JP4459665B2 - Toner, developer, toner container, process cartridge, image forming apparatus, and image forming method - Google Patents

Description

  The present invention relates to a toner used as a developer for developing an electrostatic charge image in electrophotography, electrostatic recording, electrostatic printing, and the like, a developer using the toner, a container containing toner, a process cartridge, and an image forming apparatus. And an image forming method.

  In the developing process, a developer used in electrophotography, electrostatic recording, electrostatic printing, and the like is once attached to an image carrier such as a photosensitive member on which an electrostatic image is formed, and then transferred to a transfer process. After being transferred from the photosensitive member to a transfer medium such as transfer paper, the toner is fixed on the paper surface in a fixing step. At that time, as a developer for developing the electrostatic image formed on the latent image holding surface, a two-component developer composed of a carrier and a toner, and a one-component developer that does not require a carrier (magnetic toner). And non-magnetic toners) are known. In the two-component development method, the developer deteriorates due to the toner particles adhering to the carrier surface, and since only the toner is consumed, the toner concentration in the developer decreases, so the mixing ratio with the carrier is kept constant. Must be retained. Therefore, the developing device becomes relatively large. On the other hand, in the one-component development method, the size of the apparatus has been further reduced due to the higher functionality of the developing roller and the like.

  In recent years, office automation and colorization have further progressed in offices, and not only copying originals consisting only of conventional characters, but also pictorials read from graphs created with personal computers, images taken with digital cameras, scanners, etc. Opportunities to output manuscripts with printers and make many copies as presentation materials are increasing. The printer output image has a complicated configuration mixed in a single document such as a solid image, a line image, and a halftone image, and various demands are increasing along with a demand for high reliability of the image.

  Conventional electrophotographic processes using a one-component developer are classified into a magnetic one-component developing method using magnetic toner and a non-magnetic one-component developing method using non-magnetic toner. The magnetic one-component development method uses a latent electrostatic image bearing member provided with a magnetic field generating means such as a magnet inside to hold magnetic toner containing a magnetic material such as magnetite and develop a thin layer with a layer thickness regulating member. To do. In recent years, a large number of small printers have been put into practical use. However, the magnetic material has a disadvantage that it is colored, and most of them are black and difficult to color.

  On the other hand, in the non-magnetic one-component development method, since the toner does not have magnetic force, the toner is supplied onto the electrostatic latent image carrier by pressing the toner replenishing roller or the like to the electrostatic latent image carrier and electrostatically The film is held, developed with a layer thickness regulating member, and developed. This has the advantage of being compatible with colorization because it does not contain a colored magnetic material, and since it does not use a magnet for the electrostatic latent image carrier, it has become possible to further reduce the weight and cost of the device. It has been put to practical use in small full-color printers.

  On the other hand, in the two-component development system, a carrier is used as a means for charging and transporting toner, and after the toner and the carrier are sufficiently stirred and mixed in the developing device, the toner is transported to the electrostatic latent image carrier and developed. It is possible to maintain stable chargeability and transportability even when used for a long time, and it is easy to cope with a high-speed developing device.

  Compared to this, in the one-component development system, there are still many problems to be improved. In the one-component development method, since there is no stable charging or conveying means like a carrier, charging failure and conveyance failure are likely to occur due to long-term use and high speed. That is, in the one-component developing method, after the toner is conveyed onto the electrostatic latent image carrier, the toner is thinned by the layer thickness regulating member and developed, but the toner, the electrostatic latent image carrier, and the layer thickness are developed. The contact with the frictional charging member such as the regulating member and the frictional charging time are very short, so that the amount of low-charge and reverse-charged toner tends to increase more than the two-component development method using a carrier.

  In particular, in the non-magnetic one-component developing method, means for developing a latent electrostatic image formed on a latent image carrier by conveying toner (developer) usually by at least one toner conveying member and by the conveyed toner. Has been adopted. At that time, the thickness of the toner layer on the surface of the toner conveying member must be as thin as possible. This is also true when a two-component developer having a very small carrier is used. In particular, when a one-component developer is used and a toner having a high electrical resistance is used, the toner needs to be charged by the developing device, so that the toner layer thickness must be extremely thin. On the other hand, when the toner layer thickness is thick, only the vicinity of the surface of the toner layer is charged, and the entire toner layer is hardly charged uniformly. Therefore, the toner is required to maintain a faster charging speed and an appropriate charge amount.

In order to stabilize the charging of the toner, a charge control agent or an additive is added.
The charge control agent functions to control the triboelectric charge amount of the toner and maintain the triboelectric charge amount. Typical examples of the negatively chargeable charge control agent include monoazo dyes, salicylic acid, naphthoic acid, metal salts / metal complexes of dicarboxylic acids, diazo compounds, and complex compounds of boron. Examples of the positively chargeable representative charge control agent include quaternary ammonium salt compounds, imidazole compounds, nigrosine, and azine dyes.

  However, some of these charge control agents have a chromatic color, and many cannot be used for color toners. In addition, since these charge control agents have poor compatibility with the binder resin, those present on the surface of the toner that are greatly involved in charging are easily detached, resulting in variations in toner charging. Further, there is a drawback that the developing sleeve is easily contaminated and the photosensitive member filming is likely to occur. For this reason, a good image can be obtained in the initial stage, but the image quality gradually changes, resulting in the phenomenon of background smudges and blurring. In particular, when applied to color copying and continuously used while replenishing toner, the amount of toner charge is reduced, resulting in an image that differs significantly from the color tone of the initial copied image, and it cannot withstand long-term use. The image forming unit called a process cartridge has to be replaced at an early stage only by copying to a certain extent. For this reason, the load on the environment is large, and it takes time and effort for the user. Furthermore, since many of these process cartridges contain heavy metals such as chromium, they have recently become a problem in terms of safety.

  In recent years, the demand for printers has expanded, the size and speed of devices have increased, and the cost has been reduced. As a result, higher reliability and longer life have been required for devices, and toner characteristics can be maintained over a long period of time. Accordingly, resin charge control agents have been proposed. However, these resin charge control agents cannot maintain the charge control effect, contaminate the developing sleeve and the layer thickness regulating member (blade or roller), reduce the toner charging performance, and cause the photosensitive member to film. There is a problem of end.

  In addition, a process that develops in a short time with a small amount of developer due to downsizing and speeding up, and there is a demand for a developer with better charging rise. Regarding development, various development methods have been proposed for both two-component developers and one-component developers. However, it is excellent in that it can be reduced in size and weight, and nonmagnetic one-component development that does not require the use of a carrier is suitable for printer applications. In this developing system, the toner replenishment property to the developing roller and the toner retaining property of the developing roller are poor, so the toner is forcibly rubbed against the developing roller or the amount of toner on the developing roller is regulated by a blade. As a result, there is a problem that toner tends to film on the developing roller, the life of the developing roller is shortened, and the charge amount of the toner becomes unstable, and good development cannot be performed. Therefore, in color toners for non-magnetic one-component development, in addition to the properties required for general color toners, the heat resistance of the binder resin used for the toner is often inferior, and the toner on the developing roller is often inferior. Filming is likely to occur.

  For example, Patent Document 1 proposes to use a metal complex of salicylic acid or salicylic acid as a charge control agent. However, good charge stability cannot be obtained, and environmental fluctuation is large. Patent Document 2 proposes a toner containing a saturated or unsaturated fatty acid metal salt having 8 to 35 carbon atoms. There is a problem that the effect of adding a lubricant cannot be obtained due to deterioration.

  In addition to controlling and maintaining the triboelectric charge amount of the toner, the additive also has functions such as toner transportability, developability, transferability, and storage stability. In order to improve these characteristics, for example, it has been proposed to add hydrophobic silica to the toner (see Patent Document 3 and Patent Document 4). However, in these proposals, there is a problem that defects such as dust and scattering are generated because the chargeability of silica alone becomes too high and the transferability is too good.

Patent Documents 5 and 6 disclose that titanium oxide or titanium oxide surface-treated with a coupling agent is added to the toner. However, with titanium oxide alone, sufficient chargeability and fluidity cannot be obtained, the particle size becomes large, and secondary agglomeration tends to occur, so that it does not adhere uniformly to the toner and causes abnormal images. is there.
Moreover, in patent document 7, the surface-treated fine particle titanium oxide is disclosed. According to this proposal, although the dispersibility of the particles is improved, it is still not possible to obtain a sufficient charge amount by itself, and when this titanium oxide is used in combination with silica, the charge amount increases with time. There is a problem that it occurs.
Patent Document 8 and Patent Document 9 disclose that hydrophobic silica and hydrophobic titanium oxide are used in combination. However, since the combination of highly hydrophobic additives is used, the amount of charge over time is disclosed. There is a problem that an increase occurs and causes transfer defects.

  Therefore, it is possible to stably control and maintain the triboelectric charge amount, to maintain stable triboelectric chargeability with little environmental fluctuation, and excellent transportability, developability, transferability, and storability. Toner that does not generate an abnormal image due to adhesion to the body has not yet been obtained, and it is desired to provide the toner promptly.

Japanese Patent Laid-Open No. 55-42752 JP 60-112052 A JP 56-128956 A JP 59-52255 A JP 60-112052 A JP-A-4-40467 Japanese Patent No. 3322858 JP 7-43930 A Japanese Patent No. 3160688

  An object of the present invention is to solve the conventional problems in response to the above-mentioned demands and achieve the following object. That is, according to the present invention, the triboelectric charge amount can be stably controlled and maintained, and stable triboelectric chargeability can be maintained with little environmental fluctuation, and transportability, developability, transferability, and storage can be maintained. An object of the present invention is to provide a toner that is excellent in properties and does not generate an abnormal image due to adhesion to a photoreceptor, a developer using the toner, a toner-containing container, a process cartridge, an image forming method, and an image forming apparatus.

  As a result of intensive studies to solve the above problems, the present inventors have determined that the charge control has a specific component and a component ratio with respect to a polyester resin that is suitable in terms of color developability and image strength as a binder resin for a full color toner. Agent, specific surface-treated titanium oxide, silica, and lubricant, high charge amount and sharp charge amount distribution are obtained, charging rise is good, soil resistance is excellent, and temperature and humidity change Unaffected, and can prevent contamination of development carrier (development roller or sleeve) and development layer thickness regulating member (blade and roller) and photoconductor filming over tens of thousands of sheets or more. It has been found that a highly productive toner, a developer containing the toner, a process cartridge, an image forming method, and an image forming apparatus can be obtained.

The present invention is based on the above findings of the present inventors, and means for solving the above problems are as follows. That is,
<1> In a toner containing at least a binder resin, a colorant, a charge control agent, a lubricant, and an additive,
The binder resin comprises at least one polyester resin, the polyester resin does not contain a THF-insoluble component, and the content ratio of components having a weight average molecular weight of 5 × 10 ² or less in the molecular weight distribution in gel permeation chromatography Has a main peak in the region of 4% by mass or less and a weight average molecular weight of 3 × 10 ^{3 to} 9 × 10 ³ ,
The charge control agent is either a metal salt compound of salicylic acid or a metal salt compound of a salicylic acid derivative;
The additive is hydrophobized silica having a primary particle size of 0.01 to 0.03 μm, a primary particle size of 0.01 to 0.03 μm, and a specific surface area of 60 to 140 m ² / g. Comprising hydrophobized titanium oxide
The titanium oxide is produced by a wet method and is obtained by surface-treating titanium oxide fine particles having a water-soluble component content of 0.2% by mass or more, and the titanium oxide has a transmittance of 300 nm in the UV absorption method. Is a toner characterized by having a transmittance of not less than 35% and a transmittance of 600 nm of not less than 80%.
<2> The toner according to <1>, wherein the endothermic peak in DSC of the binder resin is in the range of 60 to 70 ° C.
<3> The ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) (Mw / Mn) of the binder resin is 2 ≦ Mw / Mn ≦ 10, according to any one of <1> to <2> Toner.
<4> The toner according to any one of <1> to <3>, wherein the acid value of the binder resin is 10 KOH mg / g or less.
<5> The toner according to any one of <1> to <4>, wherein a temperature at which an apparent viscosity of the binder resin by a flow tester is 1 × 10 ³ Pa · s is 95 to 120 ° C.
<6> The toner according to any one of <1> to <5>, wherein a content of the charge control agent in the toner particles is 0.1 to 10% by mass.
<7> 2.1 parts by mass or more of silica having a primary particle diameter of 0.01 to 0.03 μm and a primary particle diameter of 0.01 to 0.03 μm with respect to 100 parts by mass of the base toner The toner according to any one of <1> to <6>, further comprising 0.4 to 1.0 part by mass of hydrophobized titanium oxide having a specific surface area of 60 to 140 m ² / g.
<8> The toner according to any one of <1> to <7>, wherein at least one lubricant is contained, and at least one of the lubricants is a fatty acid metal salt having 16 or more carbon atoms.
<9> The above <1> to <8, wherein the lubricant is contained in an amount of 0.01 to 0.1 T parts by mass (where T represents the amount of the base toner titanium oxide added) with respect to 100 parts by mass of the base toner. > The toner according to any one of the above.
<10> A developer comprising the toner according to any one of <1> to <9>.
<11> The developer according to <10>, which is one of a one-component developer and a two-component developer.
<12> A toner-containing container, wherein the toner according to any one of <1> to <9> is contained in a container.
<13> An electrostatic latent image carrier and an electrostatic latent image formed on the electrostatic latent image carrier are developed using the toner according to any one of <1> to <9> to be a visible image And a developing means for forming the process cartridge.
<14> An electrostatic latent image carrier, an electrostatic latent image forming unit that forms an electrostatic latent image on the electrostatic latent image carrier, and the electrostatic latent image of <1> to <9> Developing means for developing a visible image by developing using any of the toners, Transfer means for transferring the visible image to a recording medium, Fixing means for fixing the transferred image transferred to the recording medium, The image forming apparatus is characterized by having at least.
<15> The image forming apparatus according to <14>, wherein the electrostatic latent image forming unit includes a unit that applies an alternating electric field.
<16> The fixing unit includes a heating body including a heating element, a film in contact with the heating body, and a pressure member in pressure contact with the heating body through the film. The image forming apparatus according to any one of <14> to <15>, wherein a fixing apparatus that heats and fixes a recording material on which an unfixed image is formed between members is used.
<17> An electrostatic latent image forming step of forming an electrostatic latent image on the electrostatic latent image carrier, and the electrostatic latent image using the toner according to any one of <1> to <9> An image comprising at least a developing step for developing to form a visible image, a transferring step for transferring the visible image to a recording medium, and a fixing step for fixing the transferred image transferred to the recording medium It is a forming method.

The toner of the present invention contains at least a binder resin, a colorant, a charge control agent, a lubricant, and an additive. The binder resin contained in the toner of the present invention comprises at least one polyester resin, the polyester resin does not contain a THF-insoluble component, and has a weight average molecular weight of 5 × 10 in molecular weight distribution in gel permeation chromatography. The content ratio of the component of ² or less is 4% by mass or less, and has a main peak in the region of the weight average molecular weight of 3 × 10 ^{3 to} 9 × 10 ³ . The charge control agent contained in the toner of the present invention is either a salicylic acid metal salt compound or a salicylic acid derivative metal salt compound. In addition, the additive contained in the toner of the present invention has a hydrophobized silica having a primary particle size of 0.01 to 0.03 μm, a primary particle size of 0.01 to 0.03 μm, and It comprises titanium oxide that has been hydrophobized and has a specific surface area of 60 to 140 m ² / g. The titanium oxide is produced by a wet process and has a water-soluble component content of 0.2% by mass or more. Titanium fine particles are surface-treated, and the titanium oxide has a transmittance at 300 nm of 35% or more and a transmittance at 600 nm of 80% or more in the UV absorption method.
In the toner of the present invention, as a result of containing the above-mentioned components, a high charge amount and a sharp charge amount distribution are obtained, the charge rising is good, the soil resistance is excellent, and the influence of temperature and humidity is not affected. Over tens of thousands of sheets or more, it is possible to prevent contamination of the developing carrier (developing roller or sleeve) and developing layer thickness regulating member (blade or roller) and photoconductor filming, and to obtain a highly productive toner with good crushability. It is done.

  The developer of the present invention contains the toner of the present invention. For this reason, when an image is formed by electrophotography using the developer, a clear high image quality can be obtained without any background contamination.

  The toner-containing container of the present invention contains the toner of the present invention in a container. For this reason, when an image is formed by electrophotography using the toner contained in the toner container, high image quality can be obtained.

  The process cartridge of the present invention comprises an electrostatic latent image carrier, and developing means for developing the electrostatic latent image formed on the electrostatic latent image carrier using the toner of the present invention to form a visible image. At least. The process cartridge can be attached to and detached from the image forming apparatus, is excellent in convenience, and uses the toner of the present invention, so that a clear high image quality can be obtained without scumming.

  The image forming apparatus of the present invention includes an electrostatic latent image carrier, electrostatic latent image forming means for forming an electrostatic latent image on the electrostatic latent image carrier, and the electrostatic latent image of the present invention. The image forming apparatus includes at least a developing unit that forms a visible image by developing with toner, a transfer unit that transfers the visible image to a recording medium, and a fixing unit that fixes the transferred image transferred to the recording medium. In the image forming apparatus, the electrostatic latent image forming unit forms an electrostatic latent image on the electrostatic latent image carrier. The transfer means transfers the visible image to a recording medium. The fixing unit fixes the transferred image transferred to the recording medium. As a result, a high-quality image is formed. Furthermore, a high-definition image can be formed by providing means for applying an alternating electric field to the developing unit. Also, by providing a so-called surf fixing device in the fixing device, the rise time can be efficiently shortened.

  The image forming method of the present invention comprises an electrostatic latent image forming step of forming an electrostatic latent image on an electrostatic latent image carrier, and developing the electrostatic latent image with the toner of the present invention to make visible. It includes at least a developing step for forming an image, a transfer step for transferring the visible image to a recording medium, and a fixing step for fixing the transferred image transferred to the recording medium. In the image forming apparatus, an electrostatic latent image is formed on the electrostatic latent image carrier in the electrostatic latent image forming step. In the transfer step, the visible image is transferred to a recording medium. In the fixing step, the transferred image transferred to the recording medium is fixed. As a result, a clear high-quality image is formed with no background stains.

  According to the present invention, the toner triboelectric charge amount can be stably controlled and maintained, the triboelectric chargeability excellent in environmental stability can be maintained, and toner transportability, developability, transferability, and storage stability can be maintained. It is possible to provide a dry toner that is excellent in quality and does not generate abnormal images due to adhesion to a photoreceptor, and a one-component or two-component developer using the toner.

(toner)
The toner of the present invention contains at least a binder resin, a colorant, a charge control agent, a lubricant, and an additive, and further contains other components as necessary.

-Binder resin-
The binder resin is at least one polyester resin, the charge control agent is salicylic acid or a metal salt compound of a salicylic acid derivative, and is a dry toner containing hydrophobic silica and hydrophobic titanium oxide.
As the binder resin, a polyester resin suitable as a binder resin for a full color toner is used in terms of color developability and image strength. In a color image, several types of toner layers are stacked several times, so that the toner layer becomes thick, causing cracks and defects in the image due to insufficient strength of the toner layer, and loss of appropriate gloss. For this reason, a polyester resin is used to maintain an appropriate gloss and excellent strength.

The binder resin of the toner of the present invention has no particular THF-insoluble content, and in the molecular weight distribution in gel permeation chromatography, the content of components having a weight average molecular weight of 5 × 10 ² or less is 4% by mass or less, and the molecular weight is 3 ×. It has one peak in the region of 10 ^{3 to} 9 × 10 ³ . When THF-insoluble matter enters, the glossiness is lowered and the transparency is lowered, and a high-quality image cannot be obtained when an OHP sheet is used. In the toner of the present invention, the weight average molecular weight of 5 × 10 ² or less is specified for the molecular weight distribution of the binder resin, and preferably the ratio of the weight average molecular weight to the number average molecular weight is specified to provide a blade, a sleeve, or the like. Filming is less likely to occur. On the other hand, if the component having a weight average molecular weight of 5 × 10 ² or less exceeds 4% by mass, the blade or sleeve may be contaminated by long-term use, and filming may easily occur.

  First, the polyester resin will be described. A polyester resin that is a binder 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 an alcohol monomer, including a trifunctional or higher polyfunctional monomer, for example, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3 -Diols such as propylene glycol, 1,4-butadieneol, neopentylene glycol, 1,4-butenediol, 1,5-pentanediol, 1,6-hexanediol, bisphenol A, hydrogenated bisphenol A, poly Bisphenol A alkylene oxide adducts such as oxypropylenated 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-1,2,4-butanetriol, tri Examples thereof include methylolethane, trimethylolpropane, 1,3,5-trihydroxybenzene, and other trihydric or higher polyhydric alcohols.

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

  Among the monomers constituting the polyester resin in the present invention, examples of the acid monomer include trifunctional or higher polyfunctional monomers, such as maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, phthalic acid, and isophthalic acid. Acids, terephthalic acid, cyclohexanedicarboxylic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, malonic acid, or alkenyl succinic acids such as n-dodecenyl succinic acid, n-dodecyl succinic acid, or alkyl succinic acids, anhydrides of these acids Products, alkyl esters, other divalent carboxylic acids, and 1,2,4-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,4 -Butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1 3-dicarboxyl-2-methyl-methylenecarboxypropane, tetra (methylenecarboxyl) methane, 1,2,7,8-octanetetracarboxylic acid, empole trimer acid, and anhydrides thereof, alkyl esters, alkenyl esters , Aryl esters, and other trivalent or higher carboxylic acids.

  Specific examples of the alkyl ester, alkenyl ester or aryl ester described herein include triethyl 1,2,4-benzenetricarboxylate, trimethyl 1,2,4-benzenetricarboxylate, triethyl 1,2,4-benzenetricarboxylate. 1,2,4-benzenetricarboxylic acid tri-n-butyl, 1,2,4-benzenetricarboxylic acid isobutyl, 1,2,4-benzenetricarboxylic acid tri-n-octyl, 1,2,4-benzenetricarboxylic acid tri 2-ethylhexyl, 1,2,4-benzenetricarboxylic acid tribenzyl, 1,2,4-benzenetricarboxylic acid tris (4-isopropylbenzyl) and the like.

  The production method for obtaining the polyester resin used in the toner of the present invention is not particularly limited, and the esterification reaction can be performed by a known method. Moreover, transesterification can also be performed by a well-known method. At this time, a known transesterification catalyst can be used. Examples of the transesterification catalyst include magnesium acetate, zinc acetate, manganese acetate, calcium acetate, tin acetate, lead acetate, titanium tetrabutoxide, and the like. The polycondensation reaction can be carried out by a known method, and at this time, a known polymerization catalyst can be used. Examples of the polymerization catalyst include antimony trioxide and germanium dioxide.

The molecular weight distribution of the binder resin used in the toner of the present invention is measured by gel permeation chromatography as follows.
Specifically, the column was stabilized in a heat chamber at 40 ° C., and THF was flowed through the column at this temperature as a solvent at a flow rate of 1 ml / min, and the sample concentration was adjusted to 0.05 to 0.6% by mass. 200 μl of a THF sample solution of toner is injected and measured. Before injecting the THF sample solution, the THF-insoluble components are removed with a 0.45 μm liquid chromatography filter. In measuring the molecular weight of a toner sample, the molecular weight distribution of the sample is calculated from the relationship between the logarithmic value of a calibration curve prepared from several types of monodisperse polystyrene standard samples and the number of counts.
Examples of the standard polystyrene sample for preparing the calibration curve include Pressure Chemical Co., Ltd. Alternatively, Toyo Soda Kogyo Co., Ltd. has a molecular weight of 6 × 10 ² , 2.1 × 10 ³ , 4 × 10 ³ , 1.75 × 10 ⁴ , 5.1 × 10 ⁴ , 1.1 × 10 ⁵ , 3 It is preferable to use a standard polystyrene sample having at least about 10 points, using 1.9 × 10 ⁵ , 8.6 × 10 ⁵ , 2 × 10 ⁶ , 4.48 × 10 ⁶ . It is preferable to use an RI (refractive index) detector as the detector.

  The presence or absence of the THF-insoluble component in the binder resin is determined when the THF sample solution is prepared for molecular weight distribution measurement. That is, when a 0.45 μm filter unit is attached to the tip of the syringe and the liquid is pushed out of the syringe, it is determined that there is no THF-insoluble matter unless the filter is clogged.

The binder resin used in 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, the toner storage stability may be affected, and the toner may solidify in the cartridge or the hopper. If the temperature exceeds 70 ° C, the toner productivity is affected, and the feed during pulverization may occur. May cause problems such as degradation.
The endothermic peak in the DSC is obtained, for example, by measuring with a Rigaku THRMOFLEX TG8110 manufactured by Rigaku Corporation under the condition of a heating rate of 10 ° C./min and reading the main maximum peak of the endothermic curve.

  The binder resin preferably has a ratio (Mw / Mn) of weight average molecular weight (Mw) to number average molecular weight (Mn) of 2 ≦ Mw / Mn ≦ 10. If the Mw / Mn exceeds 10, gloss may not be obtained when the toner is fixed, and a high quality image may not be obtained. On the other hand, if the Mw / Mn is less than 2, the productivity is reduced in the pulverization process at the time of toner production, and the blade or sleeve may be contaminated by long-term use, and filming may easily occur.

The binder resin used in the present invention preferably has an acid value of 10 KOHmg / g or less in the interaction between the charge control agent and the additive described later.
It is known that the relationship between the chargeability of the polyester resin and the acid value is almost proportional, and that the higher the acid value, the greater the negative chargeability of the resin and, at the same time, affecting the environmental characteristics of charging. That is, when the acid value is high, the charge amount is high under low temperature and low humidity, and the charge amount is low under high temperature and high humidity. Due to changes in the amount of charge due to the environment, changes in background stains, image density, and color reproducibility become large, making it difficult to maintain high image quality. In general, when the acid value exceeds 20 KOHmg / g, there is a risk that an increase in charge amount or deterioration of environmental fluctuations may occur.

  In the polyester resin used in the present invention, when the acid value is 10 KOHmg / g or less, the resistance as toner particles is controlled by the charge control agent, hydrophobic silica, hydrophobic titanium oxide and the chargeability, resistance, etc., which will be described later. On the other hand, when the acid value of the polyester resin exceeds 10 KOHmg / g, the charge control effect of the charge control agent, hydrophobic silica, and hydrophobic titanium oxide is inhibited. The acid value of the polyester resin used in the present invention is preferably 10 KOHmg / g or less, and more preferably 5 KOHmg / g or less.

Furthermore, the binder resin used in the present invention preferably has a temperature of 95 to 120 ° C. at which the apparent viscosity by a flow tester is 1 × 10 ³ Pa · s. If it is less than 95 ° C., there is a case where the margin of hot offset at the time of fixing is lost, and if it exceeds 120 ° C., sufficient gloss may not be obtained.
Here, the temperature at which the apparent viscosity becomes 1 × 10 ³ Pa · s is, for example, a CFT-500 type manufactured by Shimadzu Corporation as a flow tester, a load of 10 kg / cm ² , an orifice diameter of 1 mm × length of 1 mm, Viscosity is measured at a temperature rate of 5 ° C./min, and the temperature at which the apparent viscosity becomes 1 × 10 ³ Pa · s can be read and measured.

-Charge control agent-
The charge control agent is a metal salt compound of salicylic acid or a metal salt compound of salicylic acid derivative. For example, those represented by the following general formula are suitable.

In the general formula, R ¹ , R ^2, and R ³ are a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an allyl group, and particularly preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an allyl group. Here, R ¹ , R ² and R ³ may be the same or different. Me is a metal selected from zinc, nickel, cobalt, lead, and chromium, and among these, zinc is particularly preferable.

  The metal salt compound represented by the above general formula is described in CLARK, J. et al. L. Kao, H .; (1948) J. Org. Amer. Chem. Soc. 70, 2151 can be easily synthesized. For example, 2 mol of salicylic acid sodium salt (including a sodium salt of a salicylic acid derivative) and 1 mol of zinc chloride are mixed in a solvent, mixed, heated and stirred to obtain a zinc salt. This metal salt compound is a white crystal and does not show coloration when dispersed in a toner binder. A metal salt other than a zinc salt can also be produced according to the above method.

  These metal salt compounds may be used alone or in combination of two or more. In addition, other charge control agents may be used in combination with the salicylic acid or the metal salt compound of the salicylic acid derivative. As other charge control agents used in the present invention, conventionally known charge control agents may be used in combination. For example, nigrosine dye, triphenylmethane dye, chromium-containing metal complex dye, molybdate chelate pigment, rhodamine dye, alkoxy amine, quaternary ammonium salt, fluorine-modified quaternary ammonium salt, alkylamide, phosphorus alone or Such as a compound. In particular, in a color toner, a transparent or white substance that does not impair the color tone is used in combination. For example, organic boron salts, fluorine-containing quaternary ammonium salts, calixarene compounds and the like are used, but are not limited thereto.

  The dispersion of the charge control agent in the binder resin is one factor that determines the charging performance of the toner. In the present invention, a combination of a specific binder resin and a specific charge control agent provides a toner having good chargeability and excellent charge rise. However, as described above, it is apparent that the dispersibility (compatibility) between the binder resin and the charge control agent affects the charging performance. The inventors of the present invention studied the dispersibility of the charge control agent and obtained the optimum range by paying attention to the molecular weight distribution of the binder resin, the apparent viscosity and the acid value by a flow tester.

In the toner of the present invention, the binder resin has a main peak in the region of a weight average molecular weight of 3 × 10 ^{3 to} 9 × 10 ³ , and the apparent viscosity by a flow tester is preferably 1 × 10 ³ Pa · s. And the acid value is 10 KOH mg / g or less. When a charge control agent comprising a binder resin having this characteristic and a metal salt compound of salicylic acid or a salicylic acid derivative is melt-kneaded, the charge control agent is appropriately dispersed in the binder resin, the charge rising property is good, and changes with time. Therefore, a stable toner can be obtained which is stable with a small amount and does not change greatly in the environment.

The main peak of the weight average molecular weight of the binder resin is in a region smaller than the region of 3 × 10 ^{3 to} 9 × 10 ³ , or the temperature at which the apparent viscosity by the flow tester is 1 × 10 ³ Pa · s is less than 95 ° C. If so, the binder resin becomes a low molecular weight type and the charge control agent becomes difficult to disperse, and a sufficient charge amount cannot be obtained. Further, when the main peak is in a region larger than the weight average molecular weight region, or the temperature at which the apparent viscosity by the flow tester is 1 × 10 ³ Pa · s is higher than 120 ° C., the charge control agent is finely dispersed. It will be too much, and the charge amount will be lowered. On the other hand, when the acid value of the binder resin exceeds 10 KOHmg / g, the charge amount cannot continue to increase with time in combination with the charge control agent and cannot be saturated, and charging stability with time cannot be obtained.

  The addition amount of the charge control agent is preferably 0.1 to 10% by mass, and more preferably 0.5 to 5% by mass with respect to the toner particles. When the addition amount is less than 0.1% by mass, the dispersion with the binder resin cannot be controlled, the rise of the charge and the charge amount are not sufficient, and it may easily affect the image such as background stains and dust, If it exceeds 10% by mass, the dispersion in the binder resin will be poor, the charge amount distribution will be widened, and background stains and toner scattering may easily occur.

-Additives-
Additives used in the toner of the present invention include hydrophobized silica having a primary particle size of 0.01 to 0.03 μm, a primary particle size of 0.01 to 0.03 μm, and a specific surface area of 60. Titanium oxide having a specific performance hydrophobized to ˜140 m ² / g is used. By using these additives in combination with the polyester resin and the charge control agent, a toner having stable chargeability can be obtained.

  That is, by applying hydrophobically treated silica having a primary particle diameter of 0.01 to 0.03 μm to the surface of the base toner, the necessary fluidity and chargeability are imparted to the toner, and the photosensitive drum is exposed to light from the developing roller and the developing roller. Developability to the body is improved. The amount of silica added is preferably 2.1 parts by mass or more with respect to 100 parts by mass of the base toner, whereby the thin layer of the toner on the developing roller becomes uniform, and the unevenness of the thin layer is greatly improved. White streaks due to toner fusion to the stirring developer coating blade can be prevented by stirring the developing roller. If the amount is smaller than this, the toner fluidity may not be sufficiently obtained, and a necessary amount of toner may not be supplied to the developing roller, or a necessary toner charge amount may not be obtained. In addition, a thin layer of toner on the developing roller becomes non-uniform, and there are cases where uniform development of the toner and an image cannot be obtained, or white streaks due to fusion of the toner to the stirring developer coating blade may occur.

In addition, by adhering a hydrophobized titanium oxide having a primary particle diameter of 0.01 to 0.03 μm and a specific surface area of 60 to 140 m ² / g to the surface of the base toner, the charging property of the toner is stabilized. In particular, charging rise and charge up are prevented. The amount of titanium oxide added is preferably 0.4 to 1.0 part by mass with respect to 100 parts by mass of the base toner. If the amount added is less than 0.4 parts by mass, the toner may be too charged and sufficient toner development may not be performed. On the other hand, when the amount is more than 1.0 part by mass, the chargeability of the toner is too low, and the toner may scatter from the developing roller or cause background stains.
The base toner means particles in the middle of production containing materials other than additives, at least a binder resin, a colorant, and a charge control agent.

  Among the additives used in the present invention, the hydrophobic titanium oxide is obtained by surface-treating titanium oxide fine particles having a water-soluble component amount of 0.2% by mass or more produced by a wet method, and the additive. However, in the UV absorption method, the transmittance at 300 nm is 35% or more and the transmittance at 600 nm is 80% or more.

The titanium oxide is generally produced by a wet method. In general, gold ore, anatite, plate titanium stone, ilmenite and the like are used as raw materials for ores containing titanium. There is a sulfuric acid method in which concentrated sulfuric acid is added to these ores to dissolve them, or a chlorine method in which these ores are dehydrated with carbon materials and exposed to chlorine gas. In either case, titanium hydroxide Ti (OH) ₂ is purified, and crystals of TiO ₂ are precipitated by hydrolysis in the final stage. For this reason, there are some water-soluble components. These are alkali metal ions, acid components, etc. contained in ores and catalysts and treatment agents used in the production process, such as PO ₄ ²⁻ , SO ₄ ²⁻ , Cl ⁻ , Na ⁺ , Mg ²⁺ , Li ^{+ and the} like. It is. These water-soluble components are known to affect the chargeability and resistance, and it is said that a high charge amount can be maintained by controlling to less than 0.2% by mass. However, in the present invention, the function is not found in the higher chargeability of titanium oxide but in the resistance and particle size distribution. That is, by using titanium oxide having a water-soluble component amount of 0.2% by mass or more, an increase in the charge amount with time can be suppressed, and the effect can be obtained by using it together with silica.
Here, the amount of the water-soluble component can be measured based on, for example, JIS K5116-1973.

  In order to enhance the functionality of the titanium oxide, it is common to perform surface treatment with a coupling agent or the like, but the amount of water-soluble components of titanium oxide affects the surface treatment, and the surface-treated titanium oxide obtained It also affects the resistance and charging characteristics. Furthermore, the secondary aggregation property of titanium oxide is changed depending on the degree of dispersion in the surface treatment. In general, a uniform treatment and a high dispersion treatment may be performed in order to maintain the primary particle diameter, but titanium oxide alone has many problems such as an increase in charging with time and adhesion to the photoreceptor. Therefore, although the degree of dispersion is increased in the present invention, the problem is solved by setting the resistance low. As an index representing the particle size of the titanium oxide, an index based on the transmittance in a specific solvent was adopted. In the present invention, the transmittance at 300 nm is 35% or more and the transmittance at 600 nm is 80% or more in the UV absorption method. Titanium oxide surface-treated with a large amount of water-soluble components in order to set the resistance low requires a transmittance of 35% or more at 300 nm. Since the resistance is low, the particle size is controlled to be small and easily dispersed on the toner surface. On the other hand, the transmittance at 600 nm needs to be 80% or more. If it is less than 80%, the surface treatment with a coupling agent or the like is not uniform, and aggregates are produced by the treatment.

Here, the transmittance can be measured as follows.
First, 20 g of a reagent (polyoxyethylene octylphenyl ether) is precisely weighed, placed in a beaker, and added with ion-exchanged water so that the solid content concentration becomes 1% by mass. This aqueous solution is dispersed by applying an ultrasonic vibrator (HONDA W-113), and further stirred with a magnetic stirrer to prepare a measurement solvent. Next, 25 mg of a sample (titanium oxide) is placed in a 300 ml Erlenmeyer flask, 250 g of a measurement solvent is added thereto, and the mixture is stirred and dispersed with a magnetic stirrer for 5 minutes. Thereafter, the Erlenmeyer flask is placed on an ultrasonic vibrator and dispersed for 5 minutes. Sometimes shake the flask by hand to help disperse the aggregates. Immediately after dispersion, 2 g of the dispersion is measured and placed in a 30 ml sample bottle, and 18 g of ion exchange water is added thereto. Gently shake and mix by hand so as not to disturb, take the obtained mixed solvent in a glass cell with a path width of 1 cm, set in a UV measuring device (manufactured by Shimadzu Corporation, spectrophotometric system UV-3100), 300-700 nm Measure the absorbance in the range of.

  In the present invention, the surface treatment of silica and titanium oxide can be performed by a conventionally known treatment method. The hydrophobized silica or hydrophobized titanium oxide used in the present invention can be obtained, for example, by subjecting appropriately prepared or commercially available silica or titanium oxide to a hydrophobizing treatment. The hydrophobizing treatment can be performed by a method of immersing silica or titanium oxide in a hydrophobizing agent and drying, a method of spraying a hydrophobizing agent solution on silica or titanium oxide, and drying. There is no restriction | limiting in particular as said hydrophobic treatment agent, According to the objective, it can select suitably, For example, a silane coupling agent, a silicone oil, a titanate coupling agent, an aluminum coupling agent etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together. Among these, a silane coupling agent is particularly preferable.

  As the hydrophobizing agent, for example, any of chlorosilane, alkoxysilane, silazane, and a special silylating agent can be used. Specifically, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, phenyltrichlorosilane, diphenyldichlorosilane, tetramethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, tetraethoxysilane, Methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, diphenyldiethoxysilane, isobutyltrimethoxysilane, decyltrimethoxysilane, hexamethyldisilazane, N, O- (bistrimethylsilyl) acetamide, N, N-bis (Trimethylsilyl) urea, tert-butyldimethylchlorosilane, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxy Silane, γ-methacryloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-mercapto Examples include propyltrimethoxysilane, γ-chloropropyltrimethoxysilane, and polydimethylsiloxane.

-Lubricant-
There is no restriction | limiting in particular as said lubricant, All the well-known things can be used, You may mix and use 1 or more types of several lubricants. However, at least one of the lubricants used is preferably a fatty acid metal salt having 16 or more carbon atoms. In the toner configuration composed of the binder resin, the additive, and the charge control agent, examples of the fatty acid metal salt having 16 or more carbon atoms include palmitic acid, heptadecyl acid, stearic acid, nonadecanoic acid, and arachin as fatty acids having 16 or more carbon atoms. Examples thereof include acid, behenic acid, lignoceric acid, serotic acid, heptacosanoic acid, montanic acid, melicic acid, and laccelic acid. Examples of the metal salt of the lubricant include aluminum, manganese, cobalt, lead, calcium, chromium, copper, iron, magnesium, zinc, nickel, lithium, sodium, strontium, and the like. Among these, metal palmitate (eg, aluminum palmitate, calcium palmitate, magnesium palmitate, etc.), metal stearate (eg, aluminum stearate, calcium stearate, magnesium stearate, zinc stearate, lead stearate) Etc.) are preferable.

  The content of the fatty acid metal salt is 0.01 part by mass to 0.1 T part by mass with respect to 100 parts by mass of the base toner (where T represents the content of titanium oxide in the toner in the present invention). Is preferred. When the content is less than 0.01 parts by mass, there is no action of the lubricant and there is a possibility that it does not contribute to filming and charging stability over time, and this lubricant is recognized to interact with the charge control agent and titanium oxide. If the amount of lubricant added exceeds 0.1 parts by mass of the titanium oxide content, problems such as a decrease in charge, occurrence of background stains, and a decrease in fixed image density may occur.

  The toner of the present invention can achieve the object of the present invention by the above four elements of the binder resin, the charge control agent, the additive, and the lubricant, and by optimizing and balancing their inherent characteristic values. It is.

As the colorant used in the toner of the present invention, all known dyes and pigments can be used. For example, carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), cadmium yellow, yellow Iron oxide, ocher, yellow lead, titanium yellow, polyazo yellow, oil yellow, Hansa yellow (GR, A, RN, R), pigment yellow L, benzidine yellow (G, GR), permanent yellow (NCG), Vulcan fast Yellow (5G, R), Tartrazine Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL, Isoindolinone Yellow, Bengala, Red Dan, Lead Zhu, Cadmium Red, Cadmium Mercury Red, Antimon Zhu, Permanent Red 4R, Para Red, Phi Sared, para Lortho Nitroaniline Red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carnmin BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Resol Rubin GX Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Tolujing Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake, Thioindigo Red B, Thioindigo Maroon, Oil Red, Quinacridone Red, Pi Zoron Red, Polyazo Red, Chrome Permillion, Benzidine Orange, Perinone Orange, Oil Orange, Cobalt Blue, Cerulean Blue, Alkaline Blue Lake, Peacock Blue Lake, Victoria Blue Lake, Metal Free Phthalocyanine Blue, Phthalocyanine Blue, Fast Sky Blue, Indance Ren Blue (RS, BC), Indigo, Ultramarine Blue, Bituminous Blue, Anthraquinone Blue, Fast Violet B, Methyl Violet Lake, Cobalt Purple, Manganese Purple, Dioxane Violet, Anthraquinone Violet, Chrome Green, Zinc Green, Chrome Oxide, Pyridian, Emerald Green , Pigment Green B, Naphthol Green B, Green Gold, Acid Green Lake, Malachite Gree Lake, phthalocyanine green, anthraquinone green, titanium oxide, zinc white, ritbon, or mixtures thereof can be used.
In general, the amount of the colorant used is preferably 0.1 to 50 parts by mass with respect to 100 parts by mass of the binder resin.

  The toner of the present invention includes other additives such as Teflon, fluoropolymer, low molecular weight polyolefin, metal oxide (for example, aluminum oxide, tin oxide, antimony oxide, etc.), conductivity imparting agent (for example, carbon black, Tin oxide, etc.), magnetic materials, and those obtained by surface treatment of these additives may be used in combination. These additives may be used alone or in combination of two or more, and the content of the additive is generally 0.1 to 10 parts by mass with respect to 100 parts by mass of the toner.

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

The toner production method of the present invention may be any conventionally known method, and includes a step of mechanically mixing at least toner components such as a binder resin, a charge control agent and a colorant, a step of melt-kneading, and a step of pulverizing. And a method for producing a toner having a classification step. In addition, in the mechanical mixing step and the melt-kneading step, a production method is also included in which powder other than the particles obtained as a product obtained in the pulverization or classification step is returned and reused.
Here, the powder (sub-product) other than the particles used as the product refers to fine particles and coarse particles other than the components used as the product having a desired particle size obtained in the pulverization step after the melt-kneading step, and subsequent classification. It means fine particles or coarse particles other than the components that are produced in the process and have a desired particle size. It is preferable to mix 1 to 20 parts by mass of the by-product with respect to the raw material and preferably 100 parts by mass of the main raw material in the step of mixing or melt-kneading such a by-product.

  Mixing step of mechanically mixing at least a toner component such as a binder resin, a colorant, and a resin charge control agent, and mixing for mechanically mixing a toner component including a by-product with the binder resin, the colorant, the resin charge control agent, and the like The process may be performed under normal conditions using a normal mixer with rotating wings, and is not particularly limited.

  When the above mixing process is completed, the mixture is then charged into a kneader and melt-kneaded. As the melt kneader, a uniaxial or biaxial continuous kneader or a batch 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 Kay Sea Kay Co., Ltd., PCM type twin screw extruder manufactured by Ikegai Iron Works Co., Ltd. A kneader or the like is preferably used. It is important that this melt-kneading is performed under appropriate conditions so as not to cause the molecular chains of the binder resin to be broken. Specifically, the melt kneading temperature should be carried out with reference to the softening point of the binder resin. If the temperature is lower than the softening point, the cutting is severe, and if the temperature is too high, the dispersion does not proceed.

  When the above melt-kneading process is completed, the kneaded product is then pulverized. In this pulverization step, it is preferable to first coarsely pulverize and then finely pulverize. At this time, a method of pulverizing by colliding with a collision plate in a jet stream, pulverizing particles by colliding with each other in a jet stream, or pulverizing with a narrow gap between a mechanically rotating rotor and a stator is preferably used. After the pulverization step is completed, the pulverized product is classified in an air stream by centrifugal force or the like to produce a developer having a predetermined particle size, for example, an average particle size of 5 to 20 μm.

  In order to produce the toner of the present invention, the hydrophobic silica fine powder listed above for the base toner produced as described above in order to improve fluidity, storage stability, developability and transferability as a developer. Add and mix inorganic fine particles. For mixing external additives, a general powder mixer is used, but it is preferable to equip a jacket or the like to adjust the internal temperature. In order to change the load history applied to the external additive, the external additive may be added in the middle or gradually. Of course, you may change the rotation speed of a mixer, rolling speed, time, temperature, etc. A strong load may be given first, then a relatively weak load, and vice versa. Examples of the mixing equipment that can be used include a V-type mixer, a rocking mixer, a Ladige mixer, a Nauter mixer, a Henschel mixer, and the like.

(Developer)
The developer of the present invention contains at least the toner of the present invention, and other components such as a carrier selected as appropriate. The developer may be a one-component developer or a two-component developer. However, when it is used for a high-speed printer or the like corresponding to the recent improvement in information processing speed, the service life is improved. In view of the above, the two-component developer is preferable.
In the case of the one-component developer using the toner according to the present invention, the toner particle diameter hardly fluctuates even if the balance of the toner is performed, and the filming of the toner on the developing roller or the toner is made thin. Therefore, toner is not fused to a member such as a blade, and good and stable developability and images can be obtained even when the developing device is used (stirred) for a long time. Further, in the case of the two-component developer using the toner of the present invention, even if the balance of the toner over a long period of time is performed, the fluctuation of the toner particle diameter in the developer is small, and even in the long-term stirring in the developing device, Good and stable developability can be obtained.

  There is no restriction | limiting in particular as said carrier, Although it can select suitably according to the objective, What has a core material and the resin layer which coat | covers this core material is preferable.

  There is no restriction | limiting in particular as a material of the said core material, It can select suitably from well-known things, For example, 50-90 emu / g manganese-strontium (Mn-Sr) type material, manganese-magnesium (Mn-) Mg) -based materials and the like are preferable, and highly magnetized materials such as iron powder (100 emu / g or more) and magnetite (75 to 120 emu / g) are preferable in terms of securing image density. In addition, a weakly magnetized material such as a copper-zinc (Cu—Zn) -based (30 to 80 emu / g) is advantageous in that it can weaken the contact with the photoconductor in which the toner is in a spiked state and is advantageous in improving the image quality. Is preferred. These may be used alone or in combination of two or more.

The particle diameter of the core material is preferably an average particle diameter (volume average particle diameter (D ₅₀ )) of 10 to 150 μm, and more preferably 40 to 100 μm.
When the average particle diameter (volume average particle diameter (D ₅₀ )) is less than 10 μm, the distribution of carrier particles may increase the number of fine powders, lower the magnetization per particle, and cause carrier scattering. If the thickness exceeds 150 μm, the specific surface area may decrease and toner scattering may occur. In the case of a full color having a large solid portion, the reproduction of the solid portion may be deteriorated.

  The material of the resin layer is not particularly limited and can be appropriately selected from known resins according to the purpose. For example, amino resins, polyvinyl resins, polystyrene resins, halogenated olefin resins, Polyester resin, polycarbonate resin, polyethylene resin, polyvinyl fluoride resin, polyvinylidene fluoride resin, polytrifluoroethylene resin, polyhexafluoropropylene resin, copolymer of vinylidene fluoride and acrylic monomer, fluorine And a copolymer of vinylidene fluoride and vinyl fluoride, a fluoroterpolymer such as a terpolymer of tetrafluoroethylene, vinylidene fluoride and a non-fluorinated monomer, and a silicone resin. These may be used individually by 1 type and may use 2 or more types together.

  Examples of the amino resin include urea-formaldehyde resin, melamine resin, benzoguanamine resin, urea resin, polyamide resin, and epoxy resin. Examples of the polyvinyl resin include acrylic resin, polymethyl methacrylate resin, polyacrylonitrile resin, polyvinyl acetate resin, polyvinyl alcohol resin, and polyvinyl butyral resin. Examples of the polystyrene resin include polystyrene resin and styrene acrylic copolymer resin. Examples of the halogenated olefin resin include polyvinyl chloride. Examples of the polyester resin include polyethylene terephthalate resin and polybutylene terephthalate resin.

  The resin layer may contain conductive powder or the like as necessary. Examples of the conductive powder include metal powder, carbon black, titanium oxide, tin oxide, and zinc oxide. The average particle diameter of these conductive powders is preferably 1 μm or less. When the average particle diameter exceeds 1 μm, it may be difficult to control electric resistance.

For example, the resin layer is prepared by dissolving the silicone resin or the like in a solvent to prepare a coating solution, and then uniformly coating the coating solution on the surface of the core material by a known coating method, drying, and baking. It can be formed by doing. Examples of the application method include an immersion method, a spray method, and a brush coating method.
There is no restriction | limiting in particular as said solvent, Although it can select suitably according to the objective, For example, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cersol butyl acetate, etc. are mentioned.
The baking is not particularly limited, and may be an external heating method or an internal heating method. For example, a stationary electric furnace, a fluid electric furnace, a rotary electric furnace, a burner furnace, The method of using, the method of using a microwave, etc. are mentioned.

The amount of the resin layer in the carrier is preferably 0.01 to 5.0% by mass.
When the amount is less than 0.01% by mass, the uniform resin layer may not be formed on the surface of the core material. When the amount exceeds 5.0% by mass, the resin layer becomes thick. In some cases, granulation of carriers occurs, and uniform carrier particles may not be obtained.

When the developer is the two-component developer, the content of the carrier in the two-component developer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, 90 to 98% by mass Is preferable, and 93-97 mass% is more preferable.
In general, the mixing ratio of the toner and the carrier of the two-component developer is preferably 0.5 to 20.0 parts by mass of the toner with respect to 100 parts by mass of the carrier.

Since the developer of the present invention contains the toner of the present invention, it is possible to achieve a balance between chargeability and fixability during image formation, and stably form high-quality images. .
The developer of the present invention can be suitably used for image formation by various known electrophotographic methods such as a magnetic one-component development method, a non-magnetic one-component development method, and a two-component development method. It can be particularly suitably used for containers, process cartridges, image forming apparatuses and image forming methods.

(Toner container)
The toner-containing container of the present invention contains the toner or the developer of the present invention in a container.
There is no restriction | limiting in particular as said container, It can select suitably from well-known things, For example, what has a toner container main body and a cap etc. are mentioned suitably.
The size, shape, structure, material and the like of the toner container body are not particularly limited and can be appropriately selected according to the purpose. For example, the shape is preferably a cylindrical shape, A spiral irregularity is formed on the surface, the toner as the contents can be transferred to the discharge port side by rotating, and a part or all of the spiral part has a bellows function, etc. Particularly preferred.
The material of the toner container body is not particularly limited, and those having good dimensional accuracy are preferable. For example, a resin is preferably used. Among them, for example, polyester resin, polyethylene resin, polypropylene resin, polystyrene resin, polychlorinated resin Preferred examples include vinyl resin, polyacrylic acid, polycarbonate resin, ABS resin, polyacetal resin, and the like.
The toner-containing container of the present invention is easy to store and transport, has excellent handleability, and is preferably used for replenishing toner by being detachably attached to the process cartridge and image forming apparatus of the present invention described later. Can do.

(Process cartridge)
The process cartridge of the present invention develops an electrostatic latent image carrier carrying an electrostatic latent image and the electrostatic latent image carried on the electrostatic latent image carrier using a developer to form a visible image. At least a developing means for forming the film, and other means appropriately selected as necessary.
The developing means includes a developer container that contains the toner or developer of the present invention, and an electrostatic latent image carrier that carries and transports the toner or developer contained in the developer container. And a layer thickness regulating member for regulating the thickness of the toner layer to be carried.
The process cartridge of the present invention can be detachably provided in various electrophotographic apparatuses, and is preferably detachably provided in the electrophotographic apparatus of the present invention described later.

(Image forming apparatus and image forming method)
The image forming apparatus of the present invention includes at least an electrostatic latent image carrier, an electrostatic latent image forming unit, a developing unit, a transfer unit, and a fixing unit, and further appropriately selected as necessary. It has other means, for example, static elimination means, cleaning means, recycling means, control means and the like.
The image forming method of the present invention includes at least an electrostatic latent image forming step, a developing step, a transfer step, and a fixing step, and further other steps appropriately selected as necessary, for example, a static elimination step, a cleaning step, Includes recycling and control processes.
In the image forming apparatus of the present invention, it is preferable to provide means for applying an alternating electric field in the step of developing the latent image on the latent image holding member.
By providing the means for applying the alternating electric field, when developing a latent image with a developer, a vibration bias voltage in which an AC voltage is superimposed on a DC voltage is applied, so that a high-definition image without roughness can be obtained. it can.

  The image forming method of the present invention can be preferably carried out by the image forming apparatus of the present invention, the electrostatic latent image forming step can be performed by the electrostatic latent image forming means, and the developing step is the developing The transfer step can be performed by the transfer unit, the fixing step can be performed by the fixing unit, and the other steps can be performed by the other unit.

-Electrostatic latent image forming step and electrostatic latent image forming means-
The electrostatic latent image forming step is a step of forming an electrostatic latent image on the electrostatic latent image carrier.
There are no particular restrictions on the material, shape, structure, size, etc. of the electrostatic latent image bearing member (sometimes referred to as “photoconductive insulator” or “photosensitive member”), and among the known ones The shape is preferably a drum shape, and examples of the material include inorganic photoconductors such as amorphous silicon and selenium, and organic photoconductors such as polysilane and phthalopolymethine. It is done. Among these, amorphous silicon or the like is preferable in terms of long life.

The formation of the electrostatic latent image can be performed, for example, by uniformly charging the surface of the electrostatic latent image carrier and then performing imagewise exposure, and is performed by the electrostatic latent image forming unit. be able to.
The electrostatic latent image forming means includes, for example, at least a charger that uniformly charges the surface of the electrostatic latent image carrier and an exposure device that exposes the surface of the electrostatic latent image carrier imagewise. Prepare.

The charging can be performed, for example, by applying a voltage to the surface of the electrostatic latent image carrier using the charger.
The charger is not particularly limited and may be appropriately selected depending on the purpose. For example, a known contact charging device including a conductive or semiconductive roll, brush, film, rubber blade, etc. And non-contact chargers using corona discharge such as corotrons and corotrons.

The exposure can be performed, for example, by exposing the surface of the latent electrostatic image bearing member imagewise using the exposure device.
The exposure device is not particularly limited as long as it can expose the surface of the electrostatic latent image carrier charged by the charger so as to form an image to be formed, and is appropriately selected according to the purpose. For example, various exposure devices such as a copying optical system, a rod lens array system, a laser optical system, and a liquid crystal shutter optical system can be used.
In the present invention, a back light system in which imagewise exposure is performed from the back side of the electrostatic latent image carrier may be employed.

-Development process and development means-
The developing step is a step of developing the electrostatic latent image using the toner or the developer of the present invention to form a visible image.
The visible image can be formed, for example, by developing the electrostatic latent image using the toner or the developer of the present invention, and can be performed by the developing unit.
The developing means is not particularly limited as long as it can be developed using, for example, the toner or developer of the present invention, and can be appropriately selected from known ones. For example, the toner of the present invention Preferably, a developer containing at least a developer and having at least a developing unit capable of contacting or non-contacting the toner or the developer with the electrostatic latent image is provided, and includes the toner container according to the present invention. More preferred is a developing device.

  The developing unit may be a dry developing type, a wet developing type, a single color developing unit, or a multi-color developing unit. For example, a toner having a stirrer for charging the toner or the developer by frictional stirring and a rotatable magnet roller is preferable.

  In the developing device, for example, the toner and the carrier are mixed and agitated, and the toner is charged by friction at that time, and held on the surface of the rotating magnet roller in a raised state to form a magnetic brush. . Since the magnet roller is disposed in the vicinity of the electrostatic latent image carrier (photoconductor), a part of the toner constituting the magnetic brush formed on the surface of the magnet roller is electrically attracted. It moves to the surface of the electrostatic latent image carrier (photoconductor) by force. As a result, the electrostatic latent image is developed with the toner, and a visible image is formed with the toner on the surface of the electrostatic latent image carrier (photoconductor).

  The developer accommodated in the developing device is a developer containing the toner of the present invention, but the developer may be a one-component developer or a two-component developer. The toner contained in the developer is the toner of the present invention.

-Transfer process and transfer means-
The transfer step is a step of transferring the visible image onto a recording medium. After the primary transfer of the visible image onto the intermediate transfer member using an intermediate transfer member, the visible image is transferred onto the recording medium. A primary transfer step of forming a composite transfer image by transferring a visible image onto an intermediate transfer body using two or more colors, preferably full color toner as the toner, and a composite transfer image; A mode including a secondary transfer step of transferring the transfer image onto the recording medium is more preferable.
The transfer can be performed, for example, by charging the latent electrostatic image bearing member (photoconductor) of the visible image using a transfer charger, and can be performed by the transfer unit. The transfer means includes a primary transfer means for transferring a visible image onto an intermediate transfer member to form a composite transfer image, and a secondary transfer means for transferring the composite transfer image onto a recording medium. Embodiments are preferred.
The intermediate transfer member is not particularly limited and may be appropriately selected from known transfer members according to the purpose. For example, a transfer belt and the like are preferable.

The transfer means (the primary transfer means and the secondary transfer means) is a transfer for peeling and charging the visible image formed on the electrostatic latent image carrier (photoconductor) to the recording medium side. It is preferable to have at least a vessel. There may be one transfer means or two or more transfer means.
Examples of the transfer device include a corona transfer device using corona discharge, a transfer belt, a transfer roller, a pressure transfer roller, and an adhesive transfer device.
The recording medium is not particularly limited and can be appropriately selected from known recording media (recording paper).

The fixing step is a step of fixing the visible image transferred to the recording medium using a fixing device, and may be performed each time the toner of each color is transferred to the recording medium, or for the toner of each color. You may perform this simultaneously in the state which laminated | stacked this.
There is no restriction | limiting in particular as said fixing device, Although it can select suitably according to the objective, A well-known heating-pressing means is suitable. Examples of the heating and pressing means include a combination of a heating roller and a pressure roller, a combination of a heating roller, a pressure roller, and an endless belt.
The heating in the heating and pressing means is usually preferably 80 to 200 ° C.
In the present invention, for example, a known optical fixing device may be used together with or in place of the fixing step and the fixing unit depending on the purpose.

The neutralization step is a step of performing neutralization by applying a neutralization bias to the electrostatic latent image carrier, and can be suitably performed by a neutralization unit.
The neutralization means is not particularly limited, and may be appropriately selected from known neutralizers as long as it can apply a neutralization bias to the electrostatic latent image carrier. Preferably mentioned.

The cleaning step is a step of removing the electrophotographic toner remaining on the electrostatic latent image carrier, and can be suitably performed by a cleaning unit.
The cleaning means is not particularly limited, and may be appropriately selected from known cleaners as long as it can remove the electrophotographic toner remaining on the electrostatic latent image carrier. Preferred examples include brush cleaners, electrostatic brush cleaners, magnetic roller cleaners, blade cleaners, brush cleaners, web cleaners, and the like.

The recycling step is a step of recycling the electrophotographic color toner removed in the cleaning step to the developing unit, and can be suitably performed by the recycling unit.
There is no restriction | limiting in particular as said recycling means, A well-known conveyance means etc. are mentioned.

The control means is a process for controlling the respective steps, and can be suitably performed by the control means.
The control means is not particularly limited as long as the movement of each means can be controlled, and can be appropriately selected according to the purpose. Examples thereof include devices such as a sequencer and a computer.

Here, FIG. 1 shows a schematic view of an example of an image forming apparatus provided with means for applying an alternating electric field of the present invention.
In FIG. 1, during development, a vibration bias voltage obtained by superimposing an AC voltage on a DC voltage is applied to the developing sleeve 10 as a developing bias by a power source 9. The background portion potential and the image portion potential are located between the maximum value and the minimum value of the vibration bias potential. As a result, an alternating electric field whose direction changes alternately is formed in the developing portion. In this alternating electric field, the developer toner and the carrier vibrate vigorously, the toner shakes off the electrostatic binding force to the developing sleeve and the carrier and flies to the photosensitive drum 2, and the photosensitive drum (latent image holding member) 2. It adheres corresponding to the latent image.

Difference between the maximum value and the minimum value of the vibration bias voltage (peak-to-peak voltage) is preferably 0.5～5KV, frequency 1～10KH _Z are preferred. As the waveform of the vibration bias voltage, a rectangular wave, a sine wave, a triangular wave, or the like can be used. As described above, the DC voltage component of the vibration bias is a value between the background part potential and the image part potential, but the value closer to the background part potential than the image part potential is more likely to cover the background part potential region. This is preferable for preventing toner adhesion.
When the vibration bias voltage waveform is a rectangular wave, the duty ratio is preferably 50% or less. Here, the duty ratio means a ratio of time during which the toner is directed to the photosensitive member during one period of the vibration bias. By doing so, the difference between the peak value at which the toner is directed to the photoreceptor and the time average value of the bias can be increased, so that the movement of the toner is further activated and the potential of the latent image surface is increased. It can adhere to the distribution and improve the roughness and resolution. In addition, since the toner can reduce the difference between the peak value of the carrier having the opposite polarity charge toward the photoconductor and the time average value of the bias, the movement of the carrier is calmed down, and the background portion of the latent image is reduced. The probability of carriers adhering to can be greatly reduced.

In the fixing step of the image forming apparatus of the present invention, the fixing device includes a heating body provided with a heating element, a film in contact with the heating body, and a pressure member in pressure contact with the heating body through the film. It is also possible to use a fixing device that has a recording material on which an unfixed image is formed between the film and the pressure member and heat-fixes the recording material.
The fixing device can efficiently shorten the rise time.

FIG. 2 is a schematic view showing an example of the fixing device of the present invention. This fixing device is a so-called surf fixing device that rotates and fixes a fixing film. Details will be described below.
The fixing film 20 is an endless belt-like heat-resistant film, and is fixed to a driving roller 21 that is a supporting rotating body of the fixing film 20, a driven roller 22, and a heater support provided below the two rollers. The heating body 23 is arranged in a suspended manner.
The driven roller 22 also serves as a tension roller for the fixing film 20, and the fixing film 20 is driven to rotate in the clockwise direction by the rotational driving of the driving roller 21 in the clockwise direction in the drawing. The rotational driving speed is adjusted to a speed at which the transfer material and the fixing film are equal in the fixing nip region L where the pressure roller 23 and the fixing film 20 are in contact with each other.
Here, the pressure roller is a roller having a rubber elastic layer having good releasability, such as silicone rubber, and a contact pressure with a total load of 4 to 10 kg against the fixing nip region L while rotating counterclockwise. With pressure contact.
The fixing film preferably has excellent heat resistance, releasability and durability, and preferably has a total thickness of 100 μm or less, more preferably 40 μm or less. For example, a single layer film of a heat-resistant resin such as polyimide, polyetherimide, PES (polyether sulfide), PFA (tetrafluoroethylene bar fluoroalkyl vinyl ether copolymer resin), or a composite layer film, for example, a 20 μm thick film At least the image contact surface side is made of PTFE (tetrafluoroethylene resin), PFA or other fluororesin with a release coating layer with a conductive material added to a thickness of 10 μm, or an elastic layer such as fluororubber or silicone rubber Is given.

In FIG. 2, the heating body 24 is composed of a flat substrate 25 and a fixing heater 26. The flat substrate is made of a material having high thermal conductivity such as alumina and having a high electric resistivity, A fixing heater composed of a resistance heating element is provided on the contacting surface in the longitudinal direction. The fixing heater 26 is formed by, for example, applying an electric resistance material such as Ag / Pd or Ta ₂ N in a linear or belt shape by screen printing or the like. In addition, electrodes (not shown) are formed at both ends of the fixing heater 26, and the resistance heating element generates heat when energized between the electrodes. Further, a fixing temperature sensor 27 composed of a thermistor is provided on the surface of the substrate opposite to the surface provided with the fixing heater.
The substrate temperature information detected by the fixing temperature sensor 27 is sent to control means (not shown), and the amount of electric power supplied to the fixing heater is controlled by the control means, and the heating body is controlled to a predetermined temperature. Is done.

  In the image forming apparatus of the present invention, a process cartridge that integrally supports a photosensitive member and a unit including at least a developing unit selected from a charging unit, a developing unit, and a cleaning unit, and is detachable from the main body of the image forming apparatus. May be used.

FIG. 3 is a schematic configuration diagram showing an example of an image forming apparatus having a process cartridge holding the developer of the present invention.
In the image forming apparatus having the process cartridge 1 of the present invention, the photosensitive member 2 is rotationally driven at a predetermined peripheral speed. In the rotation process, the photosensitive member 2 is uniformly charged with a predetermined positive or negative potential on the peripheral surface thereof by the charging unit 3. Next, the image exposure light from image exposure means such as slit exposure or laser beam scanning exposure is received, and thus electrostatic latent images are sequentially formed on the peripheral surface of the photoreceptor, and the formed electrostatic latent image Then, the toner is developed by the developing means 4 and the developed toner image is transferred from the paper feeding unit to the transfer material fed in synchronism with the rotation of the photoconductor between the photoconductor and the transfer means. It is sequentially transferred by means. The transfer material that has received the image transfer is separated from the surface of the photosensitive member, introduced into the image fixing means, and fixed on the image, and printed out as a copy (copy). The surface of the photoreceptor after the image transfer is cleaned by removing the transfer residual toner by the cleaning means 5, and after being further discharged, it is repeatedly used for image formation.

  EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated concretely, this invention is not limited only to these Examples.

(Synthesis Example 1)
-Synthesis of binder resin-
In a 4-neck separable flask equipped with a stirrer, a thermometer, a nitrogen inlet, a flow-down condenser, and a condenser tube, 740 g of polyoxypropylene (2,2) -2,2-bis (4-hydroxyphenyl) propane, Establish 300 g of polyoxyethylene (2,2) -2,2-bis (4-hydroxyphenyl) propane, 466 g of dimethyl terephthalate, 80 g of isododecenyl succinic anhydride, and 114 g of tri-n-butyl 1,2,4-benzenetricarboxylate Was added along with the catalyst. Under a nitrogen atmosphere, the temperature was raised to 210 ° C. in the first half, and the reaction was allowed to proceed with stirring at 210 ° C. under reduced pressure in the second half. Thus, the polyester resin of Synthesis Example 1 was synthesized (hereinafter referred to as polyester resin A).
About the obtained polyester resin A, in the molecular weight distribution in a gel permeation chromatography, content 3.5 mass% of weight average molecular weights 5 * 10 < ² > or less, weight average molecular weight main peak 7.5 * 10 < ³ >, Mw / Mn ratio was 5.1. Further, the glass transition temperature (Tg) was 62 ° C., the acid value was 2.3 KOH mg / g, and the temperature was 112 ° C. at which the apparent viscosity by a flow tester was 1 × 10 ³ Pa · s. The obtained polyester resin A contained no THF-insoluble matter.

(Synthesis Example 2)
-Synthesis of binder resin-
In Synthesis Example 1, 725 g of polyoxypropylene (2,2) -2,2-bis (4-hydroxyphenyl) propane, 165 g of polyoxyethylene (2,2) -2,2-bis (4-hydroxyphenyl) propane , Except that 500 g of terephthalic acid, 130 g of isododecenyl succinic anhydride, and 170 g of triisopropyl 1,2,4-benzenetricarboxylate were added to the flask together with the esterification catalyst, and reacted in the same apparatus and the same formulation as in Synthesis Example 1. Thus, the polyester resin of Synthesis Example 2 was synthesized (hereinafter referred to as polyester resin B).
The obtained polyester resin has a weight average molecular weight of 5 × 10 ² or less in a gel permeation chromatography of 3.0 mass%, a weight average molecular weight main peak of 8 × 10 ³ and an Mw / Mn ratio of 4.7. there were. Further, the glass transition temperature (Tg) was 62 ° C., the acid value was 0.5 KOH mg / g, and the temperature was 116 ° C. at which the apparent viscosity by a flow tester was 1 × 10 ³ Pa · s.

(Synthesis Example 3)
-Synthesis of binder resin-
In Synthesis Example 1, 650 g of polyoxypropylene (2,2) -2,2-bis (4-hydroxyphenyl) propane, 650 g of polyoxyethylene (2,2) -2,2-bis (4-hydroxyphenyl) propane , Except that 515 g of isophthalic acid, 70 g of isooctenyl succinic acid, and 80 g of 1,2,4-benzenetricarboxylic acid were added to the flask together with the esterification catalyst. The polyester resin of Example 3 was synthesized (hereinafter referred to as polyester resin C).
The obtained polyester resin has a weight average molecular weight of 5 × 10 ² or less in a gel permeation chromatography of 2.1% by mass, a weight average molecular weight main peak of 8.2 × 10 ³ , and a Mw / Mn ratio of 4. 6. Further, the glass transition temperature (Tg) was 61 ° C., the acid value was 10.0 KOH mg / g, and the apparent viscosity with a flow tester was 117 ° C. at 1 × 10 ³ Pa · s.

(Synthesis Example 4)
-Synthesis of binder resin-
In Synthesis Example 1, 1620 g of polyoxypropylene (2,2) -2,2-bis (4-hydroxyphenyl) propane, 125 g of polyoxyethylene (2,2) -2,2-bis (4-hydroxyphenyl) propane , Except for adding 650 g of dimethyl terephthalate, 120 g of isododecenyl succinic anhydride, and 135 g of tri-n-butyl 1,2,4-benzenetricarboxylate together with an esterification catalyst, the reaction was carried out in the same apparatus and the same formulation as in Synthesis Example 1. Thus, the polyester resin of Synthesis Example 4 was synthesized (hereinafter referred to as polyester resin D).
About the obtained polyester resin, the weight average molecular weight of 5 × 10 ² or less by gel permeation chromatography is 2.5% by mass, the weight average molecular weight is 2.5 × 10 ⁴ , and the Mw / Mn ratio is 12.5. there were. Further, the glass transition temperature (Tg) was 69 ° C., the acid value was 13.2 KOH mg / g, and the temperature was 128 ° C. at which the apparent viscosity by a flow tester was 1 × 10 ³ Pa · s.

-Examples of additives-
(I) Hydrophobized silica having a primary particle size of 0.01 to 0.03 μm shown in Table 1 below was used.

(Ii) Synthesis of hydrophobized titanium oxide having a primary particle diameter of 0.01 to 0.03 μm and a specific surface area of 60 to 140 m ² / g (Synthesis Example a)
Toluene in which 300 g of titanium oxide (MT-150A, manufactured by Teika Co., Ltd.) having a primary average particle size of 0.015 μm and containing 0.35% by mass of a water-soluble component produced by a wet method is dissolved in 35 g of isobutylmethoxysilane It was added to the solution and dispersed by stirring. Then, the solvent was dried up and jet mill pulverized to obtain a coupling agent-treated titanium oxide (titanium oxide II-1).

(Synthesis example b)
Toluene in which 300 g of titanium oxide (MT-150A, manufactured by Teika Co., Ltd.) having a primary average particle size of 0.015 μm and containing 0.35% by mass of a water-soluble component produced by a wet method is dissolved in 25 g of isobutylmethoxysilane It was added to the solution and dispersed with stirring. Thereafter, the solvent was dried up and pulverized with a jet mill to obtain a coupling agent-treated titanium oxide (titanium oxide II-2).

(Synthesis Example c)
300 g of titanium oxide (MT-150A, manufactured by Taika Co., Ltd.) having a primary average particle size of 0.015 μm containing 0.35% by mass of a water-soluble component produced by a wet method was dissolved in 30 g of methyltrimethoxysilane. Added to the toluene solution and dispersed. Thereafter, the solvent was dried up and pulverized with a jet mill to obtain a coupling agent-treated titanium oxide (titanium oxide II-3).

(Synthesis Example d)
300 g of titanium oxide having a primary average particle size of 0.015 μm containing 0.35% by mass of a water-soluble component produced by a wet method (MT-150A, manufactured by Teica), and 30 g of n-butyltrimethoxysilane Added to the dissolved toluene solution and dispersed. Thereafter, the solvent was dried up and pulverized with a jet mill to obtain a coupling agent-treated titanium oxide (titanium oxide II-4).

The characteristic values of the obtained titanium oxide are shown in Table 2 below.

Example 1
-Preparation of colorant-
The colorant was processed according to the following formulation.
Yellow colorant formulation:
Polyester resin A 100 parts by mass C.I. I. Pigment Yellow 180 100 parts by mass Red colorant formulation:
Polyester resin A 100 parts by mass C.I. I. Pigment Red 122 100 parts by weight Blue colorant Formula:
Polyester resin A 100 parts by mass C.I. I. Pigment Blue 15.3 100 parts by weight black colorant formulation:
100 parts by mass of polyester resin A 100 parts by mass of carbon black The above materials were mixed for each color in a Henschel mixer, and then the mixture was charged into an air-cooled two-roll mill, and melt-kneaded for 15 minutes after charging. Thereafter, the kneaded product was rolled and cooled, and coarsely pulverized with a hammer mill to obtain a polyester resin-treated colorant.

-Preparation of toner and developer-
Next, a toner was prepared according to the following formulation.
Yellow toner prescription:
Polyester resin A 94 parts by weight Polyester resin A treated yellow colorant 12 parts by weight 3,5-ditertiarybutylsalicylic acid zinc compound 3 parts by weight Magenta toner
Polyester resin A 95 parts by weight Polyester resin A treated red colorant 10 parts by weight 3,5-ditertiarybutyl salicylate compound 3 parts by weight Cyan toner formulation:
Polyester resin A 97 parts by weight Polyester resin A treated blue colorant 6 parts by weight 3,5-ditertiarybutylsalicylate zinc compound 3 parts by weight Black toner formulation:
Polyester resin A 93 parts by weight Polyester resin A treated black colorant 12 parts by weight Polyester resin A treated blue colorant 2 parts by weight 3,5-ditertiarybutylsalicylic acid zinc compound 3 parts by weight The above materials for each color in a Henschel mixer The resulting mixture was put into a roll mill heated to 110 ° C., and melted and kneaded for 20 minutes after the addition. Thereafter, the kneaded product was cooled, coarsely pulverized with a hammer mill, and finely pulverized with an air jet mill. Further, fine powder was removed by an air classifier to obtain each color toner. The following additives were mixed with a Henschel mixer with respect to 100 parts by mass of each of the obtained color toners to obtain a one-component developer.
I-2 Hydrophobic silica 2.5 parts by mass II-1 Hydrophobic titanium oxide 0.8 parts by mass Calcium stearate 0.03 parts by mass

-Image formation and evaluation-
The obtained one-component developer was set in a commercially available digital full color printer (Ricoh Co., Ltd., IPSiO Color 6500) to form an image.
The obtained image was clear and no abnormalities such as background stains were observed. When the developing roller was visually observed, the toner thin layer on the roller was uniform. The amount of charge on the developing roller was measured by a suction method. As a result, the yellow developer was −28 μC / g, the magenta developer was −23 μC / g, the cyan developer was −28 μC / g, and the black developer was −25 μC / g. there were. Images were similarly formed under high temperature and high humidity conditions of 27 ° C. and 80% RH, and under low temperature and low humidity conditions of 10 ° C. to 15% RH, but no change was observed, and a good image was formed.
Next, when a durability test was performed up to a total of 20,000 sheets with full-color images continuously under normal temperature, low temperature and low humidity, high temperature and high humidity, and normal temperature, no significant change was observed in the fixed image. The first image was also clear with no background stains.
When the developing roller was visually observed, there was no significant change in the toner thin layer on the roller. At this time, the developer charge amount was yellow developer-29 μC / g, magenta developer-21 μC / g, cyan development. Agent-26 μC / g and black developer-23 μC / g. The developing roller, doctor roller, and photoreceptor were visually observed, but no filming was observed. Further, a durability test was performed up to 50,000 sheets. Filming was not observed on the developing roller and doctor roller, the charge amount was stable, and no abnormal image was observed.

(Example 2)
-Preparation of colorant-
The colorant was processed according to the following formulation.
Yellow colorant formulation:
Polyester resin C 100 parts by mass C.I. I. Pigment Yellow 180 100 parts by mass Red colorant formulation:
Polyester resin C 100 parts by mass C.I. I. Pigment Red 146 100 parts by mass of a blue colorant
Polyester resin C 100 parts by mass C.I. I. Pigment Blue 15.3 100 parts by weight black colorant formulation:
100 parts by mass of polyester resin C 100 parts by mass of carbon black The above materials were mixed for each color in a Henschel mixer, and then the mixture was charged into an air-cooled two-roll mill and melt-kneaded for 15 minutes after charging. Thereafter, the kneaded product was rolled and cooled, and coarsely pulverized with a hammer mill to obtain a polyester resin-treated colorant.

-Preparation of toner and developer-
Next, a toner was prepared according to the following formulation.
Yellow toner formulation;
Polyester resin C 94 parts by weight Polyester resin C treated yellow colorant 12 parts by weight 3,5-ditertiarybutylsalicylic acid zinc compound 3 parts by weight Magenta toner
Polyester resin C 95 parts by weight Polyester resin C treated red colorant 10 parts by weight 3,5-ditertiarybutyl salicylate compound 3 parts by weight Cyan toner formulation:
Polyester resin C 97 parts by weight Polyester resin C-treated blue colorant 6 parts by weight 3,5-ditertiarybutyl salicylate compound 3 parts by weight Black toner formulation:
Polyester resin C 93 parts by weight Polyester resin C resin-treated black colorant 12 parts by weight Polyester resin C resin-treated blue colorant 2 parts by weight 3,5-ditertiarybutylsalicylic acid zinc compound 3 parts by weight Mix in a mixer. The obtained mixture was put into a biaxial continuous kneader heated to 80 ° C. and melt-kneaded. Thereafter, the kneaded product was cooled, coarsely pulverized with a hammer mill, and finely pulverized with an airflow pulverizer. Further, fine powder was removed by an air classifier to obtain toner of each color. The following additives were mixed with a Henschel mixer with respect to 100 parts by mass of each color toner obtained.
I-3 Hydrophobic silica 2.1 parts by weight II-4 Hydrophobic titanium oxide 1.0 part by weight Zinc stearate 0.01 part by weight The obtained toner 7 parts by weight and a silicone resin coated ferrite carrier 93 parts by weight were mixed. A two-component developer was obtained.

-Image formation and evaluation-
The obtained two-component developer was set in a commercially available digital full color printer (Ricoh Co., Ltd., IPSiO Color 7100) to form an image.
The obtained image was clear with no background stains. No abnormalities were observed in image and charging at high temperature and high humidity and low temperature and low humidity. Even when a durability test of up to 20,000 sheets with a full-color image was performed, no abnormal image was observed, and the inside of the apparatus was observed after the test, but no scattering was observed, and there was no adhesion to the photoreceptor. Further, a durability test up to 50,000 sheets was conducted, but no filming on the developing roller and doctor roller was observed, the charge amount was stable, and no abnormal image was observed.

(Example 3)
-Preparation of colorant-
The colorant was processed according to the following formulation.
Yellow colorant formulation:
Polyester resin B 100 parts by mass C.I. I. Pigment Yellow 180 100 parts by mass Red colorant formulation:
Polyester resin B 100 parts by mass C.I. I. Pigment Red 57.1 100 parts by weight Blue colorant Formula:
Polyester resin B 100 parts by mass C.I. I. Pigment Blue 15.3 100 parts by mass The above materials were mixed in a Henschel mixer for each color and mixed, then the mixture was charged into an air-cooled two-roll mill and melt-kneaded for 15 minutes. Thereafter, the kneaded product was rolled and cooled, and coarsely pulverized with a hammer mill to obtain a polyester resin-treated colorant.

-Preparation of toner and developer-
Next, a toner was prepared according to the following formulation.
Yellow toner formulation;
Polyester resin B 93 parts by weight Polyester resin B treated yellow colorant 14 parts by weight 3,5-ditertiarybutylsalicylate zinc compound 2 parts by weight Magenta toner
Polyester resin B 94 parts by weight Polyester resin B treated red colorant 12 parts by weight 3,5-ditertiarybutyl salicylate zinc compound 2 parts by weight Cyan toner Formula:
Polyester resin B 96 parts by weight Polyester resin B treated blue colorant 8 parts by weight 3,5-ditertiarybutyl salicylate compound 3 parts by weight Black toner formulation:
Polyester resin B 99 parts by mass Carbon black 6 parts by mass Polyester resin B resin-treated blue colorant 2 parts by mass 3,5-ditertiarybutyl salicylate compound 3 parts by mass The above materials were mixed in a Henschel mixer for each color. The obtained mixture was put into a biaxial continuous kneader heated to 80 ° C. and melt-kneaded. Thereafter, the kneaded product was cooled, coarsely pulverized with a hammer mill, and finely pulverized with an airflow pulverizer. Further, fine powder was removed by an air classifier to obtain each color toner. The following additives were mixed with a Henschel mixer with respect to 100 parts by mass of the obtained color toners to obtain a one-component developer.
I-2 Hydrophobic silica 2.5 parts by mass II-2 Hydrophobic titanium oxide 0.8 parts by mass Calcium stearate 0.05 parts by mass

-Image formation and evaluation-
The obtained one-component developer was set on a commercially available digital full-color PPC (manufactured by Ricoh Co., Ltd., Image Neo Neo C320) to form an image. The obtained image was clear with no background stains. No abnormalities were observed in image and charging at high temperature and high humidity and low temperature and low humidity. Even when a durability test of up to 20,000 sheets with a full-color image was performed, no abnormal image was observed, and the inside of the apparatus was observed after the test, but no scattering was observed, and there was no adhesion to the photoreceptor. Further, a durability test up to 50,000 sheets was conducted, but no filming on the developing roller and doctor roller was observed, the charge amount was stable, and no abnormal image was observed.

(Comparative Example 1)
-Treatment of titanium oxide-
Titanium oxide containing 0.35% by mass of a water-soluble component made by a wet process (manufactured by Teika Co., Ltd., MT-150A) was washed with water to obtain titanium oxide having a water-soluble component of 0.15% by mass. 300 g of this titanium oxide was added and dispersed in a toluene solution in which 35 g of isobutyltrimethoxysilane was dissolved. Thereafter, the solvent was dried up, finely pulverized by a jet mill, and further highly dispersed by a pin mill to obtain a coupling agent-treated titanium oxide (hydrophobic titanium oxide II-5). When the absorbance of the obtained surface-treated titanium oxide was measured, the transmittance at 300 nm was 21%, and the transmittance at 600 nm was 97%.

Next, the following additives were mixed with 100 parts by mass of each color toner obtained in Example 1 to obtain a one-component developer.
I-2 Hydrophobic silica 2.4 parts by mass II-5 Hydrophobic titanium oxide 0.6 parts by mass

-Image formation and evaluation-
The obtained one-component developer was set in a commercially available digital full color printer (Ricoh Co., Ltd., IPSiO Color 6500) to form an image. The obtained image was slightly low in image density, but no scum was observed. When the developing roller was visually observed, the toner thin layer on the roller was uniform, but the development amount was low overall.
The amount of charge on the developing roller was measured by a suction method. As a result, the yellow developer was −48 μC / g, the magenta developer was −40 μC / g, the cyan developer was −42 μC / g, and the black developer was −44 μC / g. there were. When an image was formed under high-temperature and high-humidity conditions of 27 ° C. to 80% RH, the image was blurred.
Further, when the same image was formed under low temperature and low humidity conditions of 10 ° C. to 15% RH, a faint image having a lower image density was obtained. When a durability test using full-color images was performed under normal conditions at room temperature, low temperature and low humidity, high temperature and high humidity, and normal temperature, abnormalities such as background stains, dust, and streaks occurred on the images. When the developing roller was visually observed at this time, streaks were generated in the circumferential direction in the toner thin layer on the roller. When the charge amount of the developer was measured, it was deteriorated to be yellow developer-23 μC / g, magenta developer-20 μC / g, cyan developer-20 μC / g, and black developer-19 μC / g.

(Comparative Example 2)
-Preparation of colorant-
In the same manner as in Example 1, the colorant was treated according to the following formulation.
Yellow colorant formulation:
Polyester resin D 100 parts by mass C.I. I. Pigment Yellow 180 100 parts by mass Red colorant formulation:
Polyester resin D 100 parts by mass C.I. I. Pigment Red 146 100 parts by mass of a blue colorant
Polyester resin D 100 parts by mass C.I. I. Pigment Blue 15.3 100 parts by weight black colorant formulation:
100 parts by mass of polyester resin D 100 parts by mass of carbon black The above materials were mixed for each color in a Henschel mixer, and then the mixture was charged into an air-cooled two-roll mill, and melted and kneaded for 15 minutes after charging. Thereafter, the kneaded product was rolled and cooled, and coarsely pulverized with a hammer mill to obtain a polyester resin D- treated colorant.

-Preparation of toner and developer-
Next, a toner was prepared according to the following formulation.
Yellow toner formulation;
Polyester resin D 94 parts by weight Polyester resin D treated yellow colorant 12 parts by weight 3,5-ditertiarybutylsalicylic acid zinc compound 3 parts by weight Magenta toner
Polyester resin D 95 parts by weight Polyester resin D treated red colorant 10 parts by weight 3,5-ditertiarybutyl salicylate compound 3 parts by weight Cyan toner formulation:
Polyester resin D 97 parts by weight Polyester resin D-treated blue colorant 6 parts by weight 3,5-ditertiarybutyl salicylate compound 3 parts by weight Black toner formulation:
Polyester resin D 93 parts by weight Polyester resin D resin-treated black colorant 12 parts by weight Polyester resin D resin-treated blue colorant 2 parts by weight 3,5-ditertiarybutylsalicylic acid zinc compound 3 parts by weight Mix in a mixer. The obtained mixture was put into a biaxial continuous kneader heated to 90 ° C. and melt-kneaded. Thereafter, the kneaded product was cooled, coarsely pulverized with a hammer mill, and finely pulverized with an airflow pulverizer. Further, fine powder was removed by an air classifier to obtain toner of each color. The following additives were mixed with a Henschel mixer with respect to 100 parts by mass of each color toner obtained.
I-2 Hydrophobic silica 2.5 parts by mass II-1 Hydrophobic titanium oxide 0.8 parts by mass

-Image formation and evaluation-
When the obtained one-component developer was set in a commercially available digital full-color printer (manufactured by Ricoh Co., Ltd., IPSiO Color 6500) in the same manner as in Example 1, an image having a smudged appearance and no image gloss was obtained. .
When the developing roller was visually observed, the toner thin layer on the roller was uniform. The amount of charge on the developing roller was measured by a suction method. As a result, the yellow developer was −23 μC / g, the magenta developer was −20 μC / g, the cyan developer was −21 μC / g, and the black developer was −19 μC / g. there were.
When image formation was performed under high temperature and high humidity conditions of 27 ° C. to 80% RH, the background stains became severe. When a durability test was performed for a total of 20,000 sheets in full-color images continuously under normal temperature, low temperature and low humidity, high temperature and high humidity, and normal temperature, an image with a noticeable deterioration of background stains and noticeable dust in about 10,000 sheets. became. When the developing roller was visually observed, the toner layer on the roller was uneven and a large number of streaks were generated in the circumferential direction.

  The toner of the present invention is used in a copying machine, a laser printer, a plain paper fax machine, and the like using a direct or indirect electrophotographic developing system. The present invention can be applied to a developer containing the toner, an image forming method using the developer, an image forming method loaded with the developer, and a process cartridge holding the developer. Further, a toner used in a full-color copying machine, a full-color laser printer, a full-color plain paper fax machine, etc. using a direct or indirect electrophotographic multicolor image developing system, a developer containing the toner, and an image formation using the developer It can be used for a method, an image forming method loaded with the developer, and a process cartridge holding the developer.

FIG. 1 is a schematic view showing an example of an image forming apparatus provided with means for applying an alternating electric field according to the present invention. FIG. 2 is a schematic view showing an example of a surf fixing device provided in the image forming apparatus of the present invention. FIG. 3 is a schematic view showing an example of an image forming apparatus having the process cartridge of the present invention.

Explanation of symbols

1 Process cartridge 2 Photoconductor (photosensitive drum)
DESCRIPTION OF SYMBOLS 3 Charging means 4 Developing means 5 Cleaning means 9 Power supply 10 Developing sleeve 20 Fixing film 21 Driving roller 22 Driven roller 23 Pressure roller 24 Heating body 25 Flat substrate 26 Fixing heater 27 Fixing temperature sensor

Claims (16)

In a toner in which a lubricant and an additive adhere to the surface of a base toner containing at least a binder resin, a colorant, and a charge control agent ,
The binder resin comprises at least one polyester resin, the polyester resin does not contain a THF-insoluble component, and the content ratio of components having a weight average molecular weight of 5 × 10 ² or less in the molecular weight distribution in gel permeation chromatography Has a main peak in the region of 4% by mass or less and a weight average molecular weight of 3 × 10 ^{3 to} 9 × 10 ³ ,
The charge control agent is either a metal salt compound of salicylic acid or a metal salt compound of a salicylic acid derivative;
The additive is hydrophobized silica having a primary particle size of 0.01 to 0.03 μm, a primary particle size of 0.01 to 0.03 μm, and a specific surface area of 60 to 140 m ² / g. Comprising hydrophobized titanium oxide
The hydrophobized titanium oxide is produced by a wet method, and is obtained by surface-treating titanium oxide fine particles having a water-soluble component content of 0.2% by mass or more, and the titanium oxide is UV-absorbed. Wherein the transmittance at 300 nm is 35% or more and the transmittance at 600 nm is 80% or more.   The toner according to claim 1, wherein an endothermic peak in DSC of the binder resin is in a range of 60 to 70 ° C.   The toner according to claim 1, wherein a ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the binder resin is 2 ≦ Mw / Mn ≦ 10.   The toner according to claim 1, wherein the acid value of the binder resin is 10 KOH mg / g or less. The toner according to any one of claims 1 to 4, wherein a temperature at which an apparent viscosity of the binder resin by a flow tester is 1 x 10 ³ Pa · s is 95 to 120 ° C.   The toner according to claim 1, wherein a content of the charge control agent in the toner particles is 0.1 to 10% by mass. 2.1 parts by mass or more of hydrophobized silica having a primary particle diameter of 0.01 to 0.03 μm and a primary particle diameter of 0.01 to 0.03 μm with respect to 100 parts by mass of the base toner, and The toner according to claim 1, comprising 0.4 to 1.0 part by mass of hydrophobized titanium oxide having a specific surface area of 60 to 140 m ² / g.   The toner according to claim 1, wherein at least one lubricant is contained, and at least one of the lubricants is a fatty acid metal salt having 16 or more carbon atoms.   9. The lubricant according to claim 1, wherein the lubricant contains 0.01 part by mass to 0.1 T part by mass (where T represents the amount of addition of the base toner titanium oxide) with respect to 100 parts by mass of the base toner. Toner.   A developer comprising the toner according to claim 1.   The developer according to claim 10, which is either a one-component developer or a two-component developer.   A toner-containing container comprising the toner according to claim 1 contained in the container.   An electrostatic latent image carrier, and a developing unit that develops the electrostatic latent image formed on the electrostatic latent image carrier using the toner according to claim 1 to form a visible image. A process cartridge having at least   An electrostatic latent image carrier, an electrostatic latent image forming unit that forms an electrostatic latent image on the electrostatic latent image carrier, and the toner according to claim 1. At least developing means for forming a visible image by developing the toner, transfer means for transferring the visible image to a recording medium, and fixing means for fixing the transferred image transferred to the recording medium. An image forming apparatus.   The fixing unit includes a heating body provided with a heating element, a film in contact with the heating body, and a pressure member in pressure contact with the heating body through the film, and between the film and the pressure member The image forming apparatus according to claim 14, wherein a fixing device that heats and fixes a recording material on which an unfixed image is formed is passed.   An electrostatic latent image forming step of forming an electrostatic latent image on the electrostatic latent image carrier, and developing the electrostatic latent image with the toner according to any one of claims 1 to 9 to form a visible image An image forming method comprising: a developing step for forming the image; a transfer step for transferring the visible image to a recording medium; and a fixing step for fixing the transferred image transferred to the recording medium.

Images