JP2000089512A - Toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a toner which is easily fixed at low temperature even in a medium- to high-speed machine using a heat roll fixer or in a medium- to low-speed machine using a pressure and heat fixing system in which the toner is heated with a fixed heater through a heat resistant film. SOLUTION: The toner contains a bonding resin, a colorant, a wax, an organometallic compd. and a saccharide compd. The saccharide compd. is cyclodextrin. The bonding resin contains a hybrid resin component having vinyl polymer units and polyester units, the acid value of the bonding resin is 5-40 mgKOH/g and the resin component of the toner contains 15-50 wt.% THF- insoluble component. The organometallic compd. is complex or a salt having aluminum as the metallic element and an arom. hydroxycarboxylic acid or the like as the ligands. The mol.wt. of the wax has the main peak in the range of 300-5,000 and the ratio of the weight average mol.wt. to the number average mol.wt. of the wax is 1.2-15.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a toner used in a recording method utilizing an electrophotographic method, an electrostatic recording method, an electrostatic printing method, a toner jet recording method, or the like.

[0002]

2. Description of the Related Art An electrophotographic method is disclosed in U.S. Pat.
Numerous 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. Generally, a photoconductive substance is used to form an electrostatic charge image on a photoreceptor by various means,
Then, the electrostatic image is developed using toner, and if necessary, a toner image is transferred to a transfer material such as paper, and then fixed by heating, pressure, heat and pressure, or solvent vapor to obtain a toner image. is there.

Various methods and apparatuses have been developed for fixing the toner image onto a sheet such as paper, which is the above-mentioned final step. The most common method at present is a fixed heat generation through a heat roller or a heat-resistant film. This is a compression heating method using a heater.

In the pressure heating method using a heating roller, the toner image is fixed by passing the surface of the heat roller having a releasing property to the toner and the toner image surface of the sheet to be fixed while pressing the sheet under pressure. Is performed. In this method, since the surface of the heat roller and the toner image on 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. Can be.

[0005] Since the surface of the heating roller and the toner image come into contact with each other in a molten state and under pressure, a part of the toner image adheres to the surface of the fixing roller and is transferred. The offset phenomenon, which stains the sheet, is greatly affected by the fixing speed and the fixing temperature. Generally, when the fixing speed is low, the surface temperature of the heating roller is set relatively low, and when the fixing speed is high, the surface temperature of the heating roller is set relatively high. This is because the amount of heat applied from the heating roller to the toner to fix the toner is made substantially constant regardless of the fixing speed.

Since the toner on the sheet to be fixed forms several toner layers, particularly in a system in which the fixing speed is high and the surface temperature of the heating roller is high, the toner layer in contact with the heating roller includes: When the surface temperature of the heating roller is high because the temperature difference between the lowermost toner layer in contact with the fixing sheet and the lowermost toner layer is large, the toner in the uppermost layer is likely to cause an offset phenomenon, and When the surface temperature is low, the toner in the lowermost layer is not sufficiently melted, so that the toner is not fixed on the sheet to be fixed and a phenomenon of low-temperature offset is likely to occur.

As a method for solving this problem, when the fixing speed is high, a method of increasing the pressure at the time of fixing and anchoring the toner to the sheet to be fixed is usually used. According to this method, the temperature of the heating roller can be reduced to some extent, and the high-temperature offset phenomenon of the uppermost toner layer can be prevented. However, since the shearing force applied to the toner becomes very large, the sheet to be fixed winds around the fixing roller, and a winding offset occurs, or after the separation claw for separating the sheet to be fixed from the fixing roller is separated. Easily appear in the fixed image. Furthermore, because of the high pressure, the line image is crushed or the toner is scattered at the time of fixing, and the image quality of the fixed image is likely to deteriorate.

Conventionally, vinyl resins such as polyester resins and styrene resins have been mainly used as toner resins. Polyester resin has excellent low-temperature fixability, but it is said that it has the disadvantage that offset phenomenon easily occurs at high temperature.To compensate for this defect, the molecular weight of the polyester resin is increased to increase the viscosity. Attempts have been made to improve the elastic properties, but in this case, there is a problem that the low-temperature fixability is impaired, and the pulverizability during the production of the toner is also deteriorated, which is not suitable for making the toner into fine particles. It becomes a binder resin.

Further, vinyl copolymers such as styrene resins are excellent in pulverizability at the time of toner production and high in high molecular weight, so they are excellent in high-temperature offset resistance, but in order to improve low-temperature fixability. However, when the molecular weight is lowered or the glass transition temperature is lowered, there is a problem that the blocking resistance and the developability deteriorate.

[0010] In order to make effective use of the advantages of these two types of resins and to compensate for the drawbacks, some methods of mixing and using these resins have been studied.

For example, Japanese Patent Application Laid-Open No. Sho 54-114245 discloses a toner containing a resin obtained by mixing a polyester resin and a vinyl copolymer. However, the compatibility between polyester resin and vinyl copolymer is poor due to the large difference in chemical structure, low-temperature fixability,
It is difficult to satisfy both high-temperature offset resistance and blocking resistance.

Further, it is difficult to uniformly disperse various additives, particularly wax, added during the production of the toner, so that not only the fixing performance of the toner, but also the developability tends to be problematic. This problem is significant for certain toners.

Further, Japanese Patent Application Laid-Open No. 56-116043,
JP-A-58-159546 discloses a toner containing a polymer obtained by polymerizing a monomer in the presence of a polyester resin.

JP-A-58-102246 and JP-A-1-156759 disclose a toner characterized by containing a polymer obtained by polymerizing a vinyl copolymer in the presence of an unsaturated polyester. It has been disclosed.

Japanese Patent Application Laid-Open No. 2-881 is characterized in that a styrene-based resin obtained by copolymerizing a monomer having an acid group and a polyester resin include a polymer in which an ester bond is formed via an acid group of the styrene-based resin. Is disclosed.

Japanese Patent Publication No. H8-16796 discloses a toner characterized by containing a polyester resin having a specific acid value and a block copolymer obtained by esterifying a styrene resin having a specific acid value and a molecular weight. It has been disclosed.

JP-A-8-47553 discloses a toner characterized in that the binder resin comprises a polycondensation resin and a vinyl resin, and has a peak in a specific chloroform-insoluble content and a specific molecular weight range. ing.

In the above-mentioned binder resin, the condensation polymerization resin and the addition polymerization resin can maintain a stable phase separation state. However, although the toner using these binder resins improves the high-temperature offset resistance to some extent, the low-temperature fixability of the toner is still insufficient, and when the toner contains wax, the dispersion state of the wax is reduced. It is difficult to control, and in a magnetic toner containing a magnetic material as a colorant in the toner, it is difficult to control the dispersion state of the magnetic material. When the toner is used, there remains a problem to be improved not only in the low-temperature fixing property but also in the developing property collectively such as image density, fog, and image quality.

JP-A-6-118719, 6-1
JP-A Nos. 24002 and 8-325305 disclose toners or methods of using an inclusion compound comprising a cyclodextrin derivative, cyclo-oligosaccharide, polysaccharide, or the like as a charge control agent. When the binder resin is used as a charge control agent for a toner having a vinyl polymer or polyester, the chargeability is not always sufficient, and improvement is required.

[0020]

SUMMARY OF THE INVENTION The present invention provides a toner which has solved the above-mentioned problems.

That is, the object of the present invention is good even for a medium-to-high-speed machine using a hot roll fixing device, or a medium-to-low-speed machine using a press-bonding heat fixing system using a fixed heat generating heater via a heat-resistant film. An object of the present invention is to provide a toner that exhibits excellent low-temperature fixability and does not cause contamination of a heating member due to offset from low to high temperatures.

An object of the present invention is to provide a low-temperature fixer which exhibits good fixability of a halftone portion even when used in a binder resin of a toner having a reduced particle diameter and an increased content of a colorant (particularly a magnetic substance). An object of the present invention is to provide a toner having excellent properties.

Another object of the present invention is to optimize the dispersion state of the magnetic substance and the dispersion state of the charge control agent even when the toner is used for a toner having a small particle diameter in which the content of the coloring agent (particularly the magnetic substance) is increased. An object of the present invention is to provide a toner which can be controlled and has a small change in image density due to durability containing a constant magnetic substance regardless of the particle size of the toner.

[0024]

According to the present invention, there is provided a toner containing at least a binder resin, a colorant, a wax, an organometallic compound and a saccharide compound, wherein (a) the saccharide compound is cyclodextrin, and (b) The binder resin contains a hybrid resin component having a vinyl polymer unit and a polyester unit, and (c) the binder resin has an acid value of 5 to 40 mgKOH / g;
(D) The resin component of the toner is tetrahydrofuran (TH
F) 15 to 50% by weight of an insoluble content, (e) the organometallic compound has aluminum as a metal element, and an aromatic hydroxycarboxylic acid, an aromatic diol or an aromatic polycarboxylic acid as a ligand. (F) the wax has a main peak (Mp) at a molecular weight of 300 to 5000 in a chromatogram measured by gel permeation chromatography (GPC), The present invention relates to a toner, wherein the ratio (Mw / Mn) to the average molecular weight is 1.2 to 15.

[0025]

According to the study of the present inventors, in order to prevent the fixing member from being contaminated by offset regardless of the heating method of the fixing device, the low-temperature fixing property and the high-temperature offset resistance of the toner are improved. Alone is not sufficient, and it has been found that it is important to improve the releasability of the toner from the fixing member.

Conventionally, the improvement of the toner offset phenomenon and the improvement of the fixing property of the toner have been regarded as the same. However, the improvement of the fixing property by the improvement of the binder resin, the wax contained in the toner, and the like is accompanied. Improving the offset in such a way is limited and inadequate.

In the case where the releasability of the fixing member and the cleaning member defined by the contact angle of water or the toner is not sufficient, if the releasability of the toner is insufficient, sufficient offset prevention is performed at an early stage of use. Even if the effect can be expected, if used for a long period of time, each member may deteriorate over time, and eventually an offset may occur.

Conventionally, it has been proposed that the binder resin of the toner has an insoluble content in an organic solvent such as THF from the viewpoint of improving the hot offset resistance of the toner. However, even such a toner has deteriorated over time. In some cases, a sufficient offset prevention effect is not exerted on the fixing member and the cleaning member. Further, the toner may contain wax for the purpose of imparting releasability, but aged fixing members,
A large amount of wax needs to be contained in the cleaning member in order to maintain a sufficient offset prevention effect. In this case, the developing property of the toner, that is, a problem such as a decrease in image density and an increase in fog density occurs. Further, it is difficult to control the dispersion state of the wax contained in the toner particles. It will contain a large amount of wax. As a result, the toner on the photoconductor may not be sufficiently cleaned and may remain, resulting in an image defect. When the binder resin contains a polyester unit, it is difficult to disperse the wax, which is more remarkable.

In the case of a toner containing a hybrid resin composition having a vinyl polymer unit and a polyester unit as a binder resin, a sufficient toner adhesion preventing effect and cleaning effect even on aged fixing members and cleaning members In order to maintain the effect, it is necessary not only to show a good mixed state with the hybrid resin composition but also to contain a saccharide compound having a specific structure that controls the dispersion of the magnetic substance and the charge control agent in a suitable state. .

The toner of the present invention contains a specific saccharide compound, preferably the saccharide compound is a cyclodextrin compound represented by the formula (1), and more preferably the cyclodextrin compound represented by the formula (2) A cyclodextrin to form an inclusion compound.

[0031]

Embedded image (Wherein, R ₁ and R ₂ represent a hydroxyl group or a linear or branched alkyl group having 1 to 30 carbon atoms, which may be the same or different. R ₃ is a hydrogen atom, a methyl group or (It represents an ester bond with a carboxylic acid having an alkyl group having 1 to 4 carbon atoms, and j represents an integer of 6 to 20.)

[0032]

Embedded image (In the formula, k represents an integer of 6 to 8.)

In the toner of the present invention, when the cyclodextrin forms an inclusion compound, it preferably forms an inclusion compound with a salt, complex salt or complex containing a quaternary ammonium compound or a metal. Preferably, the metal contains at least one selected from lithium, sodium, potassium, strontium, calcium, aluminum, iron, zirconium and zinc. Particularly preferably, it contains at least one selected from sodium, calcium, iron, zirconium and zinc.

In the toner of the present invention, when the cyclodextrin compound forms an inclusion compound, an inclusion compound which is previously reacted with a specific metal salt, complex salt or complex to form an inclusion compound is added in the toner particle manufacturing process. can do. Further, a cyclodextrin compound and a metal salt, a complex salt, a complex or an organometallic compound containing a metal atom capable of forming an inclusion compound with the cyclodextrin compound can be added in the step of kneading the toner particles. A complex in which the organometallic compound contains an aluminum element represented by the formulas (4) to (6) and coordinates an aromatic hydroxycarboxylic acid, an aromatic diol or an aromatic polycarboxylic acid as a ligand Or it is a case where it becomes a charge control agent composed of a complex salt. Contains an aluminum element which is a charge control agent, and an aromatic hydroxycarboxylic acid as a ligand,
If the complex or complex salt coordinating the aromatic diol or aromatic polycarboxylic acid and the cyclodextrin compound are simultaneously present in the toner particles, they can be uniformly dispersed without depending on the toner particle size.

[0035]

Embedded image

In the formulas (4), (5) and (6), R
Is hydrogen, alkyl, aryl, aralkyl, cycloalkyl, alkenyl, alkoxy, aryloxy, hydroxyl, acyloxy, alkoxycarbonyl, acyl, carboxyl, halogen, nitro, amino, A carbamoyl group, which may be mutually connected to form an aliphatic ring, an aromatic ring, or a heterocyclic ring; in this case, the ring may have a substituent R, and the substituents R are the same; And z represents an integer of 1 to 4, n represents 2, 3 or 4, m represents 0, 2 or 4, and an aromatic compound serving as a ligand in each complex or salt The aromatic carboxylic acids and aromatic diols may be the same or different. Also, a mixture of complex compounds having different numbers of n and m may be used.
The substituent R is preferably an alkyl group, an alkenyl group, a carboxyl group, or a hydroxyl group from the viewpoint of improving the dispersibility of the complex or the salt in the binder resin or improving the chargeability.

The organometallic compound containing aluminum which is preferably used in the toner of the present invention can be represented by the following formula (7).

[0038]

Embedded image

The chemical structure of these compounds is FAB-
It can be confirmed by analysis means such as MS, NMR and thermobalance. Although those in which 2 to 4 water molecules are coordinated are included, the description of the water molecules is omitted here. In addition, a counter ion having a plurality of types is included, but the description is omitted here.

In the toner of the present invention, the saccharide compound may be added in an amount of 0.5 to 10 parts by weight, preferably 0.7 to 7 parts by weight, per 100 parts by weight of the binder resin.
Parts by weight, more preferably 1 to 5 parts by weight.
It is the case where it is contained by weight. If the amount of the saccharide compound is less than 0.5 parts by weight, it is difficult to control the dispersion of the magnetic substance and the charge control agent, and
If the amount exceeds 0 parts by weight, the saccharide compound is a hydrophilic compound, which may adversely affect the chargeability of the toner, which is not preferable.

When the cyclodextrin compound is contained as a saccharide compound in the toner of the present invention, the cyclodextrin compound which forms an inclusion compound and the cyclodextrin compound which does not form an inclusion compound are used together. In this case, the amount of each addition may be from 1/20 to 1/1 by weight ratio, but is preferably 1/20
15 to 1/3, more preferably 1/3.
This is the case where it becomes 10 to 1/5. If the weight ratio is 1 /
When the ratio is less than 20, it is difficult to maintain a good dispersion state of the magnetic substance or the charge control agent, and when the ratio exceeds 1/1, the saccharide compound is a hydrophilic compound. Therefore, there is a possibility that the chargeability of the toner may be adversely affected, which is not preferable.

In the toner of the present invention, the hybrid resin composition having a vinyl polymer unit and a polyester unit contained in the binder resin is a vinyl resin obtained by addition polymerization of an aromatic vinyl monomer and a (meth) acrylate monomer. A polymer unit and a polyester unit are chemically bonded. The polyester unit contains an alcohol component and / or a carboxylic acid having an effect of controlling the dispersion of the wax.

The hybrid resin composition is produced by a transesterification reaction between an alcohol which is a polyester monomer and a (meth) acrylate. In the above hybrid resin composition, it is sufficient that 10 to 60 mol% of the (meth) acrylic acid ester constituting the vinyl polymer unit has undergone an esterification reaction with the polyester unit, but preferably 15 to 50 mol%. Reacting, more preferably 20 to 45 mol%
This is the case where an esterification reaction is occurring. If less than 10 mol% of the (meth) acrylic acid ester constituting the vinyl polymer unit undergoes an esterification reaction with the polyester unit, it is difficult to control the dispersion state of the wax, and it is difficult to control the dispersion of the wax. %, The component having a relatively large molecular weight increases, which may deteriorate the low-temperature fixability of the toner.

The binder resin of the toner particles of the present invention has an acid value of 5 to 40 mgKOH / g, preferably 10 to 35 mgKOH / g, in order to achieve a good dispersion state of the saccharide compound and the wax. Having an acid value, more preferably 15 to 30 mgK
It is a case where it has an OH / g acid value. If the acid value is 5m
If it is less than gKOH / g, it is difficult to maintain a good dispersion of the saccharide compound,
If it exceeds OH / g, there is no problem in the dispersion of the saccharide compound, but it is not preferable because it may adversely affect the dispersion of the wax.

When the toner of the present invention contains an organometallic compound represented by the formulas (4) to (6) as a charge control agent, it contains 0.5 to 10 parts by weight based on 100 parts by weight of the binder resin. The amount is preferably 0.7 to 7 parts by weight, more preferably 1 to 5 parts by weight. If the content is less than 0.5 part by weight, the chargeability of the toner is insufficient, and if the content is more than 10 parts by weight, the fog density of the image may be high. Absent.

In the toner of the present invention, the saccharide compound and the organometallic compound are in a weight ratio of 1/20 to 2/2.
1 and preferably 1/15 by weight.
To 1/1, more preferably 1/10 to 1/2 by weight. When the addition amount of the saccharide compound is less than 1/20 by weight, the dispersion state of the charge control agent may be adversely affected, and when it exceeds 2/1, the charge imparting power of the charge control agent is adversely affected. And either case is not preferable.

In the toner of the present invention, the THF-insoluble content contained in the binder resin not only imparts hot offset resistance to the toner, but also the melt viscosity of the binder resin in the kneading step at the time of toner production is determined by the dispersion of wax. It is also important for controlling the content, and it is sufficient that the content is 15 to 50% by weight.
The content is preferably 17 to 45% by weight, more preferably 20 to 40% by weight.
If the content is less than 15% by weight, not only the hot offset resistance of the toner is deteriorated, but also the melt viscosity in the kneading step becomes too low, so that the wax is re-agglomerated and the dispersion state can be controlled. If the content is more than 50% by weight, not only low-temperature offset is likely to occur, but also components having high and low melt viscosities in the kneading step are mixed, and the dispersed particle size of the wax becomes wide. The dispersion state cannot be controlled, which is not preferable.

According to a further study by the present inventors, tetrahydrofuran (THF) is a good solvent for the vinyl-based polymer unit of the binder resin contained in the toner of the present invention, but for the polyester unit. Is not always a good solvent. Quantifying a component insoluble in THF means quantifying a hybrid resin component having a relatively large content of a polyester unit, and can evaluate low-temperature fixability of the toner. Further, in order to achieve better low-temperature fixability, it is important that the component soluble in THF has a specific molecular weight and a specific molecular weight component.

Ethyl acetate is a good solvent for the polyester unit of the binder resin contained in the toner of the present invention, but is not necessarily a good solvent for the vinyl polymer unit. Quantifying the component insoluble in ethyl acetate means quantifying the hybrid resin component having a relatively high content of the vinyl polymer unit. And insoluble components. It is possible to evaluate not only the fixability of the toner but also the dispersion state of the wax which has a significant effect on imparting stable developability (for example, image density, fog and other environmental dependencies) to the toner.

On the other hand, chloroform is a good solvent for both the vinyl polymer unit and the polyester unit of the binder resin contained in the toner of the present invention. Determining the component that is insoluble in chloroform means determining the hybrid resin component having a very high molecular weight or the most highly crosslinked hybrid resin component. Such quantitative determination of the hybrid resin component is closely related to the high temperature offset occurrence temperature of the toner, and furthermore, the phenomenon that the toner is not cleaned by a fusion member in which the toner is fixed on the photoreceptor or a cleaning member such as a blade or the like. This is related to the occurrence of image defects.

Accordingly, the ratio of the ethyl acetate-insoluble component to the chloroform-insoluble component contained in the binder resin of the toner not only indicates the balance between wax dispersion and high-temperature offset resistance, but also causes image defects in the toner. It is an index for showing stable developability without any problem.

The content of ethyl acetate-insoluble matter (W4) may be 2 to 60% by weight, preferably 5 to 50% by weight, more preferably 10 to 40% by weight. . If the content is less than 2% by weight, a problem occurs in the hot offset resistance of the toner,
It is difficult to control the dispersion state of the wax contained in the toner, and the image density may decrease due to durability, which is not preferable. On the other hand, if the content exceeds 60% by weight, a problem occurs in the low-temperature fixing property of the toner, and the fog density may increase due to durability, which is not preferable.

The chloroform-insoluble content (W6) is 10 to 4
The content may be 5% by weight, preferably 15 to 40% by weight, more preferably 17 to 37% by weight.
% By weight. If the amount is less than 10% by weight, not only a problem occurs in the hot offset resistance, but also a phenomenon in which the toner is fused on the photoreceptor due to durability may occur, which is not preferable. In addition, 45% by weight
If the value is too high, not only does the toner have a problem of low-temperature fixability, but also the toner on the photosensitive member is hardly cleaned due to durability, which is not preferable.

The value of the ratio (W4 / W6) is 1.1 to 4.0.
However, it is preferably 1.2 to 3.5, and more preferably 1.3 to 3.0. If the value is less than 1.1 or more than 4.0, the image density is reduced due to durability.

In the chromatogram of the THF-soluble component measured by gel permeation chromatography (GPC), the main peak was found to have a molecular weight of 4000-9.
000, but preferably has a molecular weight of 50
The molecular weight ranges from 00 to 8500, and more preferably the molecular weight ranges from 4500 to 8000.
If the main peak has a molecular weight of less than 4000, the hot offset resistance of the toner may deteriorate, and if the main peak exceeds 9000, the low-temperature fixability of the toner may be impaired. Absent.

The component (A1) in the region having a molecular weight of 500 to less than 10,000 may be contained at 35.0 to 65.0%, preferably 37.0 to 60.0%, more preferably. Is 40.0 to 55.0%. If it is less than 35.0%, the low-temperature fixability of the toner may be deteriorated, and if it exceeds 65.0%, the storage stability of the toner may be deteriorated, which is not preferable.

Component (A2) having a molecular weight of 10,000 to less than 100,000
May be contained at 25.0 to 45.0%, preferably at 27.0 to 42.0%, and more preferably at 30.0 to 40.0%. If it is less than 25.0%, the hot offset resistance of the toner may deteriorate, and if it exceeds 45.0%, the low-temperature fixability of the toner may deteriorate, which is not preferable.

The component (A3) having a molecular weight of 100,000 or more comprises:
The content may be 0 to 30.0%, preferably 1%.
The case is 2.0 to 25.0%, and the more preferable case is 15.0 to 22.0%. If 1
If it is less than 0.0%, the hot offset resistance of the toner may be deteriorated, and if it is more than 30.0%, the low-temperature fixability of the toner may be undesirably deteriorated.

The value of the ratio (A1 / A2) is from 1.05 to 2.
00, but preferably 1.10 to 1.90.
And more preferably 1.15 to 1.8.
This is the case when it becomes 0. If it is less than 1.05, the low-temperature fixability of the toner may be deteriorated.
If the ratio is too large, the hot offset resistance of the toner may deteriorate, which is not preferable.

The wax contained in the toner of the present invention is
Mp measured by GPC is 300-5000, ratio (M
(w / Mn) may be 1.2 to 15, preferably 350 to 4500, and the ratio (Mw / Mn) is 1.3 to 10, more preferably 400 to 40.
00, where the ratio (Mw / Mn) is between 1.4 and 8. If Mp is less than 500 and the ratio (Mw / Mn) is 1.
If it is less than 2, the dispersed particle size of the wax in the toner particles becomes too small, the Mp exceeds 5,000, and the ratio (Mw
When (/ Mn) is more than 15, the dispersed particle size becomes too large, and in either case, it is difficult to control the dispersed particle size of the wax, which is not preferable.

The toner of the present invention may contain two or more different waxes, in which case the GPC
Mp measured at 300 to 5000, ratio (Mw / M
n) may be 1.2 to 15, but preferably 35.
0 to 4500, and the ratio (Mw / Mn) is 1.5 to 12, more preferably 400 to 4000,
This is the case where the ratio (Mw / Mn) is 2 to 10. If Mp is less than 300 and the ratio (Mw / Mn) is less than 1.2, Mp is more than 5000 and the ratio (Mw / Mn) is 1
In both cases, when the value exceeds 5, the particle size distribution of the wax in the toner particles is widened, and it is difficult to control, which is not preferable.

The wax contained in the toner of the present invention is
They are selected from hydrocarbon waxes, polyethylene waxes and polypropylene waxes.

The wax contained in the toner of the present invention is:
A wax such as a synthetic hydrocarbon obtained from the distillation residue of a hydrocarbon obtained by the Age method consisting of carbon monoxide and hydrogen or by hydrogenating them is preferred. Further, those obtained by performing separation of hydrocarbon wax by use of a press sweating method, a solvent method, vacuum distillation, or a separation crystallization method are more preferably used.

The wax contained in the toner of the present invention is:
It has a structure represented by the formula (3).

[0065]

Embedded image In the formula, A represents a hydroxyl group or a carboxyl group, and a represents 3
It represents an integer of 5 to 150, preferably A represents a hydroxyl group and a represents an integer of 40 to 120.

The wax contained in the toner of the present invention is
In the case of acid-modified polyethylene, 1 to 20 mgK
It has an acid value of OH / g and is obtained by modifying polyethylene with an acid monomer selected from at least one of maleic acid, maleic acid half ester, and maleic anhydride, preferably from 1.5 to 15mgK
It has an acid value of OH / g.

The wax contained in the toner of the present invention is:
1-20 mg when acid-modified polypropylene
Having an acid value of KOH / g and polyethylene as maleic acid,
It is modified with an acid monomer selected from at least one of maleic acid half ester and maleic anhydride, preferably 1.5 to 15 mg
It has KOH / g.

When two kinds of wax are contained in the toner of the present invention, it is preferable that at least one kind of wax uses the above-mentioned wax.

Preferred combinations of waxes when the toner of the present invention contains two types of waxes are shown in Table 1 below.

[0070]

[Table 1]

The wax contained in the toner of the present invention is
Differential scanning calorimeter (DSC) for toner containing wax
In the DSC curve measured at
° C, preferably has an endothermic main peak in the temperature range of 75 to 135 ° C, more preferably 80 to 13 ° C.
It has an endothermic main peak in the region of 0 ° C. and has an endothermic sub-peak or endothermic shoulder at the same time. If there is an endothermic main peak outside the above temperature range, it is difficult to satisfy all of the low-temperature fixing property, hot offset resistance and blocking resistance.

In the toner of the present invention, the carboxylic acid and alcohol constituting the polyester unit are preferably divalent carboxylic acids represented by the formulas (8) to (11):
A monovalent carboxylic acid represented by the formula (12) or a formula (13)
At least one of the monohydric alcohols represented by

[0073]

Embedded image [In the formula, R ₁ represents a linear, branched or cyclic alkyl group or alkenyl group having 14 or more carbon atoms. R ₃ and R ₄ represent a hydrogen atom, a linear, branched or cyclic alkyl group or alkenyl group having 3 or more carbon atoms, and may be the same substituent, but are not hydrogen atoms at the same time. R ₅ and R ₆ represent a hydrogen atom, a linear, branched or cyclic alkyl group or alkenyl group having 3 or more carbon atoms, and may be the same substituent, but are not hydrogen atoms at the same time. R ₇ and R _{8 each} represent a linear, branched or cyclic alkyl group having 12 or more carbon atoms;
Represents an alkenyl group. n represents an integer of 12 to 40. ]

As the compound represented by the formula (8), for example,

[0075]

Embedded image And the like.

As the compound represented by the formula (9), for example,

[0077]

Embedded image And the like.

As the compound represented by the formula (10), for example,

[0079]

Embedded image

As the compound represented by the formula (11), for example,

[0081]

Embedded image

As the compound represented by the formula (12), for example,

[0083]

Embedded image And the like.

As the compound represented by the formula (13), for example,

[0085]

Embedded image And the like.

The monomers of the polyester unit used in the present invention include the following.

As the alcohol component, 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 (14-
1) a bisphenol derivative represented by the formula:

[0088]

Embedded image

Diols represented by the formula (14-2);

[0090]

Embedded image And the like.

Examples of the acidic component include benzenedicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid and anhydrides thereof; alkyl dicarboxylic acids such as succinic acid, adipic acid, sebacic acid and azelaic acid and anhydrides thereof; Succinic acid or its anhydride substituted with an alkyl group of Formulas 6 to 12; fumaric acid, maleic acid, citraconic acid, or dicarboxylic acids such as anhydride, fumaric acid, maleic acid, and maleic anhydride.

[0092] Examples of the vinyl-based monomer for producing the vinyl-based polymer unit include the following.

Styrene; o-methylstyrene, m-methylstyrene, p-methylstyrene, p-phenylstyrene, p-ethylstyrene, 2,4-dimethylstyrene,
p-n-butylstyrene, p-tert-butylstyrene, p-n-hexylstyrene, p-n-octylstyrene, p-n-nonylstyrene, p-n-decylstyrene, p-n-dodecylstyrene, p -Methoxystyrene, p-chlorostyrene, 3,4-dichlorostyrene,
styrene and its derivatives such as m-nitrostyrene, o-nitrostyrene and p-nitrostyrene; styrene unsaturated monoolefins such as ethylene, propylene, butylene and isobutylene; unsaturated polyenes such as butadiene and isoprene; vinyl chloride; Vinyl halides such as vinyldene chloride, vinyl bromide and vinyl fluoride; vinyl esters such as vinyl acetate, vinyl propionate and vinyl benzoate; methyl methacrylate, ethyl methacrylate, propyl methacrylate, and n-butyl methacrylate , Isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate Α-methylene aliphatic monocarboxylic acid esters such as methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate Acrylates such as stearyl acrylate, 2-chloroethyl acrylate and phenyl acrylate; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl isobutyl ether; vinyl methyl ketone, vinyl hexyl ketone and methyl isopropenyl ketone Vinyl ketones such as N-vinyl pyrrole, N-vinyl carbazole, N-vinyl indole, N-vinyl compounds such as N-vinyl pyrrolidone; vinyl naphthalenes; acrylonitrile, methacrylonitrile And acrylic acid or methacrylic acid derivatives such as acrylamide.

Further, unsaturated dibasic acids such as maleic acid, citraconic acid, itaconic acid, alkenyl succinic acid, fumaric acid and mesaconic acid; maleic anhydride, citraconic anhydride, itaconic anhydride, alkenyl succinic 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; Le acid, methacrylic acid, crotonic acid,
Α, β-unsaturated acids such as cinnamic acid; crotonic anhydride,
Α, β-unsaturated acid anhydrides such as cinnamic anhydride;
anhydrides of β-unsaturated acids and lower fatty acids; alkenyl malonic acid, alkenyl glutaric acid, alkenyl adipic acid,
Examples thereof include monomers having a carboxyl group such as acid anhydrides and monoesters thereof.

Further, 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 hydroxy group such as (hydroxy-1-methylhexyl) styrene are exemplified.

In the toner of the present invention, the vinyl polymer unit of the binder resin may have a cross-linked structure cross-linked by a cross-linking agent having two or more vinyl groups. Examples of the agent include aromatic divinyl compounds such as divinylbenzene and divinylnaphthalene; and diacrylate compounds linked by an alkyl chain such as ethylene glycol diacrylate and 1,1.
3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6 hexanediol diacrylate, neopentyl glycol diacrylate and acrylates of the above compounds replaced with methacrylate Examples of diacrylate compounds linked by an alkyl chain containing an ether bond include, for example, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 400 diacrylate,
Polyethylene glycol # 600 diacrylate, dipropylene glycol diacrylate and those obtained by replacing acrylates of the above compounds with methacrylates; for example, polyacrylates such as polyacrylates linked by a chain containing an aromatic group and an ether bond Oxyethylene (2) -2,2-bis (4-hydroxyphenyl) propane diacrylate, polyoxyethylene (4) -2,
2-bis (4-hydroxyphenyl) propane diacrylate and those obtained by replacing the acrylate of the above compound with methacrylate; polyester-type diacrylates include, for example, MANDA (Nippon Kayaku).

As the polyfunctional cross-linking agent, pentaerythritol triacrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, tetramethylolmethanetetraacrylate, oligoester acrylate and those obtained by replacing the acrylate of the above compound with methacrylate; Triallyl cyanurate and triallyl trimellitate;

[0098] These cross-linking agents may be used in combination with other monomer components 10
0.01 to 10 parts by weight (more preferably 0.03 to 5 parts by weight) can be used with respect to 0 parts by weight.

Among these crosslinkable monomers, those which are preferably used from the viewpoint of fixing property and offset resistance to the resin for toner include an aromatic divinyl compound (particularly divinylbenzene), an aromatic group and one ether bond. And diacrylate compounds linked by a chain.

In the present invention, it is preferable that the vinyl copolymer component and / or the polyester resin component contain a monomer component capable of reacting with both resin components. Among the monomers constituting the polyester resin component, those that can react with the vinyl copolymer include, for example, phthalic acid, maleic acid,
Unsaturated dicarboxylic acids such as citraconic acid and itaconic acid and anhydrides thereof; Examples of the monomer constituting the vinyl copolymer component include those having a carboxyl group or a hydroxy group, and acrylic acid or methacrylic acid esters.

Examples of the polymerization initiator used for producing the vinyl copolymer of the present invention include, for example, 2,2′-
Azobisisobutyronitrile, 2,2′-azobis (4
-Methoxy-2,4-dimethylvaleronitrile), 2,
2′-azobis (-2,4-dimethylvaleronitrile), 2,2′-azobis (-2methylbutyronitrile), dimethyl-2,2′-azobisisobutyrate,
1,1′-azobis (1-cyclohexanecarbonitrile), 2- (carbamoylazo) -isobutyronitrile, 2,2′-azobis (2,4,4-trimethylpentane), 2-phenylazo-2,4- Dimethyl-4-methoxyvaleronitrile, 2,2′-azobis (2-methyl-propane), methyl ethyl ketone peroxide,
Ketone peroxides such as acetylacetone peroxide and cyclohexanone peroxide;
Bis (t-butylperoxy) butane, t-butyl hydroperoxide, cumene hydroperoxide,
1,1,3,3-tetramethylbutyl hydroperoxide, di-t-butyl peroxide, t-butylcumyl peroxide, di-cumyl peroxide, α,
α'-bis (t-butylperoxyisopropyl) benzene, isobutyl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, benzoyl peroxide, m- Trioil peroxide, di-isopropylperoxydicarbonate, di-2-ethylhexylperoxydicarbonate, di-n-propylperoxydicarbonate,
Di-2-ethoxyethyl peroxycarbonate, di-
Methoxyisopropyl peroxydicarbonate, di (3-methyl-3-methoxybutyl) peroxycarbonate, acetylcyclohexylsulfonyl peroxide, t-butylperoxyacetate, t-butylperoxyisobutyrate, t-butylperoxyneo Decanoate, t-butylperoxy 2-ethylhexanoate, t-butylperoxylaurate, t-butylperoxybenzoate, t-butylperoxyisopropyl carbonate, di-t-butylperoxyisophthalate, t-butyl peroxyallyl carbonate,
t-amyl peroxy 2-ethylhexanoate, di-
t-butyl peroxyhexahydroterephthalate,
Di-t-butyl peroxyazelate and the like.

In the toner of the present invention, a charge control agent may be used as needed in order to further stabilize the chargeability. The charge control agent is 0.1 to 100 parts by weight of the binder resin.
It is preferred to use 10 parts by weight, preferably 0.2 to 5 parts by weight.

Examples of the charge control agent include the following.

For example, an organic metal complex, a chelate compound, and an organic metal salt can be used. Specific examples include a monoazo metal complex; a metal complex or a metal salt of an aromatic hydroxycarboxylic acid or an aromatic dicarboxylic acid compound. Other examples include aromatic hydroxycarboxylic acids, aromatic mono- and polycarboxylic acids and their anhydrides and esters, and phenol derivatives of bisphenol.

When the toner of the present invention is used as a magnetic toner, the magnetic materials contained in the magnetic toner include 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,
Pb, 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.

Specifically, examples of the magnetic material include iron trioxide (Fe ₃ O ₄ ), iron sesquioxide (γ-Fe ₂ O ₃ ), zinc iron oxide (ZnFe ₂ O ₄ ), yttrium iron oxide ( Y ₃ Fe ₅
O ₁₂ ), iron cadmium oxide (CdFe ₂ O ₄ ), iron gadolinium oxide (Gd ₃ Fe ₅ —O ₁₂ ), iron oxide copper (CuFe)
₂ O ₄ ), lead iron oxide (PbFe ₁₂ —O ₁₉ ), nickel iron oxide (NiFe ₂ O ₄ ), and neodymium iron oxide (NdFe
₂ O ₃ ), barium iron oxide (BaFe ₁₂ O ₁₉ ), iron magnesium oxide (MgFe ₂ O ₄ ), iron manganese oxide (MnF
e ₂ O ₄ ), iron lanthanum oxide (LaFeO ₃ ), iron powder (F
e), cobalt powder (Co), nickel powder (Ni) and the like. The above-mentioned magnetic materials are used alone or in combination of two or more. Particularly preferred magnetic materials are fine powders of triiron tetroxide or gamma-iron sesquioxide.

These ferromagnetic materials have an average particle size of 0.1 to 2
μm (more preferably 0.1 to 0.5 μm) and 10K
The magnetic properties upon application of the Oersted are coercive force of 20 to 150 Oersted, saturation magnetization of 50 to 200 emu / g (preferably 50 to 100 emu / g), and residual magnetization of 2 to 20 em.
u / g is preferred.

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.

In addition to the magnetic material, carbon black, titanium white, and other pigments and / or dyes can be used as the coloring agent. For example, when using the toner of the present invention as a magnetic color toner, as the dye,
C. I. Direct Red 1, C.I. 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. 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. Pigments include mineral fast yellow, navel yellow, naphthol yellow S, Hanza yellow G, permanent yellow NCG, tartrazine lake, 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, Cobalt Blue, Alkaline Blue Lake, Victoria Blue Lake, Phthalocyanine Blue, First Sky Blue, Indanthrene Blue BC, Pigment Green B, Malachite Green Lake, Final Yellow Green G and the like.

When the toner of the present invention is used as a two-component full-color toner, the following colorants may be used. Examples of the magenta coloring pigment include C.I.
I. Pigment Red 1, 2, 3, 4, 5, 6, 7,
8, 9, 10, 11, 12, 13, 14, 15, 16,
17, 18, 19, 21, 22, 23, 30, 31, 3
2,37,38,39,40,41,48,49,5
0, 51, 52, 53, 54, 55, 57, 58, 6
0, 63, 64, 68, 81, 83, 87, 88, 8
9, 90, 112, 114, 122, 123, 163,
202, 206, 207, 209, C.I. I. Pigment Violet 19, C.I. I. Butt Red 1,2,1
0, 13, 15, 23, 29, 35 and the like.

Although the above pigments may be used alone,
It is more preferable to improve the sharpness by using a dye and a pigment in combination from the viewpoint of the image quality of a full-color image. Magenta dyes include C.I. I. Solvent Red 1,3,8,2
3,24,25,27,30,49,81,82,8
3,84,100,109,121, C.I. I. Disperse Red 9, C.I. I. Solvent Violet 8,1
3, 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, 36, 3
7, 38, 39, 40, C.I. I. Basic violet 1,3,7,10,14,15,21,25,26,
And basic dyes such as 27 and 28.

Examples of the coloring pigment for cyan include 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 the following formula.

[0113]

Embedded image

Examples of the coloring pigment 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 nonmagnetic colorant used is 100
0.1 to 60 parts by weight, preferably 0.5 part by weight,
５０50 parts by weight.

A fluidity improver may be added to the toner of the present invention. The fluidity improver can be added to the toner to increase the fluidity before and after the addition. For example, fluororesin powders such as vinylidene fluoride fine powder and polytetrafluoroethylene fine powder; fine powder silica such as wet-process silica and dry-process silica, fine powder titanium oxide, fine powder alumina, a silane coupling agent thereof, There are treated silica, treated titanium oxide, and treated alumina that have been surface-treated with a titanium coupling agent and silicone oil.

Preferred fluidity improvers are fine powders produced by vapor phase oxidation of silicon halides, and are so-called dry silica or fumed silica. 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 + 4HCl

In this manufacturing process, it is 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 the silicon halide. They are also included. The particle size is preferably in the range of 0.001 to 2 μm as an average primary particle size, and particularly preferably, fine silica powder in the range of 0.002 to 0.2 μm is used. .

Examples of commercially available fine silica powder produced by vapor phase oxidation of a silicon halide compound include, for example, those commercially available under the following trade names.

AEROSIL (Aerosil Japan) 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 WAC -CHEMIE GMBH) N20E T30 T40 DC Fine Silica (Dow Corning Co.) Fransol (Fransil)

Further, a treated silica fine powder obtained by subjecting a silica fine powder produced by gas phase oxidation of the silicon halide compound to a hydrophobic treatment is more preferable. 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 hydrophobicity is given by chemically treating with an organic silicon compound or the like which reacts with or physically adsorbs silica fine 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 the organosilicon compound include hexamethyldisilazane, trimethylsilane, trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, allylphenyldichlorosilane, benzyldimethylchlorosilane, Bromomethyldimethylchlorosilane,
α-chloroethyltrichlorosilane, ρ-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane, triorganosilylmercaptan, trimethylsilylmercaptan, triorganosilyl acrylate, vinyldimethylacetoxysilane, dimethylethoxysilane, dimethyldimethoxysilane, diphenyldiethoxysilane , Hexamethyldisiloxane, 1,3-divinyltetramethyldisiloxane, 1,3-diphenyltetramethyldisiloxane and 2 to 12 siloxane units per molecule, each having one to each of the terminal units. Examples include dimethylpolysiloxane containing a hydroxyl group bonded to Si. Further, a silicone oil such as dimethyl silicone oil may be used. These are used alone or as a mixture of two or more.

The fluidity improver has a specific surface area by nitrogen adsorption measured by the BET method of 30 m ² / g or more, preferably 5 m ² / g or more.
Those with 0 m ² / g or more give good results. Toner 1
0.01 to 8 parts by weight of the fluidity improver based on 00 parts by weight,
Preferably, 0.1 to 4 parts by weight is used.

To prepare the toner 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, and are melted, kneaded and kneaded using a hot kneader such as a kneader or an extruder. Then, the resins are mutually dissolved, and the melt-kneaded product is cooled and solidified, and then the solidified product is pulverized, and the pulverized product is classified to obtain the toner of the present invention.

The toner of the present invention preferably has a weight average particle size of 3 to 9 μm (more preferably, 3 to 8 μm) in terms of resolution and image density, and even a small particle size toner is good. And heat and pressure.

Further, in the present invention, when the volume average particle diameter (D _V ) of the toner is 2.5 μm or more, a decrease in image density hardly occurs, and a sufficient image density is obtained.
When the particle size is 0 μm or less, the volume average particle diameter (D _V ) of the toner is preferably 2.5 to 6.0 μm since the gradation of a halftone image is particularly improved.

Further, the fluidity improver and the toner are sufficiently mixed by a mixer such as a Henschel mixer to obtain a toner having a fluidity improver on the surface of toner particles.

The methods for quantifying the solvent-soluble components of the toner of the present invention and measuring other physical properties are described below.

(1) Tetrahydrofuran (TH) of toner
F) Determination of Insoluble Components in Ethyl Acetate and Chloroform 2 g of the toner is precisely weighed (TW1), placed in a cylindrical filter paper (for example, No. 86R manufactured by Toyo Roshi Kaisha, Ltd.), and subjected to a Soxhlet extractor. Reflux for 10 hours using an oil bath adjusted to about 120 ° C. TH
The component (W1) soluble in F can be quantified by concentrating and drying the THF, followed by vacuum drying at 60 ° C. for 24 hours.
When the THF-insoluble component (W2) of the toner is determined, the THF-insoluble component (T2) other than the binder resin such as a colorant (magnetic substance) is used.
W2) is calculated from the following equation.

[0132]

(Equation 1)

Similarly, by changing the solvent to ethyl acetate and chloroform, the soluble component and the insoluble component of the binder resin for each solvent can be determined.

FIG. 11 shows an example of the Soxhlet extraction apparatus.

The THF 52 contained in the container 51 is heated and vaporized by the heater 53, and the vaporized THF is led to the cooler 55 through the pipe 54. The cooler 55 includes a cooling water 56
It is always cooled. The THF cooled and liquefied by the cooler 55 accumulates in the storage section 58 having the cylindrical filter paper 57, and when the liquid level of THF becomes higher than the middle pipe 59, the THF is discharged from the storage section to the container 51. The toner or resin contained in the cylindrical filter paper 57 is subjected to extraction processing by circulating THF.

(2) Quantification of polyester resin in ethyl acetate-insoluble and soluble components by ¹ H-NMR and ¹³ C-NMR measurements The presence of each monomer composition was determined by ¹ H-NMR and ¹³ C-NMR. The ratio is determined in terms of molar ratio, and the molecular weight of each monomer is used from the ratio of each monomer composition in this molar ratio, and the content of the polyester resin component is calculated in terms of% by weight, ignoring the dehydration amount accompanying transesterification.

(Measurement of ¹ H-NMR (Nuclear Magnetic Resonance) Spectrum) Measuring apparatus: FT NMR apparatus JNM-EX400
(Manufactured by JEOL Ltd.) Measurement frequency: 400 MHz Pulse condition: 5.0 μs Data point: 32768 Frequency range: 10500 Hz Integration frequency: 10000 times Measurement temperature: 60 ° C. Sample: 50 mg of a measurement sample is placed in a φ5 mm sample tube, and CDCl is used as a solvent. Add ₃ and dissolve it in a 60 ° C. thermostat to prepare.

(Measurement of ¹³ C-NMR (Nuclear Magnetic Resonance) Spectrum) Measuring apparatus: FT NMR apparatus JNM-EX400
(Manufactured by JEOL Ltd.) Measurement frequency: 400 MHz Pulse condition: 5.0 μs Data point: 32768 Delay time: 25 sec. Frequency range: 10500 Hz Number of times of integration: 16 Measurement temperature: 40 ° C. Sample: 200 mg of a measurement sample is placed in a φ5 mm sample tube, and CDCl ₃ (TMS0.0
5%) and dissolved in a 40 ° C. thermostat to prepare.

One specific example of the determination of the content of the polyester resin in the components insoluble and soluble in ethyl acetate by ¹ H-NMR and ¹³ C-NMR measurements is shown in FIGS.
Is described below using

Alcohol component by ¹ H-NMR measurement
(See FIGS. 4 and 5) The proportions of propoxylated bisphenol A (PO-BPA) and ethoxylated bisphenol A (EO-BPA) were 5.2 ppm in the ¹ H-NMR spectrum,
The signal of hydrogen of the propoxy group at around 5.3 ppm and 5.4 ppm (corresponding to each 1H: see FIG. 6) and 4.3 ppm
And an intensity ratio of the ethoxy group to a signal of hydrogen (corresponding to 4H each) near 4.65 ppm.

Aromatic carboxyl by ¹ H-NMR measurement
Determination of the abundance ratio of the acid component (see FIGS. 4 and 5) The abundance ratio of terephthalic acid and trimellitic acid is ¹ H-
A signal of hydrogen (corresponding to 4H) of terephthalic acid at around 8 ppm in the NMR spectrum and 7.6 ppm of 7.8 p
It is determined from the intensity ratio of pm and the signal of hydrogen (corresponding to 1H each) of trimellitic acid around 8.4 ppm.

Existence ratio of styrene by ¹ H NMR measurement
Determination of ratio (see FIGS. 4 and 5) The abundance ratio of styrene is determined from the intensity ratio of the signal of hydrogen (corresponding to 1H) near 6.6 ppm in the ¹ H-NMR spectrum.

Aliphatic Carboxyl by ¹³ C-NMR Measurement
Acid, (meth) acrylate and PO-BPA, E
O-BPA (meth) acrylate compound (vinyl
Product of the reaction between a polyester polymer and a polyester resin)
Determination of the ratio (see FIG. 1) The existence ratio of the reaction product between the aliphatic carboxylic acid, the (meth) acrylic acid ester and the vinyl polymer and the polyester resin is 173.5 p in the ¹³ C-NMR spectrum.
pm and the signal of carbon (corresponding to 1C each) of the carboxyl group of the aliphatic carboxylic acid at around 174 ppm and 176 pp
The signal and intensity of the carbon (1C equivalent) of the carboxyl group of the (meth) acrylate ester near m and the newly detected peak near 169 ppm of the carbon (1C equivalent) of the carboxyl group of the (meth) acrylate ester Determined from the ratio.

Aliphatic Carboxyl by ¹³ C-NMR Measurement
Determination of the existence ratio of acid and an aromatic carboxylic acid (see FIG. 1) existence ratio of aliphatic carboxylic acids and aromatic carboxylic acids, ¹³
From the comparison of the intensity ratio of the signal of the carboxyl group carbon (corresponding to 1C) of terephthalic acid and trimellitic acid around 165 ppm in the C-NMR spectrum and the signal of the carboxyl group carbon of the aliphatic carboxylic acid (each 1C equivalent). Ask.

Existence of styrene by ¹³ C-NMR measurement
Determination of Ratio (See FIG. 1) The abundance ratio of styrene is determined from the intensity ratio of the signal of para-position carbon (corresponding to 1C) near 125 ppm in the ¹³ C-NMR spectrum.

In the components insoluble in ethyl acetate and the soluble components
Determination of Content of Polyester Resin Component in Minutes From the above ¹ H-NMR spectra, PO-B
Calculate the molar ratio of each monomer composition of PA, EO-BPA, terephthalic acid, trimellitic acid, and styrene. Further, from the above-mentioned ¹³ C-NMR spectra, the (meth) acrylic of PO-BPA, EO-BPA By calculating the molar ratio of each monomer composition of an acid ester compound (a reaction product of a vinyl polymer and a polyester resin), an aliphatic carboxylic acid, an aromatic carboxylic acid, and styrene, the composition of all constituent monomers is determined. The ratio is calculated as a molar ratio. The content of the polyester resin component is calculated in terms of% by weight, using the molecular weight of each monomer from the monomer composition existence ratio at this molar ratio and ignoring the dehydration amount accompanying the transesterification.

(3) Measurement of melting point of wax ASTM D3418-8 using a differential scanning calorimeter (DSC measuring apparatus) and DSC-7 (manufactured by PerkinElmer).
Measure according to 2.

The measurement sample is 2 to 10 mg, preferably 5 m
Weigh g precisely.

This was put in an aluminum pan, and an empty aluminum pan was used as a reference.
The measurement is performed at a temperature rising rate of 10 ° C./min and at normal temperature and normal humidity between 0 ° C.

In this heating process, an endothermic peak of the main peak of the DSC curve in the temperature range of 30 to 200 ° C. is obtained.

The temperature of the endothermic main peak is defined as the melting point of the wax.

(4) Measurement of DSC Curve of Toner A DSC curve in the process of raising the temperature of the toner is measured in the same manner as the measurement of the melting point of the wax.

(5) Glass transition temperature (Tg) of binder resin
ASTM D3418-8 using a differential scanning calorimeter (DSC measuring device) and DSC-7 (manufactured by PerkinElmer).
Measure according to 2.

The measurement sample is 5 to 20 mg, preferably 10
Weigh the mg precisely.

This was put in an aluminum pan, and an empty aluminum pan was used as a reference.
The measurement is performed at a temperature rising rate of 10 ° C./min and at normal temperature and normal humidity between 0 ° C.

In this heating process, an endothermic peak of a main peak in a temperature range of 40 to 100 ° C. is obtained.

The intersection between the line of the midpoint of the baseline before and after the endothermic peak appears and the differential heat curve is defined as the glass transition temperature Tg in the present invention.

(6) Measurement of Molecular Weight Distribution of Wax Gel Permeation Chromatography (GPC) Measuring Device: GPC-150C (Waters) Column: GMH-HT 30 cm 2 columns (manufactured by Tosoh Corporation) Temperature: 135 ° C. Solvent: o-dichlorobenzene (0.1% ionol added) Flow rate: 1.0 ml / min Sample: 0.4 ml of 0.15% sample injected

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. In addition, Mark-Hou
It is calculated by converting to polyethylene using a conversion formula derived from the wink viscosity formula.

(7) Measurement of Molecular Weight Distribution of Binder Resin Raw Material or Binder Resin of Toner The molecular weight of a chromatogram by GPC is measured under the following conditions.

The column is stabilized in a heat chamber at 40 ° C., and tetrahydrofuran (THF) is passed through the column at this temperature as a solvent at a flow rate of 1 ml per minute.
When the sample is a binder resin material, a material obtained by passing the binder resin material through a roll mill (130 ° C., 15 minutes) is used. If the sample is a toner, dissolve the toner in THF
m, and the filtrate is used as a sample.
The measurement is performed by injecting 50 to 200 μl of a THF sample solution of a resin adjusted to a sample concentration of 0.05 to 0.6% by weight. In measuring the molecular weight of a sample, the molecular weight distribution of the sample is calculated from the relationship between the logarithmic value of a calibration curve prepared from several types of monodisperse polystyrene standard samples and the count number. As standard polystyrene samples for creating calibration curves,
For example, Pressure Chemical Co.
Or Toyo Soda Kogyo Co., Ltd. has a molecular weight of 6 × 1
0 ² , 2.1 × 10 ³ , 4 × 10 ³ , 1.75 × 1
0 ⁴ , 5.1 × 10 ⁴ , 1.1 × 10 ⁵ , 3.9 × 10
⁵ , 8.6 × 10 ⁵ , 2 × 10 ⁶ , 4.48 × 10 ⁶ , and at least about 10 standard polystyrene samples are suitable. An RI (refractive index) detector is used as the detector.

In order to accurately measure the molecular weight region of 10 ³ to 2 × 10 ^6, a plurality of commercially available polystyrene gel columns are preferably used in combination.
rs Co., Ltd. μ-styragel 500, 10 ³ , 1
0 ⁴ 10 ⁵ of combinations and, shodex of Showa Denko Co., Ltd.
KA-801, 802, 803, 804, 805, 8
06,807 are preferred.

(8) ¹³ C of the binder resin contained in the toner
-NMR measurement Measurement device: FT NMR device JNM-EX400
(Manufactured by JEOL Ltd.) Measurement frequency: 100.40 MHz Pulse condition: 5.0 μs (45 °) DEPT method Data point: 32768 Delay time: 25 sec. Number of integration: 50,000 times Measurement temperature: 26 ° C. Sample: 10 g of toner is added to 100 ml of concentrated hydrochloric acid (about 12 M) at room temperature and stirred for about 70 hours to dissolve the magnetic substance contained in the toner. Next, filtration and washing are performed until the filtrate becomes weakly acidic (about pH 5). The obtained resin composition is vacuum-dried at 60 ° C. for about 20 hours to obtain a measurement sample.
About 1 g of this measurement sample was placed in a sample tube of φ10 mm, and ₃ ml of deuterated chloroform (CDCl ₃ ) was used as a solvent.
Is added and dissolved in a 55 ° C. thermostat to adjust.

(9) Measurement of Acid Value of Toner and Ethyl Acetate-Soluble Component of Toner The measurement is carried out according to the measuring method described in JIS K0070. Measurement device: Automatic potentiometric titrator AT-400 (manufactured by Kyoto Electronics) Calibration of the device: 120 ml of toluene and 30 ml of ethanol
Is used. Measurement temperature: 25 ° C. Sample preparation: 0.5 g of toner (0.3 g for a component soluble in ethyl acetate) was added to 120 ml of toluene, and room temperature (about 2 g) was added.
(5 ° C.) for about 10 hours to dissolve. Further, 30 ml of ethanol is added to make a sample solution.

The particle size distribution of the toner of the present invention is measured using a Coulter Counter TA-II or a Coulter Multisizer (manufactured by Coulter). The electrolyte is 1
A 1% NaCl aqueous solution is prepared using graded sodium chloride. For example, ISOTON-II (manufactured by Coulter Scientific Japan) can be used. As a measurement method, 0.1 to 5 ml of a surfactant, preferably an alkylbenzene sulfonate, is added as a dispersant to 100 to 150 ml of the electrolytic aqueous solution, and a measurement sample is further added to 2-2.
Add 0 mg. The electrolytic solution in which the sample was suspended was subjected to dispersion treatment for about 1 to 3 minutes using an ultrasonic disperser, and the volume and the number of toner particles having a size of 2 μm or more were measured using the measuring device with a 100 μm aperture as the aperture. The distribution and number distribution were calculated.

Then, the weight-average particle diameter (D ₄ ) and volume-average particle diameter (D _V ) obtained from the volume distribution according to the present invention (the median value of each channel is a representative value for each channel) I asked.

Next, an example of an image forming apparatus to which the toner of the present invention can be applied will be described with reference to FIGS. The surface of the electrostatic image carrier (photoconductor) 1 is charged to a negative or positive polarity by the primary charger 2 and an electrostatic image (for example, a digital latent image by image scanning) is formed by analog exposure or exposure 5 by laser light. Then, the electrostatic charge image is reverse developed or developed by the magnetic toner 13 of the developing device 9 including the magnetic blade 11 and the developing sleeve 4 including the magnet 23 having the magnetic poles N ₁ , N ₂ , S ₁ and S _2. Develop by regular development. In the developing section, between the conductive substrate 16 of the photoreceptor 1 and the developing sleeve 4, an alternating bias, a pulse bias and / or a DC bias are applied by the bias applying means 12. The magnetic toner image is transferred to a transfer material with or without an intermediate transfer member. When the transfer paper P is conveyed and reaches the transfer section, the transfer paper P is transferred by the transfer charger 3.
The negatively charged or positively charged magnetic toner image on the photoreceptor surface is electrostatically transferred onto the transfer paper P by charging positively or negatively from the back surface of the photoreceptor (the surface opposite to the photoreceptor side). You. After the charge is removed by the charge removing means 22, the transfer paper P separated from the photoreceptor 1 is heated and pressed and fixed on the toner image on the transfer paper P by the heating and pressing roller fixing device 7 including the heater 21.

The magnetic toner remaining on the photoreceptor 1 after the transfer step is removed by a cleaning means having a cleaning blade 8. After the cleaning, the photosensitive member 1 is neutralized by the erase exposure 6, and the process starting from the charging process by the primary charger 2 is repeated again.

An electrostatic image carrier (for example, a photosensitive drum) 1 has a photosensitive layer 15 and a conductive substrate 16 and moves in the direction of the arrow. Non-magnetic cylindrical developing sleeve 4 which is developing sleeve 4
Rotates so as to advance in the same direction as the surface of the electrostatic image carrier 1 in the developing section. Inside the non-magnetic cylindrical developing sleeve 4, a multi-pole permanent magnet (magnet roll) 23 as a magnetic field generating means is arranged so as not to rotate. The magnetic toner 13 in the developing device 9 is applied to the developing sleeve 4,
In addition, triboelectric charges are given to the magnetic toner particles by friction between the surface of the developing sleeve 4 and the magnetic toner particles. Further, a magnetic doctor blade 17 made of iron is placed close to the surface of the cylindrical developing sleeve 4 (at an interval of 50 μm to 500 μm).
m), the thickness of the magnetic toner layer is reduced (from 30 μm to
The magnetic toner layer is formed to have a thickness equal to or smaller than the gap between the photoconductor 1 and the developing sleeve 4 in the developing section while being regulated uniformly. By adjusting the rotation speed of the developing sleeve 4, the surface speed of the developing sleeve can be reduced.
The speed is substantially the same as or close to the speed of the surface of the substrate. The opposed magnetic poles may be formed by using permanent magnets instead of iron as the magnetic doctor blades 17. In the developing section, an AC bias or a pulse bias may be applied to the developing sleeve 4 by the bias unit 12. This AC bias is f 200-4,000H
z, V _pp may if 500~3,000V.

At the time of transfer of the magnetic toner particles in the developing section, the magnetic toner particles move to the electrostatic image side due to the electrostatic force of the photoconductor surface and the action of an AC bias or a pulse bias.

Instead of the magnetic blade 11, an elastic blade made of an elastic material such as silicone rubber may be used to regulate the thickness of the magnetic toner layer by pressing and apply the magnetic toner on the developing sleeve.

FIG. 9 shows another example of an image forming apparatus which can carry out the image forming method of the present invention.

The surface of the photosensitive drum 101 serving as an electrostatic image holding member is negatively charged by a contact (roller) charging means 119 serving as a primary charging means.
5, a digital latent image is formed on the photosensitive drum 101. A multi-pole permanent magnet 1 having an elastic regulating blade 111 as a toner layer thickness regulating member;
The digital latent image is reversal-developed by the magnetic toner 104 in the hopper 103 by a developing device provided with a developing sleeve 108 as a toner carrier in which 05 is included. As shown in FIG.
, The conductive substrate of the photosensitive drum 101 is grounded, and an alternating bias, a pulse bias, and / or a DC bias are applied to the developing sleeve 108 by a bias applying unit 109. When the recording material P is conveyed to the transfer section, a contact (roller) transfer means 1 as a transfer means
The toner image formed on the surface of the photosensitive drum 101 is charged on the recording material P by the voltage application unit 114 from the back surface (the surface opposite to the photosensitive drum side) of the recording material P by the contact transfer unit 113. Is transferred to The recording material P separated from the photosensitive drum 101 is conveyed to a heating and pressing roller fixing device 117 as a fixing unit, and the fixing device 11
7, the fixing process of the toner image on the recording material P is performed.

The magnetic toner 104 remaining on the photosensitive drum 101 after the transfer step is removed by a cleaning means 118 having a cleaning blade 108a. If the amount of the remaining magnetic toner 104 is small, the cleaning step can be omitted. Photosensitive drum 1 after cleaning
01, if necessary, is erased by the erase exposure 116, and the above-described steps starting from the charging step by the contact (roller) charging means 119 as the primary charging means are repeated again.

In the above-described series of steps, the photosensitive drum (that is, the electrostatic latent image holder) 101 has a photosensitive layer and a conductive substrate, and moves in the direction of the arrow. The non-magnetic cylindrical developing sleeve 108 serving as a toner carrier rotates so as to advance in the same direction as the surface of the photosensitive drum 101 in the developing area D. Inside the developing sleeve 108, a multi-pole permanent magnet (magnet roll) 105 as a magnetic field generating means is arranged so as not to rotate. The magnetic toner 104 in the developer container 103 is applied and carried on the developing sleeve 108, and for example, a negative triboelectric charge is given by friction with the surface of the developing sleeve 108 and / or friction between the magnetic toners. . Further, an elasticity regulating blade 111 is provided so as to elastically press the developing sleeve 108, and the thickness of the toner layer is regulated thinly (30 to 300 μm) and uniformly, so that the photosensitive drum 101 in the developing area D is formed.
And a toner layer thinner than the gap between the toner and the developing sleeve 108. By adjusting the rotation speed of the developing sleeve 108, the surface speed of the developing sleeve 108 is made substantially equal to or close to the speed of the surface of the photosensitive drum 101. In the developing region D, an AC bias or a pulse bias may be applied to the developing sleeve 108 as a developing bias voltage by the bias applying unit 109. This AC bias is f 200 to 4,
000Hz, V _pp may if 500~3,000V. At the time of transfer of the magnetic toner in the developing region D, the magnetic toner is transferred to the electrostatic latent image side by the electrostatic force on the surface of the photosensitive drum 101 and the action of a developing bias voltage such as an AC bias or a pulse bias.

In the image forming method of the present invention, instead of the hot roll fixing device used in the fixing step, a film heat fixing device can be used as another heat fixing means. FIG. 12 is a schematic view of the film heating and fixing apparatus.

In the fixing device shown in FIG.
It has a smaller heat capacity than conventional heat rolls and has a linear heating part, and the maximum temperature of the heating part is 100 to 30
Preferably it is 0 ° C.

The film located between the heating element and the pressing member is preferably a heat-resistant sheet having a thickness of 1 to 100 μm. Examples of the heat-resistant sheet include high heat-resistant polyester, PET (polyethylene) and the like. Terephthalate), PFA (tetrafluoroethylene-perfluoroalkylvinyl ether copolymer), PTFE (polytetrafluoroethylene), polyimide, polymer sheet such as polyamide, metal sheet such as aluminum, and metal sheet and polymer sheet. A laminate sheet is used.

[0179] A more preferable structure of the film is that these heat resistant sheets have a release layer and / or a low resistance layer.

A specific example of the fixing device will be described with reference to FIG.

Reference numeral 61 denotes a low-heat-capacity linear heating element fixedly supported by the apparatus.
mm, an alumina substrate 70 having a longitudinal length of 240 mm coated with a resistance material 69 having a width of 1.0 mm, and electricity is supplied from both ends in the longitudinal direction. Energization is DC100V cycle 20msec
A pulse corresponding to the desired temperature and the amount of energy release controlled by the temperature detecting element 71 is given by changing the pulse width. Approximate pulse width is 0.5ms
ec to 5 msec. The fixing film 62 moves in the direction of the arrow in the figure by contacting the heating element 61 whose energy and temperature are controlled in this manner.

An example of the fixing film has a thickness of 20 μm.
m is a heat-resistant film (for example, polyimide, polyetherimide, PES or PFA, and at least the image contacting surface side is a fluororesin such as PTFE or PFA) coated with a release layer having a thickness of 10 μm. Generally, the layer thickness is less than 100 μm, more preferably less than 40 μm. Drive roller for film drive 6
It moves without wrinkles in the direction of the arrow due to the drive and tension by 3 and the driven roller 64.

Reference numeral 65 denotes a pressure roller having a rubber elastic layer having good releasability such as silicone rubber.
The heating element is pressurized through the film with the pressure of kg, and is rotated by pressing against the film. The unfixed toner 67 on the transfer material 66 is guided to a fixing unit by an entrance guide 68 and obtains a fixed image by the above-described heating.

The above description has been made with reference to the endless belt.
A sheet feeding shaft and a winding shaft are used, and the fixing film may be an edged film.

When the above-described image forming apparatus of the present invention is applied to a facsimile printer, the light image exposure L is an exposure for printing received data. FIG. 10 is a block diagram showing an example of this case.

The controller 131 is an image reading unit 130
And the printer 139. Controller 131
Are controlled by the CPU 137. The read data from the image reading unit is transmitted to the partner station through the transmission circuit 133. The data received from the partner station is
2 to the printer 139. Predetermined image data is stored in the image memory. The printer controller 138 controls the printer 139. 134
Is a telephone.

The image received from the line 135 (image information from a remote terminal connected via the line) is demodulated by the receiving circuit 132, and then the CPU 137 performs a decoding signal of the image information to sequentially execute the image memory 136. Is stored in When the image of at least one page is stored in the memory 136, the image of the page is recorded. CPU 137
Reads out one page of image information from the memory 136 and sends out the combined one page of image information to the printer controller 138. Printer controller 138
The printer 13 receives the image information of one page from the CPU 137 and records the image information of the page.
9 is controlled.

The CPU 137 receives the next page during recording by the printer 139.

As described above, image reception and recording are performed.

[0190]

Hereinafter, the present invention will be described with reference to Examples.
The present invention is not limited to these examples.

Examples of the production method applicable to the binder resin of the toner of the present invention include the following production methods.

(1) A method in which a vinyl polymer unit, a polyester unit, and a hybrid resin component are blended after production, respectively. The blend is dissolved in an organic solvent (for example, xylene) and swelled, and then the organic solvent is distilled off. And preferably manufactured by adding a wax in this blending step.

(2) After the production of the vinyl polymer unit,
This is a method for producing a polyester unit and a hybrid resin component in the presence of this. The hybrid resin component is produced by reacting a vinyl-based polymer unit (a vinyl-based monomer can be added if necessary) with a polyester monomer (such as an alcohol or a carboxylic acid) and / or a polyester. Also in this case, an organic solvent can be appropriately used. Preferably, a wax is added in this step.

(3) This is a method of producing a vinyl-based polymer unit and a hybrid resin component in the presence of a polyester unit after the production. The hybrid resin component is produced by reacting a polyester unit (a polyester monomer can be added if necessary) with a vinyl monomer and / or a vinyl polymer unit. Preferably, a wax is added in this step.

(4) After the production of the vinyl polymer unit and the polyester unit, a hybrid resin component is produced by adding a vinyl monomer and / or a polyester monomer (alcohol, carboxylic acid, etc.) in the presence of these polymer units. Is done. Also in this case,
Organic solvents can be used. Preferably, a wax is added in this step.

(5) After the production of the hybrid resin component, a vinyl-based monomer and / or a polyester monomer (alcohol, carboxylic acid, etc.) are added to carry out addition polymerization and polycondensation, thereby obtaining a vinyl-based polymer unit and a polyester unit. Is manufactured. In this case, as the hybrid resin component, those produced by the above-mentioned production methods (2) to (4) can be used, and if necessary, those produced by a known production method can be used. Further, an organic solvent can be appropriately used.
Preferably, a wax is added in this step.

(6) A vinyl-based polymer unit, a polyester unit and a hybrid resin component are produced by mixing a vinyl-based monomer and a polyester monomer (alcohol, carboxylic acid, etc.) and continuously performing addition polymerization and polycondensation reaction. Is done. Further, an organic solvent can be appropriately used. Preferably, a wax is added in this step.

In the production methods (1) to (5), a plurality of polymer units having different molecular weights and different degrees of crosslinking can be used as the vinyl polymer unit and / or polyester unit.

Of the above-mentioned production methods (1) to (6), the production method (3) is particularly easy to control the molecular weight of the vinyl polymer unit and can control the production of the hybrid resin component. When a wax is added, the dispersion state is preferably controlled.

Production Example I of Binder Resin: (Resin Production Example 1) Production of Low Crosslinking Resin Composition (Production of Resin Composition Containing Chloroform-Insoluble Content of Substantially 0 to 10% by Weight) Terephthalic acid: 5.0 mol-Succinic acid derivative represented by formula (5-1): 1.8 mol-Trimellitic anhydride: 1.5 mol-PO-BPA: 7.0 mol-EO-BPA: 3.0 mol

The above-mentioned polyester monomer was charged into an autoclave together with an esterification catalyst, and equipped with a decompression device, a water separation device, a nitrogen gas introduction device, a temperature measurement device and a stirrer under a nitrogen atmosphere under reduced pressure according to a conventional method.
A condensation polymerization reaction was carried out while heating to 0 ° C., to obtain a polyester resin having a low degree of crosslinking containing about 7% by weight of a chloroform-insoluble content.

Next, 80 parts by weight of the polyester resin obtained above, 16 parts by weight of styrene, 4 parts by weight of 2-ethylhexyl acrylate and 0.3 part by weight of dibutyltin oxide as an esterification catalyst were added to 50 parts by weight of xylene. And heated to 110 ° C. to dissolve and swell. Under a nitrogen atmosphere, a solution prepared by dissolving 1 part by weight of t-butyl hydroperoxide as a radical polymerization initiator in 10 parts by weight of xylene was added dropwise over about 30 minutes. The temperature was further maintained for 10 hours to complete the radical polymerization reaction. The pressure is reduced while heating and the solvent is removed to remove the solvent, thereby comprising a low-crosslinking polyester resin, a vinyl-based polymer, and a hybrid resin component having a polyester unit and a vinyl-based polymer unit. As a result, a resin composition having a low degree of cross-linking containing about 10 wt% was obtained.

Production of Resin Composition with High Crosslinking Degree (Production of Resin Composition Containing 15 to 70% by Weight of Chloroform-Insoluble Content) Terephthalic acid: 3.0 mol Succinic acid derivative represented by formula (1-3): 3. 0 mol ・ Trimellitic anhydride: 4.5 mol ・ PO-BPA: 10.0 mol ・ EO-BPA: 4.0 mol

The above-mentioned polyester monomer was charged into an autoclave together with an esterification catalyst, and equipped with a decompression device, a water separation device, a nitrogen gas introduction device, a temperature measurement device, and a stirring device under a nitrogen atmosphere while reducing the pressure according to a conventional method.
The condensation polymerization reaction was carried out while heating to 0 ° C. to obtain a polyester resin having a high degree of crosslinking containing about 28% by weight of a chloroform-insoluble content.

Next, 50 parts by weight of xylene, 80 parts by weight of the polyester resin obtained here, 10 parts by weight of styrene, 10 parts by weight of 2-ethylhexyl acrylate, 0.01 part by weight of divinylbenzene, and dibutyltin oxide as an esterification catalyst 0.3 parts by weight, 11
It was heated to 0 ° C. to dissolve and swell. Under a nitrogen atmosphere, a solution prepared by dissolving 1 part by weight of t-butyl hydroperoxide as a radical polymerization initiator in 10 parts by weight of xylene was added to about 3 parts.
It was added dropwise over 0 minutes. The temperature was further maintained for 10 hours to complete the radical polymerization reaction. By further reducing the pressure while heating and removing the solvent, the resin is composed of a polyester resin having a high degree of crosslinking, a vinyl-based polymer and a hybrid resin component having a polyester unit and a vinyl-based polymer unit. % Was obtained.

Production of Binder Resin 60 parts by weight of a resin composition having a low degree of crosslinking, 30 parts by weight of a resin composition having a high degree of crosslinking, 6 parts by weight of styrene, 4 parts by weight of 2-ethylhexyl acrylate and 0.01 part by weight of divinylbenzene were added to 100 parts by weight of xylene. The mixture was heated to 110 ° C. and swelled and dissolved. Under a nitrogen atmosphere, a solution prepared by dissolving 1 part by weight of t-butyl hydroperoxide as a radical polymerization initiator in 10 parts by weight of xylene was added dropwise over about 30 minutes. The temperature was further maintained for 10 hours to complete the radical polymerization reaction. By further reducing the pressure while heating and removing the solvent, the resin is made up of a low cross-linking degree polyester resin, a high cross-linking degree polyester resin, a vinyl polymer and a hybrid resin component having a polyester unit and a vinyl polymer unit, and chloroform. A binder resin (1) containing about 19% by weight of an insoluble content was obtained.

(Resin Production Examples 2 to 12) In the resin production example 1, 16.6 parts by weight of the wax (3) shown in Table 5 was used with respect to 80 parts by weight of the polyester resin when producing the resin composition having a high degree of crosslinking. Was added together with styrene and 2-ethylhexyl acrylate to obtain a highly crosslinked resin composition containing wax and containing 21% by weight of a chloroform-insoluble content. Except that 35 parts by weight of the high cross-linking degree resin composition (including 5 parts by weight of wax) was used, a low cross-linking degree polyester resin, a high cross-linking degree polyester resin, a vinyl polymer, a polyester unit and a vinyl A binder resin (2) comprising a hybrid resin component having a polymer unit and containing about 22% by weight of a chloroform-insoluble content was obtained.

In addition, binder resins (3) to (12) were obtained by changing the added wax.

(Resin Production Examples 13 to 16) Chloroform was prepared in the same manner as in Resin Production Example 1 except that the monomers used in the production of the resin composition having a low degree of crosslinking were changed to the following monomers. A low cross-linking degree resin composition containing about 8% by weight of an insoluble content was obtained. -Terephthalic acid: 4.0 mol-Dicarboxylic acid derivative represented by the formula (6-2): 1.0 mol-Trimellitic anhydride: 1.5 mol-PO-BPA: 7.0 mol-EO-BPA: 3.0 mol

Next, a polycondensation reaction was carried out in the same manner as in the high-crosslinking resin composition of Production Example 1 except that the following monomers were used, and a high-crosslinking resin composition containing about 29% by weight of a chloroform-insoluble content was obtained. Obtained. -Terephthalic acid: 3.0 mol-Dicarboxylic acid derivative represented by the formula (6-2): 3.5 mol-Trimellitic anhydride: 4.0 mol-PO-BPA: 8.0 mol-EO-BPA: 3.0 mol

Resin Preparation Example I- except that 60 parts by weight of the low-crosslinking resin composition and 30 parts by weight of the high-crosslinking resin composition were used.
In the same manner as in Example 1, a binder resin (13) comprising a polyester resin having a high degree of crosslinking, a polyester resin having a low degree of crosslinking, a vinyl polymer, and a hybrid resin component having a polyester unit and a vinyl polymer unit was obtained.

Hereinafter, the binder resin (14) to (1) is added by adding a wax during the production of the resin composition having a high degree of crosslinking.
6) was obtained.

(Comparative Resin Production Example 1) The comparative binder resin (1) was prepared in the same manner as in Resin Production Example 1, except that trimellitic acid was used instead of the succinic acid derivative (5-1).
I got

(Resin Comparative Production Example 2) A styrene-2-hexyl acrylate copolymer (84 parts by weight of styrene, 2 parts by weight of styrene) was placed in an autoclave equipped with a pressure reducing device, a water separator, a nitrogen gas introducing device, a temperature measuring device, and a stirring device. -16 parts by weight of ethylhexyl acrylate, Mw = 19,000, Mw
/Mn=2.3) 200 parts by weight of a polyester monomer having the following composition and a polycondensation reaction while being heated to 210 ° C. in a nitrogen atmosphere under reduced pressure in a conventional manner under a nitrogen atmosphere to obtain a comparative binder resin ( 2) was obtained. -Fumaric acid: 191 parts by weight-Trimellitic anhydride: 168 parts by weight-EO-BPA: 463 parts by weight-PO-BPA: 551 parts by weight

Example 1 100 parts by weight of a hybrid resin composition (1) of the present invention 1 part by weight of a cyclodextrin compound represented by the formula (15) (see Table 4) 1 organometallic compound represented by the formula (7) 2 parts wax (3) 7 parts by weight magnetic iron oxide 100 parts (average particle size 0.18 .mu.m, coercive force 10.7KA / m, residual magnetization 11.2Am ² / kg, the saturation magnetization 81.5Am ² / kg)

The above mixture was melt-kneaded with a twin-screw extruder heated to 130 ° C., and the cooled mixture was roughly pulverized with a hammer mill. The coarsely pulverized product was finely pulverized with a jet mill while changing the pulverization conditions to obtain three types of finely pulverized products having different volume average particle diameters. These finely pulverized products are classified by an air classifier to obtain a volume average particle size of 10.4 μm, 7.6 μm and 6.
1 μm magnetic toner was obtained. The amount of wax, magnetic substance and charge control agent is determined for each toner having a different volume average particle diameter, and the respective amounts of wax, magnetic substance and charge control agent are determined based on the toner having a volume average particle diameter of 7.6 μm. When the ratios were compared, as shown in Table 5, it was almost constant and it was confirmed that the ratio was good.

The T of the toner with respect to 100 parts by weight of the binder resin
The HF, ethyl acetate and chloroform insolubles were constant at about 23% by weight, 20% by weight and 18% by weight, respectively, in terms of the resin composition excluding the amount of the wax mixed regardless of the weight average particle diameter of the toner. Was. The acid value of the binder resin calculated by excluding the magnetic iron oxide and the wax contained in the toner was 25.9 mgKOH / g.

The presence of the hybrid resin composition contained in the binder resin of the toner was confirmed by ¹³ C-NMR measurement of the binder resin of the toner shown in FIG. 1 and Table 2, and contained in the vinyl polymer unit. It was confirmed that 29 mol% of the 2-ethylhexyl acrylate was subjected to a transesterification reaction or an esterification reaction with the polyester unit to form a hybrid resin composition. Further, other physical properties of the binder resin were as shown in Table 6.

[0219]

[Table 2]

With respect to 100 parts by weight of the magnetic toner having a volume average particle diameter of 7.6 μm, hydrophobic dry silica (BET = 2)
(00 m ² / g) 1.0 part by weight was externally added using a Henschel mixer to obtain a toner. Using this toner, a Canon digital copying machine GP-215 (process speed: 105 mm / sec, surf fixing) and a Canon copying machine N
Modifications to remove the toner cleaning member from the fixing device of P-6250 (process speed: 320 mm / sec, hot roll fixing) were added, and the image characteristics and the toner of the fixing member heating member (heat-resistant film, heating roller, pressure roller) were removed. When the state of adhesion was evaluated, good results were obtained as shown in Table 8.

Further, the fixing devices of GP-215 and NP-6250 were removed, and an external drive device and a temperature control device of the fixing device were attached. When a fixing test was performed with the fixing speed set to be the same as that of each copying machine and the fixing temperature was changed, good results were obtained as shown in Table 8.

Examples 2 to 16 Toners (2) to (16) of the present invention were obtained in the same manner as in Example 1 except that the binder resins and waxes shown in Table 7 were used. The results of analysis and evaluation in the same manner as in Example 1 are shown in Tables 7 and 8, respectively.

[Comparative Example 1] A comparative toner (1) was produced in the same manner as in Example 1 except that the comparative resin (1) was not used and the cyclodextrin compound was not used. Tables 5 to 8 show the results of analysis and evaluation.

Comparative Example 2 A comparative toner (1) was produced in the same manner as in Example 1 except that the comparative resin (1) was used. Tables 7 and 8 show the results of analysis and evaluation.

[0225]

[Table 3]

[0226]

[Table 4]

[0227]

[Table 5]

[0228]

[Table 6]

[0229]

[Table 7]

[0230]

[Table 8]

(Rank of low-temperature fixability according to GP-215) An image density of 1.3 to 1.
The image was fixed by passing a solid black image of No. 4 and then rubbing with a Dasper (manufactured by Ozu Sangyo Co., Ltd.) under a load of 50 g / cm ² to determine the density reduction rate. Rank 5: Density reduction rate due to rubbing is less than 5% Rank 4: Density reduction rate due to rubbing is less than 10% Rank 3: Density reduction rate due to rubbing is less than 15% Rank 2: Density reduction rate due to rubbing is 20 Less than% Rank 1: Density reduction rate by rubbing is 20% or more

(Rank of low-temperature fixability according to NP-6550) GP-2 except that the set temperature of the fixing unit was set to 180 ° C.
15 was performed under the same conditions as in the fixing test. Rank 5: Density reduction rate due to rubbing is less than 5% Rank 4: Density reduction rate due to rubbing is less than 10% Rank 3: Density reduction rate due to rubbing is less than 15% Rank 2: Density reduction rate due to rubbing is 20 Less than% Rank 1: Density reduction rate by rubbing is 20% or more

(Rank of Hot Offset) Rank 5: Not generated at all Rank 4: Slight offset generated, but practically acceptable Rank 3: Offset generated easily discriminated visually Rank 2: Notable offset generated Rank 1: Paper wraps around rollers

(Rank of Toner Contamination of Heating Member of Fixing Unit) Rank 5: No toner contamination was found. Rank 4: Minor contamination was found, but practically acceptable. Rank 3: Contamination that could be easily visually discriminated. Rank 2: Remarkable contamination is observed Rank 1: Contaminated toner adheres to the front and back surfaces of paper

[0235]

According to the present invention, the toner can be used for a long time regardless of the heating method of the fixing device because the toner has a sufficient low-temperature fixing property and high-temperature offset resistance and has an improved releasing property from the fixing member. Offset does not occur, and a high-quality image can be obtained.

[Brief description of the drawings]

FIG. 1 shows a ¹³ C-NMR spectrum of a binder resin (1) according to the present invention.

FIG. 2 ¹³ C-NM of low cross-linking degree polyester resin composition
2 shows an R spectrum.

FIG. 3 shows a ¹³ C-NMR spectrum of a styrene / 2-ethylhexyl acrylate copolymer.

FIG. 4 shows a ¹ H-NMR spectrum of an ethyl acetate-soluble component of the binder resin (1) according to the present invention.

FIG. 5 shows a ¹ H-NMR spectrum of an ethyl acetate-insoluble component of the binder resin (1) according to the present invention.

FIG. 6 is an explanatory diagram showing assignment of ¹ H-NMR signals of PO groups of PO-BPA.

FIG. 7 is a schematic configuration diagram of an image forming apparatus capable of performing an image forming method using the toner of the present invention.

8 is a partially enlarged view of a developing unit of the image forming apparatus shown in FIG.

FIG. 9 is a schematic structural view of another embodiment of an image forming apparatus capable of performing the image forming method using the toner of the present invention.

FIG. 10 is a block diagram showing a case where the image forming method using the toner of the present invention is applied to a printer of a facsimile machine.

FIG. 11 is a schematic diagram showing a specific example of a Soxhlet extraction device used for Soxhlet extraction.

FIG. 12 is a schematic view of a film heat fixing device as another heat fixing means used in the fixing step in the image forming method using the toner of the present invention.

[Explanation of symbols]

 REFERENCE SIGNS LIST 1 electrostatic latent image carrier (photoconductor) 4 toner carrier (developing sleeve) 7 fixing device 9 developing device 11 blade 13 toner P recording material

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Tadashi Michigami 3-30-2 Shimomaruko, Ota-ku, Tokyo Inside Canon Inc. (72) Inventor Yuichi Mizoo 3- 30-2 Shimomaruko, Ota-ku, Tokyo Canon (72) Inventor Yasuko Shibayama 3-30-2 Shimomaruko, Ota-ku, Tokyo F-term in Canon Inc. (reference) 2H005 AA01 AA06 AB03 CA04 CA08 CA13 CA14 CA17 CA20 CA25 DA02 EA03 EA06 EA07 EA10

Claims (54)

[Claims] 1. A toner containing at least a binder resin, a colorant, a wax, an organometallic compound and a saccharide compound, wherein (a) the saccharide compound is cyclodextrin, and (b) the binder resin is a vinyl polymer. (C) an acid value of the binder resin is 5 to 40.
mgKOH / g, (d) the resin component of the toner contains 15 to 50% by weight of a tetrahydrofuran (THF) insoluble matter, (e) the organometallic compound has aluminum as a metal element, and A complex or salt coordinating an aromatic hydroxycarboxylic acid, an aromatic diol or an aromatic polycarboxylic acid, and (f) a wax having a molecular weight of 300 in a chromatogram measured by gel permeation chromatography (GPC). To 5
000 and a ratio (Mw / Mn) of weight average molecular weight to number average molecular weight of 1.2 to 15
A toner characterized in that: 2. The toner according to claim 1, wherein the saccharide compound is a cyclodextrin comprising a saccharide unit represented by the formula (1). Embedded image (Wherein, R ₁ and R ₂ represent a hydroxyl group or a linear or branched alkyl group having 1 to 30 carbon atoms, which may be the same or different. R ₃ is a hydrogen atom, a methyl group or (It represents an ester bond with a carboxylic acid having an alkyl group having 1 to 4 carbon atoms, and j represents an integer of 6 to 20.) 3. The toner according to claim 1, wherein the saccharide compound is a cyclodextrin comprising a saccharide unit represented by the formula (2). Embedded image (In the formula, k represents an integer of 6 to 8.) 4. The toner according to claim 1, wherein the saccharide compound forms an inclusion compound. 5. The toner according to claim 1, wherein the saccharide compound forms an inclusion compound with a salt containing a metal. 6. The method according to claim 1, wherein the metal is lithium, sodium, potassium, strontium, calcium, aluminum, iron,
The toner according to claim 5, wherein the toner contains at least one selected from zirconium and zinc. 7. The saccharide compound is a binder resin 100.
7. The toner according to claim 1, wherein the toner is added in an amount of 0.5 to 10 parts by weight based on parts by weight. 8. The method according to claim 1, wherein the saccharide compound is a binder resin 100.
7. The toner according to claim 1, wherein the toner is added in an amount of 0.7 to 7 parts by weight based on parts by weight. 9. The method according to claim 1, wherein the saccharide compound is a binder resin 100.
7. The toner according to claim 1, wherein the toner is added in an amount of 1 to 5 parts by weight based on parts by weight. 10. The binder resin having an acid value of 10 to 35 mgK.
The toner according to any one of claims 1 to 9, wherein the toner content is OH / g. 11. The binder resin having an acid value of 15 to 30 mgK.
The toner according to any one of claims 1 to 9, wherein the toner content is OH / g. 12. The binder resin has a THF insoluble content of 15 to 4
The toner according to claim 1, wherein the toner content is 5% by weight. 13. The binder resin has a THF insoluble content of 20 to 4
The toner according to any one of claims 1 to 11, wherein the toner content is 0% by weight. 14. The wax having a molecular weight of 350 to 4500.
The toner according to any one of claims 1 to 13, wherein the toner has a main peak and a ratio (Mw / Mn) is 1.5 to 10. 15. The wax having a molecular weight of 400 to 4000.
14. The toner according to claim 1, wherein the toner has a main peak and a ratio (Mw / Mn) is 1.7 to 8. 16. The toner according to claim 1, wherein the wax is one of a hydrocarbon wax, a polyethylene polymer, and a polypropylene polymer. 17. The toner according to claim 1, wherein the wax has a structure represented by Formula (3). Embedded image (In the formula, A represents a hydroxyl group or a carboxyl group, and a represents an integer of 35 to 150.) 18. Wax is 1 to 20 mg KOH / g
The toner according to any one of claims 1 to 15, wherein the toner is an acid-modified polypropylene having the following acid value: 19. Wax is 1 to 20 mgKOH / g
The toner according to any one of claims 1 to 15, wherein the toner is an acid-modified polyethylene having an acid value of: 20. It contains two different waxes, has a main peak at a molecular weight of 300 to 5000, and has a ratio (Mw
The toner according to any one of claims 1 to 14, wherein (/ Mn) is from 1.2 to 15. 21. It contains two different waxes, has a main peak at a molecular weight of 350 to 4500, and has a ratio (Mw
The toner according to any one of claims 1 to 14, wherein (/ Mn) is from 1.5 to 12. 22. It contains two different waxes, has a main peak at a molecular weight of 400 to 4000, and has a ratio (Mw
/ Mn) is 2 to 10.
15. The toner according to any one of items 1 to 14. 23. The method according to claim 1, wherein the at least one wax is a hydrocarbon wax, a polyethylene polymer or a polypropylene polymer.
23. The toner according to any one of the above items. 24. The at least one wax of formula (3)
3. A structure having a structure represented by:
3. The toner according to any one of 2. Embedded image (In the formula, A represents a hydroxyl group or a carboxyl group, and a represents an integer of 35 to 150.) 25. The method according to claim 25, wherein the at least one kind of wax is 1 to 2
23. The toner according to claim 1, wherein the toner is an acid-modified polypropylene having an acid value of 0 mgKOH / g. 26. The method according to claim 26, wherein the at least one wax is from 1 to 2
The toner according to any one of claims 1 to 22, wherein the toner is an acid-modified polyethylene having an acid value of 0 mgKOH / g. 27. The wax is a differential scanning calorimeter (DSC)
The toner according to any one of claims 1 to 26, wherein a melting point defined by an endothermic peak temperature at the time of temperature rise measured at 70 to 140 ° C. 28. The method according to claim 28, wherein the wax is a differential scanning calorimeter (DSC).
The toner according to any one of claims 1 to 26, wherein a melting point defined by an endothermic peak temperature at the time of temperature rise measured at 80 to 135 ° C. 29. A method in which the wax is a differential scanning calorimeter (DSC).
The toner according to any one of claims 1 to 26, wherein a melting point defined by an endothermic peak temperature at the time of temperature rise measured at 85 to 130 ° C. 30. The toner according to claim 1, wherein at least one kind of wax is added during the production of the binder resin. 31. The toner according to claim 1, wherein the organometallic compound containing aluminum as a metal element can be represented by Formulas (4) to (6). Embedded image Wherein R is hydrogen, alkyl, aryl, aralkyl, cycloalkyl, alkenyl, alkoxy, aryloxy, hydroxyl, acyloxy, alkoxycarbonyl, acyl, carboxyl, halogen, nitro, Group, amino group, carbamoyl group,
They may be connected to each other to form an aliphatic ring, an aromatic ring, or a heterocyclic ring. In this case, the ring may have a substituent R, and the substituents R may be the same or different. And z represents an integer of 1 to 4, n represents 2, 3 or 4, m represents 0, 2 or 4, and an aromatic carboxylic acid or an aromatic carboxylic acid which serves as a ligand in each complex or salt. The group diols may be the same or different. Also, a mixture of complex compounds having different numbers of n and m may be used. ] 32. An organic metal compound containing an aluminum element represented by the formulas (4) to (6),
32. The toner according to claim 1, wherein the toner is contained in an amount of 0.5 to 10 parts by weight based on parts by weight. 33. An organic metal compound containing an aluminum element represented by the formulas (4) to (6),
32. The toner according to claim 1, wherein the toner is contained in an amount of 0.7 to 7 parts by weight based on parts by weight. 34. An organic metal compound containing an aluminum element represented by the formulas (4) to (6),
32. The toner according to claim 1, wherein the toner is contained in an amount of 1 to 5 parts by weight based on parts by weight. 35. The toner according to claim 1, wherein the saccharide compound and the organometallic compound containing an aluminum element are added in a weight ratio of 1/20 to 2/1. . 36. The toner according to claim 1, wherein the saccharide compound and the organometallic compound containing an aluminum element are added in a weight ratio of 1/15 to 1/1. . 37. The toner according to claim 1, wherein the saccharide compound and the organometallic compound containing an aluminum element are added in a weight ratio of 1/10 to 1/2. . 38. The binder resin contains (A) 50 to 85% by weight of a THF-soluble component (W1) by soxhlet extraction for 10 hours using tetrahydrofuran (THF) as a solvent, and a THF-insoluble component (W2). 15 to 50% by weight, and (B) 40 to 98% by weight of an ethyl acetate-soluble component (W3) and a ethyl acetate-insoluble component (W4) by Soxhlet extraction for 10 hours using ethyl acetate as a solvent. 2
(C) chloroform-soluble component (W5) by 55-90 wt% and chloroform-insoluble matter (W6) by 10-45 wt% by Soxhlet extraction for 10 hours using chloroform as a solvent. Containing (D) W
4 / W6 is 1.1 to 4.0, and (E) THF
Gel permeation chromatography (G
PC), the chromatogram has a main peak in the molecular weight range of 4000 to 9000, and the component (A1) in the molecular weight range of 500 to less than 10,000 has a component (A1) of 35.0 to 65.000.
0%, the component (A2) in the region having a molecular weight of 10,000 to less than 100,000 is 25.0 to 45.0%,
The component according to any one of claims 1 to 37, wherein 10,000 or more components (A3) are 10.0 to 30.0%, and the value of A1 / A2 is 1.05 to 2.00. toner. 39. The toner according to claim 1, comprising 5 to 50% by weight of an ethyl acetate insoluble component. 40. The toner according to claim 1, comprising 10 to 40% by weight of an ethyl acetate insoluble component. 41. A chloroform-insoluble component of 15 to 40.
41. The toner according to any one of claims 1 to 40, wherein the content of the toner is about 1% by weight. 42. A chloroform-insoluble component of 17 to 37.
41. The toner according to any one of claims 1 to 40, wherein the content of the toner is about 1% by weight. 43. The toner according to claim 1, wherein the value of the ratio (W4 / W6) is 1.2 to 3.5. 44. The toner according to claim 1, wherein the value of the ratio (W4 / W6) is 1.5 to 3.0. 45. The toner according to claim 1, wherein the THF-soluble component has a peak at a molecular weight of 5,000 to 8,500. 46. The toner according to claim 1, wherein the THF-soluble component has a peak at a molecular weight of 5,000 to 8,000. 47. A THF-soluble component having a molecular weight of 50
Component (A1) of 0 to less than 10,000 is 37.0 to 60.0
The toner according to any one of claims 1 to 46, wherein the ratio is%. 48. A THF-soluble component having a molecular weight of 50
Component (A1) of 0 to less than 10,000 is 40.0 to 50.0
The toner according to any one of claims 1 to 46, wherein the ratio is%. 49. In the THF-soluble component, the component (A2) having a molecular weight of 10,000 to less than 100,000 contains 27.0 to 42.0.
The toner according to any one of claims 1 to 46, wherein the ratio is%. 50. In the THF-soluble component, the component (A2) having a molecular weight of 10,000 to less than 100,000 is 30.0 to 40.0.
The toner according to any one of claims 1 to 46, wherein the ratio is%. 51. A THF-soluble component having a molecular weight of 10
The toner according to any one of claims 1 to 46, wherein 10,000 or more of the component (A3) is 12.0 to 25.0%. 52. A THF-soluble component having a molecular weight of 10
The toner according to any one of claims 1 to 46, wherein 10,000 or more components (A3) are 15.0 to 20.0%. 53. In the THF-soluble component, the ratio (A1 /
47. The toner according to claim 1, wherein the value of A2) is from 1.10 to 1.90. 54. In the THF-soluble component, the ratio (A1 /
The toner according to any one of claims 1 to 46, wherein the value of A2) is from 1.15 to 1.80.