JPH1073956A - Toner for electrostatic charge image development, picture image formation method and resin component for its tonner and its manufacturing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner for electrostatic charge image development excellent in a fixing property and an offset resistance property and capable of stably realizing a high grade picture image for a long period of time. SOLUTION: A binding resin component in a toner for electrostatic charge image development formed of a component dispersing binding resin, a colorant and low molecular weight wax (a) does not actually include a tetrahydrofuran(THF) insoluble matter, (b) in molecular weight distribution of gel permeation chromatography(GPC) of a THF soluble matter, i) is a polymer mixture including low molecular weight polyester a low molecular weight component corresponding to an area of less than 50,000 molecular weight of which is denatured by the low molecular weight wax having an expression: R-Y; (R: shows a hydrocarbon radical. Y: shows either of a hydroxyl group, a carboxyl group, an alkylether group, an ester group and a sulfonyl group,) ii) and a hydroxyl value of a high molecular weight component corresponding to an area exceeding 50,000 molecular weight is less than 20(mgKOH/g).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a toner for visualizing an electrostatic latent image in an image forming method such as electrophotography, electrostatic printing and magnetic recording, and an image forming method using the toner. It is. Further, the present invention relates to a resin composition that can be used as a binder resin component constituting a toner and a method for producing the same.

[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 pressure, heat and pressure, or a solvent vapor to obtain a copy, and the remaining toner not transferred onto the photoreceptor is cleaned by various methods, and the above 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 a process of fixing a toner image to a sheet such as paper, and 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. . According to 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 thermal efficiency at the time of fusing the toner image onto 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 so-called offset phenomenon of toner transfer to the heating roller. 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.

On the other hand, Japanese Patent Application Laid-Open No. 62-78569 proposes a toner using a polyester having a saturated or unsaturated aliphatic hydrocarbon group having 3 to 22 carbon atoms in a side chain.

Japanese Patent Application Laid-Open No. 63-225244 proposes a toner using two types of polyester as a binder resin.

However, even in these toners, poor compatibility between the polyester resin and the polyolefin wax tends to cause poor dispersion of the polyolefin wax during the production of the toner. Many of them are mixed in the toner, impairing the chargeability of the toner, deteriorating the developability, and hindering the durability and the storability of the toner. In particular, when two types of polyesters having different melt viscosities are used, the dispersibility of the polyolefin wax in the polyester resin having a low viscosity is not sufficient, and the above-mentioned problem becomes remarkable. Also,
This causes cleaning failure, fusion to a photosensitive member, filming, and the like, and causes a problem in matching with the image forming apparatus.

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 in order 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 Nos. 2-129653 and 3-46668 propose a toner using a polyester obtained by treating a polyester resin with an acid or an alcohol as a binder resin.

Although these toners have some improvement in fixability and chargeability, the monoalcohol used has only 10 carbon atoms in the alkyl group, and therefore contributes little to the improvement in the dispersibility of the polyolefin wax. Or
Conversely, the introduction of the monoalcohol softens the polyester resin and the plasticizing effect of the unreacted alcohol causes new problems such as high-temperature offset resistance and storage stability, and durability of the toner during long-term use.

Further, in Japanese Patent Application Laid-Open No. Hei 7-36210,
There is disclosed a technique in which a long-chain primary alcohol and a polyisocyanate are used during the production of a toner, melt-mixed with a binder resin having a hydroxyl group, and grafted. However, in this case, since the entire binder resin is plasticized, low-temperature fixing is improved, but offset resistance is deteriorated. That is, the effective fixing area is not expanded. Further, an unpleasant odor due to unreacted polyisocyanate is not preferable for the toner.

Japanese Patent Application Laid-Open No. Hei 7-56386 discloses a technique in which a reaction product of a long-chain alcohol and an aromatic diisocyanate is added to a toner. Absent. Further, since the dispersibility in the toner is not taken into consideration, high-definition development and matching with the image forming apparatus become insufficient. The various properties required for the toners listed above are often reciprocal to each other, and it is increasingly desired in recent years to satisfy both of them with high performance, and furthermore, the development properties are also included. Research on holistic responses has been undertaken, but not enough.

[0020]

SUMMARY OF THE INVENTION It is an object of the present invention to greatly 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. A toner for developing an electrostatic image, which does not adversely affect a photoreceptor or a developer carrier and is highly applicable to an electrophotographic process, an image forming method using the toner, and a resin composition for the toner And a method for manufacturing the same.

[0021]

Means for Solving the Problems As a result of intensive studies, the present inventors have specified the composition and constitution of the resin composition and the respective polymer components constituting the resin composition, and the method of producing them. The present invention has been found to have an extremely wide fixable temperature range and to be able to stably form a good image with excellent dot reproducibility, thereby completing the present invention.

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, a colorant and a low molecular weight wax are dispersed, wherein the binder resin component in the toner is represented by the following formula: A) a molecular weight distribution substantially free of tetrahydrofuran (THF) -insoluble components, and (b) a molecular weight distribution of gel soluble permeation chromatography (GPC) of THF-soluble components, i) a low molecular weight component corresponding to a region having a molecular weight of 50,000 or less. Is a polymer mixture containing a low-molecular-weight polyester modified with a low-molecular-weight wax having the following general formula: RY; (R: a hydrocarbon group; Y: a hydroxyl group, a carboxyl group, an alkyl ether group, an ester Ii) a hydroxyl value of a high molecular weight component corresponding to a region having a molecular weight of more than 50,000 having a hydroxyl value of 20 (mg KO); / G) or less, a toner for developing electrostatic images, characterized in that.

The present invention also relates to an image forming method using the toner.

The present invention further relates to the resin composition for toner and a method for producing the same.

[0025]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.

The toner for developing an electrostatic image of the present invention comprises a low molecular weight polymer component (C) obtained by a modification reaction of a low molecular weight polyester (A) with a low molecular weight wax (B) having a specific structure, and a low hydroxyl value. Having a binder resin component composed of a high molecular weight polymer (D) exhibiting a high degree of compatibility between low-temperature fixing and high-temperature offset resistance, and dispersion of a wax component and other additives in the binder resin component. This greatly improves the toner charging characteristics and improves the matching property with the image forming apparatus, and prevents various problems such as poor cleaning and toner fusion. Further, the production efficiency can be improved in terms of toner production.

In the present invention, the hydroxyl value of the resin composition,
The oxidation is measured by the following method.

To measure the hydroxyl value (OH value), first, a sample was precisely weighed in a 100 ml eggplant flask, and
Add 0 ml and dissolve in an oil bath at 120 ° C. Take 50 ml of xylene as a blank in another eggplant flask,
Hereinafter, the same operation is performed.

After dissolution, 5 ml of a mixed solution of acetic anhydride / pyridine (1/4) is added. After heating for 3 hours or more, the temperature of the oil bath is raised to 80 ° C., a small amount of distilled water is added, and the temperature is maintained for 2 hours. After cooling, the flask wall is thoroughly washed with a small amount of an organic solvent. A phenolphthalein (methanol solution) indicator was added, and a 1 / 2N KOH / methanol titrant was used.
Potentiometric titration is performed, and the OH value is determined from the following equation.

OH value = 28.05 × fx (T _b −T _s ) / S + AS S: sample amount (g) T _s : sample titer (ml) T _b : blank titer (ml) f: titrant Factor A: Sample acid value

On the other hand, the measurement of the acid value is performed according to “JIS K155
The sample is weighed, dissolved in a mixed solvent, and added with water. This solution was added to a glass electrode using 0.1 g.
Potentiometric titration is performed with 1N-NaOH to obtain an acid value.

The low molecular weight polymer component (C) according to the present invention
Low molecular weight polyester resin (A) preferably used for
Is as follows.

That is, in the composition of the low molecular weight polyester resin (A), 45 to 55 mol% of all components are an alcohol component and 55 to 45 mol% are an acid component.

Examples of the alcohol component include ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol,
1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 2-ethyl-1,3-hexanediol, hydrogenated bisphenol A, and a bisphenol derivative represented by the formula (a);

[0035]

Embedded image

Diols represented by the formula (b):

[0037]

Embedded image And the like.

Among these, the bisphenol derivative represented by the above formula (A) is particularly preferable as the alcohol component, and the bisphenol derivative is added so as to be 70 mol% or more of the total alcohol component. In particular, ethylene oxide adducts (hereinafter referred to as EO-
BPA) and a propylene oxide adduct (hereinafter referred to as PO-BPA) are preferably used together, and if the content ratio is represented by a molar ratio, EO-
BPA / PO-BPA may be 0.01 to 10, preferably 0.05 to 5, and more preferably 0.1 to 3.

If the molar fraction of EO-BPA / PO-BPA is less than 0.01, the alkyl reaction with the low molecular weight wax (B) will not be sufficient.
On the other hand, if the molar fraction exceeds 10, it is difficult to control the reaction between the low molecular weight polyester (A) and the competitive reaction, which is not preferable.

When the above alcohol component is used, particularly preferred acid components include benzenedicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid and phthalic anhydride or anhydrides thereof; succinic acid, adipic acid and sebacic acid. , Succinic acid or its anhydride substituted with an alkyl group having 6 to 18 carbon atoms, such as azelaic acid, and unsaturated acids such as fumaric acid, maleic acid, citraconic acid, and itaconic acid; Examples thereof include dicarboxylic acids and anhydrides thereof, which are added so as to be 50 mol% or more of the total acid components.

The low molecular weight wax (B) according to the present invention comprises:
It is represented by the following general formula.

RY; (R: a hydrocarbon group; Y: any of a hydroxyl group, a carboxyl group, an alkyl ether group, an ester group, and a sulfonyl group). 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 OOH (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) and the like. 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.

Particularly preferred as the low molecular weight wax (B) are those having a carbon number distribution of at least 25, more preferably at least 35, especially at least 45 in the carbon number distribution measured by gas chromatography (GC). Are preferred. The low molecular weight synthetic wax component, in which the peak appearing according to the number of carbon atoms (one methylene chain) and the intensity of the regularity appears for each carbon number, is easy to control the plastic effect,
It is preferably used in the present invention.

In order to achieve a good balance of toner characteristics such as development characteristics, fixing properties, and high-temperature offset resistance, the maximum peak should be 25 or more, especially 30 or more, and more preferably 35 to 150 carbon atoms. Some are preferably used.

In the present invention, the carbon number distribution of the wax by GC is measured under the following conditions.

<GC measurement conditions> Apparatus: HP 5890 Series II (manufactured by Yokogawa Electric Corporation) Column: SGE HT-56 6m × 0.53mm
ID × 0.15 μm Carrier gas: He 20 ml / min Consta
nt FlowMode Oven temperature: 40 ° C → 450 ° C Inlet temperature: 40 ° C → 450 ° C Detector temperature: 450 ° C Detector: FID Inlet: With pressure control

Under the above conditions, the injection port was pressure-controlled, and the measurement was performed while maintaining the optimum flow rate constant, and n-paraffin was used as a standard sample.

The low molecular weight polymer component (C) contained in the binder resin component according to the present invention is a low molecular weight polyester (A)
And a polymer mixture obtained by a modification reaction with a low molecular weight wax (B) having a specific structure.

The low molecular weight polyester (A) according to the present invention
An example of improving the reactivity of the low molecular weight wax (B) with a diisocyanate compound and / or a polyisocyanate compound is given. In this case, the low molecular weight polyester (A) exhibits a hydroxyl value of 10 to 70 mgKOH / g, more preferably 10 to 40 mgKOH / g.
Adjust the composition to mgKOH / g. Hydroxyl value is 10mgK
If it is less than OH / g, the conversion with the isocyanate compound will be low, and the effect of modification with the low molecular weight wax (B) will not be exhibited. On the other hand, if it exceeds 70 mgKOH / g, a side reaction between the low molecular weight polyester (A) is promoted, and the low molecular weight polyester (A) is polymerized.

The low molecular weight polymer component (C) contained in the binder resin component according to the present invention has a modification rate of 20 to 95% in the modification reaction between the low molecular weight polyester (A) and the low molecular weight wax (B). The low molecular weight wax (B) so that
It is preferable to control the amount and method of addition, the reaction temperature, the time, and the like to obtain a polymer mixture of the low-molecular weight modified polyester (A ′) and the unreacted low-molecular weight wax (B ′). When the conversion of the modification reaction is less than 20%, the dispersion state of the unreacted low molecular weight wax (B ') in the binder resin component becomes unstable, and the developing property and durability, and the image forming method, This causes inconvenience in matching. On the other hand, when the modification ratio exceeds 95%, the effect of adding the low-molecular-weight wax is lost, and not only the offset resistance is deteriorated, but also the Tg of the binder resin component is lowered, causing a problem in storage stability and the like.

In the present invention, the modification rate of the modification reaction between the low molecular weight polyester (A) and the low molecular weight wax (B) is determined from the molecular weight distribution of gel permeation chromatography (high temperature GPC) under high temperature measurement conditions. Can be

That is, when the solubility of the low molecular weight modified polyester (A ′) in THF is low or when it is expected that the modification rate is high, the THF insoluble matter previously separated is heated under heating. O-dichlorobenzene (OD
Dissolved in a high boiling point solvent such as CB) and obtained from the molecular weight distribution of the obtained high-temperature GPC,

[0053]

(Equation 1) (Method 1).

Hereinafter, a specific example of calculating the denaturation rate by the above method 1 will be described.

<High Temperature GPC Measurement Conditions for Calculation of Modification Ratio of Low Molecular Weight Polyester> Apparatus: GPC-150C (manufactured by Waters) Column: HT-806M (manufactured by Showa Denko KK) and HT-800P ( (Showa Denko KK) Temperature: 135 ° C Solvent: O-dichlorobenzene (0.1% ionol added) Flow rate: 1.0 ml / min Sample: 0.1 ml of 0.3% by weight sample is injected

The high-temperature GPC measured under the above conditions and obtained
The area% of the low molecular weight modified polyester (A ') and the area% of the unreacted low molecular weight wax (B') are determined from the molecular weight distribution of the above. When the molecular weight distributions of the low molecular weight modified polyester and the unreacted low molecular weight wax overlap as illustrated in FIG. 1, a value obtained by doubling the area% of the left half of the peak (S) from the area% of the entire peak was subtracted. (W)
Is defined as the area% of the unreacted low molecular weight wax, and the modification rate is calculated from the above formula (1).

On the other hand, when the low-molecular-weight modified polyester (A ′) has high solubility in THF or is expected to have a low modification rate, the THF-soluble component and the insoluble Are dissolved in ODCB or the like under heating so as to have the same concentration, and from the molecular weight distribution of the obtained GPC, in the same manner as in the above method 1,

[0058]

(Equation 2) (Method 2).

The low molecular weight wax (B) has a number average molecular weight (Mn) of 200 to 2,000 and a weight average molecular weight (M
It is preferable that w) is 400 to 3000 and Mw / Mn is 3.0 or less. By providing such a molecular weight distribution, the alkyl modification of the low molecular weight polyester (A) can be improved, and the toner can have preferable physical properties. If the molecular weight is smaller than the above range, the composition is susceptible to thermal and mechanical effects excessively, and causes problems in offset resistance and storage stability. When the ratio is larger than the above range, the reaction efficiency decreases, and the residue of the unreacted isocyanate compound adversely affects the toner characteristics,
The effect of adding the low molecular weight wax (B) disappears.

In the present invention, the low molecular weight wax (B)
May be measured under the following conditions in addition to the measurement by high temperature GPC.

<Measurement conditions of high-temperature GPC of wax> Apparatus: GPC-150C (manufactured by Waters) Column: Duplex of GMH-HT (manufactured by Tosoh Corporation) Temperature: 135 ° C Solvent: O-dichlorobenzene (0.1% ionol) Addition) Flow rate: 1.0 ml / min Sample: 0.4 ml of 0.15 wt% concentration 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. In addition, Mark-Houw
It is calculated by converting into polyethylene using a conversion formula derived from the ink viscosity formula.

The low molecular weight wax (B) according to the present invention comprises
In a DSC curve measured by a differential scanning calorimeter,
Shows a maximum endothermic peak in the range of 70 to 130 ° C. at the time of temperature rise, has a maximum exothermic peak at the time of temperature fall in a range of ± 15 ° C. with respect to the peak temperature of the maximum endothermic peak, and includes the maximum endothermic peak The onset temperature at the start of the endothermic peak is 5
The temperature is preferably 0 ° C. or higher.

In the DSC curve at the time of temperature rise, the low molecular weight wax melts in the above temperature range, so that a proper plasticizing effect is exerted on the binder resin at the time of toner production, and a uniform toner composition can be obtained. Further, after the toner is produced, the releasing effect of the appropriately dispersed low-molecular-weight wax is effectively exerted in addition to the good fixing performance, and a wide fixing area is secured. At the same time, the developing property of the toner is improved and the matching property with the image forming apparatus is also improved.

On the other hand, in the DSC curve at the time of cooling, an exothermic peak accompanying the coagulation and crystallization of the low molecular weight wax (B) is observed. The presence of this exothermic peak in a temperature region close to the endothermic peak at the time of temperature increase indicates that the wax component is more homogeneous, and by reducing this difference, the thermal responsiveness of the low molecular weight wax is reduced. At the same time, the excessive plasticizing effect can be suppressed. Therefore, the low-molecular-weight wax (B) according to the present invention greatly plasticizes the binder resin when the toner composition containing the low-molecular-weight wax (B) is heated in a fixing device. While contributing, the synergistic effect with the binder resin can also effectively exert the releasability, and it is possible to achieve both low-temperature fixability and high-temperature offset resistance at a high level. Further, the dispersion of the wax in a homogeneous state does not adversely affect the triboelectric charging, thereby further improving the developing characteristics of the toner. However, such a wax component has a high recrystallization speed and is liable to cause phase separation. Therefore, poor dispersion in the toner, deterioration of the toner due to external force received from the image forming apparatus, and blooming of the wax component due to long-term storage, etc. As described above, the low molecular weight component in the binder resin component in the toner composition is alkyl-modified with the low molecular weight component as described above. Is dramatically improved, and various characteristics of the toner are remarkably improved.

Further, D represented by the low molecular weight wax (B)
By setting the onset temperature of the start point of the endothermic peak including the maximum endothermic peak of the SC curve to 50 ° C. or more, the plasticization of the binder resin can be appropriately suppressed, so that the blocking resistance without impairing the low-temperature fixing property Is maintained, and the durability of the toner is improved.

In the present invention, in the DSC measurement, since the exchange of heat of the wax is measured and its behavior is observed, it is preferable from the principle of measurement that the measurement is performed by a high-precision internal heating input compensation type differential scanning calorimeter. For example, DSC-7 manufactured by PerkinElmer can be used.

The measurement method is described in “ASTM D3418-8.
2). The DSC curve used in the present invention is:
After raising and lowering the temperature once and taking the previous history, the temperature rate is 10 ° C.
A DSC curve measured when the temperature is raised at a rate of / min is used.

Each temperature exhibited by the low molecular weight wax (B) precisely specified in the present invention is defined as follows.

(Maximum Endothermic Peak) DS Obtained During Temperature Rise
In the C curve, the peak top temperature of the peak showing the maximum endothermic peak in the temperature region of 70 to 130 ° C. (P _{1 in} FIG. 2)
P).

(Onset temperature at the starting point of the endothermic peak) The temperature at the intersection of the tangent of the curve and the base line at the point where the differential value of the DSC curve obtained at the time of the temperature rises first (S-OP in FIG. 2) Equivalent).

(Maximum exothermic peak temperature) The peak top temperature of the peak showing the maximum exothermic peak in the DSC curve obtained when the temperature is lowered (corresponding to P ₂ P in FIG. 3).

It is a preferred embodiment of the present invention to add another low molecular weight wax not represented by the above general formula to the low molecular weight wax (B) in advance.

Other low molecular weight waxes applicable to the present invention include waxy substances such as polypropylene, polyethylene, microcrystalline wax, carnauba wax, sasol wax and paraffin wax;
And their oxides and graft-modified products. These can be used alone or in combination.

The weight average molecular weight of these low molecular weight waxes is 30,000 or less, preferably 10,000 or less. By using 20 to 70 parts by weight based on 100 parts by weight of the low molecular weight wax (B),
The matching with the low molecular weight polyester (A), the low molecular weight wax (B) and the high molecular weight polymer (D) is very good, and the object of the present invention can be highly achieved.

The low-molecular-weight polyester (A) has a content of 3 as long as it does not inhibit the reactivity with the isocyanate compound.
A polyhydric alcohol component or a polycarboxylic acid component having a valency or higher may be added.

Particularly preferred polyhydric alcohol components include, for example, sorbitol, 1,2,3,6-hexanetetol, 1,4-sorbitan, pentaerythritol,
Dipentaerythritol, tripentaerythritol,
Sucrose, 1,2,4-menthatriol, glycerin,
2-methylpropanetriol, 2-methyl-1,2,2
4-butanetriol, trimethylolethane, trimethylolpropane, and 1,3,5-trihydroxymethylbenzene.

Examples of the polycarboxylic acid include trimellitic acid, pyromellitic acid, cyclohexanetricarboxylic acids, 2,5,7-naphthalenetricarboxylic acid,
1,2,4-naphthalenetricarboxylic acid, 1,2,4-
Butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methylenecarboxylpropane, 1,3-dicarboxyl-2-methyl-methylenecarboxylpropane, tetra (methylenecarboxyl) methane, , 2,7,8-octanetetracarboxylic acid and their anhydrides.

These polyhydric alcohols and polycarboxylic acids may be contained in an amount of 0.5 to 10 mol%, preferably 1 to 7 mol%, based on all alcohol components or all acid components. And more preferably 1.5 to 5 mol%.

The diisocyanate compound and / or polyisocyanate compound which can be reacted with the mixture of the low molecular weight polyester (A) and the low molecular weight wax (B) include the following.

For example, examples of the diisocyanate compound include threlin diisocyanate (hereinafter referred to as TDI), hexamethylene diisocyanate, isophorone diisocyanate, tetramethylxylylene diisocyanate, and the like.

The following are examples of the tri- to hexa-functional polyisocyanate compounds.

[0083]

Embedded image

The amount of the isocyanate compound added depends on the low-molecular-weight polyester (A) and the low-molecular-weight wax (B).
0.1 to 1.0 mol equivalent per 1 mol equivalent of hydroxyl group,
Preferably it is 0.15-0.85 mol equivalent. When the addition amount of the isocyanate compound is less than 0.1 mol equivalent, the reaction amount is small, so that it is difficult to form a sufficient high molecular weight region, and the hot offset resistance cannot be satisfied. Also, if it exceeds 1.0 mol equivalent,
In order to cause remarkable high molecular weight, low temperature fixability may be impaired,
The dispersibility of other additives becomes difficult, which adversely affects the developability. On the production side, not only the operation becomes difficult due to the increase in the viscosity of the resin, but also the pulverization efficiency of the toner decreases.

The high molecular weight polymer component (D) according to the present invention
Any known resins can be used as long as the hydroxyl value is 20 mg KOH / g or less, but polyester resins and vinyl resins are suitable for toner.

As the polyester resin used for the high molecular weight polymer component (D), the alcohol component and the acid component of the low molecular weight polyester (A) can be used.

The glass transition temperature (T
g) is 40-80 ° C, preferably 50-70 ° C;
The number average molecular weight (Mn) is 2000 to 40,000, preferably 2
500 to 20,000 and a weight average molecular weight (Mw) of 500
It is adjusted to 0 to 150,000, preferably 6000 to 80,000.

Examples of the vinyl monomer for producing the vinyl resin 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 and its derivatives such as p-tert-butylstyrene, pn-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene, pn-dodecylstyrene; 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 ester acids such as vinyl acetate, vinyl propionate and vinyl benzoate; methyl methacrylate, ethyl methacrylate, propyl methacrylate, methacrylic acid α-methylene aliphatic monomers such as n-butyl, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate Carboxylic esters;
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; vinyl naphthalenes; acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile and acrylamide; esters of the above-mentioned α, β-unsaturated acids and diesters of dibasic acids.

Unsaturated dibasic acids such as maleic acid, citraconic acid, itaconic acid, alkenylsuccinic acid, fumaric acid and mesaconic acid; maleic anhydride, citraconic anhydride, itaconic anhydride, alkenylsuccinic anhydride Unsaturated dibasic acid anhydrides such as those; methyl maleate half ester, maleic acid ethyl half ester, maleic acid butyl half ester, citraconic acid methyl half ester, citraconic acid ethyl half ester, citraconic acid butyl half ester, methyl itaconate Half esters of unsaturated dibasic acids such as half ester, methyl alkenyl succinate half ester, methyl fumarate half ester and methyl half mesaconic acid; unsaturated dibasic acid esters such as dimethyl maleic acid and dimethyl fumaric acid; Acid, methacrylic acid, crotonic acid, such as cinnamic acid alpha, beta-unsaturated acid; crotonic acid anhydride, such as alpha of cinnamic acid anhydride, beta-unsaturated acid anhydride, the alpha, beta
-Anhydrides of unsaturated acids and lower fatty acids; and monomers having a carboxyl group such as alkenyl malonic acid, alkenyl glutaric acid, alkenyl adipic acid, acid anhydrides and monoesters thereof.

Also, acrylic acid or methacrylic acid esters such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate, 4- (1-hydroxy-1-methylbutyl) styrene, 4- (1- Monomers having a hydroxyl group such as (hydroxy-1-methylhexyl) styrene are exemplified.

As a polymerization method which can be used in the present invention as a method for synthesizing the vinyl resin used for the high molecular weight polymer component (D), an emulsion polymerization method or a suspension polymerization method, and further an additional solvent is added. Bulk polymerization and the like.

Among them, the emulsion polymerization method is a method in which a monomer (monomer) almost insoluble in water is dispersed as small particles in an aqueous phase with an emulsifier, and polymerization is 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,
It is advantageous as a method for producing a binder resin for a toner because it can be easily mixed 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.

In order to achieve the object of the present invention, a polyfunctional polymerization initiator having a polyfunctional structure as exemplified below is used for the vinyl resin used in the high molecular weight polymer component (D). Is preferred.

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-butylperoxyacetate, 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.

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, and 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 methacrylates instead of the above compounds; 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 the acrylates of the above compounds instead of methacrylates 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; and 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 into methacrylate Alternatives; triallyl cyanurate, triallyl trimellitate; and the like.

When these crosslinking monomers are used in an amount of 1% by weight or less with respect to 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, and a carboxylic anhydride group. 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 according to the present invention, a polymer containing at least one of a carboxyl group, a carboxylic acid 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 monomers usable in the present invention include, 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-octenyl succinate, 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 carboxylic acid groups and carboxylic acid ester sites in the copolymer obtained by the above method can be saponified by alkali treatment.

In the present invention, a low molecular weight polyester (A) is reacted with a low molecular weight wax (B) having a specific structure to produce a low molecular weight polymer component (C) to obtain a binder resin according to the present invention. Examples of the method include a method exemplified below.

<1> Mixture 1 of low molecular weight polyester (A) and low molecular weight wax (B) having a specific structure
0.1 to 10 parts by weight to 00 parts by weight is added all at once or continuously in small amounts. Reaction temperature is 100-2
In the range of 00 ° C., the temperature can be changed stepwise in some cases, and the reaction time varies depending on the reaction temperature.
It is about 1 minute to 6 hours, and there are a case where batch processing is performed using a reaction vessel and a case where continuous processing is performed using a kneader such as a single-screw or twin-screw extruder. The obtained low molecular weight polymer component (C) is blended with the high molecular weight polymer component (D) by various known methods, and can be used as a binder resin according to the present invention.

<2> The production method described above, except that the isocyanate is reacted with a mixture of the low molecular weight polyester (A) and the low molecular weight wax (B) having a specific structure in the presence of the high molecular weight polymer component (D). It can be manufactured in the same manner as <1>.

The binder resin component in the toner composition according to the present invention has a main peak in a molecular weight region of 2,000 to 30,000 and a molecular weight of less than 50,000 in a GPC molecular weight distribution measured by a THF-soluble component. Low molecular weight component and molecular weight 1
Those comprising a high molecular weight component having a molecular weight of 50,000 or more having a subpeak or a shoulder in a region of not less than 100,000 are preferred.

When the peak molecular weight of the high molecular weight component of the binder resin is less than 100,000, not only the high temperature offset resistance of the toner becomes unsatisfactory, but also the wax component of the present invention has a good dispersibility and a good dispersion state. Is insufficient, and image defects such as a decrease in image density are likely to occur. Also. When the peak molecular weight of the low molecular weight component of the binder resin is less than 2,000, the plasticization by the wax component becomes abrupt, which causes a serious problem in high-temperature offset resistance and storage stability. Further, since phase separation easily occurs locally, the frictional charging of the toner becomes non-uniform, and the developing characteristics deteriorate.
On the other hand, when the peak molecular weight exceeds 30,000, the dispersion state of the wax component is improved to some extent, and although the developing characteristics are improved, the fixability is not sufficient. Further, when the toner is manufactured by a pulverization method or the like, the productivity is reduced.

That is, by specifying the molecular weight distribution of GPC of the binder resin component as described above, it is possible to easily balance various properties required for the toner.

Further, the binder resin component in the toner composition according to the present invention does not substantially contain a THF-insoluble component, and has a molecular weight distribution of not more than 1,000 in a GPC molecular weight distribution measured by a THF-soluble component. The area ratio of the low molecular weight components shown is 15
% And a high molecular weight component having a molecular weight of 1,000,000 or more with an area ratio of 0.5 to 25%, the matching with the wax component according to the present invention becomes very good. That is, when the area ratio of the low molecular weight component having a molecular weight of 1,000 or less exceeds 15%, plasticization is rapidly accelerated by the wax component, and the above-mentioned problem becomes more remarkable. Furthermore, toner fusion to the photosensitive drum surface, etc.
There is also a problem in matching with the image forming apparatus. on the other hand,
When the high molecular weight component having a molecular weight of 1,000,000 or more is less than 0.5%, it is difficult to maintain a good dispersion state of the wax component, and the toner is liable to be deteriorated by an external force received from the image forming apparatus. For this reason, the developing characteristics and the storability of the toner, and the durability may be deteriorated. In particular, image fog in a low-temperature and low-humidity environment and a decrease in image density in a high-temperature and high-humidity environment become significant. Conversely, THF insolubles and molecular weight 10
If there are more than 100,000 high molecular weight components in excess of 25%,
In addition to impairing low-temperature fixability and toner productivity, it is difficult to uniformly disperse the toner constituent materials, so that uniform triboelectric charging of the toner cannot be obtained, and the developing characteristics deteriorate. Also,
Even if the mixing force is increased externally by hot-melt kneading etc. during toner production to improve the dispersion state, polymer chains are cut by mechanical shearing force, and balance low-temperature fixability and high-temperature offset resistance It becomes difficult. These tendencies become remarkable especially in a magnetic toner in which the particle diameter of the toner is reduced to a fine particle or magnetic particles having high specific gravity are required to be uniformly dispersed.

Further, in the binder resin component in the toner composition according to the present invention, the high molecular weight component corresponding to a region having a molecular weight of 100,000 or more in the THF-soluble GPC molecular weight distribution has a THF insoluble content of 30 wt. % By applying a shearing force by kneading or the like during kneading or the like during the production of the toner to cut the molecular chain, thereby achieving high low-temperature fixability and high-temperature offset resistance, Without breaking the balance, the development characteristics and durability of the toner, and further the storage stability and the like can be remarkably improved.

The present inventors consider the reason why the toner according to the present invention exerts the effects of the present invention as follows.

That is, loose cross-linking soluble in THF,
Or by including the high molecular weight component having a branched structure in the toner composition, without increasing the melt viscosity of the toner at the time of heat fixing compared to the conventional crosslinkable polymer,
The elasticity of the semi-molten toner can be maintained. Further, the matching with the wax component according to the present invention is good, and the elasticity as described above is not lost even when plasticized. Thereby, the low-temperature fixing property and the high-temperature offset resistance were remarkably improved. Further, by adding a high molecular weight component having the structure as described above, a low melt viscosity portion plasticized by the volatile component or the wax component that is locally phase-separated by undergoing hot melt kneading during toner production. And the uniform mixing force can be enjoyed in the toner composition, so that the dispersion state is synergistically improved and the developing characteristics of the toner are improved. Further, since the mechanical strength of the toner can be increased, it is possible to suppress the deterioration of the toner against external force received from the image forming apparatus, and the matching with the image forming apparatus becomes easy.

The THF insoluble content in the resin composition was 40%.
If the content is more than wt%, it may be a factor of hindering low-temperature fixation or poor dispersion of the toner composition. Applying stronger shearing force to eliminate these phenomena is a problem in toner production.
It is very uneconomical and unfavorable.

In the present invention, the molecular weight distribution of the binder resin component is measured by GPC under the following conditions.

<Conditions for GPC Measurement of Resin> Apparatus: GPC-150C (manufactured by Waters) Column: KF801-7 (manufactured by Shodex) Seven consecutive temperatures: 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
1 Injection A sample is prepared as follows.

[0125] The sample is placed in THF, left for several hours, shaken sufficiently and mixed well with THF (until the sample is no longer united), and allowed to stand still for 12 hours or more. Then T
The time of leaving in HF is set to 24 hours or more.
After that, the sample processing filter (pore size 0.45
０．５0.5 μm, for example, Myshodisk H-25-
5 The product passed through Tosoh Co., Ltd., and can be used as a sample of GPC. The sample concentration is
The concentration is adjusted so that the resin component has the above concentration.

Measurement is performed under the above conditions, and a molecular weight calibration curve prepared from a monodisperse polystyrene standard sample is used in calculating the molecular weight of the sample.

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 component in the present invention indicates the polymerization 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 the toner sample was weighed (W ₁ g), and a cylindrical filter paper (for example, No. ₁ made by Toyo Filter Paper Co., Ltd.) was used.
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.

[0130]

(Equation 3)

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

In the toner for developing an electrostatic image of the present invention, a charge control agent can be used if necessary in order to further stabilize the chargeability. The charge control agent is a binder resin 100
0.1 to 10 parts by weight, preferably 0.1 to 5 parts by weight
It is preferred to use parts by weight.

The charge control agents known in the art today include the following.

For example, organic metal complexes and chelate compounds are effective. Examples thereof include a monoazo metal complex, an aromatic hydroxycarboxylic acid, a metal complex, and an aromatic dicarboxylic acid-based metal complex. Others include aromatic hydroxycarboxylic acids, aromatic mono- and polycarboxylic acids and their metal salts, anhydrides,
Examples include esters and phenol derivatives of bisphenol.

When the toner of the present invention is used as a magnetic toner, the magnetic material contained in the magnetic toner includes iron oxides such as magnetite, maghemite and ferrite, and iron oxides containing other metal oxides; Fe, Co, Ni Or a metal such as Al, Co, Cu, P
b, Mg, Ni, Sn, Zn, Sb, Be, Bi, C
Alloys with metals such as d, Ca, Mn, Se, Ti, W, and V, and mixtures thereof, and the like. The magnetic material, conventionally, triiron tetroxide (Fe ₃ O _4), iron sesquioxide _{(γ-Fe 2 O 3)} , iron oxide, zinc (ZnFe _{2 4),}
Yttrium iron oxide (Y ₃ e ₅ O ₁₂ ), cadmium iron oxide (CdFe ₂ O ₄ ), gadolinium oxide (Gd ₃ Fe ₅₎
-O ₁₂ ), copper iron oxide (CuFe ₂ O ₄ ), lead iron oxide (Pb
Fe ₁₂ -O _19), iron oxide nickel (NiFe ₂ O _4), iron oxide, neodymium (NdFe ₂ O _3), barium iron oxide (Ba
Fe ₁₂ O ₁₉ ), iron magnesium oxide (MgFe ₂ O ₄ ),
Iron manganese oxide (MnFe ₂ O ₄ , iron lanthanum oxide (L
aFeO ₃ ), iron powder (Fe), cobalt powder (Co), nickel powder (Ni), etc. are known. According to the present invention, the above-mentioned magnetic materials are selected alone or in combination of two or more. use. Particularly preferred magnetic materials for the purposes of the present invention are fine powders of iron tetroxide or γ-iron sesquioxide.

These ferromagnetic materials have an average particle size of 0.1 to 2
about 10 μm, the magnetic characteristics when a 10K Oersted is applied show a coercive force of 20 to 150 Oersted saturation magnetization of 50 to 200 e
mu / g (preferably 50 to 100 emu / g) and a residual magnetization of 2 to 20 emu / g are desirable.

The magnetic substance 1 was added to 100 parts by weight of the binder resin.
It is preferable to use 0 to 200 parts by weight, preferably 20 to 150 parts by weight.

As the colorant irrespective of one component or two components, carbon black, titanium white, and any other pigments and / or dyes can be used. For example, when the toner of the present invention is used as a magnetic color toner, C.I. I. Direct Red 1,
C. I. Direct Red 4, C.I. I. Acid Red 1, C.I. I. Basic Red 1, C.I. I. Modant Red 30, C.I. I. Direct Blue 1, C.I. I. Direct Blue 2, C.I. I. Acid Blue 9, C.I.
I. Acid Blue 15, C.I. I. Basic Blue 3, C.I. I. Basic Blue 5, C.I. I. Modant Blue 7, C.I. I. Direct Green 6, C.I. I. Basic Green 4, C.I. I. Basic Green 6 and the like. Examples of pigments include: graphite, cadmium yellow, mineral fast yellow, navel yellow, naphthol yellow S, Hansa yellow G, permanent yellow NCG, tartrazine lake, red-mouthed graphite, molybdenum orange, permanent orange GTR, pyrazolone orange, benzidine orange G , Cadmium Red, Permanent Red 4R, Watching Red Calcium Salt, Eosin Lake, Brilliant Carmine 3B, Manganese Purple, Fast Violet B, Methyl Violet Lake, Navy Blue, Cobalt Blue, Alkaline Blue Lake, Victoria Blue Lake, Phthalocyanine Blue,
First Sky Blue, Indanthrene Blue BC,
Chrome green, chromium oxide, pigment green B,
Malachite Green Lake, Final Yellow Green G, etc.

When the toner of the present invention is used as a two-component full-color toner, the following may be mentioned. Examples of the magenta coloring pigment include C.I. I. Pigment Red 1,2,3,4,5,6,7,8,9,1
0, 11, 12, 13, 14, 15, 16, 17, 1
8, 19, 21, 22, 23, 30, 31, 32, 3
7, 38, 39, 40, 41, 48, 49, 50, 5
1,52,53,54,55,57,58,60,6
3,64,68,81,83,87,88,89,9
0, 112, 114, 122, 123, 163, 20
2,206,207,209, C.I. I. Pigment Violet 19, C.I. I. Butt Red 1,2,10,1
3, 15, 23, 29, 35 and the like.

Although such a pigment may be used alone, it is more preferable to use the dye and the pigment together to improve the sharpness from the viewpoint of the image quality of a full-color image. Examples of such magenta dyes include C.I. I. Solvent Red 1,
3, 8, 23, 24, 25, 27, 30, 49, 81,
82, 83, 84, 100, 109, 121, C.I. I.
Disperse Red 9, C.I. I. Solvent Violet 8, 13, 14, 21, 27, C.I. I. Oil-soluble dyes such as Disperse Violet 1, C.I. I. Basic Red 1,2,9,12,13,14,15,17,18,
22, 23, 24, 27, 29, 32, 34, 35, 3
6, 37, 38, 39, 40, C.I. I. Basic Violet 1,3,7,10,14,15,21,25
And basic dyes such as 26, 27 and 28.

Other color pigments include cyan color pigments such as C.I. I. Pigment Blue 2, 3, 15,
16, 17, C.I. I. Bat Blue 6, C.I. I. Acid Blue 45 or a copper phthalocyanine pigment in which 1 to 5 phthalimidomethyl groups are substituted on a phthalocyanine skeleton having a structure represented by Chemical Formula 3.

[0142]

Embedded image

The coloring pigments for yellow include C.I. I. Pigment Yellow 1,2,3,4,5,6,7,10,
11, 12, 13, 14, 15, 16, 17, 23, 6
5, 73, 83, C.I. I. Bat Yellow 1,3,20
And the like.

The amount of the colorant is 0.1 to 60 parts by weight, preferably 0.5 to 5 parts by weight, per 100 parts by weight of the binder resin.
0 parts by weight.

As the negatively chargeable fluidizing agent used in the present invention, any one may be used as long as it can be added to the colorant-containing resin particles to increase the fluidity before and after the addition. It is possible. For example, fluorine-based resin powders such as vinylidene fluoride fine powder and polytetrafluoroethylene fine powder, fine powder silica such as wet-process silica, dry-process silica, and the like, silane coupling agent, titanium coupling agent, silicon oil, etc. And the like, surface-treated silica.

Preferred fluidizing agents are fine powders produced by the vapor phase oxidation of silicon halide compounds.
It is what is called dry silica or fumed silica, and is manufactured by a conventionally known technique. For example, it utilizes the thermal decomposition oxidation reaction of silicon tetrachloride gas in an oxyhydrogen flame, and the basic reaction formula is as follows.

SiCl ₂ + 2H ₂ + O ₂ → SiO ₂ +4
HCl

In this production process, it is also possible to obtain a composite fine powder of silica and another metal oxide by using another metal halide such as aluminum chloride or titanium chloride together with a silicon halide. Is also included. The particle size is desirably in the range of 0.001 to 2 μm as an average primary particle size, and it is particularly preferable to use silica fine powder in the range of 0.002 to 0.2 μm. .

The commercially available silica fine powder produced by vapor phase oxidation of a silicon halide used in the present invention includes, for example, those commercially available under the following trade names.

AEROSIL (Aerosil Nippon) 130 200 300 380 TT600 MOX170 MOX80 COK84 Ca-O-SiL (CABOT Co.) M-5 MS-7 MS-75 HS-5 EH-5 Wacker HDK N20 V15 WAK -CHEMIE GMBH) N20E T30 T40 DC Fine Silica (Dow Corning Co.) Fransol (Fransil)

Further, it is more preferable to use a treated silica fine powder obtained by subjecting a silica fine powder produced by vapor phase oxidation of the silicon halide compound to a hydrophobic treatment. It is particularly preferable that the treated silica fine powder is obtained by treating the silica fine powder such that the degree of hydrophobicity measured by a methanol titration test shows a value in the range of 30 to 80.

The method of hydrophobizing is applied by chemically treating with an organic silicon compound or the like which reacts or physically adsorbs with the fine silica powder. As a preferred method, silica fine powder produced by vapor phase oxidation of a silicon halide is treated with an organosilicon compound.

Examples of such organosilicon compounds include hexamethyldisilazane, trimethylsilane, trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, allylphenyldichlorosilane, benzyl Dimethylchlorosilane, bromomethyldimethylchlorosilane, α-chloroethyltrichlorosilane, ρ-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane, triorganosilylmercaptan, trimethylsilylmercaptan, triorganosilyl acrylate, vinyldimethylacetoxysilane, dimethylethoxy Silane, dimethyldimethoxysilane, diphenyldiethoxysilane, hexamethyldisiloxane, 1,3-divinyltetramethyl Disiloxane, 1,3-diphenyltetramethyldisiloxane and 2 to 12 per molecule
For example, dimethylpolysiloxane having a hydroxyl group bonded to Si and having one siloxane unit as a terminal unit may be used. These are used alone or as a mixture of two or more.

As the fluidizing agent used in the present invention, those obtained by treating the above-mentioned dry process silica with the following coupling agent having an amino group or silicone oil are necessary to achieve the object of the present invention. They may be used accordingly.

[0155]

Embedded image

[0156]

Embedded image

As the silicone oil, an amino-modified silicone oil having a partial structure having an amino group in a side chain represented by the following formula is generally used.

[0158]

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(Where R ₁ represents hydrogen, an alkyl group, an aryl group or an alkoxy group, R ₂ represents an alkylene group or a phenylene group, and R ₃ and R ₄ represent a hydrogen, an alkyl group or an aryl group. However, the alkyl group, the aryl group, the alkylene group, and the phenylene group may contain an amine, or may have a substituent such as halogen as long as the chargeability is not impaired. Indicates a positive integer.)

Examples of the silicone oil having such an amino group include the following.

Viscosity at 25 ° C. Amine Equivalent Trade name (cps) SF8417 (Toray Silicone Co., Ltd.) 1200 3500 KF393 (Shin-Etsu Chemical Co., Ltd.) 60 360 KF857 (Shin-Etsu Chemical Co., Ltd.) 70 830 KF860 (Shin-Etsu Chemical Co., Ltd.) 250 7600 KF861 (Shin-Etsu Chemical Co., Ltd.) 3500 2000 KF862 (Shin-Etsu Chemical Co., Ltd.) 750 1900 KF864 (Shin-Etsu Chemical Co., Ltd.) 1700 3800 KF865 (Shin-Etsu Chemical Co., Ltd.) 90 4400 KF369 (Shin-Etsu Chemical Co., Ltd.) 20 320 KF383 (Shin-Etsu Chemical Co., Ltd.) 20 320 X-22-3680 (Shin-Etsu Chemical Co., Ltd.) 90 8800 X-22-380D (Shin-Etsu Chemical Co., Ltd.) 2300 3800 X-22-3801C (Shin-Etsu Chemical Co., Ltd.) 3500 3800 X-22-3810B (Shin-Etsu Chemical Co., Ltd.) Shinetsu Gakusha, Ltd.) 1300 1700

The amine equivalent is a value obtained by dividing the molecular weight by the number of amines per molecule in terms of the equivalent per amine (g / equiv).

The fluidizing agent used in the present invention has good results when it has a specific surface area of 30 m ² / g or more, preferably 50 m ² / g or more measured by nitrogen adsorption according to the BET method. Fluidizer 0.01 for 100 parts by weight of toner
To 8 parts by weight, preferably 0.1 to 4 parts by weight.

To prepare the toner for developing an electrostatic image of the present invention, a binder resin, a colorant and / or a magnetic substance, a charge control agent or other additives are sufficiently mixed by a mixer such as a Henschel mixer or a ball mill. Then, using a hot kneader such as a kneader or an extruder, melting, kneading and kneading to make the resins compatible with each other. The toner of the present invention can be obtained.

Further, the fluidizing agent and the toner are sufficiently mixed by a mixer such as a Henschel mixer to obtain the developer for developing an electrostatic image of the present invention having an additive on the surface of the toner particles.

[0166]

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

Table 1 shows the contents of the wax components used in the present invention together with the measurement results of DSC and GPC.
Put together.

That is, the higher alcohol of C ₅₀
polyethylene wax A containing t% (invention), C ₅₀
Polyethylene wax B containing 67 wt% of higher fatty acid of the present invention (the present invention), wax C mainly containing a higher alcohol of C ₃₀ (the present invention), wax D obtained by pyrolysis of polyethylene (for comparison), and Wax E (for toner addition) obtained by thermal decomposition of polypropylene.

[0169]

[Table 1]

[Production Example 1 of Resin Composition] Synthesis of Low-Molecular-Weight Polyester Resin (A-1) In a four-necked flask, 43 mol% of isophthalic acid and 2.0 mol% of trimellitic anhydride were represented by the above formula (A). 20 mol% of a propylene oxide adduct (PO-BPA), 20 mol% of the same ethylene oxide adduct (EO-BPA), 3.0 mol% of trimethylolpropane, and a small amount of an organotin compound as a dehydration catalyst, The temperature was raised to 220 ° C. while passing nitrogen through the flask, and dehydration-condensation polymerization was performed to obtain a low-molecular-weight polyester resin (A-1).

The obtained low molecular weight polyester resin (A-
When 1) was analyzed, the weight average molecular weight (Mw) was 88.
The number average molecular weight (Mn) was 4,300, the peak molecular weight (PMw) was 5,900, and the hydroxyl value (OH value) was 29 mgKOH / g at Tg = 54 ° C.

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-
A mixture 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 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.

To the suspension after completion of the reaction, an aqueous solution of NaOH 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 = 110,000, PMw = 1.2 million, Tg = 60 ° C, OH
The value was 9 mg KOH / g.

Preparation of Resin Composition (I) In a four-necked flask, 300 parts by weight of xylene, 60 parts by weight of the low-molecular-weight polyester resin (A-1) and 30 parts by weight of a high-molecular-weight polymer (H-1) were added. And the low molecular weight wax <a> (a typical structural formula is CH ₃ (CH ₂ ) ₄₈ C)
20 parts by weight of a higher alcohol wax represented by H ₂ OH) were added. The mixture was stirred while raising the temperature under a nitrogen stream to dissolve the resin composition in xylene. Under xylene reflux, a xylene solution containing 5 parts by weight of resin incyanate (TDI) was added dropwise. After completion of the dropping, stirring was further continued for 1 hour, and after the reaction was performed, the internal temperature was gradually increased to distill off xylene, and the obtained resin was cold-rolled, solidified, and then pulverized to obtain a resin composition for toner ( I) was obtained.

When the resin composition for toner (I) was analyzed, it had molecular weight peaks at 5400 and 1.09 million,
The F insoluble content was 3.7% by weight.

The modification ratio with the low molecular weight wax <a> was 70%.

[Production Example 2 of Resin Composition ] Production of Resin Composition (II ) 60 parts by weight of a low molecular weight polyester resin (A-1) pulverized so as to pass through a mesh having a diameter of 1 mm and a high molecular weight polymer (H) -1) 30 parts by weight and the low molecular weight wax <a> (a typical structural formula is CH ₃ (CH ₂ ) ₄₈ CH ₂ )
20 parts by weight of a higher alcohol wax represented by OH) were premixed with a Henschel mixer.

Next, the resin mixture preliminarily mixed was mixed with a kneading temperature of 140 using a quantitative feeder.
° C. to a twin-screw kneader set at a constant rate so that the average residence time is 20 minutes,
Melt, knead, and mix. At this time, the volatile matter in the resin is removed from the first vent port provided in the twin-screw kneader by vacuum, and then a predetermined amount of diphenylmethane diisocyanate (MDI) is continuously supplied from the second vent port using a metering pump. And the reaction was allowed to proceed. After cooling and solidifying the obtained resin composition, it was pulverized to obtain a resin composition (II).

When the resin composition (II) for toner was analyzed, it had molecular weight peaks at 7000 and 960,000,
The F insoluble content was 2.6% by weight.

The modification ratio with the low molecular weight wax <a> was 65%.

[Production Example 3 of Resin Composition] Synthesis of low molecular weight polyester resin (A-2) 43 mol% of isophthalic acid, trimellitic anhydride 2.0
mol%, PO-BPA 45 mol%, EO-BPA5
mol% and trimethylolpropane 5.0 mol%, except that the synthesis of the low-molecular-weight polyester resin (A-1) was carried out.
I got

The low-molecular-weight polyester resin (A-
Analysis of 2) showed that Mw = 16600 and Mn = 43.
At 00, PMw = 8200, and Tg = 53 ° C., the hydroxyl value (OH value) was 38 mgKOH / g.

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 charged into a four-necked flask, and 70 parts by weight of styrene and acrylic acid 20 parts by weight of n-butyl, 10 parts by weight of monobutyl maleate, 0.03 parts by weight of divinylbenzene, and 1,1-bis (di-tert
(Butyl peroxy) 3,3,5-trimethylcyclohexane (10-hour half-life temperature; 90 ° C.), 0.1 part by weight of a liquid mixture was added, and the mixture was 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 = 150,000, PMw = 800,000, Tg = 60 ° C., and OH value = 14 mgKOH / g.

Production of Resin Composition (III ) 60 parts by weight of the above low molecular weight polyester resin (A-2)
30 parts by weight of a high molecular weight polymer (H-2) and a low molecular weight wax <b> shown in Table 1 (a typical structural formula is CH
₃ (CH ₂ ) _{48 The} higher fatty acid wax represented by COOH) was used in the same manner as in the production of the resin composition (I) except that the amount was 20 parts by weight to obtain a resin composition (III) for a toner.

When the resin composition for toner (III) was analyzed, it had molecular weight peaks at 9800 and 700,000,
The HF insoluble content was 6.5% by weight.

The modification ratio with the low molecular weight wax <b> was 40%.

[Production Example 4 of Resin Composition] As a low molecular weight wax, a low molecular weight wax <c> shown in Table 1 (a higher alcohol represented by a structural formula of CH ₃ (CH ₂ ) ₂₈ CH ₂ OH) A resin composition for toner (IV) was obtained in the same manner as in the production of the resin composition (III) except that 20 parts by weight of the (system wax) was used.

When the resin composition (IV) for toner was analyzed, it had molecular weight peaks at 11500 and 750,000,
The HF insoluble content was 7.7 wt%.

The modification ratio with the low molecular weight wax <c> was 62%.

[Production Example 5 of Resin Composition] The above resin was used except that 12 parts by weight of the low molecular weight wax <c> and 8 parts by weight of the low molecular weight wax <d> shown in Table 1 were used as the low molecular weight wax. Performed in the same manner as in the production of the composition (III),
A resin composition for toner (V) was obtained.

When the resin composition (V) for toner was analyzed, it had molecular weight peaks at 11,000 and 690,000,
The F insoluble content was 5.2% by weight.

The modification ratio with the low molecular weight wax <c> was 94%.

[Production Example 6 of Resin Composition] Synthetic of low molecular weight polyester resin (A-3) 53 mol% of isophthalic acid, 42 mol of PO-BPA
% And diethylene glycol of 5.0 mol%, to obtain a low molecular weight polyester resin (A-3) in the same manner as in the synthesis of the low molecular weight polyester resin (A-1).

The obtained low molecular weight polyester resin (A-
Analysis of 3) showed that Mw = 7900 and Mn = 320.
0, PMw = 5600, and Tg = 61 ° C., OH value is 3
It was 5 mgKOH / g.

After sufficiently replacing the inside of the synthesis flask of the high molecular weight polymer (H-3) with nitrogen, 72 parts by weight of styrene, 13 parts by weight of n-butyl acrylate, and 15 parts by weight of monobutyl maleate were added. Temperature to 120 ° C,
The polymerization was started. It was kept at the same temperature for 10 hours. At this time, the polymerization conversion was 25%. Next, 30 parts by weight of xylene and 0.02 parts by weight of 2,2-bis {4- (methacryloxy / polyethoxy) phenyl} propane were added, and 0.1 part by weight of dibutyl peroxide mixed and dissolved in advance and 50 parts by weight of xylene. The reaction was continued for another 5 hours under xylene reflux. After completion of the reaction, xylene was distilled off, and the obtained resin was cold-rolled, solidified and pulverized to obtain a high molecular weight polymer (H-3).

When the high molecular weight polymer (H-3) was analyzed, Mw = 960,000, Mn = 320,000, PMw = 300,000,
At Tg = 60 ° C., the OH value was 14 mgKOH / g.

Production of Resin Composition (VI ) 60 parts by weight of the above low molecular weight polyester resin (A-3),
Resin composition (I) except that 30 parts by weight of high molecular weight polymer (H-3) and 20 parts by weight of low molecular weight wax <c> shown in Table 1 were used and heated so that xylene was not refluxed. Of the resin composition for toner (V
I) was obtained.

The analysis of the resin composition for toner (VI) showed that it had molecular weight peaks at 24900 and 220,000,
The HF insoluble content was 26% by weight.

The modification ratio with the low molecular weight wax <c> was 22%.

[Production Example of Comparative Resin Composition (i)] Synthesis of High Molecular Weight Polymer (H-4) 180 parts by weight of degassed water and 20 parts by weight of a 2% by weight aqueous solution of polyvinyl alcohol were placed in a four-necked flask. Was added, a mixed solution of 77 parts by weight of styrene, 23 parts by weight of n-butyl acrylate, and 0.1 part by weight of benzoyl peroxide was added, followed by stirring to form a suspension.

After the inside of the flask was sufficiently replaced with nitrogen, 8
The temperature was raised to 0 ° C. to initiate polymerization. The polymerization was completed by maintaining the same temperature for 24 hours.

The high molecular weight polymer (H-4) was separated by filtration, washed with water, dried and analyzed. Mw = 960,000, Mn
= 450,000, PMw = 600,000, and Tg = 60 ° C.

Preparation of Comparative Resin Composition (i ) 70 parts by weight of the above low molecular weight polyester resin (A-1)
Except that 30 parts by weight of a high molecular weight polymer (H-4) and 10 parts by weight of a low molecular weight wax <e> shown in Table 1 were used.
The same procedure as in the production of the resin composition (I) was carried out to obtain a comparative resin composition (i).

When the comparative resin composition (i) was analyzed, it had molecular weight peaks at 5600 and 130,000, and the THF-insoluble content was 26 wt%.

Further, no alkyl modification reaction with the low molecular weight wax <e> was confirmed.

[Production Examples of Toner and Comparative Production Examples] Production examples and comparative production examples of the toner of the present invention will be described.

Toner Production Example 1 100 parts by weight of resin composition (I) obtained in Resin Production Example 1 100 parts by weight of magnetic particle powder (spherical, 0.27 μm, BET = 7.2 m ² / g)・ 3 parts by weight of negative charge control agent (salicylic acid-based iron oxide represented by the following structural formula)

[0212]

Embedded image

The mixture was melt-kneaded with a twin-screw extruder heated to 130 ° C., the cooled kneaded material was coarsely pulverized with a hammer mill, and the coarsely pulverized material was finely pulverized with a jet mill. The powder was classified with a fixed wall air classifier to produce a classified powder. Further, the obtained classified powder is strictly classified and removed by a multi-segmentation classifier (elbow jet classifier manufactured by Nippon Steel Mining Co., Ltd.) utilizing the Coanda effect at the same time to remove the weight average particle diameter (D ₄ A negatively-charged magnetic toner classified powder having a particle size of 6.3 μm was obtained.

100 parts by weight of the magnetic toner classifying powder, 1.5 parts by weight of hydrophobic silica fine powder (BET 250 m ² / g) treated with dimethyldichlorosilane, hexamethyldisilazane, and dimethylsilicone oil And 0.04 parts by weight of styrene-acrylic fine particles (average particle size 0.03 μm) obtained by soap-free polymerization were dry-mixed with a Henschel mixer to prepare toner (I) of the present invention.

Toner Production Examples 2 to 6 and Comparative Production Example The resin composition (I) obtained in the above resin composition production example
Toners (II) to (VI) of the present invention in the same manner as in Production Example 1 of the toner except that 100 parts by weight of each of I) to (VI) and the comparative resin composition (i) were used. as well as,
Comparative toner (i) was prepared.

The toners (II) to (VI) obtained above
Is summarized in Table 2.

[0219]

[Table 2]

[Examples and Comparative Examples] In this example,
Commercially available laser beam printer LBX-
EX (manufactured by Canon) was modified as shown below, and was used again after resetting.

Examples 1 to 6 and Comparative Example 1 As a primary charging roller, a rubber roller (diameter 12 mm, contact pressure 50 g / cm) in which conductive carbon coated with nylon resin was dispersed was used. The image carrier is exposed to a laser beam (600 dpi), and the dark portion potential V _D = −700.
V, a light portion potential V _L = −200 V was formed. A developing sleeve whose surface roughness Ra (μm) was adjusted to 1.4 was used as a toner carrier, and then a gap (between SD) between the photosensitive drum and the developing sleeve was set to 300 μm, and a developing magnetic pole 800
Gauss, 1.0mm thick, 8 free as toner regulating member
mm urethane rubber blade was contacted with a linear pressure of 15 g / cm. DC bias component V _dc as development bias
= -500V, superposed AC bias component _Vpp = 160
0 V and a frequency of 2200 Hz were used. The set temperature of the heat fixing device was 150 ° C.

Under the above set conditions, room temperature and normal humidity (25 ° C., 6
0% RH) and a low-temperature and low-humidity (15 ° C., 10% RH) environment at a printout speed of 12 sheets (A4 size) / minute in the toner production examples 1 to 6 and comparative production examples. While the toners (I) to (VI) of the present invention and the comparative toner (i) are successively replenished, the developing device is stopped for 10 seconds for every one printout. A printout test was performed in a mode that promotes toner deterioration), and the printout image obtained was evaluated for the following items.

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

Example 7 and Comparative Example 2 As the evaluation machine, the modified LPX-EX used in the above example was fitted with a reuse mechanism as shown in FIG. 4, and the toner obtained in Production Example 1 of the toner was obtained. Printing out in a continuous mode (that is, a mode in which toner consumption is promoted without stopping the developing device) while sequentially replenishing each of (I) and the comparative toner (i) obtained in the comparative production example. A test was performed and evaluated similarly.

[0223] The reuse mechanism is a cleaner 1 that contacts untransferred toner on the photosensitive drum with the photosensitive drum.
After being scraped off by the 16 elastic blades 212, it is sent into the cleaner by a cleaner roller, and further passes through a cleaner screw 204, and is supplied to a hopper 209 by a supply pipe 206 provided with a transport screw.
The system returns to the developing device 140 via the printer and uses the collected toner again.

The above evaluation results are summarized in Tables 3 to 5.

[0225]

[Table 3]

[0226]

[Table 4]

[0227]

[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 Evaluation was performed based on image density characteristics at the end of printing out 10,000 sheets on ordinary plain 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) 良好: 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. 5 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 measured by the "Reflectometer" (manufactured by Tokyo Denshoku Co., Ltd.) and the whiteness of the transfer paper. Image fog was evaluated.

◎: very good (less than 1.5%) ○: good (1.5% or more, less than 2.5%) △: 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.
After printing out the halftone image Y of length 1 in a), the grayscale difference appearing on the halftone image (FIG. 6)
(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.
/ M ² ) when characters are printed (Fig. 7 (b)
Was visually evaluated.

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

<6> Fixability The fixability was evaluated by applying a load of 50 g / cm ² , rubbing the fixed image with soft thin paper, and evaluating the rate of decrease (%) in 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 effect on image) ×: bad (conspicuous)

[Evaluation of Storage Stability] After the toner was allowed to stand in a dryer set at 45 ° C. for one week, a printout test was performed on the left toner in a normal temperature and normal humidity environment, and the image density of the obtained image was determined. , And image quality.

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

◎: very good (no occurrence) ：: good (almost no occurrence) Δ: normal (there is sticking but little influence 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 adhesion of residual toner and the effect on printout images were visually evaluated.

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

<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 state of occurrence of scratches and scraping on the surface of the fixing roller was visually evaluated.

◎: very good (not generated) ：: 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 fixing roller surface after the completion of the printout test was visually evaluated.

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

[0253]

As described above, according to the present invention,
By specifying each component constituting the binder resin, it has a good fixable area, is excellent in dot reproducibility, stabilizes a good image without image fog or sleeve ghost, and can be formed for a long time. I was able to do it.

[Brief description of the drawings]

FIG. 1 is a schematic explanatory diagram of measurement results of high-temperature GPC used for calculating a modification rate of an alkyl modification reaction of a low-molecular-weight polyester and a low-molecular-weight wax according to the present invention.

FIG. 2 is a schematic explanatory diagram of a DSC curve when the temperature of the low-molecular weight wax according to the present invention is raised.

FIG. 3 is a schematic explanatory diagram of a DSC curve when the temperature of the low molecular weight wax according to the present invention is lowered.

FIG. 4 is a schematic diagram illustrating an image forming apparatus that reuses untransferred toner.

FIG. 5 is an explanatory diagram of a checker pattern for checking development characteristics of toner.

FIG. 6 is an explanatory diagram of a sleeve ghost.

FIG. 7 is a schematic diagram showing a state where a character image is hollow;

[Explanation of symbols]

 REFERENCE SIGNS LIST 100 photosensitive drum 102 developing sleeve (toner carrier) 103 contact blade 114 transfer charging roller 116 cleaner 117 primary charging roller 140 developing device 141 stirring rod 204 cleaner screw 206 collected toner supply pipe provided with transport screw 209 hopper

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical display location G03G 15/20 101 G03G 9/08 365 381

Claims (30)

[Claims] 1. A toner for developing an electrostatic charge image formed of a composition in which at least a binder resin, a colorant and a low molecular weight wax are dispersed, wherein the binder resin component in the toner is substantially (a) It contains no tetrahydrofuran (THF) -insoluble matter, and (b) in the molecular weight distribution of gel-permeation chromatography (GPC) of the THF-soluble matter, i) a low molecular weight component corresponding to a region having a molecular weight of 50,000 or less is represented by the following general formula A polymer mixture containing a low-molecular-weight polyester modified with a low-molecular-weight wax having the formula: RY; (R: a hydrocarbon group; Y: a hydroxyl group, a carboxyl group, an alkyl ether group, an ester group, a sulfonyl group; Ii) the high molecular weight component corresponding to the region having a molecular weight exceeding 50,000 has a hydroxyl value of 20 (mg KOH / g) or less; The toner for developing electrostatic images which is characterized and. 2. The modification ratio of the low-molecular-weight component in the modification reaction between the low-molecular-weight polyester and the low-molecular-weight wax in the low-molecular-weight component is 2%.
The electrostatic image developing toner according to claim 1, wherein the toner content is 0 to 95%. 3. The low molecular weight wax has a number average molecular weight (M
n) is 200 to 2000, and the weight average molecular weight (Mw) is 4
3. The electrostatic image developing toner according to claim 1, wherein Mw / Mn is 3.0 or less and Mw / Mn is 3.0 or less. 4. 4. A low-molecular-weight wax having a viscosity of 70 to 70 at a temperature rise in a DSC curve measured by a differential scanning calorimeter.
It shows the maximum endothermic peak in the region of 130 ° C., has a maximum exothermic peak at the time of temperature fall in a range of ± 15 ° C. with respect to the peak temperature of the maximum endothermic peak, and is the starting point of the endothermic peak including the maximum exothermic peak. The electrostatic image developing toner according to any one of claims 1 to 3, wherein the onset temperature is 50 ° C or higher. 5. A low molecular weight polymer component forming a main peak in a molecular weight region of 2,000 to 30,000 in a molecular weight distribution of GPC measured by a THF soluble component of a binder resin component in the toner, and a molecular weight of 50,000. The toner for developing an electrostatic image according to any one of claims 1 to 4, wherein a high molecular weight polymer component that forms a subpeak or a shoulder is contained in a region exceeding the above range. 6. The binder resin component in the toner has an area ratio of a low molecular weight component having a molecular weight of 1000 or less of 15% or less and a molecular weight of 1,000,000 or more in a molecular weight distribution of GPC of a THF-soluble component. 6. The area ratio of the high molecular weight component showing 0.5 to 25%.
The toner for developing electrostatic images according to any one of the above. 7. A charging step of charging a member to be charged by applying a voltage to a charging member from the outside, a step of forming an electrostatic charge image on the charged member to be charged, and a step of converting the electrostatic charge image with toner. A developing step of developing and forming a toner image on the member to be charged, and a toner image on the member to be charged via the intermediate transfer member,
Alternatively, there is provided an image forming method including a transfer step of transferring to a transfer material without intervention and a fixing step of heating and fixing a toner image on the transfer material, wherein the toner has at least a binder resin and a colorant dispersed therein. The binder resin component in the toner is substantially free of tetrahydrofuran (THF) -insoluble components, and (b) gel-permeation chromatography (GPC) of THF-soluble components. In the molecular weight distribution of (i), i) a low molecular weight component corresponding to a region having a molecular weight of 50,000 or less is a polymer mixture containing a low molecular weight polyester modified with a low molecular weight wax having the following general formula; R: represents a hydrocarbon group, Y: represents any of a hydroxyl group, a carboxyl group, an alkyl ether group, an ester group, and a sulfonyl group.) Ii) The molecular weight exceeds 50,000 The hydroxyl value of the high molecular weight components corresponding to frequency is 20 (mgKOH / g) or less, an image forming method, characterized in that. 8. The heat fixing step, wherein the toner image is heat-fixed to the recording material by a heat fixing device which does not supply an offset preventing liquid or does not have a fixing device cleaner. 2. The image forming method according to 1., 9. The recording material according to claim 1, wherein said heating and fixing step comprises: a heating member fixed and supported; and a pressing member which is in pressure contact with said heating member and closely adheres to said heating member via a film. 9. The heat fixing method according to claim 7, wherein
2. The image forming method according to 1., 10. The method according to claim 7, 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 to be charged. 2. The image forming method according to 1., 11. A step of developing an electrostatic latent image on an electrostatic latent image carrier with a developer, and electrostatically transferring the developed image to a transfer material via a transfer device. The image forming method according to claim 7, wherein the carrier and the transfer device are in contact with each other. 12. Surface roughness Ra carrying toner on the surface
8. The method according to claim 7, further comprising the step of: causing a toner carrier having (μm) of 1.5 or less to face the electrostatic latent image carrier and developing the latent image on the electrostatic latent image carrier. 12. The image forming method according to any one of 11. 13. The image forming method according to claim 7, wherein a ferromagnetic metal blade is arranged at a minute interval so as to face the toner carrier. 14. The image forming method according to claim 7, wherein a blade made of an elastic body is brought into contact with said toner carrier. 15. The image according to claim 7, wherein the electrostatic latent image carrier and the toner carrier have a certain interval, and are developed while applying an alternating electric field. Forming method. 16. The method according to claim 7, 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 to be charged. 2. The image forming method according to 1., 17. A step of developing an 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. 17. The image forming method according to claim 7, wherein the carrier and the transfer device are in contact with each other. 18. An electrostatic latent image bearing member, wherein the untransferred residual toner on the electrostatic latent image carrier after the transfer is cleaned and collected, and the collected toner is supplied to a developing unit and held again by the developing unit. 18. The image forming method according to claim 7, further comprising a toner reuse mechanism for developing an electrostatic latent image on the carrier. 19. The toner according to claim 2, wherein the toner is the toner according to claim 2. Description:
9. The image forming method according to any one of items 8. 20. A resin composition for a toner used for a toner for developing an electrostatic image, wherein the binder resin component contained in the resin composition for the toner includes: (a) a tetrahydrofuran (THF) -insoluble content of 30 wt.
(B) In a molecular weight distribution of gel permeation chromatography (GPC) of a THF-soluble component, i) a low molecular weight component corresponding to a region having a molecular weight of 50,000 or less is a low molecular weight wax having the following general formula: A polymer mixture containing a modified low-molecular-weight polyester, RY; (R: a hydrocarbon group; Y: a hydroxyl group, a carboxyl group, an alkyl ether group, an ester group, or a sulfonyl group; Ii) A resin composition for a toner, wherein a hydroxyl value of a high molecular weight component corresponding to a region exceeding a molecular weight of 50,000 is 20 (mgKOH / g) or less. 21. The resin composition for a toner according to claim 20, wherein a modification ratio in a modification reaction between the low molecular weight polyester and the low molecular weight wax in the low molecular weight component is 20 to 95%. 22. The low molecular weight wax has a number average molecular weight (Mn) of 200 to 2,000 and a weight average molecular weight (Mw).
22. The resin composition for a toner according to claim 20, wherein Mw / Mn is 3.0 or less and Mw / Mn is 3.0 or less. 23. DS measured by a differential scanning calorimeter
In the C curve, a maximum endothermic peak is shown in the range of 70 to 130 ° C. at the time of temperature rise, and a maximum exothermic peak at the time of temperature fall is within ± 15 ° C. with respect to the peak temperature of the maximum endothermic peak;
23. The resin composition for a toner according to claim 20, wherein an onset temperature of a starting point of an endothermic peak including the maximum exothermic peak is 50 ° C. or higher. 24. GPC measured by THF soluble matter
And a low molecular weight polymer component that forms a main peak in the molecular weight region of 2000 to 30,000, and a molecular weight of 5
24. The resin composition for a toner according to any one of claims 20 to 23, comprising a high molecular weight polymer component forming a subpeak or a shoulder in a region exceeding 10,000. 25. A method for producing a resin composition used for an electrostatic image developing toner, comprising: a low molecular weight component having a molecular weight of 50,000 or less in a GPC molecular weight distribution measured by a THF soluble component of the resin composition. Is produced by subjecting a low-molecular-weight polyester to a low-molecular-weight wax having the following general formula by a modification reaction. RY; (R: represents a hydrocarbon group; Y: represents any of a hydroxyl group, a carboxyl group, an alkyl ether group, an ester group, and a sulfonyl group) 26. The resin for toner according to claim 25, wherein a modification ratio in a modification reaction between the low molecular weight polyester and the low molecular weight wax in the low molecular weight component is controlled to be 20 to 97%. A method for producing the composition. 27. The method for producing a resin composition for a toner according to claim 25, wherein the modification reaction is performed in the presence of a high molecular weight polymer having a hydroxyl value of 20 mg KOH / g or less. 28. The low molecular weight wax has a number average molecular weight (Mn) of 200 to 2,000 and a weight average molecular weight (Mw).
28. The method for producing a resin composition for a toner according to claim 25, wherein Mw / Mn is 3.0 or less and Mw / Mn is 3.0 or less. 29. The low molecular weight wax shows a value of 70% at the time of temperature rise in a DSC curve measured by a differential scanning calorimeter.
A maximum endothermic peak in a region of about 130 ° C., a maximum exothermic peak at the time of temperature fall within a range of ± 15 ° C. with respect to the peak temperature of the maximum endothermic peak, and a starting point of an endothermic peak including the maximum exothermic peak The method for producing a resin composition for a toner according to any one of claims 25 to 28, wherein the onset temperature of the resin composition is 50 ° C or higher. 30. 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. The resin composition for toner according to any one of claims 25 to 29, wherein the resin composition is polymerized and mixed so as to form a main peak and to form a subpeak or a shoulder in a region having a molecular weight exceeding 50,000. Manufacturing method.