JP2007240896A - Method for manufacturing electrostatic charge image developing toner - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide high-quality images for a long period of time even under severe use conditions by solving problems with a toner obtained by recycling unpredetermined grain size components in a method for manufacturing the toner containing at least a carbon black as a colorant. <P>SOLUTION: The method for manufacturing the electrostatic charge image developing toner containing at least a binder resin and a colorant, in which at least the carbon black is included as the colorant in the toner. The method for manufacturing the toner is characterized in that the unpredetermined grain size components produced in a classification process are recycled as the recycling components for the toner in a rekneading process, and the toner is manufactured by performing kneading of the toner including the recycling components under the conditions under which the tanδ<SB>A</SB>(1 KHz) of the toner not including the unpredetermined grain size components being the recycling components and the tanδ<SB>B</SB>(1 KHz) of the toner in the state including the recycling components have the relation of general formula, where tanδ(1 KHz) is the dielectric loss of the toner at a frequency 1 KHz. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a method for producing a toner for developing an electrostatic charge image used in an image forming apparatus such as a printer, a copying machine, or a facsimile.

Developers used in electrophotography, electrostatic recording, electrostatic printing, and the like are once attached to an image carrier on which an electrostatic charge image is formed, for example, in the development process, and then from the photoreceptor in a transfer process. After being transferred to a transfer medium such as transfer paper, it is fixed on the paper surface in a fixing step.
As a developer used in the development process, a two-component developer composed of a carrier and a toner and a one-component developer composed of only a toner without using a carrier (magnetic toner, non-magnetic toner) are known. Yes.
In the two-component development system, the developer deteriorates due to the toner particles adhering to the carrier surface, and the toner concentration in the developer decreases because only the toner is consumed. There is a disadvantage that the developing device is enlarged because it must be held at a certain ratio.
On the other hand, the one-component development method does not have the above-mentioned drawbacks, and has an advantage such as downsizing of the apparatus, and the development method because it is easy to use in any environment (low temperature, low humidity, high temperature, high humidity). Is becoming mainstream.
Further, the one-component development method using a one-component developer is further classified into a magnetic one-component development method using a magnetic toner and a non-magnetic one-component development method using a non-magnetic toner. The magnetic one-component development system uses a developing sleeve provided with a magnetic field generating means such as a magnet inside, holds magnetic toner containing a magnetic material such as magnetite, and develops a thin layer with a layer thickness regulating member. In recent years, a large number of small printers have been put to practical use.
In contrast, in the non-magnetic one-component development method, since the toner does not have a magnetic force, the toner is supplied onto the developing sleeve by pressing the toner supply roller or the like against the developing sleeve, and is electrostatically held, and the layer thickness It is developed with a thin layer by the regulating member, and has the advantage of being able to cope with colorization because it does not contain a colored magnetic material. Also, since a magnet is not used for the developing sleeve, the device is lighter and less expensive. In recent years, it has been put to practical use in small full-color printers and the like.

In the production of the toner used in each of the above developing methods, when carbon black is used as a colorant among the additives, there are many problems.
First, since carbon black has a smaller primary particle size and a larger specific surface area than other pigments, it is very difficult to disperse, and it is likely to be unevenly distributed on the surface of toner particles or to produce free carbon black. Since carbon black is a fine powder with high tackiness, the presence of free carbon black causes a decrease in toner fluidity, hinders good triboelectric charging, and particularly reproducibility of halftone images. Further, when the carbon black is not sufficiently dispersed, there arises a problem that a sufficient image density cannot be obtained.
Second, because carbon black is conductive, if it is present on the toner surface, the charge is likely to leak. When image formation is performed using such toner, fogging and toner scattering may occur. The transfer may be lost.
Therefore, many proposals for improving the dispersibility of carbon black have been made, but it has not yet been fully solved (for example, Patent Documents 1 to 3). In particular, in a process such as a non-magnetic one-component development method in which a toner supply roller or a layer thickness regulating member is pressed against the developing sleeve to supply a thin layer toner having a charge on the developing sleeve, the toner is long. Since damage is likely to occur over a period of time, problems specific to non-magnetic one-component development such as white streaks arise. When the carbon black is not sufficiently dispersed, a resin single region is easily present in the toner particles, and thus toner aggregates are generated and white streaks become more prominent.

  In addition, there is a movement to use all resources effectively due to heightened awareness of the global environment. Some considerations have been given to the toner, and one of the considerations is the reuse of a component having a predetermined outer particle diameter. This is a method for reducing waste by returning the specified external particle size component (fine powder and coarse powder) generated in the classification process, which is a part of the toner manufacturing process, to the kneading process and reusing it as the specified internal particle size component again. This is a useful production method from the economic aspect of environmental and cost reduction. However, since this method repeats the kneading process twice, the thermal history is received twice, and there is a problem that the damage to the resin is large and the above-mentioned white streaks are likely to occur.

Japanese Patent Application Laid-Open No. 64-35457 JP-A-1-145664 JP 2004-78206 A

  An object of the present invention is a toner obtained by reusing a predetermined outer particle diameter component in a method for producing a toner containing at least carbon black as a colorant, and solves the above-mentioned problems even under severe use conditions. An object is to provide high-quality images over a long period of time.

The above problems are solved by the present invention described below.
(1) “In the method for producing a toner containing at least a binder resin and a colorant, at least carbon black is included as the colorant, and the toner production method includes a predetermined outer particle size component generated in the classification step, The toner is reused as a reusable component in the re-kneading step, and the toner contains tan δ _A (1 KHz) of the toner that does not contain a predetermined outer particle size component that is a reusable component, and a state that includes the reusable component A method for producing a toner for developing an electrostatic charge image, characterized in that kneading including the reusable component is carried out under the following relationship of tan δ _B (1 kHz) of the toner:

（ただしtanδ（１ＫHz）は周波数１ＫHzにおけるトナーの誘電体損である。）」；

(Where tan δ (1 kHz) is the dielectric loss of the toner at a frequency of 1 kHz.)

(2) The item (1) is characterized in that the reuse component is used in the re-kneading step at a ratio of 5 to 40 parts by weight with respect to 100 parts by weight of the toner composition excluding the reuse component. A process for producing the toner for developing an electrostatic image according to the description ";
(3) "The method for producing a toner for developing an electrostatic charge image according to (1) or (2) above, wherein an average primary particle diameter of the carbon black is 15 nm to 50 nm";
(4) "The BET specific surface area of the carbon ^black, 80m ² / ^g~140m 2 / g wherein the (1), characterized in that a term, second (3) The electrostatic image according to any one of Items Manufacturing method of developing toner ";
(5) “The method for producing a toner for developing an electrostatic charge image according to any one of (1) to (4) above, wherein the tan δ _A (1 kHz) is smaller than 0.003”;
(6) Any of the items (1) to (5), wherein the carbon black kneaded together with the reusable component is used in the rekneading step without pretreatment with a binder resin. A method for producing a toner for developing an electrostatic image according to claim 1;
(7) “In the re-kneading step, the reusable component and the toner composition raw material excluding the reusable component are melt kneaded in the range of 40 ° C. to 65 ° C. ) To (6), a method for producing a toner for developing an electrostatic charge image according to any one of items];
(8) “T _A (%) is the total light transmittance by halogen light of the supernatant when the toner in a state not containing the reuse component is dissolved / dispersed in tetrahydrofuran (THF), and contains the reuse component. when the supernatant total light transmittance by the halogen light when dissolved / dispersed in tetrahydrofuran (THF) the toner state was T _{B (%),} characterized in that T _a and T _B satisfy the following equation The method for producing a toner for developing an electrostatic image according to any one of items (1) to (7)

」；
（９）「前記再利用成分を含まない状態のトナーのガラス転移温度Ｔｇ_Ａと前記再利用成分を含む状態のトナーのＴｇ_Ｂと、前記結着樹脂Ｔｇ_Ｒの関係が下記関係式を満たすことを特徴とする前記第（１）項乃至第（８）項のいずれかに記載の静電荷像現像用トナーの製造方法

";
(9) “The relationship between the glass transition temperature Tg _A of the toner not including the reusable component, the Tg _B of the toner including the reusable component, and the binder resin Tg _R satisfies the following relational expression. A method for producing a toner for developing an electrostatic charge image according to any one of items (1) to (8), wherein:

」；
（１０）「前記トナーは、静電荷像保持体に対向して配置されるトナー担持体と、トナー担持体に加圧接触し、トナーをトナー担持体上に供給する供給部材を備えた非磁性一成分現像装置に用いることを特徴とする前記第（１）項乃至第（９）項のいずれかに記載の静電荷像現像用トナーの製造方法」

";
(10) “The toner includes a toner carrier disposed opposite to the electrostatic charge image carrier, and a non-magnetic member provided with a supply member that is in pressure contact with the toner carrier and supplies the toner onto the toner carrier. The method for producing a toner for developing an electrostatic charge image according to any one of items (1) to (9), wherein the toner is used for a one-component developing device.

The above-mentioned object of the present invention is solved by the following present invention.
(11) “Toner containing at least a binder resin and a colorant, wherein the colorant contains at least carbon black. It is obtained by a production method including a re-kneading step that is reused as a used component, and does not contain the tan δ _B (1 KHz) of the toner containing the reused component in the re-kneading step and the reused component. The toner for developing an electrostatic charge image is characterized in that the tan δ _A (1 KHz) of the toner in the state is a condition satisfying the following relationship:

（ただしtanδ（１ＫHz）は周波数１ＫHzにおけるトナーの誘電体損である。）」；
（１２）「前記再利用成分は、該再利用成分を除くトナー組成物１００重量部に対し、５〜４０重量部の比率で再混練に用いられたものであることを特徴とする前記第（１１）項に記載の静電荷像現像用トナー」；
（１３）「前記カーボンブラックの平均一次粒子径は、１５ｎｍ〜５０ｎｍであることを特徴とする前記第（１１）項又は第（１２）項に記載の静電荷像現像用トナー」；
（１４）「前記カーボンブラックのＢＥＴ比表面積は、８０ｍ^２／ｇ〜１４０ｍ^２／ｇであることを特徴とする前記第（１１）項乃至第（１３）項のいずれかに記載の静電荷像現像用トナー」；
（１５）「前記tanδ_Ａ（１ＫHz）が０．００３より小さいことを特徴とする前記第（１１）項乃至第（１４）項のいずれかに記載の静電荷像現像用トナー」；
（１６）「前記カーボンブラックは、結着樹脂との前処理が行われず、前記再混練工程で、再利用成分と共に混練に用いられたものであることを特徴とする前記第（１１）項乃至第（１５）項のいずれかに記載の静電荷像現像用トナー」；
（１７）「前記再混練工程は、前記再利用成分と、該再利用成分を除くトナー組成物原料とを４０℃〜６５℃の範囲で溶融混練するものであることを特徴とする前記第（１１）項乃至第（１６）項のいずれかに記載の静電荷像現像用トナー」；
（１８）「前記再利用成分を含まない状態のトナーをテトラヒドロフラン（ＴＨＦ）に溶解／分散させたときの上澄み液のハロゲン光による全光線透過率をＴ_Ａ（％）、前記再利用成分を含む状態のトナーをテトラヒドロフラン（ＴＨＦ）に溶解／分散させたときの上澄み液のハロゲン光による全光線透過率をＴ_Ｂ（％）としたとき、Ｔ_ＡとＴ_Ｂが下記関係式を満たすことを特徴とする前記第（１１）項乃至第（１７）項のいずれかに記載の静電荷像現像用トナー

(Where tan δ (1 kHz) is the dielectric loss of the toner at a frequency of 1 kHz.)
(12) The above-mentioned recycle component is used for re-kneading at a ratio of 5 to 40 parts by weight with respect to 100 parts by weight of the toner composition excluding the recycle component. The toner for developing an electrostatic charge image according to item 11);
(13) “The toner for developing an electrostatic charge image according to (11) or (12) above, wherein an average primary particle diameter of the carbon black is 15 nm to 50 nm”;
(14) "The BET specific surface area of the carbon ^black, 80m ² / ^g~140m 2 / the first (11), characterized in that g is a term to the (13) electrostatic charge image according to any one of Items Developing toner ";
(15) "The toner for developing an electrostatic charge image according to any one of (11) to (14) above, wherein the tan δ _A (1 kHz) is smaller than 0.003";
(16) The item (11) to the item (11), wherein the carbon black is used for kneading together with a reuse component in the re-kneading step without being pretreated with a binder resin. The electrostatic image developing toner according to any one of Items (15);
(17) The above-mentioned re-kneading step is characterized in that the reusable component and the toner composition raw material excluding the reusable component are melt kneaded in the range of 40 ° C. to 65 ° C. The toner for developing an electrostatic image according to any one of items 11) to (16) ";
(18) “T _A (%) is the total light transmittance by halogen light of the supernatant when the toner in a state not containing the reusable component is dissolved / dispersed in tetrahydrofuran (THF), and the reusable component is contained. when the supernatant total light transmittance by the halogen light when dissolved / dispersed in tetrahydrofuran (THF) the toner state was T _{B (%),} characterized in that T _a and T _B satisfy the following equation The electrostatic image developing toner according to any one of (11) to (17)

」；
（１９）「前記再利用成分を含まない状態のトナーのガラス転移温度Ｔｇ_Ａと前記再利用成分を含む状態のトナーのＴｇ_Ｂと、前記結着樹脂Ｔｇ_Ｒの関係が下記関係式を満たすことを特徴とする前記第（１１）項乃至第（１８）項のいずれかに記載の静電荷像現像用トナー

";
(19) “The relationship between the glass transition temperature Tg _A of the toner not containing the reusable component, the Tg _B of the toner containing the reusable component, and the binder resin Tg _R satisfies the following relational expression. The electrostatic image developing toner according to any one of (11) to (18), wherein

」；

";

Furthermore, the above object of the present invention is solved by the following present invention.
(20) A non-magnetic one-component developing device comprising a toner carrier disposed opposite to an electrostatic charge image carrier, and a supply member that is in pressure contact with the toner carrier and supplies toner onto the toner carrier Wherein the toner is the toner according to any one of (11) to (19) above;
(21) “Non-magnetic one-component developer is supplied onto a developer carrying member by a developer supply member, and is supplied to an electrostatic charge image holding member disposed opposite to the developer carrying member, thereby forming an electrostatic image. A non-magnetic one-component development, wherein the toner according to any one of (11) to (19) is used as the non-magnetic one-component developer. apparatus"

  According to the present invention, in a method for producing a toner containing at least carbon black as a colorant, the toner is obtained by reusing a predetermined outer particle diameter component, and a high quality image can be obtained over a long period of time even under severe use conditions. It became possible to provide.

Hereinafter, the present invention will be described in detail.
The present inventors have used carbon black-containing toner under process conditions where the toner is easily damaged like the non-magnetic one-component development method by improving the dispersibility of carbon black in the toner particles. It was found that a stable image can be provided over a long period of time.
Furthermore, it is possible to prevent carbon black from agglomerating in the toner particles and to provide a stable image over a long period of time by controlling the production conditions even when a production method in which the predetermined outer particle size component is returned to the kneading process is applied. I found it.

  As an index indicating the degree of dispersibility of carbon black, as shown on page 241 of “Characteristics of Carbon Black and Optimum Formulation and Utilization Technology (issued by Technical Information Association)”, dielectric loss factor ε ″ and dielectric constant ε ′ There is a loss tangent tan δ expressed by the ratio of (in the present invention, the dielectric loss tan δ is synonymous). The smaller this value, the better the dispersibility of carbon black. The inventors of the present invention have found that the value of tan δ at a frequency of 1 KHz is closely related to toner aggregates that are generated by long-term use in the non-magnetic one-component development system. Further, when the production method for returning the predetermined outer particle size component back to the kneading step is applied, the generation of toner aggregates by repeating the kneading step twice has been a problem until now. The value of tan δ at a frequency of 1 KHz is as follows: It has been found that the above problem can be solved by producing toner by the production method specified as follows.

That is, the toner manufacturing method of the present invention reuses the predetermined outer particle size component generated in the classification step as a toner reuse component in the kneading step again, and does not include the reuse component (predetermined outer particle size component). Kneading is performed including a predetermined outer particle size component which is a recycle component under the condition that tan δ _A (1 KHz) of the toner in the state and tan δ _B (1 KHz) of the toner including the recycle component are as follows.

（ただしtanδ（１ＫHz）は周波数１ＫHzにおけるトナーの誘電体損である。）
この値が１．１５より大きい場合、再練トナー粒子中でカーボンブラックが凝集体を作った状態で存在するため、トナー粒子中での樹脂単独領域が多くなることもあって、長期間での使用で樹脂同士が融着しトナー凝集体が発生しやすくなる。また、再利用成分（所定外粒径成分）を含まない状態のトナーのtanδ_Ａは０．００３より小さいことが好ましい。０．００３以上であると上記同様、再利用成分を含まない状態のトナー粒子中でカーボンブラックが凝集体を作った状態で存在するため、トナー粒子中での樹脂単独領域が多くなる等の理由で、長期間での使用で樹脂同士が融着しトナー凝集体が発生しやすくなることが判った。

(Where tan δ (1 kHz) is the dielectric loss of the toner at a frequency of 1 kHz.)
If this value is larger than 1.15, carbon black is present in the state of agglomerated in the re-milled toner particles, and the resin single region in the toner particles may increase, In use, the resins are fused together, and toner aggregates are easily generated. Further, it is preferable that the tan δ _A of the toner not containing the reusable component (predetermined outer particle size component) is smaller than 0.003. The reason why carbon black is present in an aggregated state in the toner particles that do not contain a reusable component, if the number is 0.003 or more, as described above. Thus, it was found that the toner aggregates easily when the resins are fused for a long period of time.

The toner of the present invention has a total light transmittance when dissolved / dispersed in tetrahydrofuran (THF).
In the case of a state, without reuse component toner When _{T A 5 ≦ T A ≦ 40} ,
If in the case of conditions including reusable component toner and _{T B 60 ≦ T B ≦ 95} ,
When the ratio between _{T B / T A 1.5 ≦ T} B / T A ≦ 9.5
It is preferable that
T _A, 5% T _B respectively, but the dispersion state of the carbon black in the toner particles is less than 60% means that a good, correspondingly, free is likely to occur to the toner particle surfaces. The presence of free carbon black leads to a decrease in toner fluidity and hinders good tribocharging. On the other hand, when T _A and T _B are larger than 40% and 95%, respectively, it means that the dispersion state of carbon black in the toner particles is bad, and carbon black aggregates exist. As a result, the resin single region in the toner particles increases, and the resin is fused with each other over a long period of use, and toner aggregates are easily generated.

When the toner of the present invention has a glass transition temperature Tg _A for a toner containing no reusable component, Tg _B for a toner containing a reusable component, and Tg _R for a binder resin. , | Tg _A −Tg _B | ≦ | Tg _R −Tg _B | When this relationship is lost, the resin is fused with each other over a long period of time, and toner aggregates are easily generated.

  The carbon black used in the present invention is not particularly limited, and commercially available ones can be used, but the average primary particle diameter is preferably 15 nm to 50 nm, more preferably 20 nm to 40 nm. If the average primary particle size is smaller than 15 nm, uniform dispersion is difficult and free carbon black is likely to be generated. On the other hand, if the average primary particle diameter is larger than 50 nm, the coloring power will be insufficient even if dispersed well, and if it is used in a large amount to increase the coloring power, the charge amount of the toner will decrease.

It is preferable that the BET specific surface area is ^{80m 2} / ^g~140m 2 / g, more preferably ^{90m 2} / ^g~120m 2 / g. When the BET specific surface area is less than 80 m ² / g, the coloring power is lowered and it is difficult to obtain a high-quality image. Conversely, if the BET specific surface area is smaller than 140 m ² / g, control in the kneading step becomes difficult to improve dispersion with the resin.

  The amount of carbon black used is preferably 2 to 10 parts by weight with respect to 100 parts by weight of toner in terms of colorability and dispersibility. Further, the carbon black used in the present invention is preferably used in the kneading step in the state of powder as it is without pretreatment with a binder resin (usually called a master batch). The cause is not clear, but the presence of carbon black aggregates in the toner particles is less when the powder is kneaded.

  As the binder resin used in the present invention, it is preferable to use a polyester resin that is suitable as a binder resin for a full-color toner from the viewpoint 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, and cracks and defects of the image due to insufficient strength of the toner layer occur, or an appropriate gloss is lost. For this reason, a polyester resin is used to maintain an appropriate gloss and excellent strength. The polyester resin can be generally obtained by an esterification reaction of a polyhydric alcohol and a polycarboxylic acid.

  Among the monomers constituting the polyester resin in the present invention, examples of alcohol monomers include trifunctional or higher polyfunctional monomers such as ethylene glycol, diethylene glycol triethylene glycol, 1,2-propylene glycol, and 1,3-propylene. Diols such as glycol, 1,4-butadieneol, neopentyl glycol, 1,4-butenediol, 1,5-pentanediol, 1,6-hexanediol, bisphenol A, hydrogenated bisphenol A, polyoxypropylene Bisphenol A alkylene oxide adducts such as 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, trimethylolethane , Trimethylolpropane, 1,3,5-trihydroxybenzene, and other trihydric or higher polyhydric alcohols.

  Among these monomers, those using bisphenol A alkylene oxide adduct as the main component monomer are particularly 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. In addition, the presence of alkyl groups on both sides of the bisphenol A skeleton acts as a soft segment in the polymer, and the color developability and image strength during toner fixing are improved. Of the bisphenol A alkylene oxide adducts, 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 -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, empor trimer acid , And their anhydrides, alkyl esters, alkenyl esters, aryl esters, and other trivalent or higher carboxylic acids.
Specific examples of the alkyl group, alkenyl group or aryl ester described herein include trimethyl 1,2,4-benzenetricarboxylate, triethyl 1,2,4-benzenetricarboxylate, and 1,2,4-benzenetricarboxylic acid. Tri-n-butyl, isobutyl 1,2,4-benzenetricarboxylate, tri-n-octyl 1,2,4-benzenetricarboxylate, tri-2-ethylhexyl 1,2,4-benzenetricarboxylate, 1,2,4- Examples thereof include tribenzyl benzenetricarboxylate and tris (4-isopropylbenzyl) 1,2,4-benzenetricarboxylate. Non-ester 1,2,4-benzenetricarboxylic acid can also be used as the acid monomer.

[Colorant]
The colorant used in the present invention includes at least a carbonaceous black colorant such as carbon black or lamp black. The carbonaceous colorant includes known colorants such as those obtained by adding a carboxy group to the surface, or those obtained by graft polymerization of a monomer to the surface active site.

[Additive]
As the charge control agent used in the present invention, a positive or negative charge control agent may be appropriately used according to the positive / negative of the charge charged on the photoreceptor.
As the negative charge control agent, for example, a resin or compound having an electron donating functional group, an azo dye, or a metal complex of an organic acid can be used.
Specifically, Bontron (product numbers: S-31, S-32, S-34, S-36, S-37, S-39, S-40, S-44, E-81, E-82, E -84, E-86, E-88, A, 1-A, 2-A, 3-A) (above, manufactured by Orient Chemical Industry Co., Ltd.)), Kaya Charge (part numbers: N-1, N-2), Kaya Set Black (Part No .: T-2, 004) (Nippon Kayaku Co., Ltd.), Eisenspiron Black (T-37, T-77, T-95, TRH, TNS-2) Tsuchiya Chemical Industry Co., Ltd.)), FCA-1001-N, FCA-1001-NB, FCA-1001-NZ (manufactured by Fujikura Kasei Co., Ltd.)) and the like can be used.
As the positive charge control agent, for example, a basic compound such as a nigrosine dye, a cationic compound such as a quaternary ammonium salt, a metal salt of a higher fatty acid, or the like can be used. Specifically, Bontron (part numbers: N-01, N-02, N-03, N-04, N-05, N-07, N-09, N-10, N-11, N-13, P -51, P-52, AFP-B) (above, manufactured by Orient Chemical Co., Ltd.), TP-302, TP-415, TP-4040 (above, manufactured by Hodogaya Chemical Co., Ltd.), Copy Blue PR, Copy Charge ( Product number: PX-VP-435, NX-VP-434) (manufactured by Hoechst), FCA (product number: 201, 201-B-1, 201-B-2, 201-B-3, 201-PB, 201-PZ, 301) (manufactured by Fujikura Kasei Co., Ltd.), PLZ (product numbers: 1001, 2001, 6001, 7001) (manufactured by Shikoku Kasei Kogyo Co., Ltd.) and the like can be used.
In particular, it is preferable to use a salicylic acid metal salt from the viewpoint that the charge rising property of the toner replenished by the replenishment mechanism is fast and the charge amount distribution is sharp even in a usage environment where stress on the toner is applied over a long period of time. . The amount of the charge control agent used is preferably 2 parts by weight or more based on the toner particles. When the amount is less than 2 parts by weight, the charge rising property and the charge amount are not sufficient, and the image is easily affected. This is particularly noticeable when a low acid value binder resin is used. Such a charge control agent can also be used externally added to the toner.

In addition to the binder resin, the colorant, and the charge control agent, a wax for preventing offset can be added to the toner particles of the present invention as necessary. Examples of the wax include animal wax such as rice wax, candelilla wax, carnauba wax, lanolin, petroleum wax such as paraffin wax, microcrystalline wax, petrolatum, low density polyethylene, high density polyethylene, polyethylene copolymer. Polyolefin, polypropylene copolymer, acid value-modified polyethylene, acid-modified polyethylene, graft-modified polyethylene with an aromatic monomer, thermal decomposable low-density polyethylene, thermal decomposable polypropylene and other olefinic waxes can be used. .
Specifically, HNP (part numbers: 1, 3, 9, 10, 11, 12), SP (part numbers: 0145, 1035, 3040, 3035, 0110), Hi-Mic (part numbers: 2095, 1080, 3080, 1070). , 2065, 1045, 2045), POLYCOAT (part number: 1025, 1455, 2255, 3030, 3155), NEOPALAX (part number: 2545, 3240), PALVAX (part number: 1230, 1335, 1430), CARTOWAX-3025, BONTEX (part number) : 0011, 2266), S-0750, OX (part numbers: 261BN, 0550, 2251, 1949), NSP-8070, NPS (part numbers: L-70, 6010, 9210), HAD (part numbers: 5080, 5670), WEISSEN -0453, JP-150 , LUVAX (product numbers: 1266, 2191, 1151, 0321), EMUSTAR (product numbers: 0001, 042X, 0135, 0136, 0164, 358) (above, manufactured by Nippon Wax Co., Ltd.), high wax (product numbers: 800P, 400P, 200p) , 100P, 720P, 410P, 420P, 320P, 210P, 220P, 110P, 405MP, 310MP, 320MP, 210MP, 220MP, 4051E, 4052E, 4202E, 1105A, 2203A, 1120H, 1140H, 1160H, NL100, NL200, NL500, NL800 NP055, NP105, NP505, NP805) (manufactured by Mitsui Petrochemical Co., Ltd.) and the like can be used. The amount of the wax used is preferably 1 to 15 parts by weight with respect to 100 parts by weight of the toner from the viewpoint of fixability and developability.

  Silica, titania, alumina, cerium oxide, strontium titanate, calcium carbonate, magnesium carbonate, calcium phosphate, etc. can be used as the inorganic fine particles as additives used in the present invention. It is more preferable to use silica fine particles that have been subjected to chemical treatment or titanium oxide that has undergone a specific surface treatment. As silica fine particles, Aerosil (Part No .: 130, 200V, 200CF, 300, 300CF, 380, OX50, TT600, MOX80, MOX170, COK84, RX200, RY200, R972, R974, R976, R805, R811, R812, T805, R202, VT222, RX170, RXC, RA200, RA200H, RA200HS, RM50, RY200, REA200 (above, manufactured by Nippon Aerosil Co., Ltd.), HDK (part numbers: H20, H2000, H3004, H2000 / 4, H2050EP, H2015EP, H3050EP, KHD50), HVK2150 (above, manufactured by Wacker Chemical Co., Ltd.), Cabozil (Part No .: L-90, LM-130, LM-150, M-5, PTG, MS-55, H-5, HS- , EH-5, LM-150D, M-7D, MS-75D, TS-720, TS-610, TS-530) (or, can be used Cabot Corp.).

  The amount of the additive is preferably 0.1 to 3.0 parts by weight with respect to 100 parts by weight of the toner base. If the amount is less than 0.1 parts by weight, a necessary charge amount cannot be obtained. On the other hand, if the amount is more than 3.0 parts by weight, the initial characteristics cannot be maintained such that the external additive is detached from the toner surface or buried in the toner particles due to long-term stirring in the developing device.

[Production of toner]
Next, a toner manufacturing method will be described.
The toner of the present invention is manufactured through a mechanical mixing step, a melt-kneading step, a pulverizing step, and a classification step in order from a toner composition containing at least a binder resin, a colorant, carbon black, and a charge control agent. The Further, the toner of the present invention is produced by mechanically mixing again a predetermined outer particle size component obtained in the pulverization step and / or classification step as a toner composition in the mechanical mixing step. When a predetermined outer particle size component is mechanically mixed again as a toner composition for production, the used amount of the predetermined outer particle size component is 5 to 40 with respect to 100 parts by weight of the toner composition excluding the predetermined outer particle size component. It is preferable that it is a ratio of a weight part, More preferably, it is 10-35 weight part. The predetermined outer particle size component becomes relatively brittle when kneading is repeated twice, and this can be used to improve grindability. Therefore, if the amount is less than 5 parts by weight, this effect is weakened. On the other hand, if the amount exceeds 40 parts by weight, there will be problems in storage stability and durability, and the reason is not clear, but the carbon black is present in the toner particles as aggregates, and the resins are fused with each other over a long period of use. Toner aggregates are likely to occur.
Here, the “predetermined outer particle size particle” in the present invention means that toner particles having a particle size of 4 μm or less are 70% by number or more, and the “predetermined particle size (product)” is a particle of 4 μm or less. It means toner particles having a diameter of 10% by number or less. The intermediate toner particles having a particle diameter of 4 μm or less exceeding 10% by number and less than 70% by number may be further subjected to wind classification if used in large quantities. A small amount such as a used developer can be reused in the kneading step in the present invention.
The kinetic properties (tan δ value ratio) in the present invention can be achieved, for example, by improving the dispersibility of carbon black in toner particles. For this purpose, as described above, the kneading time (usually 25 minutes to 4 hours) is important. In addition, the kneading time is set to a lower value (for example, a temperature lower than Tg of the binder resin component), and the carbon black is firmly included in the harder binder resin component, not only the importance of the kneading time. Applying a shearing force that unwinds the carbon black agglomerates that are held in it by stretching mechanically (stretching and shredding) while preventing the viscosity of non-kneaded components from decreasing. Is effective. It is also effective to use carbon black in the kneading step in the state of powder as it is without pretreatment with binder resin (usually called masterbatch), and as a fluidity improver for powder toner. It is also effective to add a large amount of inorganic fine particles, and to reduce the amount of wax added if it is not a magnetic toner, and to increase the dispersion of wax particles (reduce the particle size). Is even more effective.

  In the method for producing a toner of the present invention, a mixing step (pre-kneading step) in which a binder resin (virgin resin component), an additive (carbon black, a charge control agent), and a predetermined outer particle size component are mechanically mixed. There is no particular limitation as long as it is carried out using a normal mixer with rotating blades.

  After the above mixing step 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. It is important that this melt-kneading is performed under appropriate conditions so as not to break the molecular chain of the binder resin. Specifically, for example, when the binder resin component is a polyester resin, it is preferably melt-kneaded in the range of 40 ° C to 65 ° C. When the melt kneading temperature is lower than 40 ° C, the cutting is severe, and when it is higher than 65 ° C, the dispersion does not proceed as described above.

  After 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 or pulverizing with a narrow gap between a rotating rotor and a stator that rotate mechanically is preferably used. After the above pulverization process is completed, the pulverized product is classified in an air stream by centrifugal force or the like to produce a toner base having a predetermined particle size, for example, a weight average particle size of 5 to 12 μm. At this time, it is particularly preferable that the toner has a weight average particle diameter of 5 to 9 μm, a small particle diameter such that 10% by number or less of toner particles having a particle diameter of 4 μm or less are present, and a sharp particle size distribution. In addition, the predetermined outer particle size component obtained in the pulverization step and / or the classification step is used by returning to the mixing step as a reused portion.

  Next, in order to improve fluidity, storage stability, developability and transferability as a toner, inorganic fine particles such as hydrophobic silica and titanium oxide fine powder mentioned above are further added to the toner base obtained through the above steps. You may mix. For mixing the additives, a general powder mixer is used, but it is preferable to adjust the internal temperature by installing a jacket or the like. In order to change the load history applied to the additive, the additive may be added in the middle or gradually. Of course, the rotation speed, time, temperature, etc. of the mixer may be changed. For example, a strong load may be given first and then a relatively weak load, or vice versa. Examples of the mixer that can be used include a V-type mixer, a rocking mixer, a lady gay mixer, a nauter mixer, and a Henschel mixer.

Next, the developing device of the present invention will be described.
FIG. 1 is a schematic diagram for explaining a developing apparatus according to the present invention, and the following modifications also belong to the category of the present invention. The photoreceptor (1) is formed by providing an outermost layer containing a photosensitive layer and a filler on a conductive support. The photoreceptor (1) has a belt-like shape, but may be a drum-like one. The developing device (2) includes a developing sleeve (6), a toner replenishing roller (8), a layer regulating member (7), and a developer conveying member (9), and the layer thickness regulating member (7) and the toner replenishing. Each of the rollers (8) is in contact with the developing sleeve (6). The toner supply roller (8) is located upstream of the layer thickness regulating member (7) in the rotation direction of the developing sleeve (6), and the developing sleeve (6) is in contact with the latent image carrier, for example, the photosensitive member (1). It is facing non-contact. The surface of the toner supply roller (8) rotates in the forward direction at the contact portion with the developing sleeve (6). The toner supply roller (8) is rotatable. Further, the layer thickness regulating member (7) may be cylindrical as shown in the figure, may be a blade or the like, may be rotatable, may be intermittently rotated, or may be fixed.

  The toner is agitated by the developer conveying member (9), slidably rubbed against the developing sleeve (6) by the rotation of the toner replenishing roller (8), and then regulated by the layer thickness regulating member (7). It is carried as a thin layer on top. In the developing unit, by applying a bias between the developing sleeve (6) and the photosensitive member (1), the toner on the developing sleeve (6) adheres to the electrostatic image on the photosensitive member (1), and development is performed. Done. The developing device shown in FIG. 1 has a toner replenishing cartridge (10) and a developing unit. When the toner in the toner replenishing cartridge runs out, only the toner replenishing cartridge is replaced. The connecting portion between the toner replenishing cartridge and the developing unit may or may not have a partition (partition plate (11)), and may further prevent backflow of toner from the developing unit to the toner replenishing cartridge. For example, a method of preventing the backflow of the toner by installing it with a mylar or the like so as to be opened only on the side of the development unit so as to prevent the backflow of the toner from the development unit to the toner supply cartridge is preferable.

<Measurement of dielectric loss of toner>
A TR-10C type dielectric loss measuring device (Ando Electric Co., Ltd.) was used as an apparatus for measuring the dielectric loss of toner. First, 3.0 to 3.1 g of toner is weighed, and a 6 t / cm ² load is applied for 1 minute to form a disk having a diameter of 40 mm and a thickness of 2.2 to 2.5 mm to obtain a measurement sample. This sample is fixed to a jig and measured at room temperature (25 ° C.). The frequency is 1 kHz and the ratio is 1 × 10 ⁻⁹ (ratio is a constant determined for each measurement frequency at the time of measurement, and when the measurement frequency is 1 kHz, the corresponding ratio is 1 × 10 ⁻⁹ . is there.).
From the capacitance (C) and conductance (R) obtained by the measurement, the dielectric loss tan δ was determined by the following equation.
Dielectric loss tan δ = ratio × (R−R ₀ ) / 2πfC × 10 ⁻¹²
C (pf): Capacitance R ₀ (S): Conductance at zero adjustment R (S): Conductance at measurement f (Hz): Measurement frequency

<Measurement of transmittance of toner in THF>
The toner transmittance can be measured as follows.
(I) Preparation of Toner Dispersion 20 ml of tetrahydrofuran (THF) solution is placed in a 30 ml sample bottle (Nippon Denka Glass: SV-30), and 30 mg of toner is immersed on the liquid surface to cover the bottle. Then, it is made to shake for 2 minutes at 200 times / min with a Yayoi type shaker (model: YS-8D). At this time, with respect to the shaking angle, if the top (vertical) of the shaker is 0 degree, the shaking column is moved 15 degrees forward and 20 degrees backward. After shaking, the sample bottle is taken out and the dispersion-finished liquid after standing for 24 hours is used as a measurement dispersion liquid.
(Ii) Transmittance measurement The dispersion obtained in (i) is placed in a cell having a length of 10 mm, a width of 30 mm, and a height of 45 mm, and a total light transmittance T (using a haze computer HGM-2DP (manufactured by Suga Test Instruments Co., Ltd.)). %).

<Measurement of Glass Transition Temperature Tg of Toner>
A TG-DSC system TAS-100 (manufactured by Rigaku Corporation) was used as an apparatus for measuring Tg, which is the glass transition temperature of the toner. First, about 10 mg of a sample is placed in an aluminum sample container, which is placed on a holder unit and set in an electric furnace. DSC measurement (first time) was performed by heating from room temperature to 150 ° C. at a temperature rising rate of 10 ° C./min. Thereafter, the sample was allowed to stand at 150 ° C. for 10 minutes, the sample was cooled to room temperature, left for 10 minutes, and again heated to 150 ° C. at a heating rate of 10 ° C./min in a nitrogen atmosphere to perform DSC measurement (second time). Tg was calculated from the contact point between the tangent line of the endothermic curve near the Tg and the base line using the analysis system in the TAS-100 system. In the present invention, Tg of the first DSC measurement was used.

<Measurement of toner particle size and particle size distribution>
As an apparatus for measuring the particle size distribution of toner particles by the Coulter counter method, there are Coulter Counter TA-II and Coulter Multisizer II (both manufactured by Coulter). The measurement method is described below.
First, 0.1 to 5 ml of a surfactant (preferably alkylbenzene sulfonate) is added as a dispersant to 100 to 150 ml of an aqueous electrolytic solution. Here, the electrolytic solution is a solution prepared by preparing a 1% NaCl aqueous solution using first grade sodium chloride. For example, ISOTON-II (manufactured by Coulter) can be used. Here, 2 to 20 mg of a measurement sample is further added. The electrolytic solution in which the sample is suspended is subjected to a dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes, and the measuring device is used to measure the volume and number of toner particles or toner using a 100 μm aperture as an aperture. Volume distribution and number distribution are calculated. From the obtained distribution, the weight average particle diameter (D4) and the number average particle diameter of the toner can be obtained.
As channels, 2.00 to less than 2.52 μm; 2.52 to less than 3.17 μm; 3.17 to less than 4.00 μm; 4.00 to less than 5.04 μm; 5.04 to less than 6.35 μm; 6 .35 to less than 8.00 μm; 8.00 to less than 10.08 μm; 10.08 to less than 12.70 μm; 12.70 to less than 16.00 μm; 16.00 to less than 20.20 μm; Uses 13 channels of less than 40 μm; 25.40 to less than 32.00 μm; 32.00 to less than 40.30 μm, and targets particles having a particle size of 2.00 μm to less than 40.30 μm.

<Measurement of average particle size of carbon black>
The average particle size can be measured as follows.
After adding 0.3 parts by weight of carbon black to 100 parts by weight of chloroform and dispersing by irradiating with 200 KHz ultrasonic waves for 20 minutes, the obtained dispersion sample is fixed to the support film. This was photographed with a transmission electron microscope, and the particle diameter was measured by the diameter on the photograph and the magnification of the photograph. This operation was performed 1500 times and obtained by calculating the average of those values.

<Measurement of BET specific surface area of carbon black>
The BET specific surface area was determined by a nitrogen adsorption method using the BET equation. That is, the nitrogen adsorption amount of carbon black was measured by a low temperature nitrogen adsorption method using a low temperature nitrogen adsorption apparatus Soptomatic 1800 (manufactured by Carlo Elba Co.), and then calculated by a multipoint method using the BET equation.

Hereinafter, the present invention will be specifically described with reference to production examples and examples, but this is not intended to limit the scope of the present invention. In the following, “parts” indicating the blending amount of the mixture and the like are all parts by weight.
<Examples of polyester resin synthesis>
Synthesis Example 1 [Polyester resin a]
In a four-necked separable flask with a stirrer, thermometer, nitrogen inlet, flow-down condenser, and condenser, 740 g of polyoxypropylene (2,2) -2,2-bis (4-hydroxyphenyl) propane, polyoxy Esterification catalyst of 300 g of ethylene (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 Added with.
Subsequently, it was made to react at 210 degreeC under nitrogen atmosphere for 8 hours, and then it was made to react for 5 hours, stirring at 210 degreeC pressure reduction, and the [polyester resin a] was synthesize | combined. [Polyester resin a] had a glass transition temperature (Tg) of 69 ° C. and an Mw / Mn ratio of 5.1.

Synthesis Example 2 [Polyester resin b]
A stirrer, a thermometer, a nitrogen inlet, a flow-down condenser, a four-neck separable flask with a cooling tube, 650 g of polyoxypropylene (2,2) -2,2-bis (4-hydroxyphenyl) propane, polyoxy 650 g of ethylene (2,2) -2,2-bis (4-hydroxyphenyl) propane, 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. [Polyester Resin b] was synthesized using the same equipment and the same formulation as [Polyester Resin a] with the reaction time shortened.
[Polyester resin b] obtained had a glass transition temperature (Tg) of 66 ° C. and an Mw / Mn ratio of 2.7.

Synthesis Example 3 [Polyester resin c]
[Polyester resin c] was synthesized in the same manner as [Polyester resin b] with respect to the prescription amount, and by the same method as [Polyester resin a] with respect to other synthesis methods.
The obtained [Polyester resin c] had a glass transition temperature (Tg) of 71 ° C. and an Mw / Mn ratio of 4.6.

<Preparation example of titanium oxide>
Titanium oxide was produced by using a wet precipitation method in which ilmenite was used as an ore, dissolved in sulfuric acid to separate iron, and TiOSO ₄ was hydrolyzed to produce titanium oxide. After firing the titanium oxide fine particles, wet pulverization is performed, coarse particles are cut, filtered, washed with water, dried, a dilute hydrous alumina solution is added, filtered and dried to obtain alumina-coated titanium oxide. It was. Next, wet pulverization is again carried out in an aqueous solution, coarse particles are cut, treated with an organic treatment agent, filtered, washed with water, dried, and pulverized in a dry manner to obtain an external additive. As raw material titanium oxide, untreated titanium oxide having a primary particle size of 0.01 to 0.03 μm and a specific surface area of 60 to 140 m ² / g was used. Table 1 shows the surface treatment conditions of the obtained titanium oxide (T1 to T3).

<Example 1>
(Raw material composition)
Binder resin: Polyester resin a: 100 parts Colorant: Carbon black C-44
(Mitsubishi Chemical Corporation average particle size: 24 nm, BET specific surface area: 125 m ² / g)
... 5 parts Charge control agent: Bontron E-84 (manufactured by Orient Chemical Co., Ltd.) ... 2 parts The toner material was mixed using a Henschel mixer (manufactured by Mitsui Miike), and then the roll surface was brought to 60 ° C. Kneading was performed for 30 minutes with the set two rolls. Thereafter, after rolling and cooling and coarse pulverization, a jet mill type pulverizer (I-2 type mill: manufactured by Nippon Pneumatic Industrial Co., Ltd.) and a wind classifier using a swirling flow (DS classifier: manufactured by Nippon Pneumatic Industrial Co., Ltd.) A black toner base having a weight average particle diameter of 6.8 μm and toner particles having a particle diameter of 4 μm or less is 9.8% by number. Furthermore, 2.4 parts of hydrophobic silica (H2000: manufactured by Clariant Japan, BET specific surface area 120 m ² / g) and 0.4 parts of titania T1 were added and mixed with a Henschel mixer to obtain virgin toner A1. The toner A1 has a weight average particle diameter of 6.8 μm, toner particles having a particle diameter of 4 μm or less, 9.6% by number, dielectric loss tan δ _A is 0.0023, transmittance T _A is 30%, and glass transition temperature Tg. _A was 68 ° C.
Next, 20 parts of a predetermined outside particle size component generated in the process of producing the virgin toner, other toner compositions (raw materials), and the production method were the same as those of the virgin toner to obtain a re-kneaded toner B1. The weight average particle diameter of the toner B1 is 6.8 [mu] m, the toner particles are 9.1% by number having a particle size 4 [mu] m, dielectric loss tan [delta _B is 0.0026, transmittance _{T B} is 80%, the glass transition temperature Tg _B was 66 ° C.

<Examples 2-7, Comparative Examples 1-3>
Virgin toners A2 to A10 and re-kneaded toners B2 to B10 were prepared in the same manner as in Example 1 except for the raw materials and the kneading temperature. Details are shown in Table 2. Table 3 shows the content of toner particles having a particle size of 4 μm or less, dielectric loss tan δ _A and dielectric loss tan δ _B , transmittance T, and glass transition temperature Tg of each toner. The carbon black used is shown below.
Carbon black C-44
(Mitsubishi Chemical Corporation average particle size: 24 nm, BET specific surface area: 125 m ² / g)
Carbon black REGAL400R
(Mitsubishi Chemical Corporation average particle size: 25 nm, BET specific surface area: 96 m ² / g)
Carbon black C-20
(Mitsubishi Chemical Corporation average particle size: 40 nm, BET specific surface area: 56 m ² / g)

  The toner for developing electrostatic images obtained in each of Examples and Comparative Examples was subjected to a copy test using “IMAIO NEO C320” (manufactured by Ricoh), and evaluated the following items. In the copy test, toner replenishment was repeated 6 times, and the copy test was performed in the 100,000-sheet monochrome mode. Immediately after the start of the copy test and after copying 100,000 sheets, measurement of the toner charge amount on the developer carrier in the developing unit, image density, background stain, and presence of white streak image using the obtained image evaluated.

<Evaluation items>
(1) Charge amount on developer carrier Q / M
The toner adhering on the developer carrying member during solid image development was sucked, and the charge amount was measured with a Q meter to determine the weight and ratio of the sucked toner. The average of the three points of the center and both ends (50 mm closer to the center from both ends) of the developer carrier was used.
(2) Image density After outputting a solid image, the image density was measured with a 938 spectrodensitometer (manufactured by X-Rite).
(3) Background stain The blank image is stopped during development, the developer on the developed photoreceptor is transferred to tape, and the difference from the image density of the untransferred tape is measured by 938 Spectrodensitometer (manufactured by X-Rite) ).
(4) White streaks Immediately after the start of the copy test and after 100,000 copies were made, the toner carrier thin layer formation and the presence of white streak images were evaluated. In the table, ◯, Δ and × indicate the following states.
○: Uniform and good condition Δ: White streak with a width of less than 0.3 mm is slightly seen, but the image does not show a streak clearly.
X: A white streak having a width of 0.3 mm or more is generated, and the image is clearly missing as a white streak in the image.

  The above evaluation results are shown in Table 4. From Table 4, the electrostatic image developing toners of Examples 1 to 7 of the present invention showed good performance in charge and image quality in the test using “IMAIO NEO C320” (manufactured by Ricoh) and maintained. It can be seen that there is almost no problem from the viewpoint of sex. On the other hand, the electrostatic charge image developing toners of Comparative Examples 1 and 3 already have a low image density in the initial stage. Further, after 100,000 sheets, white streaks and background stains occurred on the image. Further, the electrostatic charge image developing toner of Comparative Example 2 had no particular problem at the beginning, but after 100,000 sheets, the toner charge was reduced and white streaks and background stains were generated on the image.

It is the schematic for demonstrating the image development apparatus concerning this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Photoconductor 2 Developing device 6 Developing sleeve 7 Layer regulating member 8 Toner replenishing roller 9 Developer conveying member 10 Toner replenishing cartridge 11 Partition plate

Claims (21)

In the method for producing a toner containing at least a binder resin and a colorant, at least carbon black is included as the colorant, and the toner production method is configured to recycle a predetermined outer particle size component generated in the classification step. The toner is reused in the re-kneading step, and the toner contains tan δ _A (1 KHz) of the toner that does not contain the predetermined outer particle size component that is the reuse component, and tan δ of the toner that contains the reuse component. _A method for producing a toner for developing an electrostatic charge image, wherein _{B 2} (1 kHz) is kneaded containing the reusable component under the following relationship.

(Where tan δ (1 kHz) is the dielectric loss of the toner at a frequency of 1 kHz.) 2. The electrostatic charge image developing device according to claim 1, wherein the reuse component is used in the re-kneading step at a ratio of 5 to 40 parts by weight with respect to 100 parts by weight of the toner composition excluding the reuse component. Toner manufacturing method. 3. The method for producing a toner for developing an electrostatic charge image according to claim 1, wherein the carbon black has an average primary particle diameter of 15 nm to 50 nm. BET specific surface area of the carbon ^black, 80m ² / ^g~140m 2 / g A method of manufacturing a toner according to any one of claims 1 to 3, characterized in that. The method for producing a toner for developing an electrostatic charge image according to claim 1, wherein the tan δ _A (1 kHz) is smaller than 0.003. 6. The electrostatic image developing toner according to claim 1, wherein the carbon black kneaded together with the reuse component is used in the re-kneading step without pretreatment with a binder resin. Production method. 7. The re-kneading step includes melt-kneading the reusable component and a toner composition raw material excluding the reusable component in a range of 40 ° C. to 65 ° C. A method for producing a toner for developing an electrostatic image as described in 1. T _A (%) of the total light transmittance of the supernatant obtained by dissolving / dispersing the toner not containing the reusable component in tetrahydrofuran (THF) by halogen light, and the toner containing the reusable component tetrahydrofuran when the supernatant total light transmittance by the halogen light when dissolved / dispersed and the T _{B (%)} in (THF), claims T _a and T _B is characterized by satisfying the following relationships A method for producing a toner for developing an electrostatic image according to any one of 1 to 7.

The relationship between the glass transition temperature Tg _A of the toner not containing the reuse component, the Tg _B of the toner containing the reuse component, and the binder resin Tg _R satisfies the following relational expression: A method for producing a toner for developing an electrostatic charge image according to claim 1.

The toner is a non-magnetic one-component developing device comprising a toner carrier disposed opposite to an electrostatic charge image carrier, and a supply member that is in pressure contact with the toner carrier and supplies the toner onto the toner carrier. The method for producing a toner for developing an electrostatic image according to claim 1, wherein the toner is used for a toner. A toner containing at least a binder resin and a colorant, wherein the toner contains at least carbon black as the colorant, and the toner recycles a predetermined outside particle size component generated in the classification process as a reuse component for the toner. Obtained by a manufacturing method including a re-kneading step to be used, and tan δ _B (1 KHz) of the toner containing the reusable component in the re-kneading step, and the toner in a state not containing the reusable component _A toner for developing an electrostatic charge image, wherein tan δ _A (1 KHz) is under the following condition.

(Where tan δ (1 kHz) is the dielectric loss of the toner at a frequency of 1 kHz.) 12. The static component according to claim 11, wherein the reuse component is used for re-kneading at a ratio of 5 to 40 parts by weight with respect to 100 parts by weight of the toner composition excluding the reuse component. Toner for charge image development. The electrostatic image developing toner according to claim 11 or 12, wherein the carbon black has an average primary particle diameter of 15 nm to 50 nm. BET specific surface area of the carbon ^black, 80m ² / ^g~140m 2 / g a toner according to any one of claims 11 to 13, characterized in that. The electrostatic image developing toner according to claim 11, wherein the tan δ _A (1 KHz) is smaller than 0.003. 16. The carbon black according to any one of claims 11 to 15, wherein the carbon black is used for kneading together with a reuse component in the re-kneading step without being pretreated with a binder resin. Toner for developing electrostatic images. 17. The re-kneading step includes melt-kneading the reusable component and a toner composition raw material excluding the reusable component in a range of 40 ° C. to 65 ° C. The electrostatic image developing toner according to claim 1. T _A (%) of the total light transmittance of the supernatant obtained by dissolving / dispersing the toner not containing the reusable component in tetrahydrofuran (THF) by halogen light, and the toner containing the reusable component tetrahydrofuran when the supernatant total light transmittance by the halogen light when dissolved / dispersed and the T _{B (%)} in (THF), claims T _a and T _B is characterized by satisfying the following relationships The toner for developing an electrostatic charge image according to any one of 11 to 17.

The relationship between the glass transition temperature Tg _A of the toner not containing the reuse component, the Tg _B of the toner containing the reuse component, and the binder resin Tg _R satisfies the following relational expression: The toner for developing an electrostatic image according to claim 11.

A non-magnetic one-component developing device comprising a toner carrier disposed opposite to an electrostatic charge image carrier and a supply member that pressurizes and contacts the toner carrier and supplies toner onto the toner carrier, A nonmagnetic one-component developing device, wherein the toner is the toner according to any one of claims 11 to 19. A non-magnetic one-component developer is supplied onto a developer carrying member by a developer supply member, and is supplied to an electrostatic charge image holding member disposed opposite the developer carrying member to develop an electrostatic charge image. 20. A non-magnetic one-component developing apparatus, wherein the toner according to claim 11 is used as the non-magnetic one-component developer.

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