JP2000292968A - Dry toner - Google Patents

Abstract

(57) [Summary] [Problem] To be able to fix at low temperature, to be excellent in offset resistance, to stably obtain high image quality even when used under high and low humidity, and to obtain image defects even with time. Of a dry toner that does not cause a problem. SOLUTION: The binder resin is a resin having a carboxyl group or an acid anhydride group, and the oxazoline-based compound having two or more oxazoline groups in the molecule is 0.001 to 100 parts by weight of the binder resin. A dry component containing 0.01 to 50 parts by weight of a resin component having a resin component having two or more oxazoline groups in the molecule or containing a compound represented by the following formula as a release agent: toner.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to electrophotography, an image forming method for visualizing an electrostatic charge image, and a dry toner used for a toner jet.

[0002]

2. Description of the Related Art Conventionally, electrophotography has been disclosed in U.S. Pat. No. 2,297,691, Japanese Patent Publication No. 42-23910.
Many methods are known, as described in Japanese Patent Publication No. JP-B-43-24748 and Japanese Patent Publication No. 43-24748. Generally, using a photoconductive substance, an electric latent image is formed on a photoreceptor by various means, and then the latent image is developed with a toner to form a visible image. After a toner image is transferred onto a transfer material such as paper, the toner image is fixed on the transfer material by heat, pressure or the like to obtain a copy. Further, the toner remaining on the photoreceptor without being transferred is cleaned and removed by various methods, and then the above steps are repeated.

[0003] In recent years, such copying apparatuses have been strictly pursued for smaller size, lighter weight, higher speed, and higher reliability. In addition, not only a copy machine for office work, which is generally referred to as simply copying an original document, but also a digital printer as an output device of a computer, or a printing machine for printing high-definition images such as graphic designs has begun to be used. Therefore, as for the image quality, higher definition and higher image quality have been demanded, and as a result, the performance required for the toner has also become higher. By the way, in digital printers and copying of high-definition images, fixing performance is the most important performance required of toner.

Various methods and apparatuses have been developed for the fixing step, but the most common method at present is a pressure heating method using a heat roller. Briefly, in the pressure heating method using a heat roller, the surface of the heat roller whose surface is formed of a material having a release property with respect to the toner,
The toner image formed on the sheet to be fixed is caused to pass therethrough while being brought into contact under pressure, and the toner image is fixed by heat and pressure. In this method, since the surface of the heat roller and the toner image of the sheet to be fixed come into contact 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, which is very effective in a high-speed electrophotographic copying machine. However, in the above method, on the other hand, since the surface of the heat roller and the toner image are in a molten state and in contact with each other under pressure, a part of the toner image adheres to the surface of the fixing roller, and the adhered substance is transferred to the fixing roller. May be stained (so-called offset phenomenon). Therefore, preventing the toner from adhering to the surface of the heat fixing roller is one of the essential conditions of the heat roller fixing method.

[0005] Recently, instead of a heat roller, a fixing device having a pressure member for opposing pressure contact with a heating member and for adhering a recording material (fixed sheet) to the heating member via a film has been developed. Although practically used, it is a device that is advantageous in terms of thermal efficiency. However, in this method, since the toner surface is melted, the offset phenomenon is more likely to occur, and it is necessary to prevent this phenomenon.

On the other hand, as one of proposals for preventing the occurrence of the offset phenomenon, many proposals have been made on a system in which a crosslinking agent is added to a binder resin. For example,
Japanese Patent Publication No. 51-23354 proposes a toner using a resin composed of an appropriately crosslinked vinyl polymer by adding a crosslinking agent and a molecular weight modifier. In addition, Tokiko Sho 55
Japanese Patent Application Laid-Open No. 6805 discloses that the molecular weight distribution is broadened so that the ratio of the number average molecular weight to the weight average molecular weight having α, β-unsaturated ethylenic monomer as a constitutional unit is 3.5 to 4.0. There has been proposed a toner using the above resin. Certainly, these toners have a lower fixing temperature (the lowest temperature at which fixing is possible) and an offset temperature (a temperature at which offset begins to occur), compared to a toner consisting of a single binder resin having a sharp molecular weight distribution. Although the temperature range in which the fixing can be performed is widened, it is difficult to sufficiently lower the fixing temperature when sufficient offset prevention performance is imparted. Conversely, if the low-temperature fixing property is emphasized, there arises a problem that the offset prevention performance becomes insufficient.

In place of these vinyl resins, a toner using a resin obtained by crosslinking a polyester resin which is considered to be essentially superior to the vinyl resin in terms of low-temperature fixability and further adding an offset preventing agent. However, JP-A-57-2
No. 08559 proposes this. This toner is excellent in both low-temperature fixability and offset prevention, but has a problem in terms of toner productivity (particularly, pulverizability). Further, in JP-A-56-116043, a vinyl monomer is polymerized in the presence of a reactive polyester resin, and is polymerized through a crosslinking reaction, an addition reaction, and a grafting reaction in the course of polymerization. A toner using a resin has been proposed.

The toner having a crosslinked vinyl polymer or gel component as described above is certainly preferable in terms of offset resistance, but has the following problems. That is, when the crosslinked vinyl polymer is used as a toner raw material when these are contained in the toner, the internal friction in the polymer becomes extremely large at the time of melt-kneading during the production of the toner, and a large shearing force is generated. In many cases, the polymer chains are cut off during melt-kneading, resulting in a decrease in melt viscosity and adversely affecting offset properties. So, in order to solve the above problems,
JP-A-55-90509, JP-A-57-1782
No. 49, JP-A-57-178250 and JP-A-60-4946, a resin having a carboxylic acid and a metal compound are used as toner raw materials, and a heat reaction is performed during melt-kneading. A crosslinked polymer is formed and contained in a toner.

Further, JP-A-63-214760, JP-A-63-217362, and JP-A-63-217
No. 363 proposes that a vinyl polymer, a vinyl resin having a more specific half-ester compound as an essential constitutional unit, and a polyvalent metal compound are reacted, cross-linked, and used. I have.

JP-A-63-214760, JP-A-63-217362 and JP-A-63-21736.
In Japanese Patent Publication No. 3 (2003), a compound obtained by forming a molecular weight distribution divided into two groups of a low molecular weight and a high molecular weight and reacting a carboxyl group of a specific half-ester compound contained on the low molecular weight side with a polyvalent metal ion is used. It has been proposed to.
Japanese Patent Application Laid-Open No. 2-53078 discloses that a polyester resin which is essentially superior to a vinyl resin in terms of low-temperature fixability is provided with an oxazoline which is a crosslinking agent for an organic compound different from a conventional crosslinking agent. It has been proposed to use a resin obtained by crosslinking a system monomer to improve the offset property of the toner. However, when any of the crosslinking agents is used, it is still insufficient to satisfy both the offset resistance and the low-temperature fixing property, and further improvement is required.

Further, in recent years, it has been required to prevent the offset phenomenon, and at the same time, it has been required to realize a fixing method in which the wait time is short and the power consumption is low in the fixing. Therefore, there is a need for a design that can realize fixing at a lower temperature with respect to the toner. For example, JP-A-51-14333, JP-A-57-14852, JP-A-58-97
056, JP-A-60-247250, JP-A-4-362953, JP-A-6-230600 and JP-A-8-030036, as solid silicone varnish and higher fatty acid-based release agents. It has been proposed to use waxes, higher alcohol waxes, natural plant waxes (carnauba, rice) and montan ester waxes. However, these waxes are also insufficient, and it is necessary to further improve the low-temperature fixability and the offset resistance of the toner.

In general, when such a low softening point wax is contained in a toner as a release agent, the fluidity of the toner is reduced, so that the developing characteristics and transfer characteristics of the toner tend to be reduced. In addition, the chargeability, durability, and storability tend to be adversely affected. Further, although these waxes are hard to be uniformly dispersed in the toner, the wax which is free or unevenly distributed in the toner is liable to adversely affect the developing property and the durability, and there is still room for improvement in these points.

[0013] To solve these problems, various monomers
Modified waxes that have been grafted or block copolymerized have been proposed. For example, Japanese Patent Application Laid-Open No. Sho 59-121052 discloses that a polyolefin grafted / block-copolymerized with an α-methylene aliphatic monocarboxylic acid ester monomer is used.
JP, JP-A-59-121053, JP-A-60-12053
JP-A-93456 and JP-A-63-34550 propose to use a polyolefin obtained by graft / block copolymerization with an aromatic vinyl monomer. However, although these toners are improved in fluidity, they are inferior in offset resistance, and further need to be further improved in developability (chargeability) and durability.

JP-A-62-226260, JP-A-63-139365, JP-A-3-50559, JP-A-6-208244, and JP-A-10-208
Japanese Patent No. 90939 proposes a toner containing a polypropylene modified with a carboxylic acid or a maleic acid, or a resin composition for a toner. Further, Japanese Patent Laid-Open No. 9-1
JP-A-27722 and JP-A-9-127723 propose a toner having improved low-temperature fixability and offset resistance by combining a polymer component with a polyolefin modified with an aromatic vinyl monomer. However, the above configuration is still insufficient for a high-speed copying system required in recent years. That is, when the copying speed becomes higher, the time required for the recording material (sheet to be fixed) to pass through the fixing device is shortened even if the heating temperature and pressure during fixing are the same as those in the related art. In other words, the total amount of heat (work amount) applied to the recording material tends to decrease, so that it is indispensable to further improve the fixability of the toner.

[0015]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to enable low-temperature fixing, excellent offset resistance, and stable image quality even when used under high and low humidity. Another object of the present invention is to provide a dry toner which does not cause image defects even with the passage of time.

[0016]

The following objects are achieved by the present invention described below. That is, the present invention is a dry toner having toner particles containing at least a binder resin, a colorant, an oxazoline-based compound or a resin component having an oxazoline group, and a release agent, wherein the binder resin has a carboxyl group or an acid. An oxazoline-based compound having two or more oxazoline groups in a molecule is a resin having an anhydride group and 100 parts by weight of the binder resin.
30 parts by weight, or 0.01 to 50 parts by weight of a resin component having two or more oxazoline groups in a molecule, and at least a compound represented by the following formula (1) as a release agent: It is a dry toner characterized by being contained.

Embedded image

[0017]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in more detail by way of preferred embodiments of the present invention. The present inventors have conducted intensive studies on the above-mentioned problems of the prior art,
By using an oxazoline-based compound or a resin component having an oxazoline group as a raw material of the toner in combination with the compound represented by the above formula (1) to be added as a release agent, excellent low-temperature fixability and offset resistance are obtained. Furthermore,
The inventors of the present invention have found that a high quality image can be stably obtained even in a high humidity environment and a low humidity environment, and that the dry toner has no image defects over time.

The dry toner of the present invention is an oxazoline compound in which the binder resin is a resin having a carboxyl group or an acid anhydride and has two or more oxazoline groups in the molecule, or two or more oxazoline compounds in the molecule. And a compound represented by the above formula (1) as a release agent. An oxazoline-based compound, or two or more oxazoline groups contained in a resin component having an oxazoline group, undergo a ring-opening addition reaction with a carboxyl group or an acid anhydride group contained in a binder resin,
An amide group is formed to form a crosslinked structure. It is considered that this crosslinked structure improves the offset resistance of the toner. Further, in the toner particles, a releasing agent represented by the above formula (1) is used.
It is considered that the combined use of the hydrocarbon wax represented by the formula (2) improves the low-temperature fixability of the toner, which has been insufficient with only the oxazoline compound or the resin component having an oxazoline group. Further, according to the study of the present inventors, not only those effects, but also excellent quality images can be obtained under any environment, and a dry toner that does not cause image defects over time can be obtained. I understand.

This is because of the difference between the carboxyl group or carboxyester group constituting the compound represented by the above formula (1) contained as a release agent and the carboxyl group or acid anhydride group contained in the binder resin. The good compatibility between them and the oxazoline-based compound or the resin component having an oxazoline group function as a cross-linking agent for the organic compound, resulting in good compatibility with the binder resin or the release agent. This is considered to be due to preventing the mold agent from dropping from the toner particles. Further, by the cross-linking structure generated in this way, the kneading share at the time of melt-kneading during the production of toner particles further improves the dispersibility of raw materials such as a release agent, a magnetic material, a pigment, and a charge control agent in the toner particles. It is thought that it was due to what was done. That is, it can be said that the uniformity of charging and the durability stability of charging were obtained by the synergistic effect of the combined use of the oxazoline-based compound or the resin having an oxazoline group and the compound represented by the above formula (1).

Hereinafter, each material constituting the dry toner of the present invention will be described. First, an oxazoline-based compound having two or more oxazoline groups in the molecule will be described. As the oxazoline-based compound used in the present invention, those represented by the following general formula are preferably used.

Embedded image In the above formula, R represents an n-valent aliphatic, alicyclic or aromatic hydrocarbon residue, and R ₁ , R ₂ , R ₃ and R ₄ may be the same or different , Each represents hydrogen or a lower alkyl group, and n represents an integer of 2 to 4.

The hydrocarbon residue represented by R is, for example, a residue of a saturated aliphatic hydrocarbon having about 1 to 20 carbon atoms such as methane, ethane, propane, butane, pentane and hexane, or ethylene, propylene. , A residue of an unsaturated aliphatic hydrocarbon having about 1 to 20 carbon atoms such as butene and pentene, or a residue of an alicyclic hydrocarbon having about 4 to 30 carbon atoms such as cyclobutane, cyclopentane, cyclohexane and cyclohexene Or a residue of an aromatic hydrocarbon having about 6 to 30 carbon atoms such as benzene, toluene, xylene, and naphthalene. Examples of the lower alkyl group represented by R ₁ , R ₂ , R ₃ and R ₄ include alkyl groups having about 1 to 4 carbon atoms such as methyl, ethyl, propyl and butyl. n is an integer of 2 to 4, but 2 or 3 is common.

Further, as specific compounds represented by the above general formula, for example, the following compounds can be favorably used. 1,2-bis - (Δ ² - oxazolinyl -2) benzene 1,3-bis - (Δ ² - oxazolinyl -2) benzene 1,4-bis - (Δ ² - oxazolinyl -2) benzene 1,2-bis - (Δ ² - oxazolinyl -2) cyclohexane 1,3-bis - (Δ ² - oxazolinyl -2) cyclohexane 1,4-bis - (Δ ² - oxazolinyl -2) cyclohexane 1,1-bis - (Δ ² - oxazolinyl -2) methylene-bis - (Δ ² - oxazolinyl -2) ethylene 1,3-bis - (Δ ² - oxazolinyl -2) propane 1,4-bis - (Δ ² - oxazolinyl -2) butane 1,3-bis- (4,4,5,5-tetramethyl-Δ ² −
Oxazolinyl-2) cyclohexane 1,4-bis- (4,4-dimethyl-5,5-dipropyl-Δ ² -oxazolinyl-2) benzene 1,2,4-tris- (Δ ² -oxazolinyl-2) benzene 1 , 2,4,5-tetrakis - (Δ ² - oxazolinyl -2) benzene 1,2,4,5-tetrakis - (Δ ² - oxazolinyl -2) cyclohexane

In the dry toner of the present invention, when an oxazoline compound having two or more oxazoline groups in the molecule is used, 0.001 to 30 parts by weight based on 100 parts by weight of the binder resin. , And preferably in a proportion of 0.01 to 20 parts by weight. That is, when the amount is less than 0.001 part by weight, sufficient high-temperature offset resistance cannot be obtained, and the image density tends to decrease. On the other hand, when the content is more than 30 parts by weight, the toner becomes too hard and may damage the photoreceptor.
Further, there is a possibility that toner fusion may occur due to this.

Next, the resin component having two or more oxazoline groups in the molecule used in the present invention will be described.
Examples of monomers having an oxazoline group that can be used to obtain such a resin component include, for example, 2-vinyl-2
-Oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline,
2-vinyl-4-ethyl-2-oxazoline, 2-vinyl-5-ethyl-2-oxazoline, 2-isopropenyl-2-oxazoline, 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl -5-methyl-2-oxazoline, 2-isopropenyl-4-ethyl-2-oxazoline, 2-isopropenyl-5-ethyl-2-oxazoline, 2-isopropenyl-4,5-
Examples thereof include oxazoline group-containing polymerizable monomers such as dimethyl-2-oxazoline, and one or more kinds selected from these can be used. These oxazoline group-containing monomers have a content of 1 to
It is used in an amount of 60 parts by weight, preferably 1 to 40 parts by weight.

The monomers copolymerizable with the above-mentioned monomers having an oxazoline group include, for example, styrene, o-methylstyrene, p-methylstyrene, pt
-Butyl styrene, 1,3-dimethylstyrene, α-methylstyrene, vinylnaphthalene, vinyl aromatic compounds such as vinylanthracene, acrylonitrile, vinyl cyanide compounds such as methacrylonitrile, acrylic acid,
Examples thereof include unsaturated carboxylic acids such as methacrylic acid, and esters thereof. These are not only one kind, but two
It can be used as a mixture of more than two species. The molecular weight of the resin component formed from these monomers is 3,000 to 300,000 by weight average molecular weight, preferably 50,000 to 300,000.
It should just be 00-250,000.

The resin component having an oxazoline group used in the present invention can be prepared by various known methods. For example, in the solution polymerization method, it can be obtained by copolymerizing a mixture of monomers in a solvent at 40 to 150 ° C. in the presence of an appropriate radical generator or chain transfer agent. In addition, it can also be produced by a generally known suspension polymerization method or emulsion polymerization method. When the dry toner of the present invention contains a resin component having two or more oxazoline groups in the molecule formed as described above, the amount of the resin component is 0 to 100 parts by weight of the binder resin. 0.1 to 50 parts by weight, preferably 0.05 to 30 parts by weight.
It is blended in the range of parts by weight. That is, if less than 0.01 parts by weight, sufficient hot offset resistance cannot be obtained,
In addition, the image density tends to decrease. On the other hand, when the amount is more than 50 parts by weight, the toner becomes too hard and may damage the photoreceptor, which may cause toner fusion.

In the dry toner of the present invention, a binder resin having a carboxyl group or an acid anhydride group is used. As described above, these groups and the oxazoline group undergo a ring-opening addition reaction. By forming a crosslinked structure,
The offset resistance is improved. At this time, as a method of crosslinking the binder resin having a carboxyl group or an acid anhydride group with the compound or the resin component having an oxazoline group, a polymer may be optionally used under a temperature condition of 20 to 350 ° C. A method of stirring and mixing in the presence of a substance, an organic solvent, or another catalyst, a method of heat-melting and mixing a binder resin and a compound or a resin component having an oxazoline group using a heat kneader, or toner production Sometimes, a method of heating and melting and mixing with other toner raw materials by using a heat kneader is used. Among these, a method in which a binder resin and a compound or a resin component having an oxazoline group are heated and melt-mixed, and a method in which heat-melt mixing is performed at the time of toner production, are preferable in that the productivity of the toner and the crosslinking reaction are easily controlled. .

Next, the release agent constituting the dry toner of the present invention will be described. In the present invention, at least a compound represented by the following formula (1) (hydrocarbon wax) is contained in the toner particles as a release agent.

Embedded image Further, the release agent used in the present invention has an acid value of 1 to 30 m.
gKOH / g, more preferably 1 to 15 m
It is preferably gKOH / g. That is, when the acid value of the release agent used is less than 1 mgKOH / g, the compatibility with the binder resin or the oxazoline-based compound or the resin component having an oxazoline group is deteriorated, and the dispersion of the release agent in the toner particles is reduced. Tends to deteriorate. Further, the dispersion diameter of the release agent in the toner particles becomes small, and sufficient release properties and low-temperature fixability may not be obtained. On the other hand, when the acid value of the release agent exceeds 30 mgKOH / g, the cohesiveness between the release agents becomes strong, and there is a possibility that a problem occurs in the fluidity and developability of the toner.

The release agent used in the present invention has a molecular weight distribution measured by gel permeation chromatography (GPC) and a weight average molecular weight (Mw) of 50,000.
It is preferably 0 or less, and more preferably 30,000 or less. When the molecular weight distribution is within the above range, thermal characteristics such as low-temperature fixability characteristic of the present invention can be imparted. As a method of synthesizing the above-mentioned release agent used in the present invention, for example, a propylene-ethylene copolymer is synthesized from monomers of propylene and ethylene by increasing the molecular weight to some extent, and the obtained propylene-ethylene is obtained. The copolymer is pyrolyzed to the extent that the desired endothermic peak is obtained,
After further modifying by reacting a monomer having an acid group,
There is a method of performing thermal decomposition again.

The acid monomer used for modifying the release agent used at this time preferably contains at least one of a carboxyl group, a carboxylic anhydride group and a carboxylate group. For example, acrylic acid, Acrylic acid such as methacrylic acid, α-ethylacrylic acid and crotonic acid, and α- or β-alkyl derivatives thereof, fumaric acid, maleic acid, unsaturated dicarboxylic acids such as citraconic acid, and monoester derivatives or anhydrides thereof There is
These acid monomers can be used alone or as a mixture.

In particular, a preferable release agent constituting the dry toner of the present invention is one modified with at least one acid monomer selected from maleic acid, maleic acid half ester and maleic anhydride.
It is preferable to use a hydrocarbon wax, for example, a polypropylene wax. Further, in the dry toner of the present invention, a release agent having no acid value may be used in combination with the release agent having an acid value as described above. The amount of the release agent is preferably about 1 to 20 parts by weight based on 100 parts by weight of the binder resin.

The molecular weight distribution of the compound represented by the above formula (1), for example, a hydrocarbon-based wax used as a releasing agent contained in the toner particles constituting the dry toner of the present invention is determined by gel permeation chromatography. Graphy (G
PC) under the following conditions. (GPC measurement conditions) • Apparatus: 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 was injected The above conditions were measured. In calculating the molecular weight of the sample,
A molecular weight calibration curve generated with monodisperse polystyrene standards is used. Further, it is calculated by a conversion formula derived from the Mark-Houwink viscosity formula, which is converted according to wax such as polypropylene conversion.

The acid value of the release agent (wax) contained in the dry toner of the present invention was determined by the following method. <Separation of wax component> Toner sample 0.5 to 1.0
g, and weighed in a cylindrical filter paper (for example, No. 86 manufactured by Toyo Roshi Kaisha, Ltd.).
R) and put 100-200 ml of toluene as a solvent
Soxhlet extraction for 20 hours. Next, after the soluble component extracted by the solvent is evaporated to evaporate the solvent, the resultant is vacuum-dried at 100 ° C. for several hours. After adding 20 ml of chloroform to the obtained extract and allowing it to stand for 1 hour, the extract is filtered through a membrane filter with a pore size of 0.45 μm and dried to obtain a wax component to be measured.

<Measurement of acid value> (Apparatus and equipment used)-Direct balance-Erlenmeyer flask (200 ml)-Measuring cylinder (100 ml)-Microburet (10 m)-Electric heater (reagent)-Xylene-Dioxane-N / 10 caustic potassium standard methanol solution ・ 1% phenolphthalein solution (indicator)

(Measurement method) In an Erlenmeyer flask, 1 to 1.5 g of the wax obtained by the above extraction is precisely weighed, and after adding 20 ml of xylene, the mixture is heated and dissolved. After dissolution, 20 ml of dioxane was added, and the solution was diluted with 1/10 N / 10 caustic potassium standard methanol solution while the solution did not cause smudge or blemishes.
Titrate as soon as possible with% phenolphthalein as indicator. Perform a blank test at the same time. From these titration values, the acid value of the wax is calculated by the following equation.

[0036]

(Equation 1) (However, A is the number of ml of N / 10 caustic potassium standard methanol solution required for this test, B is N / 10 required for blank test)
Number of ml of caustic potassium standard methanol solution, f is N / 10
The caustic potash standard methanol solution factor, S, is the number of grams of sample. )

As a binder resin constituting the dry toner of the present invention, a resin having a carboxyl group or an acid anhydride group is used, and the acid value of the resin is 0.5 to 50 mg KOH.
/ G, more preferably 1 to 30 mg KOH
/ G is more preferable. In the present invention, the acid value of the binder resin was determined by the following method.

<Measurement of Acid Value> The basic operation is JIS K-0.
070 in accordance with the following procedures. About 0.5 to 2.0 (g) of the pulverized binder resin is precisely weighed, and the measured value is defined as the weight W (g) of the binder resin. The sample weighed above was placed in a 300 (ml) beaker, and a toluene / ethanol (4/1) mixed solution 15 was prepared.
Add 0 (ml) and dissolve. Using a 0.1N KOH methanol solution, titration is performed using a potentiometric titrator. At this time, for example, a potentiometric titrator AT-400 manufactured by Kyoto Electronics Co., Ltd. (win
workstation) and automatic titration using an ABP-410 motorized burette. The amount of the KOH solution obtained at this time is S (ml)
The blank is measured at the same time, and the amount of the KOH solution used at that time is defined as B (ml). Calculate the acid value by the following formula. f is a factor of KOH.

(Equation 2)

The binder resin constituting the dry toner of the present invention may be any one which has been conventionally used as a binder resin for a toner and has a carboxyl group or an acid anhydride group. , A vinyl polymer, a polyester resin, and the like. In order to obtain the binder resin used in the present invention, the following can be used as the monomer of the vinyl polymer. For example, unsaturated dibasic acids such as maleic acid, citraconic acid, dimethyl maleic acid, itaconic acid, alkenyl succinic acid, and anhydrides thereof; fumaric acid, metaconic acid, dimethyl fumaric acid; Furthermore,
There are monoesters of the above unsaturated dibasic acids. Also, acrylic acid, methacrylic acid, crotonic acid, cinnamic acid and their anhydrides; anhydrides of the α, β-unsaturated acids, and
Anhydrides with lower fatty acids; α, β-unsaturated acids, such as anhydride monomers thereof; alkenyl malonic acid, alkenyl glutaric acid, alkenyl adipic acid and anhydrides thereof,
Monoesters can be used. Among these,
In particular, maleic acid, maleic acid half ester, and maleic anhydride are preferred as monomers for obtaining the binder resin of the present invention.

Further, examples of the comonomer of the vinyl polymer include the following. For example, styrene,
o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, 3,4-dichlorostyrene,
p-ethylstyrene, 2,4-dimethylstyrene, p-
n-butylstyrene, p-tert-butylstyrene,
Styrene such as pn-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene, pn-dodecylstyrene and derivatives thereof; ethylene, propylene, butylene, isobutylene, etc. Ethylenically unsaturated monoolefins; unsaturated polyenes such as butadiene; vinyl halides such as vinyl chloride, vinylidene chloride, vinyl bromide, and vinyl fluoride; vinyl esters such as vinyl acetate, vinyl propionate, and vinyl benzoate Methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate;
Isobutyl methacrylate, n-octyl methacrylate,
Α-methylene aliphatic monocarboxylic esters such as dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate; methyl acrylate, ethyl acrylate, Acrylic esters such as n-butyl acrylate, isobutyl acrylate, propyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate; Vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl isobutyl ether; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and methyl isopropenyl ketone; Nirupiroru, N- vinylcarbazole, N- vinyl indole, N- vinylpyrrolidone N- vinyl compounds such as pyrrolidone; vinyl naphthalenes; acrylonitrile, methacrylonitrile, acrylic acid or methacrylic acid derivatives such as acrylamide; the aforementioned alpha, beta-
And vinyl esters of unsaturated acid esters and dibasic acid diesters.
One or more can be selected and used.

Of these, a combination of monomers that results in a styrene-based copolymer or a styrene-acrylic-based copolymer is preferred. The reason that it is preferable to use a styrene-based copolymer as the binder resin is that an acid component such as maleic acid present in some places of the polymer chain of the styrene-based copolymer is effectively the oxazoline-based compound described above. Alternatively, it is considered that as a result of the reaction with the oxazoline group of the resin component having an oxazoline group, the dispersibility of the raw materials such as the release agent and the magnetic material is improved.

The binder resin in the present invention may be a polymer crosslinked with a crosslinkable monomer as exemplified below, if necessary. As the crosslinkable monomer that can be used at this time, a monomer having mainly two or more polymerizable double bonds as described below can be used. Specifically, aromatic divinyl compounds, for example,
Divinylbenzene, divinylnaphthalene, etc .; diacrylate compounds linked by an alkyl chain, for example, ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate Acrylate, 1,
6-hexanediol diacrylate, neopentyl glycol diacrylate, and methacrylates instead of the above compounds; diacrylate compounds linked by an alkyl chain containing an ether bond, for example, diethylene glycol diacrylate, triethylene Glycol diacrylate, tetraethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 400 diacrylate, polyethylene glycol # 600 diacrylate, dipropylene glycol diacrylate, and those obtained by replacing the acrylate of the above compound with methacrylate; Diacrylate compounds linked by a chain containing an aromatic group and an ether bond, for example, polyoxyethylene (2) -2,2-bis ( - hydroxyphenyl) propane diacrylate, polyoxyethylene (4) -2,
2-bis (4-hydroxyphenyl) propane diacrylate and those obtained by replacing the acrylates of the above compounds with methacrylates; and polyester-type diacrylate compounds, for example, trade name MANDA (Nippon Kayaku) . Examples of polyfunctional crosslinking agents include pentaerythritol triacrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, tetramethylol methanetetraacrylate,
Oligoester acrylates and those obtained by replacing the acrylates of the above compounds with methacrylates; trialisyanurates, triallyl trimellitates; and the like. These crosslinkers contain 100% by weight of other monomer components.
It is preferably used at a ratio of about 0.01 to 5% by weight, more preferably about 0.03 to 3% by weight.

An initiator used in forming a binder resin;
The selection of the type of the solvent or the reaction conditions is an important factor for obtaining the binder resin having the above-described properties used in forming the dry toner of the present invention. Examples of the initiator include benzoyl peroxide, 1,1-di (t-butylperoxy) -3,3,5-trimethylcyclohexane, n-butyl-4,4-di (t-butylperoxy) valerate, Dicumyl peroxide, α,
organic peroxides such as α'-bis (t-butylperoxydiisopropyl) benzene, t-butylperoxycumene, di-t-butyl peroxide, azo such as azobisisobutyronitrile and diazoaminoazobenzene, and A diazo compound or the like can be used. In addition, as a method of synthesizing the binder resin used in the present invention, a method such as a bulk polymerization method, a solution polymerization method, a suspension polymerization method, and an emulsion polymerization method can be used.

The dry toner of the present invention can be made a magnetic toner by incorporating a magnetic substance as a colorant in the toner particles. As the magnetic material used at this time, for example,
Iron oxides such as magnetite, maghematite, and ferrite; metals such as iron, cobalt, and nickel, or metals such as aluminum, cobalt, copper, lead, magnesium, manganese, selenium, titanium, tungsten, and vanadium An alloy and a mixture thereof are used, and those containing a non-ferrous element on the surface or inside of the magnetic material are preferable.

As the magnetic material used in the present invention, magnetic iron oxides such as magnetite, maghematite, and ferrite containing different elements, and mixtures thereof are preferably used.
Among these, lithium, beryllium, boron, magnesium, aluminum, silicon, phosphorus, germanium, titanium, zirconium, tin, lead, zinc, calcium, barium, scandium, vanadium, chromium, manganese, cobalt, copper, nickel, gallium, Cadmium, indium, silver, palladium, gold, mercury, platinum, tungsten, molybdenum, niobium, osmium, strontium, yttrium, technetium, ruthenium,
A magnetic iron oxide containing at least one element selected from rhodium and bismuth is preferable. Particularly, lithium, beryllium, boron, magnesium, aluminum, silicon, phosphorus, germanium, zirconium, tin, and a transition metal element of the fourth period are preferable elements. These elements may be taken into the iron oxide crystal lattice, may be taken into the iron oxide as an oxide, or may be present as an oxide or hydroxide on the surface. In particular, those contained as oxides are more preferred forms.

The amount of these magnetic substances contained in the toner is from 20 to 100 parts by weight of the binder resin component.
The amount is preferably 200 to 100 parts by weight, particularly preferably 40 to 150 parts by weight based on 100 parts by weight of the binder resin component. In some cases, the magnetic iron oxide as described above may be one subjected to a hydrophobic treatment with a silane coupling agent, a titanium coupling agent, titanate, aminosilane, or the like. The coloring material that can be added to the dry toner of the present invention is not limited to the above-mentioned magnetic substance, and conventionally known pigments such as carbon black and copper phthalocyanine, or dyes can also be used.

Further, a charge controlling agent can be added to the dry toner of the present invention having the above-described structure, which is a preferable embodiment. Hereinafter, the charge control agent used at that time will be described. Specific examples of the negative charge control agent include, for example, JP-B-41-20153 and JP-B-42-2.
7596, JP-B-44-6397, JP-B-45-26478 and the like, and metal complexes of monoazo dyes described in JP-B-50-133338. And a salt thereof, or C.I. I. Dyes and pigments such as 14645;
No. 752, Japanese Patent Publication No. 58-41508, Japanese Patent Publication No. 58-7384, Japanese Patent Publication No. 59-7385, and the like. Salicylic acid, naphthoic acid, dicarboxylic acid Zn, Al, Co, Cr, Metal complexes such as Fe and Zr, sulfonated copper phthalocyanine pigments, nitro groups,
Styrene oligomers into which halogen has been introduced, chlorinated paraffins, and the like can be given. These negative charge control agents can be used alone or in combination of two or more.

In the present invention, particularly, the dispersibility is excellent.
Use of an azo-based metal complex represented by the following general formula (I) or a basic organic acid metal complex represented by the following general formula (II), which has an effect on image density stability and fog reduction. Is preferred. Among them, an azo-based metal complex represented by the following formula (I) is more preferred, and an azo-based iron complex represented by the following formula (III) in which the central metal is Fe is particularly preferred.

[0049]

Embedded image (Wherein, M represents a coordination center metal, and Cr, Co, Ni,
Mn, Fe, Ti or Al is shown. Ar is an aryl group such as a phenyl group and a naphthyl group, and may have a substituent. In this case, the substituent includes a nitro group,
There are a halogen group, a carboxyl group, an anilide group, an alkyl group having 1 to 18 carbon atoms, and an alkoxy group having 1 to 18 carbon atoms. X, X ', Y, Y' are -O-, -CO-,-
NH- and -NR- (R is an alkyl group having 1 to 4 carbon atoms). A ⁺ represents hydrogen, sodium ion, potassium ion, ammonium ion or aliphatic ammonium ion. )

[0050]

Embedded image

[0051]

Embedded image

Next, specific examples of the azo-based iron complex represented by the above formula (III) are shown below.

Embedded image

[0053]

Embedded image

The above-mentioned metal complex compounds can be used alone or in combination of two or more. The amount of the charge control agent is preferably 0.1 to 5.0 parts by weight per 100 parts by weight of the binder resin from the viewpoint of the charge amount of the toner.

On the other hand, the following substances can be used to impart positive charge to the toner, and any of them can be used in the dry toner of the present invention. For example, denatured products such as nigrosine and fatty acid metal salts, quaternary ammonium salts such as tributylbenzylammonium-1-hydroxy-4-naphthosulfonate, tetrabutylammonium tetrafluoroborate, and phosphonium salts which are analogs thereof Onium salts of these and their lake pigments, triphenylmethane dyes, and these lake pigments (as the lake-forming agent, phosphotungstic acid, phosphomolybdic acid, phosphotungsten molybdic acid, tannic acid, lauric acid, gallic acid, ferric acid, Metal salts of higher fatty acids; diorganotin oxides such as dibutyltin oxide, dioctyltin oxide, dicyclohexyltin oxide; dibutyltin borate, dioctyltin borate, dicyclohexane Diorgano tin borate such may be mentioned such Shirusuzuboreto, can be used in combination these alone, or two or more kinds.

Further, the dry toner of the present invention is preferably formed by mixing inorganic fine powder or hydrophobic inorganic fine powder as an external additive. Specifically, for example, it is preferable to add silica fine powder for use. As the silica fine powder used in the present invention, both a so-called dry method produced by vapor-phase oxidation of a silicon halide and a so-called wet silica produced from dry silica called fumed silica and water glass are used. Although it is possible, dry silica having few silanol groups on the surface and inside and having no production residue is preferable.

The silica fine powder as mentioned above used in the present invention is particularly preferably subjected to a hydrophobic treatment. The hydrophobization treatment is provided by chemically treating with an organic silicon compound or the like which reacts or physically adsorbs with the silica fine powder. As a preferable method, a method of treating a dry silica fine powder produced by a vapor phase oxidation of a silicon halide compound with a silane coupling agent or treating with a silane coupling agent and simultaneously with an organosilicon compound such as silicone oil. Is mentioned.

Examples of the silane coupling agent used for the hydrophobizing treatment include hexamethyldisilazane, trimethylsilane, trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, allyl Phenyldichlorosilane, benzyldimethylchlorosilane,
Bromomethyldimethylchlorosilane, α-chloroethyltrichlorosilane, β-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane, triorganosilanemercaptan, trimethylsilylmercaptan,
Triorganosilyl acrylate, vinyldimethylacetoxysilane, dimethylethoxysilane, dimethyldimethoxysilane, diphenyldiethoxysilane, hexamethyldisiloxane, 1,3-divinyltetramethyldisiloxane, 1,3-diphenyltetramethyldisiloxane .

Examples of the organosilicon compound include silicone oil. As preferred silicone oils, those having a viscosity at 25 ° C. of about 30 to 1,000 centistokes are used. For example, dimethyl silicone oil, methylphenyl silicone oil, α-
Preferred are methylstyrene-modified silicone oil, chlorophenyl silicone oil, and fluorine-modified silicone oil. As a method of hydrophobizing treatment with silicone oil, for example, silica fine powder treated with a silane coupling agent and silicone oil may be directly mixed using a mixer such as a Henschel mixer, or silica as a base. Alternatively, a method of spraying silicone oil may be used. Alternatively, after dissolving or dispersing the silicone oil in an appropriate solvent, mix with the base silica fine powder,
It may be prepared by removing the solvent.

Further, the dry toner of the present invention may contain, if necessary, the following external additives in addition to the silica fine powder. Examples thereof include resin fine particles and inorganic fine particles that function as a charge auxiliary agent, a conductivity-imparting agent, a fluidity-imparting agent, an anti-caking agent, a release agent for fixing a hot roll, a lubricant, an abrasive, and the like. As a specific compound, for example, a lubricant such as Teflon, zinc stearate and polyvinylidene fluoride is preferable, and polyvinylidene fluoride is particularly preferable. Or,
Abrasives such as cerium oxide, silicon carbide and strontium titanate, among which strontium titanate are preferred.
Alternatively, for example, a fluidity-imparting agent such as titanium oxide and aluminum oxide, particularly a hydrophobic agent is preferable. Anti-caking agent, or, for example, carbon black, zinc oxide, antimony oxide, a conductivity imparting agent such as tin oxide,
Also, small amounts of fine particles of white and black having opposite polarities can be used as a developing property improver. When the inorganic fine powder or the hydrophobic inorganic fine powder as described above is externally added and mixed, 0.1 to 5 parts by weight, based on 100 parts by weight of the toner,
Preferably, it is used in the range of 0.1 to 3 parts by weight.

In preparing the toner of the present invention having the above-described structure, the following method can be used. For example, after sufficiently mixing the above-described toner constituent materials with a ball mill or other mixer, kneading them well using a heat kneader such as a hot roll kneader or an extruder, cooling and solidifying, and then mechanically pulverizing and classifying. A method for obtaining a toner having a desired particle size is preferable. As another method, after mixing a polymerizable monomer as a constituent material of the binder resin with a predetermined material such as an oxazoline-based compound to form an emulsified suspension, the polymerizable monomer is polymerized. In a method for producing a polymerized toner for obtaining toner particles, or a method for forming toner particles having a so-called microcapsule structure composed of a core material and a shell material, a core material or a shell material;
Alternatively, a method of forming toner particles by including a predetermined material in both of them, or a method of dispersing a constituent material in a binder resin solution and then obtaining the toner particles by spray drying can be applied. Further, if desired, the desired additives can be sufficiently mixed by a mixer such as a Henschel mixer to produce the dry toner of the present invention.

[0062]

The basic structure and characteristics of the dry toner of the present invention have been described above. The present invention will be described in more detail below with reference to examples and comparative examples. However, this does not limit the present invention in any way.
The number of parts is part by weight. << Production of Binder Resin >> First, Table 1 shows compositions of binder resins used in Examples and Comparative Examples. When a binder resin was prepared, a styrene resin was synthesized by a solution polymerization method, and a polyester resin was synthesized by a dehydration condensation method.

[0063]

[Table 1] Table 1: Binder resin composition

<< Production of Oxazoline Group-Containing Resin Component >> Next, the oxazoline group-containing resin components A-1 to A-3 used in Examples of the present invention were produced by the following method. (Production of oxazoline group-containing resin component A-1) A reflux condenser, a thermometer, a dropping funnel, and a nitrogen gas blowing tube were attached to a 2 L glass four-necked flask equipped with a stirrer, and 1250 parts of deionized water and polyvinyl chloride were added. 0.55 parts of alcohol was charged and heated to 80 ° C. in a nitrogen gas atmosphere to dissolve the polyvinyl alcohol, and then cooled to 50 ° C. or,
570 parts of styrene and 30 parts of 2-isopropenyl-2-oxazoline are mixed in a separate container, 2.6 parts of benzoyl peroxide is added, and a uniform polymerizable monomer composition solution (hereinafter simply referred to as a simple monomer) (Referred to as body solution). The monomer solution thus obtained was added to the flask, and kept in a nitrogen gas atmosphere under stirring at 300 rpm for 10 minutes to form a suspended state. Then, the internal temperature was raised to 80 ° C. to perform polymerization. Was started. Thereafter, this temperature was maintained for 7 hours to complete the polymerization of the polymerizable monomer. Next, the obtained reaction solution was filtered through a 200-mesh wire gauze, washed sufficiently with deionized water, and then filtered.
Drying was performed day and night with a hot air circulating dryer at 0 ° C. As a result, the diameter was about 0.18 mm, the weight average molecular weight was 135,
Thus, 000 granular oxazoline group-containing resin component A-1 was obtained.

(Production of oxazoline group-containing resin component A-2) In the production example of oxazoline group-containing resin component A-1, the monomer composition in the monomer solution was changed to styrene 450
Parts, 2-isopropenyl-2-oxazoline 50 parts, and benzoyl peroxide 1.2 parts, in the same manner as in the production example of A-1, having a diameter of about 0.21 mm and a weight average molecular weight of 142 parts. Thus, 2,000 granular oxazoline group-containing resin components A-2 were obtained.

(Production of oxazoline group-containing resin component A-3) In the production example of oxazoline group-containing resin component A-1, the monomer composition in the monomer solution was changed to styrene 495
Part, 2-isopropenyl-2-oxazoline 5 parts,
Except that 28 parts of benzoyl peroxide was used, a particulate oxazoline group-containing resin component A-3 having a diameter of about 0.22 mm and a weight average molecular weight of 145,000 was obtained in the same manner as in the production example of A-1 except that 28 parts of benzoyl peroxide was used. .

<< Production of Release Agent >> Then, use the following method
Release agents ad used in the examples of the invention were produced. Table 2
Table 2 shows the types and characteristics of the obtained release agents. (Production of release agent a) High molecular weight propylene-ethylene copolymer
Combined (Ethylene content 5% by weight)
400 ° C while continuously passing through a tube incorporating the xer
For 2 hours. The obtained propylene-ethylene
100 parts by weight of a copolymer, and 1.0 parts by weight of maleic anhydride
Parts, equipped with a nitrogen inlet pipe, thermometer, cooling pipe, and stirring rod.
Prepared in a 1-liter four-necked kolben, inside the kolben
While heating with a mantle heater while passing nitrogen through
The reaction was carried out at 200 ° C. for 12 hours with stirring. After the reaction,
While maintaining the temperature at 200 ° C, the inside of the system was depressurized and degassed.
After cooling, a mold release agent with an acid value of 3.5 mg KOH / g
a was obtained.

(Production of release agent b) A release agent b was obtained in the same manner as in the production example of release agent a, except that the amount of maleic anhydride was changed to 2.0 parts by weight. Table 2 shows the results.

(Production of release agent c) Release agent c was obtained in the same manner as in the production example of release agent a, except that 5.0 parts by weight of acrylic acid was used instead of maleic anhydride.

(Production of release agent d) A release agent d was obtained in the same manner as in the production example of release agent a, except that the amount of maleic anhydride was changed to 0.5 part by weight.

[0071]

Table 2: Components and properties of release agent

<Example 1> Binder resin A 100 parts Oxazoline group-containing resin component A-1 5 parts Magnetic material (spherical magnetic iron oxide having a number average particle diameter of 0.2 μm) 90 parts Release agent b 4 parts ・ Charge control agent (azo iron complex compound (1) of the following formula) 2 parts

[0073]

Embedded image

After the above materials were premixed by a Henschel mixer, they were melted and kneaded by a twin screw extruder set at 130 ° C. The obtained kneaded material was cooled, coarsely pulverized by a cutter mill, then pulverized by a fine pulverizer using a jet stream, and the obtained finely pulverized powder was classified using a multi-part classifier utilizing the Coanda effect. , Weight average particle size 6.5 μm
Was obtained. Methanol wettability 80% hydrophobized with 10 parts by weight of hexamethyldisilazane and 10 parts by weight of dimethyl silicone based on 100 parts by weight of the obtained toner particles, and a BET specific surface area of 120 m ² / g.
1.2 parts by weight of hydrophobic silica fine powder of
In this embodiment, the toner No. 1 was prepared.

This toner No. 1 is a commercially available LBP printer (LBP-) using a fixing device consisting of a pressing member for bringing a recording material into close contact with the heating member via a film.
430 (manufactured by Canon Inc.), which was remodeled to have a print speed three times higher, and an image output test was performed. The fixability and the anti-offset property were evaluated by the method and criteria described below. A commercially available LBP printer (LBP-930, manufactured by Canon Inc.) modified to 1.3 times the print speed was used under an environment of 23 ° C., 5% RH and 30 ° C., 8%.
In an environment of 0% RH, a print test of 15,000 sheets was performed. Table 4 shows the evaluation results.

Example 2 The procedure of Example 1 was repeated, except that the formulation of the toner was changed to the formulation shown in Table 3 using 10 parts of A-2 as the oxazoline group-containing resin component. Toner No. 2 was created. The same test as in Example 1 was performed using the obtained toner, and the obtained evaluation results are shown in Table 4.

Example 3 The same procedure as in Example 1 was carried out except that the formulation of the toner was changed to the formulation shown in Table 3 using 20 parts of A-3 as the oxazoline group-containing resin component. Toner No. 3 was created. The same test as in Example 1 was performed using the obtained toner, and the obtained evaluation results are shown in Table 4.

Example 4 The toner formulation was such that 1,4-bis- (Δ ² -oxazonyl-2) benzene was used as an oxazoline-based compound A-4 in place of 3 parts of the oxazoline group-containing resin component A-3. In the same manner as in Example 1 except that the formulation shown in Table 3 was used, the toner N of this example was used.
o. 4 was created. Example 1 using the obtained toner
The same test as that described above was performed, and the obtained evaluation results are shown in Table 4.

<Example 5> An oxazoline compound A was used instead of the oxazoline group-containing resin component.
As -5, 1,3-bis- (Δ ² -oxazonyl-2)
In the same manner as in Example 1 except that the formulation shown in Table 3 using 13 parts of propane was used, the toner No. 1 of this example was used. 5
It was created. The same test as in Example 1 was performed using the obtained toner, and the obtained evaluation results are shown in Table 4.

Example 6 The procedure of Example 1 was repeated, except that the formulation of the toner was changed to the formulation shown in Table 3 in which the amount of the oxazoline group-containing resin component A-1 was 0.03 parts. In the toner No. of the embodiment, No. 6 was created. The same test as in Example 1 was performed using the obtained toner, and the obtained evaluation results are shown in Table 4.

Example 7 This example was carried out in the same manner as in Example 1 except that the formulation of the toner was changed to the formulation shown in Table 3 in which the amount of the oxazoline group-containing resin component A-1 was 40 parts. Of toner No. 7 was created. The same test as in Example 1 was performed using the obtained toner, and the obtained evaluation results are shown in Table 4.
It was shown to.

Comparative Example 1 An azo chromium complex compound (2) of the following formula was used as a charge control agent instead of the azo iron complex compound (1), and the composition of the toner is shown in Table 3. In the same manner as in Example 1 except that the formulation was changed to the toner No. 8 was created. The obtained toner No. The same test as in Example 1 was performed using No. 8, and the evaluation results obtained are shown in Table 4.

[0083]

Embedded image

<Comparative Example 2> Toner No. of this comparative example was prepared in the same manner as in Example 1 except that the formulation of the toner was as shown in Table 3. 9 was created. The same test as in Example 1 was performed using the obtained toner, and the obtained evaluation results are shown in Table 4.

[0085]

Table 3: Toner formulations of Examples and Comparative Examples

<< Evaluation >> The toner Nos. Of Examples 1 to 7 and Comparative Examples 1 and 2 obtained above were used. 1 to No. An image-drawing test was performed using No. 9 and evaluated by the following methods and criteria. The obtained evaluation results are summarized in Table 4. (1) Developability Normally used plain paper for copying machines (75 g / m ² )
Then, 15,000 sheets were continuously printed out, and evaluation was made based on whether or not the image density at the end was maintained as compared with the initial period. The image density was measured using a “Macbeth reflection densitometer” (manufactured by Macbeth Co., Ltd.) and the original density was 0.00
Was measured relative to the printout image of the white background portion, and evaluated according to the following criteria.

(2) Fixing Property The fixing property was determined by rubbing a fixed image with a soft thin paper while applying a load of 50 g / cm ² , and calculating the reduction rate (%) of the image density before and after rubbing. Evaluation was based on criteria.

(3) Offset Resistance The offset resistance was evaluated according to the following criteria by printing out a sample image having an image area ratio of about 5%, observing the degree of contamination on the image after 3,000 sheets, and evaluating the following criteria. .

[0089]

[Table 4] Table 4: Evaluation results

[0090]

As described above, according to the present invention,
Oxazoline-based compound or a resin component having an oxazoline group, a binder resin having a carboxyl group or an acid anhydride group, and a configuration containing a specific release agent, offset resistance, excellent low-temperature fixability, furthermore, A dry toner having excellent developability and durability even under such an environment is provided.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Yoshihiro Ogawa 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Inventor Koichi Toyama 3-30-2 Shimomaruko, Ota-ku, Tokyo Non-corporation F term (reference) 2H005 AA01 AA02 AA06 CA04 CA13 CA14 CA18 CA28 CA30 DA06 DA10 EA07 EA10

Claims (8)

[Claims] 1. A dry toner having toner particles containing at least a binder resin, a colorant, an oxazoline-based compound or a resin component having an oxazoline group, and a release agent, wherein the binder resin has a carboxyl group or an acid anhydride. An oxazoline-based compound having two or more oxazoline groups in the molecule is contained in an amount of 0.001 to 30 parts by weight based on 100 parts by weight of the binder resin. A dry component characterized by containing 0.01 to 50 parts by weight of a resin component having two or more oxazoline groups therein and further containing at least a compound represented by the following formula (1) as a release agent: toner. Embedded image 2. An oxazoline-based compound is contained in an amount of 0.01 to 20 parts by weight based on 100 parts by weight of a binder resin, or a resin component having an oxazoline group is contained in an amount of 0.05 to 20 parts by weight.
The dry toner according to claim 1, which is contained in an amount of 30 parts by weight. 3. The dry toner according to claim 1, wherein a wax having an acid value of 1 to 30 mgKOH / g is contained as a release agent. 4. The dry toner according to claim 1, wherein a wax having an acid value of 1 to 15 mgKOH / g is contained as a release agent. 5. The method according to claim 1, wherein the release agent is modified with an acid monomer selected from at least one of maleic acid, maleic acid half ester, and maleic anhydride. 4. The dry toner according to item 1. 6. The carboxyl group or acid anhydride group of the binder resin is formed from an acid monomer selected from at least one of maleic acid, maleic acid half ester, and maleic anhydride. The dry toner according to any one of claims 1 to 5. 7. The dry toner according to claim 1, wherein the binder resin is a styrene-based copolymer. 8. The dry toner according to claim 1, wherein the toner particles are magnetic toner particles containing a magnetic substance as a colorant.