JP2002040701A - Toner for thermal fixation - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner for thermal fixation which exhibits satisfactory low temperature fixation and offset resistance, even in the long duration, does not cause a deterioration of picture density, a stain of picture such as fogging and the contamination to a photosensitive member and is excellent in a preservation property in a long term, too. SOLUTION: This toner containing binding resin, colorant and wax features that a resin composition of the toner substantially contain no THF insoluble component, in the GPC(gel permeation chromatogram) of THF soluble component of the toner, at least a main peak in the region of molecular weight of 3×103-2×104 is observed, the Mw/Mn of a main part of the main peak is <2.5 and the rations in mass basis of respective components of a component M1 of molecular weight of <2×103, a component M2 of molecular weight of >=2×103 to <2×104, a component M3 of molecular weight of >=1×105 to <1×106 and a component M4 of molecular weight of >=3×106 to the total THF soluble component are respectively <7%, 50-75%, 15-30% and 1.0-5.0%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a toner used in a recording method utilizing an electrophotographic method, an electrostatic recording method, a magnetic recording method, a toner jet or the like. In particular, the present invention relates to a heat-fixing toner used in a fixing method of heating and fixing an image formed with toner on a recording material.

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

[0003] One of the important properties required of a toner is low-temperature fixability and offset resistance. In order to prevent offset resistance, from the idea of giving the toner good fixability and offset resistance without providing a fixing device with a wiper for offset toner,
A method using a binder resin having two peaks in the molecular weight distribution as a binder resin of the toner is disclosed in, for example,
-16144, JP-A-2-23569,
JP-A-63-127254, JP-A-3-2683
No. 1, Japanese Patent Application Laid-Open No. 62-9356, Japanese Patent Application Laid-Open No. 3-7
No. 2505, and the like. Japanese Patent Laid-Open No. 52-33 discloses a method of adding a low molecular weight wax to a toner.
04, JP-A-52-3305, JP-A-57
-52574, JP-A-58-215659, JP-A-60-217366, and JP-A-60-2
No. 52361, JP-A-60-252362,
It is disclosed in JP-A-4-97162.

Further, various proposals have been made such as precise control of the ratio and molecular weight distribution of high molecular weight components and low molecular weight components, and control of gels such as THF-insoluble components.

[0005] For example, Japanese Patent Application Laid-Open No. 5-158280 discloses that the GPC molecular weight peak is 4 × 10 ^{3 to} 5 × 10 ⁴ and Mw /
Low molecular weight compound having Mn of less than 3.5, GPC molecular weight peak 3
A toner using a styrene-based copolymer containing a specific amount of a medium molecular weight of × 10 ^{4 to} 5 × 10 ⁵ and a cross-linked high molecular weight has been proposed, and JP-A-7-295291 discloses a toner. A THF-insoluble content of less than 10% by mass, a low-molecular-weight component having a maximum molecular weight distribution of 5 × 10 ^{3 to} 5 × 10 ⁴ in the GPC molecular weight distribution of the THF-soluble component, and a maximum of 1 × 10 ^{6 to} 5 × 10 ⁶ And a high molecular weight component having a molecular weight of 2
A toner using a resin in which the ratio H / L of the component (H) larger than × 10 ⁵ and the component (L) smaller than the component (H) is 20/80 to 50/50 has been proposed. These toners have a high content of gel components and are therefore excellent in the fixing area, but have insufficient low-temperature fixing properties.

[0006] In order to highly apply the fixing property at a lower temperature and the anti-offset property at a higher temperature, it is necessary to broaden the molecular weight distribution of the binder resin. When this is applied to a binder resin having two peaks, Further, since the compatibility between the low-molecular component and the high-molecular component is further degraded due to further polarization, the above-mentioned serious problem is likely to occur. As described above, conventional techniques such as precise control of the ratio and molecular weight distribution of the high molecular weight component / low molecular weight component in the resin component contained in the toner, and control of gel such as THF-insoluble matter, etc. In, although some improvement in fixability and offset resistance is 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 of specific components. It is easy for separation or the like to occur, which causes image stains such as fog, fusion to a photosensitive member or the like, filming, and the like.

For example, in order to improve the compatibility and dispersibility of the toner components, when the kneading conditions during the melt kneading during the production of the toner are strengthened, the molecular chains of the binder resin in the toner are cut by the kneading. As a result, the molecular weight at the time of toner decreases, which causes problems such as deterioration of offset resistance, particularly hot offset resistance at a 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, JP-A-4-97162 proposes a toner in which a specific aliphatic alcohol is contained in a binder resin having two peaks. However, such a conventional toner shows relatively good low-temperature fixing property due to the plasticizing effect of the aliphatic alcohol, but the amount of offset toner to the fixing roller increases drastically.
When the toner is used at a high temperature or used or stored at room temperature for a long time, the aliphatic alcohol grows into a large spherulite in the toner particles or blooms. This causes serious problems such as toner fog. In particular, when applied to a magnetic toner that requires uniform dispersion of high-specific-gravity magnetic fine particles, the above-described problems become apparent, and further fine-tuning of the toner particle size is attempted for the purpose of high-quality development. This causes new problems such as fusion of toner to the surface of the photosensitive drum and poor cleaning, and causes difficulty in combination with other image forming means.

JP-A-8-44110 discloses a toner in which the content of volatile components in the toner is small, the wax contains a low melting point, and the peak position in the GPC molecular weight distribution and the low molecular weight of 1000 or less are specified. Has been proposed. Although this toner satisfies a certain degree of fixability and anti-offset properties, it is excellent in the dispersibility, durability and storage stability of the toner constituents. There is a demand for a reduction, and the low-temperature fixability of the toner is also required to further reduce the amount of heat required for fixing.

However, increasing the low molecular weight component of the toner or lowering the glass transition point of the toner in order to achieve low-temperature fixability even more than the above-described conventional techniques requires offset resistance and blocking resistance. This tends to adversely affect the durability and the developing performance, as well as the contamination of the photosensitive member and other members, and it is difficult to achieve further low-temperature fixing.

[0011]

SUMMARY OF THE INVENTION An object of the present invention is to provide a heat fixing toner which solves the above-mentioned problems.

An object of the present invention is to exhibit sufficient low-temperature fixability and offset resistance even when the amount of heat required for fixing is reduced, and to reduce image density even in long-term durability.
It is an object of the present invention to provide a heat fixing toner which is free from image stains such as fog and contamination of a device member such as a photosensitive member, has stable durability, and is excellent in long-term storage stability.

It is a further object of the present invention to provide a toner for heat fixing which achieves both low-temperature fixability, offset resistance and high durability of the toner even at a high process speed.

[0014]

According to the present invention, there is provided a toner containing at least a binder resin, a colorant, and a wax, wherein the resin composition of the toner contains substantially no THF-insoluble matter,
In a GPC (gel permeation chromatogram) of a THF-soluble portion of the toner, at least a molecular weight of 3 × 1
A main peak in the region of 0 ^{3 to} 2 × 10 ^4, the main part of the main peak having Mw / Mn of less than 2.5, a component (M1) having a molecular weight of less than 2 × 10 ³ , and a molecular weight of 2 × 10 ³ The components (M2) having a molecular weight of at least 2 × 10 ^4, the components having a molecular weight of at least 1 × 10 ^{5 and} less than 3 × 10 ⁶ (M3), and the components having a molecular weight of 3 × 10 ⁶ or more (M4) are all soluble in THF. Component (M1) having a molecular weight ratio of less than 2 × 10 ³ (M1): less than 7% Component (M2) having a molecular weight of 2 × 10 ³ or more and less than 2 × 10 ⁴ : 5
0 to 75% Component (M3) having a molecular weight of 1 × 10 ⁵ or more and less than 3 × 10 ⁶ : 1
5 to 30% Component having a molecular weight of 3 × 10 ⁶ or more (M4): 1.0 to 5.0
%, The above-mentioned problem is solved by a heat fixing toner.

[0015]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present inventors have conducted various studies to achieve a reduction in the amount of heat required for fixing a toner image to a level lower than the current level, and as a result, have reached the present invention.

[0016] In the THF resin-insoluble and soluble components of the binder resin component in the toner, and in the GPC (gel permeation chromatogram) molecular weight distribution of the THF-soluble component, which region component plays a role and what role it plays As a result of detailed examination, it is most effective to increase the amount of the component having a molecular weight of 2 × 10 ³ or more and less than 2 × 10 ⁴ and to reduce the amount of the THF-insoluble component for the low-temperature fixability, that is, the molecular weight is 2 × 10 ³ or more. It has been found that when the amount of the component less than 2 × 10 ⁴ is 50% or more by mass based on the total THF-soluble components, very good low-temperature fixability is achieved when almost no THF-insoluble content is contained.

Conventionally, however, such a toner which is rich in low molecular weight components and does not contain ultrahigh molecular weight components in the gel region, has anti-offset properties, anti-blocking properties, developability, and contamination of photosensitive members and other members. However, it was found that the addition of a THF-soluble high-molecular-weight component was sufficient to guarantee the offset resistance. For the contamination of the equipment components, the molecular weight is 2
An ultra-low molecular weight component of less than × 10 ³ is greatly involved,
It has been found that when the content of this component is reduced, the adverse effects on storage stability and contamination of the components of the device are drastically reduced.

Further, as to the influence on the low-temperature fixability, it was found that the component amount having a molecular weight of 2 × 10 ⁴ or more and less than 1 × 10 ⁵ had little effect, and the component having a molecular weight of 1 × 10 ⁵ or more had an adverse effect.

From the above results, the main peak was found to have a molecular weight of 3
By having in the region of × 10 ^{3 to} 2 × 10 ⁴ , a low molecular weight component effective for low-temperature fixability is sufficiently ensured, and a sharp molecular weight distribution with a small content of components having a molecular weight of less than 2 × 10 ³ is obtained. In addition, since it contains substantially no THF-insoluble components, there is no problem in the intended low-temperature fixability and storage stability, and there is no problem of contamination to the constituent members of the apparatus. It was found that a toner having an excellent balance with the offset property was obtained.

The respective components will be described below in detail.

In the present invention, the binder resin component of the toner is
Substantially free from components insoluble in tetrahydrofuran (THF insolubles). The THF-insoluble content indicates the mass ratio of the polymer component (substantially crosslinked polymer) insoluble in the THF solvent in the binder resin component of the toner, and can be used as a parameter indicating the degree of crosslinking of the resin. .

A toner containing a THF-insoluble component is extremely effective in offset resistance, but significantly lowers low-temperature fixability. Therefore, in the present invention, THF in the toner
The insoluble content is 5.0 mass% or less based on all resin components, and is substantially absent. When the content is preferably 3.0% by mass or less, more preferably 1.0% by mass or less, the amount of heat required for fixing can be further reduced, and sufficient low-temperature fixability can be obtained.

When the THF-insoluble content is more than 5.0% by mass, it is difficult to sufficiently reduce the amount of heat required for fixing the toner image, and it is impossible to achieve the desired low-temperature fixability. .

The THF-insoluble matter is defined by a value measured as follows.

0.5 to 1.0 g of the toner sample is weighed (w1 g), and a cylindrical filter paper (for example, No. 86 manufactured by Toyo Roshi Kaisha, Ltd.) is used.
R) and run through a Soxhlet extractor, where T
After extracting with 100 to 200 ml of HF for 6 hours and evaporating the soluble component extracted with the solvent, 10
After vacuum drying at 0 ° C. for several hours, the amount of the THF-soluble resin component is weighed (w2 g). The mass of the components other than the resin components such as the magnetic substance, the pigment and the wax in the toner is defined as (w3 g).
The THF-insoluble content is obtained from the following equation.

THF insoluble matter (%) = [｛w1- (w3 +
w2)｝ / (w1-w3)] × 100 In the present invention, in the GPC (gel permeation chromatogram) molecular weight distribution of the THF-soluble component, at least a region having a molecular weight of 3 × 10 ^{3 to} 2 × 10 ⁴ is used. Having a peak, and Mw /
Mn is less than 2.5, molecular weight 2 × 10 ³ less than component (M1), molecular weight 2 × 10 ³ or more 2 × 10 ⁴ less than component (M2), the molecular weight 1 × 10 ⁵ or more 3 × 10 under ⁶ The mass-based ratio of each component of the component (M3) and the component (M4) having a molecular weight of 3 × 10 ⁶ or more to all THF-soluble components is as follows: Component (M1) having a molecular weight of less than 2 × 10 ³ (M1): less than 7% Molecular weight 2 × 10 ³ or more and less than 2 × 10 ⁴ components (M2): 5
0 to 75% Component (M3) having a molecular weight of 1 × 10 ⁵ or more and less than 3 × 10 ⁶ : 1
5 to 30% Component having a molecular weight of 3 × 10 ⁶ or more (M4): 1.0 to 5.0
%.

The main peak has a molecular weight of 3 × 10 ^{3 to} 2 ×
Has 10 ^fourth region, and a molecular weight 2 × 10 less sharp distribution of components content of less than ^3, still substantially T
By not containing HF-insoluble matter, there is no problem in the intended low-temperature fixability and storage stability, and contamination of equipment components. Further, by controlling the content ratio of other molecular weight components within the above range, anti-offset property can be obtained. A toner excellent in balance with the properties can be obtained.

The main peak has a molecular weight of 3 × 10 ^{3 to} 2 ×
By being in a region as low as 10 ⁴ , a sufficient amount of the fixing property improving component can be secured, so that sufficient low-temperature fixing property can be obtained.

When the main peak molecular weight is less than 3 × 10 ³ , the amount of ultra-low molecular weight components having a molecular weight of less than 2 × 10 ^{3, which} adversely affect the storage stability of the toner and the contamination of components of the apparatus, is reduced. since it is difficult, contamination of the toner storage stability and device components, a decrease in image density at long-term durability, exerts an adverse effect on the degradation of the fogging image quality, more than 2 × 10 ⁴ the significantly low temperature fixing The sex worsens. When the main peak molecular weight is less than 1.5 × 10 ⁴ , the low-temperature fixability is further improved.

The Mw / Mn of the main part of the main peak is set at 2.
Less than 5 (preferably less than 2.2, more preferably 2.
0), the molecular weight distribution is sharpened, and the molecular weight 2
By keeping the ultra-low molecular weight component (M1) of less than × 10 ³ as low as less than 7%, the main peak molecular weight can be reduced without causing problems such as storage stability of the toner and contamination of components of the apparatus, and the overall This makes it possible to achieve a low-molecular-weight-rich configuration. Also, by sharpening the main peak, the Tg of the resin composition constituting the main peak portion is increased.
Can be set slightly lower without any problem, which is a preferable configuration for low-temperature fixability.

When the Mw / Mn of the main part of the GPC main peak of the THF-soluble component is 2.5 or more, the storage stability of the toner, contamination of the components of the apparatus, a decrease in image density during long-term durability, and image quality such as fog As a result, it is difficult to reduce the main peak molecular weight to a low range, and it is difficult to obtain the desired low-temperature fixability. T
The “main portion of the GPC main peak” of the HF-soluble component is defined as a straight line tangent to the bottom of the high molecular weight side of the peak from the low molecular weight side point at 50% of the peak height from the molecular weight of 1000 to the high molecular weight side. Shows up to the intersection.

The storage stability of the toner and the contamination of the components of the apparatus are greatly influenced by the component (M1) having a molecular weight of less than 2 × 10 ^3, and in order to eliminate these adverse effects, the molecular weight is preferably 2 × 10 ^3. It is preferable to reduce the content of the component (M1) of less than 7%, and when it is less than 7% by mass based on all THF-soluble components, the main peak / peak molecular weight is low, and the molecular weight is 2 × 10 ³ to 2 × 10 ^4. Even if the content ratio of the low molecular weight component increases, the adverse effect on the storage stability and the contamination of the components of the device can be significantly reduced.

When the component (M1) having a molecular weight of less than 2 × 10 ³ is 7
% Or more, the lower the molecular weight peak,
As the low molecular weight component having a molecular weight of 2 × 10 ^{3 to} 2 × 10 ⁴ increases, the storage stability and the contamination of the components of the apparatus are adversely affected, which is not preferable.

Further, the ultra low molecular weight component (M0) having a molecular weight of less than 1 × 10 ³ has a particularly bad influence on the storage stability and durability of the toner, and is preferably less than 3%.

The amount of the component having a molecular weight of 2 × 10 ³ or more and less than 2 × 10 ⁴ is 50 to 50% by mass relative to all THF-soluble components.
When it is 75%, very good low-temperature fixability is exhibited when almost no THF-insoluble content is contained. Molecular weight 2 × 1
If the amount of the component of 0 ³ or more and less than 2 × 10 ^{4 is} less than 50%, the low-temperature fixability is not sufficient, and if it exceeds 75%, the components which are relatively effective in the offset resistance are reduced. Problems easily occur.

The component having a molecular weight of 2 × 10 ⁴ or more and less than 1 × 10 ⁵ has little effect on both the low-temperature fixing property and the anti-offset property, and it is not necessary to particularly limit the content. Since the latitude of resistance and offset resistance becomes narrow, it is preferable to set the mass-based ratio to all THF-soluble components to 20% or less.

The component (M3) having a molecular weight of 1 × 10 ⁵ or more and less than 3 × 10 ⁶ is effective for offset resistance when the content ratio is large, but has an adverse effect on low-temperature fixability and pulverizability. Exert. Component with a molecular weight of 3 × 10 ⁶ or more (M4)
Then, the tendency of (M3) becomes stronger. Molecular weight 1 × 1
The component (M3) having a molecular weight of at least 0 ^{5 and} less than 3 × 10 ⁶ is 15 to 30% by mass based on the total THF-soluble components, and has a molecular weight of 3 × 1.
0 ⁶ The above components (M4) shows a sufficient offset resistance by containing 1.0 to 5.0%.

When the component (M3) having a molecular weight of 1 × 10 ⁵ or more and less than 3 × 10 ⁶ (M3) is less than 15%, or the component (M4) having a molecular weight of 3 × 10 ⁶ or more is less than 1.0%, sufficient anti-offset property is obtained. Properties cannot be exhibited, and the molecular weight is 1 × 10 ⁵ or more and 3 × 10 ⁶
Less than 30% of component (M3) or molecular weight 3 × 1
0 when ⁶ or more components (M4) is 5.0 percent, which is not preferable negative effect on low-temperature fixability.

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

<GPC Measurement Conditions for Resin Composition> Apparatus: GPC-150C (manufactured by Waters) Column: KF801 to 7 (manufactured by Shodex) Temperature: 40 ° C. Solvent: THF (tetrahydrofuran) Flow rate: 1. 0 ml / min. Sample: 0.1 ml of a sample having a concentration of 0.05 to 0.6% by mass
Injection

The binder resin used in the toner of the present invention is not particularly limited except for the above-mentioned conditions, but a vinyl copolymer, particularly a vinyl copolymer containing styrene, can be preferably used. , And preferably has an acid value.

The acid value of the resin is 2 to 35 mgKOH /
g (more preferably 5 to 25 mg KOH / g) is good.
If it is less than 2 mgKOH / g, the rise of charging is poor and 3
If it exceeds 5 mgKOH / g, environmental stability is poor. Furthermore, Tg is 45 to 70 ° C., particularly preferably 45 to 60 ° C., and the softening point of the flow tester is 80 to 150 ° C., particularly preferably 80 to 135 ° C., so that the effect of the present invention is sufficiently exhibited.
Less adverse effects are preferred.

Examples of the resin preferably used include styrene-acrylate copolymer, styrene-methacrylate copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl Styrenes such as methyl ether copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile indene copolymer Copolymers and the like are preferable, and particularly, styrene-acrylate copolymers and styrene-methacrylate copolymers are preferably used.

Examples of the comonomers for the styrene monomer of the styrene copolymer include acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, dodecyl acrylate, octyl acrylate, and acrylic acid.
Monocarboxylic acids having a double bond such as 2-ethylhexyl, phenyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, butyl methacrylate, octyl methacrylate, acrylonitrile, methacrylonitrile, acrylamide and the like, and substituted products thereof;
For example, dicarboxylic acids having a double bond such as maleic acid, butyl maleate, methyl maleate, dimethyl maleate and the like;
Vinyl esters such as vinyl acetate and vinyl benzoate; ethylene-based olefins such as ethylene, propylene, butylene; vinyl ketones such as vinyl methyl ketone and vinyl hexyl ketone; vinyl methyl ether and vinyl Vinyl monomers such as ethyl ether, vinyl isobutyl ether and the like; and vinyl monomers such as one or two or more are used.

The binder resin used in the present invention is cross-linked as long as it satisfies the requirements for the THF-insoluble portion and the soluble portion of the binder resin component in the toner, which is a feature of the present invention when the toner is used. Or a mixed resin.

As the crosslinking agent for the binder resin, a compound having two or more polymerizable double bonds may be mainly used. For example, aromatic divinyl compounds such as divinylbenzene and divinylnaphthalene; carboxylic acid esters having two double bonds such as ethylene glycol diacrylate, ethylene glycol dimethacrylate, and 1,3-butanediol dimethacrylate; Divinyl compounds such as divinylaniline, divinyl ether, divinyl sulfide and divinyl sulfone; and 3
Compounds having at least two vinyl groups are used alone or as a mixture.

As a method for synthesizing the styrenic copolymer, any of a bulk polymerization method, a solution polymerization method, a suspension polymerization method and an emulsion polymerization method may be used. Known chain transfer agents such as t-dodecyl mercaptan, n-dodecyl mercaptan, α-methylstyrene dimer, and terpinolene can be used. In the present invention, α-methylstyrene dimer is particularly preferably used. In order to obtain a low molecular weight component constituting the main peak portion of the present invention having a sharp molecular weight distribution, a method of synthesizing by a suspension polymerization method using α-methylstyrene dimer as a chain transfer agent is particularly preferable. Further, in order to obtain a desired sharp molecular weight distribution, an ultra-low molecular weight component may be removed and purified.

It is preferable to use a method in which a low-molecular-weight component is first obtained by a suspension polymerization method and dissolved in a monomer for producing a high-molecular weight, followed by polymerization or by dissolution in a resin solution polymerized by solution polymerization. One.

The initiators used in these polymerization methods include t-butyl peroxy-2-ethylhexanoate, cumin perpivalate, t-butyl peroxy laurate, benzoyl peroxide, lauroyl peroxide, octa-peroxy. Noyl peroxide, di-t-butyl peroxide, t-butylcumyl peroxide, dicumyl peroxide, 2,2-azobisisobutyronitrile, 2,2-azobis (2-methylbutyronitrile), 2 , 2-Azobis (2,4-dimethylvaleronitrile), 2,2-azobis (4-methoxy-2,4-dimethylvaleronitrile), 1,1-bis (t-butylperoxy) 3,3,5 -Trimethylcyclohexane, 1,
1-bis (t-butylperoxy) cyclohexane-
1,4-bis (t-butylperoxydicarbonyl) cyclohexane, 2,2-bis (t-butylperoxy) octane, n-butyl 4,4-bis (t-butylperoxy) valerate, 2,2 -Bis (t-butylperoxy) butane, 1,3-bis (t-butylperoxy-isopropyl) benzene, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2.5 -Dimethyl-2,5-di (t-butylperoxy) hexane, 2.5
-Dimethyl-2,5-di (benzoylperoxy) hexane, di-t-butylcyperoxyisophthalate,
2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane, di-t-butylperoxy α-methylsuccinate, di-t-butylperoxydimethylglutarate, di-t-butyl Peroxyhexahydroterephthalate, di-t-butylperoxyazelate, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, diethylene glycol-bis (t-butylperoxycarbonate), di- T-butylperoxytrimethyl adipate, tris (t-butylperoxy) triazine, vinyltris (t-butylperoxy) silane, etc., can be used alone or in combination.

The used amount is 0.05 parts by mass or more (preferably 0.1 to 15 parts by mass) with respect to 100 parts by mass of the monomer.

The wax used in the toner of the present invention has a maximum endothermic peak of 6 as measured by a differential scanning calorimeter (DSC).
When the temperature is 0 to 135 ° C., the toner of the present invention rich in low molecular weight components has good compatibility, and the effect of low-temperature fixability is particularly large. Preferably from 60 to 125 ° C, more preferably from 60 to 1.
The temperature is preferably 20 ° C. from the viewpoint of low-temperature fixability. 60 ° C
If a toner in a smaller area is used, the developability tends to decrease, and the storage stability of the toner tends to be unstable. Therefore, it is preferable that the main peak does not exist in a temperature range lower than 60 ° C., more preferably in a temperature range lower than 70 ° C.

Examples of waxes having one or more DSC endothermic main peaks in the above range include, for example,
Paraffin wax, microcrystalline wax,
Petroleum waxes and derivatives thereof such as petrolactam, montan waxes and derivatives thereof, hydrocarbon waxes and derivatives thereof by the Fischer-Tropsch method, polyolefin waxes and derivatives thereof represented by polyethylene, carnauba wax, candelilla wax, and other natural waxes. And derivatives thereof. The derivatives include oxides, higher aliphatic alcohols including block copolymers with vinyl monomers, and graft-modified products; fatty acids such as stearic acid and palmitic acid, or compounds thereof, acid amides, esters, ketones, and cured products. Castor oil and derivatives thereof, vegetable wax, animal wax, etc., DSC
If the maximum endothermic peak is within the above range, these can be used.

In the present invention, among these, GPC
Weight average molecular weight (Mw) and number average molecular weight (M
When the ratio (Mw / Mn) of n) is 1.0 to 2.0, the dispersibility of the wax in the toner of the present invention is very good, and the preservability and contamination of members such as a photoreceptor are obtained. This is preferable because the film has high durability and good durability, and a good image can be stably obtained.

The wax used in the present invention has a number average molecular weight Mn of from 200 to 2,000, more preferably from 300 to 2,000.
000, and Mw is 200-2.
When it is 500, more preferably 300 to 2500, the dispersibility of the wax in the toner of the present invention is very good, and the durability is good since the storage stability and the resistance to contamination of members such as photoreceptors are strong. It is preferable because a good image can be stably obtained.

In the present invention, the wax is resin 100
It is preferably used in the range of 0.3 to 15 parts by mass with respect to parts by mass. If the amount is less than 0.3 part by mass, the effects of low-temperature fixing property and offset resistance are not sufficient, and it is difficult to separate the fixing member from the fixing member at the time of fixing. It has an adverse effect on the contamination of members such as the body.

For measuring the DSC endothermic peak of the wax used in the present invention or the glass transition point Tg of the toner,
For example, such as Perkin Elmer's DSC-7,
The measurement is performed by a method using a high-precision internal heating type input compensation type differential scanning calorimeter and a DSC curve obtained thereby.

In the present invention, the molecular weight of the wax was measured under the following conditions. -Apparatus: GPC-150C (waters forest)-Column: GMH-HT 30 cm, 2 columns (manufactured by Tosoh Corporation)-Temperature: 135 ° C-Solvent: o-dichlorobenzene (0.1% by mass ionol addition)-Flow rate: 1. 0 ml / min ・ Sample: 0.4 ml of 0.15 mass% sample was injected In calculating the molecular weight of the wax sample, a molecular weight calibration curve created by a monodisperse polystyrene standard sample was used, and the conversion derived from the Mark-Houwink viscosity equation was used. It was calculated by converting into polyethylene by the formula.

As the colorant used in the toner of the present invention, carbon black, a magnetic substance, and a black-toned colorant using a yellow / magenta / cyan colorant shown below are used.

Examples of the yellow colorant include condensed azo compounds, isoindolinone compounds, anthraquinone compounds,
A compound represented by an azo metal complex, a methine compound or an allylamide compound is used. Specifically, C.I. I. Pigment Yellow 12, 13, 14, 15, 17, 6
2, 74, 83, 93, 94, 95, 97, 109, 1
10, 111, 120, 127, 128, 129, 14
7, 168, 174, 176, 180, 181, 191
Etc. are preferably used.

Examples of the magenta colorant include condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds and perylene compounds. Specifically, C.I.
I. Pigment Red 2, 3, 5, 6, 7, 23, 4
8: 2, 48: 3, 48: 4, 57: 1, 81: 1, 1
44, 146, 166, 169, 177, 184, 18
5, 202, 206, 220, 221, 254 are particularly preferred.

As the cyan coloring agent, a copper phthalocyanine compound and its derivative, an assoraquinone compound, a basic dye lake compound and the like can be used. Specifically, C.I. I.
Pigment Blue 1, 7, 15, 15: 1, 15: 2,
15: 3, 15: 4, 60, 62, 66, etc. can be particularly preferably used.

These colorants can be used alone or as a mixture or in the form of a solid solution. The colorant of the present invention is selected from the viewpoints of hue angle, saturation, lightness, weather resistance, OHP transparency, and dispersibility in toner. The colorant is used in an amount of 1 to 20 parts by mass per 100 parts by mass of the resin.

When a magnetic material is used as a black coloring agent, unlike other coloring agents, 30 parts by mass relative to 100 parts by mass of the resin is used.
Used in an amount of up to 200 parts by mass.

As the magnetic material, iron, cobalt, nickel,
Examples include metal oxides containing elements such as copper, magnesium, manganese, aluminum, and silicon. Among them, ferric oxide,
Those containing iron oxide as a main component, such as γ-iron oxide, are preferred.
Further, other metal elements such as a silicon element or an aluminum element may be contained from the viewpoint of controlling the chargeability of the toner. These magnetic particles, BET specific surface area by nitrogen adsorption method 2 to 3 m ² / g, particularly preferably 3~28m ² / g, further Mohs hardness magnetic powder 5-7 is preferred.

The shape of the magnetic material includes an octahedron, a hexahedron, a sphere, a needle, a scale, and the like. It is preferable in increasing the value. The average particle size of the magnetic material is 0.05 to 1.0 μm
m is preferable, and 0.1 to 0.6 μm is more preferable.
Further, the thickness is preferably 0.1 to 0.4 μm.

The amount of the magnetic substance is 3 with respect to 100 parts by mass of the binder resin.
0 to 200 parts by mass, preferably 40 to 200 parts by mass, more preferably 50 to 150 parts by mass. If the amount is less than 30 parts by mass, in a developing device that uses a magnetic force to transport the toner, the transportability is insufficient, and the developer layer on the developer carrier tends to be uneven, resulting in image unevenness. , The image density tends to decrease. On the other hand, if it exceeds 200 parts by mass, a problem tends to occur in the fixing property.

In the toner of the present invention, it is preferable to use a charge control agent mixed (internally added) with toner particles or mixed (externally added) with toner particles. The charge control agent makes it possible to control the amount of charge optimally according to the development system.

The following substances control the toner to be negatively charged.

For example, organic metal complexes and chelate compounds are effective, and examples thereof include monoazo metal complexes, acetylacetone metal complexes, aromatic hydroxycarboxylic acids, and aromatic dicarboxylic acid-based metal complexes. Other examples include aromatic hydroxycarboxylic acids, aromatic mono- and polycarboxylic acids and their metal salts, anhydrides, esters, and phenol derivatives such as bisphenol.

The following substances are controlled to be positively charged.

Modified products of nigrosine and fatty acid metal salts; quaternary ammonium salts such as tributylbenzylammonium-1-hydroxy-4-naphthosulfonate, tetrabutylammonium tetrafluoroborate, and phosphonium salts which are analogs thereof Onium salts such as, for example, these lake pigments, triphenylmethane dyes and these lake pigments (as the lacating agent, phosphotungstic acid, phosphomolybdic acid, phosphotungsten molybdic acid, tannic acid, lauric acid, gallic acid, ferricyanic acid) , Ferrocyanide, etc.), metal salts of higher fatty acids; diorganotin oxides such as dibutyltin oxide, dioctyltin oxide, dicyclohexyltin oxide; dibutyltin borate, dioctyltin borate, dicyclohexyl Diorgano tin borate such as Suzuboreto; can be used in combination singly or two or more kinds.

The above-mentioned charge control agents are preferably used in the form of fine particles. In this case, the number average particle size of these charge control agents is preferably 4 μm or less, more preferably 3 μm or less. When these charge control agents are internally added to the toner,
It is preferable to use 0.1 to 20 parts by mass, particularly 0.2 to 10 parts by mass, based on 100 parts by mass of the binder resin.

As the inorganic fine powder contained in the toner of the present invention, known ones are used.
In order to improve developability, fluidity, and storage stability, it is preferable to select from silica, alumina, titania or a composite oxide thereof. Furthermore, silica is more preferable. For example, as the silica, both a so-called dry method produced by a vapor phase oxidation of a silicon halide and an alkoxide or a so-called wet silica produced from an alkoxide, a water glass and the like, or a fumed silica can be used. some, but less silanol groups on the inner surface and the silica fine powder, also Na ^₂ O, SO ₃ ^2-
Dry silica with less production residue such as is preferred. In the case of fumed silica, 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 and titanium chloride together with a silicon halide in the manufacturing process. They are also included.

The inorganic fine powder used in the present invention is BET.
The specific surface area by measuring nitrogen adsorption in law 30 m ² / g or more, especially given the 50 to 400 m ² / g good results in the range of fine silica powder of 0.1 to 8 mass with respect to 100 mass parts of the toner Part by weight, preferably 0.5 to 5 parts by weight, more preferably more than 1.0 to 3.0 parts by weight.

The inorganic fine powder used in the present invention comprises:
Silicon varnish, various modified silicone varnishes, silicone oil, various modified silicone oils, silane coupling agents, silane coupling agents having functional groups, other organosilicon compounds, organic It is possible and preferable to use a treating agent such as a titanium compound or a combination of various treating agents.

Further, in addition to the inorganic fine powder, the primary particle size further exceeds 30 nm (preferably, the specific surface area is 50
It is also one of the preferable embodiments to further add inorganic or organic particles having a shape close to sphere having a particle size of less than 50 m ² / g, more preferably 50 nm or more (preferably having a specific surface area of less than 30 m ² / g). For example, spherical silica particles, spherical polymethylsilsesquioxane particles, spherical resin particles and the like are preferably used.

In the toner of the present invention, other additives, for example, lubricant powders such as Teflon (registered trademark) powder, zinc stearate powder, polyvinylidene fluoride powder; Abrasives such as powder, silicon carbide powder and strontium titanate powder; fluidity imparting agents such as titanium oxide powder and aluminum oxide powder; anti-caking agents; or conductive materials such as carbon black powder, zinc oxide powder and tin oxide powder. A small amount of a property imparting agent or organic and inorganic fine particles of opposite polarity can also be used as a developing property improver.

For producing the toner according to the present invention, a known method is used. For example, a binder resin, a wax, a pigment as a colorant, a dye, or a magnetic substance, a charge control agent if necessary, After the other additives, etc. are sufficiently mixed by a mixer such as a Henschel mixer, a ball mill, etc., and then melt-kneaded using a heat kneader such as a heating roll, kneader, extruder, and the like, while the resins are mutually compatible. After dispersing or dissolving a metal compound, a pigment, a dye, and a magnetic substance, solidifying and pulverizing by cooling, classification is performed to obtain toner particles, and the inorganic fine powder and other additives are mixed to obtain the toner according to the present invention. I can do it. In the classification step, it is preferable to use a multi-division classifier in terms of production efficiency.

[0079]

EXAMPLES The present invention will be described below with reference to specific examples, but the present invention is not limited to these examples. All parts in the following formulations are parts by mass.

(Production Example of Resin Composition) ・ Synthesis of Low Molecular Weight Polymers L1 to L3 52 parts of styrene 6 parts of α-methylstyrene 6 parts of n-butyl acrylate 30 parts of monobutyl maleate 10 parts of α-methylstyrene dimer 2 Part benzoyl peroxide 9.2 parts polyvinyl alcohol partially saponified product
170 parts of water in which 12 parts were dissolved was added, and the mixture was vigorously stirred to obtain a suspension dispersion. The suspension dispersion was added to a reactor charged with 500 parts of water and purged with nitrogen, and a suspension polymerization reaction was performed at a reaction temperature of 80 ° C. for 8 hours. After completion of the reaction, the resultant was washed with water, dehydrated and dried to obtain a low molecular weight polymer (L1). GP of the obtained resin
In the molecular weight measurement by the method C, the number average molecular weight Mn =
4200, weight average molecular weight Mw = 8100, peak molecular weight = 6200, and glass transition temperature Tg = 58.9 ° C.
Met.

In the same manner, by adjusting the amount of the initiator, a low molecular weight polymer L2 (Mn: 12,000) having a peak molecular weight of 12,000 was obtained.
5900, Mw: 130000), low molecular weight polymer L3 having a peak molecular weight of 4400 (Mn: 2700, Mw: 530)
0) was obtained.

Synthesis of Low-Molecular-Weight Polymer L4 300 parts by mass of xylene were charged into a reaction vessel, and the inside of the vessel was sufficiently purged with nitrogen while stirring, and then heated to reflux. Under the reflux, a mixed solution having the following composition was added dropwise over 4 hours, and then maintained for 2 hours to complete the polymerization, thereby obtaining a low molecular weight polymer L4 solution. Styrene 67 parts n-butyl acrylate 22 parts monobutyl maleate 10 parts α-methylstyrene dimer 1 part divinylbenzene 0.03 parts di-tert-butyl peroxide 1.5 parts

A part of the polymer solution was sampled,
After drying under reduced pressure, the GP of the obtained low molecular weight polymer L4 was obtained.
When the C and the glass transition point (Tg) were measured, the number average molecular weight Mn was 6,800, and the weight average molecular weight Mw was 1.
80,000, peak molecular weight 16,000, and glass transition temperature T
g = 60.3 ° C.

Synthesis of Low-Molecular-Weight Polymer L5 300 parts by mass of xylene were charged into a reaction vessel, and the vessel was sufficiently purged with nitrogen while stirring, and then heated to reflux. Under the reflux, a mixed solution having the following composition was dropped over 4 hours, and then maintained for 2 hours to complete the polymerization, thereby obtaining a low molecular weight polymer L5 solution. Styrene 68 parts n-butyl acrylate 22 parts monobutyl maleate 10 parts divinylbenzene 0.03 parts di-tert-butyl peroxide 1.0 part

A part of this polymer solution was sampled,
After drying under reduced pressure, GP of the obtained low molecular weight polymer L5 was obtained.
When the C and the glass transition point (Tg) were measured, the number average molecular weight Mn was 8,100 and the weight average molecular weight Mw was 2.
80,000, peak molecular weight 24,000, and glass transition temperature T
g = 61.0 ° C.

Synthesis of High Molecular Weight Polymer H1 300 parts by mass of xylene was charged into a reaction vessel, and the vessel was sufficiently purged with nitrogen while stirring, and then heated to reflux. Under the reflux, a mixed solution having the following composition was added dropwise over 4 hours, and then kept for 2 hours to complete the polymerization to obtain a high molecular weight polymer H1 solution. Styrene 70 parts n-butyl acrylate 25 parts monobutyl maleate 5 parts divinylbenzene 0.03 parts di-tert-butyl peroxide 0.2 parts

A part of this polymer solution was sampled,
The GP of the high molecular weight polymer H1 obtained by drying under reduced pressure
When the C and the glass transition point (Tg) were measured, the number average molecular weight Mn was 380,000 and the weight average molecular weight Mw was 154.
The glass transition temperature Tg was 59.5 ° C.
The THF insoluble content was 1%.

Synthesis of high molecular weight polymer H2 72 parts styrene 18 parts n-butyl acrylate 18 parts monobutyl maleate 10 parts 0.2 parts divinylbenzene 0.5 parts benzoyl peroxide 0.5 parts polyvinyl alcohol Compound 0.
170 parts of water in which 12 parts were dissolved was added, and the mixture was vigorously stirred to obtain a suspension dispersion. The suspension dispersion was added to a reactor charged with 500 parts of water and purged with nitrogen, and a suspension polymerization reaction was performed at a reaction temperature of 80 ° C. for 8 hours. After completion of the reaction, the resultant was washed with water, dehydrated and dried to obtain a high molecular weight polymer (H2). GP of the obtained resin
In the molecular weight measurement by the method C, the number average molecular weight Mn =
260,000, the weight average molecular weight Mw was 2.8 million, and the glass transition temperature Tg was 60.1 ° C. The THF insoluble content was 1
2%.

Production of Resin Composition 1 In a dissolution vessel, 300 parts by weight of xylene and 75 parts of the low molecular weight polymer L1 were charged and dissolved. In a separate container, 100 parts by weight of xylene is added in advance to the high molecular weight polymer H12.
The solution in which 5 parts were dissolved was mixed, and 4 parts of low molecular weight polyethylene (DSC endothermic peak 106.7 ° C., Mw
/Mn=1.08) and mixing under reflux, the organic solvent was distilled off, and the obtained resin was cooled, solidified and pulverized to obtain a resin composition 1 for toner. The acid value of the resin composition 1 is 1
It was 8 mgKOH / g.

Production of Resin Compositions 2 and 3 Resin compositions 2 and 3 were obtained in the same manner as resin composition 1 except that low-molecular-weight polymer L1 was changed to L2 and L4, respectively. The acid value of each of the resin compositions 2 and 3 is 18 mgK
OH / g.

Production of resin compositions 4 and 4 ' Low molecular weight polymer L1 / high molecular weight polymer H1 = 75/25
Of low molecular weight polymer L3 / high molecular weight polymer H2 = 80 /
Resin composition 4 was obtained in the same manner as resin composition 1 except that the composition was changed to 20. Further, the resin composition 4 was washed with isopropyl alcohol heated to 60 ° C. for 12 hours, filtered,
An additional step of drying was performed to remove ultra-low molecular weight components to obtain a resin composition 4 ′. The acid value of each of the resin compositions 4 and 4 ′ was 24 mgKOH / g.

Preparation of Resin Composition 5 Resin composition 5 was obtained in the same manner as resin composition 1 except that low-molecular-weight polymer L1 was changed to L5. The acid value of the resin composition 5 was 18 mgKOH / g.

Example 1 100 parts of resin composition 1 95 parts of magnetic material (shape: spherical, average particle size: 0.20 μm) 2 parts of iron complex of monoazo dye (average particle size: 1.5 μm) The above materials were mixed by a blender, melt-kneaded by a biaxial extruder heated to 130 ° C., and the cooled mixture was roughly pulverized by a hammer mill and then finely pulverized by a jet mill. Next, the obtained finely pulverized material was strictly classified by a multi-segment classifier using the Coanda effect to obtain a weight average diameter of 6.8.
μm toner particles were obtained. THF of the obtained toner particles
Table 1 shows the insoluble content, the measurement data of the THF-soluble component by GPC chromatogram, and the content ratio of each molecular weight component. FIG. 1 shows a conceptual diagram of the molecular weight distribution of the THF-soluble component in the toner.

To 100 parts of the obtained toner particles, 1.2 g of dry silica (primary average particle size 0.02 μm) hydrophobized with silicone oil and hexamethylsilazane was used.
And the mixture was mixed with a mixer to obtain toner 1. Using this toner, a Canon printer LBP-850 equipped with an on-demand type fixing device (print speed: A4
Using an evaluator modified from double feed (16 sheets / min) to a double speed of 32 sheets / min, evaluation of fixability and image output durability was performed by the following tests.

(Evaluation of low-temperature fixability) Since the modified machine used for the evaluation has a double fixing speed, the time required to pass through the fixing nip is 1/2 of that of the product, and the toner image is affected during fixing. The amount of heat is also halved. No modification was made except for the fixing speed.

[0096] Three 25 mm square solid black images are
The pattern arranged at 40 mm intervals in the step was adjusted by adjusting the amount of laser so that the amount of applied toner in the solid portion became approximately 0.6 g / cm ^2, and 100 sheets of A4 vertical feed continuous printing were performed. The reflection density of each sample was measured using a "Reflectometer" (manufactured by Tokyo Denshoku Co., Ltd.) before and after the fixed image was rubbed with a soft thin paper under a load of 4900 N / m ² . The number of sheets when the rate of decrease in image density after rubbing exceeded 10% was evaluated according to the following criteria. A: The reduction rate of the image density is 10% or less at 100 sheets. B: The reduction rate of the image density exceeds 10% after 60 sheets. C: The reduction rate of the image density exceeds 10% within 60 sheets.

(Evaluation of offset resistance)
Fifteen seconds after the stop of the printing of 0 sheets (at this time, the temperature of the fixing device is the highest), the light amount is returned to the standard and the A3 front end
One solid black image of 00 mm was printed, and the offset of the non-sheet passing portion of the A4 vertical feed was visually evaluated. A: No hot offset has occurred B: Minor and inconspicuous hot offset has occurred (a level that has no practical problem) C: Obvious hot offset has occurred

(Evaluation of Durability) An English type character image having a printing ratio of about 5% is set to a mode of 1 sheet / 10 which is the most severe mode against image density reduction and contamination of members such as a photoconductor and a fixing device.
10,000 prints in intermittent mode for 1 second
A solid black image and a solid white image are printed one at a time in A4 landscape mode on one million sheets, and the reflection density of the solid black image is measured using a "Reflectometer" (manufactured by Tokyo Denshoku Co., Ltd.) to measure the average value of five points of reflection density. Evaluation was made based on a decrease in density at the time of 1000 sheets and at the time of 10,000 sheets. A: Density decrease less than 0.05 B: Density decrease 0.05 or more and less than 0.1 C: Density decrease 0.1 or more

The solid black image, solid white image and English type character image were visually inspected after printing 10,000 sheets for abnormal images resulting from contamination of members such as a photoconductor and a fixing device. A: No abnormality B: Almost inconspicuous, but an abnormal image is present. (Practically no problem level) C: There is clearly an abnormal image.

The above evaluation results were all excellent as shown in Table 2.

<Examples 2 to 4> Toners were prepared in the same manner as in Example 1 except that the resin composition 1 used in Example 1 was changed to a resin composition 2, a resin composition 3, and a resin composition 4 ', respectively. Was prepared and evaluated in the same manner as in Example 1. Table 1 shows the physical properties of the resin components of each toner. The above evaluation results were all excellent as shown in Table 2.

Comparative Example 1 A toner was prepared in the same manner as in Example 1 except that the resin composition 1 used in Example 1 was changed to the resin composition 4, and evaluation was performed in the same manner as in Example 1. .
Table 1 shows the physical properties of the resin components of the toner. As shown in Table 2, the above evaluation results show that although the low-temperature fixability is excellent,
All other properties were inferior.

Comparative Example 2 A toner was produced in the same manner as in Example 1 except that the resin composition 1 used in Example 1 was changed to the resin composition 4. Table 1 shows the physical properties of the resin components of the toner. When the low-temperature fixability was evaluated in the same manner as in Example 1, the density reduction rate exceeded 10% on 20 sheets, and a sufficient result was not obtained. Other evaluations were discontinued.

Comparative Example 3 50 parts of low molecular weight polymer L1 50 parts of high molecular weight polymer H2 95 parts of magnetic substance (shape: spherical, average particle size: 0.20 μm) 95 parts Iron complex of monoazo dye (average) Particle size: 1.5 μm) 2 parts ・ Low molecular weight polyethylene 4 parts (DSC endothermic peak: 106.7 ° C., Mw / Mn = 1.08) A toner was produced in the same manner as in Example 1 except that the above formulation was used. Table 1 shows the physical properties of the resin components of the toner. When the low-temperature fixing property was evaluated in the same manner as in Example 1, the density reduction rate exceeded 10% from the first sheet, and a sufficient result was not obtained. Other evaluations were discontinued.

[0105]

[Table 1]

[0106]

[Table 2]

[0107]

According to the present invention, sufficient low-temperature fixability and anti-offset property can be exhibited even if the amount of heat required for fixing is lower than in the past, and image density is reduced, fog, etc., even during long-term durability. No image contamination and no contamination of the constituent members of the apparatus such as the photosensitive member, and excellent fixability and stable durability can be realized even at a high process speed.

[Brief description of the drawings]

FIG. 1 is an explanatory diagram showing the molecular weight distribution of THF soluble components in a toner of Example 1.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Yuki Karaki 3-30-2 Shimomaruko, Ota-ku, Tokyo Inside Canon Inc. (72) Inventor Yoshihiro Ogawa 3-30-2 Shimomaruko, Ota-ku, Tokyo Non-corporation F term (reference) 2H005 AA01 AA06 CA13 CA14 DA06 DA10 EA03 EA06 EA07

Claims (7)

[Claims] 1. A toner containing at least a binder resin, a colorant and a wax, wherein the resin composition of the toner is substantially free of a THF-insoluble component, and a GPC (gel permeation chromatograph) of a THF-soluble component of the toner. G), at least a molecular weight of 3 × 1
A main peak in a region of 0 ^{3 to} 2 × 10 ^4, a main part of the main peak having Mw / Mn of less than 2.5, a component (M1) having a molecular weight of less than 2 × 10 ³ , and a molecular weight of 2 × 10 ³
The components (M2) having a molecular weight of at least 2 × 10 ^4, the components having a molecular weight of at least 1 × 10 ^{5 and} less than 3 × 10 ⁶ (M3), and the components having a molecular weight of 3 × 10 ⁶ or more (M4) are all soluble in THF. Component (M1) having a molecular weight ratio of less than 2 × 10 ³ (M1): less than 7% Component (M2) having a molecular weight of 2 × 10 ³ or more and less than 2 × 10 ⁴ : 5
0 to 75% Component (M3) having a molecular weight of 1 × 10 ⁵ or more and less than 3 × 10 ⁶ : 1
5 to 30% Component having a molecular weight of 3 × 10 ⁶ or more (M4): 1.0 to 5.0
%, Which is a toner for heat fixing. 2. The heat fixing toner according to claim 1, wherein Mw / Mn of the main part of the main peak is less than 2.2. 3. The heat fixing toner according to claim 1, wherein Mw / Mn of the main part of the main peak is less than 2.0. 4. A GPC (gel permeation chromatogram) of a THF-soluble portion of the toner, wherein the molecular weight is 1
4. The heat fixing toner according to claim 1, wherein the mass-based ratio of the component (M0) of less than × 10 ³ to all THF-soluble components is less than 3%. 5. The method according to claim 5, wherein the wax is a differential scanning calorimeter (DS).
5. The heat fixing toner according to claim 1, wherein the maximum endothermic peak measured by C) is 60 to 135 [deg.] C. 6. The wax has a molecular weight distribution determined by gel permeation chromatography (GPC), which is a ratio of a weight average molecular weight to a number average molecular weight (Mw / Mw).
The heat fixing toner according to claim 5, wherein n) is 1.0 to 2.0. 7. The wax has a number average molecular weight (Mn) of 200 to 2,000 in a molecular weight distribution by gel permeation chromatography (GPC),
7. The heat fixing toner according to claim 5, wherein the weight average molecular weight (Mw) is from 200 to 2500.