JPH07191492A - Color toner for flash fixing and its production - Google Patents

Abstract

PURPOSE:To obtain sufficient tone, electrifying characteristic and flash fixing property of a color toner for flash fixing by physically or chemically preventing, suppressing or compensating the reaction between an IR absorbent and a positive charge controlling agent. CONSTITUTION:The toner contains a binder resin, IR absorbent of aluminum salt compd. expressed by formula I and/or formula II, coloring agent, positive charge controlling agent. As for the binder resin, a mixture of several kinds of resins is used. The IR absorbent is selectively dispersed or dissolved in a specified resin among these resins to suppress the reaction between the IR absorbent and the positive charge controlling agent. Or, by using a compd. expressed by formula III for the IR absorbent, and further by mixing the compd. with one or more kinds of specified compds., decrease in the absorptivity and the charge controlling performance due to the reaction of the IR absorbent and the positive charge controlling agent can be compensated.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a color toner for flash fixing used for visualizing an electrostatic latent image in electrophotography and the like, and more particularly to a method for producing the same. The present invention relates to a color toner for flash fixing in which a triboelectric charging property of a toner containing a near-infrared light absorber as an essential component can be controlled, and a manufacturing method thereof.

[0002]

2. Description of the Related Art Conventionally, US Pat. No. 2 has been used as an electrophotographic method.
Although the method described in 297,691 is well known,
This generally uses a photoconductive insulator (such as a photocondrum) to give a uniform electrostatic charge on the photoconductive insulator by corona discharge or the like, and the photoconductive insulator by various means. An electrostatic latent image is formed by irradiating a light image on it, and then the latent image is developed and visualized by using fine powder called toner.

Then, after the toner image is transferred onto a recording medium such as paper, if necessary, the toner image is melted by pressure, heat, solvent vapor, light, etc. and fixed on the recording medium to obtain a printed matter. Is what you get. As a toner for developing these electrostatic latent images, a toner obtained by dispersing an additive such as a colorant and, if necessary, a charge control agent in a binder resin made of a natural or synthetic polymer substance has been used. 30 μm
Finely pulverized particles are used.

In the electrophotographic two-component developing method, such a toner is usually mixed with a ferromagnetic substance such as iron powder and a carrier substance such as glass beads and used for developing an electrostatic latent image. In the case of the magnetic brush development method using ferromagnetic particles such as iron powder or ferrite as the carrier, the developer composed of the toner and the carrier is triboelectrically charged by being mixed and stirred in the developing device. It is held by a magnet roll to form a magnetic brush, and when the magnet roll rotates, the magnetic brush is carried to the latent image portion on the photoconductive insulator, and only the charged toner adheres to the latent image by the electric attraction force. By doing so, development is performed.

Here, since the binder resin constituting the toner is required to melt quickly in the process of fixing on the recording medium and exhibit good fixing property, it is generally called an oligomer having a low melt viscosity and a low molecular weight. Polymer resins are widely used. On the other hand, the fixing is that the toner on the surface of the recording paper is melted by pressure, heat, solvent vapor, light, etc., and is fixed to the recording paper. Among these fixing methods, the following characteristics are provided. The optical fixing method that is being used is attracting attention.

(1) Since it is non-contact fixing, the resolution of the image is not deteriorated during the fixing process. (2) Quick start is possible because there is no waiting time after turning on the power to the device. (3) Even if the recording paper is jammed in the fixing device due to system down, it does not ignite. (4) Fixing is possible regardless of the material and thickness of the recording paper, such as glued paper, preprinted paper, and paper of different thickness.

At present, the most common optical fixing method is a flash fixing method using xenon flash light as a light source. The optical fixing method that uses a light source with a high emission intensity in the infrared region, such as the xenon flash fixing method, improves the light absorption capacity of the toner and expands the range of use of the optical fixing method that has the above advantages. As an example, a method of adding an infrared light absorber of an ammoniumyl compound such as an aminium salt compound to the toner is disclosed in JP-A-61-1.
32959 and the like.

[0008]

Compounds having a high infrared light absorption ability often have a brown to black hue, while aminium salt compounds show excellent infrared light absorption ability. Since some compounds exhibit a light color tone in the visible light region, they have little influence on the original color tone of the toner, and are considered to be very useful compounds for supplementing the light absorbing ability of the color toner.

However, this aminium salt compound is

[0010]

[Chemical 13]

As described above, since it is a salt structure substance having a counter ion, a strong polar site (for example, a tertiary amine such as dimethylaminoethyl methacrylate) in the toner or an ionic compound having a high reactivity (for example, a tertiary amine). If there is a quaternary ammonium salt or the like), the counterion of the aminium salt-based compound undergoes abstraction by the polar group, or a counterion exchange reaction occurs with the ionic compound.

Therefore, since the structural change of the aminium salt compound occurs, the light absorption band of the aminium salt compound shifts, and in a remarkable case, the light absorption ability for the wavelength of the flash light region is completely lost. There's a problem. On the other hand, the quaternary ammonium salt has excellent charge controllability as a colorless positive polarity charge control agent and is commonly used in color toners. Further, as a method of imparting a positive chargeability to the toner without using the quaternary ammonium salt, whether an amine compound other than the quaternary ammonium salt is added to the toner, or an amine functional group is introduced into the binder resin, etc. However, as described above, these amine compounds are also highly likely to cause the structural change of the aminium salt compound.

From the above, an aminium salt-based compound that improves the light absorption ability of the color toner and an amine-based compound such as a quaternary ammonium salt that imparts the charge control ability (hereinafter, referred to as
(Charge control agent) cannot be used together, and the positively chargeable color toner that has excellent light absorption and good photofixability has poor charging characteristics, and the positively chargeable color toner that has excellent charging characteristics has optical fixation. There is a problem that it is inferior in sex.

The present invention has been made in view of the above-mentioned circumstances, and the coexistence of the aminium salt-based compound and the charge control agent in the toner is intended to minimize the structural change of the aminium salt-based compound, and An object of the present invention is to provide a toner for flash fixing which has both flash fixability and charging characteristics, and a method for producing the same.

[0015]

In order to achieve the above object, the present invention provides a binder resin and the following general formulas (1) and / or (2).

[0016]

[Chemical 14]

An infrared light absorber of an aminium salt compound represented by: a colorant, and a positive polarity charge control agent,
The reaction between the infrared light absorber and the positive polarity charge control agent or / and the positive polarity charge control resin (hereinafter, the positive polarity charge control agent and the positive polarity charge control agent are also simply referred to as positive polarity control agent). The light absorption ability and the charge control ability which are suppressed by any of the means (i) to (Vi) below or reduced by the reaction between the infrared light absorber and the positive charge control agent are described below (vii).
Alternatively, there is provided a color toner for flash fixing, characterized by being complemented by the means (viii).

(I) A mixture of plural kinds of resins is used as the binder resin, and the infrared absorber is selectively dispersed or melted in a part of the specific resin. (Ii) A positive electrode charge control agent and / or a binder resin containing a positive electrode charge control agent is coated on or adhered as fine particles to the outer peripheral portion of a toner containing an infrared light absorber, a colorant, and a binder resin. .

(Iii) An infrared light absorbing agent and / or a binder resin containing an infrared light absorbing agent is coated or attached as fine particles on the outer peripheral portion of a toner containing a colorant and a positive polarity charge control agent. . (Iv) As a binder resin, an amine-containing functional group resin containing a functional group of a secondary amine and / or a tertiary amine and / or a quaternary amine, and / or a quaternary ammonium salt, and a resin containing an acidic functional group. The mixture is used to block the amine-containing functional group resin and / or the quaternary ammonium salt with a resin containing an acidic functional group.

(V) As the binder resin, a thermoplastic resin having an amide group and / or a pendant group of a nitrogen-containing ring, an amide compound, a polyamide resin, an amine-modified polyester resin, a urethane-modified polyester resin, an amine-modified epoxy crosslinked with a diamine. At least one resin is used. (Vi) General formula (3) as a positive polarity charge control agent

[0021]

[Chemical 15]

A quaternary ammonium salt represented by is used. (Vii) As the infrared light absorber, the compound represented by the general formula (1) and the compound represented by the general formula (2) are used in combination and the anion X ⁻ is commonly used, or the compound represented by the general formula (1) is used. Two or more kinds of the represented compounds are used. (Viii) As the infrared light absorber, one or more of the compounds represented by the general formulas (4) to (8) are further mixed and used.

[0023]

[Chemical 16]

[0024]

[Chemical 17]

[0025]

[Chemical 18]

[0026]

[Chemical 19]

[0027]

[Chemical 20]

A detailed description will be given below. The toner of the present invention relates to a color toner for flash fixing, and for this reason, a binder resin contains a colorant, an infrared light absorber, and a positive charge control agent. The binder resin is not particularly limited, and thermoplastic resins made of various natural or synthetic polymer substances can be used, but typically, an epoxy resin having a weight average molecular weight of about 5,000 to 100,000 and a melting point of 90 to 140 ° C. , Styrene-acrylic resin, polyamide resin,
Polyester resin, polyvinyl resin, polyurethane resin, polybutadiene resin, etc. may be used alone or in combination.

The colorant (coloring agent) is not particularly limited either, and a dye,
Any of pigments and the like may be used, for example, quinacridone (red), phthalocyanine (blue, etc.), anthraquinone (red), bisazo (red or yellow), monoazo (red),
Anilide compounds (yellow), benzidine (yellow), halogenated phthalocyanine (green), etc. are used. As the infrared light absorber, aminium salt compounds represented by the general formulas (1) and (2) are used. These aminium salt-based compounds have high absorption ability in the infrared light region and have a light color in the visible light region, and therefore have little effect of contaminating the color tone of the toner, and are suitable for color toners. Infrared light absorbers other than the aminium salt compounds represented by the general formulas (1) and (2) may be used in combination. Black dyes and pigments such as carbon black have a high ability to absorb infrared light, but have a high degree of blackness and stain the tone of the toner, so they cannot be used for color toners.

In the general formulas (1) and (2), anions
X^-As perchloric acid (CClO_Four ^-), Boron fluoride
Acid (BF_Four ^-), Trichloroacetic acid (CCl₃ CO
O^-), Trifluoroacetic acid (CF₃ COO^-), Picuri
Acid ((NO₂)₃ C₆ H₂ O^-), Hexafluoroarsenic
Acid (AsF₆ ^-), Hexafluoroantimonic acid (Sb
F₆ ^-), Benzenesulfonic acid (C₆ H_Five SO
₃ ^-), Ethanesulfonic acid (C₂H_Five SO₃ ^-), Phosphorus
Acid (PO_Four ^2-), Sulfuric acid (SO_Four ^-), Chlorine (Cl^-) of
Each ion is representative.

The positive charge control agent is also not particularly limited as long as it has the ability to positively charge the toner by stirring the developer, but preferably a quaternary ammonium salt (colorless), a nigrosine dye (black), triphenyl. A methane derivative (blue) or the like is used. In addition, the compounds and resins described below can also be used as the positive charge control agent. Further, in order to adjust the charge controllability, a negative charge control agent such as a zinc naphthoate complex (colorless) and a zinc salicylate complex (colorless) can be used in combination.

Various other additives can be added to the color toner for flash fixing, and waxes (for example, polypropylene wax) and surfactants (for example, silicone varnish) can be particularly mentioned. The average particle size of the toner is generally about 1 to 30 μm, but is not particularly limited.

According to the present invention, in such a color toner for flash fixing, it is described below that the infrared light absorbing agent of the aminium salt type reacts particularly with the positive polarity charge control agent to lower or lose the infrared light absorbing performance. It is characterized in that it is prevented, suppressed or supplemented by the means of.

Means (i) As schematically shown in FIG. 1, binder resins 1-1 and 1-2 having poor compatibility are used as a binder resin, and an aminium salt-based infrared light absorber 2 is used. A specific binder resin 1-1 among them is selectively dispersed or melted. In particular, the positive charge control agent 3 is selectively dispersed or melted in the other binder resin 1-2.

A plurality of binder resins 1-1 and 1-2 have a so-called "sea-island structure", and the infrared light absorber 2 is selectively present in a specific binder resin 1-1 (or 1-2). By making the positive polarity charge control agent 3 selectively exist in the other binder resin 1-2 (or 1-1), the infrared light absorber 2 and the positive polarity charge control agent 3 are By reducing the chance of contact, these mutual reactions could be prevented or suppressed, which made it possible to achieve both fixability and charging characteristics in the color toner for flash fixing.

As described above, the aminium salt-based compound loses its function when the counter ion is disturbed, but the substance causing such a reaction is widely used as the charge control agent for the positively charged toner. Quaternary ammonium salts, amine-containing functional group resins, and the like. According to the study by the present inventors, a resin having a strong charging property such that one or more binders among a plurality of binders used for toner have an amine compound in the molecular skeleton (amine-containing functional group resin).
It is also possible to make the resin itself a so-called “sea” or “island” while giving the resin a function as a positive charge control agent.

For example, as the positive charge control agent, a gel resin of an amine-containing functional group resin having a melting point of 200 ° C. or higher can be used. The reason why it is more preferable to use a gel-like resin having a melting point of 200 ° C. or higher is that the reaction with an aminium salt-based compound during toner production is suppressed when a resin that does not soften at a general toner kneading temperature is selected. .

The solubility parameter of the binder resin 1-1 for dispersing or melting the aminium salt compound 2 and the binder resin 1-2 for dispersing or melting the positive charge control agent 3 is 0.5 or more, preferably 1 or more. You need to be proficient. This is for each binder resin 1-2 and 1-1.
When the compatibility is high, both binder resins are homogeneously mixed without adopting the “sea-island structure”, and therefore the aminium salt-based compound 2
This is because the chances of the positive charge control agent 3 approaching each other increase and the object of the present invention is difficult to achieve.

According to the studies made by the present inventors, combinations of thermoplastic resins satisfying these conditions are: polyester resin and epoxy resin; polyester resin and styrene-acrylic resin; polyester resin and polyamide resin; polyester resin and styrene. -Butadiene resin, epoxy resin and styrene-acrylic resin, epoxy resin and polyamide resin, epoxy resin and styrene-butadiene resin, polyamide resin and styrene-acrylic resin, polyamide resin and styrene-butadiene resin, styrene-acrylic and styrene-butadiene resin It has been found that such various combinations as described above satisfy such a difference in the meltability parameters and satisfy various characteristics required for the binder for flash fixing.

According to the study by the present inventors, the best combination among the above combinations is polyester resin, styrene-acrylic resin, styrene-butadiene resin,
And a combination of styrene, acrylate, and butadiene copolymer resin. This is different from the subject matter of the present invention, but is good while preventing the "void phenomenon" that occurs when the toner particles are melted and agglomerated during flash fixing, which is discussed in JP-A-4-56869. Achieving the melt viscoelastic properties required to maintain good fixability by using a combination of the above polyester resin and a styrene-acrylic resin, a styrene-butadiene resin, and a copolymer resin of styrene, acrylate, butadiene, and the like. This is because it is easy to do.

According to the studies by the present inventors, a polyester resin is more preferable as the binder resin in which the aminium salt compound is dispersed. This is because even if the resin does not contain an amine compound as described above, the degree is lighter than that of the amine compound depending on the type of the monomer constituting the binder resin. This is to carry out the reaction.

Such an example is sometimes found when a binder such as styrene-acrylic resin is used. For example, in a styrene-n-butyl acrylate copolymer, a reaction with an aminium salt compound is not observed, but a styrene-n-butyl acrylate copolymer is used. The inventors of the present invention have obtained results such as a considerably strong salt abstraction reaction with the 2-ethylhexyl acrylate copolymer.

On the other hand, the polyester resin is a diol,
Various binder resins were produced by changing the monomer type such as dicarboxylic acid and the monomer composition ratio, and the reactivity was investigated, but it reacts with aminium salt compounds except when some nitrogen-containing monomers are used. There was nothing. Therefore,
When two kinds of resins having different solubility parameters, for example, two kinds of resins such as polyester and styrene-acryl are selected, an aminium salt compound is dispersed on the polyester side and a charge control agent is dispersed on the styrene-acryl side. Is more desirable.

According to the experience of the present inventors, it is desirable that the resin in which the charge control agent is dispersed has a higher melt viscosity. This is because it is often the case that the charge control agent is dispersed in a resin having a high melt viscosity to obtain a desired charge control effect by adding a smaller amount of the charge control agent. As such a resin having a high melt viscosity, a polyfunctional acid such as trimellitic acid or pentaerythritol, a cross-linkable polyester resin containing a polyfunctional alcohol as an essential constituent monomer, or a cross-linking resin containing divinylbenzene or the like as an essential constituent monomer Styrene-acrylic resins and the like are known.

According to the knowledge of the present inventors, as a configuration which satisfies the above-mentioned requirements and satisfies the gist of the present invention,
It is more desirable to add an aminium salt-based compound to a polyester-based resin or a polyamide-based resin. On the other hand, a resin having a solubility parameter greatly different from that of the polyester resin or the polyamide resin is required as the resin in which the positive charge control agent is dispersed. Therefore, in order to effectively bring out the effect of the present invention, it is more preferable to use a styrene-acrylic resin or a styrene-butadiene resin which has a property of a slightly high viscosity resin and which has crosslinking and the like.

The method of carrying out the present invention is as follows.
It is necessary to disperse the aminium salt-based compound in any one of a plurality of binder resins having different melting parameters and the positive charge control agent in another binder resin. As a method of dispersing an internal additive such as an aminium salt-based compound or a positive polarity charge control agent in these binder resins, a method of dispersing these internal additives during the polymerization of the binder resin, after manufacturing the binder resin There is a method of dispersing the internal additive by kneading, and the present invention can be carried out by any method.

In the method of dispersing the internal additive during resin polymerization and the method of dispersing the internal additive by kneading, it is preferable to disperse the internal additive during resin polymerization in view of dispersion efficiency of the internal additive and manufacturing cost. Although advantageous, aminium salt compounds and quaternary ammonium salts that are commonly used as charge control agents have poor heat resistance and change in characteristics at temperatures below 200 ° C., so binder resin systems for toner are limited. The problem is included.

Next, a binder resin containing an internal additive, which is an essential component thereof, is combined to form a toner. This method includes kneading and pulverizing, and aggregation and heating in a liquid phase. There are two methods available. One is a method of forming a toner by kneading and pulverizing, but a binder resin containing an aminium salt compound and a binder resin containing a positive charge control agent, and if necessary, an internal additive such as a coloring agent and a wax. Are mixed, the above materials are melt-kneaded by using a kneader, an extruder or the like, and then crushed and classified by using a crusher such as a jet mill to obtain a desired toner. For example, a polyester resin containing terephthalic acid as a main component and a bisphenol A alkylene oxide adduct as a main diol is used as a resin for dispersing or melting an aminium salt compound, the dispersion is performed by kneading, and then a rotoplex grinder is used. And particle size 1
By obtaining a pelletized pulverized product of about 5 mm, it is possible to obtain a resin fine powder in which an aminium salt compound is melted or dispersed.

However, when the binder resin in which the aminium salt compound is dispersed and the resin in which the positive charge control agent is dispersed are too low in degree of dispersion during kneading, the toner particles in the toner particles after crushing and classification are too small. In addition, it is not preferable because a toner composed of only one resin component is present. Conversely, when the kneading strength is strong and both resins are well dispersed, the so-called “sea” and “island” interface is formed. This is not preferable because the ratio of the reacting aminium salt compound to the positive charge control agent increases, and the toner cannot achieve both desired light absorption ability and charge control ability.

Therefore, based on the experience of the present inventors, it is desirable that the binder resin of both be kneaded relatively gently. When the dispersion state of other internal additives such as colorants and waxes does not reach a desired state by such gentle kneading, the binder resin is charged with a positive charge control agent or an aminium salt compound. It is also possible to disperse other internal additives such as coloring agents and waxes at the time of dispersion.

On the other hand, a method of forming a toner by aggregating and heating in a liquid phase is a resin fine powder in which an aminium salt compound is dispersed or melted and a resin fine powder in which a positive charge control agent is dispersed or melted (charged). A resin fine powder having controllability) may be dispersed in the liquid phase, the resin powder may be agglomerated by means such as controlling the charging characteristics of the resin fine powder in the liquid phase, and the resin powder may further be heated. The toner is formed by partially melting and fixing the agglomerates. For example, a fine powder of a binder resin in which an aminium salt compound is previously dispersed or melted, a fine powder of a binder resin in which a positive polarity charge control agent is previously dispersed or melted, and / or a thermoplastic resin of an amine-containing functional group resin. It is possible to obtain a toner by aggregating and fixing tens to tens of thousands of particles of a thermoplastic resin fine powder containing the resin fine powder in a liquid phase, using the fine powder of (1) as an essential component.

The toner prepared by this method is prepared by
Compared to pulverized toner, "sea" which is the subject of the present invention
Since this is the most suitable production method for carrying out the present invention because the "islands" are clearly formed, the problem in putting the production method into practical use is that the aminium salt compound or the charge control agent is dispersed. It is how to obtain the fine resin fine powder (primary particles) thus obtained.

According to the study of the present inventors, when a styrene-acrylic resin is used as the binder resin, it is possible to use a polymerization method such as a suspension polymerization method or an emulsion polymerization method.
Spherical particles having a size of submicron to 2 μm can be obtained, and a charge control agent can be contained in these particles. On the other hand, a large difference in solubility parameter with styrene-acrylic resin, in the case of epoxy resin or polyester resin, fine resin powder cannot be obtained by the above-mentioned polymerization method, and aminium salt-based compound is a polymer of these resins. In the process, a decomposition reaction occurs and the function is lost.

Therefore, the inventors of the present invention used bisphenol A type or F type resin as the resin for dispersing the aminium salt compound.
It has been found that a type epoxy resin and a short-chain linear diol having a methyl side chain and an asymmetric carbon and an amorphous polyester resin containing terephthalic acid as a main monomer are used. These resins have extremely high pulverization efficiency, and it becomes possible to easily obtain a fine powder having a particle size of 2 μm or less even by using an ordinary jet mill.

Specifically, the aminium salt compound (2)
As the essential constituent monomer of the binder that disperses or melts, a polyester resin containing 30 mol% or more of a short chain diol having an asymmetric carbon and 5 or less carbon atoms and 30 mol% or more of terephthalic acid, or a bisphenol A type resin or A resin in which the aminium salt compound (2) is melted or dispersed by kneading the dispersion using a bisphenol F type epoxy resin, and then pulverizing it to have an average particle size of 2 μm or less and a maximum particle size of 5 μm or less. A fine powder is obtained.

Further, according to the study by the present inventors,
In the case of forming a toner by heating, in addition to a binder resin in which an aminium salt compound is dispersed and a binder resin in which a positive charge control agent is dispersed, resin fine powder having a low melting point is further added, and these three kinds of resins are added in a liquid phase. Only a resin with a low melting point is melted by a binder resin in which an aminium salt-based compound is dispersed,
When the binder resin in which the positive polarity charge control agent is dispersed is melted and fixed at a temperature that does not melt, the reaction between the aminium salt compound and the positive polarity charge control agent is minimized, and excellent light absorption ability and charge control ability are both achieved. It becomes possible to do.

Specifically, a binder resin fine powder (first resin fine powder) in which an aminium salt compound is dispersed or melted in advance, and a binder in which a positive polarity charge control agent (3) is dispersed or melted in advance. Resin fine powder and / or thermoplastic resin fine powder of amine-containing functional group resin (second resin fine powder) and third thermoplastic resin having a lower melting temperature than the first and second resin fine powders After agglomerating tens to tens of thousands of particles of the thermoplastic resin fine powder containing the fine resin powder as an essential constituent component in the liquid phase, the first and second resin fine powders do not melt. By heating the liquid phase to a temperature at which the third resin fine powder melts, the resin fine powders are fixed to each other.

Means (ii) First, a toner containing an aminium salt-based compound is produced, and thereafter, a charge control agent or resin powder containing the charge control agent is adhered to the outer peripheral portion of the toner (hereinafter, referred to as “external”). Or a resin film containing a charge control agent is formed on the surface layer of the toner containing an aminium salt-based compound, so that the charge control ability can be provided on the toner surface layer, and It has been made possible to have excellent light absorption ability. As a result, a toner having both fixing property and charging property can be obtained.

The average particle size of the externally added resin is preferably 0.5 μm or less. As the charge control agent, a quaternary ammonium salt or an amine-containing functional group resin can be used. As means for imparting charge controllability to the surface layer of the toner, there are a method of externally adding a resin powder having excellent charge controllability and a method of forming into a film. Although it has advantages such as simplicity and cost merit, since the externally added resin powder is held on the surface of the toner base containing the aminium salt-based compound by the electrostatic force of triboelectric charging between them, If the triboelectrification characteristic of No. 1 does not exist at an appropriate level, it is necessary to consider the effect that external additive powder is separated from the toner surface due to stress such as stirring in the developing device. Therefore, it is more desirable to adopt a method of forming a resin film layer having excellent charge controllability on the surface layer of the toner base particles.

As a method of forming the film layer on the toner surface layer, a method of dissolving the material of the film layer in a solvent and coating the surface of the toner base particles by a method such as spray drying can be adopted. The film-forming method most suited to the purpose of the present application is a mechanofusion method, that is, the surface of the toner base particles is electrostatically adsorbed with a fine powder of a resin used as a material for the film layer, and then the toner surface is heated by mechanical impact. The most suitable method is to pressurize and, as a result, melt the fine powder of the resin used as the material of the film layer to form a film. This is because the mechanofusion method does not use a solvent or the like as a medium and does not cause a wide range of dissolution on the surface of the toner base, and as a result, the reaction between the aminium salt in the toner base and the charge control agent in the film layer material is minimal. Because it can be suppressed to the limit.

Means (iii) Therefore, as a means for solving this problem, the present inventors
The charge control agent reacts with the aminium salt compound by using a function-separated toner in which the base of the toner particles has charge controllability, and the thermoplastic resin powder externally added to the surface of the toner particles has light absorption ability. Preventing, and with respect to the charging characteristics, mainly utilizing the function of the charge control agent added to the toner base, and in the fixing step, the aminium salt-based compound added to the externally added resin shows good light absorption ability and generates heat, It has been found that the heat is transferred from the externally added resin to the toner base, whereby the entire toner is melted and excellent flash fixing ability can be obtained.

The average particle size of the resin fine powder added externally is 0.5 μm.
m or more and 5.0 μm or less, the content of the aminium salt compound in the resin fine powder is 10% by weight or more and 50% by weight or less, and the external addition amount of the resin fine powder to the toner is 2% by weight. % Or more and 5% by weight or less, and the content of the aminium salt compound with respect to the total weight of the toner is preferably 0.5% by weight or more. this is,
This is because if the average particle size is smaller than the above range, the amount of the aminium salt compound-containing resin fine powder adhering to the toner surface becomes small, while if it is too large, it becomes difficult to adhere to the toner surface. Further, when the amount of the resin fine powder and the amount of the aminium salt-based compound added in the resin fine powder are less than the above range, the toner fixing becomes difficult because the amount of the aminium salt-based compound added to the total amount of the toner is insufficient. On the other hand, if the amount is too large, the effect of the color tone of the aminium salt-based compound on the toner color tone cannot be ignored, and the electrical resistance of the resin fine powder becomes low, so that the resin fine powder is less likely to electrostatically adhere to the toner base. This is because

Further, the material of the resin fine powder for external addition according to the present invention is arbitrary as long as it is a thermoplastic resin having no reactivity with the aminium salt compound.
When a method of obtaining a desired resin fine powder by pulverization such as jet mill pulverization after melt-kneading an aminium salt compound with the resin fine powder, bisphenol A type or bisphenol F type epoxy resin, methyl side chain An amorphous polyester resin containing 30 mol% or more of a short-chain linear diol (having 5 or less carbon atoms) and having an asymmetric carbon and 30 mol% or more of terephthalic acid is recommended. This is because the above resin has no reactivity with an aminium salt-based compound, has extremely good pulverizability, and a resin fine powder having a desired particle size can be easily obtained. As a method of producing resin fine powder other than the pulverization method, it is also possible to spray a molten mixture of a thermoplastic resin and an aminium salt compound dissolved in an organic solvent by a spray dry method.

Means (iv) In a toner containing an aminium salt-based compound, when a substance having a basic site having high reactivity with the aminium salt-based compound is allowed to coexist in the toner, the base is more than the aminium salt-based compound. By introducing a substance having a functional group having high reactivity with a substance containing a basic moiety, for example, a substance having a sulfonic acid or a carboxylic acid, it is possible to moderate the reaction of the substance containing a basic site with an aminium salt compound. I found it.

Functional groups that can exert the effects of the present invention include acidic functional groups such as carboxylic acid and sulfonic acid, and substances having these functional groups include carboxylic acid-containing monomers such as polyester resin and acrylic acid. It is possible to find polyacrylic resins, styrene-acrylic resins, and the like in which is an essential monomer. In order to effectively bring out the effect of the present invention, it is desirable that the acid value of the acidic functional group is 30 mg / KOH or more.

Further, the substance containing a basic site introduced for the purpose of imparting positive charging property in the present invention is 4
It is a primary ammonium salt or an amine-containing functional group resin, and is effective in any case where the amine-containing functional group resin is a copolymer containing styrene and / or acrylate and / or amino acrylate as an essential monomer. However, the more effective effect is that amine-modified polyacrylate and amine-modified styrene-containing amino acrylate as an essential monomer in the skeleton as a substance containing a basic site to be introduced for the purpose of imparting positive chargeability. Acrylates.

In this case, it is desirable that the equivalent of the acidic functional group of the resin containing the acidic functional group is 1/2 to 2 times the amine equivalent of the amine-containing functional group resin. The toner according to the present invention is manufactured by a conventional method in which an aminium salt-based compound, a resin that imparts positive chargeability and / or a positive charge control agent, an acidic functional group-containing binder resin, a colorant, etc. are melt-kneaded and then pulverized and classified. Although it is possible to obtain by the process, in order to effectively exert the effect of the present invention,
First, a resin and / or a positive charge control agent that imparts positive chargeability to a binder resin containing an acidic functional group, such as 4
After producing a resin mixture melt-kneaded with a resin containing an amine functional group such as a quaternary ammonium or a styrene-dimethylaminoethyl methacrylate copolymer, the resin mixture, a colorant and an aminium salt compound are melt-kneaded again.
It is more effective to carry out stepwise kneading.

The mixing of the binder resin containing an acidic functional group with the resin imparting positive chargeability and / or the positive charge control agent is carried out by adding the other resin in the process of polymerizing one resin. It is also possible to do by.

Means (v) It was found that the binder resin having a specific chemical structure shows a gradual positive charging property and does not impair the light absorption property and the charge imparting property of the aminium salt compound. The binder resin according to the present invention is compared with aliphatic tertiary amines and quaternary ammonium salts represented by styrene-dimethylaminoethyl methacrylate copolymer,
Since the basicity is a little weak, it is difficult to cause the salt-withdrawing reaction of the aminium salt-based compound, and it has a positive charge to supplement the positive charging property of the aminium salt-based compound. The binder resin satisfying the above characteristics is a nitrogen-containing cyclic structure such as an imidazole ring, a pyrimidine ring, a pyrrolidone ring, a pyrazole ring, a pyrroline ring, a pyrrole ring and / or -RCONH ₂ (R is a benzene ring or a C 0-2 aliphatic group). It can be found in a thermoplastic resin having a structure in which an amide group represented by (hydrocarbon) is pendantly coordinated to a binder molecular chain. A thermoplastic resin having such a structure and satisfying the heat melting property and the rheological property required as a binder resin for toner is a vinyl-based monomer and / or an acrylamide-based monomer having a nitrogen-containing cyclic structure such as vinylpyrrolidone. Can be obtained as a styrene and a styrene-acrylate copolymer in which is an essential constituent monomer.

The copolymerization ratio of the acrylamide monomer and the monomer having a nitrogen-containing cyclic structure is 10 mol% or more 2
It is preferably 0 mol% or less. This is because when the copolymerization ratio is less than 10 mol%, the binder resin may not show the desired positive charging characteristics in some cases, and when it exceeds 20 mol%, the binder resin for toner is often used while frequently using such monomers. This is because it becomes difficult to satisfy the heat melting property and the rheological property required as above, and in some rare cases, the degree of salt abstraction reaction with respect to the aminium salt compound may exceed the allowable limit.

Further, as a binder which exhibits a gentle positive charging property and does not impair the light absorption property and the charge imparting property of the aminium salt compound, other than the above-mentioned binder having a pendant structure of an amide group and a nitrogen-containing ring. , Amide-based resins such as amide monomers and polyamide resins, amine-modified polyester resins containing aminodicarboxylic acid-containing or aminodiol-containing monomers as essential constituent monomers (more specifically, for polyester resins having an acid value of 15 or more, 10-30% of the carboxylic acid terminal is amide-capped with a monoamine or cross-linked with a diamine), and a urethane-modified polyester resin in which a terminal hydroxyl group is urethane-sealed with isocyanate or the like (more specifically, 10 For polyester resin with OH value above, Urethane sealed urethane modified polyester resin) 20% or more of alcohol end of both ends of the diamine and an amine modified epoxy resin obtained by crosslinking by reacting with the hydroxyl group of the epoxy resin have been found.

When the amide monomer is used as the binder, it is desirable to use a compound having a molecular weight of about 500 to 3000 in order to achieve both the heat melting property and the filming resistance with respect to the photosensitive drum. In addition, since polyester resin generally has a negative charging property, the positive chargeability is imparted by using the amino-containing monomer, and the copolymerization ratio of the amino-containing monomer is required in order to satisfy the requirements of the present invention. Is preferably not less than 10 mol% and not more than 30 ml%, and in the case of a urethane-modified polyester resin, it is desirable to seal 20% or more of the alcohol end of the polyester resin having an OH value of 10 or more with urethane.

Means (vi) When a charge control agent having a salt structure such as a quaternary ammonium salt is used to prevent a salt exchange reaction, a charge control agent having a salt structure with an anion constituting an aminium salt compound is used. The constituent anions were the common ions. That is,
General formula (3) as a positive charge control agent

[0074]

[Chemical 21]

A quaternary ammonium salt represented by is used. As a result, a structure change between the aminium salt compound and the charge control agent does not occur, the aminium salt compound and the charge control agent maintain their original functions, and a toner having both fixability and charge characteristics can be obtained. As the aminium salt-based compound having a high infrared light absorption ability and a light color tone in the visible light region, perchlorates, fluoroborates, hexafluoroarsenates, hexafluoroantimonates, alkyl sulfonates Salts have been found. On the other hand, what is commonly used as a quaternary ammonium salt having a high charge control ability is a sulfonate quaternary ammonium salt or a molybdate quaternary ammonium salt. Light absorption capacity of aminium salt compounds,
We have found anions of sulfonates and molybdates as anions exhibiting excellent properties in terms of both charge control ability of quaternary ammonium salts.
In addition, when the perchlorate ion or the fluoroboron ion is used as the anionic species, the characteristics are relatively good, but when the perchlorate ion or the fluoroboron ion is used as the ionic species, the quaternary ammonium is used. There is some room for improvement in the charge controllability on the salt side, especially the charge rising ability. Therefore, in toner that requires a high level of charge control function,
When perchlorate ion or fluoroboron ion is selected as the common anion species, by using an extremely small amount of sulfonate quaternary ammonium salt or molybdate quaternary ammonium salt as the charge control agent, , Have confirmed that excellent performance is obtained. In this case, if a quaternary ammonium salt having an anion different from the anion of the aminium salt compound is used, there is a risk that the salt exchange reaction may occur, but the addition amount of the quaternary ammonium salt having a different anion may be increased. 1 / Aminium salt-based compound
When the amount is 5 equivalents or less, some of the aminium salt-based compound loses its function, but the infrared light absorption ability of the entire toner does not deteriorate so much, and an excellent charge control function and infrared light absorption ability can both be achieved. Is possible.

It is also possible to improve the toner charge control function by using an amine compound as a binder resin or other additives. In this case, the amine compound also has a possibility of causing an ion abstraction reaction of the aminium salt compound, but like the sulfonate quaternary ammonium salt and molybdate quaternary ammonium salt in the toner, When the amount of the amine-based compound present in the toner is less than 1/5 equivalent of the added amount of the aminium salt, the infrared light absorbing ability of the entire toner does not decrease so much, and the presence of the amine group reduces the charge control function of the toner. It is possible to improve both the charge control function and the infrared light absorbing ability.

Means (vii) According to the research conducted by the present inventors, comparing the compound represented by the general formula (1) with the compound represented by the general formula (2), the compound represented by the general formula (2) Compared with the compound represented by 1), it has advantages of high positive chargeability and high light absorption ability, but on the other hand, it has a problem that the color tone is slightly dark, and therefore it has a general formula (2) as an infrared light absorber. When only the compound represented by the formula (1) was used, the color tone of the color toner tended to be slightly dull. Therefore, the present inventors obtained a compound satisfying the charging ability, light absorption ability, and color tone by blending and using the compound represented by the general formula (1) and the compound represented by the general formula (2). I found that I could be.

According to the study of the present inventors, in order to prevent the influence on the color toner, the blend ratio of the general formula (1) and the general formula (2) is set to the compound of the general formula (1). It is desirable that the (monovalent) is 60 to 80% by weight and the compound (divalent) of the general formula (2) is 20 to 40% by weight. In addition, the inventors of the present invention use an aminium salt-based compound in a suitable combination depending on the anionic species, since their charging ability, color tone in the visible region, light absorption ability, and reactivity with a charge control agent are slightly different. It has been found that, as in the case of using the compounds of the general formulas (1) and (2) in combination, a toner satisfying the charging ability, the light absorbing ability and the color tone can be obtained.

Means (viii) According to the research conducted by the present inventors, the compound represented by the general formula (1), the aminium salt compound represented by the general formula (2) and the aminium salt-based compound represented by the general formulas (4) to (8) are shown. Quaternary ammonium salt-based charge control for toners by using together an ammonium salt of aromatic dithiol, mercaptophenol, and diamine-based metal complex or a compound having infrared light absorption ability such as polyenylidene bisbenzoquinone and phthalocyanine The compounds represented by the general formulas (4) to (8), which do not react with the quaternary ammonium salt-based charge control agent when the agent is added, are light-absorbing ability of the aminium salt-based compound lost by the reaction with the quaternary ammonium salt. In order to compensate for the above, it was found that it is possible to impart a good light absorbing ability to the color toner.

The compounds of general formula (4) are dithiol compounds, the compounds of general formula (5) are mercaptophenol and mercaptonaphthol compounds, the compounds of general formula (6) are diamine compounds, and the compounds of general formula (7) are Polyenylidene bisbenzoquinone type, the compound of the general formula (8) is phthalocyanine,
It is a naphthalocyanine type. When using aromatic dithiol, mercaptophenol, and ammonium salt of diamine-based metal complex or polyenylidene bisbenzoquinones as infrared light absorbers to be used in combination, the generated fixing odor and the influence on the color tone of color toner are allowed. In order to keep the content within the range, the content of the infrared light absorber used in combination must be 1% by weight or less, preferably 0.5% by weight or less.

On the other hand, when a phthalocyanine compound is used as the infrared light absorber to be used in combination, the fixing odor is not a serious problem, but the color tone of these phthalocyanine compounds in the visible region is intense blue to green. In many cases, even when added in a small amount to the toner, it has a great effect on the toner color tone, so red, yellow toner, etc.
When it is added to a toner having a color tone different from the color tone specific to the phthalocyanine compound, the content must be suppressed to 1% by weight or less, preferably 0.2% by weight or less.

In a preferred embodiment of the present invention, the amide compound fine particles represented by the general formulas (9) to (11) are further attached (externally added) to the toner surface.

[0083]

[Chemical formula 22]

[In the formulas (9) and (10), l, m and n are 0.
Is an integer of 4 to 4, R ^{5 to} R ⁸ are hydrogen, an alkyl group, a halogen-substituted alkyl group, an aryl group or a halogen-substituted aryl group. ]

[0085]

[Chemical formula 23]

[In the formula (11), l and m are positive integers, R ⁵
To R ⁷ are as defined above. By externally adding an appropriate amount of amide compound powder having a hydroxyl group in the molecular structure to the toner, it is possible to improve the flash fixability of the toner without causing side effects such as toner blocking and filming on the photosensitive drum. I found it.

It is presumed that the following phenomenon occurs as a mechanism showing this effect. First, in this toner, the amide compound as the externally added resin is melted slightly before the entire toner is melted. The molten amide compound has a highly polar site such as an amide group (including amide bond) and a hydroxyl group in the molecular structure, has a high affinity for paper fibers, and constitutes a toner. Since it has a lower melting point and a lower melt viscosity than the binder resin, it quickly penetrates between the fibers of the paper. Due to this effect, the wettability of the molten binder resin with respect to the fibers of the paper is enhanced, and the binder resin (toner base) having a slightly high melt viscosity also penetrates between the fibers of the paper to exert a strong fixing property. For this reason, the amount of light absorbed by the toner is not sufficient, and since the binder resin is at a low temperature, good fixability can be imparted even when the melt viscosity is high.

The amide compound exhibiting such characteristics can be found among hydroxy fatty acid monoamides, hydroxy fatty acid bisamides, and low molecular weight hydroxy group-containing polyamide oligomers. The weight average molecular weight of the amide compound is preferably 500 or more and 3000 or less. This is because if the molecular weight is less than this range, the amide compound becomes soft and drum filming easily occurs. On the other hand, if the molecular weight is 3,000 or more, the viscosity at the time of melting is high and the effect is difficult to be exhibited. .

In order to exert the effect well,
The amide resin must melt faster than the toner base,
Moreover, it is necessary that the viscosity at the time of melting is low. Therefore, the melting temperature of the externally added amide compound is lower than the melting temperature of the binder resin forming the toner base by 10 ° C. or more, and
This is the melting temperature region of the molten toner near the recording paper. 100
The melt viscosity in the range of up to 150 ° C. needs to be lower than the melt viscosity of the binder resin forming the toner base.

A similar effect can be obtained in a toner in which the amide compound is internally added to the toner (melt kneading with a binder resin), but in this case, the amide compound is at least 5% by weight. As described above, it is desirable to add 20% by weight or more. However, many amide compounds used are relatively soft and brittle, and if a large amount of amide compound having such characteristics is added to the toner, a long film is formed on the photosensitive drum when printing is performed for a long time. So-called drum filming occurs, which causes printing defects such as background fog. In order to prevent the occurrence of drum filming even after long-term use, the amount of amide compound in the total amount of toner is at least 2% by weight or less, preferably 1% or less.
It must be below wt%. In order to exert the above-mentioned good fixing effect with the addition amount of such an amide compound,
It is desirable to add the amide compound to the toner by external addition.

It is desirable that the average particle size of the externally added amide compound is 2 μm or less and the maximum particle size is 5 μm or less. This is because if the particle size of the externally added amide compound exceeds the above range, the amide compound does not uniformly adhere to the toner surface and is easily separated from the toner, so that problems such as accumulation of the amide compound in the developing device tend to occur. This is because. In addition,
It is noted that this embodiment is effective not only when combined with the means (i) to (viii) but also for any flash fixing toner.

Method of Manufacturing Toner The method of manufacturing the color toner for flash fixing of the present invention described in each of the above means is provided by the present invention in both a general manufacturing method and a special manufacturing method. The specific description is as described above, and although not repeated, the manufacturing method described in the claims is unique.

[0093]

EXAMPLES The present invention will be described in more detail below by showing more detailed examples, but the present invention is not limited to these examples.

Light Absorption Wavelength Measurement of Binder Resin Added with Infrared Light Absorber The strongest emission wavelength of the xenon lamp for flash fixing is 800 to 1000 nm. Therefore, various kinds of 1% by weight of an aminium salt-based compound represented by the general formula (1) in which an anion is a perchlorate ion (this aminium salt-based compound was used unless otherwise specified in the following examples). Regarding the resin, the evaluation resin powder and the aminium salt-based compound are put into a stainless petri dish, and gently melt-mixed on a hot plate at 150 ° C (check the color tone at this time). After the resin is left to cool, it is cut into a thin film. The light absorption characteristics were investigated with an infrared absorption spectrometer.

The results are shown in Table 1.

[0096]

[Table 1]

Means (i) [Example 1] As one binder resin 1-1, a polyester resin containing an ethylene oxide adduct of bisphenol A as a main diol component and terephthalic acid as a main dicarboxylic acid component was used. On the other hand, 2% of an aminium salt-based compound 2 represented by the general formula (1), whose anion is a perchlorate ion, is added and melt-kneaded. This kneaded product is called A.

Next, styrene was used as the binder resin 1-2.
Acrylic resin (styrene-methylmethacrylate-n-butylmethacrylate copolymer) was used, 1% of quaternary ammonium salt was added as a positive charge control agent 3, and 2% of brominated copper phthalocyanine was added as a colorant 4, fixing aid. As the agent 5, 1% of polypropylene wax is added and melt-kneaded. This kneaded product is called B.

The difference in solubility parameter between the polyester resin used and the styrene-acrylic resin was calculated, and the value was about 0.8. Next, after that, the coarsely pulverized products of the kneaded product A and the kneaded product B were blended at a ratio of 7: 3, further melt-kneaded, and then pulverized and classified to obtain a toner C. This toner C was combined with a ferrite carrier to form a developer, which was mounted on a printer (manufactured by Fujitsu) with a product number of F6718K, and the flash fixability and the charging ability in a high temperature and high humidity environment were investigated.

As a result, an excellent fixing property was shown with a fixing rate of 90% (tape peeling test). Regarding the charging ability, when the developer was exposed to the environment of 35 ° C. and 80% RH for 12 hours, and the developer was stirred for 3 minutes in the same environment,
It was confirmed that it has an excellent charging ability by showing a charge recovery up to about 80% of the charge amount at room temperature and normal humidity (hereinafter, this value is called a charge recovery rate) by stirring for 3 minutes. It was

Even if a polyester resin and / or a polyamide resin is used in place of the polyester resin used in this example, and a styrene-butadiene resin is used in place of the styrene-acrylic resin, the same effect as in this example is obtained. The effect can be obtained. Polyester resin and styrene-
The following table shows the effect of the combination of the binder resins other than the acrylic resin.

Binder Resin 1-1 Binder Resin 1-2 Fixing Rate% Charge Recovery Rate% Polyester Styrene-Acrylic 90 80 Polyester Styrene-Acrylic 85 95 Polyester Styrene-Butadiene 80 95 Epoxy Styrene-Acrylic 100 80 Polyamide Styrene-Acrylic 75 80

Example 2 As the binder resin 1-1,
A polyester resin containing an ethylene oxide adduct of bisphenol A as a main diol component and terephthalic acid as a main dicarboxylic acid component was used, and 2% of an aminium salt compound and 2% of brominated copper phthalocyanine were used.
%, Polypropylene wax 1%, and melt-kneaded. This kneaded product is called D.

This kneaded product D and an amine-modified styrene-acrylic binder resin 1-2 containing dimethylaminoethyl methacrylate as an essential constituent monomer were melt-kneaded at a ratio of 9: 1 and then pulverized and classified to obtain a toner E. Got When the fixing property and the charging ability of this toner E were examined by the same method as in Example 1, excellent properties such as a fixing rate of 85% and a charge recovery rate of 70% were obtained.

Example 3 A toner F was obtained in the same manner as in Example 2 except that the amine-modified styrene-acrylic resin in Example 2 was fine particles having a submicron particle size and a melting point of 200 ° C. or higher. The toner F was examined for fixing property and chargeability by the same method as in Example 1, and found to have a fixing ratio of 80.
%, An excellent property of 90% of charge recovery rate was obtained.

[Example 4] The kneaded product D formed in Example 2 and a resin styrene-acrylic resin (styrene-n-butyl acrylate copolymer) to which 2% of a quaternary ammonium salt was added at the time of resin synthesis were 7: 3. Toner G was obtained by melt-kneading at a ratio of 1 and then pulverized and classified. When the fixing property and the charging ability of this toner G were examined by the same method as in Example 1, excellent properties such as a fixing ratio of 85% and a charge recovery ratio of 70% were obtained.

[Example 5] Aminium salt-based compound was melt-kneaded with 3% of bisphenol A type epoxy resin (epoxy equivalent: 900), and then finely ground to 2 µm or less by a jet mill to obtain a ground product H. . Further, a spherical resin having a submicron particle diameter of a styrene-n-butyl acrylate-methyl methacrylate copolymer containing a quaternary ammonium salt was obtained by an emulsion polymerization method. These resins and the ground product H, brominated copper phthalocyanine were
Toner I was obtained by heating to 20 ° C., aggregating and fixing.

The toner I was examined for fixing property and charging ability in the same manner as in Example 1. The fixing ratio was 90%.
Excellent characteristics with a charge recovery rate of 70% were obtained.

Example 6 The bisphenol A type epoxy resin formed in Example 5 is changed to a polyester resin containing 1,2-propylene glycol, neopentyl glycol and terephthalic acid as essential constituent monomers and having a weight average molecular weight of about 6000. Toner J is the same as in Example 5 except for the above.
Got

The toner J was examined for fixing ability and charging ability in the same manner as in Example 1. The fixing rate was 90%.
Excellent characteristics with a charge recovery rate of 75% were obtained.

Example 7 Toner K is obtained in the same manner as in Example 6 except that 30 parts by weight of a styrene-n-butyl acrylate resin having a melting point of 90 ° C. is added and the heating temperature is 90 ° C. It was The toner K was examined for fixing ability and charging ability in the same manner as in Example 1 and found to have a fixing rate of 10
Excellent characteristics of 0% and charge recovery rate of 85% were obtained.

[Comparative Example 1] As the binder resin, a polyester resin containing an ethylene oxide adduct of bisphenol A as a main diol component and terephthalic acid as a main dicarboxylic acid component was used. Toner L was obtained by adding 2% of brominated copper phthalocyanine and 1% of polypropylene wax, melt-kneading, and then pulverizing and classifying.

The toner L was examined for fixing ability and charging ability in the same manner as in Example 1. The fixing rate was 100%.
However, the charge recovery rate was 30% or less, and since the positive charge control agent was not added in this comparative example, the charging ability was extremely low.

[Comparative Example 2] Chemically as a positive charge control agent
Formula [(C₁₄H₂₉)₂(CH₃)₂ N⁺]_Four Mo₈ O₂₆ ^Four-Table
Except the addition of 1% quaternary ammonium salt
In the same manner as in Comparative Example 1, a toner M was obtained. This toner
In the same manner as shown in Example 1 for M, the fixing property and charging ability are improved.
A survey shows that the fixing rate is 20% or less, and the charge recovery rate is 40%.
Below, the light absorption and charging characteristics are low, and
In addition, the color tone of the toner changes from the color tone of the colorant to green to brown.
Colored.

In this comparative example, since the positive charge control agent and the aminium salt compound were added to a single binder instead of a plurality of binder resins, the above-mentioned inconvenient results were obtained.

[Comparative Example 3] A kneaded product A was obtained in the same manner as in Example 1. Furthermore, a carboxylic acid-modified styrene-acrylic resin containing methacrylic acid as an essential constituent monomer was used, and 1% of a quaternary ammonium salt was used as a positive charge control agent.
Then, 2% of brominated copper phthalocyanine as a coloring agent and 1% of polypropylene wax as a fixing aid are added and melt-kneaded. This kneaded product is called N. In addition,
Polyester resin used and carboxylic acid modified styrene-
When the difference in the solubility parameter of the acrylic resin was calculated, the value was about 0.2. Toner O was obtained by melt-kneading the kneaded product A and the kneaded product N at a ratio of 8: 2 and pulverizing and classifying.

When the fixing property and the charging ability of this toner were investigated by the same method as in Example 1, the fixing ratio was 45.
%, The charge recovery rate was 60%, and the target performance was not reached. In addition, when the dispersion state of the kneaded product A and the kneaded product N in the toner O was examined, a clear "sea-island structure" was not found although they were not completely compatible.

Comparative Example 4 As a resin for dispersing an aminium salt compound, a polyester resin containing a bisphenol A type epoxy resin as a main diol component of an ethylene oxide adduct of bisphenol A and a terephthalic acid as a main dicarboxylic acid component is used. An attempt was made to manufacture a toner in the same manner as in Example 5 except for the above.

However, the resin in which the aminium salt-based compound was dispersed in Comparative Example 4 had a particle size of 4 to 6 by ordinary jet grinding.
It was only possible to pulverize up to about μm, and it was impossible to obtain a toner of about 10 to 12 μm by aggregating and fixing in the aqueous phase using this pulverized product.

Means (ii) [Example 8] Divinylbenzene was used as the toner L of Comparative Example 1.
Styrene-dimethylaminoethyl methacrylate copolymer resin powder (copolymerization ratio; divinylbenzene: styrene:
Dimethylaminoethyl methacrylate = 5: 75: 20
2% by weight of (/ average particle size 0.1 μm) was mixed and stirred using a Henschel mixer to obtain a toner P to which the divinylbenzene-styrene-dimethylaminoethyl methacrylate copolymer resin powder was externally added.

When the charge amount in combination with the Mn-Zn type ferrite carrier coated with methyl methacrylate was measured, the charge amount of the toner P in a normal temperature and normal humidity environment was 20 μC / g. Then, 35 ℃, 80%
After exposing the developer to the environment under RH for 12 hours, and stirring the developing device for 3 minutes in the same environment, the charge of up to about 75% of the charge amount at room temperature and normal humidity was obtained by stirring for 3 minutes. It showed recovery (hereinafter, this value is referred to as charge recovery rate), and it was confirmed that it has an excellent charging ability.

Further, by combining the above-mentioned methyl methacrylate-coated ferrite carrier and toner P, F6718 is used.
When mounted on a K printer (manufactured by Fujitsu) and examined for printing characteristics, it showed excellent printing characteristics over 100,000 sheets.

Example 9 [(C ₁₄ H ₂₉ ) ₂ (CH ₃ ) ₂ N
⁺ ] ₄ Mo ₈ O ₂₆ ⁴⁻ Styrene-n-butyl acrylate copolymer resin powder (copolymerization ratio: styrene: n-) in which a quaternary ammonium salt represented by the chemical formula is incorporated in the polymerization process.
Butyl acrylate = 75: 25 / average particle size 0.1μ
2% by weight of m) was mixed with the toner L of Comparative Example 1 using a Henschel mixer, and externally added to obtain a toner Q.

When the charge amount was measured in combination with a Mn-Zn type ferrite carrier coated with methyl methacrylate, the charge amount of the toner Q in a normal temperature and normal humidity environment was 22 μC / g. Then, 35 ℃, 80%
After exposing the developer to the environment under RH for 12 hours, and stirring the developing device for 3 minutes in the same environment, the charge of up to about 90% of the charge amount at room temperature and normal humidity was obtained by stirring for 3 minutes. It showed recovery and was confirmed to have excellent charging ability.

Further, by combining the above-mentioned methyl methacrylate-coated ferrite carrier and toner Q, F6718
When mounted on a K printer (manufactured by Fujitsu) and examined for printing characteristics, it showed excellent printing characteristics over 100,000 sheets.

[Example 10] Styrene-n-butyl acrylate copolymer resin powder containing quaternary ammonium salt used in Example 2 (copolymerization ratio; styrene: n-butyl acrylate = 75: 25 / average particle size 0. 1 μm) 4 wt%,
A styrene-n-butyl acrylate copolymer containing a quaternary ammonium salt was added to the toner L of Comparative Example 1 and charged into a hybridizer (manufactured by Nara Instruments Co., Ltd.) to apply pressure and impact to the surface of the toner L. A toner R coated with resin was obtained.

When the charge amount was measured in combination with a Mn-Zn type ferrite carrier coated with methyl methacrylate, the charge amount of the toner R in a normal temperature and normal humidity environment was 25 μC / g. Then, 35 ℃, 80%
After exposing the developer to the environment under RH for 12 hours, and stirring the developer for 3 minutes in the same environment, the charge of up to about 85% of the charge amount at room temperature and normal humidity was obtained by stirring for 3 minutes. It showed recovery and was confirmed to have excellent charging ability.

Further, by combining the above-mentioned methyl methacrylate-coated ferrite carrier and toner R, F6718
When mounted on a K printer (manufactured by Fujitsu) and examined for printing characteristics, it showed excellent printing characteristics over 100,000 sheets.

Example 11 With respect to Toner L of Comparative Example 1, styrene-methylmethacrylate-dimethylaminoethylmethacrylate copolymer resin powder (copolymerization ratio; styrene: methylmethacrylate: dimethylaminoethylmethacrylate = 75: 10). : 15 / average particle size 0.1μ
4% by weight of m) was added, and in the same manner as in Example 10, a toner S having a surface layer coated with a styrene-methyl methacrylate-dimethylaminoethyl methacrylate copolymer resin was obtained.

When the charge amount was measured in combination with a Mn-Zn type ferrite carrier coated with methyl methacrylate, the charge amount of the toner S in a normal temperature and normal humidity environment was 22 μC / g. Then, 35 ℃, 80%
After exposing the developer to the environment under RH for 12 hours, and stirring the developing device for 3 minutes in the same environment, the charge of up to about 90% of the charge amount at room temperature and normal humidity was obtained by stirring for 3 minutes. It showed recovery and was confirmed to have excellent charging ability.

Further, by combining the above-mentioned methyl methacrylate-coated ferrite carrier and toner S, F6718
When mounted on a K printer (manufactured by Fujitsu) and examined for printing characteristics, it showed excellent printing characteristics over 100,000 sheets.

[Comparative Example 5] Toner L exemplified in Comparative Example 1
Was measured in combination with a Mn-Zn-based ferrite carrier coated with methyl methacrylate, the charge amount in a normal temperature and normal humidity environment was 12 μm.
It was C / g. Next, after exposing the developer to an environment of 35 ° C. and 80% RH for 12 hours, and agitating the developing device for 3 minutes in the same environment, the charge amount in the normal temperature and normal humidity state was obtained by stirring for 3 minutes. Of about 40%, and it was found that it was difficult to recover the charge.

Further, by combining the above-mentioned methyl methacrylate-coated ferrite carrier and toner L, F6718
When mounted on a K printer (manufactured by Fujitsu) and examined for printing characteristics, it showed excellent printing characteristics over 100,000 sheets in a continuous running test under a normal temperature environment, but after stopping the printer for 2 days or more. In the re-driving or running test under high temperature and high humidity environment, background fog and overdevelopment occurred due to insufficient charge amount of the developer, and satisfactory printing characteristics were not obtained.

[Comparative Example 6] Resin fine powder to be externally added was styrene-methylmethacrylate-dimethylaminoethylmethacrylate copolymer resin powder (copolymerization ratio; styrene: methylmethacrylate: dimethylaminoethylmethacrylate = 75: 10: 15 / A resin externally added toner T was obtained in the same manner as in Example 8 except that the average particle diameter was 1.0 μm).

When the charge amount of Toner T was measured in combination with a Mn-Zn type ferrite carrier coated with methyl methacrylate, the charge amount in a normal temperature and normal humidity environment was 22 μC / g. Then 35 ° C,
After exposing the developer to an environment of 80% RH for 12 hours, and agitating the developing device for 3 minutes in the same environment, the agitating for 3 minutes resulted in about 80% of the charge amount at room temperature and normal humidity. It was confirmed that it has an excellent charging ability.

Further, by combining the above-mentioned methyl methacrylate-coated ferrite carrier and toner T, F6718 is used.
When mounted on a K printer (manufactured by Fujitsu) and investigated the printing characteristics, it showed excellent printing characteristics for about 20,000 sheets from the beginning, but after that, the charge amount suddenly increased and faint printing was shown. Became. Upon investigating the cause, it was found that the externally added resin powder was not sufficiently retained on the toner surface, and the resin powder gradually detached from the toner surface due to long-term use and accumulated in the developing device. .

Means (iii) [Example 12] Bisphenol A was used as the binder resin.
Polyethylene resin containing terephthalic acid as main dicarboxylic acid component with ethylene oxide adduct as main component, 1% quaternary ammonium salt as charge control agent, and 2% brominated phthalocyanine as colorant are fixed. 1% polypropylene wax as an auxiliary agent
Base toner U was obtained by adding, melt-kneading, and pulverizing to a particle size of 5 to 20 μm.

A bisphenol A type epoxy resin was used as a binder resin, and 20 wt% of an aminium salt-based compound was added thereto and melt-kneaded to obtain an aminium salt-based compound-containing resin fine powder V having a particle size of 0.5 to 5 μm. Obtained. Next, a toner W was obtained by externally adding 3 wt% of the resin fine powder V containing an aminium salt compound to the base toner U using a super mixer.

This toner W was combined with a ferrite carrier to form a developer, which was mounted on an F6718K printer (manufactured by Fujitsu), and the flash fixability and the charging ability in a high temperature and high humidity environment were investigated. As a result, excellent fixability with a fixing rate of 75% (tape peeling test) was exhibited. Regarding the charging ability, the developer was exposed to the environment of 35 ° C. and 80% RH for 12 hours, and then the developing device was agitated for 3 minutes in the same environment. About 75 of the charge amount of
% Charge recovery (hereinafter, this value is called charge recovery rate)
Was confirmed, and it was confirmed to have an excellent charging ability.

Example 13 As the binder resin, 1,
Using a polyester resin containing 3 butanediol as a main diol component and terephthalic acid as a main dicarboxylic acid component, 20 wt% of an aminium salt-based compound is added and melt-kneaded to form an aminium salt-based resin having a particle size of 0.5 to 5 μm. A compound-containing resin fine powder X was obtained.

Then, 4 wt% of the resin fine powder X containing an aminium salt compound was externally added to the base toner U using a super mixer to obtain a toner Y. This toner Y is combined with a ferrite carrier to form a developer,
It was mounted on a 6718K printer (manufactured by Fujitsu) and the flash fixability and the charging ability in a high temperature and high humidity environment were investigated. As a result, excellent fixability was shown with a fixing rate of 80% (tape peeling test). Further, regarding the charging ability, it showed a charging recovery rate of about 85%, and it was confirmed that the charging ability was excellent.

Example 14 A bisphenol A type epoxy, 60 wt% and an aminium salt compound of 40 wt% were dissolved in a methyl ethyl ketone solvent and then spray-dried with a spray dryer to obtain an aminium salt having a particle size of 0.5 to 2.0 μm. A resin-containing resin fine powder Z was obtained. Next, 2 wt% of the aminium salt compound-containing resin fine powder Z was externally added to the base toner U using a super mixer to obtain a toner α.

This toner α was combined with a ferrite carrier to form a developer, which was mounted on an F6718K printer (manufactured by Fujitsu), and flash fixability and charging ability in a high temperature and high humidity environment were investigated. As a result, excellent fixability with a fixing rate of 90% (tape peeling test) was exhibited. Further, regarding the charging ability, a charging recovery rate of about 90% was shown, and it was confirmed that the charging ability was excellent.

[Comparative Example 7] With respect to the base toner U exemplified in Example 12, the fixing property and the charging ability of the toner were examined by the same method as in Example 12, and the charge recovery rate was 80%. , Did not fix at all and was unsatisfactory.

[Comparative Example 8] A polyester resin containing an ethylene oxide adduct of bisphenol A as a main diol component and terephthalic acid as a main dicarboxylic acid component was used, to which 20 wt% of an aminium salt compound was added and melt-kneaded. Then, an attempt was made to produce an aminium salt-based compound-containing resin fine powder having a particle size of 0.5 to 5 μm.
Only powder of about μm was obtained (externally added resin powder β), and 3 wt% of this resin powder with respect to the base toner U was externally added using a super mixer to obtain toner γ. Was not electrostatically attached to the base toner γ, and the externally added resin powder was scattered in the printer device, which was not practical.

Means (iv) According to the knowledge of the present inventors, when the binder resin and the aminium salt-based compound are not reactive when the aminium salt-based compound is kneaded and added to the binder resin, the kneaded product is an aminium salt. The color tone of the compound is light yellow green to light green, but when the binder resin and the aminium salt compound react, the kneaded product has a reddish brown to dark brown color.

Utilizing this phenomenon, prior to toner production,
Aminium salt compounds are melt-added to a mixture of a binder resin containing an acidic functional group and a resin having a positive charge property and / or a positive charge control agent, and the reactivity between the binder resin and the aminium salt compound is investigated. did. The results are shown in Table 1. The manufactured toner is combined with a Mn-Zn ferrite carrier coated with methylmethacrylate to form a developer, which is used as an F6718K printer (manufactured by Fujitsu).
It was mounted on and the flash fixability and the charging ability in a high temperature and high humidity environment were investigated. The results are shown in Table 2. The criteria shown in Table 2 are ⊚ for those showing excellent fixability with a fixing rate of 95% or more (tape peeling test), ◯ for those showing a fixing rate of 90% to 80%, and fixing below that. Those with sex were marked with x.
Also, regarding the charging ability in a high temperature and high humidity environment, the developer is
After exposing to an environment of 5 ° C. and 80% RH for 12 hours, stir the developing device for 3 minutes in the same environment, and stir for 3 minutes to recover the charge of 80% or more of the charge amount at room temperature and normal humidity. The ones shown are ⊚, those showing a charge recovery of 70 to 80% are ◯, and those having a charge recovery rate of less than that are X.

[Example 15] A polyester resin having an acid value of 48 mg / KOH was used as a binder resin in an amount of 80% of the total amount of the binder resin, and a styrene-dimethylaminoethyl methacrylate copolymer (styrene: dimethylaminoethyl methacrylate =) was used as a positively charged binder resin. 66:34) in an amount of 20% by weight based on the total amount of the binder resin, 2% of an aminium salt (infrared absorber) is added thereto, 2% of brominated phthalocyanine (coloring agent), and 1% of polypropylene wax as a fixing aid. %, Added, melt-kneaded, and further pulverized and classified to obtain a toner δ.

Example 16 As a binder resin, a sulfonic acid-modified polyester resin having an acid value of 30 mg / KOH containing terephthalic acid, an ethylene oxide adduct of bisphenol A, and bis (4hydroxyphenyl) sulfonic acid as essential constituent monomers was used as a binder. 80% of the total amount of the resin, and 20% by weight of the total amount of the binder resin, a styrene-dimethylaminoethyl methacrylate copolymer (styrene: dimethylaminoethyl methacrylate = 66.34) was used as the positively charged binder resin. 2%, brominated phthalocyanine 2% (coloring agent), polypropylene wax 1% as a fixing aid, melt-kneaded, and pulverized and classified to obtain a toner ε.

[Example 17] A polyester resin having an acid value of 48 mg / KOH was used as a binder resin in an amount of 80% of the total amount of the binder resin, and a styrene-dimethylaminoethyl methacrylate copolymer (styrene: dimethylaminoethyl methacrylate = positively charged binder resin) was used. 66:34) was used in an amount of 20% by weight based on the total amount of the binder resin. First, both were melt-kneaded and then pulverized to a particle size of about 1 mm to obtain a resin melt-kneaded product. Next, 2% of an aminium salt-based compound, 2% of a brominated phthalocyanine (coloring agent) and 1% of polypropylene wax as a fixing aid are added to the melt-kneaded product of the resin, melt-kneaded, and further pulverized and classified to obtain a toner ζ. Got

Example 18 A styrene-dimethylaminoethylmethacrylate copolymer (styrene: dimethylaminoethylmethacrylate = as a positively charged binder resin)
66:34) to produce styrene-dimethylaminoethylmethacrylate copolymer particles by introducing them into a styrene-acrylic acid copolymer having an acid value of 25 mg / KOH. A styrene-acrylic acid copolymer encapsulating was obtained. The weight ratio of the styrene-dimethylaminoethyl methacrylate copolymer and the styrene-acrylic acid copolymer was 50:50. This styrene-dimethylaminoethyl methacrylate copolymer particle-encapsulated styrene-acrylic acid copolymer was added to 80% of the total amount of binder resin, 1,3 propane glycol,
Acid value with terephthalic acid as main constituent monomer 15mg / KO
The total amount of the polyester resin of H is 20%, the aminium salt compound is 2%, the brominated phthalocyanine is 2% (coloring agent), and the polypropylene wax is 1% as a fixing aid. The mixture is melt-kneaded, and further pulverized and classified. Toner η was obtained.

[Comparative Example 9] An acid value of 3 was used as the binder resin.
The total amount of binder resin is 7 mg of polyester resin of mg / KOH.
0%, a styrene-dimethylaminoethylmethacrylate copolymer (styrene: dimethylaminoethylmethacrylate = 66: 34) was used as a positively charged binder resin in an amount of 30% by weight based on the total amount of the binder resin, and an aminium salt compound was added in an amount of 2%. Toner θ was obtained by adding 2% of brominated phthalocyanine (coloring agent), 1% of polypropylene wax as a fixing aid, melt-kneading, and further pulverizing and classifying.

[0153]

[Table 2]

Means (v) The reactivity of the binder resin with the aminium salt-based compound and the characteristics of the produced toner were evaluated by the method described in the example of means (iv). The results are shown in Table 3.

Example 19 A styrene-vinylpyrrolidone copolymer (styrene: vinylpyrrolidone = 80: 20) was used as a positively chargeable binder resin in an amount of 50% by weight of the total amount of the binder resin, and terephthalic acid and bisphenol A ethylene oxide were used. 50% by weight of the total amount of binder resin of polyester resin whose main component is an adduct
To this, 2% of an aminium salt-based compound, 2% of brominated phthalocyanine (coloring agent), and 1% of polypropylene wax as a fixing aid were added, melt-kneaded, and further pulverized and classified to obtain a toner ι. Obtained.

Example 20 Methyl methacrylate-vinyl pyrimidine copolymer (methyl methacrylate: vinyl pyrimidine = 85:
30% by weight of the total amount of the binder resin is used, and 70% by weight of the total amount of the binder resin is used as a polyester resin containing terephthalic acid and bisphenol A ethylene oxide adduct as a main monomer component. 2% and brominated phthalocyanine 2%
(Coloring agent), 1 polypropylene wax as fixing aid
%, Melt-kneaded, and further pulverized and classified to obtain a toner κ.

Example 21 A methylmethacrylate-dimethylacrylamide copolymer (methylmethacrylate: dimethylacrylamide = 80: 20) was used as a positively chargeable binder resin in an amount of 40% by weight based on the total amount of the binder resin, and terephthalic acid and bisphenol A were used. A polyester resin containing an ethylene oxide adduct as a main monomer component was used in an amount of 60% by weight based on the total amount of the binder resin. On the other hand, 2% of an aminium salt compound, 2% of brominated phthalocyanine (coloring agent), and a fixing aid were used. Toner λ was obtained by adding 1% of polypropylene wax, melt-kneading, and further pulverizing and classifying.

[Example 22] Amide-modified polyester obtained by reacting a carboxylic acid of polyester with an amine as a positively chargeable binder resin (15 mol% of amine monomer)
2% of the aminium salt-based compound,
Toner μ was obtained by adding 2% of brominated phthalocyanine (coloring agent), 1% of polypropylene wax as a fixing aid, melt-kneading, and further pulverizing and classifying.

[Example 23] Urethane-modified polyester (about 30% of the terminal OH groups are urethane with a hydroxyl group of a polyester resin containing terephthalic acid and a bisphenol A ethylene oxide adduct as an essential monomer component as a binder resin is reacted with isocyanate. Sealing), 2% of aminium salt compound, 2% of brominated phthalocyanine (coloring agent), 1% of polypropylene wax as a fixing aid, melt-kneaded, and further pulverized and classified. To obtain a toner ν.

Example 24 An amine-crosslinked epoxy resin obtained by crosslinking bisphenol A type epoxy with N-aminoethylpiperazine as a positively chargeable binder resin was used in an amount of 30% by weight based on the total amount of the binder resin, and terephthalic acid and bisphenol A ethylene were used. A polyester resin containing an oxide adduct as a main monomer component was used in an amount of 70% by weight based on the total amount of the binder resin, an aminium salt compound was 2%, a brominated phthalocyanine was 2% (coloring agent), and a polypropylene was used as a fixing aid. Toner ξ was obtained by adding 1% of wax, melt-kneading, and further pulverizing and classifying.

Example 25 Propylene bishydroxyarachidamide was used as a positively chargeable binder in an amount of 20% by weight based on the total amount of the binder resin, and a polyester resin containing terephthalic acid and a bisphenol A ethylene oxide adduct as a main monomer component was used as a binder. 80% by weight of the total amount of resin is used, 2% of an aminium salt compound, 2% of brominated phthalocyanine (coloring agent), 1% of polypropylene wax as a fixing aid are melt-kneaded, and further ground and classified. By doing so, toner π was obtained.

Comparative Example 10 A styrene-2 ethylhexyl acrylate copolymer (styrene: 2 ethylhexyl acrylate = 75: 25) was used as a binder resin in an amount of 50% by weight based on the total amount of the binder resin, and terephthalic acid and bisphenol A ethylene oxide were added. 50% by weight of the total amount of the binder resin is used as a polyester resin whose main component is a monomer, and 2% of an aminium salt compound, 2% of a brominated phthalocyanine (coloring agent), and polypropylene wax as a fixing aid are used. Toner ρ was obtained by adding 1%, melt-kneading, and further pulverizing and classifying.

[Comparative Example 11] A styrene-dimethylaminoethylmethacrylate copolymer (styrene: dimethylaminoethylmethacrylate = 90: 1) was used as an alternative binder to the positively chargeable binders shown in Examples 19 to 21.
Toner σ was obtained in the same manner as in Examples 19 to 21, except that 0) was used in an amount of 20% by weight based on the total amount of the binder resin.

[Comparative Example 12] A styrene-methylmethacrylate dimethylacrylamide copolymer (styrene: methylmethacrylate: dimethylacrylamide = 35: 30: 35) was used as a binder resin instead of the positively chargeable binders shown in Examples 19 to 21. 20 in total
Toner τ was obtained in the same manner as in Examples 19 to 21 except that the toner was used in an amount of wt%.

[Comparative Example 13] Example 13 except that the positively chargeable binders shown in Examples 19 to 21 were not used and a quaternary ammonium salt-based charge control agent (P-51: Orient Chem.) Was added in an amount of 2 wt%. Toner υ was obtained in the same manner as in 19 to 21. The evaluation results are summarized in Table 3, and when the toner having a positive chargeability is provided by using a binder having dimethylaminoethylmethacrylate as a binder as a binder, or by using a quaternary ammonium salt-based charge control agent, the positive charge is obtained. When the property is imparted, the aminium salt is affected and the fixability is extremely lowered.

On the other hand, a toner which does not use a positive charge control agent or a binder having a positive charge imparting property has a poor charge recovery ability when re-stirred after being left, and there are many practical problems. In order to satisfy these problems, a nitrogen-containing cyclic structure such as an imidazole ring, a pyrimidine ring, a pyrrolidone ring, a pyrazole ring, a pyrroline ring, and a pyrrole ring described in the present application and / or -RCONH ₂ (R is a benzene ring or a carbon number A thermoplastic resin having a structure in which an amide group represented by 0 to 2 aliphatic hydrocarbon) is pendantly coordinated to a binder molecular chain, a specific polyester, epoxy, or amide resin is required.

[0167]

[Table 3]

Means (vi) [Example 26] As a binder resin, bisphenol A was used.
Ethylene oxide adduct of as the main diol component,
A polyester resin containing terephthalic acid as the main dicarboxylic acid component is used, and 2% of an aminium salt compound having hexafluoroantimonic acid as an anion, 1% of a quaternary ammonium salt having the same anion, and a color 2% of brominated phthalocyanine as an agent and 1% of polypropylene wax as a fixing aid are added and melt-kneaded. Then, toner φ was obtained by pulverizing and classifying.

This toner φ was combined with a ferrite carrier to form a developer, which was mounted on an F6718K printer (manufactured by Fujitsu), and the flash fixability and the charging ability in a high temperature and high humidity environment were investigated. As a result, excellent fixability with a fixing rate of 85% (tape peeling test) was exhibited. Regarding the charging ability, the developer was exposed to the environment of 35 ° C. and 80% RH for 12 hours, and then the developing device was agitated for 3 minutes in the same environment. About 80 of the charge amount of
%, And it was confirmed to have excellent charging ability.

Example 27 Using the same binder resin as in Example 26, 3% of an aminium salt compound containing perchloric acid as a common anion, 1% of a quaternary ammonium salt, and 4 molybdate salt were used. 0.2% of primary ammonium salt, 2% of brominated phthalocyanine and 1% of polypropylene wax are added and melt-kneaded. Then, toner χ was obtained by pulverizing and classifying.

The toner χ was investigated for fixing property and charging ability in the same manner as in Example 26.
%, An excellent property of 90% of charge recovery rate was obtained.

Means (vii) [Example 28] As a binder resin, bisphenol A was used.
Polyethylene resin containing ethylene oxide as the main diol component and terephthalic acid as the main dicarboxylic acid component is used, on the other hand, 1.5 wt% of the compound of structural formula (1) having perchloric acid as the anion, and perchlorine 0.5 wt% of compound of structural formula (2) having acid as anion, 2.5 wt% of quinacridone red pigment as colorant, and 1% of polypropylene wax as fixing aid are added, melt-kneaded, and pulverized By classifying, a toner ψ having a highly saturated red color tone was obtained.

This toner ψ was combined with a ferrite carrier to form a developer, which was mounted on an F6718K printer (manufactured by Fujitsu), and flash fixability and charging ability in a high temperature and high humidity environment were investigated. As a result, excellent fixability with a fixing rate of 85% (tape peeling test) was exhibited. Regarding the charging ability, the developer was exposed to the environment of 35 ° C. and 80% RH for 12 hours, and then the developing device was agitated for 3 minutes in the same environment. About 80 of the charge amount of
%, And it was confirmed to have excellent charging ability.

Example 29 As the binder resin, a polyester resin containing ethylene oxide of bisphenol A as a main diol component and terephthalic acid as a main dicarboxylic acid component was used, and perchloric acid was used as an anion. 1.5 wt% of the compound of (1), 0.5 wt% of the compound of structural formula (1) having hexafluoroantimonic acid as an anion, 2.5 wt% of a quinacridone red pigment as a coloring agent, and a fixing aid. As a result, 1% of polypropylene wax was added, melt-kneaded, and then pulverized and classified to obtain a toner ω having a red color tone with high saturation.

This toner ω was combined with a ferrite carrier to form a developer, which was mounted on an F6718K printer (manufactured by Fujitsu), and flash fixability and charging ability in a high temperature and high humidity environment were investigated. As a result, excellent fixability with a fixing rate of 85% (tape peeling test) was exhibited. Further, regarding the charging ability, it showed a charging recovery rate of about 80%, and it was confirmed that the charging ability was excellent.

[Comparative Example 14] As a binder resin, a polyester resin containing ethylene oxide of bisphenol A as a main diol component and terephthalic acid as a main dicarboxylic acid component was used, and perchloric acid was used as an anion. 2.0% by weight of the compound of (1), 2.5% by weight of a quinacridone red pigment as a colorant, and 1% of polypropylene wax as a fixing aid are added, melt-kneaded, and then pulverized and classified to obtain high saturation. Toner a having a red color tone was obtained.

This toner a was combined with a ferrite carrier to form a developer, which was mounted on an F6718K printer (manufactured by Fujitsu), and the flash fixability and the charging ability in a high temperature and high humidity environment were investigated. As a result, excellent fixability with a fixing rate of 85% (tape peeling test) was exhibited. However, it was found that the charging ability was only about 50%, and there was a problem with the charging ability.

[Comparative Example 15] As the binder resin, a polyester resin containing ethylene oxide of bisphenol A as a main diol component and terephthalic acid as a main dicarboxylic acid component was used, and perchloric acid was used as an anion. Toner b was obtained by adding 2.0 wt% of the compound (2), 2.5 wt% of quinacridone red pigment as a colorant, and 1% of polypropylene wax as a fixing aid, melt-kneading, and pulverizing and classifying. It was The color tone of this toner b was reddish brown, and it was not suitable as a red toner (the color quality was deteriorated).

Means (viii) [Example 30] Bisphenol A was used as a binder resin.
Polyethylene resin containing ethylene oxide as the main diol component and terephthalic acid as the main dicarboxylic acid component is used, on the other hand, 0.5 wt% of a quaternary ammonium salt containing molybdic acid as an anion as a charge control agent and a coloring agent 2.5% by weight of quinacridone red pigment, 1% of polypropylene wax as a fixing aid, and 1.5% by weight of an aminium salt-based compound having perchloric acid as an anion as an infrared light absorber. Bis (1,
Toner d was obtained by adding 0.5 wt% of (2 dithiophenolate) nickel tetra-n-butylammonium salt, melt-kneading, and pulverizing and classifying.

This toner d was combined with a ferrite carrier to form a developer, which was mounted on an F6718K printer (manufactured by Fujitsu), and flash fixability and charging ability in a high temperature and high humidity environment were investigated. As a result, excellent fixability with a fixing rate of 85% (tape peeling test) was exhibited. Regarding the charging ability, the developer was exposed to the environment of 35 ° C. and 80% RH for 12 hours, and then the developing device was agitated for 3 minutes in the same environment. About 80 of the charge amount of
%, And it was confirmed to have excellent charging ability.

Example 31 Toner e was prepared in the same manner as in Example 30 except that bis (1 mercapto 2 naphtholate) platinum tetra-n-butylammonium salt was used in an amount of 1.0 wt% as an infrared light absorber to be used in combination. Obtained. This toner e was combined with a ferrite carrier to form a developer, which was mounted on an F6718K printer (manufactured by Fujitsu), and flash fixability and charging ability in a high temperature and high humidity environment were investigated.
As a result, excellent fixability with a fixing rate of 90% (tape peeling test) was exhibited. In addition, the charge recovery rate was 75%, and it was confirmed that the film had excellent chargeability.

[Example 32] A toner f was obtained in the same manner as in Example 30 except that 0.5 wt% of bithienylidenebisbenzoquinone was used as the infrared light absorber used in combination. This toner f was combined with a ferrite carrier to form a developer, which was mounted on an F6718K printer (manufactured by Fujitsu), and flash fixability and charging ability in a high temperature and high humidity environment were investigated.
As a result, excellent fixability with a fixing rate of 90% (tape peeling test) was exhibited. In addition, the charge recovery rate was 85%, and it was confirmed to have excellent chargeability.

[Example 33] Toner g was obtained in the same manner as in Example 30 except that vanadyloxyhexadecamethylphthalocyanine was used in an amount of 0.3 wt% as the infrared light absorber used in combination. This toner is combined with a ferrite carrier to make a developer, and an F6718K printer (made by Fujitsu)
It was mounted on and the flash fixability and the charging ability in a high temperature and high humidity environment were investigated. As a result, excellent fixability with a fixing rate of 90% (tape peeling test) was exhibited. The charge recovery rate is 85
%, And it was confirmed to have excellent charging ability.

[Example 34] Toner C was obtained by the method described in Example 1. To the toner C, 0.8% of a powder of propylenebishydroxyarachimic acid amide (average particle size: 1.5 μm) was externally added using a Henschel mixer to obtain a toner h. When the fixing property and the charging ability of the toner h were investigated by the same method as in Example 1, it showed 95% fixing ability and 90% charge recovery ability, and the toner characteristics were further improved by the external addition of the hydroxyamide compound. Was confirmed to improve.

Example 35 As a binder resin, a polyester resin (melting temperature 135 ° C.) containing an ethylene oxide adduct of bisphenol A as a main diol component and terephthalic acid as a main dicarboxylic acid component was used. Dye and carbon were added, melt-kneaded, and then jet mill pulverized to an average particle size of about 10 μm to obtain a mother toner j. To the mother toner j, a powder of propylenebishydroxyarachimic acid amide (average particle size 1.5 μm) was externally added using a 0.5 wt% Henschel mixer to obtain a toner 1.

This toner l is combined with a ferrite carrier to form a developer, and an F6700 printer (manufactured by Fujitsu)
Then, the changes in the flash fixability of the toner, the blocking resistance, the toner filming characteristics for the photocondrum, and the printing characteristics in the long-term running test were investigated. As a result, blocking did not occur even when left in a 60 ° C environment for 24 hours, and the flash fixing rate was 90%.
(Tape peeling test) showed excellent fixability. further,
Even after continuous printing of 1 million sheets, toner filming did not occur on the photocondrum, and excellent printing characteristics were maintained for a long period of time.

[Example 36] An amide oligomer powder (weight average molecular weight 2000, average particle size 1 µm) Henschel mixer containing malic acid and methylenediamine as essential constituent monomers was used for the same base toner j as in Example 34. 1.0 wt% was added externally to obtain a toner m. This toner m is combined with a ferrite carrier to form a developer,
No. 00 printer (manufactured by Fujitsu Ltd.) and investigated the toner flash fixability, anti-blocking property, toner filming property for photocondrum, and printing property in long-term running test.

As a result, no blocking occurred even when left in a 60 ° C. environment for 24 hours, and the flash fixing rate was 8%.
It showed excellent fixability of 5% (tape peeling test). Further, toner filming on the photocondrum did not occur even after continuous printing of 1 million sheets, and the printing characteristics were maintained for a long time.

[Reference Example] Example 34 except that the powder of propylene bishydroxyarachidamide was not added externally.
In the same manner as the above, changes in the toner's flash fixability, blocking resistance, toner filming characteristics for photocondrum, and printing characteristics in a long-term running test were investigated.

As a result, although no blocking occurred even when left in a 60 ° C. environment for 24 hours, the flash fixing rate was low at 60% (tape peeling test).

[0191]

According to the present invention, in a color toner for flash fixing, an aminium salt-based red which has a highly efficient infrared light absorption capacity and has a light color in the visible light region (does not interfere with the color tone of the colorant). An external light absorber is used, and generally, a positive polarity charge control agent that reacts with an aminium salt-based infrared light absorber to inhibit its light absorption ability is used. Since the reaction with the agent is physically or chemically prevented, suppressed, or complemented, all of the color tone, charging characteristics, and flash fixability of the color toner for flash fixing can be satisfied. The effect is obtained.

[Brief description of drawings]

FIG. 1 is a schematic diagram showing the structure of a toner according to an aspect of means (i) of the present invention.

[Explanation of symbols]

 1-1, 1-2 ... Binder resin 2 ... Aminium salt-based compound 3 ... Positive charge control agent 4 ... Coloring agent 5 ... Fixing aid

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yasushi Nakamura 1015 Kamiodanaka, Nakahara-ku, Kawasaki City, Kanagawa Prefecture, Fujitsu Limited (72) Inventor, Hideyoshi Fujioka 35, Saho, Kato-gun, Hyogo Prefecture (no address) Fujitsu Peripheral Aircraft Co., Ltd. (72) Inventor Masahiro Nishihata 1015 Kamiodanaka, Nakahara-ku, Kawasaki City, Kanagawa Prefecture Fujitsu Limited (72) Inventor, Kazuya Hamada 1015, Kamedotachu, Nakahara-ku, Kawasaki City, Kanagawa Prefecture Fujitsu Limited (72 ) Inventor Shoichi Kinoshita No. 35 Saho, Shrine-cho, Kato-gun, Hyogo Prefecture (no address) Inside Fujitsu Peripheral Machine Co., Ltd. (72) Inventor Yuzo Horikoshi 1015 Uedotachu, Nakahara-ku, Kawasaki-shi, Kanagawa Within Fujitsu Limited (72) Invention Masaki Nagaoka 1015 Kamiodanaka, Nakahara-ku, Kawasaki City, Kanagawa Prefecture Fujitsu Limited (72) Inventor Yumi Fujisaki Kawasaki, Kanagawa Prefecture 1015 Kamiodanaka, Nakahara-ku, Fujitsu Limited Fujitsu Limited (72) Yuko Kinashi 1015 Kamikodanaka, Nakahara-ku, Kawasaki City, Kanagawa Prefecture (72) Inventor Hitoshi Kusaba, 35, Saho, Shrine-cho, Kato-gun, Hyogo Prefecture (no address) Inside Fujitsu Peripheral Co., Ltd. (72) Inventor, Ikuya Yamabata 1015 Uedoda, Nakahara-ku, Kawasaki-shi, Kanagawa Fujitsu Limited (72) Inventor Haruo Kuroda 1015 Kamiodanaka, Nakahara-ku, Kawasaki City, Kanagawa Prefecture Fujitsu Limited (72) Inventor Tetsuro Baba 1015, Kamedotachu, Nakahara-ku, Kawasaki City, Kanagawa Prefecture Fujitsu Limited

Claims (13)

[Claims] 1. A binder resin and the following general formulas (1) and / or (2): Infrared light absorber of aminium salt-based compound represented by,
A colorant and a positive polarity charge control agent and / or a positive polarity charge control resin (hereinafter, the positive polarity charge control agent and the positive polarity charge control resin are collectively referred to as a positive polarity charge control agent).
And by suppressing the reaction between the infrared light absorber and the positive charge control agent by any of the means (i) to (vi) below, or by reacting the infrared light absorber with the positive charge control agent The light absorption ability and charge control ability to be reduced are as follows (vii)
A color toner for flash fixing, which is complemented by means of i). (I) A mixture of plural kinds of resins is used as the binder resin, and the infrared light absorber is selectively dispersed or melted in a part of the specific resin. (Ii) A positive electrode charge control agent and / or a binder resin containing a positive electrode charge control agent is coated on or adhered as fine particles to the outer peripheral portion of a toner containing an infrared light absorber, a colorant, and a binder resin. . (Iii) An infrared light absorbing agent and / or a binder resin containing an infrared light absorbing agent is coated or adhered as fine particles to the outer peripheral portion of a toner containing a colorant and a positive polarity charge control agent. (Iv) As a binder resin, an amine-containing functional group resin containing a functional group of secondary amine and / or tertiary amine and / or quaternary amine, and / or a quaternary ammonium salt, and a resin containing an acidic functional group. The amine-containing functional group resin and / or the quaternary ammonium salt is blocked with a resin containing an acidic functional group using a mixture of (V) As a binder resin, a thermoplastic resin having an amide group and / or a pendant group of a nitrogen-containing ring, an amide compound, a polyamide resin, an amine-modified polyester resin,
At least one of urethane-modified polyester resin and amine-modified epoxy resin crosslinked with diamine is used. (Vi) General formula (3) as a positive charge control agent The quaternary ammonium salt represented by (Vii) As the infrared light absorber, the compound represented by the general formula (1) and the compound represented by the general formula (2) are used in combination and the anion X ⁻ is commonly used, or the compound represented by the general formula (1) is used. Two or more kinds of the represented compounds are used. (Viii) As the infrared light absorber, one or more of the compounds represented by the general formulas (4) to (8) are further mixed and used. [Chemical 3] [Chemical 4] [Chemical 5] [Chemical 6] [Chemical 7] 2. The toner according to claim 1, wherein when the means (i) is adopted, the infrared light absorber and the positive charge control agent are selectively dispersed or melted in different binder resins. 3. The toner according to claim 2, wherein the binder resin in which the infrared light absorber is dispersed or melted and the binder resin in which the positive polarity charge control agent is dispersed or melted have a solubility parameter of 0.5 or more. 4. The toner according to claim 1, wherein the positive charge control agent is a quaternary ammonium salt or an amine-containing functional group resin containing a gel component at a melting point of 200 ° C. or higher. 5. When the means (iv) is adopted, the resin having an acidic functional group is a polyester resin having a carboxylic acid and / or a sulfonic acid, and the amine-containing functional group resin is a copolymer of styrene and amino acrylate. The toner according to claim 1, which is a polymer. 6. When the means (vi) is adopted, the common anion of the compound represented by the general formula (1) and / or (2) and the compound represented by the general formula (3) is perchloric acid. sulfone represented by (wherein, R is alkyl group of 4 or less, a fluoroalkyl group or a phenyl group having a carbon) ^- ion, boron fluoride ion, hexafluoroarsenate ion, a hexafluoroantimonate ion, RSO ₃ It is any one of acid ions.
The toner described. 7. The toner according to claim 1, wherein another anionic quaternary ammonium salt having an anion different from the anionic anion of the quaternary ammonium salt represented by the general formula (3) is used in combination. 8. The toner according to claim 1, wherein when the means (vii) is adopted, the anion of the aminium salt-based compound of the general formula (1) is a perchlorate ion. 9. A toner for flash fixing, characterized in that fine particles of amide compound represented by the general formulas (9) to (11) are adhered to the surface of the toner. [Chemical 8] [In the formulas (9) and (10), l, m, and n are integers of 0 to 4, and R ^{5 to} R ⁸ are hydrogen, an alkyl group, a halogen-substituted alkyl group, an aryl group, or a halogen-substituted aryl group. ] [Chemical 9] [In the formula (11), l and m are positive integers, and R ^{5 to} R ⁷ are the same as defined above. ] 10. General formulas (1) and / or (2) A first binder resin in which the aminium salt-based compound represented by is dispersed or melted, and a second binder resin different from the first binder resin in which the positive charge control agent is dispersed or melted are prepared. A method for producing a color toner for flash fixing, comprising a step of kneading a second binder resin and pulverizing the same to obtain a toner. 11. General formulas (1) and / or (2) A fine powder of a first binder resin in which an aminium salt-based compound represented by is dispersed or melted, and a positive charge control agent and / or a positive charge control resin (hereinafter, positive charge control agent and positive charge). A positive binder charge control agent together with a control resin) is dispersed or melted to form a second binder resin and / or an amine-containing functional group containing a functional group of a secondary amine and / or a tertiary amine and / or a quaternary amine. Base resin and / or secondary quaternary ammonium salt
The method for producing a color toner for flash fixing, which comprises a step of aggregating and fixing several tens to tens of thousands of the fine powder of 1. in a liquid phase to obtain a toner. 12. Along with the first fine powder and the second fine powder,
After agglomerating tens to tens of thousands of third fine powders of a thermoplastic resin having a lower melting temperature than the first and second fine powders, the first and second fine powders did not melt The method according to claim 11, wherein the liquid phase is heated to a temperature at which the third fine powder is melted to fix the fine powder to each other. 13. General formulas (1) and / or (2): After the fine particles of the second binder resin containing the positive charge control agent are electrostatically adhered to the outer peripheral portion of the toner containing the infrared light absorbing agent, the colorant and the first binder resin represented by A method for producing a color toner for flash fixing, comprising the step of forming a film of the second binder resin on the toner surface by a fusion method.