JP3347533B2 - Electrostatic image developing toner, image forming method, resin composition for the toner, and manufacturing method thereof - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to electrophotography, electrostatic printing,
In an image forming method such as magnetic recording, the present invention relates to a toner for visualizing a latent electrostatic image. In particular, a toner for developing an electrostatic image used in a fixing method of heating and fixing a visible image formed by a toner to a recording material, an image forming method using the toner, and a resin composition used for the toner and the same It relates to a manufacturing method.

[0002]

2. Description of the Related Art An electrophotographic method is disclosed in U.S. Pat.
A number of methods are known, as described in Japanese Patent Publication No. 7,691, Japanese Patent Publication No. 42-23910, and Japanese Patent Publication No. 43-24748, but generally, a photoconductive substance is used. An electric latent image is formed on the photoreceptor by various means, then the latent image is developed using toner, and if necessary, a toner image is transferred to a transfer material such as paper. The toner is fixed by pressurization or solvent vapor to obtain a copy, and the remaining toner not transferred onto the photoreceptor is cleaned by various methods, and the above-described steps are repeated.

In recent years, such copying apparatuses have been strictly pursued for smaller size, lighter weight, higher speed, and higher reliability, and as a result, the performance required for toner has also become higher. ing. For example, various methods and apparatuses have been developed for the process of fixing a toner image on a sheet such as paper, but the most common method at present is a heat compression method using a heat roller. The heat compression bonding method using a heat roller performs fixing by allowing the toner image surface of a sheet to be fixed to pass through the surface of a heat roller having a surface formed of a material having releasability with respect to toner while contacting the surface under pressure. . In this method, since the surface of the heat roller and the toner image of the sheet to be fixed come into contact with each other under pressure, the heat efficiency when fixing the toner image on the sheet to be fixed is extremely good, and the fixing can be performed quickly. It is very effective in high-speed electrophotographic copying machines.

However, in the above-described heat roller fixing which has been frequently used, (1) there is a so-called wait time during which the image forming operation is prohibited until the heat roller reaches a predetermined temperature.

(2) The optimum temperature of the heating roller is set in order to prevent defective fixing due to the fluctuation of the temperature of the heating roller due to the passage of the recording material or other external factors and the transfer of toner to the heating roller, ie, the so-called offset phenomenon. In order to achieve this, the heat capacity of the heating roller or the heating element must be increased, which requires a large amount of electric power and causes a rise in the temperature inside the image forming apparatus.

(3) Since the pressure roller has a lower temperature than the fixing roller, when the recording material is discharged through the heating roller, the recording material and the toner on the recording material are cooled slowly. The toner becomes highly sticky, and in combination with the curvature of the roller, a paper jam may occur due to offset or entanglement of the recording material. Etc. are not fundamentally solved.

JP-A-63-313182 by the present applicant
In Japanese Patent Application Laid-Open Publication No. H10-209, an image with a short wait time and a low power consumption is fixed by a fixing device that heats a toner visible image through a heat-resistant sheet moved by a low-heat-capacity heating element heated in a pulse shape and fixes the recording material. A forming device has been proposed. Similarly, Japanese Patent Application Laid-Open No. Hei.
No. 7582 discloses a fixing device for heating and fixing a visible image of a toner to a recording material via a heat-resistant sheet.
A fixing device has been proposed in which the heat-resistant sheet has a heat-resistant layer and a release layer or a low-resistance layer to effectively prevent the offset phenomenon.

However, in order to realize a fixing method that has a short wait time and low power consumption while achieving excellent fixability of a toner-visible image to a recording material, prevention of offset, and the like, a fixing device as described above is used. In addition, the characteristics of the toner are greatly affected.

Conventionally, a method using a toner having two peaks in the molecular weight distribution as a binder resin of the toner, and a low molecular weight wax are typified by the idea of giving the toner itself good fixability and offset resistance. A method of adding a low molecular weight polyolefin polymer to a toner has been proposed.

The method described in, for example, JP-A-56-1
6144, JP-A-2-23569, JP-A-63-127254, JP-A-3-26831, JP-A-62-9356, JP-A-3-725
Japanese Patent Application Laid-Open No. 52-3304 and Japanese Patent Application Laid-Open No. 52-330
No. 5, JP-A-57-52574, JP-A-58-58574
JP-A-215659, JP-A-60-217366, JP-A-60-252361, JP-A-60-2
No. 52362 is disclosed.

However, simply using a binder resin having two peaks in the molecular weight distribution or including a certain release agent in the toner does not improve the fixing property and the offset resistance to some extent. Although it can be seen, not only does the binder component in the toner cause non-uniformity, but also hinders the dispersion of other components such as wax, and uneven distribution and release of specific components are likely to occur. This may cause fusion to a photosensitive member or filming.

In a binder resin having two peaks, the use of a polyfunctional initiator to increase the molecular weight on the high molecular weight side is also described in JP-A-2-272559 and JP-A-3-72505. Although described, it is necessary to broaden the molecular weight distribution of the binder resin in order to apply it to the fixing property at lower temperature and the anti-offset property at higher temperature, and this is applied to the binder resin having two peaks. In such a case, the compatibility between the low-molecular component and the high-molecular component is further deteriorated due to the further polarization of the low-molecular component and the high-molecular component, so that the above-described serious problem is likely to occur.

Therefore, for example, the compatibility of the toner constituent components,
In order to improve the dispersibility, when the kneading conditions at the time of melt kneading during the production of the toner is strengthened, the molecular weight of the toner at the time of toner decreases due to the breaking of the molecular chain of the binder resin in the toner due to kneading, There are problems such as deterioration of the offset resistance, particularly the hot offset on the high temperature side.
Also, when a large amount of wax is added to exert a sufficient effect on the offset resistance, the blocking resistance is deteriorated, and the dispersion of the wax is further deteriorated. This promotes contamination of the surface, deteriorates the image, and poses a practical problem.

On the other hand, Japanese Patent Application Laid-Open No. 61-114246 discloses that a vinyl monomer is grafted on a high molecular weight polymer component having a number average molecular weight of 30,000 or more, so that the molecular weight distribution of the resin is shifted toward the high polymer region. It has been proposed to widen and consequently improve the offset resistance. However, with such a binder resin, it is possible to broaden the molecular weight distribution to a certain extent in a state of relatively good compatibility, but the polymer-side component is selectively selected due to the shearing force applied during melt-kneading during toner production. The effect is halved inevitably because it is cut into pieces. In particular, when applied to a magnetic toner that requires a uniform dispersion of high-specific-gravity magnetic fine particles, it is very difficult to achieve both improvement in offset resistance and securing of developability. In addition, as a result of our investigation, when a resin having a relatively large molecular weight such as a number average molecular weight exceeding 30,000 is used, the grafting ratio becomes low, and as a result, the generation of by-products is promoted. The charging characteristics of a developer using such a resin become unstable, causing not only difficulty in combination with the image forming means, but also a problem that when the toner particle size is reduced for the purpose of high quality development, the New problems such as low density, toner fogging on a white background, and defective cleaning occur.

On the other hand, JP-A-6-75427 discloses that
Electrophotographic toner composition comprising as a main structural component a low molecular weight polymer component having a Mw / Mn of less than 3.0 produced using a polyfunctional unsaturated monomer and / or a polyfunctional polymerization initiator Things have been suggested. Also, Japanese Patent Application Laid-Open No. 6-130
No. 721 discloses a compound having three or more peroxy groups in the molecule and / or a compound having one or more unsaturated functional groups and one or more peroxy groups in the molecule. (Mw; weight average molecular weight, M
b; weight average molecular weight between crosslinking points) is 2 to 99, and Mw / M
An electrophotographic toner resin composition containing a low molecular weight polymer component having n of 2.6 to 5.0 is disclosed. However, although these compositions are effective in improving the toner strength, they have not yet achieved both low-temperature fixing and high-temperature offset resistance. Further, when the toner is made to have a fine particle size for the purpose of high-definition development, an improvement in toner strength significantly lowers productivity. Further, when a large amount of a polyfunctional polymerization initiator is used in the production of the binder resin, poor charging of the toner due to the residue of the initiator occurs, and the raw material cost and production efficiency must be improved.

By the way, the untransferred toner which has not been transferred and remains on the photoreceptor is cleaned and removed by various methods, then collected and discharged as so-called "waste toner", and is not used again. Did not. Since the waste toner is treated as waste (waste plastic), the waste toner is reused from the viewpoints of effective use of resources, reduction of waste, and consideration of living environment, so-called toner reuse. Considerations have been widely conducted. If the waste toner can be reused, other merits such as not only effective use of the toner as described above but also downsizing of the image forming apparatus can be considered.

However, in practice, when the waste toner is reused, the image quality is adversely affected due to a reduction in image density or a fogging phenomenon, or a problem occurs in matching with an image forming apparatus.

Therefore, the toner applied to the toner reuse as described above includes a developing property, an environmental stability, a low-temperature fixing property, an offset resistance, and a developing property conventionally desired for the toner.
In addition to various properties such as storability, it is also required to have excellent mechanical strength and durability against external force, and also excellent transportability of waste toner to a developing portion.

The various properties required for the above-mentioned toners are often reciprocal to each other, and it is increasingly desired in recent years to satisfy them with high performance. Under such circumstances, each toner constituent material plays a large role, and it is required to have high functionality, and it is important to design an image forming system that brings out excellent characteristics of the toner. However, there is not yet enough comprehensive response to comprehensively address the above issues.

[0020]

SUMMARY OF THE INVENTION An object of the present invention is to significantly improve the disadvantages of the prior art, improve the fixability and the anti-offset property, and stably realize a high-quality image for a long period of time. And a toner for developing an electrostatic image capable of being highly applied to an electrophotographic process that does not adversely affect a photoreceptor or a developer carrier, an image forming method using the toner, a resin composition for the toner, and production thereof It provides a method.

[0021]

Means and Action for Solving the Problems The present inventors have
As a result of intensive studies, by specifying the structure of the resin composition and the polymer components constituting the resin composition, and the method of producing them, the resin composition has an extremely wide fixable temperature range, and
The present inventors have found that excellent reproducibility of fine lines can be formed and a stable and good image can be formed, and the present invention has been completed.

That is, the present invention relates to a toner for developing an electrostatic image formed of at least a composition in which a binder resin and a colorant are dispersed, wherein the binder resin component in the composition is soluble in tetrahydrofuran (THF). The component showing a molecular weight distribution of 50,000 or less by gel permeation chromatography (GPC) measured by

[0023]

(Equation 5) This is a toner for developing an electrostatic image.

Further, the present invention is an image forming method using the toner.

Further, the present invention relates to the resin composition for toner and a method for producing the same.

Hereinafter, the present invention will be described in detail.

In the present invention, the branched structure and the molecular chain spread of the low molecular weight polymer component having a molecular weight distribution of GPC of 50,000 or less as measured by the THF soluble component of the binder resin component in the toner composition are controlled. By doing so, the low-temperature fixability and the high-temperature offset resistance, the toner developability, and the matching with the image forming apparatus can be highly satisfied without impairing the productivity of the toner.

The molecular structure of the low molecular weight component is such that the weight average molecular weight <Mw ^l > measured by the light scattering method and the weight average molecular weight <Mw ^g > measured by the GPC method satisfy 1.2 ≦
<Mw ^l> / meet the <Mw ^g> ≦ 3.0 of the relationship, and,
Inertial square radius <S ² > ^1/2 measured by the light scattering method is 1
It is controlled so as to be not less than 00 °.

In the GPC method, when a measurement molecule passes through the column, it undergoes a molecular sieving effect due to pores of the filler, and elutes in order from the one having a larger molecular size, and the molecular weight is measured. In this case, the linear polymer and the branched polymer having the same molecular weight are eluted earlier because the former has a larger molecular size in the solution. Therefore, the molecular weight of the branched polymer measured by the GPC method is measured to be smaller than the actual molecular weight. On the other hand, in the light scattering method, Ra
The dependence of the incident angle of the light and the concentration of the sample on the intensity of the scattered light is measured by using ileigh scattering, and the Zimm Plo is measured.
Since the absolute molecular weight is approximately determined by the t-analysis, <M <M is measured by the GPC method and the light scattering method, respectively.
w ^g> and using the ratio of <Mw ^l>, it may be a parameter representing the degree of branching. For example, the <Mw ^l>
As the value of </ Mw ^g > increases, the sum of the molecular weights of the branched chain portions increases, indicating that the branched structure is developed.

[0030] In the present invention, the low molecular weight polymer component ^{<Mw l> / <Mw g} > is structured such that 1.2 to 3.0 is controlled. As a result, the length of the branched chains in the molecular chains and the state of the entanglement between the molecular chains accompanying the lengths of the branched chains improve the various properties required of the toner as described above, and become favorable. That is, the mobility of the molecular chain at the time of heat melting is improved and the viscosity is improved due to the increase in the free terminal due to the introduction of the branched chain. In addition, elasticity is maintained by having a branch structure. As a result, the low-temperature fixability and the offset resistance can both be highly compatible. Further, when the toner is manufactured by the melt-kneading method, the shearing force at the time of kneading can be efficiently received, the dispersibility of the toner constituent materials is improved, the chargeability of the toner is improved, and image fog is reduced. .

On the other hand, the radius of inertia <S ² > ^1/2 of the low molecular weight polymer component measured by the light scattering method is controlled to be 100 ° or more. Preferably 100-1500
場合, more preferably 100 to 1000
This is the case of Å. The radius of gyration of inertia of the low molecular weight component is 10
By setting the angle to 0 ° or more, the molecular chain in the toner composition is ensured, so that the high-temperature offset resistance is improved, and the durability and the dot reproducibility during continuous use of the toner are improved. Note that even if <S ² > ^{1/2 is set} to 100 ° or more, the above-described <M ² >
fixing interference caused by entanglement of molecular chains because w ^l> / <is controlled Mw ^g> than 3.0 is prevented.

[0032] When the above ^{<Mw l> / <Mw g} > is less than 1.2, and / or <S ^{2> 1/2} is less than 100 Å, the above effect is not expressed. In addition, <Mw ^l> / <M
If w ^g > 3.0, the entanglement between the molecular chains becomes dominant, which hinders the low-temperature fixing of the toner,
Since the dispersibility of the toner constituent material is impaired, it hinders the developing property of the toner and the matching with the image forming apparatus.

[0033] In the present invention, the weight average molecular weight of the binder resin component by a light scattering method <Mw ^l> the inertial square radius <S ^2>
1/2 is based on the static light scattering method and is measured under the following conditions.

Apparatus: DLS-700 (manufactured by Otsuka Electronics Co., Ltd.) Light source: He-Ne laser 10 mW Cell: φ21 mm cylindrical cell Temperature: 25 ° C. Measurement angle: Select and set seven or more points in the range of 30 ° to 150 ° (for example, , 30 °, 40 °, 50 °, 60 °, 90
°, 120 °, 150 °) Sample: THF solution of any four or more binder resin components adjusted to a concentration range of 3 to 30 mg / l (for example, 4,
8, 12, 20 mg / l 4 points)

As a pretreatment of the sample, the sample is filtered and purified several times with a filter having a pore size of 0.2 μm. If foreign matter is mixed in the sample and interferes with the measurement, remove it using a centrifuge so as not to affect the dissolved binder resin component, or elute by dropping a small amount of hydrochloric acid. Removal can be used.

Further, the rate of change (dn / dc) of the differential refractive index of the sample to be measured with respect to the sample concentration was measured separately using a high sensitivity differential refractometer "DRM-1020" (manufactured by Otsuka Electronics Co., Ltd.).

The measurement from the results obtained in the above measurement conditions, performs ZimmPlot analysis based on the following equation (1), the weight average molecular weight of the binder resin component by light scattering method <Mw ^l> an inertial square radius <S ² > ^1/2 was calculated.

[0038]

(Equation 6)

Where Rayleigh ratio (R (θ)), optical constant (K), sample concentration (C), scattering vector (q), and second virial coefficient (A ₂ )

[0040]

(Equation 7)

[0041]

(Equation 8)

[0042]

(Equation 9) It becomes the relationship.

On the other hand, THF of the binder resin component according to the present invention
In the molecular weight distribution of GPC measured by the soluble component,
When a portion corresponding to a region having a molecular weight of 50,000 or less is fractionated, the fractionation is performed by the following method using a preparative liquid chromatograph.

Apparatus: Recycling preparative HPLC LC-
908 type (manufactured by Nippon Kagaku Kogyo Co., Ltd.) Column: JAIGEL-1H to 6H, JAIGEL-L
S255 (above, manufactured by Nippon Kagaku Kogyo Co., Ltd.) as appropriate. Sample: A sample that is sufficiently mixed and dissolved with THF, allowed to stand for 24 hours, and then passed through a sample processing filter (for example, Myshoridisk H-25-2 (manufactured by Tosoh Corporation)).

It should be noted that the confirmation of the sample after the fractionation is performed by the G
Follow the PC measurement method.

The toner composition according to the present invention has a substantially T
Preferably, it does not contain HF insolubles. Specifically, the content is 5% by weight or less, preferably 3% by weight or less based on the resin composition.

The THF-insoluble content in the present invention indicates the weight ratio of the polymer component (substantially crosslinked polymer) insoluble in the THF solvent in the resin composition in the toner,
It can be used as a parameter indicating the degree of crosslinking of the resin composition containing the crosslinking component. The THF-insoluble matter is defined by a value measured as follows.

That is, 0.5 to 1.0 g of a toner sample was weighed (W ₁ g), and a cylindrical filter paper (for example, No. No.
86R), subjected to a Soxhlet extractor, extracted with 100 to 200 ml of THF as a solvent for 6 hours, and evaporated the soluble components extracted by the solvent.
After vacuum drying at 100 ° C. for several hours, the amount of the THF-soluble resin component is weighed (W ₂ g). The weight of a component other than the resin component such as a magnetic substance or a pigment in the toner is defined as (W ₃ g). T
The HF insoluble content is obtained from the following equation.

[0049]

(Equation 10)

If the THF-insoluble content exceeds 5% by weight, high-temperature fixing cannot be achieved at a high degree.

The binder resin component in the toner composition according to the present invention has a low molecular weight of less than 50,000 having a main peak in a molecular weight region of 2,000 to 30,000 in a molecular weight distribution of GPC measured by a soluble matter in THF. Molecular weight component and molecular weight 10
It is composed of a high molecular weight component having a molecular weight of 50,000 or more having a subpeak or a shoulder in a region of 10,000 or more.

In the present invention, the molecular weight distributions of the binder resin component and wax described later by GPC are measured under the following conditions.

<GPC Measurement Conditions for Resin> Apparatus: GPC-150C (manufactured by Waters) Column: KF801 to 7 (manufactured by Shodex) Temperature: 40 ° C. Solvent: THF Flow rate: 1.0 ml / min. Sample: 0.1 m of a sample having a concentration of 0.05 to 0.6% by weight
l injection

<GPC Measurement Conditions for Wax> Apparatus: GPC-150C (manufactured by Waters) Column: Duplex of GMH-HT (manufactured by Tosoh Corporation) Temperature: 135 ° C. Solvent: o-dichlorobenzene (added with 0.1% ionol) ) Flow rate: 1.0 ml / min. Sample: 0.4 ml of 0.15% by weight sample is injected

Measurement is performed under the above conditions, and the molecular weight of the sample is calculated using a molecular weight calibration curve prepared from a monodisperse polystyrene standard sample. Further, the molecular weight of the wax is calculated by conversion using a conversion formula derived from the Mark-Houwink viscosity formula.

Further, the weight average molecular weight (Mw) / number average molecular weight (Mn) of the resin composition according to the present invention is preferably larger than 35. When Mw / Mn is 35 or less, the low-temperature fixing property and the offset resistance cannot be sufficiently satisfied. More preferably, Mw / Mn is 40 or more.

By controlling the molecular structure of each component in the resin composition of the present invention as described above, good durability can be maintained without impairing the developing characteristics even when Mw / Mn increases. . In particular, when applied to a toner in which an additive having a high specific gravity such as magnetic fine particles is added to a resin composition having a bipolar molecular weight distribution, a remarkable effect is exhibited.

As a method for producing the binder resin according to the present invention, a high molecular weight polymer and a low molecular weight polymer are separately synthesized by a solution polymerization method, then they are mixed in a solution state, and then the solvent is desolvated. Alternatively, a low-molecular-weight polymer obtained by melt-kneading with an extruder or the like, and a low-molecular-weight polymer obtained by a solution polymerization method or the like are dissolved in a monomer constituting a high-molecular-weight polymer, and suspension polymerization is performed. A two-stage polymerization method for drying and obtaining a binder resin is exemplified. However, the dry blending method has problems in uniform dispersion and compatibility, and the two-stage polymerization method has many advantages in uniform dispersibility and the like, but increases the amount of low molecular weight to higher than high molecular weight. I can't do that. In the presence of a low molecular weight component, not only is it very difficult to synthesize a desired high molecular weight component desired in the present invention, but also there are disadvantages such as unnecessary low molecular weight components being by-produced. For this purpose, the solution blending method is most suitable.

As a method for synthesizing the low molecular weight component of the binder resin according to the present invention, the second monomer may be added in the presence of a polymer which contains a group which easily causes a chain transfer reaction in the repeating monomer unit or terminal group. A chain transfer method for performing radical polymerization, a polymer initiator method for polymerizing a second monomer using a polymer having a repeating unit or an end group in a terminal group as an initiator, a radiation grafting method by irradiation with radiation, a mechanical method. Known methods such as a chemical reaction method, a bonding reaction method using an addition or condensation reaction, and the like, can be used to easily obtain a low-molecular-weight polymer under mild conditions by adjusting the amount of the initiator and the reaction temperature. Particularly, a chain transfer method using solution polymerization, which can use a difference in radical chain transfer caused by the above, is particularly preferable. Specifically, after the prepolymer is polymerized, hydrogen is extracted from the prepolymer by using an initiator having excellent hydrogen abstraction ability, a polymer radical is generated, and graft polymerization of the second monomer is started from the radical. The method is preferred.

At this time, since the graft polymerization of the second monomer to the prepolymer is a competitive reaction with the growth reaction of the second monomer alone, the molecular structure exerted by the respective concentrations of the prepolymer, the second monomer, and the initiator is affected. The impact on can not be ignored. At the stage of extracting hydrogen from the prepolymer and generating a polymer radical, the amount of the solvent is 50 to 400 parts by weight, preferably 100 to 400 parts by weight, based on 100 parts by weight of the prepolymer.
The concentration is adjusted to 200 parts by weight. Solvent amount is 50
If the amount is less than parts by weight, the concentration of the polymer radicals increases and the crosslinked structure develops. On the other hand, if it exceeds 400 parts by weight, the polymer radicals are deactivated and cause molecular breakage.

Various methods other than the above can be considered.
50,000 following ingredients in the molecular weight distribution of GPC are, i) weight average molecular weight measured by a light scattering method <Mw ^l> a weight average molecular weight measured by GPC <Mw ^g> is 1.2 ≦
<Mw ^l> / meet the <Mw ^g> ≦ 3.0 of the relationship, and,
ii) Inertial square radius <S ² > measured by light scattering method
Any method may be used as long as ^1/2 becomes 100 ° or more.

As a polymerization initiator having excellent hydrogen abstraction ability, it is effective to use a peroxide having the following structure in the molecule of the polymerization initiator.

[0063]

Embedded image

Specific examples of the polymerization initiator having such a structure include 1,1-bis (tert-butylperoxy) cyclohexane, 1,1-bis (tert-butylperoxy) 3,3,5- Trimethylcyclohexane,
2,2-bis (tert-butylperoxy) octane, di-tert-butyl peroxide, tert-
Butyl cumyl peroxide, 2,5-dimethyl-2,
5-di (tert-butylperoxy) hexane, te
tert-butyl peroxyacetate, tert-butyl peroxyisobutyrate, tert-butyl peroxypivalate, tert-butyl peroxy neodecanoate, tert-butyl peroxy 2-ethylhexanoate, tert-butyl pert Oxy 3,5,5-trimethyl hexanoate, tert-butyl peroxy laurate, tert-butyl peroxy benzoate, di-tert-butyl peroxy isophthalate,
tert-butyl peroxyisopropyl carbonate and the like.

Of the above polymerization initiators, when decomposed to generate free radicals, it is difficult to form a crosslinked structure starting from the initiator, and 1,1-bis (tert-butylperoxy) 3,3,5 -Trimethylcyclohexane, di-te
rt-butyl peroxide, tert-butyl cumyl peroxide and the like are preferred.

These polymerization initiators are used singly or as a mixture of two or more kinds. In order to control a desired molecular structure, 0.2 to 5 parts by weight based on 100 parts by weight of the prepolymer is used. Is added together with the second monomer. When the polymerization reaction proceeds in the presence of the second monomer, the polymerization temperature is set at -10 ° C to + 20 ° C, more preferably -5 ° C to + 20 ° C, more than the decomposition temperature at which the polymerization initiator obtains a half-life of 1 minute.
Adjust to 10 ° C range.

When the low molecular weight component of the binder resin according to the present invention is a combination of a monomer such as a styrene-based copolymer or a styrene-acrylic copolymer described below, a low-temperature fixation is achieved and the initiator is obtained. In the sense of minimizing the amount used and minimizing the effect of the initiator residue on the charging characteristics,
The prepolymer may be polymerized under pressure.

On the other hand, it is preferable to add the second monomer so that the content of the acrylic component is higher than the monomer constituting the prepolymer. By doing this,
Not only are the preservability and the low-temperature fixability of the developer highly satisfactory, but also the developing characteristics are improved.

The second monomer is the prepolymer 100
It is added in the range of 5 to 50 parts by weight based on parts by weight. Second
When the amount of the monomer is less than 5 parts by weight, a crosslinking reaction between polymer radicals generated by abstraction of hydrogen is promoted, a crosslinking density is increased, and low-temperature fixability is impaired. If it exceeds 50 parts by weight, the generation of by-products such as oligomers is promoted, which adversely affects the storage stability and charging characteristics of the developer, and also causes a problem in matching with the image forming method.

As a method for synthesizing the high molecular weight component of the binder resin according to the present invention, an emulsion polymerization method or a suspension polymerization method can be used as a polymerization method that can be used in the present invention.

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 using an emulsifier, and polymerization is carried out using a water-soluble polymerization initiator. . In this method, the reaction heat can be easily adjusted, and the phase in which the polymerization is performed (oil phase composed of a polymer and a monomer)
And the aqueous phase are separate, so that the termination reaction rate is low, resulting in a high polymerization rate and a high degree of polymerization. Further, due to the relatively simple polymerization process and the fact that the polymerization product is fine particles, in the production of toner,
There is an advantage as a method for producing a binder resin for a toner because it is easy to mix with a colorant, a charge control agent and other additives.

However, the resulting polymer tends to be impure due to the added emulsifier, and an operation such as salting out is required to take out the polymer. To avoid this inconvenience, suspension polymerization is advantageous.

In the suspension polymerization, 100 parts by weight or less of the monomer (preferably 1 part by weight) is added to 100 parts by weight of the aqueous solvent.
(0 to 90 parts by weight). Examples of usable dispersants include polyvinyl alcohol, partially saponified polyvinyl alcohol, calcium phosphate, and the like. There is an appropriate amount in terms of the amount of a monomer relative to an aqueous solvent, and generally 0.05 to 1 based on 100 parts by weight of an aqueous solvent. Used in parts by weight. The polymerization temperature is suitably from 50 to 95 ° C, but should be appropriately selected depending on the initiator used and the intended polymer.

As the high molecular weight component of the binder resin used in the present invention, in order to achieve the object of the present invention, it is preferable to use a polyfunctional polymerization initiator having a polyfunctional structure as exemplified below.

Specific examples of the polyfunctional polymerization initiator include:
1,1-di-t-butylperoxy-3,3,5-trimethylcyclohexane, 1,3-bis- (t-butylperoxyisopropyl) benzene, 2,5-dimethyl-
2,5- (t-butylperoxy) hexane, 2,5-
Dimethyl-2,5-di- (t-butylperoxy) hexyne-3, tris- (t-butylperoxy) triazine, 1,1-di-t-butylperoxycyclohexane, 2,2-di-t -Butyl peroxybutane, 4,4
-Di-t-butylperoxyvaleric acid-n-
Butyl ester, di-t-butylperoxyhexahydroterephthalate, di-t-butylperoxyazelate, di-t-butylperoxytrimethyladipate, 2,2-bis- (4,4-di-t-butyl Peroxycyclohexyl) propane, 2,2-t-butylperoxyoctane and various polymer oxides, etc., a polyfunctional polymerization initiator having a functional group having a polymerization initiation function such as two or more peroxide groups in one molecule. And 1 such as diallyl peroxydicarbonate, t-butyl peroxymaleic acid, t-butyl peroxyallyl carbonate and t-butyl peroxyisopropyl fumarate
It is selected from a polyfunctional polymerization initiator having both a functional group having a polymerization initiation function such as a peroxide group and a polymerizable unsaturated group in a molecule.

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

These polyfunctional polymerization initiators are preferably used in combination with a monofunctional polymerization initiator in order to satisfy various performances required for a resin composition for a toner.
In particular, the use of a monofunctional polymerization initiator having a decomposition temperature lower than the decomposition temperature for obtaining a half-life of 10 hours of the polyfunctional polymerization initiator improves the developing characteristics of the toner.

Specifically, organic peroxides such as di-t-butyl peroxide, dicumyl peroxide, benzoyl peroxide, t-butyl peroxy-2-ethylhexanoate, t-butyl peroxybenzoate, etc. And azo compounds such as azobisisobutyronitrile and diazoaminoazobenzene, and diazo compounds.

These monofunctional polymerization initiators may be added to the monomer at the same time as the above-mentioned polyfunctional polymerization initiator. However, in order to maintain the initiator efficiency of the polyfunctional polymerization initiator properly, It is preferable to add the compound after the half-life of the polyfunctional polymerization initiator has elapsed under any polymerization conditions. The monofunctional polymerization initiator is used in an amount of 0.05 to 2 parts by weight based on 100 parts by weight of the monomer.

The high molecular weight polymer component of the binder resin used in the present invention preferably contains a crosslinkable monomer as exemplified below in order to achieve the object of the present invention.

As the crosslinkable monomer, a monomer having two or more polymerizable double bonds is mainly used. Specific examples thereof include aromatic divinyl compounds such as divinylbenzene and divinylnaphthalene; Diacrylate compounds; for example, ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate,
1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, and acrylates of the above compounds replaced with methacrylates; diacrylate compounds linked by an alkyl chain containing an ether bond , Such as diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 400 diacrylate, polyethylene glycol # 600 diacrylate, dipropylene glycol diacrylate, and acrylates of the above compounds instead of methacrylate Diacrylate compounds linked by a chain containing an aromatic group and an ether bond, for example, polyoxyethylene (2) -2,2-bis ( - hydroxyphenyl) propane diacrylate, polyoxyethylene (4) -2,
2-bis (4-hydroxyphenyl) propane diacrylate and those obtained by replacing the acrylates of the above compounds with methacrylates; further, polyester-type diacrylate compounds, for example, trade name MANDA (Nippon Kayaku) . As multifunctional crosslinking agents, pentaerythritol acrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, tetramethylolpropane triacrylate, tetramethylolmethanetetraacrylate, oligoester acrylate, and acrylates of the above compounds to methacrylate Alternatives; triallyl cyanurate, triallyl trimellitate; and the like.

When these crosslinkable monomers are used in an amount of 1% by weight or less based on 100% by weight of the other monomer components, not only satisfactory low-temperature fixability and anti-offset property are satisfied, but also the storage of toner. The performance is also improved.

Among these crosslinking monomers, those preferably used include aromatic divinyl compounds (particularly divinylbenzene) and diacrylate compounds linked by a chain containing an aromatic group and an ether bond. It is preferable to use it in the range of 0.001 to 0.05% by weight based on 100% by weight of the monomer component. As a result, even when the particle diameter of the toner is reduced, the developing characteristics of the developer under each environment are stabilized, and the durability is improved. Also, it shows good matching with the wax component described later.

The polymer side component of the binder resin of the toner composition according to the present invention contains a monomer unit having at least one of a carboxyl group, a carboxylate group or a carboxylic anhydride group, and contains a developer. The crosslinking reaction may be promoted through a hot-melt kneading step at the time of production. In particular, when a binder resin having a low melt viscosity is used, the components constituting the developer can enjoy a stronger and more uniform shearing force than before, due to the thickening effect of the crosslinking reaction, so that they are synergistic. Not only that the dispersibility is improved and the developability is stabilized, but also a good matching with the wax component described later is exhibited.

In order to exhibit a predetermined effect by the crosslinking reaction, it is preferable that a certain amount or more of the above-mentioned carboxyl group capable of forming a crosslinking bond is contained within a range that does not impair the developing characteristics. Specifically, the acid value of the polymer-side component constituting the binder resin according to the present invention is adjusted so as to be 0.5 to 30.

As the polymer component having a polar group capable of forming a cross-linking bond of the present invention, a polymer containing at least one of a carboxyl group, a carboxylic anhydride group and a carboxylate group has the best reactivity. Is shown. Examples of the carboxyl group-containing monomer for synthesizing a vinyl polymer include acrylic acid such as acrylic acid, methacrylic acid, α-ethylacrylic acid, crotonic acid and α- or β-acrylic acid thereof.
-Alkyl derivatives, fumaric acid, maleic acid, unsaturated dicarboxylic acids such as citraconic acid and its monoester derivatives or maleic anhydride, etc., such monomers alone or mixed and copolymerized with other monomers Thus, a desired polymer can be produced. Among them, it is particularly preferable to use a monoester derivative of an unsaturated dicarboxylic acid.

The carboxyl group-containing monomer usable in the present invention includes, for example, monomethyl maleate, monoethyl maleate, monobutyl maleate, monooctyl maleate, monoallyl maleate,
Monoesters of α, β-unsaturated dicarboxylic acids such as monophenyl maleate, monomethyl fumarate, monoethyl fumarate, monobutyl fumarate, monophenyl fumarate, etc .; monobutyl n-butenylsuccinate, monomethyl n-octenylsuccinate, Monoesters of alkenyl dicarboxylic acids such as monoethyl n-butenylmalonate, monomethyl n-dodecenylglutarate and monobutyl n-butenyladipate; monomethyl phthalate, monoethyl phthalate, monobutyl phthalate and the like And monoesters of aromatic dicarboxylic acids.

The above-mentioned carboxyl group-containing monomer may be added in an amount of 1 to 30% by weight, preferably 3 to 20% by weight, based on all monomers constituting the polymer side of the binder resin.

The reason that the monoester monomer of dicarboxylic acid is selected as described above is that it is not appropriate to use an acid monomer having high solubility in an aqueous suspension in the suspension polymerization. This is because it is preferable to use the compound in the form of an ester having low solubility.

In the present invention, the carboxyl group and the carboxylic acid ester site in the copolymer obtained by the above method can be saponified by alkali treatment. That is, it is preferable that the carboxyl group or the carboxylic acid ester moiety is changed to a polar functional group by reacting with a cationic component of alkali. This is because, even if the polymer side component of the binder resin contains a carboxyl group that reacts with the metal-containing compound, if the carboxyl group is dehydrated, that is, the ring is closed, the efficiency of the crosslinking reaction decreases.

This alkali treatment may be carried out after the production of the binder resin, by introducing it as an aqueous solution into the solvent used during the polymerization and stirring. Examples of the alkali that can be used in the present invention include Na, K, Ca, Li, Mg, and Ba.
Hydroxides of alkali metals and alkaline earth metals such as;
There are hydroxides of transition metals such as Zn, Ag, Pb, and Ni; hydroxides of quaternary ammonium salts such as ammonium salts, alkylammonium salts, and pyridium salts. Particularly preferred examples include NaOH and KOH. .

In the present invention, the saponification reaction does not need to be carried out over all of the carboxyl groups and carboxylic acid ester sites in the copolymer. It should just be.

The amount of the alkali used in the saponification reaction is difficult to determine unconditionally depending on the type of the polar group in the binder resin, the dispersion method, the type of the constituent monomers, and the like. What is necessary is just 02-5 times equivalent. When the amount is less than 0.02 equivalent, the saponification reaction is not sufficient, and the number of polar functional groups generated by the reaction is reduced, and as a result, the subsequent crosslinking reaction becomes insufficient. On the other hand, when the amount exceeds 5 times equivalent, the functional group such as a carboxylic acid ester site is adversely affected by hydrolysis of the ester, generation of a salt by a saponification reaction, and the like.

When the alkali treatment is carried out at an equivalent of 0.02 to 5 times the acid value, the residual cation ion concentration after the treatment is contained between 5 and 1000 ppm, which is preferable for defining the amount of alkali. Can be used.

To the toner according to the present invention, a metal-containing organic compound may be added in order to promote the crosslinking between the polymer chains of the resin composition during the production of the toner, and it is particularly rich in vaporization and sublimation. Those containing an organometallic compound as a ligand or counter ion give excellent results.

Among the organic compounds which form a ligand or a counter ion with a metal ion, those having the above properties include, for example, salicylic acid, salicylamide, salicylamine, salicylaldehyde, salicylosalicylic acid, ditert Salicylic acid such as -butylsalicylic acid and derivatives thereof, for example, β-diketones such as acetylacetone and propionacetone, and low-molecular carboxylate salts such as acetate and propionic acid.

Examples of the monomers for obtaining the binder resin according to the present invention include the following.

For example, styrene, o-methylstyrene, m
-Methylstyrene, p-methylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, 3,4-dichlorostyrene, p-ethylstyrene,
2,4-dimethylstyrene, pn-butylstyrene,
Styrene such as p-tert-butylstyrene, pn-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene, pn-dodecylstyrene and derivatives thereof; ethylene , Ethylenically unsaturated monoolefins such as propylene, butylene and isobutylene; unsaturated polyenes such as butadiene; vinyl halides such as vinyl chloride, vinylidene chloride, vinyl bromide, and vinyl fluoride; vinyl acetate, vinyl propionate, Vinyl esters such as vinyl benzoate; methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, methacrylic acid Stearyl, meta Phenyl acrylic acid, dimethylaminoethyl methacrylate, alpha-methylene aliphatic monocarboxylic acid esters such as diethylaminoethyl methacrylate;
Methyl acrylate, ethyl acrylate, acrylic acid n-
Butyl, isobutyl acrylate, propyl acrylate,
Acrylic esters such as n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate and phenyl acrylate; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl isobutyl ether Vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and methyl isopropenyl ketone; N-vinyl pyrrole, N-vinyl carbazole, N
N- such as vinylindole and N-vinylpyrrolidone
Vinyl compounds of vinyl compounds; vinyl naphthalenes; acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile, and acrylamide; used alone or in combination of two or more.

Of these, a combination of monomers that will result in a styrene copolymer and a styrene acrylic copolymer is preferred.

The addition of a low molecular weight wax to the toner according to the present invention is one of the preferred embodiments of the present invention.

Examples of the low molecular weight wax applicable to the present invention include wax-like substances such as polypropylene, polyethylene, microcrystalline wax, carnauba wax, sasol wax, paraffin wax, and oxides and graft-modified products thereof. , Or in combination.

The weight average molecular weight of these low molecular weight waxes is desirably 30,000 or less, preferably 10,000 or less.
The amount of addition is 1 to 2 parts per 100 parts by weight of the binder resin.
0 parts by weight is preferred.

Further, the low molecular weight wax used in the present invention represents a hydrocarbon group having a weight average molecular weight of 3000 or less according to the following general formula RY [R: gel permeation chromatography. Y represents a hydroxyl group, a carboxyl group, an alkyl ether group, an ester group, or a sulfonyl group. 6
The object of the present invention can be highly achieved by containing 0% by weight or more, preferably 70% by weight or more.
That is, the matching with the binder resin is very good.

Specific examples of the compound include (A) CH ₃ (CH ₂ ) _n CH ₂ OH (B) CH ₃ (CH ₂ ) _n CH ₂ COOH (C) CH ₃ (CH ₂ ) _n CH ₂ OCH _{2 (CH 2) m CH 3} (D) CH 3 (CH 2) n CH 2 COO (CH 2) m CH 3 (E) CH 3 (CH 2) n CH 2 OSO 3 H (n = about 20 to about 200, m = 0 to about 100). These compounds are derivatives of the compound (A), and the main chain is a linear saturated hydrocarbon. As long as the compound is derived from the compound (A), those other than those shown in the above examples can also be used.

The above compound has a number average molecular weight (Mn) of 20.
0 to 2000, weight average molecular weight (Mw) 400 to 30
Mw / Mn is preferably 3.0 or less. By having such a molecular weight distribution, the toner can have preferable physical characteristics. In other words, when the molecular weight is smaller than the above range, the composition is susceptible to thermal or mechanical influences excessively, and causes problems in offset resistance and storage stability. Further, when the molecular weight is larger than the above range, not only the effect of adding the compound is lost, but also a problem occurs in matching with the image forming apparatus.

It is preferable that these low-molecular-weight waxes and the like are added to and mixed with the binder resin in advance in the production of the toner. In particular, a method in which the low molecular weight wax component and the high molecular weight polymer are preliminarily dissolved in a solvent during the production of the binder resin, and then mixed with the low molecular weight polymer solution is preferable. By preliminarily mixing the low molecular weight wax component and the high molecular weight component, phase separation in the micro region is reduced, the high molecular weight component is not re-aggregated, and a good dispersion state with the low molecular weight component is obtained.

The solid concentration of the polymer solution is determined by the dispersion efficiency,
In consideration of prevention of deterioration of the resin at the time of stirring, operability, etc., 5 to 70
It is preferably not more than 5% by weight, the preliminary solution of the high molecular weight polymer component and the low molecular weight wax component is preferably 5% to 60% by weight, and the low molecular weight polymer solution is preferably 5% to 70% by weight.

The method of dissolving or dispersing the high molecular weight polymer component and the low molecular weight wax component is performed by stirring and mixing.
A batch type or a continuous type may be used.

The method of mixing the low molecular weight polymer solution is to add 10 to 1000 parts by weight of the low molecular weight polymer solution to the solid content of the preliminary solution and to carry out stirring and mixing. But it can be continuous.

Examples of the organic solvent used for mixing the solution of the resin composition according to the present invention include benzene, toluene, and toluene.
Xylol, solvent naphtha 1, solvent naphtha 2, solvent naphtha 3, cyclohexane, ethylbenzene, hydrocarbon solvents such as Solvesso 100, Solvesso 150, mineral spirits, methanol, ethanol, iso-propyl alcohol, n-butyl alcohol, alcohol solvents such as sec-butyl alcohol, iso-butyl alcohol, amyl alcohol, and cyclohexanol; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; and ester solvents such as ethyl acetate, n-butyl acetate, and cellosolve acetate. Solvents include ether solvents such as methyl cellosolve, ethyl cellosolve, butyl cellosolve, and methyl carbitol. Aromatic in these,
Ketone and ester solvents are preferred. They may be used in combination.

It is preferable to remove the organic solvent by heating the organic solvent solution of the polymer, removing 10 to 80% by weight of the organic solvent under normal pressure, and then removing the remaining solvent under reduced pressure. At this time, the organic solvent solution needs to be maintained at a temperature not lower than the boiling point of the used organic solvent and not higher than 200 ° C. Below the boiling point of the organic solvent, not only is the efficiency at the time of solvent distillation low, but also unnecessary shearing force is applied to the polymer in the organic solvent, and the redispersion of each constituent polymer is promoted, and in a micro state, Causes phase separation. On the other hand, if the temperature exceeds 200 ° C., the depolymerization of the polymer proceeds, and not only oligomer formation due to molecular cleavage, but also incorporation of residual monomers into the product resin due to monomer generation, which is unsuitable as a resin composition for toner. Becomes

The resin composition for a toner obtained by the above production method is excellent in the compatibility between the low molecular weight polymer and the high molecular weight polymer, not to mention the dispersibility of the low molecular weight wax component. Thus, significant improvements are made.

The glass transition temperature (Tg) of the resin composition contained in the toner according to the present invention is adjusted so as to be 50 to 70 ° C. When Tg is lower than 50 ° C., it causes deterioration of the developer in a high-temperature atmosphere and offset during heating and fixing. On the other hand, if the temperature exceeds 70 ° C., the overall fixing property is adversely affected.

In the present invention, the Tg of the resin was measured using a differential thermal analyzer (DSC analyzer) and DSC-7 (manufactured by PerkinElmer).

The measurement sample is 5 to 20 mg, preferably 10
Weigh the mg precisely. This is put in an aluminum pan, and an empty aluminum pan is used as a reference, and the measurement is performed at a temperature rising rate of 10 ° C./min. During this heating process, a temperature of 40 to 100
An endothermic peak of the main peak in the range of ° C is obtained. The intersection between the line at the midpoint of the baseline before and after the endothermic peak appeared and the differential heat curve was obtained.

In the developer of the present invention, it is preferable to add a charge control agent in order to improve charge stability and developability.

Specific examples of the positive charge control agent include generally nigrosine, an azine dye having an alkyl group having 2 to 16 carbon atoms (Japanese Patent Publication No. 42-1627), and a basic dye (for example, CI Basic Yellow). 2 (CI.41
000), C.I. I. Basic Yellow 3, C.I.
I. Basic Red 1 (CI. 45160),
C. I. Basic Red 9 (CI.4250
0), C.I. I. Basic Violet 1 (CI.
42535), C.I. I. Basic Violet 3
(CI. 42555), C.I. I. Basic Violet 10 (CI. 45170), C.I. I. Basic Violet 14 (CI. 42510), C.I.
I. Basic Blue 1 (CI. 42025),
C. I. Basic Blue 3 (CI.5100
5), C.I. I. Basic Blue 5 (CI.421
40), C.I. I. Basic Blue 7 (CI.4
2595), C.I. I. Basic Blue 9 (C.I.
I. 52015), C.I. I. Basic Blue 24
(CI. 52030), C.I. I. Basic Blue 25 (CI.52025), C.I. I. Basic Blue 26 (CI.44025), C.I. I. Basic Green 1 (CI. 42040), C.I. I. Basic Green 4 (CI.42000), etc.
Lake pigments of these basic dyes (as the lacking agent, phosphotungstic acid, phosphomolybdic acid, phosphotungsten molybdic acid, tannic acid, lauric acid, gallic acid, ferricyanide, ferrocyanide, etc.),
C. I. Solvent Black 3 (CI. 2615)
0), Hansa Yellow G (CI. 11680), C.I.
I. Mordrant Black 11, C.I. I. Pigment Black 1 and the like.

Further, for example, polyamide resins such as quaternary ammonium salts such as benzolmethyl-hexadecylammonium chloride and decyl-trimethylammonium chloride, vinyl polymers having an amino group, and condensation polymers having an amino group can be used. Preferably, nigrosine, a quaternary ammonium salt, a triphenylmethane-based nitrogen-containing compound, polyamide or the like is used.

Specific examples of the negative charge control agent are described in JP-B-41-20153, JP-B-42-27596, and JP-B-42-27596.
Metal complexes of monoazo dyes described in JP-A-4-6397 and JP-A-45-26478;
Nitroamine acids and salts thereof described in JP-A-33338; I. Dyes and pigments such as 14645;
No. 42755, No. 58-41508, No. 5
No. 8-7384, JP-B-59-7385 and the like, Z of salicylic acid, naphthoic acid and dicarboxylic acid.
Examples include metal complexes such as n, Al, Co, Cr, and Fe; sulfonated copper phthalocyanine pigments; styrene groups having nitro groups and halogens; and chlorinated paraffins. In particular, from the viewpoint of dispersibility, the general formula [I]
And an organic metal complex of a basic organic acid represented by the general formula [II] are preferable.

[0120]

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[0121]

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[0122]

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Specific examples of the azo metal complex [I] and the basic organic acid metal complex [II] are shown below.

[0124]

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[0125]

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[0126]

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[0127]

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[0128]

Embedded image

[0129]

Embedded image

[0130]

Embedded image

[0131]

Embedded image

[0132]

Embedded image

[0133]

Embedded image

[0134]

Embedded image

[0135]

Embedded image

[0136]

Embedded image

[0137]

Embedded image

[0138]

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[0139]

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[0140]

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These metal complexes can be used alone or in combination of two or more.

When the above-mentioned metal complex is used as a charge control agent, the amount of addition is such that, as described above, while maintaining good triboelectricity, the development power is reduced due to contamination of the developing sleeve surface by the charge control agent and environmental stability is reduced. 100 parts by weight of the binder resin to minimize the adverse effects
An addition amount of 0.1 to 5 parts by weight is preferred.

In the toner of the present invention, charging stability,
In order to improve developability, fluidity and durability, it is preferred to add an inorganic fine powder.

The inorganic fine powder used in the present invention includes:
For example, fine silica powder, titanium oxide, alumina and the like can be mentioned. Among them, the specific surface area by nitrogen adsorption measured by the BET method is 30 m ² / g or more (particularly 50 to 400 m ² / g).
Those within the range give good results. It is preferable to use 0.01 to 8 parts by weight, preferably 0.1 to 5 parts by weight of the inorganic fine powder with respect to 100 parts by weight of the toner.

Further, the inorganic fine powder used in the present invention includes:
Silicon varnish, various modified silicone varnishes, silicone oil, various modified silicone oils, silane coupling agents, silane coupling agents having functional groups, and other organosilicon compounds for purposes such as hydrophobicity and charge control, if necessary It is also preferred that the composition is treated with such a treating agent or in combination with various treating agents.

As other additives, for example, lubricants such as Teflon, zinc stearate, and polyvinylidene fluoride, among which polyvinylidene fluoride are preferable. Or an abrasive such as cerium oxide, silicon carbide, strontium titanate,
Among them, strontium titanate is preferable. Alternatively, for example, a fluidity imparting agent such as titanium oxide and aluminum oxide, particularly a hydrophobic agent is preferable. Anti-caking agent,
Alternatively, for example, a conductivity imparting agent such as carbon black, zinc oxide, antimony oxide, tin oxide, or the like, or fine particles of white and black having opposite polarities may be used in a small amount as a developing property improver.

When the toner of the present invention is used as a two-component developer, it is used by mixing with a carrier powder.
In this case, the mixing ratio of the toner and the carrier powder is 0.1 to 50% by weight as a toner concentration, preferably 0.5 to 1%.
0% by weight, more preferably 3 to 5% by weight is desirable.

As the carrier usable in the present invention, all known carriers can be used. For example, magnetic powders such as iron powder, ferrite powder and nickel powder, glass beads, etc. Those treated with a resin, a vinyl-based resin, a silicon-based resin, or the like can be given.

Further, the toner of the present invention may be used as a magnetic toner by further containing a magnetic material. In this case, the magnetic material also serves as a colorant. Examples of the magnetic material contained in the magnetic toner of the present invention include iron oxides such as magnetite, hematite, and ferrite; metals such as iron, cobalt, and nickel; or aluminum, cobalt, copper, lead, magnesium, and tin of these metals. Zinc, antimony,
Examples include alloys of metals such as beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten, and vanadium, and mixtures thereof.

These magnetic materials have an average particle size of 0.1 to 2 μm.
m, preferably about 0.1 to 0.5 μm, and the amount contained in the toner is preferably about 20 to 200 parts by weight, more preferably 40 to 100 parts by weight of the resin component. ~ 150 parts by weight is good.

The magnetic characteristics when 10K Oersted was applied were such that the coercive force was 20 to 250 Oersted, the saturation magnetization was 50 to 250 Oersted.
Desirable is 200 emu / g and residual magnetization of 2 to 20 emu / g.

As the colorant that can be used in the toner of the present invention, any suitable pigment or dye can be used. Toner colorants are well known and include, for example, pigments such as carbon black, aniline black, acetylene black, naphthol yellow, hansa yellow, rhodamine lake, alizarin lake, bengalara, phthalocyanine blue, and indanthrene blue. These are used in amounts necessary and sufficient to maintain the optical density of the fixed image.
0.1 to 20 parts by weight, preferably 2 to 10 parts by weight per part by weight
Good addition amount by weight. A dye is further used for the same purpose. For example, azo dyes, anthraquinone dyes,
There are xanthene dyes, methine dyes and the like, and 0.1 to 20 parts by weight, preferably 0.3 to
The addition amount of 3 parts by weight is good.

To prepare the toner for developing an electrostatic image according to the present invention, a binder resin, a metal compound, a pigment or dye as a colorant, a magnetic substance, a charge control agent, and other additives as necessary are used. , Henschel mixer, after sufficiently mixing with a mixer such as a ball mill, heated rolls, kneader, using a hot kneader such as an extruder, melted, kneaded and kneaded metal compounds in the binder resin, pigment,
The toner according to the present invention can be obtained by dispersing or dissolving the dye and the magnetic substance, and solidifying by cooling, followed by pulverization and classification.

Further, if necessary, desired additives are sufficiently mixed with a mixer such as a Henschel mixer to obtain the toner for developing an electrostatic image according to the present invention.

Further, the toner of the present invention has a weight average diameter D
₄ (μm) is 3.5 ≦ D ₄ ≦ 6.5, and the abundance ratio N of particles of 3.17 μm or less in the number particle size distribution.
Relationship between the (% by number) is preferably having a particle size distribution satisfying the _{35-D 4 × 5 ≦ N} ≦ 180-D 4 × 25.

The toner of the present invention can achieve higher image quality by adjusting the particle size distribution so as to exhibit a fine particle size as described above. Conventionally, a toner exhibiting such a particle size distribution has caused poor cleaning and toner fusion. However, the use of the binder resin of the present invention has made it possible to obviate these problems. .

In the present invention, the particle size distribution of the toner can be measured by various methods such as Coulter Counter TA-II or Coulter Multisizer (manufactured by Coulter Co.).
An interface (manufactured by Nikkaki) that outputs the number distribution and volume distribution using a type II (manufactured by Coulter) and PC9
801 personal computer (manufactured by NEC) is connected, and the electrolyte is 1% NaCl using primary sodium chloride.
Prepare an aqueous solution. For example, ISOTON R-II
(Manufactured by Coulter Scientific Japan) can be used. As a measuring method, the electrolytic aqueous solution 100 to 1
In 50 ml, 0.1 to 5 ml of a surfactant, preferably an alkylbenzene sulfonate, is added as a dispersant, and 2 to 20 mg of a measurement sample is further added. The electrolytic solution in which the sample was suspended was subjected to dispersion treatment for about 1 to 3 minutes using an ultrasonic disperser, and the volume and number of toner particles having a size of 2 μm or more were measured using a 100 μm aperture as the aperture by the Coulter Counter TA-II. The volume distribution and number distribution were calculated.

The toner of the present invention has a porosity of 0.50-0.
By setting the ratio to 70, the charging characteristics of the toner are improved. Porosity = (true density-tap density) / true density

Generally, the toner is charged by friction mainly between the developer carrier and the toner regulating blade. If the frictional charging is repeated in a state where the porosity at the time of packing the toner is less than 0.50, not only the frictional charging becomes excessive, but also the deterioration of the toner particle surface is accelerated. On the other hand, if it exceeds 0.70, sufficient triboelectric charging cannot be obtained. In particular, this tendency is remarkable in the case of the toner having the fine particle diameter as described above.

In the present invention, the true density of the toner is measured as follows.

About 1 g of the toner is put in a tableting machine for IR measurement, and is molded by applying a pressure of about 200 kgf / cm ² for 1 minute. The volume and weight of this sample are measured to determine the density γ.

The tap density of the toner of the present invention was measured using a powder tester manufactured by Hosokawa Micron Corp., using a container attached to the powder tester, and following the procedure described in the instruction manual for the powder tester. Say value.

Next, the image forming method of the present invention will be specifically described with reference to the drawings.

In FIG. 1, reference numeral 100 denotes a photosensitive drum, around which a primary charging roller 117, a developing device 140, a transfer charging roller 114, a cleaner 116, a register roller 124 and the like are provided. And the photosensitive drum 100
Is charged to −800 V by the primary charging roller 117. The photosensitive drum 100 is exposed by irradiating the photosensitive drum 100 with a laser beam 123 by a laser generator 121. The electrostatic latent image on the photosensitive drum 100 is
0, the toner is developed with a one-component magnetic toner, and is transferred onto a transfer material by a transfer roller 114 that is in contact with the photosensitive drum via the transfer material (applied DC voltage of 2 kV). The transfer material on which the toner image has been placed is transferred to the fixing device
26 and is fixed on the transfer material. Further, the toner left partially on the electrostatic latent image carrier is
Cleaning.

As shown in FIG. 2, the developing device 140 is provided with a cylindrical toner carrier 102 (hereinafter referred to as a developing sleeve) made of a non-magnetic metal such as aluminum or stainless steel in the vicinity of the photosensitive drum 100. The gap between the photosensitive drum 100 and the developing sleeve 102 is maintained at about 300 μm by a sleeve / drum gap holding member (not shown). Further, a stirring rod 141 is provided in the developing device. Inside the developing sleeve, a magnet roller 104 is fixed and disposed concentrically with the developing sleeve 102. However, the developing sleeve 102 is rotatable. The magnet roller 104 is provided with a plurality of magnetic poles as shown in the figure. S ₁ is for development, N ₁ is for controlling the amount of toner coating, S ₂ is for taking in / conveying toner, and N ₂ is for preventing toner blowing. I have. The elastic blade 1 serves as a member for regulating the amount of magnetic toner adhered to and conveyed to the developing sleeve 102.
03 is provided and the developing sleeve 10 of the elastic blade 103 is provided.
The contact pressure with respect to 2 controls the amount of toner conveyed to the development area. In the developing area, a developing bias is applied between the photosensitive drum 100 and the developing sleeve 102, and the toner on the developing sleeve is changed according to the electrostatic latent image.
Fly up and become a visible image.

[0166]

EXAMPLES The present invention will be described below with reference to specific examples, but the present invention is not limited to these examples.

[Production Example 1 of Resin Composition] 300 parts by weight of xylene was put into a synthetic glass autoclave of low molecular weight polymer (L-1) and (L-2), and the inside of the container was stirred. After replacing with sufficient nitrogen,
It sealed and heated up to 200 degreeC.

A mixture of 90 parts by weight of styrene, 10 parts by weight of n-butyl acrylate, and 2 parts by weight of di-tert-butyl peroxide was added dropwise over 3 hours while maintaining a pressurized reflux state at the same temperature. Hold for 1 hour to complete polymerization. Further, 150 parts by weight of xylene was distilled off to obtain a low molecular weight polymer (L-1) solution.

A part of this polymer solution was taken out, dried under reduced pressure, and the obtained low molecular weight polymer (L-1) was analyzed. Mw (= <Mw ^g >) = 6,800, Mn
= 3,000, peak molecular weight PMw = 5,400, Tg
= 60 ° C, the polymer conversion was 97%.

[0170] The weight average molecular weight measured by a light scattering method <Mw ^l> at ^{7,000 <Mw l> / <Mw} g>
Was calculated to be 1.03.

Next, 250 parts by weight of the low molecular weight polymer (L-1) solution was charged into a four-necked flask, and the inside of the vessel was sufficiently purged with nitrogen while stirring, and then the xylene reflux temperature (144 ° C.) ).

While maintaining the reflux state at the same temperature, styrene 2
1 part by weight, 4 parts by weight of n-butyl acrylate, and 1,
1-bis (tert-butylperoxy) 3,3,5-
Trimethylcyclohexane (1 minute half-life temperature; 148
C) 2 parts by weight of the mixed solution was added dropwise over 4 hours, and the mixture was held for 2 hours to complete the polymerization, thereby obtaining a low molecular weight polymer (L-2) solution.

A part of this polymer solution was sampled and dried under reduced pressure. The obtained low molecular weight polymer (L-2) was analyzed, and it was found that Mw = 7,000 and Mn = 2.80.
0, PMw = 5,400, Tg = 55 ° C., and the conversion of the polymer was 97%.

[0174] In addition, by the light scattering method <Mw ^l> = 12,
400, was measured to be ^{<S 2> 1/2 = 250Å,} <Mw l>
/ <Mw ^g > = 1.78.

Synthesis of High Molecular Weight Polymer (H-1) 180 parts by weight of degassed water and 20 parts by weight of a 2% by weight aqueous solution of polyvinyl alcohol were charged into a four-necked flask, and then 68 parts by weight of styrene and acrylic acid 27 parts by weight of n-butyl, 5 parts by weight of monobutyl maleate, 0.005 parts by weight of divinylbenzene, and 2,2-bis (4,4-di-t
A mixed solution of 0.1 part by weight of tert-butylperoxycyclohexyl) propane (10-hour half-life temperature; 92 ° C.) was added, and stirred to form a suspension.

After sufficiently replacing the inside of the flask with nitrogen, 8
The temperature was raised to 0 ° C. to initiate polymerization. After maintaining at the same temperature for 32 hours, 0.1 part by weight of benzoyl peroxide (10-hour half-life temperature; 72 ° C.) was additionally added. Furthermore,
The polymerization was completed by holding for 12 hours.

To the suspension after completion of the reaction, an aqueous NaOH solution equivalent to twice the acid value (AV = 8.0) of the obtained high molecular weight polymer (H-1) was added, and the mixture was stirred for 2 hours. Was.

The high molecular weight polymer (H-1) was separated by filtration, washed with water, dried and analyzed.
n = 160,000, PMw = 1.15 million, Tg = 60 ° C., THF
The insoluble content was 2.8%, which was substantially not contained.

Preparation of Binder In a four-necked flask, 100 parts by weight of xylene, 30 parts by weight of the high molecular weight polymer (H-1), 2 parts by weight of low molecular weight polyethylene (Mw = 800), and a representative structure 5 parts by weight of a higher alcohol represented by the formula CH ₃ (CH ₂ ) ₄₈ CH ₂ OH is added, and the mixture is heated, stirred under reflux, and pre-dissolved. After maintaining in this state for 12 hours, a uniform preliminary solution (Y-1) of the high molecular weight polymer (H-1), the low molecular weight polyethylene and the higher alkyl alcohol was obtained.

The Tg of the solid content in this pre-dissolved solution was 57 ° C.
Met.

On the other hand, the low molecular weight polymer (L-
155 parts by weight of the homogeneous solution of 2) is charged and refluxed.

After the above pre-dissolved solution (Y-1) and the low molecular weight polymer (L-2) solution were mixed under reflux, the solvent was distilled off, and the obtained resin was cold-rolled, solidified and pulverized. Thus, a resin composition for toner (I) was obtained.

When the resin composition (I) was analyzed, the peak molecular weight in the low molecular weight region P ₁ Mw = 5,900, the peak molecular weight in the high molecular weight region P ₂ Mw = 950,000, Mw /
Mn = 82 and Tg = 56 ° C.

[0184] The molecular weight of 50,000 or less of the polymer component is, by the light scattering ^{method, <Mw l> = 12,400,} <S 2> 1/2
= Measured to ^{260Å, <Mw l> / <} Mw g> = 1.8
It was 5.

Further, when the flakes of the resin composition were observed with a video microscope (manufactured by Wilson), good dispersion was confirmed without reaggregation.

[Production Example 2 of Resin Composition] Synthesis of Low Molecular Weight Polymer (L-3) 250 parts by weight of the above low molecular weight polymer (L-1) solution was charged into a four-necked flask and stirred. After sufficiently replacing the inside of the vessel with nitrogen, the temperature was raised to the xylene reflux temperature.

While maintaining the reflux state at the same temperature, styrene 4
Parts by weight, 1 part by weight of n-butyl acrylate, and 1,1
A mixture of 2 parts by weight of -bis (tert-butylperoxy) 3,3,5-trimethylcyclohexane was added dropwise over 4 hours, and then maintained for 1 hour to complete the polymerization, thereby obtaining a low molecular weight polymer (L-3). A solution was obtained.

A part of this polymer solution was sampled and dried under reduced pressure. The obtained low molecular weight polymer (L-3) was analyzed, and it was found that Mw = 6,900 and Mn = 2,90.
0, PMw = 5,400, Tg = 57 ° C., and the polymer conversion was 98%.

[0189] In addition, by the light scattering method <Mw ^l> = 8,6
00, measured to be ^{<S 2> 1/2 = 120Å,} <Mw l> /
<Mw ^g > = 1.25.

Preparation of Binder In the same manner as in Preparation Example 1 of the resin composition, the pre-solution (Y-
After preparing 1), the low molecular weight polymer (L-3) solution 1
After mixing 00 parts by weight under reflux, the solvent was distilled off, and the obtained resin was cold-rolled, solidified and pulverized to obtain a resin composition for toner (II).

Analysis of the resin composition (II) showed that
P ₁ Mw = 5,900, P ₂ Mw = 960,000, Mw / Mn =
At 82, the Tg was 57 ° C.

The polymer component having a molecular weight of 50,000 or less is <M
w ^l > / <Mw ^g > = 1.29 and <S ² > ^1/2 = 120 °.

[Production Example 3 of Resin Composition] Synthesis of Low-Molecular-Weight Polymer (L-4) 250 parts by weight of the low-molecular-weight polymer (L-1) solution were put into a four-necked flask and stirred. After sufficiently replacing the inside of the vessel with nitrogen, the temperature was raised to the xylene reflux temperature.

While maintaining the reflux state at the same temperature, styrene 4
3 parts by weight, 7 parts by weight of n-butyl acrylate, and 1,
1-bis (tert-butylperoxy) 3,3,5-
After a mixture of 2 parts by weight of trimethylcyclohexane was added dropwise over 4 hours, the mixture was held for 1 hour to complete the polymerization, thereby obtaining a low molecular weight polymer (L-4) solution.

A part of this polymer solution was sampled and dried under reduced pressure. The obtained low molecular weight polymer (L-4) was analyzed, and it was found that Mw = 7,500 and Mn = 3,20.
0, PMw = 5,500, Tg = 54 ° C., and the conversion of the polymer was 97%.

[0196] In addition, by the light scattering method <Mw ^l> = 20,
300, was measured to be ^{<S 2> 1/2 = 390Å,} <Mw l>
/ <Mw ^g > = 2.71.

Preparation of Binder A pre-dissolved solution (Y-
After preparing 1), the low molecular weight polymer (L-4) solution 1
40 parts by weight were mixed under reflux. Thereafter, the solvent was distilled off, and the obtained resin was cold-rolled, solidified and pulverized to obtain a resin composition for toner (III).

When the resin composition (III) was analyzed, P ₁ Mw = 6,000, P ₂ Mw = 960,000, Mw / M
n = 82 and Tg = 57 ° C.

The polymer component having a molecular weight of 50,000 or less is
^{<Mw l> / <Mw g} > = 2.82, <S 2> 1/2 = 380
Was Å.

[Production Example 4 of Resin Composition] Synthesis of High Molecular Weight Polymer (H-2) 180 parts by weight of degassed water and 20 parts by weight of a 2% by weight aqueous solution of polyvinyl alcohol were put into a four-necked flask. 75 parts by weight of styrene, 25 parts by weight of n-butyl acrylate, 0.003 parts by weight of divinylbenzene, and 1-bis (tert-butylperoxy) 3,3,5-trimethylcyclohexane (10-hour half-life temperature; 90 ° C) 0.
One part by weight of the mixture was added and stirred to form a suspension.

After sufficiently replacing the inside of the flask with nitrogen, 8
The temperature was raised to 5 ° C. to initiate polymerization. After maintaining at the same temperature for 24 hours, 0.1 part by weight of benzoyl peroxide (10-hour half-life temperature; 72 ° C.) was further added. Furthermore,
The polymerization was completed by holding for 12 hours.

The high molecular weight polymer (H-2) was separated by filtration, washed with water, dried, and analyzed.
n = 120,000, PMw = 890,000, Tg = 59 ° C., and the THF-insoluble content was 1.8%, which is a level substantially not contained.

Preparation of Binder In a four-necked flask, 100 parts by weight of xylene, 30 parts by weight of the above high molecular weight polymer (H-2), 2 parts by weight of low molecular weight polyethylene (Mw = 800), and 5 parts by weight of a higher fatty acid having a structural formula of CH ₃ (CH ₂ ) ₄₈ COOH is added, and the mixture is heated, stirred under reflux, and pre-dissolved. This state was maintained for 12 hours to obtain a uniform preliminary solution (Y-2) of the high molecular weight polymer (H-2), the low molecular weight polyethylene, and the higher fatty acid.

The Tg of the solid content in the pre-dissolved solution was 56 ° C.
Met.

After mixing the above pre-dissolved solution (Y-2) and 260 parts by weight of the low molecular weight polymer (L-2) solution under reflux,
The solvent was distilled off, and the obtained resin was cold-rolled, solidified and pulverized to obtain a resin composition for toner (IV).

When the resin composition (IV) was analyzed,
P ₁ Mw = 5,800, P ₂ Mw = 710,000, Mw / Mn =
At 45, the Tg was 55C.

The polymer component having a molecular weight of 50,000 or less is
^{<Mw l> / <Mw g} > = 1.82, <S 2> 1/2 = 260
Was Å.

[Production Example 5 of Resin Composition] Production of Binder In a four-necked flask, 100 parts by weight of xylene, 30 parts by weight of the above high molecular weight polymer (H-2) and low molecular weight polypropylene (Mw = 800) 5 A part by weight is added, and the mixture is heated and stirred under reflux to perform preliminary dissolution. This state was maintained for 12 hours to obtain a uniform preliminary solution (Y-3) of the high molecular weight polymer (H-2) and the low molecular weight polypropylene.

The Tg of the solid content in this pre-dissolved solution was 59 ° C.
Met.

After mixing the above pre-dissolved solution (Y-3) and 260 parts by weight of the low molecular weight polymer (L-2) solution under reflux,
The solvent was distilled off, and the obtained resin was cold-rolled, solidified and pulverized to obtain a resin composition for toner (V).

Analysis of the resin composition (V) revealed that P
₁ Mw = 5,800, P ₂ Mw = 440,000, Mw / Mn = 3
At 8, Tg = 57 ° C.

Further, the polymer component having a molecular weight of 50,000 or less is
^{<Mw l> / <Mw g} > = 1.79, <S 2> 1/2 = 260
Was Å.

[Comparative Production Example 1 of Resin Composition] Synthesis of High Molecular Weight Polymer (H-3) 180 parts by weight of degassed water and 20 parts by weight of a 2% by weight aqueous solution of polyvinyl alcohol were charged into a four-necked flask. Thereafter, 75 parts by weight of styrene, 25 parts by weight of n-butyl acrylate, and 1-bis (tert-butylperoxy) 3,
A mixture of 0.1 part by weight of 3,5-trimethylcyclohexane (10-hour half-life temperature; 90 ° C.) was added, and stirred to form a suspension.

After sufficiently replacing the inside of the flask with nitrogen, 8
The temperature was raised to 5 ° C. to initiate polymerization. After maintaining at the same temperature for 24 hours, 0.1 part by weight of benzoyl peroxide (10-hour half-life temperature; 72 ° C.) was further added. Furthermore,
The polymerization was completed by holding for 12 hours.

The high molecular weight polymer (H-3) was separated by filtration, washed with water, dried and analyzed. Mw = 950,000, Mn
= 60,000, PMw = 600,000, Tg = 59 ° C., and the THF-insoluble content was 0.4%, which was substantially not included.

Preparation of Binder In a four-necked flask, 100 parts by weight of xylene, 70 parts by weight of the above low molecular weight polymer (L-1), and the high molecular weight polymer (H
-3) 30 parts by weight and low molecular weight polyethylene (Mw
= 1,500), 7 parts by weight, and the temperature is raised to 1 under reflux.
After stirring and mixing for 2 hours, the organic solvent was distilled off, and the obtained resin was cold-rolled, solidified and pulverized to obtain a comparative resin composition (i).

When the comparative resin composition (i) was analyzed, P ₁ Mw = 5,700, P ₂ Mw = 370,000, Mw / M
n = 29 and Tg = 57 ° C.

The polymer component having a molecular weight of 50,000 or less is
^{<Mw l> / <Mw g} > = 1.06, <S 2> 1/2 = 70Å
Met.

[Comparative Production Example 2 of Resin Composition] Synthesis of Low Molecular Weight Polymer (L-5) 100 parts by weight of xylene was charged into a four-necked flask, and the inside of the container was sufficiently purged with nitrogen while stirring. Thereafter, the temperature was raised to xylene reflux.

While maintaining the reflux temperature at the same temperature, styrene 7
0 parts by weight, 30 parts by weight of n-butyl acrylate, and
A mixture of 0.5 parts by weight of 2,2-bis (4,4-di-tert-butylperoxycyclohexyl) propane was added dropwise, and the mixture was polymerized for 8 hours. Then, 20 parts by weight of styrene,
A mixture of 3 parts by weight of tert-butyl peroxy-2-ethylhexanoate was added to complete the polymerization, and a low molecular weight polymer (L-5) solution was obtained.

A part of the polymer solution was sampled,
The polymer was dried under reduced pressure, and the obtained low molecular weight polymer (L-5) was obtained.
Analysis showed that Mw = 19,100 and Mn = 7.2.
00, PMw = 12,100, Tg = 52 ° C., and the conversion of the polymer was 94%.

[0222] In addition, by the light scattering method <Mw ^l> = 59,
200, was measured to be ^{<S 2> 1/2 = 96Å,} <Mw l> /
<Mw ^g > = 3.10.

Synthesis of high molecular weight polymer (H-4) In a four-necked flask, 72 parts by weight of styrene and acrylic acid
After charging 28 parts by weight of n-butyl and raising the internal temperature to 120 ° C., the temperature was maintained at the same temperature, and bulk polymerization was performed for 10 hours. At this time, the conversion of the polymer was 55%. Xylene 1
Add 30 parts by weight, mix and dissolve in advance
0.1 parts by weight of t-butyl peroxide, xylene 50
The weight part was continuously dropped for 8 hours while keeping the temperature at 130 ° C., and then the reaction was continued for 1 hour to terminate the polymerization, thereby obtaining a high molecular weight polymer (H-4) solution.

A part of the polymer solution was sampled,
The polymer was dried under reduced pressure, and the obtained high molecular weight polymer (H-4) was obtained.
Was analyzed, Mw = 360,000, Mn = 60,000, PMw
= 170,000, Tg = 56 ° C, and the THF-insoluble content was 0.4%, which is substantially free from the content.

Preparation of Binder In a four-necked flask, 90 parts by weight of the low molecular weight polymer (L-5) solution, 200 parts by weight of the high molecular weight polymer (H-4) solution, and 10 parts by weight of low molecular weight polypropylene were used. And mixed under reflux. Thereafter, the organic solvent was distilled off, and the obtained resin was cold-rolled, solidified and pulverized to obtain a comparative resin composition (ii).

When the comparative resin composition (ii) was analyzed, P ₁ Mw = 12,000, P ₂ Mw = 170,000, Mw
/ Mn = 32 and Tg = 54 ° C.

The polymer component having a molecular weight of 50,000 or less is <M
w ^l > / <Mw ^g > = 3.21 and <S ² > ^1/2 = 93 °.

[Comparative Production Example 3 of Resin Composition] Synthesis of Low Molecular Weight Polymer (L-6) 100 parts by weight of xylene was charged into a four-necked flask, and the inside of the container was sufficiently purged with nitrogen while stirring. Thereafter, the temperature was raised to xylene reflux.

While maintaining the reflux temperature at the same temperature, styrene 7
0 parts by weight, 30 parts by weight of n-butyl acrylate, and
A mixture of 40 parts by weight of divinylbenzene was added dropwise and polymerized for 8 hours. Thereafter, 20 parts by weight of styrene and ter
A mixture of 3 parts by weight of t-butylperoxy-2-ethylhexanoate was added to complete the polymerization, and a low molecular weight polymer (L-6) solution was obtained.

A part of the polymer solution was sampled,
The polymer was dried under reduced pressure, and the obtained low molecular weight polymer (L-6) was obtained.
Analysis showed that Mw = 14,900 and Mn = 7.1.
00, PMw = 11,700, Tg = 51 ° C, and the polymer conversion was 96%.

[0231] In addition, the light scattering method <Mw ^l> = 46,80
0, is measured and ^{<S 2> 1/2 = 480Å,} <Mw l> /
<Mw ^g > = 3.14.

Production of Binder A comparative production example except that 70 parts by weight of the low molecular weight polymer (L-6) solution, 200 parts by weight of the high molecular weight polymer (H-4) solution, and 10 parts by weight of the low molecular weight polypropylene were used. In the same manner as in 2, a comparative resin composition (iii) was obtained.

When the comparative resin composition (iii) was analyzed, it was found that P ₁ Mw = 11,500, P ₂ Mw = 170,000, M
w / Mn = 32 and Tg = 53 ° C.

The polymer component having a molecular weight of 50,000 or less is <M
w ^l > / <Mw ^g > = 3.45 and <S ² > ^1/2 = 490 °.

Further, when the flakes of this resin composition were observed with a video microscope, reaggregates were confirmed.

[Toner Production Examples 1 to 5 and Comparative Production Example 1] The resin compositions (I) to (V) obtained in the above resin composition production examples and the comparative compositions obtained in the comparative production examples. 100 parts by weight of each of the resin compositions (i) for use were mixed with 10 parts of magnetic fine powder.
After uniformly mixing 0 parts by weight and 2 parts by weight of a negative charge control agent (azo dye-based iron complex: complex [I] -7), the mixture is melt-kneaded with a twin-screw extruder heated to 110 ° C. did. After cooling the kneaded material, coarsely pulverized with a hammer mill,
Furthermore, it was finely pulverized by a jet mill, and the obtained pulverized product was subjected to air classification to obtain a classified powder and a comparative classified powder.

1.2 parts by weight of hydrophobic oil-treated silica fine powder (BET) was added to 100 parts by weight of each of these classified powders.
(Specific surface area: 200 m ² / g) were dry-mixed to obtain toners (A) to (E) and comparative toner (a).

[Toner Production Example 6 and Comparative Production Examples 2 and 3] The resin composition (I) obtained in the above resin composition production examples and the comparative resin composition obtained in the comparative production examples 100 parts by weight of each of (ii) and (iii), 5 parts by weight of carbon black (BET specific surface area: 130 m ² / g),
Negative charge control agent (azo dye-based iron complex: complex [II] above)
-1) was uniformly mixed with 3 parts by weight, and then subjected to melt kneading with a uniaxial extruder to obtain a classified powder and a comparative classified powder in the same manner as in the above-mentioned toner production example.

To 100 parts by weight of each of these classified powders, 1.5 parts by weight of a hydrophobic titanium oxide fine powder (BET specific surface area: 150 m ² / g) was dry-mixed, and a toner (F) and a comparative toner were used. Toners (b) and (c) were obtained.

Table 1 summarizes the analysis results of the molecular weight distribution of the obtained toner by the GPC method and the light scattering method and the measurement results such as the particle size distribution of the toner.

[0241]

[Table 1]

[Examples and Comparative Examples] In this example, a commercially available laser beam printer was modified as shown below and used after resetting.

Examples 1 to 6 and Comparative Examples 1 to 3 LBP-EX (manufactured by Canon Inc.) was used. A rubber roller (diameter: 12 m) in which conductive carbon coated with nylon resin is dispersed as a primary charging roller
m, contact pressure 50 g / cm), and the latent image carrier is exposed to a laser (600 dpi) to obtain a dark portion potential V _D =
−700 V and a light portion potential _VL = −200 V were formed. Next, the gap between the photosensitive drum and the developing sleeve (between SD)
Was set to 300 μm, and a urethane rubber blade having a thickness of 1.0 mm and a free length of 4 mm as a toner regulating member was brought into contact with the developing magnetic pole at 800 gauss at a linear pressure of 15 g / cm. DC bias component V _dc = -500 V, superimposed AC bias component V _pp = 1600 V, frequency 220 as development bias
0 Hz was used. The set temperature of the heat fixing device is 15
0 ° C.

When a non-magnetic toner is used, a sponge-made developer application roller is attached to the back of the developing sleeve in the developing device to form an image.

Under the above set conditions, room temperature and normal humidity (25 ° C., 6
Production Example 1 to 6 of the toner and Comparative Production Example 1 at a printout speed of 12 sheets (A4 size) / min under an environment of 0% RH) and low temperature and low humidity (15 ° C., 10% RH).
In the continuous mode (that is, each time one sheet is printed out) while sequentially replenishing each of the toners (A) to (F) according to the present invention and the comparative toners (a) to (c) obtained in The printout test was performed in a mode in which the printout was continuously operated without stopping the printout, and the obtained printout images were evaluated for the items described below.

At the same time, the matching between the used image forming apparatus and the toner was also evaluated.

The above evaluation results are summarized in Tables 2 and 3.

[0248]

[Table 2]

[0249]

[Table 3]

Embodiments 7 to 9 As the evaluation machines, the reuse mechanism shown in FIG. 3 was attached to the modified LBP-EX used in the above embodiment, and the present invention obtained in the above-mentioned toner production examples 1 to 3 was used. (A)
To (C) were similarly evaluated.

Tables 4 and 5 summarize the evaluation results.

[0252]

[Table 4]

[0253]

[Table 5]

The evaluation items described in the examples of the present invention and the comparative examples and the evaluation criteria will be described.

[Evaluation of Printout Image] <1> Image Density The image density was evaluated by maintaining the image density at the end of printing out 10,000 sheets on ordinary paper for copying machines (75 g / m ² ).
The image density was measured by using a "Macbeth reflection densitometer" (manufactured by Macbeth Co., Ltd.) with respect to a printout image of a white background portion having a document density of 0.00.

◎: Very good (1.40 or more) ：: Good (1.35 or more and less than 1.40) Δ: Normal (1.00 or more and less than 1.35) ×: Bad (less than 1.00) )

<2> Dot Reproducibility The pattern shown in FIG. 4 was printed out, and the dot reproducibility was evaluated.

◎: Very good (2 or less defects / 100) ○: Good (3 to 5/100 defects) Δ: Normal (6 to 10/100 defects) ×: Bad (11 defects) Above / 100)

<3> Image fog The fog density (%) was calculated from the difference between the whiteness of the white background portion of the printout image and the whiteness of the transfer paper measured by a “Reflectometer” (manufactured by Tokyo Denshoku Co., Ltd.). Image fog was evaluated.

◎: very good (less than 1.5%) ○: good (1.5% or more, less than 2.5%) Δ: normal (2.5% or more, less than 4.0%) ×: bad (4.0% or more)

<4> Sleeve Ghost Solid black band image X of width a and length 1 shown in FIG.
Is printed out, and the width b (>) shown in FIG.
When a halftone image Y having a length of 1 is printed out in a), the grayscale difference appearing on the halftone image (FIG. 5)
(A), (B), and (C) in (C)) were visually evaluated.

A: very good (no shading difference is observed at all) o: good (a slight shading difference is observed between B and C) Δ: normal (a slight shading difference is observed in each of A, B and C) (Seen) ×: poor (significant shading difference is observed)

<5> Hollow-out The “surprise” character pattern shown in FIG.
g / m ² ) when printing characters (Fig. 6
(State (b)) was visually evaluated.

◎: very good (not generated) ：: good (almost no occurrence) Δ: normal (little effect on image) ×: bad (conspicuous)

<6> Fixing Property The fixing property was evaluated by applying a load of 50 g / m ² , rubbing the fixed image with soft thin paper, and decreasing the image density before and after rubbing (%).

◎: Very good (less than 5%) ○: Good (5% or more and less than 10%) Δ: Normal (10% or more and less than 20%) ×: Bad (20% or more)

<7> Offset Resistance The offset resistance was evaluated by printing out a sample image having an image area ratio of about 5% and visually checking the degree of stain on the image after 3000 sheets.

◎: very good (not generated) ：: good (almost no occurrence) Δ: normal (little influence on image) ×: bad (conspicuous)

[Evaluation of Matching of Image Forming Apparatus] <1> Matching with Developing Sleeve After completion of the printout test, the state of fixation of residual toner on the surface of the developing sleeve and the influence on the printout image were visually evaluated.

◎: very good (not generated) ：: good (almost no occurrence) Δ: normal (there is sticking, but there is little effect on the image) ×: bad (many sticking and image unevenness occurs)

<2> Matching with Photosensitive Drum The occurrence of scratches on the surface of the photosensitive drum and sticking of residual toner and the effect on printout images were visually evaluated.

◎: very good (not generated) ：: good (slight scratches are observed, but there is no effect on the image) Δ: normal (there is sticking or scratches, but little effect on the image) ×: Bad (Many sticking causes vertical streak-like image defects)

<3> Matching with Fixing Device The state of the surface of the fixing roller was observed, and its durability was evaluated.

(1) Surface Properties After the completion of the printout test, the appearance of scratches and scraping on the surface of the fixing film was visually evaluated.

◎: very good (not generated) 良好: good (almost no occurrence) Δ: normal (scratch or scraping, but little effect on image) ×: bad (notable)

(2) Fixing Status of Residual Developer The fixing condition of the residual developer on the surface of the fixing roller after completion of the printout test was visually evaluated.

◎: very good (not generated) ：: good (almost no occurrence) Δ: normal (there is sticking, but there is little effect on the image) ×: bad (notable)

[0278]

As described above, the present invention controls the structure of each polymer component constituting the resin composition in the developer and specifies the physical properties of the toner, so that an extremely wide fixing temperature range can be obtained. And excellent reproducibility of fine lines, and can form a stable and good image without fog for a long period of time.

[Brief description of the drawings]

FIG. 1 is a schematic explanatory view showing a specific example of an image forming apparatus for performing an image forming method of the present invention.

FIG. 2 is an enlarged view of a main part of FIG.

FIG. 3 is a schematic explanatory diagram of an image forming apparatus that reuses untransferred toner.

FIG. 4 is an explanatory diagram of a checker pattern for checking development characteristics of toner.

FIG. 5 is an explanatory diagram of a sleeve ghost.

FIG. 6 is a schematic diagram showing a state in which a character image is hollow;

[Explanation of symbols]

 REFERENCE SIGNS LIST 100 photosensitive drum 102 developing sleeve (toner carrier) 103 contact blade 104 magnet roller 114 transfer charging roller 116 cleaner 117 primary charging roller 140 developing device 141 stirring bar

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. ⁷ , DB name) G03G 9/08

Claims (23)

(57) [Claims] 1. An electrostatic image developing toner formed of a composition in which at least a binder resin and a colorant are dispersed,
Tetrahydrofuran (TH) as a binder resin component in the composition
F) A component showing a molecular weight distribution of 50,000 or less by gel permeation chromatography (GPC) measured by a soluble component is represented by the following formula: A toner for developing electrostatic images, characterized in that: 2. A low molecular weight which forms a main peak in a molecular weight region of 2000 to 30,000 in a molecular weight distribution of gel permeation chromatography (GPC) measured by a tetrahydrofuran (THF) soluble component of the binder resin component. sub-peak in the region beyond the polymer component and molecular weight of 100,000, or, the toner according to claim 1, characterized by containing a high-molecular weight polymer component forming the shoulder. 3. The toner contains a wax component, and the wax component has the following general formula: RY [R: a hydrocarbon group having a weight average molecular weight of 3000 or less by GPC. Y represents a hydroxyl group, a carboxyl group, an alkyl ether group, an ester group, or a sulfonyl group. The toner for developing electrostatic images according to claim 1, wherein the compound has a content of at least 60% by weight. 4. The toner according to claim 1, wherein the weight average diameter D ₄ (μm) of the toner is
The relationship between 3.5 ≦ D ₄ ≦ 6.5 and the proportion N (number%) of particles having a particle size of 3.17 μm or less in the number particle size distribution is as follows: 35−D ₄ × 5 ≦ N ≦ 180-D _2. A particle size distribution satisfying ₄ × 25.
4. The toner for developing an electrostatic image according to any one of items 1 to 3. 5. The toner for developing an electrostatic image according to claim 1, wherein the porosity of the toner is from 0.5 to 0.7. 6. A charging step of bringing a charging member into contact with a member to be charged and applying a voltage to the charging member from the outside to charge the member to be charged, and forming an electrostatic image on the charged member to be charged. a step, a developing step of forming on the member to be charged toner image by developing the electrostatic image with a toner, the toner image on the member to be charged
A transfer step of transferring to a transcription material, in the image forming method having a heat fixing step of heat-fixing the toner image on the transfer material, the toner is formed with a composition obtained by dispersing at least a binder resin and a colorant Gel permeation chromatography (GP) as measured by a tetrahydrofuran (THF) -soluble component of a binder resin component in the composition.
A component having a molecular weight distribution of 50,000 or less in C) is represented by the following formula: An image forming method comprising: 7. The image forming apparatus according to claim 6 , wherein in the charging step, the charging member is brought into contact with the member to be charged, and a voltage is externally applied to the charging member to charge the member. Method. 8. A step of developing the electrostatic latent image on the electrostatic latent image carrier with toner, and electrostatically transferring the developed image to a transfer material via a transfer device. the image forming method according to claim 6 or 7 and carrier and transfer device is characterized in that the abutment. 9. The image forming method according to any one of claims 6 to 8 wherein the toner is a toner according to any one of claims 2 to 5. 10. A toner resin composition used for an electrostatic image developing toner, wherein the binder resin component in the toner resin composition is represented by the following formula: A resin composition for a toner, comprising a low molecular weight polymer component having a molecular weight of 50,000 or less. 11. A GPC molecular weight distribution measured by a THF-soluble component of the binder resin component, wherein the molecular weight is 200
Low molecular weight polymer component and a sub-peak in the region exceeding a molecular weight of 100,000 to form a main peak in 0-30000 area, or, according to claim 10, characterized by containing a high-molecular weight polymer component forming a shoulder 3. The resin composition for toner according to item 1. 12. low molecular weight polymer component, the prepolymer and second monomer coexistence, claim 10 or, characterized in that the polymerization by adding a peroxide having a functional group described below as a polymerization initiator 12. The resin composition for a toner according to item 11 . Embedded image 13. High molecular weight polymer to form a polymeric region, toner resin composition according to any one of claims 10 to 12, characterized in that the polymerization by adding a polyfunctional initiator. 14. A polymer obtained by dissolving or dispersing a high molecular weight polymer forming a high molecular weight region, a low molecular weight polymer having a main peak and a low molecular weight wax in an organic solvent, and then removing the organic solvent. Claims 10 to
14. The resin composition for a toner according to any one of 13 . 15. A high molecular weight polymer forming a high molecular weight region and a low molecular weight wax are dissolved or dispersed in an organic solvent in advance, and then mixed with an organic solvent solution of a low molecular weight polymer having a main peak, and the organic solvent is removed. The resin composition for a toner according to any one of claims 10 to 14 , which is obtained by removing the resin composition. 16. The low molecular weight wax has the following general formula: RY [R: a hydrocarbon group having a weight average molecular weight of 3000 or less by GPC. Y represents a hydroxyl group, a carboxyl group, an alkyl ether group, an ester group, or a sulfonyl group. The resin composition for toner according to any one of claims 10 to 15 , comprising at least 60% by weight of a compound having the following formula: 17. A method for producing a resin composition used in a toner for developing an electrostatic image, wherein the low molecular weight polymer component in the resin composition is represented by the following formula: It is characterized by polymerizing so that the molecular weight is 50,000 or less.
Method for manufacturing a belt toner resin composition. 18. A low molecular weight polymer component and a high molecular weight polymer component contained in the resin composition for a toner in a molecular weight distribution of GPC measured by a THF-soluble component in a region having a molecular weight of 2,000 to 30,000. forming a main peak, the sub peak in a region where the molecular weight exceeds 100,000, or polymerized to form a shoulder, method for producing a toner resin composition according to claim 17, characterized in that the mixing. 19. The polymerization of the low molecular weight polymer component by adding a peroxide having two or more of the following functional groups in one molecule as a polymerization initiator in the presence of a prepolymer and a second monomer. The method for producing a resin composition for a toner according to claim 17 or 18 , wherein Embedded image 20. High molecular weight polymer to form a polymeric region, the production of toner resin composition according to any one of claims 17 to 19, characterized in that the polymerization by adding a polyfunctional initiator Method. 21. A method comprising dissolving or dispersing a high molecular weight polymer forming a high molecular weight region, a low molecular weight polymer having a main peak and a low molecular weight wax in an organic solvent, and removing the organic solvent. Item 21. The method for producing a resin composition for a toner according to any one of Items 17 to 20 . 22. A high molecular weight polymer forming a high molecular weight region and a low molecular weight wax are dissolved or dispersed in an organic solvent in advance, and then mixed with an organic solvent solution of a low molecular weight polymer having a main peak. The method for producing a resin composition for a toner according to any one of claims 17 to 21 , wherein the resin composition is removed. 23. The low-molecular-weight wax has the following general formula: RY [R: a hydrocarbon group having a weight average molecular weight of 3,000 or less by GPC. Y represents a hydroxyl group, a carboxyl group, an alkyl ether group, an ester group, or a sulfonyl group. The method for producing a resin composition for a toner according to any one of claims 17 to 22 , wherein the compound having the following formula is contained in an amount of 60% by weight or more.