JP4307297B2 - Magnetic toner - Google Patents

Description

  The present invention relates to a magnetic toner used in a recording method using an electrophotographic method, an electrostatic recording method, an electrostatic printing method, or a toner jet recording method.

  Conventional electrophotography uses a photoconductive substance to form an electrical latent image on a photoconductor by various means, and then develops the latent image with toner, such as paper if necessary. A method is known in which a toner image is transferred to a transfer material and then fixed by heating, pressure, heating and pressing, or solvent vapor to obtain a toner image.

  In the method for developing the toner, a magnetic one-component development system using a magnetic toner is preferably used because it does not require a carrier and is advantageous in downsizing the apparatus. In the toner used for the magnetic one-component development system, a considerable amount of fine powdered magnetic material is mixed and dispersed, and this presence state greatly affects the fluidity and triboelectric charging property of the toner.

  In magnetic toners, the particle size is reduced to improve dot reproducibility and the like. In this case, in order to improve the balance between the charging characteristics and the magnetic characteristics, conventionally, the amount of the magnetic material to be added is increased. However, in this case, the following problems occur. For one, the binder component in the toner is relatively reduced, so that the low-temperature fixability is inhibited. Second, fluidity tends to decrease as the saturation magnetization and true specific gravity of the toner increase, and the earing state on the toner carrier tends to exist as an aggregate, so that an appropriate earing state is formed. It becomes difficult to do. For this reason, the toner behaves as an agglomerate during development on the latent image carrier, and particularly when developing with an alternating electric field, the dielectric properties of the toner are involved in the formation of the agglomerate, resulting in image quality such as tailing. Deterioration and an increase in the amount of toner applied to the latent image tend to cause problems such as deterioration in image quality that causes an image to be crushed during transfer as well as fixing, and an increase in consumption. In order to solve these problems, attempts have been made to control the dielectric properties of the toner in order to improve the developability of the magnetic toner. For example, a toner is known in which the dispersibility of the magnetic material is improved by adjusting the dielectric loss tangent (see, for example, Patent Document 1). However, in this case, there is an effect in stabilizing the charging characteristics in a certain environment. However, when the toner particle size is reduced or the amount of magnetic material is reduced, the charging characteristics associated with environmental fluctuations and changes with time. The stabilization is not sufficient.

  In addition, a toner is known in which a ratio of dielectric loss tangent in a high temperature range and a normal temperature range is defined to reduce a change in chargeability due to the environment (see, for example, Patent Document 2). However, even in this case, it cannot be said that the environmental stability and low consumption of the magnetic toner are sufficient.

  It is also known to improve developability due to temperature characteristics of dielectric loss tangent at a low frequency, particularly reproducibility of an electrostatic charge image on a photoreceptor (see, for example, Patent Document 3). Furthermore, a developing method based on the correlation between the toner and the dielectric characteristics of the toner regulating member is known (see, for example, Patent Document 4). However, these techniques have not yet reached a level that can sufficiently satisfy the image disturbance due to the effect of applying the paper on the second side of the double-sided image formation described below.

If the separation output of the separation charge is small, the recording material will stick to the separated conveyance path, the recording material conveyance will become unstable, and the vibration caused by the friction between the conveyance path and the recording material will increase. Clogging and image distortion are major problems. Especially in high-speed output machines, the separation output is set large to avoid this point. However, because the separation output is large, even the toner image on the paper is strongly discharged, and the electrostatic adhesion between the paper and the toner is reduced. There is a problem that the toner image on the paper is similarly distorted due to minute vibrations or shocks on the subsequent conveyance path. In particular, when the image is disturbed when the paper after transfer separation enters the fixing device, it is very serious and may appear as a large image defect.

  The above-mentioned image defect due to the disturbance of the toner image at the time of separating the recording material (paper) appears not only in the low density image but also in the image formed by a thin line such as a line even in the high density image. . Particularly in a low density image, since the total amount of toner is small, the toner is easily neutralized, the adhesion between the toner image and the recording material is easily reduced, and a defective image is likely to occur.

Japanese Patent Laid-Open No. 10-221881 JP-A-6-118700 Japanese Patent Application Laid-Open No. 2002-221813 JP 2003-330223 A

  An object of the present invention is to provide a toner that solves the above-described problems. Specifically, an object of the present invention is to provide a magnetic toner capable of obtaining a stable image over a long period of time even in double-sided output regardless of the use environment.

  Another object of the present invention is to provide a magnetic toner excellent in offset property in high-speed fixing.

  Still another object of the present invention is to provide a magnetic toner that can reduce toner consumption.

  The inventors have improved the quality of double-sided images by controlling the true specific gravity, the amount of magnetization, and the dielectric properties of the toner, and are excellent in offset characteristics in high-speed fixing, and have stable charging characteristics even in various environments. The inventors have found that a toner can be obtained and have completed the present invention.

（２）前記トナーの１００ｋＨｚ、４０℃における誘電正接が２．０×１０^−３〜２．０×１０^−２であることを特徴とする（１）に記載の磁性トナー。
（３）前記磁性体の平均粒径が０．０８〜０．３０μｍであることを特徴とする（１）又は（２）に記載の磁性トナー。
（４）前記トナーは、トナー中のクロロホルム可溶分の酸価が１．０〜２０ｍｇＫＯＨ／ｇで、かつクロロホルム可溶分のエポキシ量が２．０〜０．１ｍｍｏｌ／ｇであることを特徴とする（１）〜（３）の何れかに記載の磁性トナー。

That is, the present invention is as follows.
(1) In a magnetic toner containing at least a binder resin and a magnetic material,
(I) The binder resin is a) a vinyl resin having a carboxyl group and a vinyl resin having an epoxy group, b) a vinyl resin having a carboxyl group and an epoxy group, and c) a vinyl in which the carboxyl group and the epoxy group are reacted. Contains one or more vinyl resins selected from the group consisting of resins,
(Ii) the weight average particle diameter of the toner is 5.0 to 9.0 μm;
(Iii) the true specific gravity of the toner is 1.1 to 1.6 g / cm ³ ;
(Iv) the saturation magnetization of the toner at a magnetic field of 796 kA / m is 20 to 35 Am ² / kg;
(V) The toner has a dielectric constant of 15 to 40 (pF / m) at 100 kHz and 40 ° C.
(Vi) A magnetic toner characterized in that the frequency dependence of the dielectric loss tangent (tan δ) of the toner at 40 ° C. satisfies the following formula (1).

(2) The magnetic toner according to (1), wherein the dielectric loss tangent of the toner at 100 kHz and 40 ° C. is 2.0 × 10 ^{−3 to} 2.0 × 10 ⁻² .
(3) The magnetic toner according to (1) or (2), wherein an average particle diameter of the magnetic material is 0.08 to 0.30 μm.
(4) The toner has an acid value of 1.0 to 20 mgKOH / g in a chloroform-soluble component in the toner and an epoxy amount in a chloroform-soluble component of 2.0 to 0.1 mmol / g. The magnetic toner according to any one of (1) to (3).

  According to the present invention, a magnetic toner that provides high-quality images stably with high-speed double-sided output without being affected by separation and neutralization application under various environments, has excellent offset characteristics in high-speed fixing, and consumes less toner. We were able to.

  Hereinafter, the present invention will be described in detail.

The magnetic toner of the present invention is a magnetic toner containing at least a binder resin and a magnetic material, wherein the binder resin is a) a vinyl resin having a carboxyl group and a vinyl resin having an epoxy group, and b) a carboxyl group and an epoxy group. C) one or more vinyl resin units selected from the group consisting of a vinyl resin having a carboxyl group and an epoxy group reacted, and the weight average particle size of the toner is 5.0. Is 9.0 μm, the true specific gravity of the toner is 1.1 to 1.6 g / cm ³ , the saturation magnetization of the toner at a magnetic field of 796 kA / m is 20 to 35 Am ² / kg, and the toner has a frequency of 100 kHz. The dielectric constant at 40 ° C. is 15 to 40 (pF / m), and the frequency dependence of the dielectric loss tangent (tan δ) at 40 ° C. of the toner is expressed by the following formula (1). Is a magnetic toner characterized by satisfying

  Conventionally, the value of dielectric loss tangent in a magnetic toner has been used as an index representing the ease of holding the charge amount. The lower this value, the higher the charge retention ability.

On the other hand, in the present invention, the rate of change due to the frequency of dielectric loss tangent is used as an index representing the stability of the charging characteristics of the toner in an electric field. In particular, when the separation charge is applied after transfer, the toner on the transfer paper is affected by an alternating electric field, and the electrostatic adhesion between the transfer paper and the toner is reduced.
Thin transfer paper images and second-side images in double-sided output are greatly affected by separation charge removal. The rate of change depending on the frequency of the dielectric loss tangent defined in the present invention represents a dielectric characteristic peculiar to the magnetic toner that can suppress the influence of this separation charge removal as much as possible. It is possible to quantitatively indicate the rate at which the toner charging characteristic on the transfer paper changes to the bias applied for separation of the transfer material.

  The study by the present inventors has found that the rate of change of the dielectric loss tangent of the toner at 2000 Hz and 100 KHz in particular has a high correlation with the change in the toner charging characteristics due to the application of the toner's separation and charge removal. The value of the dielectric loss tangent mainly represents the dispersion state of the colorant in the toner, and in the case of the magnetic toner, it is mainly affected by the dispersion state of the magnetic material. Therefore, when the same material is compared, the dielectric loss tangent takes a low value by improving the dispersibility. Further, the value of the dielectric loss tangent tends to take a large value as the measurement frequency increases, and this change increases as the amount of magnetic substance added decreases. This is because the influence of the dispersion state on the charge maintaining characteristics of the toner surface increases due to the relatively low content of the magnetic substance in the toner. The change in the toner surface charge due to the application of separation charge can be regarded as space charge polarization. By measuring the dielectric loss tangent at 100 KHz and comparing it with the dielectric loss tangent at 2000 Hz as the post-development state by the alternating electric field before the separation charge removal application. By measuring the rate of change, the image stability after separation and neutralization can be evaluated.

Here, when the rate of change in frequency of tangent tangent (tan δ _{100 K−} tan δ _2k ) / tan δ _2k exceeds 1.7, the toner has a small electrostatic adhesion force due to separation and neutralization application, and the halftone due to scattering in the line image or rush shock in fixing. The image uniformity becomes worse. In particular, fixing failure (low temperature offset) is likely to occur due to a decrease in heat of vaporization due to water evaporation of the paper.

When (tan δ _100K -tan δ _2k ) / tan δ _2k is less than 0.7, the effect of separation charge removal is small, but charge accumulation is high and toner charging becomes excessive in a low-humidity environment. Charging non-uniformity occurs and fogging becomes significant. Further, the retransfer property that the toner once transferred onto the transfer material is reversely transferred onto the photosensitive drum tends to be strong. Also, a phenomenon called electrostatic offset is likely to occur due to the repulsion due to the interaction between the charging of the fixing roller itself rotating at high speed and the charging with the toner on the transfer.
Therefore, in the present invention, it is preferable that the value specified by the above-described equation is satisfied.

  In the present invention, the temperature for measuring dielectric characteristics such as dielectric loss tangent is set to 40 ° C., especially when the temperature in the electrophotographic apparatus of high-speed output is around 40 ° C. This is because the temperature inside the apparatus becomes higher because the process proceeds to the development, transfer, and separation processes on the second surface in a state where the film is heated and fixed, and therefore, it is suitable for conditions for measuring the effect of the separation charge removal. When the measurement temperature exceeds 50 ° C., the influence of the glass transition temperature of the resin is increased, which is not preferable.

  In the present invention, the dielectric constant of the toner is 15 to 40 (pF / m). By controlling the rate of change of dielectric loss tangent and controlling the dielectric constant, charging stability can be dramatically improved. If the dielectric constant is less than 15, the charge amount becomes too high, and it becomes difficult to have stable image characteristics in a low humidity environment. On the other hand, when the dielectric constant is greater than 40, the rising of the charge of the toner is delayed, and the charge amount due to being left is liable to decrease.

In the present invention, the true specific gravity of the magnetic toner is 1.1 to 1.6 g / cm ³ and the magnetic field 7
The saturation magnetization at 96 kA / m is 20 to 35 Am ² / kg. True specific gravity is 1.7g /
When it is larger than cm ³ or when the saturation magnetization is larger than 35 Am ² / kg, that is, when a relatively large amount of magnetic material is contained, the excessive toner is likely to be developed due to the magnetic cohesiveness, and at the time of fixing. Problems such as image degradation and increased consumption occur, and low-temperature fixability deteriorates. On the other hand, when the true specific gravity is less than 1.3 g / cm ³ or the saturation magnetization is less than 20 Am ² / kg, that is, when the amount of the magnetic material is small, the ear-forming ability on the toner carrier decreases. Therefore, image quality is likely to deteriorate. Further, the frequency dependence of the dielectric loss tangent becomes too large, and the change in charging characteristics due to the environment becomes large.

  In the present invention, the weight average particle diameter of the magnetic toner is 5.0 to 9.0 μm. This is because, in order to develop a high-definition electrostatic latent image, the toner weight average diameter of the magnetic toner is preferably 9.0 μm or less, and when the toner weight average diameter of the magnetic toner is less than 5.0 μm, This is because the transferability is likely to be affected by the mirror image force.

In the present invention, it is preferable that the toner has an acid value of 1.0 to 20 mg KOH / g of a chloroform soluble component and an epoxy amount of 2.0 to 0.1 mmol / g of a chloroform soluble component in the toner. .

This is because the chloroform-soluble component is close to the composition of the binder resin in the toner surface layer, and in the case of a pulverized toner, it is pulverized and manufactured by impact in the gas phase (air). There is a tendency that a composition which is difficult to wet becomes an interface. Therefore, when measurement is performed using chloroform, which is a highly hydrophobic solvent, if the acid value of the chloroform-soluble component is less than 1.0 mgKOH / g , the dispersion of the magnetic material becomes insufficient and fogging becomes prominent. In addition, when the amount of epoxy soluble in chloroform is less than 0.1 mmol / g, the dielectric properties according to the present invention, particularly the dielectric constant, is low, and it is difficult to have stable image properties in a low humidity environment. is there. On the other hand, when the acid value of the chloroform-soluble component exceeds 20 mgKOH / g , the rate of change of the frequency characteristic of the dielectric loss tangent is high, and the charge retention of the toner is reduced when the separation charge is applied, and scattering during fixing is conspicuous. This is because when the amount of epoxy soluble in chloroform exceeds 2.0 mmol / g, the dielectric constant increases and the amount of charge due to standing tends to decrease.

Furthermore, the toner of the present invention preferably has a dielectric loss tangent (tan δ) measured at a frequency of 100 kHz and 40 ° C. in the range of 2.0 × 10 ^{−3 to} 2.0 × 10 ⁻² . When the dielectric loss tangent is within this range, the dispersibility of the magnetic substance in the toner becomes good, the charge retention ability is good, and it becomes easy to suppress fluctuations in the charging characteristics due to charge removal. When the dielectric loss tangent (tan δ) is less than 2.0 × 10 ^{−3, an} excessive charge relaxation tendency is observed, and the image density tends to decrease. Also, if the dielectric loss tangent (tan δ) exceeds 2.0 × 10 ⁻² , this may be due to variations in individual toner surface charges.
The edge effect of the line image is strong and there is an adverse effect of increasing the toner consumption.

  In the present invention, in order to control dielectric properties, in a magnetic toner containing at least a binder resin and a magnetic substance, the binder resin includes a) a vinyl resin having a carboxyl group and a vinyl resin having an epoxy group, and b) a carboxyl group. And a vinyl resin having an epoxy group, and c) one or more vinyl resins selected from the group consisting of a vinyl resin in which a carboxyl group and an epoxy group are reacted.

When an epoxy group or a carboxy group is present in the binder resin, the magnetic substance is considered to form a specific dispersion state because it is attracted by the reactivity of the functional groups of each other. Thereby, the dielectric constant of the magnetic toner is increased, and it is considered that a magnetic toner exhibiting desired dielectric characteristics and frequency characteristics of dielectric loss tangent according to the present invention can be obtained.
Then, the dielectric properties of the magnetic toner are desired by taking into consideration the melting conditions in the binder resin production, the raw material mixing conditions of the binder resin and the magnetic material in the toner production, the hot melt kneading conditions, etc. Can be controlled within the range. As a method for controlling to show desired dielectric properties, etc., for example, in the raw material mixing step at the time of toner production, the particle size of the binder resin according to the present invention is reduced to 100 to 400 μm and the dispersion of the magnetic substance is performed. Determine the raw material charging order in the mixing tank while taking into consideration the properties, or adjust the temperature at the time of heat melting in the binder resin production or toner production to 150 ° C. or higher and the epoxy groups and carbokill in the binder resin Examples thereof include a method in which a group is reacted or placed in a reaction proximity state. By combining these methods, a magnetic toner exhibiting the desired dielectric properties according to the present invention can be obtained more easily.

  In the present invention, as described above, the binder resin includes a) a vinyl resin having a carboxyl group and a vinyl resin having an epoxy group, b) a vinyl resin having a carboxyl group and an epoxy group, and c) a carboxyl group and an epoxy group. At least one vinyl resin selected from the group consisting of vinyl resins reacted with.

  Examples of the monomer having a carboxyl group unit constituting a vinyl resin having a carboxyl group include acrylic acid, methacrylic acid, α-ethylacrylic acid, crotonic acid, cinnamic acid, vinyl acetic acid, isocrotonic acid, tiglic acid, and angelic acid. Acrylic acid and α- or β-alkyl derivatives of the above; unsaturated dicarboxylic acids such as fumaric acid, maleic acid, citraconic acid, alkenyl succinic acid, itaconic acid, mesaconic acid, dimethyl maleic acid, dimethyl fumaric acid, monoester derivatives thereof , Anhydrides and α- or β-alkyl derivatives.

  The vinyl resin which has a carboxyl group can be obtained by individual or mixing the monomer which has the above carboxyl group units, and making it copolymerize with another vinyl type monomer by a well-known polymerization method.

  In the vinyl resin having a carboxyl group, the number average molecular weight (Mn) is preferably 1,000 to 40,000, in order to achieve good fixability and the effect of the dielectric properties according to the present invention, and the weight average molecular weight (Mw). ) Is preferably 10,000 to 2,000,000 in order to achieve good offset resistance, blocking resistance and dielectric properties according to the present invention.

The vinyl resin having a carboxyl group is preferably composed of a low molecular weight component and a high molecular weight component. The peak molecular weight of the low molecular weight component is preferably 4,000 to 30,000 in order to achieve good fixability and developability, and the peak molecular weight of the high molecular weight component is good offset resistance, blocking resistance and durability. In order to achieve 100,000 to 1,
000,000 is preferred.

  Examples of the synthesis method of the high molecular weight component resin used in the present invention include a bulk polymerization method, a solution polymerization method, an emulsion polymerization method, a suspension polymerization method, and the like.

  Among them, the emulsion polymerization method is a method in which a monomer (monomer) almost insoluble in water is dispersed as small particles in an aqueous phase with an emulsifier, and polymerization is performed using a water-soluble polymerization initiator. In this method, the heat of reaction can be easily adjusted, and since the phase in which the polymerization is carried out (the oil phase consisting of the polymer and the monomer) and the aqueous phase are different, the termination reaction rate is low, resulting in a high polymerization concentration. A product having a high degree of polymerization is obtained. Furthermore, since the polymerization process is relatively simple and the polymerization product is fine particles, the toner can be easily mixed with colorants, charge control agents and other additives in the production of the toner. It is effective as a method for producing a binder resin. However, because of the added emulsifier, the polymer tends to be impure, and in order to take out the polymer, an operation such as salting out is necessary. To avoid this inconvenience, the solution polymerization method and the suspension polymerization method are better. .

  In the suspension polymerization method, the monomer is preferably 100 parts by mass or less (preferably 10 to 90 parts by mass) with respect to 100 parts by mass of the aqueous solvent. Examples of usable dispersants include polyvinyl alcohol, partially saponified polyvinyl alcohol, calcium phosphate, and the like. Generally, 0.05 to 1 part by mass is preferably used with respect to 100 parts by mass of the aqueous solvent. The polymerization temperature is suitably 50 to 95 ° C., but is appropriately selected depending on the initiator used and the target polymer.

  In order to achieve the object of the present invention, the high molecular weight component resin used in the preparation of the binder resin composition is a polyfunctional polymerization initiator as exemplified below alone or in combination with a monofunctional polymerization initiator. It is good to generate by doing.

  Specific examples of the polyfunctional polymerization initiator having a polyfunctional structure include 1,1-di-tert-butylperoxy-3,3,5-trimethylcyclohexane, 1,3-bis- (tert-butylperoxy Isopropyl) benzene, 2,5-dimethyl-2,5- (tert-butylperoxy) hexane, 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane, tris- (tert-butyl) Peroxy) triazine, 1,1-di-tert-butylperoxycyclohexane, 2,2-di-tert-butylperoxybutane, 4,4-di-tert-butylperoxyvaleric acid-n-butyl ester Di-tert-butylperoxyhexahydroterephthalate, di-tert-butylperoxyazelate, di- In one molecule such as tert-butylperoxytrimethyladipate, 2,2-bis- (4,4-di-tert-butylperoxycyclohexyl) propane, 2,2-tert-butylperoxyoctane and various polymer oxides A polyfunctional polymerization initiator having a functional group having a polymerization initiating function such as two or more peroxide groups; and diallyl peroxydicarbonate, tert-butylperoxymaleic acid, tert-butylperoxyallylcarbonate, and tert- A polyfunctional polymerization initiator having both a functional group having a polymerization initiating function such as a peroxide group and a polymerizable unsaturated group in one molecule such as butyl peroxyisopropyl fumarate is exemplified.

  Of these, more preferred are 1,1-di-tert-butylperoxy-3,3,5-trimethylcyclohexane, 1,1-di-tert-butylperoxycyclohexane, di-tert-butylperoxy. Hexahydroterephthalate, di-tert-butylperoxyazelate and 2,2-bis- (4,4-di-tert-butylperoxycyclohexane) propane and tert-butylperoxyallyl carbonate.

  The polyfunctional polymerization initiator may be used in combination with a monofunctional polymerization initiator in order to satisfy various performances required as a binder for toner. In particular, the monofunctional polymerization initiator having a lower decomposition temperature for obtaining a half-life of 10 hours of a monofunctional polymerization initiator than a decomposition temperature for obtaining a half-life of 10 hours of a polyfunctional polymerization initiator. It is good to use together.

  Specific examples of the monofunctional polymerization initiator include benzoyl peroxide, 1,1-di (tert-butylperoxy) -3,3,5-trimethylcyclohexane, n-butyl-4,4-di (tert- Organic peroxides such as butylperoxy) valerate, dicumyl peroxide, α-α'-bis (tert-butylperoxydiisopropyl) benzene, tert-butylperoxycumene, di-tert-butylperoxide, azo Examples thereof include azo and diazo compounds such as bisisobutyronitrile and diazoaminoazobenzene.

  These monofunctional polymerization initiators may be added to the monomer at the same time as the polyfunctional polymerization initiator. However, in order to maintain the efficiency of the polyfunctional polymerization initiator appropriately, the polyfunctional polymerization initiator may be added in the polymerization step. It is preferably added after the half-life indicated by the functional polymerization initiator has elapsed.

  These polyfunctional and / or monofunctional polymerization initiators are preferably used in an amount of 0.01 to 10 parts by mass with respect to 100 parts by mass of the monomer from the viewpoint of efficiency.

Next, as a synthesis method of the low molecular weight component resin used for adjusting the binder resin composition, a known method can be used. However, in the bulk polymerization method, a polymer having a low molecular weight can be obtained by polymerizing at a high temperature to increase the termination reaction rate, but there is a problem that the reaction is difficult to control. On the other hand, in the solution polymerization method, a low molecular weight polymer can be easily obtained under mild conditions by utilizing the difference in radical chain transfer by a solvent and adjusting the amount of initiator and reaction temperature. In order to obtain a low molecular weight component resin in a vinyl resin having a carboxyl group, this polymerization method is preferred.

  As the solvent used in the solution polymerization, xylene, toluene, cumene, cellosolve acetate, isopropyl alcohol or benzene is used. The solvent is appropriately selected depending on the polymer to be polymerized. The reaction temperature varies depending on the solvent to be used, the polymerization initiator, and the polymer to be polymerized, but it is usually preferable to carry out at 70 to 230 ° C. In solution polymerization, it is preferable to carry out by 30-400 mass parts of monomers with respect to 100 mass parts of solvents.

  Furthermore, it is also preferable to mix other polymers in the solution at the end of the polymerization, and several types of polymers can be mixed.

  In the vinyl resin having an epoxy group used in the present invention, the epoxy group in the vinyl resin is a functional group in which an oxygen atom is bonded to two carbon atoms in the same molecule, and has a cyclic ether structure. Have. Typical cyclic ether structures include a 3-membered ring, a 4-membered ring, a 5-membered ring, and a 6-membered ring. Among them, a 3-membered ring structure is preferable.

  The following are mentioned as a monomer which has an epoxy group unit which comprises the vinyl resin which has an epoxy group. Examples include glycidyl acrylate, glycidyl methacrylate, β-methyl glycidyl acrylate, β-methyl glycidyl methacrylate, allyl glycidyl ether, allyl β-methyl glycidyl ether, and the like. A glycidyl monomer represented by the following formula (i) is preferably used.

（上記式中、Ｒ₁、Ｒ₂及びＲ₃は、水素、アルキル基、アリール基、アラルキル基、カル
ボキシル基及びアルコシキカルボニル基を示す。）

(In the above formula, R ₁ , R ₂ and R ₃ represent hydrogen, an alkyl group, an aryl group, an aralkyl group, a carboxyl group and an alkoxycarbonyl group.)

  Such a monomer having an epoxy group unit can be obtained alone or in combination and copolymerized with a vinyl monomer by a known polymerization method to obtain a vinyl resin having the epoxy group.

  The vinyl resin having an epoxy group has a weight average molecular weight (Mw) of preferably 2,000 to 100,000, more preferably 2,000 to 50,000, still more preferably 3,000 to 40,000. Is good. When the weight average molecular weight is less than 2,000, a crosslinking reaction occurs in the binder resin, the molecular weight is increased, and during the kneading step, many molecules are cut and durability is deteriorated. On the other hand, when the weight average molecular weight exceeds 100,000, the fixing property is deteriorated.

  In the present invention, the amount of epoxy soluble in chloroform in the toner is in the range of 2.0 to 0.1 mmol / g, and the binder resin is a vinyl resin having a carboxyl group and a vinyl resin having an epoxy group. Inducing a cross-linking reaction is more effective in obtaining a magnetic toner exhibiting desired dielectric properties.

  Next, in the vinyl resin having a carboxyl group and an epoxy group, the number average molecular weight (Mn) is preferably 1,000 to 40,000 in order to achieve good developability and magnetic dispersibility. The weight average molecular weight (Mw) is preferably 10,000 to 2,000,000 in order to achieve offset resistance, blocking resistance and durability.

  The vinyl resin having a carboxyl group and an epoxy group can be obtained by mixing a monomer having a carboxyl group unit and a monomer having an epoxy group unit and copolymerizing with another vinyl monomer by a known polymerization method.

  In addition, the vinyl resin used in the present invention in which a carboxyl group and an epoxy group react with each other is obtained by previously reacting a vinyl resin having a carboxyl group and a vinyl resin having an epoxy group at the time of producing a binder resin. There may be. Here, as a reaction means, 1) a vinyl resin having a carboxyl group and a vinyl resin having an epoxy group are mixed in a solution state, and a crosslinking reaction is caused by applying heat in a reaction kettle. Take out a vinyl resin having a group and a vinyl resin having an epoxy group from a reaction kettle, dry blend with a Henschel mixer, etc., and heat-melt knead with a biaxial extruder, etc. to cause a crosslinking reaction, etc. Can be mentioned.

  Here, as a vinyl monomer to be copolymerized with a monomer having a carboxyl group unit or a monomer having an epoxy group unit, for example, styrene; o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, p-phenyl Styrene, p-chlorostyrene, 3,4-dichlorostyrene, p-ethylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p-tert-butylstyrene, pn-hexylstyrene, p- styrene derivatives such as n-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene; ethylene unsaturated monoolefins such as ethylene, propylene, butylene, isobutylene; butadiene, Unsaturated polyenes such as isoprene; salts Vinyl halides such as vinyl, vinylidene chloride, vinyl bromide and vinyl fluoride; vinyl esters such as vinyl acetate, vinyl propionate and vinyl benzoate; methyl methacrylate, ethyl methacrylate, propyl methacrylate, methacryl Α- such as n-butyl acid, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, methacrylic acid (2-ethylhexyl), stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate Methylene aliphatic monocarboxylic acid esters; methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, propyl acrylate, 1-octyl acrylate, dodecyl acrylate, acrylic acid ( 2-ethylhexyl), stearyl acrylate, acrylic acid (2-chloroethyl), acrylic esters such as phenyl acrylate; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether; vinyl methyl ketone, vinyl Vinyl ketones such as hexyl ketone and methyl isopropenyl ketone; N-vinyl compounds such as N-vinyl pyrrole, N-vinyl carbazole, N-vinyl indole and N-vinyl pyrrolidone; vinyl naphthalenes; acrylonitrile, methacrylonitrile, Examples include acrylic acid derivatives such as acrylamide or methacrylic acid derivatives. These vinyl monomers can be used alone or in admixture of two or more monomers.

  Among these, a combination of monomers that becomes a styrene copolymer and a styrene-acrylic copolymer is preferable. In this case, at least a styrene copolymer component or a styrene-acrylic copolymer component is contained in the binder resin. It is preferable from the viewpoint of fixing property and mixing property that the content is 70% by mass or more.

In the present invention, the binder resin preferably contains 40% by mass or more of one or more kinds of vinyl resins selected from the specific group described above.

  In addition to the above-described polymers, the following polymers can be added to the binder resin used in the toner of the present invention. For example, homopolymers of styrene such as polystyrene, poly-p-chlorostyrene, and polyvinyltoluene, and substituted products thereof; styrene-p-chlorostyrene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer , Styrene-acrylic acid ester copolymer, styrene-methacrylic acid ester copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl Styrene copolymers such as ethyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer; polyvinyl chloride, phenol Resin, natural modified film Nord resin, natural resin modified maleic acid resin, acrylic resin, methacrylic resin, polyvinyl acetate, silicone resin, polyester resin, polyurethane, polyamide resin, furan resin, epoxy resin, xylene resin, polyvinyl butyral, terpene resin, coumarone indene resin Petroleum resin can be used.

  In the present invention, a polyester resin may be included as a part of the binder resin.

  The polyester resin is a resin produced by polycondensation of a polyhydric alcohol and a polybasic acid, and examples of the monomer of the polyester resin component include the following.

  Examples of the divalent alcohol component include ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol, 1,5-pentanediol, 1, 6-hexanediol, neopentyl glycol, 2-ethyl-1,3-hexanediol, hydrogenated bisphenol A, bisphenol derivatives represented by the following formula (ii), and diols represented by the following formula (iii): Can be mentioned.

  Divalent carboxylic acids include benzene dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid, and phthalic anhydride, or anhydrides thereof; alkyl dicarboxylic acids such as succinic acid, adipic acid, sebacic acid, azelaic acid, or the like. An succinic acid substituted with an alkyl group or an alkenyl group having 6 to 18 carbon atoms or an anhydride thereof; an unsaturated dicarboxylic acid such as fumaric acid, maleic acid, citraconic acid, itaconic acid, or an anhydride thereof; Can be mentioned.

  Other monomers of the polyester resin include glycerin, pentaerythritol, sorbit, sorbitan, and polyhydric alcohols such as oxyalkylene ethers of novolak type phenol resins; trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid And polyhydric carboxylic acids such as anhydride thereof.

  In the present invention, a hybrid resin containing a polyester resin component and a styrene-acrylic resin component may be included.

  In the hybrid resin, examples of the vinyl monomer for producing the styrene-acrylic resin component include the following.

  Styrene monomers include styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, p-phenyl styrene, p-ethyl styrene, 2,4-dimethyl styrene, pn-butyl styrene, p-tert. -Butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p-methoxy styrene, p-chloro styrene, 3 Styrene such as 1,4-dichlorostyrene, m-nitrostyrene, o-nitrostyrene, p-nitrostyrene and derivatives thereof.

  Examples of acrylic monomers include acrylic acid, methyl acrylate, ethyl acrylate, propyl acrylate, acrylic acid-n-butyl, acrylic acid isobutyl, acrylic acid-n-octyl, acrylic acid dodecyl, acrylic acid-2- Acrylic acid and acrylic esters such as ethylhexyl, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, -n-butyl methacrylate, methacrylic acid Such as isobutyl acid, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate And α- methylene aliphatic monocarboxylic acids and esters thereof, acrylonitrile, methacrylonitrile, and the like such as acrylic acid or methacrylic acid derivatives of acrylamide.

  Furthermore, as a monomer of styrene-acrylic resin, acrylic acid or methacrylic acid esters such as 2-hydroxylethyl acrylate, 2-hydroxylethyl methacrylate, 2-hydroxylpropyl methacrylate, 4- (1-hydroxy-1-methylbutyl) Examples thereof include monomers having a hydroxyl group such as styrene and 4- (1-hydroxy-1-methylhexyl) styrene.

  As the magnetic material used in the toner of the present invention, a conventionally known magnetic material is used. Examples of the magnetic material contained in the magnetic toner include iron oxides such as magnetite, maghemite, and ferrite, and iron oxides including other metal oxides: metals such as Fe, Co, and Ni or these metals and Al, Co, And alloys with metals such as Cu, Pb, Mg, Ni, Sn, Zn, Sb, Be, Bi, Cd, Ca, Mn, Se, Ti, W, and V; and mixtures thereof.

Specifically, iron trioxide (Fe ₃ O ₄ ), iron sesquioxide (γ-Fe ₂ O ₃ ), zinc iron oxide (ZnFe ₂ O ₄ ), iron yttrium oxide (Y ₃ Fe ₅ O ₁₂ ), Cadmium iron oxide (CdFe ₂
O ₄ ), iron gadolinium oxide (Gd ₃ Fe ₅ O ₁₂ ), copper iron oxide (CuFe ₂ O ₄ ), lead iron oxide (PbFe ₁₂ O ₁₉ ), nickel iron oxide (NiFe ₂ O ₄ ), neodymium iron oxide ( NdFe ₂ O ₃ ), iron barium oxide (BaFe ₁₂ O ₁₉ ), iron magnesium oxide (MgFe ₂ O ₄ ), iron oxide manganese (MnFe ₂ O ₄ ), iron lanthanum oxide (LaFeO ₃ ), iron powder (Fe), Examples thereof include cobalt powder (Co) and nickel powder (Ni). In the present invention, at least magnetic iron is contained as a magnetic material, and one or more of the above magnetic materials can be arbitrarily selected and used as necessary.

The magnetic characteristics of these magnetic materials when 795.8 kA / m (10 k Oersted) is applied include a coercive force of 1.5 kA / m to 12 kA / m and a saturation magnetization of 50 to 200 Am ² / kg (preferably 50 to 100 Am ^2). / Kg) and a residual magnetization of ² to 20 Am ² / kg is preferable. The magnetic properties of the magnetic material can be measured using a vibration type magnetometer such as VSM P-1-10 (manufactured by Toei Kogyo Co., Ltd.) under the conditions of 25 ° C. and an external magnetic field of 769 kA / m.

  In the magnetic toner of the present invention, the magnetic material is preferably magnetic iron oxide, and examples thereof include fine powders of triiron tetroxide and γ-iron sesquioxide.

In the present invention, the magnetic properties and addition amount of the magnetic material may be controlled so that the saturation magnetization amount in a magnetic field of 796 kA / m after toner formation is 20 to 35 Am ² / kg.

  In the present invention, the average particle size of the magnetic material is preferably 0.08 μm or more and 0.3 μm or less. When the thickness is 0.08 μm or less, the magnetic material itself becomes reddish, and the color of the toner also increases redness, and the fine dispersibility in the resin deteriorates, thereby controlling the rate of change of dielectric loss tangent. Becomes difficult. On the other hand, when the thickness is 0.3 μm or more, the coloring power of the toner is lowered, and when the magnetic substance content is low, the frequency change rate of the dielectric loss tangent is increased, and it is difficult to set the proper range.

  In the present invention, it is preferable that a different metal such as silicon, zinc or titanium is contained inside and / or on the surface of the magnetic material. This is because the magnetic cohesiveness can be lowered, and the dispersibility of the magnetic substance in the toner can be improved.

  Moreover, it is preferable that the magnetic body of the present invention reduces the magnetic cohesive force by applying mechanical shear in the slurry state after the synthesis of the magnetic body. By performing such a process, the fine dispersibility at the time of toner production is drastically improved.

  In the present invention, other colorants may be contained as required. As the colorant, carbon black or any other conventionally known pigment or dye may be used, or one or more of them may be used.

  In the present invention, other additives may be added to the toner particles as necessary. As such other additives, various additives conventionally known to be added to the inside of toner particles can be used, and examples thereof include a release agent and a charge control agent.

  Preferred examples of the release agent include aliphatic hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, microcrystalline wax, and paraffin wax; oxides of aliphatic hydrocarbon waxes such as oxidized polyethylene wax or the like. Block copolymers of these: waxes based on fatty acid esters such as carnauba wax, sazol wax, and montanic acid ester wax; deoxidized part or all of fatty acid esters such as deoxidized carnauba wax Saturated fatty acids such as palmitic acid, stearic acid, and montanic acid; unsaturated fatty acids such as brandic acid, eleostearic acid, and valinalic acid; Saturated alcohols such as melyl alcohol, polyhydric alcohols such as sorbitol; Fatty acid amides such as linoleic acid amide, oleic acid amide, lauric acid amide; Methylene bis stearic acid amide, ethylene biscapric acid amide, ethylene bis Saturated fatty acid bisamides such as lauric acid amide and hexamethylene bis stearic acid amide; ethylene bis oleic acid amide, hexamethylene bis oleic acid amide, N, N′-dioleyl adipic acid amide, N, N′-dioleyl sebacic acid Unsaturated fatty acid amides such as amides; Aromatic bisamides such as m-xylene bis-stearic acid amide and N, N′-distearylisophthalic acid amide; Calcium stearate, calcium furate, zinc stearate, magnesium stearate, etc. Aliphatic metal salts (generally referred to as metal soaps); waxes grafted with aliphatic hydrocarbon waxes using vinyl monomers such as styrene and acrylic acid; fatty acids such as behenic acid monoglycerides Examples include partially esterified products of monohydric alcohols; methyl ester compounds having a hydroxyl group obtained by hydrogenation of vegetable oils and fats; long-chain alkyl alcohols or long-chain alkyl carboxylic acids having 12 or more carbon atoms; and the like.

  Examples of the release agent particularly preferably used in the present invention include aliphatic hydrocarbon waxes. As such an aliphatic hydrocarbon wax, for example, a low molecular weight alkylene polymer obtained by radical polymerization of alkylene at a high pressure or a Ziegler catalyst at a low pressure; a high molecular weight alkylene polymer is thermally decomposed. Alkylene polymers obtained; synthetic hydrocarbon waxes obtained from the distillation residue of hydrocarbons obtained by the age method from synthesis gas containing carbon monoxide and hydrogen, and synthetic hydrocarbon waxes obtained by hydrogenating them; these aliphatics And hydrocarbon waxes separated by press sweating, solvent method, vacuum distillation and fractional crystallization.

  Examples of the hydrocarbon as the base of the aliphatic hydrocarbon wax include those synthesized by the reaction of carbon monoxide and hydrogen using a metal oxide catalyst (often a multi-component system of two or more types) (for example, Hydrocarbon compounds synthesized by the Gintor method and Hydrocol method (using a fluidized catalyst bed); Up to several hundred carbon atoms can be obtained by the Age method (using an identified catalyst bed) in which many waxy hydrocarbons are obtained Hydrocarbons; hydrocarbons obtained by polymerizing alkylene such as ethylene with a Ziegler catalyst. Among such hydrocarbons, in the present invention, it is preferable that the hydrocarbon is a linear hydrocarbon having a small number of branches and a long saturation, and particularly a hydrocarbon synthesized by a method not based on polymerization of alkylene has a molecular weight distribution. Is also preferable.

  In the present invention, the release agent is contained in the toner particles so that when the toner particles containing the release agent are measured with a differential scanning calorimeter, an endothermic main peak appears in the region of 70 to 140 ° C. in the obtained DSC curve. It is preferable from the viewpoint of low-temperature fixability and high-temperature offset resistance of the toner.

  The endothermic peak temperature can be measured according to ASTM D3418-82 using a highly accurate internal heat input compensation type differential scanning calorimeter, for example, DSC-7 manufactured by PerkinElmer, Inc. The appearing temperature can be adjusted by using a release agent in which the melting point, glass transition point, polymerization degree, and the like are appropriately adjusted. The DSC-7 is applied to the measurement of the temperature indicating the thermal properties of the toner particles and the toner particle material, such as the glass transition point of the binder resin, the softening point, and the melting point of the wax, in addition to the peak temperature. Can do.

  Specific examples of the wax that can be used as a release agent in the present invention include Biscol (registered trademark) 330-P, 550-P, 660-P, TS-200 (Sanyo Chemical Industries), high wax 400P, 200P. , 100P, 410P, 420P, 320P, 220P, 210P, 110P (Mitsui Chemicals), Sazol H1, H2, C80, C105, C77 (Schumann Sazol), HNP-1, HNP-3, HNP-9, HNP -10, HNP-11, HNP-12 (Nippon Seiki Co., Ltd.), Unilin (registered trademark) 350, 425, 550, 700, Unicid (registered trademark), Unicid (registered trademark) 350, 425, 550, 700 ( Toyo Petrolite), wood wax, beeswax, rice wax, candelilla wax, carnauba wax Available), and the like by the Corporation Cerarica NODA.

  The release agent is preferably contained in the toner particles at a ratio of 2 to 15 parts by mass per 100 parts by mass of the binder resin from the viewpoint of fixability and charging characteristics.

  In the toner of the present invention, a charge control agent can be used as described above in order to stabilize the chargeability. The charge control agent varies depending on the type of charge control agent and the physical properties of other toner particle constituent materials, but generally 0.1 to 10 parts by mass per 100 parts by mass of the binder resin is preferably contained in the toner particles. More preferably, 0.1 to 5 parts by mass are contained. As such charge control agents, there are known ones for controlling the toner to be negatively charged and those for controlling the toner to be positively charged. One or two kinds of various kinds of charge control agents are used depending on the kind and use of the toner. The above can be used.

  For controlling the toner to be negatively charged, for example, an organometallic complex and a chelate compound are effective. Examples thereof include a monoazo metal complex; an acetylacetone metal complex; a metal complex of aromatic hydroxycarboxylic acid or aromatic dicarboxylic acid; A metal salt. In addition, examples of the toner that controls the toner to be negatively charged include aromatic mono- and polycarboxylic acids and metal salts and anhydrides thereof; phenol derivatives such as esters and bisphenol;

Examples of toners that can be positively charged include, for example, modified products of nigrosine and fatty acid metal salts; quaternary ammoniums such as tributylbenzylammonium-1-hydroxy-4-naphthosulfonate and tetrabutylammonium tetrafluoroborate. Salts, and onium salts such as phosphonium salts and analogs thereof and lake pigments thereof; triphenylmethane dyes and lake pigments thereof (as rake agents, phosphotungstic acid, phosphomolybdic acid, phosphotungstic molybdic acid, Tannic acid, lauric acid, gallic acid, ferricyanic acid, ferrocyanic compound, etc.); metal salts of higher fatty acids; diorganotin oxides such as dibutyltin oxide, dioctyltin oxide, dicyclohexyltin oxide; dibutyltin borate Dioctyl tin borate, diorgano tin borate such as dicyclohexyl tin borate; and the like. In the present invention, these can be used alone or in combination. Among them, charge control agents such as nigrosine compounds and quaternary ammonium salts are particularly preferably used for controlling the toner to be positively charged.

  More specifically, for negative charging, for example, Spiro Black TRH, T-77, T-95 (Hodogaya Chemical Co., Ltd.), BONTRON (registered trademark) S-34, S-44, S-54, E- 84, E-88, E-89 (Orient Chemical Co., Ltd.) are more preferable, and for positive charging, for example, TP-302, TP-415 (Hodogaya Chemical Co., Ltd.), BONTRON (registered trademark) N- Preferable examples include 01, N-04, N-07, P-51 (Orient Chemical Co.), and Copy Blue PR (Clariant).

  The toner of the present invention is preferably a negatively chargeable charge control agent from the viewpoint of the physical properties of the toner material, and in particular, an azo iron complex is preferably used from the viewpoint of dispersibility with the binder resin and the magnetic material. The

  The toner of the present invention is used by externally adding various materials according to the type of toner to the toner particles described above. Examples of the externally added material include a fluidity improver that improves the fluidity of the toner, such as inorganic fine powder, and a conductive fine powder that adjusts the chargeability of the toner, such as metal oxide fine particles. And other external additives.

  Examples of the fluidity improver include those that can improve the fluidity of the toner by external addition to the toner particles. Examples of such fluidity improvers include fluorine resin powders such as fine vinylidene fluoride powder and polytetrafluoroethylene fine powder; fine powder silica such as wet process silica and dry process silica, fine powder titanium oxide, and fine powder. Alumina; treated silica, surface treated with a silane coupling agent, titanium coupling agent, silicone oil, etc., treated titanium oxide, treated alumina; and the like.

The fluidity improver preferably has a specific surface area by nitrogen adsorption measured by the BET method of 30 m ² / g or more, and more preferably 50 m ² / g or more. Although a fluidity improver changes with kinds of fluidity improver, it is preferable to mix | blend 0.01-8 mass parts with respect to 100 mass parts of toner particles, for example, and mix | blend 0.1-4 mass parts. Is more preferable.

  A preferred fluidity improver is a fine powder produced by vapor phase oxidation of a silicon halogen compound, and is referred to as dry process silica or fumed silica. Such silica utilizes, for example, a thermal decomposition oxidation reaction of silicon tetrachloride gas in oxygen and hydrogen, and the basic reaction formula is represented by the following formula (iv).

  In this production process, it is also possible to obtain a composite fine powder of silica and another metal oxide by using other metal halogen compounds such as aluminum chloride or titanium chloride together with silicon halogen compounds. The silica fine powder used as an improving agent also includes them. The average particle size is preferably within the range of 0.001 to 2 μm, and more preferably within the range of 0.002 to 0.2 μm.

Examples of commercially available silica fine powders produced by vapor phase oxidation of silicon halogen compounds include those sold under the following trade names: AEROSIL (Nippon Aerosil Co., Ltd.) 130, 200, 300, 380, TT600, MOX170, MOX80, COK84; Ca—O—SiL (CABOT Co.) M-5, MS-7, MS-75, HS-5, EH-5; Wacker HDK N 20 (WACKER-CHEMIE GMBH) V15, N20E, T30, T40; DC Fine Silica (Dow Corning CO.); Franco1 (Fransil).

  In the present invention, the silica fine powder is preferably hydrophobized. In addition, the above-mentioned silica fine powder is obtained by treating the silica fine powder so that the degree of hydrophobicity measured by a methanol titration test is in the range of 30 to 80 degrees. It is particularly preferable for expression. The degree of hydrophobicity is expressed as a percentage of methanol in a liquid mixture of methanol and water at the end of sedimentation of the silica fine powder by dropping methanol onto a predetermined amount of the silica fine powder stirred in water. Examples of the method for hydrophobizing silica fine powder include a method of chemically treating silica fine particles with an organosilicon compound or silicone oil that reacts with silica fine powder or is physically adsorbed on silica fine particles. More preferably, it is a hydrophobic treatment with an organosilicon compound.

  Here, as the organosilicon compound, hexamethyldisilazane, trimethylsilane, trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, allylphenyldichlorosilane, benzyldimethylchlorosilane , Bromomethyldimethylchlorosilane, α-chloroethyltrichlorosilane, β-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane, triorganosilylmercaptan, trimethylsilylmercaptan, triorganosilylacrylate, vinyldimethylacetoxysilane, dimethylethoxysilane, dimethyl Dimethoxysilane, diphenyldiethoxysilane, hexamethyldisiloxane, 1,3-divirtetramethyldisiloxa , 1,3-diphenyltetramethyldisiloxane, and dimethylpolysiloxane having 2 to 12 siloxane units per molecule and having a hydroxyl group bonded to Si in the terminal unit. These may be used alone or as a mixture of two or more.

  In the hydrophobization treatment of the silica fine powder, it is possible to use one or more silane coupling agents having a nitrogen atom among the organosilicon compounds. Examples of such nitrogen-containing silane coupling agents include aminopropyltrimethoxysilane, aminopropyltriethoxysilane, dimethylaminopropyltrimethoxysilane, diethylaminopropyltrimethoxysilane, dipropylaminopropyltrimethoxysilane, and dibutylaminopropyltrimethoxysilane. Methoxysilane, monobutylaminopropyltrimethoxysilane, dioctylaminopropyldimethoxysilane, dibutylaminopropyldimethoxysilane, dibutylaminopropylmonomethoxysilane, dimethylaminophenyltriethoxysilane, trimethoxysilyl-γ-propylphenylamine, trimethoxysilyl -Γ-propylbenzylamine and the like.

  In the present invention, a preferable silane coupling agent is hexamethyldisilazane (HMDS).

Moreover, as a silicone oil preferably used in the hydrophobization treatment of silica fine powder, the viscosity at 25 ° C. is preferably 0.5 to 10,000 centistokes, more preferably 1 to 1000 centistokes, Even more preferably 200 centistokes. Particularly preferred silicone oils include, for example, dimethyl silicone oil, methylphenyl silicone oil, α-methylstyrene modified silicone oil, chlorophenyl silicone oil, and fluorine modified silicone oil.

  As a method for surface hydrophobization treatment of silica fine powder using silicone oil, for example, silica fine powder treated with a silane coupling agent and silicone oil are directly mixed using a mixer such as a Henschel mixer; A method in which silicone oil is sprayed onto a silica fine powder; a method in which silicone oil is dissolved or dispersed in a suitable solvent, and then the silica fine powder is added and mixed to remove the solvent.

  In the case where the surface of the silica fine powder is hydrophobized with silicone oil, the silica fine powder is heated to 200 ° C. or higher (more preferably 250 ° C. or higher) in an inert gas after the silicone oil treatment to stabilize the surface coat. More preferably.

  In the present invention, it is possible to use both the silane coupling agent and the silicone oil described above for the surface hydrophobization treatment of the silica fine powder. Examples thereof include a method of treating with a silane coupling agent and then treating with silicone oil, or a method of treating a silica fine powder simultaneously with a silane coupling agent and silicone oil.

  The production method of the toner of the present invention is not particularly limited, but the binder resin, magnetic material, and, if necessary, other additives are sufficiently mixed by a mixer such as a Henschel mixer or a ball mill, By melting, kneading and kneading using a heat kneader such as an extruder to make the resins compatible with each other, cooling and solidifying the molten kneaded product, and then crushing the solidified product and classifying the crushed product A method of obtaining toner particles is preferred. The toner particles and an external additive such as a fluidity improver can be obtained by sufficiently mixing them as necessary with a mixer such as a Henschel mixer.

  In the production of the toner of the present invention, the classification can be performed at any time after the toner particles are generated. For example, the classification may be performed after mixing with an external additive. Further, an appropriate impact such as mechanical or thermal may be applied to the generated toner particles to control the particle shape of the toner particles (more specifically, spheroidization).

  In the present invention, as a method of pulverizing the solidified product, a method of applying a mechanical impact force is preferable. Examples of the treatment that gives mechanical impact force include a method using a mechanical pulverizer such as a pulverizer KTM manufactured by Kawasaki Heavy Industries, Ltd., a turbo mill manufactured by Turbo Industry Co., Ltd., a mechano-fusion system manufactured by Hosokawa Micron, and Nara Machinery Co., Ltd. The method of processing with apparatuses, such as a manufactured hybridization system, is mentioned. These apparatuses can be used as they are or after being appropriately improved.

  The following are commonly used devices for toner production, but are not limited to these. Table 1 shows an example of a pulverizing device for toner production, Table 2 shows an example of a classification device for toner production, Table 3 shows an example of a sieve device for toner production, and Table 4 shows an example of a mixing device for toner production. Table 5 gives examples of kneading apparatuses for toner production.

  A method for measuring physical properties of the toner of the present invention is as follows. Examples described later are also based on this method.

(1) Measurement of Toner Particle Size The particle size distribution can be measured by various methods. In the present invention, the particle size distribution was measured using a Coulter counter multisizer.
The measuring device is a Coulter Counter Multisizer II (manufactured by Coulter Co.), connected to an interface (manufactured by Nikkiki) that outputs number distribution and volume distribution, and a computer for analysis. The electrolyte is a special grade or first grade sodium chloride. Is used to prepare a 1% NaCl aqueous solution. As a measuring method, 0.1 to 5 ml of a surfactant (preferably alkylbenzene sulfonate) is added as a dispersant to 100 to 150 ml of the above electrolytic aqueous solution, and further 2 to 20 mg of a measurement trial is added. The electrolyte in which the sample is suspended is subjected to a dispersion process for about 1 to 3 minutes with an ultrasonic disperser. When measuring the toner particle diameter as an aperture with the multisizer type II of the Coulter counter, a 100 μm aperture is used. taking measurement. The volume and number of toners were measured, and the volume distribution and number distribution were calculated. Then, the weight-based weight average particle diameter obtained from the volume distribution is obtained.

(2) Measurement of True Specific Density of Toner The true specific gravity of the toner is measured using a dry automatic densimeter Accupick 1330 manufactured by Shimadzu Corporation.

(3) Saturation magnetization measurement of toner The saturation magnetization intensity of the magnetic toner was measured using an oscillating magnetometer VSMP-1-10 (manufactured by Toei Kogyo Co., Ltd.) at an external magnetic field of 796 kA / m at a room temperature of 25 ° C. taking measurement.

(4) Measurement of magnetic particle size The average particle size of the magnetic material is measured using, for example, a laser diffraction particle size distribution meter (manufactured by Horiba, Ltd.).

(5) Measurement of dielectric constant and dielectric loss tangent of toner Using a 4284A precision LCR meter (manufactured by Hewlett-Packard), after calibrating the frequencies of 1 kHz and 1 MHz, the complex dielectric constant is measured at frequencies of 2000 Hz and 100 kHz. obtain.

The toner is weighed 1.0 g, molded with a load of 19600 kPa (200 kgf / cm ² ) over 1 minute, and is a disk-shaped measurement sample having a diameter of 25 mm and a thickness of 2 mm or less (preferably 0.5 mm to 1.5 mm). To. This measurement sample is mounted on ARES (manufactured by Rheometric Scientific F.E.) equipped with a dielectric constant measuring jig (electrode) having a diameter of 25 mm, heated to a temperature of 80 ° C., and melted and fixed. Then, it is obtained by measuring in a temperature range of 40 ° C. with a frequency of 2000 Hz and a frequency of 100 KHz in a state of cooling to a temperature of 20 ° C. and applying a load of 0.49 to 1.96 N (50 to 200 g). .

(6) Measurement of Epoxy Content of Toner Chloroform-soluble Component The sample was used after removing the chloroform-insoluble component of the toner in advance or extracted with a chloroform solvent by a Soxhlet extractor obtained by the above-mentioned measurement of chloroform-insoluble content. A soluble component is used as a sample. Sample ground product 0.5 (g): W is precisely weighed.
The sample is put in a beaker, and 20 ml of 0.2N HCl / dioxane solution and 20 ml of chloroform are added and dissolved.

Titrate with a potentiometric titrator using 0.5N KOH ethanol solution. (For example, automatic titration using a potentiometric titrator AT-400 (win workstation) manufactured by Kyoto Electronics Co., Ltd. and an ABP-410 electric burette can be used.)
The amount of KOH solution used at this time is S (ml), and a blank is measured simultaneously. The amount of KOH solution used at this time is B (ml).
The amount of epoxy is calculated by the following equation (2). f is a factor of KOH.

(7) Measurement of acid value Basic operation conforms to JIS K-0070.
1) The sample is used after removing the chloroform insoluble component of the toner and the binder resin in advance, or the soluble component extracted with the chloroform solvent by the Soxhlet extractor obtained by the above-mentioned measurement of the chloroform insoluble content is used as the sample. . The pulverized sample 0.5 to 2.0 (g) is precisely weighed, and the weight of the soluble component is defined as W (g).
2) A sample is put into a 300 (ml) beaker, and a mixed solution 150 (ml) of toluene / ethanol (4/1) is added and dissolved.
3) Titrate with 0.1 mol / l KOH ethanol solution using potentiometric titrator. (For example, automatic titration using a potentiometric titrator AT-400 (win workstation) manufactured by Kyoto Electronics Co., Ltd. and an ABP-410 electric burette can be used.) 4) The amount of KOH solution used at this time is S (ml At the same time, a blank is measured, and the amount of KOH solution used at this time is B (ml).
5) The acid value is calculated by the following formula (3). f is a factor of KOH.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples.

(Production Example H-1 of High Molecular Weight Component Resin)
・ Styrene 75 parts by mass ・ n-butyl acrylate 18 parts by mass ・ acrylic acid 7 parts by mass ・ 2,2-bis (4,4-di-tert-butylperoxycyclohexyl) propane
1 part by mass

  While stirring 200 parts by mass of xylene in a four-necked flask, the above components were sufficiently replaced with nitrogen and heated to 125 ° C., and then dropped over 5 hours. Further, the polymerization was completed under reflux of xylene, and the solvent was distilled off under reduced pressure. The resin thus obtained is designated as H-1.

(Production Example H-2 of High Molecular Weight Component Resin)
In Production Example H-1,
-Styrene 75 parts by mass-n-butyl acrylate 18 parts by mass-methacrylic acid 4 parts by mass-glycidyl methacrylate 3 parts by mass-2,2-bis (4,4-di-tert-butylperoxycyclohexyl) propane
Except having changed into 0.8 mass part, it carried out similarly to manufacture example H-1, and obtained resin H-2.

(Production Example H-3 of High Molecular Weight Component Resin)
In Production Example H-1,
-Styrene 77 parts by mass-N-butyl acrylate 15 parts by mass-Divinylbenzene 8 parts by mass-2,2-bis (4,4-di-tert-butylperoxycyclohexyl) propane
3 Resin H-3 was obtained in the same manner as in Production Example H-1, except that the amount was changed to 3 parts by mass.

(Production Example P-1 of Vinyl Resin Having Carboxyl Group)
-High molecular weight component resin H-1 35 parts by mass-Styrene 50 parts by mass-N-butyl acrylate 9 parts by mass-Acrylic acid 6 parts by mass-Di-tert-butyl peroxide 1.4 parts by mass

  The raw material was dropped into 200 parts by mass of xylene over 4 hours. Further, the polymerization is completed under reflux of xylene, the solvent is distilled off under reduced pressure, and the resin thus obtained is designated P-1.

(Production Example P-2 of Vinyl Resin Having Carboxyl Group)
-High molecular weight component resin H-1 35 parts by mass-Styrene 55 parts by mass-N-butyl acrylate 12 parts by mass-Methacrylic acid 3 parts by mass-Di-tert-butyl peroxide 1.2 parts by mass

  The raw material was dropped into 200 parts by mass of xylene over 3 hours. Furthermore, the polymerization is completed under reflux of xylene, the solvent is distilled off under reduced pressure, and the resin thus obtained is designated P-2.

(Production Example P-3 of Vinyl Resin Having Carboxyl Group)
-High molecular weight component resin H-2 30 parts by mass-Styrene 55 parts by mass-N-butyl acrylate 13.5 parts by mass-Methacrylic acid 1.5 parts by mass-Di-tert-butyl peroxide 1.0 part by mass

  The raw material was dropped into 200 parts by mass of xylene over 4 hours. Furthermore, the polymerization is completed under reflux of xylene, the solvent is distilled off under reduced pressure, and the resin thus obtained is designated P-3.

(Production Example P-4 of Vinyl Resin)
-High molecular weight component resin H-3 30 parts by mass-Styrene 55 parts by mass-N-butyl acrylate 15 parts by mass-Di-tert-butyl peroxide 1.8 parts by mass

  The raw material was dropped into 200 parts by mass of xylene over 4 hours. Furthermore, the polymerization is completed under reflux of xylene, the solvent is distilled off under reduced pressure, and the resin thus obtained is designated P-4.

(Production Example E-1 of Vinyl Resin Having Epoxy Group)
-Styrene 77 parts by mass-N-butyl acrylate 20 parts by mass-Glycidyl methacrylate 3 parts by mass-Di-tert-butyl peroxide 4 parts by mass

  While stirring 200 parts by mass of xylene in a four-necked flask, the inside of the container was sufficiently replaced with nitrogen, and the temperature was raised to 140 ° C., followed by dropwise addition over 4 hours. Furthermore, the polymerization is completed under reflux of xylene, the solvent is distilled off under reduced pressure, and the resin thus obtained is designated E-1.

(Production Example E-2 of Vinyl Resin Having Epoxy Group)
-Styrene 78 parts by mass-N-butyl acrylate 16 parts by mass-Glycidyl methacrylate 6 parts by mass-Di-tert-butyl peroxide 3 parts by mass

  While stirring 200 parts by mass of xylene in a four-necked flask, the inside of the container was sufficiently replaced with nitrogen, and the temperature was raised to 135 ° C., followed by dropwise addition over 4 hours. Furthermore, the polymerization is completed under reflux of xylene, the solvent is distilled off under reduced pressure, and the resin thus obtained is designated E-2.

(Production Example E-3 of Vinyl Resin Having Epoxy Group)
-Styrene 70 parts by mass-N-butyl acrylate 8 parts by mass-Monobutyl maleate 15 parts by mass-Glycidyl methacrylate 7 parts by mass-Di-tert-butyl peroxide 3 parts by mass

  While stirring 200 parts by mass of xylene in a four-necked flask, the inside of the container was sufficiently replaced with nitrogen, and the temperature was raised to 140 ° C., followed by dropwise addition over 4 hours. Furthermore, the polymerization is completed under reflux of xylene, and the solvent is distilled off under reduced pressure. The resin thus obtained is designated as E-3.

(Epoxy resin production example EP-1)
100 g of bisphenol A type liquid epoxy resin (Epomic R-140P), 47 g of bisphenol A, 30 g of p-cumylphenol, and about 20 g of xylene were added to a separable flask equipped with a stirrer, a thermometer, a nitrogen inlet, and a cooling tube.
After heating up to 70 ° C. in a nitrogen atmosphere, 0.03 g / H ₂ O of lithium chloride was added and 170
The reaction was carried out for 6 hours at ° C. Thereafter, 9.0 g of ε-caprolactone was added and reacted for 6 hours to obtain an epoxy resin EP-1.

(Magnetic substance production example 1)
An aqueous solution containing zinc-containing ferrous salt as a main component is prepared so that the mass ratio (mass%) of Zn / Fe is 0.5 mass%. A sodium oxide aqueous solution is mixed to obtain a ferrous hydroxide slurry. The pH of this ferrous hydroxide slurry is maintained at 12, and an oxidation reaction is performed at 80 ° C. The obtained slurry containing magnetite particles was subjected to dispersion treatment by applying mechanical shearing force, and then filtered, washed, dried and pulverized to obtain a magnetic body 1.
The obtained magnetic material had an average particle diameter of 0.13 μm, magnetic characteristics at a magnetic field of 796 kA / m, saturation magnetization of 87 Am ² / kg, residual magnetization of 10 Am ² / kg, and coercive force of 12 kA / m.

(Magnetic substance production example 2)
An aqueous solution containing a ferrous salt containing titanium as a main component is prepared so that the mass ratio (mass%) of Ti / Fe is 0.7 mass%. A sodium oxide aqueous solution is mixed to obtain a ferrous hydroxide slurry. The pH of this ferrous hydroxide slurry is maintained at 12, and an oxidation reaction is performed at 85 ° C. The obtained slurry containing magnetite particles was subjected to dispersion treatment by applying mechanical shearing force, and then filtered, washed, dried and pulverized to obtain a magnetic body 2.
The obtained magnetic material had an average particle size of 0.24 μm, magnetic properties of a saturation magnetization of 81 Am ² / kg, a residual magnetization of 9 Am ² / kg, and a coercive force of 12 kA / m.

(Magnetic substance production example 3)
An aqueous solution containing a ferrous salt containing silicon as a main component is prepared so that the mass ratio (mass%) of Si / Fe is 0.5 mass%, and water equivalent to or more than iron and silicon is added to the aqueous solution. A sodium oxide aqueous solution is mixed to obtain a ferrous hydroxide slurry. The pH of this ferrous hydroxide slurry is maintained at 12, and an oxidation reaction is performed at 80 ° C. The obtained slurry containing magnetite particles was subjected to dispersion treatment by applying a mechanical shearing force, and then filtered, washed, dried and pulverized to obtain a magnetic body 3.
The obtained magnetic material had an average particle size of 0.08 μm, magnetic properties of saturation magnetization of 87 Am ² / kg, residual magnetization of 13 Am ² / kg, and coercive force of 12 kA / m.

(Magnetic substance production example 4)
A sodium hydroxide aqueous solution equal to or more than iron in an aqueous solution containing a ferrous salt as a main component is mixed to obtain a ferrous hydroxide slurry. The pH of this ferrous hydroxide slurry was maintained at 12 and 8
The oxidation reaction is performed at 0 ° C. The obtained slurry containing magnetite particles was filtered, washed, dried and pulverized to obtain a magnetic body 4.
The obtained magnetic material had an average particle size of 0.33 μm, magnetic properties of saturation magnetization of 78 Am ² / kg, residual magnetization of 8 Am ² / kg, and holding force of 9 kA / m.

<Example 1>
Resin P-1: 85 parts by mass and resin E-1: 15 parts by mass were mixed with a Henschel mixer, kneaded at 190 ° C. with a biaxial kneading extruder, cooled, and then crushed to an average particle size of 200 μm Resin 1 was obtained. The binder resin 1 has a vinyl resin in which a carboxyl group and an epoxy group are reacted.

-Binder resin 1 100 parts by mass-Magnetic material 1 50 parts by mass-T-77 (Hodogaya Chemical Co., Ltd.) 2 parts by mass-Fischer-Tropsch wax (melting point = 105 ° C) 4 parts by mass

The above materials are put into a Henschel mixer in the order of binder resin, Fischer-Tropsch wax, T-77, and magnetic material (the magnetic material having a high specific gravity is placed above the raw material mixture to improve the pre-dispersibility of the magnetic material. ) After sufficiently premixing, the mixture was melt kneaded by a biaxial kneading extruder set at 130 ° C. The obtained kneaded product was cooled with a cooling belt (cooling water 15 ° C.), and the mixture was coarsely pulverized with a hammer mill. The coarsely pulverized product was finely pulverized by a turbo mill (manufactured by Turbo Kogyo Co., Ltd.), and the obtained finely pulverized product was classified by an air classifier to obtain a magnetic toner having a weight average particle diameter of 7.1 μm.
To 100 parts by mass of this magnetic toner, 1.2 parts by mass of hydrophobic dry silica (BET 180 m ² / g) was externally added using a Henschel mixer to obtain toner 1 shown in Table 6. Table 6 summarizes the toner physical properties.

(Evaluation of magnetic toner)
A commercially available Canon digital copying machine IR6010 was used, the process speed was changed from 265 mm / s to 320 mm / s, and high-speed output modification was performed so that 75 sheets of A4 horizontal size could be passed per minute. With this modification, when continuous double-sided paper feeding is performed, the separation material of the transfer material becomes severe, so the separation charging wire is brought closer to the 1 mm transfer paper direction. Both the in-machine temperature and the temperature in the vicinity of the developing device are easy to rise. In this state, using the toner 1 of the present invention, a double-sided endurance test of 100,000 sheets of 64 g / m ² Canon White Recycled Paper EW-100A4 paper in a low temperature and low humidity environment (temperature 23 ° C., humidity 5%) was performed. went. Thereafter, another 100,000 sheet passing durability test was conducted in a high temperature and high humidity environment (temperature 30 ° C., humidity 80%). The original used a chart with an image ratio of 5%. Evaluation on images was performed as follows.

(Image evaluation)
1. Image density Image density is measured with a Macbeth densitometer (Macbeth Co., Ltd.) using an SPI filter, and the reflection density of 5mm circle (1.1 density) of the chart is measured before and after the endurance test in the low temperature and low humidity environment and in the high temperature and high humidity environment. Concentration stability was evaluated by comparing before and after the durability test.

2.2 Evaluation of line image scattering and digital image sharpness Using a manuscript containing lines and text, the second surface image after a double-sided durability test in a low-temperature and low-humidity environment and a high-temperature and high-humidity environment was visually and magnified. Was used and evaluated according to the following criteria. (Confirmation of influence on image by applying separation static elimination)

A: Both the character image and the line image are faithfully reproduced to the details. B: The details are slightly disturbed or scattered, but there is a problem with visual inspection.
C: A level at which visual perception of disturbances and scattering is observed. D: Many disturbances and scattering occur, and the document is not reproduced.

3. Evaluation of halftone uniformity on the second side of both sides After 10K sheets of double-sided paper endurance under high temperature and high humidity, an A4 halftone image with an image density of 0.6 is output, and the resulting A4 image is 6 Dividing into equal parts, the difference between the maximum value and the minimum value of the halftone image density was judged according to the following criteria.

A: Change less than 0.03 and homogeneous image B: Change is 0.03 to 0.10 and is not visually confirmed as a heterogeneous image C: Change is 0.11 to 0.20 and can be visually confirmed as a heterogeneous image D : Change is 0.21 or more, clearly recognized as a heterogeneous image

4. Evaluation of retransferability After 10 k sheets of each environment, the separation charging wire was returned to the normal position, and double-sided paper was passed through the paper thickness 64 g / m ² Canon White Recycled Paper EW-100A3 recycled paper. A character original image within 100 mm from the leading edge of the paper was evaluated as “line or character dropout” by retransfer.

A: Almost no line or character void is seen B: Some voids are slightly missing, but there is no practical problem C: Missing voids can be recognized D: Clear voids can be clearly recognized

5. Evaluation of toner consumption In the image formation test, the toner was obtained from the initial developing device weight and the developing device weight after outputting 2000 sheets by the following equation (4).

6. Evaluation of offset property in high-speed fixing Process speed from 265mm / s to 320m in low temperature (15 ° C) and normal humidity (30%) environment
The IR6010, which was converted to high-speed output so that 75 sheets of A4 horizontal size can be passed in 1 minute, was installed, and the input power supply was changed from 100 V to 95 V with a stabilized power supply. In this state, an original (A3 size) with an image ratio of 5% was continuously passed through a sheet of 105 g / m ² Canon color laser copier paper with a paper thickness of 105 g / m ² . The evaluation of offset property in high-speed fixing was judged according to the following criteria under the condition that the charging of the fixing roller due to continuous paper passing increased and the fixing roller temperature also decreased due to vaporization of continuous paper passing water as the input voltage decreased.

A: No offset is seen during 1000 sheets passed B: A slight offset is seen between 800 and 1000 sheets C: Offset is seen between 500 sheets and 800 sheets D: Up to 500 sheets passed Table 7 shows the results of each evaluation. As a result, good results were obtained as shown in Table 7.

<Example 2>
Resin P-1: 83 parts by mass and Resin E-1: 17 parts by mass were mixed with a Henschel mixer, kneaded at 190 ° C. with a biaxial kneading extruder, cooled, and then crushed to an average particle size of 200 μm Resin 2 was obtained. The binder resin 2 has a vinyl resin in which at least a carboxyl group and an epoxy group are reacted.

-Binder resin 2 100 parts by mass-Magnetic material 1 50 parts by mass-T-77 (Hodogaya Chemical Co., Ltd.) 2 parts by mass-Fischer-Tropsch wax (melting point = 105 ° C) 4 parts by mass

The above materials were put in a Henschel mixer in the order of binder resin, Fischer-Tropsch wax, T-77, and magnetic material and sufficiently premixed, and then melt-kneaded by a biaxial kneading extruder set at 130 ° C. The obtained kneaded product was cooled with a cooling belt (cooling water 15 ° C.), and the mixture was coarsely pulverized with a hammer mill. The coarsely pulverized product was finely pulverized by a turbo mill (manufactured by Turbo Kogyo Co., Ltd.), and the obtained finely pulverized product was classified by an air classifier to obtain a magnetic toner having a weight average particle diameter of 7.1 μm.
To 100 parts by mass of this magnetic toner, 1.2 parts by mass of hydrophobic dry silica (BET 180 m ² / g) was externally added with a Henschel mixer to obtain toner 2 shown in Table 6. Table 6 summarizes the toner physical properties.
Evaluation similar to Example 1 was performed and the results of each evaluation are shown in Table 7. As a result, good results were obtained as shown in Table 7.

<Example 3>
Resin P-1: 83 parts by mass and Resin E-1: 17 parts by mass were mixed with a Henschel mixer and then 150 ° C. with a biaxial kneading extruder (the temperature was lowered to suppress the reaction between carboxylic acid and epoxy group) ), And after cooling, binder resin 3 pulverized to an average particle size of 200 μm was obtained. The binder resin 3 has a vinyl resin in which at least a carboxyl group and an epoxy group are reacted.

-Binder resin 3 100 parts by mass-Magnetic material 1 50 parts by mass-T-77 (Hodogaya Chemical Co., Ltd.) 2 parts by mass-Fischer-Tropsch wax (melting point = 105 ° C) 4 parts by mass

The above materials were put in a Henschel mixer in the order of binder resin, Fischer-Tropsch wax, T-77, and magnetic material and sufficiently premixed, and then melt-kneaded by a biaxial kneading extruder set at 130 ° C. The obtained kneaded product was cooled with a cooling belt (cooling water 15 ° C.), and the mixture was coarsely pulverized with a hammer mill. The coarsely pulverized product was finely pulverized by a turbo mill (manufactured by Turbo Kogyo Co., Ltd.), and the obtained finely pulverized product was classified by an air classifier to obtain a magnetic toner having a weight average particle diameter of 7.1 μm.
To 100 parts by mass of this magnetic toner, 1.2 parts by mass of hydrophobic dry silica (BET 180 m ² / g) was externally added using a Henschel mixer to obtain toner 3 shown in Table 6. Table 6 summarizes the toner physical properties.
Evaluation similar to Example 1 was performed and the results of each evaluation are shown in Table 7. As a result, good results were obtained as shown in Table 7.

<Example 4>
Resin P-4: 75 parts by mass, Resin P-3: 23 parts by mass, Resin E-1: 2 parts by mass were mixed with a Henschel mixer, kneaded at 170 ° C. with a biaxial kneading extruder, cooled, Binder resin 4 pulverized to an average particle size of 150 μm was obtained. The binder resin 4 includes at least a vinyl resin having a carboxyl group, a vinyl resin having an epoxy group, and a vinyl resin in which a carboxyl group and an epoxy group are reacted.

-Binder resin 4 100 parts by mass-Magnetic material 1 50 parts by mass-T-77 (Hodogaya Chemical Co., Ltd.) 2 parts by mass-Fischer-Tropsch wax (melting point = 105 ° C) 4 parts by mass

The above materials were put into a Henschel mixer in the order of binder resin, Fischer-Tropsch wax, T-77, and magnetic material and sufficiently premixed, and then melt-kneaded by a twin-screw kneading extruder set at 140 ° C. The obtained kneaded product was cooled with a cooling belt (cooling water 15 ° C.), and the mixture was coarsely pulverized with a hammer mill. The coarsely pulverized product was finely pulverized by a turbo mill (manufactured by Turbo Kogyo Co., Ltd.), and the obtained finely pulverized product was classified by an air classifier to obtain a magnetic toner having a weight average particle diameter of 7.4 μm.
To 100 parts by mass of this magnetic toner, 1.2 parts by mass of hydrophobic dry silica (BET 180 m ² / g) was externally added with a Henschel mixer to obtain toner 4 shown in Table 6. Table 6 summarizes the toner physical properties.
Evaluation similar to Example 1 was performed and the results of each evaluation are shown in Table 7. As a result, good results were obtained as shown in Table 7.

<Example 5>
Resin P-1: 75 parts by mass, Resin P-2: 15 parts by mass, Resin E-1: 10 parts by mass were mixed with a Henschel mixer, kneaded at 200 ° C. with a biaxial kneading extruder, cooled, Binder resin 5 pulverized to an average particle size of 150 μm was obtained. The binder resin 5 includes at least a vinyl resin having a carboxyl group, a vinyl resin having an epoxy group, and a vinyl resin in which a carboxyl group and an epoxy group are reacted.

-Binder resin 5 100 parts by mass-Magnetic material 2 70 parts by mass-T-77 (Hodogaya Chemical Co., Ltd.) 2 parts by mass-Fischer-Tropsch wax (melting point = 105 ° C) 4 parts by mass

The above materials were put in a Henschel mixer in the order of binder resin, Fischer-Tropsch wax, T-77, and magnetic material and sufficiently premixed, and then melt-kneaded by a biaxial kneading extruder set at 130 ° C. The obtained kneaded product was cooled with a cooling belt (cooling water 15 ° C.), and the mixture was coarsely pulverized with a hammer mill. The coarsely pulverized product was finely pulverized with a turbo mill (manufactured by Turbo Kogyo Co., Ltd.), and the obtained finely pulverized product was classified with an air classifier to obtain a magnetic toner having a weight average particle size of 7.3 μm.
To 100 parts by mass of this magnetic toner, 1.2 parts by mass of hydrophobic dry silica (BET 180 m ² / g) was externally added with a Henschel mixer to obtain toner 5 shown in Table 6. Table 6 summarizes the toner physical properties.
Evaluation similar to Example 1 was performed and the results of each evaluation are shown in Table 7. As a result, good results were obtained as shown in Table 7.

<Example 6>
Resin P-3: 85 parts by mass and resin E-1: 15 parts by mass were mixed with a Henschel mixer, kneaded at 160 ° C. with a biaxial kneading extruder, cooled, and then crushed to an average particle size of 300 μm Resin 6 was obtained. The binder resin 6 has a vinyl resin in which at least a carboxyl group and an epoxy group are reacted.

Binder resin 6 100 parts by mass Magnetic substance 2 70 parts by mass T-77 (Hodogaya Chemical Co., Ltd.) 2 parts by mass Fischer-Tropsch wax (melting point = 105 ° C) 4 parts by mass

The above materials were put in a Henschel mixer in the order of binder resin, Fischer-Tropsch wax, T-77, and magnetic material and sufficiently premixed, and then melt-kneaded by a biaxial kneading extruder set at 130 ° C. The obtained kneaded product was cooled with a cooling belt (cooling water 15 ° C.), and the mixture was coarsely pulverized with a hammer mill. The coarsely pulverized product was finely pulverized with a turbo mill (manufactured by Turbo Kogyo Co., Ltd.), and the obtained finely pulverized product was classified with an air classifier to obtain a magnetic toner having a weight average particle size of 7.3 μm.
To 100 parts by mass of this magnetic toner, 1.2 parts by mass of hydrophobic dry silica (BET 180 m ² / g) was externally added with a Henschel mixer to obtain toner 6 shown in Table 6. Table 6 summarizes the toner physical properties.
Evaluation similar to Example 1 was performed and the results of each evaluation are shown in Table 7. As a result, good results were obtained as shown in Table 7.

<Example 7>
Resin P-2: 95 parts by mass, Resin E-1: 5 parts by mass were mixed with a Henschel mixer, kneaded at 200 ° C. with a biaxial kneading extruder, cooled, and then crushed to an average particle size of 100 μm Resin 7 was obtained. The binder resin 7 has a vinyl resin in which at least a carboxyl group and an epoxy group are reacted.

-Binder resin 7 100 parts by mass-Magnetic material 3 35 parts by mass-T-77 (Hodogaya Chemical Co., Ltd.) 2 parts by mass-Fischer-Tropsch wax (melting point = 105 ° C) 4 parts by mass

The above materials were put in a Henschel mixer in the order of binder resin, Fischer-Tropsch wax, T-77, and magnetic substance, and sufficiently mixed, and then melt-kneaded by a twin-screw kneading extruder set at 130 ° C. The obtained kneaded product was cooled with a cooling belt (cooling water 15 ° C.), and the mixture was coarsely pulverized with a hammer mill. The coarsely pulverized product was finely pulverized with a turbo mill (manufactured by Turbo Kogyo Co., Ltd.), and the obtained finely pulverized product was classified with an air classifier to obtain a magnetic toner having a weight average particle size of 7.3 μm.
To 100 parts by mass of this magnetic toner, 1.2 parts by mass of hydrophobic dry silica (BET 180 m ² / g) was externally added with a Henschel mixer to obtain toner 7 shown in Table 6. Table 6 summarizes the toner physical properties.
Evaluation similar to Example 1 was performed and the results of each evaluation are shown in Table 7. As a result, good results were obtained as shown in Table 7.

<Example 8>
Resin P-2: 85 parts by mass, Resin E-2: 15 parts by mass were mixed with a Henschel mixer, kneaded at 200 ° C. with a biaxial kneading extruder, cooled, and then crushed to an average particle size of 100 μm Resin 8 was obtained. The binder resin 8 includes a vinyl resin having at least a carboxyl group and an epoxy group, and a vinyl resin in which the carboxyl group and the epoxy group are reacted.

-Binder resin 8 100 parts by mass-Magnetic material 3 35 parts by mass-T-77 (Hodogaya Chemical Co., Ltd.) 1 part by mass-TN-105 (Hodogaya Chemical Co., Ltd.) 2 parts by mass Fischer-Tropsch wax (melting point = 105 ° C) 4 parts by mass

The above materials were put into a Henschel mixer in the order of binder resin, Fischer-Tropsch wax, T-77, TN-105, and magnetic material, sufficiently premixed, and then melt-kneaded by a twin-screw kneading extruder set at 150 ° C. . The obtained kneaded product was cooled with a cooling belt (cooling water 15 ° C.), and the mixture was coarsely pulverized with a hammer mill. The coarsely pulverized product is finely pulverized with a turbo mill (manufactured by Turbo Kogyo Co., Ltd.), and the resulting finely pulverized product is classified with an air classifier to obtain a weight average particle size of 5.3 μm.
Magnetic toner was obtained.
To 100 parts by mass of this magnetic toner, 1.2 parts by mass of hydrophobic dry silica (BET 180 m ² / g) was externally added with a Henschel mixer to obtain toner 8 shown in Table 6. Table 6 summarizes the toner physical properties.
Evaluation similar to Example 1 was performed and the results of each evaluation are shown in Table 7. As a result, good results were obtained as shown in Table 7.

<Example 9>
Resin P-2: 90 parts by mass and resin E-1: 10 parts by mass were mixed with a Henschel mixer, kneaded at 200 ° C. with a biaxial kneading extruder, cooled, and then crushed to an average particle size of 100 μm Resin 9 was obtained. The binder resin 9 has a vinyl resin in which at least a carboxyl group and an epoxy group are reacted.

-Binder resin 9 100 parts by mass-Magnetic material 1 50 parts by mass-T-77 (Hodogaya Chemical Co., Ltd.) 2 parts by mass-Fischer-Tropsch wax (melting point = 105 ° C) 4 parts by mass

The above materials were put in a Henschel mixer in the order of binder resin, Fischer-Tropsch wax, T-77, and magnetic material, and sufficiently premixed, and then melt-kneaded by a biaxial kneading extruder set at 120 ° C. The obtained kneaded product was cooled with a cooling belt (cooling water 15 ° C.), and the mixture was coarsely pulverized with a hammer mill. The coarsely pulverized product was finely pulverized by a turbo mill (manufactured by Turbo Kogyo Co., Ltd.), and the obtained finely pulverized product was classified by an air classifier to obtain a magnetic toner having a weight average particle diameter of 8.7 μm.
To 100 parts by mass of this magnetic toner, 0.8 part by mass of hydrophobic dry silica (BET 180 m ² / g) was externally added with a Henschel mixer to obtain toner 9 shown in Table 6. Table 6 summarizes the toner physical properties.
Evaluation similar to Example 1 was performed and the results of each evaluation are shown in Table 7. As a result, good results were obtained as shown in Table 7.

<Example 10>
Resin P-4: 65 parts by mass, Resin P-3: 5 parts by mass, Resin E-1: 30 parts by mass were mixed with a Henschel mixer, kneaded at 200 ° C. with a biaxial kneading extruder, cooled, Binder resin 10 pulverized to an average particle size of 100 μm was obtained. The binder resin 10 has a vinyl resin in which at least a carboxyl group and an epoxy group are reacted.

-Binder resin 10 100 parts by mass-Magnetic material 1 50 parts by mass-T-77 (Hodogaya Chemical Co., Ltd.) 2 parts by mass-Fischer-Tropsch wax (melting point = 105 ° C) 4 parts by mass

The above materials were put in a Henschel mixer in the order of binder resin, Fischer-Tropsch wax, T-77, and magnetic material, and sufficiently premixed, and then melt-kneaded by a biaxial kneading extruder set at 120 ° C. The obtained kneaded product was cooled with a cooling belt (cooling water 15 ° C.), and the mixture was coarsely pulverized with a hammer mill. The coarsely pulverized product was finely pulverized with a turbo mill (manufactured by Turbo Kogyo Co., Ltd.), and the obtained finely pulverized product was classified with an air classifier to obtain a magnetic toner having a weight average particle diameter of 7.3 μm.
To 100 parts by mass of this magnetic toner, 1.2 parts by mass of hydrophobic dry silica (BET 180 m ² / g) was externally added with a Henschel mixer to obtain toner 10 shown in Table 6. Table 6 summarizes the toner physical properties.
Evaluation similar to Example 1 was performed and the results of each evaluation are shown in Table 7. As a result, good results were obtained as shown in Table 7.

<Comparative Example 1>
60 parts by mass of resin E-3 and 40 parts by mass of resin EP-1 were mixed with a Henschel mixer, then kneaded at 130 ° C. with a biaxial kneading extruder, cooled and pulverized to obtain comparative binder resin 1. .

-Comparative binder resin 1 100 parts by mass-Magnetic material 4 100 parts by mass-T-77 (Hodogaya Chemical Co., Ltd.) 2 parts by mass-Fischer-Tropsch wax (melting point = 105 ° C) 4 parts by mass

The above materials were put into a Henschel mixer in the order of magnetic material, Fischer-Tropsch wax, T-77, and binder resin, sufficiently premixed, and then melt-kneaded by a biaxial kneading extruder set at 120 ° C. The obtained kneaded product was cooled with a cooling belt (cooling water 15 ° C.), and the mixture was coarsely pulverized with a hammer mill. The coarsely pulverized product was finely pulverized by a turbo mill (manufactured by Turbo Kogyo Co., Ltd.), and the obtained finely pulverized product was classified by an air classifier to obtain a magnetic toner having a weight average particle diameter of 7.1 μm.
To 100 parts by mass of this magnetic toner, 1.2 parts by mass of hydrophobic dry silica (BET 180 m ² / g) was externally added with a Henschel mixer to obtain Comparative Toner 1 shown in Table 6. Table 6 summarizes the toner physical properties.
Evaluation similar to Example 1 was performed and the results of each evaluation are shown in Table 7. As a result, as shown in Table 7, the image scattering on both sides of both surfaces under high humidity is remarkable due to the effect of the separation charge removal, and the halftone uniformity is further deteriorated due to the decrease in the adhesion of the toner to the transfer paper due to charge removal. Further, the developed image density stability, toner consumption, offset property in high-speed fixing, etc. were poor.

<Comparative example 2>
99 parts by mass of resin H-3 and 1 part by mass of resin EP-1 were mixed with a Henschel mixer, then kneaded at 220 ° C. with a biaxial kneading extruder, cooled and pulverized to obtain comparative binder resin 2. .

-Comparative binder resin 2 100 parts by mass-Magnetic material 2 25 parts by mass-T-77 (Hodogaya Chemical Co., Ltd.) 2 parts by mass-Fischer-Tropsch wax (melting point = 105 ° C) 4 parts by mass

The above materials were put into a Henschel mixer in the order of magnetic material, Fischer-Tropsch wax, T-77, and binder resin, sufficiently premixed, and then melt-kneaded by a biaxial kneading extruder set at 150 ° C. The obtained kneaded product was cooled with a cooling belt (cooling water 15 ° C.), and the mixture was coarsely pulverized with a hammer mill. The coarsely pulverized product was finely pulverized by a turbo mill (manufactured by Turbo Kogyo Co., Ltd.), and the obtained finely pulverized product was classified by an air classifier to obtain a magnetic toner having a weight average particle diameter of 7.1 μm.
To 100 parts by mass of this magnetic toner, 1.2 parts by mass of hydrophobic dry silica (BET 180 m ² / g) was externally added with a Henschel mixer to obtain comparative toner 2 shown in Table 6. Table 6 summarizes the toner physical properties.
Evaluation similar to Example 1 was performed and the results of each evaluation are shown in Table 7. As a result, as shown in Table 7, retransfer occurred, and the image density was significantly reduced under a low humidity environment.

<Comparative Example 3>
60 parts by mass of resin E-3 and 40 parts by mass of resin E-1 were mixed with a Henschel mixer, then kneaded at 130 ° C. with a biaxial kneading extruder, cooled and pulverized to obtain comparative binder resin 3. .

-Comparative binder resin 3 100 parts by mass-Magnetic material 1 50 parts by mass-T-77 (Hodogaya Chemical Co., Ltd.) 2 parts by mass-Fischer-Tropsch wax (melting point = 105 ° C) 4 parts by mass

The above materials were put into a Henschel mixer in the order of magnetic material, Fischer-Tropsch wax, T-77, and binder resin, sufficiently premixed, and then melt-kneaded by a biaxial kneading extruder set at 120 ° C. The obtained kneaded product was cooled with a cooling belt (cooling water 15 ° C.), and then the mixture was coarsely pulverized with a hammer mill. The coarsely pulverized product was finely pulverized by a turbo mill (manufactured by Turbo Kogyo Co., Ltd.), and the obtained finely pulverized product was classified by an air classifier to obtain a magnetic toner having a weight average particle diameter of 7.1 μm.
To 100 parts by mass of this magnetic toner, 1.2 parts by mass of hydrophobic dry silica (BET 180 m ² / g) was externally added with a Henschel mixer to obtain Comparative Toner 3 shown in Table 6. Table 6 summarizes the toner physical properties.
Evaluation similar to Example 1 was performed and the results of each evaluation are shown in Table 7. As a result, as shown in Table 7, as in Comparative Example 1, the image characteristics under high humidity, the toner consumption, and the offset property in high-speed fixing were inferior.

<Comparative example 4>
98 parts by mass of resin P-4 and 2 parts by mass of resin E-1 were mixed with a Henschel mixer, then kneaded at 130 ° C. with a biaxial kneading extruder, cooled and pulverized to obtain comparative binder resin 4. .

-Comparative binder resin 4 100 parts by mass-Magnetic material 1 50 parts by mass-T-77 (Hodogaya Chemical Co., Ltd.) 2 parts by mass-Fischer-Tropsch wax (melting point = 105 ° C) 4 parts by mass

The above materials were put into a Henschel mixer in the order of magnetic material, Fischer-Tropsch wax, T-77, and binder resin, sufficiently premixed, and then melt-kneaded by a biaxial kneading extruder set at 120 ° C. The obtained kneaded product was cooled with a cooling belt (cooling water 15 ° C.), and the mixture was coarsely pulverized with a hammer mill. The coarsely pulverized product was finely pulverized by a turbo mill (manufactured by Turbo Kogyo Co., Ltd.), and the obtained finely pulverized product was classified by an air classifier to obtain a magnetic toner having a weight average particle diameter of 7.1 μm.
To 100 parts by mass of this magnetic toner, 1.2 parts by mass of hydrophobic dry silica (BET 180 m ² / g) was externally added with a Henschel mixer to obtain Comparative Toner 5 shown in Table 6. Table 6 summarizes the toner physical properties.
Evaluation similar to Example 1 was performed and the results of each evaluation are shown in Table 7. As a result, as shown in Table 7, retransfer was remarkable and the image density stability was inferior to that of Example 1.

Claims (4)

In a magnetic toner containing at least a binder resin and a magnetic material,
(I) The binder resin is a) a vinyl resin having a carboxyl group and a vinyl resin having an epoxy group, b) a vinyl resin having a carboxyl group and an epoxy group, and c) a vinyl in which the carboxyl group and the epoxy group are reacted. Contains one or more vinyl resins selected from the group consisting of resins,
(Ii) the weight average particle diameter of the toner is 5.0 to 9.0 μm;
(Iii) the true specific gravity of the toner is 1.1 to 1.6 g / cm ³ ;
(Iv) the saturation magnetization of the toner at a magnetic field of 796 kA / m is 20 to 35 Am ² / kg;
(V) The toner has a dielectric constant of 15 to 40 (pF / m) at 100 kHz and 40 ° C.
(Vi) A magnetic toner characterized in that the frequency dependence of the dielectric loss tangent (tan δ) of the toner at 40 ° C. satisfies the following formula (1).

2. The magnetic toner according to claim 1, wherein a dielectric loss tangent of the toner at 100 kHz and 40 ° C. is 2.0 × 10 ^{−3 to} 2.0 × 10 ⁻² .   3. The magnetic toner according to claim 1, wherein the magnetic material has an average particle size of 0.08 to 0.30 μm. The toner has an acid value of 1.0 to 20 mgKOH / g in a chloroform-soluble component in the toner, and an epoxy amount of 2.0 to 0.1 mmol / g in a chloroform-soluble component. The magnetic toner according to claim 1.