for 9 hours, the content was 2.0% with a molecular weight of 500 or less,
A polyol resin having a molecular weight peak of 9100 was obtained and pulverized with a simple pulverizer to obtain a polyol resin (G) having a weight average particle diameter of 0.42 mm.

Synthesis Example of Charge Control Agent Synthesis Example 1 600 parts of 3,4-dichlorophenylmaleimide, 100 parts of perfluorooctanesulfonic acid and 300 parts of n-butyl acrylate in toluene at a boiling point of AIBN as an initiator for 8 hours. After the copolymerization, toluene was distilled off under reduced pressure to obtain a resin withstand voltage control agent A having a number average molecular weight of 8000.

Synthesis Example 2 600 parts of m-nitrophenylmaleimide, 150 parts of 2-acrylamido-2-methylpropanesulfonic acid, 400 parts of n-butyl acrylate, and 200 parts of styrene in toluene under boiling point for 10 hours using AIBN as an initiator. After the polymerization, toluene was distilled off under reduced pressure to obtain a resin charge control agent B having a number average molecular weight of 14,000.

Synthetic Example 3 BONTRON E-84 manufactured by Orient Science Co., Ltd. was purified by recrystallization with methanol, and a charge control agent (C) having a weight average particle diameter of 3.0 μm and a charge control of 0.6 μm were used. The agent (D) was obtained. At this time, the particle size was measured by a particle size measuring device by X-ray diffraction.

(Toner Production Example) Toner Production Example 1 A colorant was treated according to the following formulation. Polyester resin (A) 100 parts by weight C.I. I. Pigment Red 57.1 100 parts by weight Water 50 parts by weight After mixing the above materials with a Henschel mixer, the mixture is put into a two-roll mill heated to 100 ° C.
The mixture was melt-kneaded. Then, the kneaded product was cooled and pulverized to obtain a magenta-treated pigment having a weight average particle diameter of 0.12 mm. Next, a toner was prepared with the following formulation. Polyester resin (A) 95 parts by weight Charge control agent (A) 2 parts by weight The magenta-treated pigment 10 parts by weight is mixed by a Henschel mixer, and the resulting mixture is melt-kneaded by a twin-screw kneader TEM48 manufactured by Toshiba Machine Co., Ltd. After kneading, it was rolled and cooled. After that, a collision plate type crusher (I-2 type mill: manufactured by Nippon Pneumatic Mfg. Co., Ltd.) using a jet mill and an air classifier (DS classifier: manufactured by Nippon Pneumatic Mfg. Co., Ltd.) by a swirling flow were used to obtain a weight average particle size. 7.5 μm
Toner base particles of Further, to 100 parts by weight of the base particles, 0.8 parts by weight of hydrophobic silica and 0.6 parts by weight of hydrophobic acid value titanium were mixed by a Henschel mixer to obtain a toner (A).

Toner Production Example 2 A coloring agent was treated according to the following formulation. Polyester resin (D) 100 parts by weight C.I. I. Pigment Red 57.1 100 parts by weight Water 50 parts by weight After mixing the above materials with a Henschel mixer, the mixture is put into a two-roll mill heated to 100 ° C.
The mixture was melt-kneaded. Then, the kneaded product was cooled and pulverized to obtain a magenta-treated pigment having a weight average particle diameter of 0.83 mm. Next, a toner was prepared with the following formulation. 95 parts by weight of polyester resin (D) 2 parts by weight of charge control agent (A) 10 parts by weight of the magenta-treated pigment were made into toner by the same method as in Toner Production Example 1 to obtain a toner (B) having a weight average particle diameter of 8 μm.

Toner Production Example 3 A colorant was treated according to the following formulation. Polyester resin (A) 100 parts by weight C.I. I. Pigment Yellow 180 100 parts by weight Water 50 parts by weight After mixing the above materials with a Henschel mixer, the mixture is put into a two-roll mill heated to 100 ° C.
The mixture was melt-kneaded. Then, the kneaded product was cooled and pulverized to obtain a magenta-treated pigment having a weight average particle diameter of 0.35 mm. Next, a toner was prepared with the following formulation. 93 parts by weight of polyester resin (A) 2 parts by weight of charge control agent (B) 14 parts by weight of the yellow-treated pigment are tonerized in the same manner as in Toner Production Example 1 to obtain a toner (C) having a weight average particle diameter of 7.6 μm. It was

Toner Production Example 4 A coloring agent was treated according to the following formulation. Polyester resin (E) 100 parts by weight C.I. I. Pigment Blue 15.1 100 parts by weight Water 50 parts by weight After mixing the above materials with a Henschel mixer, the mixture is put into a two-roll mill heated to 100 ° C.
The mixture was melt-kneaded. Then, the kneaded product was cooled and pulverized to obtain a magenta-treated pigment having a weight average particle diameter of 0.52 mm. Next, a toner was prepared with the following formulation. Polyester resin (E) 97 parts by weight Charge control agent (A) 2 parts by weight The cyan-treated pigment 6 parts by weight is made into a toner in the same manner as in Toner Production Example 1 to obtain a toner (D) having a weight average particle diameter of 7.8 μm. It was Further, with respect to the obtained toner, a ferrite carrier having an average particle size of 50 μm coated with silicon resin in an average thickness of 0.3 μm was used, and 5 parts by weight of the toner was uniformly mixed with 100 parts by weight of the carrier by using a turbuler mixer. Then, they were electrically charged to prepare a two-component developer.

Toner Production Example 5 A coloring agent was treated according to the following formulation. Polyester resin (D) 100 parts by weight C.I. I. Pigment Red 57.1 100 parts by weight Water 50 parts by weight After mixing the above materials with a Henschel mixer, the mixture is put into a two-roll mill heated to 100 ° C.
The mixture was melt-kneaded. Then, the kneaded product was cooled and pulverized to obtain a magenta-treated pigment having a weight average particle diameter of 0.15 mm. Next, a toner was prepared with the following formulation. 95 parts by weight of polyester resin (D) 2 parts by weight of charge control agent (B) 10 parts by weight of the magenta-treated pigment are made into toner by the same method as in Toner Production Example 1 to obtain toner (E) having a weight average particle diameter of 7.3 μm. It was

Toner Production Example 6 A toner was prepared according to the following formulation. 95 parts by weight of polyester resin (D) 2 parts by weight of charge control agent (C) 10 parts by weight of the magenta-treated pigment used in Production Example 5 was made into toner by the same method as in Production Example 1 of toner and had a weight average particle diameter of 7.5 μm. Toner (F) was obtained.

Toner Production Example 7 The colorant was pretreated by the method of Toner Production Example 1 and pulverized to obtain a magenta-treated pigment having a particle diameter of 0.05 mm. Next, a toner was prepared with the following formulation. 95 parts by weight of polyester resin (A) 2 parts by weight of charge control agent (A) 10 parts by weight of the magenta-treated pigment are tonerized in the same manner as in Toner Production Example 1 to obtain a toner (G) having a weight average particle diameter of 7.5 μm. It was

Toner Production Example 8 A toner was prepared according to the following formulation. Polyester resin (A) 100 parts by weight Charge control agent (A) 2 parts by weight C.I. I. Pigment Red 57.1 (5 parts by weight) was tonerized in the same manner as in Toner Production Example 1 to obtain a toner (H) having a weight average particle diameter of 7.2 μm.

Toner Production Example 9 A coloring agent was treated according to the following formulation. Polyester resin (F) 100 parts by weight C.I. I. Pigment Red 57.1 100 parts by weight Water 50 parts by weight After mixing the above materials with a Henschel mixer, the mixture is put into a two-roll mill heated to 100 ° C.
The mixture was melt-kneaded. Then, the kneaded product was cooled and pulverized to obtain a magenta-treated pigment having a weight average particle diameter of 0.12 mm. Next, a toner was prepared with the following formulation. 95 parts by weight of polyester resin (F) 2 parts by weight of charge control agent (A) 10 parts by weight of the magenta-treated pigment are made into toner by the same method as in Toner Production Example 1 to obtain toner (I) having a weight average particle size of 7.6 μm. It was

Toner Production Example 10 A coloring agent was treated according to the following formulation. Polyester resin (B) 100 parts by weight C.I. I. Pigment Red 57.1 100 parts by weight Water 50 parts by weight After mixing the above materials with a Henschel mixer, the mixture is put into a two-roll mill heated to 100 ° C.
The mixture was melt-kneaded. Then, the kneaded product was cooled and pulverized to obtain a magenta-treated pigment having a weight average particle diameter of 0.33 mm. Next, a toner was prepared with the following formulation. 95 parts by weight of polyester resin (B) 2 parts by weight of charge control agent (A) 10 parts by weight of the magenta-treated pigment are made into toner by the same method as in Toner Production Example 1 to obtain toner (J) having a weight average particle diameter of 8.0 μm. It was

Toner Production Example 11 A toner was prepared according to the following formulation. 95 parts by weight of polyester resin (D) 2 parts by weight of charge control agent (D) 10 parts by weight of magenta-treated pigment in Production Example 5 are made into toner by the same method as in Toner Production Example 1 and toner having a weight average particle diameter of 7.3 μm ( K) was obtained.

Toner Production Example 12 A coloring agent was treated according to the following formulation. Polyester resin (E) 100 parts by weight C.I. I. Pigment Red 57.1 100 parts by weight Water 50 parts by weight After mixing the above materials with a Henschel mixer, the mixture is put into a two-roll mill heated to 100 ° C.
The mixture was melt-kneaded. Then, the kneaded product was cooled and pulverized to obtain a magenta-treated pigment having a weight average particle diameter of 0.51 mm. Next, a toner was prepared with the following formulation. 95 parts by weight of polyester resin (E) 2 parts by weight of charge control agent (A) 10 parts by weight of the magenta-treated pigment are made into toner in the same manner as in Toner Production Example 1 to obtain a toner (L) having a weight average particle diameter of 7.8 μm. It was

Toner Production Example 13 A coloring agent was treated according to the following formulation. Polyester resin (G) 100 parts by weight C.I. I. Pigment Red 57.1 100 parts by weight Water 50 parts by weight After mixing the above materials with a Henschel mixer, the mixture is put into a two-roll mill heated to 100 ° C.
The mixture was melt-kneaded. Then, the kneaded product was cooled and pulverized to obtain a magenta-treated pigment having a weight average particle diameter of 0.45 mm. Next, a toner was prepared with the following formulation. Polyester resin (G) 95 parts by weight Charge control agent (A) 2 parts by weight 10 parts by weight of the magenta-treated pigment are made into toner by the same method as in Toner Production Example 1 to obtain a toner (M) having a weight average particle diameter of 7.0 μm. It was

Toner Production Example 14 A coloring agent was treated according to the following formulation. Polyester resin (C) 100 parts by weight C.I. I. Pigment Red 57.1 100 parts by weight Water 50 parts by weight After mixing the above materials with a Henschel mixer, the mixture is put into a two-roll mill heated to 100 ° C.
The mixture was melt-kneaded. Then, the kneaded product was cooled and pulverized to obtain a magenta-treated pigment having a weight average particle diameter of 0.23 mm. Next, a toner was prepared with the following formulation. 95 parts by weight of polyester resin (C) 2 parts by weight of charge control agent (B) 10 parts by weight of the magenta-treated pigment are made into toner by the same method as in Toner Production Example 1 to obtain toner (N) having a weight average particle diameter of 7.2 μm. It was

Table 1 shows the components and the like of the toners obtained by these toner production examples. With regard to these toners, a non-magnetic one-component developer for a one-component developer is sequentially developed for each color on one belt photosensitive member, sequentially transferred to an intermediate transfer member, and transferred to a sheet or the like in a full-color laser printer. Ipsio color5
000 (manufactured by Ricoh Co., Ltd .: Evaluator A), for two-component developer, one color photosensitive drum is used to develop each color in sequence, and then sequentially transferred to an intermediate transfer member, and then transferred in a batch to a transfer paper, etc. Full color laser copying Image was formed and evaluated using a machine Imagio Color 2800 (manufactured by Ricoh Co .: Evaluation machine B).

(Evaluation Items) In all the items, the image charts having a 5% image area were run up to 30,000 sheets, and then the following evaluations were performed. The results are shown in Table 2. 1) Image density After outputting a solid image, the image density is set to X-RITE938 (x-
Rite). This was measured at 5 points independently and determined as the average concentration. 2) Stop the background stain white paper image during development, transfer the developer on the photoconductor after development to tape, and measure the difference from the untransferred tape image density by X.
-Measured by RITE938. 3) Measurement of charge amount In the one-component developing method, toner was conveyed onto a developing roller (sleeve), and measurement was performed by a suction tribo measuring method. For the two-component developing method, 6 g of the developer was weighed and charged into a metal cylinder that can be sealed and blown to obtain the charge amount. 4) Filming The presence or absence of occurrence of toner filming on the developing roller, the layer regulating member, and the photoconductor was observed. It was evaluated that ∘ did not have filming, Δ had filming on streaks, and x had filming as a whole. 5) Haze Degree A solid image was prepared as an OHP sheet sample at 160 ° C. at a fixing speed of 90 mm / sec. The transparency was measured using a haze meter (Suga Test Instruments Co., Ltd.).
○ A haze of 15% or less, 30% over 15%
Those with less than 30 were evaluated as Δ, and those with 30% or more were evaluated as x. 6) Observation of dispersed particle size An ultrathin section of the toner was cut and stained with ruthenium oxide or the like, and then the transmission electron microscope H-80 manufactured by Hitachi, Ltd.
The dispersed state was confirmed using a photographic image magnified 5000 to 20000 times at 0.

[0085]

[Table 1]

[0086]

[Table 2]

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According to the present invention, in either one-component or two-component color developing system, after continuous printing for a long period of time, filming on the photoreceptor, the developer layer thickness regulating member, the developing sleeve, etc. can be performed. It is possible to provide a dry electrophotographic toner that does not generate, has excellent transparency, stabilizes toner charging and conveyance, and can maintain an image density equivalent to an initial image and a high-quality output image, and a manufacturing method thereof. . Furthermore, since there is little reduction in charging during continuous use, there are no problems such as fluctuations in image density, low developability, background stains, toner scattering in the developing machine, etc., and dry electrophotography that provides images with excellent color development and color reproducibility. And a method for manufacturing the same can be provided.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Toshiki Minatani             1-3-3 Nakamagome, Ota-ku, Tokyo Stocks             Company Ricoh (72) Inventor Shinichiro Yagi             1-3-3 Nakamagome, Ota-ku, Tokyo Stocks             Company Ricoh (72) Inventor Mitsuteru Kato             1-3-3 Nakamagome, Ota-ku, Tokyo Stocks             Company Ricoh F-term (reference) 2H005 AA01 AA06 AA21 AB02 CA02                       CA08 DA02 EA05 EA06

Claims (12)

[Claims] 1. A dry electrophotographic color toner containing at least a binder resin, a charge control agent, and a colorant, wherein the binder resin does not contain a THF insoluble component, and gel permeation chromatography (GPC).
In the molecular weight distribution, the content of the component having a molecular weight of 500 or less is 4% by weight or less, and the molecular weight is 3000.
A polyester resin and / or a polyol resin having one peak in the region of ˜9000 and having a weight average particle diameter Dr of 0.1 mm ≦ Dr ≦ 0.7 mm, and further the weight average particle diameter of the charge control agent. Dc is 0.001 ≦ D
A color toner for dry electrophotography, wherein c / Dr ≦ 1. 2. The charge control agent comprises: (a) a sulfonate group-containing monomer, (b) an aromatic monomer having an electron-withdrawing group, and (c) an acrylic acid ester monomer and / or a methacrylic acid ester monomer. And / or (d) a resin charge control agent containing an aromatic vinyl monomer as a constitutional unit, the dry electrophotographic color toner according to claim 1. 3. The dispersed particle size of the charge control agent in the toner has a major axis of 0.05 μm to 1.5 μm and a minor axis of 0.02.
3. The color toner for dry electrophotography according to claim 1, wherein the color toner has a thickness of 1.00 μm. 4. The weight average particle diameter Dc of the charge control agent
Is 0.1 ≦ Dc / Dr ≦ 1. The color toner for dry electrophotography according to claim 1, wherein 5. The color toner for dry electrophotography according to claim 1, wherein the colorant is previously treated with the binder resin. 6. The color toner for dry electrophotography according to claim 5, wherein the pretreatment product of the colorant has a weight average particle diameter of 0.1 to 1 mm. 7. A binder resin, a charge control agent, and a colorant are mixed and stirred, the resulting mixture is melt-kneaded, and the resulting kneaded product is cooled and then ground, and the obtained ground product is classified. Further, in the method for producing a dry electrophotographic color toner in which the obtained classification product and an additive are mixed to obtain a toner, a THF-insoluble component is not included as the binder resin, and the molecular weight in gel permeation chromatography (GPC) is Molecular weight of 5 in distribution
The content ratio of the components of 00 or less is 4% by weight or less, has one peak in the molecular weight range of 3000 to 9000, and the weight average particle diameter Dr is 0.1 mm ≦ Dr ≦
A color for dry electrophotography, which comprises using a polyester resin and / or a polyol resin having a size of 0.7 mm and further having a weight average particle diameter Dc of 0.001 ≦ Dc / Dr ≦ 1 as the charge control agent. Toner manufacturing method. 8. The charge control agent comprises: (a) a sulfonate group-containing monomer, (b) an aromatic monomer having an electron-withdrawing group, and (c) an acrylic acid ester monomer and / or
8. The method for producing a dry electrophotographic color toner according to claim 7, which is a resin charge control agent containing a methacrylic acid ester monomer and / or (d) an aromatic vinyl monomer as a constitutional unit. 9. The dispersed particle diameter of the charge control agent in the toner is such that the major axis is 0.05 μm to 1.5 μm and the minor axis is 0.02 to 0.02 μm.
9. The method for producing a color toner for dry electrophotography according to claim 7, wherein the color toner has a thickness of 1.00 μm. 10. The weight average particle diameter Dc of the charge control agent.
Is 0.1 ≦ Dc / Dr ≦ 1. The method for producing a color toner for dry electrophotography according to claim 7, wherein 11. The method for producing a dry electrophotographic color toner according to claim 7, wherein the colorant is previously treated with the binder resin. 12. The pretreatment product of the colorant has a weight average particle diameter of 0.1 to 1 mm.
The method for producing a color toner for dry electrophotography according to item 1.