JPH1165167A - Flash fixing toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner hardly causing blocking and filming to a photoreceptor drum and having reduced melt viscoelasticity at the time of melting it and enhanced flash fixability under low energy by adding the particles of a specified amide compd. to the surface of a toner. SOLUTION: A very small amt. of a powdery amide compd. represented by formula I, II or III is added as an essential constituent component of a toner. In the formulae I, II, (l), (m) and (n) are each integers of 0-4 and R<5> -R<8> are each H, alkyl, halogen substd. alkyl, aryl or halogen substd. aryl. In the formula III, (l) and (m) are positive integers and R<5> -R<7> are the same groups as R<5> -R<8> . The amide compd. preferably has a wt. average mol.wt. of 500-3,000, <=2 μm average particle diameter and <=5 μm max. particle diameter. The amide compd. is preferably added by 0.2-1.0 wt.%.

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 a method for producing the same. The present invention relates to a color toner for flash fixing which enables control of frictional charging characteristics of a toner containing a near-infrared light absorber as an essential component and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, as an electrophotographic method, US Pat.
Although the method described in No. 297691 is well known,
This is generally done by using a photoconductive insulator (such as a photo-condrum), applying a uniform electrostatic charge to the photoconductive insulator by corona discharge or the like, and applying various means to the photoconductive insulator. An electrostatic latent image is formed by irradiating a light image thereon, and the latent image is developed and visualized using a fine powder called toner.

[0003] If necessary, the toner image is transferred onto a recording medium such as paper, and then the toner image is melted by pressurization, heating, solvent vapor, light, or the like, and is fixed on the recording medium. Is what you get. As a toner for developing these electrostatic latent images, a toner in which an additive such as a colorant and, if necessary, a charge control agent is dispersed in a binder resin composed of a natural or synthetic polymer substance is conventionally used. 30 μm
Finely pulverized particles are used.

In the electrophotographic two-component developing method, such a toner is usually mixed with a ferromagnetic material such as iron powder and a carrier material (carrier) such as glass beads and used for developing an electrostatic latent image. In the case of the magnetic brush developing method using ferromagnetic particles such as iron powder or ferrite as a carrier, a developer composed of a toner and a carrier is triboelectrically charged by being mixed and stirred in a developing device, and furthermore, a developer in a developing device. The magnetic brush is held by the 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 electric attraction. By doing so, development is performed.

Here, the binder resin constituting the toner must be quickly melted in the process of fixing to the recording medium and exhibit good fixability. Therefore, the binder resin is generally referred to as an oligomer having a low melt viscosity and a low molecular weight. Polymer resins are widely used. On the other hand, the fixing is to fuse the toner on the recording paper surface by pressurizing, heating, solvent vapor, light or the like and fix the toner on the recording paper. Among these fixing methods, the following characteristics are provided. The light fixing method being used is attracting attention.

(1) Since non-contact fixing is performed, the resolution of an image is not degraded during the fixing process. (2) Quick start is possible without waiting time after the apparatus is turned on. (3) No ignition occurs even if recording paper is jammed in the fixing unit due to the system down. (4) Fixing is possible regardless of the material and thickness of the recording paper, such as glued paper, preprinted paper, and paper of different thicknesses.

Incidentally, the flash fixing method using xenon flash light as a light source is currently the most common method as the light fixing method. In an optical fixing method using a light source having a strong emission intensity at a wavelength in the infrared region, such as a xenon flash fixing method, the light absorbing ability of the toner is improved, and the use range of the optical fixing method having the above advantages is expanded. Japanese Patent Laid-Open No. 61-1 / 1986 discloses a method of adding an infrared light absorber of an ammonium compound such as an aminium salt compound to a toner.
No. 32959 and the like.

[0008]

Many compounds having a high infrared light absorbing ability have a brown to black hue, while aminium salt compounds exhibit excellent infrared light absorbing ability, Since some compounds have 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]

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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) or a highly reactive ionic compound (for example, When a quaternary ammonium salt or the like is present, the counter ion of the aminium salt-based compound is extracted by the polar group, or a counter ion exchange reaction occurs with the ionic compound.

[0012] Therefore, the structural change of the aminium salt compound occurs, so that the light absorption band of the aminium salt compound shifts, and in a remarkable case, the light absorbing ability for the wavelength in the flash light region is completely lost. There's a problem. On the other hand, the quaternary ammonium salt has excellent charge control ability as a colorless positive charge control agent, and is commonly used in color toners. Methods for imparting positive chargeability to the toner without using a quaternary ammonium salt include adding an amine compound other than the quaternary ammonium salt to the toner, or introducing an amine functional group into the binder resin. As described above, these amine-based compounds also have a high possibility of causing a structural change of the aminium salt-based compound.

From the above, it can be seen that an aminium salt-based compound for improving the light absorbing ability of a color toner and an amine-based compound such as a quaternary ammonium salt for imparting a charge controlling ability (hereinafter, referred to as "a").
(Charge control agent) cannot be used in combination, and a positively chargeable color toner having excellent light absorbing ability and excellent light fixability has poor chargeability, and a positively chargeable color toner having excellent chargeability has light fixation. There is a problem that the property is poor.

The present invention has been made in view of the above circumstances, and it is intended to minimize the structural change of an aminium salt compound while coexisting an aminium salt compound and a charge control agent in the toner. An object of the present invention is to provide a flash fixing toner having both flash fixing properties and charging characteristics, and a method for producing the same. In addition, since the toner for light fixing needs to absorb and instantaneously melt and fix the light energy of the instantaneous flash light of several milliseconds or less, it generally melts at about 10 to 40 ° C. in comparison with the conventional hot roll fixing toner. It was composed of a binder resin having a low temperature. In recent years, studies on reducing the energy consumption of printers have been actively pursued, and as a part of this, toner having a higher melting temperature has been demanded because of the need to reduce flash fixing energy. However, if the melting temperature of the binder is lowered as a method for further imparting low-temperature fixability to the flash fixing toner, the thermal stability of the toner itself is impaired, and problems such as blocking easily occur even in an environment at about room temperature. Also, in order to improve the melt viscoelasticity at the time of melting the toner by kneading a large amount of low-viscosity components such as polypropylene wax in order to impart low-temperature fixability by lowering the melt viscosity of the toner, the toner becomes soft. Problems such as filming on the photosensitive drum are likely to occur. Another object of the present invention is to solve this problem.

[0015]

In order to achieve the above-mentioned object, the present invention provides a binder resin comprising the following general formula (1) and / or (2)

[0016]

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Comprising an infrared absorber of an aminium salt compound represented by the formula (1), a coloring agent, and a positive charge control agent,
The reaction between the infrared light absorber and the positive charge control agent or / and the positive charge control resin (hereinafter, the positive charge control agent and the positive charge control agent are also simply referred to as the positive control agent). The light absorbing ability and the charge controlling ability which are suppressed by any of the following means (i) to (Vi) or reduced by the reaction between the infrared light absorbing agent and the positive charge controlling agent are shown in the following (vii)
Alternatively, there is provided a color toner for flash fixing, wherein the color toner is supplemented by means of (viii).

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

(Iii) An infrared light absorbing agent and / or a binder resin containing the infrared light absorbing agent is coated on the outer peripheral portion of the toner containing the colorant and the positive charge control agent, or is attached as fine particles. . (Iv) As the binder resin, an amine-containing functional group resin containing a secondary amine and / or a tertiary amine and / or a quaternary amine functional group, and / or a resin containing an acidic functional group and / or a quaternary ammonium salt. Using the mixture, an amine-containing functional group resin and / or a quaternary ammonium salt are blocked 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 having a nitrogen-containing ring, an amide compound, a polyamide resin, an amine-modified polyester resin, a urethane-modified polyester resin, and an amine-modified epoxy cross-linked with a diamine One or more resins are used. (Vi) General formula (3) as a positive charge control agent

[0021]

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

[0023]

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[0024]

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[0025]

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[0026]

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[0027]

Embedded image According to another aspect of the present invention, toner blocking and filming on the photosensitive drum occur by externally adding a small amount of the amide compound powder represented by the general formulas (9) to (11) as an essential component of the toner. Without, and
Provided is a toner in which the melting and viscoelasticity of a toner at the time of melting is reduced to improve the flash fixing ability under low energy. Preferred embodiments are as follows. The toner for flash fixing according to the toner, wherein the weight average molecular weight of the amide compound powder to be externally added is 500 or more and 3000 or less. In the toner, the average particle size of the amide compound powder to be externally added is 2 μm or less and the maximum particle size is 5 μm or less, and the external addition weight of the amide compound is 0.2% by weight to 1.0% by weight.
% By weight. In the toner, the melting temperature of the amide compound powder to be externally added is 10 to 30 ° C. lower than the melting temperature of the binder resin constituting the toner, and the temperature of the binder resin constituting the toner is 100 ° C. to 150 ° C. A toner for flash fixing, wherein the melt viscosity is higher than the melt viscosity of an externally added amide compound powder.

Hereinafter, a specific description will be given. The toner of the present invention relates to a color toner for flash fixing, and for that purpose, a binder resin contains a colorant, an infrared light absorber, and a positive charge control agent. The binder resin is not particularly limited, and a thermoplastic resin made of various natural or synthetic polymer substances can be used. 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 and the like are used alone or in combination.

The coloring agent (coloring agent) is not particularly limited either.
Any pigment may be used, for example, quinacridone (red), phthalocyanine (blue or the like), anthraquinone (red), bisazo (red or yellow), monoazo (red),
Anilide compounds (yellow), benzidine (yellow), halogenated phthalocyanines (green) and the like are used. As the infrared light absorber, an aminium salt-based compound represented by the general formulas (1) and (2) is used. These aminium salt compounds have a high absorption capacity in the infrared light region and a light color in the visible light region, so that they have little effect of contaminating the color tone of the toner, and are suitable for color toners. An infrared light absorber other than the aminium salt-based 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 infrared light absorbing ability, but have a high degree of blackness and contaminate the color of the toner, and therefore cannot be used for color toners.

In the general formulas (1) and (2), an anion
X^-As perchloric acid (CClO_Four ^-), Boron fluoride
Acid (BF_Four ^-), Trichloroacetic acid (CCl_ThreeCO
O^-), Trifluoroacetic acid (CF_ThreeCOO^-), Pikuri
Acid ((NO_Two)_ThreeC₆H_TwoO^-), Hexafluoroarsenic
Acid (AsF₆ ^-), Hexafluoroantimonic acid (Sb
F₆ ^-), Benzenesulfonic acid (C₆H_FiveS
O_Three ^-), Ethanesulfonic acid (C_TwoH_FiveSO_Three ^-),
Phosphoric acid (PO_Four ^2-), Sulfuric acid (SO_Four ^-), Chlorine (Cl^-)
Are representative.

The positive charge control agent is not particularly limited as long as it has the ability to positively charge the toner by stirring the developer, but is preferably a quaternary ammonium salt (colorless), a nigrosine dye (black), or triphenyl. A methane derivative (blue) or the like is used. In addition, the following compounds and resins can also be used as the positive charge control agent. 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 in particular, waxes (for example, polypropylene wax and the like) and surfactants (for example, silicone varnish and the like) can be 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, it is described that in such a color toner for flash fixing, an aminium salt-based infrared light absorbent reacts particularly with a positive charge control agent to reduce or lose the infrared light absorption performance. It is characterized by preventing, suppressing or supplementing by means of (1).

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

The 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 the specific binder resin 1-1 (or 1-2). More preferably, more preferably, the positive charge control agent 3 is selectively present in the other binder resin 1-2 (or 1-1) so that the infrared light absorber 2 and the positive charge control agent 3 By reducing the chance of contact, these mutual reactions could be prevented or suppressed, so that it was possible to achieve both fixability and charging characteristics in the color toner for flash fixing.

As described above, the aminium salt compound loses its function when the counter ion is disturbed, but a substance which causes such a reaction is frequently used as a charge control agent for positively charged toner. Quaternary ammonium salts and amine-containing functional group resins. According to the studies made by the present inventors, a resin having a strong charging property (an amine-containing functional group resin) having at least one of a plurality of types of binders used for toner having an amine compound in a molecular skeleton is used.
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 more can be used. The reason why it is more desirable to use a gel resin having a melting point of 200 ° C. or more is that if a resin that does not soften at a general toner kneading temperature is selected, the reaction with an aminium salt-based compound during toner production is suppressed. .

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 have a solubility parameter of 0.5 or more, preferably 1 or more. You need to be separated. This is because each of the binder resins 1-2 and 1-1
Is highly compatible, the two binder resins are homogeneously mixed without adopting the “sea-island structure”.
This is because the chances of the positive and negative charge control agents 3 approaching each other increase, making it difficult to achieve the object of the present invention.

According to the studies by the present inventors, the combination of thermoplastic resins satisfying these conditions is as follows: polyester resin and epoxy resin, polyester resin and styrene-acryl resin, polyester resin and polyamide resin, polyester resin and styrene resin. -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 various combinations such as these satisfy such a difference in the degree of melting parameter and also satisfy various properties required for a flash fixing binder.

According to the studies by the present inventors, the best combination among the above combinations is a polyester resin, a styrene-acryl resin, a styrene-butadiene resin,
And styrene, acrylate, butadiene copolymer resins and the like. Although this is different from the subject of the present invention, it is desirable to prevent the "void phenomenon" that occurs when toner particles are melted and aggregated during flash fixing as discussed in Japanese Patent Application Laid-Open No. 4-56869 and the like. Melt viscoelastic properties required to maintain excellent fixability are achieved by using a combination of the above polyester resin with a styrene-acrylic resin, a styrene-butadiene resin, and a copolymer resin of styrene, acrylate, and butadiene. This is because it is easy to do.

According to the study of 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, depending on the monomer species constituting the binder resin, the degree is lighter than the amine compound, but salt extraction of the aminium salt compound. This is for performing the reaction.

Such an example is occasionally observed when styrene-acrylic resin or the like is used as a binder. For example, in a styrene-n-butyl acrylate copolymer, no reaction with an aminium salt compound is observed, The inventors of the present invention have obtained results such as a considerably strong salt extraction reaction in the 2-ethylhexyl acrylate copolymer.

On the other hand, polyester resins include diols,
Monomer species such as dicarboxylic acid, and various binder resins were manufactured by changing the monomer composition ratio, and the reactivity was investigated.Except when some nitrogen-containing monomers were used, they react with aminium salt-based compounds. There was nothing. Therefore,
When two kinds of resins having different solubility parameters are selected, for example, polyester and styrene-acrylic resin, an aminium salt-based compound is dispersed on the polyester side and a charge control agent is dispersed on the styrene-acrylic side. It is more desirable.

According to the experience of the present inventors, the resin in which the charge control agent is dispersed is preferably a resin having a higher melt viscosity. This is because when a charge control agent is dispersed in a resin having a high melt viscosity, a desired charge control effect can often be obtained by adding a smaller amount of the charge control agent. Examples of such a resin having a high melt viscosity include a cross-linked polyester resin having a polyfunctional acid such as trimellitic acid and pentaerythritol and a polyfunctional alcohol as an essential constituent monomer, and a cross-linkable resin having a divinylbenzene and the like as an essential constituent monomer. Styrene-acrylic resins and the like are known.

According to the knowledge of the present inventors, a configuration satisfying the purpose of the present invention based on each of the above requirements is as follows.
It is more preferable to add an aminium salt-based compound to a polyester-based resin or a polyamide-based resin.On the other hand, as a resin for dispersing a positive charge control agent, a resin having a solubility parameter greatly different from that of the polyester resin or the polyamide resin is required. Therefore, in order to effectively exert the effects of the present invention, it is more preferable to use a styrene-acrylic resin or a styrene-butadiene-based resin having a cross-linking property and exhibiting the characteristics of a slightly high-viscosity resin.

The method of implementing the present invention is as follows.
It is necessary to disperse an aminium salt-based compound in any one of a plurality of types of binder resins having a difference in melting degree parameter, and disperse a 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 charge control agent in these binder resins, a method of dispersing these internal additives during polymerization of the binder resin, after producing the binder resin, And a method of dispersing the internal additive by kneading, and the present invention can be carried out using any method.

In the method of dispersing the internal additive during the polymerization of the resin and the method of dispersing the internal additive by kneading, it is preferable to disperse the internal additive during the polymerization of the resin in view of the dispersion efficiency of the internal additive and the production cost. Advantageously, an aminium salt compound or a quaternary ammonium salt commonly used as a charge control agent has poor heat resistance and changes its properties at a temperature lower than 200 ° C., which limits the binder resin system for toner. Includes the problem.

Next, a toner is formed by combining a binder resin containing an internal additive, which is an essential component, by kneading and pulverizing, or by aggregating and heating in a liquid phase. , Two methods can be adopted. One is a method of kneading and pulverizing to form a toner. A binder resin containing an aminium salt-based 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 and melt-kneaded with a kneader, an extruder, or the like, and then pulverized and classified using a pulverizer such as a jet mill to obtain a desired toner. For example, as a resin for dispersing or melting an aminium salt-based compound, terephthalic acid is used as a main component, and a polyester resin containing a bisphenol A alkylene oxide adduct as a main diol is used. The above-described dispersion is performed by kneading, and thereafter, a rotoplex crusher is used. And particle size 1
By obtaining a pulverized product having a size of about 5 mm, a fine resin powder in which an aminium salt compound is melted or dispersed can be obtained.

However, if the degree of dispersion between the binder resin in which the aminium salt-based compound is dispersed and the resin in which the positive charge control agent is dispersed is too low during kneading, the toner particles after pulverization and classification will not be able to be used. However, it is not preferable because there is a toner composed of only one resin component, and conversely, if the kneading strength is strong and both resins are well dispersed, at the interface between the so-called "sea" and "island" The ratio of the reacting aminium salt-based compound and the positive charge control agent becomes large, and the toner cannot achieve both the desired light absorption ability and charge control ability, which is not preferable.

For this reason, based on the experience of the present inventors, it is desirable to perform relatively gentle kneading when kneading both binder resins. When the dispersion state of other internal additives such as a coloring agent and a wax does not reach a desired state by such gentle kneading, a positive charge control agent or an aminium salt-based compound is added to the binder resin. At the time of dispersion, other internal additives such as a coloring agent and wax can be dispersed.

On the other hand, a method of forming a toner by agglomeration and heating in a liquid phase is based on fine resin powder in which an aminium salt compound is dispersed or melted and fine resin powder in which a positive charge control agent is dispersed or melted (charged resin). The fine resin powder having controllability may be dispersed in the liquid phase, and the resin powder may be aggregated by means of controlling the charging characteristics of the fine resin powder in the liquid phase. The aggregate is partially melted and fixed to form a toner. For example, a fine powder of a binder resin in which an aminium salt compound is dispersed or melted in advance, and a fine powder of a binder resin in which a positive charge control agent is dispersed or melted in advance and / or a thermoplastic resin of an amine-containing functional group resin The toner can be obtained 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 as an essential component.

The toner according to the present method uses the above-described kneading and mixing method.
Compared to the toner obtained by the pulverization method, the "sea"
And "islands" are clearly formed, so this is the most suitable manufacturing method for carrying out the present invention. However, the problem in realizing the present manufacturing method is that an aminium salt-based compound or a charge controlling agent is dispersed. It is how to obtain the fine resin fine powder (primary particles).

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

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

Specifically, the aminium salt compound (2)
As an essential constituent monomer of a binder that disperses or melts, a polyester resin containing 30 mol% or more of a short-chain linear diol having an irregular carbon and having 5 or less carbon atoms and 30 mol% or more of terephthalic acid, or bisphenol A type A resin obtained by melting or dispersing an aminium salt-based compound (2) by kneading the kneaded mixture with a bisphenol F type epoxy resin and then pulverizing the mixture to 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 of the present inventors, it was found that the aggregation
When a toner is formed by heating, in addition to a binder resin in which an aminium salt-based compound is dispersed and a binder resin in which a positive charge control agent is dispersed, fine powder of a resin having a low melting point is further added. Only the resin having a low melting point is melted, and a binder resin in which an aminium salt compound is dispersed,
When the binder resin in which the positive charge control agent is dispersed is melted and fixed at a temperature at which the binder resin does not melt, the reaction between the aminium salt compound and the positive charge control agent is minimized, and both excellent light absorption ability and charge control ability are achieved. It is possible to do.

Specifically, a binder resin fine powder (first resin fine powder) in which an aminium salt-based compound is dispersed or melted in advance, and a binder resin in which a positive charge control agent (3) is dispersed or melted in advance. Resin fine powder and / or amine-containing functional group resin thermoplastic resin fine powder (second resin fine powder) and third thermoplastic resin having a lower melting temperature than the first and second resin fine powders The fine powder is an essential component, and after the thermoplastic resin fine powder containing the resin fine powder is aggregated in the liquid phase for several tens to tens of thousands of particles, the first and second resin fine powders are not melted. 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 controlling agent or a resin powder containing the charge controlling agent is adhered to an outer peripheral portion of the toner (hereinafter referred to as “external”). ), Or by forming a film of a charge control agent or a resin containing a charge control agent on the surface layer of a toner containing an aminium salt-based compound, so that the toner has a charge control ability on the surface layer and the toner inside. It is possible to have excellent light absorption ability. As a result, a toner that achieves both fixing properties and charging characteristics 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. Incidentally, as a means for imparting charge control ability to the surface layer of the toner, there are two methods of externally adding a resin powder having excellent charge controllability, and a film forming method. Although it has advantages such as simple and cost-effective, the externally added resin powder is held on the surface of the toner matrix containing the aminium salt-based compound by the electrostatic force of triboelectric charging between the two, so that both are If the frictional charging characteristic of the toner does not exist at an appropriate level, it is necessary to take into account the influence of, for example, agitation in the developing device and the detachment of the external additive powder from the toner surface. For this reason, 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 surface layer of the toner, 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 may be employed. The most suitable film forming method for the purpose of the present application is a mechanofusion method, that is, a method in which a fine powder of a resin serving as a material of a film layer is electrostatically adsorbed on a surface layer of a toner base particle, and then the toner surface is heated by mechanical shock. The most suitable method is to apply pressure and, as a result, to melt a resin fine powder to be a material of the film layer to form a film. This is because the mechanofusion method does not involve a solvent or the like, and thus does not cause widespread dissolution of the surface of the toner matrix. As a result, the reaction between the aminium salt in the toner matrix and the charge control agent in the film layer material is minimized. Due to being limited to

Means (iii) Therefore, the present researchers have proposed a means for solving this problem.
The function of the charge control agent and the aminium salt-based compound can be controlled by using a charge-separating type toner in which the toner particle base has charge controllability and the thermoplastic resin powder externally added to the surface of the toner particles has a light absorbing ability. Prevention, and with respect to the charging characteristics, mainly utilizing the function of the charge control agent added to the toner matrix, and in the fixing step, the aminium salt-based compound added to the externally added resin shows good light absorbing ability and generates heat, It has been found that when the heat is transferred from the externally added resin to the toner matrix, the entire toner is melted, and excellent flash fixing ability can be obtained.

The average particle size of the resin fine powder to be externally added is 0.5 μm.
m to 5.0 μm, the content of the aminium salt compound in the fine resin powder is 10% to 50% by weight, and the external addition amount of the fine resin powder to the toner is 2%. % Or more and 5% by weight or less, and the content of the aminium salt-based compound relative to the total weight of the toner is preferably 0.5% by weight or more. this is,
If the average particle diameter is smaller than the above range, the amount of the fine powder of the aminium salt-based compound-containing resin adhering to the toner surface decreases, while if 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 compound in the resin fine powder are below the above range, the toner fixing becomes difficult because the amount of the aminium salt compound added to the total amount of the toner is insufficient, On the other hand, if the amount is too large, the influence of the color tone of the aminium salt-based compound on the toner color tone cannot be ignored, and the electric resistance of the resin fine powder becomes low, so that the resin fine powder hardly electrostatically adheres to the toner matrix. It is because it becomes.

The material of the resin fine powder for external addition according to the present invention is not particularly limited as long as it is a thermoplastic resin having no reactivity with the aminium salt-based compound.
When a method for obtaining a desired resin fine powder by pulverization such as jet mill pulverization after melt-kneading the resin fine powder with an aminium salt-based compound is employed, 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) having an asymmetric carbon and 30 mol% or more of terephthalic acid is recommended. This is because the resin has no reactivity with the aminium salt-based compound, has extremely good pulverizability, and can easily obtain a fine resin powder having a desired particle size. As a method for producing a 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-based 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 containing 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 site, 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.

The functional groups that can exert the effects of the present invention include acidic functional groups such as carboxylic acid and sulfonic acid, and the substances having these functional groups include carboxylic acid monomers such as polyester resin and acrylic acid. Can be found, such as polyacrylic resin and styrene-acrylic resin, which are essential monomers. In order to effectively exert the effects of the present invention, the acid value of the acidic functional group preferably has an acid value of 30 mg / KOH or more.

In the present invention, the substance containing a basic site introduced for the purpose of imparting positive chargeability includes
It is a quaternary ammonium salt or an amine-containing functional group resin, and is effective in the case where the amine-containing functional group resin is a copolymer containing styrene and / or acrylate and / or aminoacrylate as an essential monomer. However, a more excellent effect is exhibited by an amine-modified polyacrylate and an amine-modified styrene having an aminoacrylate as an essential monomer in a skeleton as a substance containing a basic site 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 melt-kneading an aminium salt compound, a resin imparting positive chargeability and / or a positive charge control agent, a binder resin containing an acidic functional group, a colorant, and the like, and then pulverizing and classifying the toner. Although it can be obtained in the process, in order to further exert the effect of the present invention,
First, in a binder resin containing an acidic functional group, a resin and / or a positive charge control agent for imparting a positive charge property, for example, 4
After preparing a resin mixture which is melt-kneaded with a resin containing an amine functional group such as quaternary ammonium or styrene-dimethylaminoethyl methacrylate copolymer, the resin mixture is again melt-kneaded with a coloring agent, an aminium salt-based compound, etc.
Performing stepwise kneading is more effective.

The mixing of the binder resin containing an acidic functional group with a resin imparting a positive charge and / or a positive charge control agent involves adding one of the resins in the process of polymerizing one of the resins. Can also be performed.

Means (v) It has been found that a binder resin having a specific chemical structure exhibits a moderately positive chargeability and does not impair the light absorption characteristics and the charge imparting characteristics of the aminium salt compound. Binder resin according to the present invention, compared with aliphatic tertiary amines and quaternary ammonium salts represented by styrene-dimethylaminoethyl methacrylate copolymer and the like,
Since the basicity is slightly weak, a salt withdrawal reaction of the aminium salt-based compound hardly occurs, and it has a positive charge enough to supplement the positive charge characteristics of the aminium salt-based compound. The binder resin satisfying the above properties includes 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, and / or -RCONH ₂ (R is a benzene ring or an aliphatic group having 0 to 2 carbon atoms). An amide group represented by (hydrocarbon) can be found in a thermoplastic resin having a structure in which the amide group is pendantly coordinated with a binder molecular chain. The thermoplastic resin having such a structure and satisfying the heat melting property and the rheological property required as a binder resin for a toner is a vinyl monomer and / or an acrylamide monomer having a nitrogen-containing cyclic structure such as vinylpyrrolidone. As an essential constituent monomer.

The copolymerization ratio of the acrylamide monomer and the monomer having a nitrogen-containing cyclic structure is at least 10 mol%.
Desirably, it is 0 mol% or less. If the copolymerization ratio is less than 10 mol%, the binder resin may not exhibit the desired positive charging characteristics in some cases. If the copolymerization ratio exceeds 20 mol%, such a monomer is frequently used while the binder resin is used. This is because it becomes difficult to satisfy the heat melting property and the rheological property required as the above, and in rare cases, the degree of the salt extraction reaction with respect to the aminium salt compound may exceed the allowable limit.

Examples of the binder exhibiting a moderately positive chargeability and not impairing the light absorption characteristics and the charge imparting characteristics of the aminium salt-based compound include the binders having a pendant structure of the amide group or the nitrogen-containing ring. Amide resins such as amide monomers and polyamide resins, amine-modified polyester resins having amino-containing dicarboxylic acids or amino-diols as essential constituent monomers, (more specifically, for polyester resins having an acid value of 15 or more, Amine-modified polyester in which 10-30% of the carboxylic acid terminals are amide-sealed with a monoamine or cross-linked with a diamine), or a urethane-modified polyester resin in which the terminal hydroxyl groups are urethane-sealed with isocyanate or the like (more specifically, 10%). For polyester resins with the above OH value, 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 an 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 to the photosensitive drum. In addition, since the polyester resin generally has a negative charging property, a positive charging property is imparted by using an amino-containing monomer, and in order to satisfy the requirements of the present invention, the copolymerization ratio of the amino-containing monomer is required. In the case of a urethane-modified polyester resin, it is desirable that 20% or more of the alcohol terminal of the polyester resin having an OH value of 10 or more be urethane-sealed.

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

[0074]

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A quaternary ammonium salt represented by the following formula is used. As a result, a structural change between the aminium salt-based compound and the charge control agent does not occur, and the aminium salt-based compound and the charge control agent maintain their original functions, and a toner having both fixing properties and charge characteristics can be obtained. Aminium salt compounds having a high infrared light absorption capacity and a light color tone in the visible light region include perchlorates, fluoroborates, hexafluoroarsenates, hexafluoroantimonates, and alkyl sulfonates. Salts have been found. On the other hand, those commonly used as quaternary ammonium salts having high charge control ability are sulfonate-based quaternary ammonium salts and molybdate-based quaternary ammonium salts. Light absorption capacity of aminium salt compound,
As the anion species exhibiting both excellent charge control ability of the quaternary ammonium salt, sulfonate ions and molybdate ion anions have been found.
In addition, when perchlorate ion and fluoroboronate ion are used as anionic species, relatively good characteristics are exhibited. When perchlorate ion and fluoroborate ion are used as ionic species, quaternary ammonium is used. There is still room for improvement in the charge control ability on the salt side, particularly the charge rise ability. Therefore, for toners that require advanced charging control functions,
When a perchlorate ion or a fluoroborate ion is selected as the common anion species, a very small amount of a sulfonate-based quaternary ammonium salt or a molybdate-based quaternary ammonium salt is used in combination as a charge control agent. It has been confirmed that excellent performance can be obtained. In this case, when a quaternary ammonium salt having an anion different from the anion of the aminium salt-based compound is used, there is a risk that the salt exchange reaction occurs, but the amount of the quaternary ammonium salt having a different anion is reduced. 1/1/3 of the added amount of the aminium salt compound
When the amount is less than 5 equivalents, although the function of some of the aminium salt compounds is lost, the infrared light absorbing ability of the whole toner does not decrease so much, and both excellent charge control function and infrared light absorbing ability are achieved. Becomes possible.

The charge control function of the toner can be improved by using an amine compound as a binder resin or other additives. The amine compound in this case also has a possibility of causing an ion abstraction reaction of the aminium salt compound, but like the sulfonate-based quaternary ammonium salt and molybdate-based quaternary ammonium salt, the amine compound may be used in the toner. When the amount of the amine compound present in the toner is not more than 1/5 equivalent of the amount of the aminium salt added, the infrared light absorbing ability of the whole toner does not decrease so much, and the charge control function of the toner is reduced by the presence of the amine group. Thus, it is possible to achieve both excellent charge control function and infrared light absorption ability.

Means (vii) The present inventors have studied and compared 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 to the compound represented by the formula (1), the compound has the advantage that the positive chargeability is high and the light absorption ability is high, but it has a problem that the color tone is slightly dark, and the compound represented by the general formula (2) 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 have obtained a compound satisfying the charging ability, the light absorbing ability and the color tone by blending and using the compound represented by the general formula (1) and the compound represented by the general formula (2). Was found to be able to.

According to the study of the present inventors, in order to prevent the influence on the color toner, the blending ratio of the general formula (1) and the general formula (2) should be adjusted according to the compound of the general formula (1). It is desirable that (monovalent) is 60 to 80% by weight, and the compound of formula (2) (divalent) is 20 to 40% by weight. In addition, the present inventors have found that the aminium salt-based compound has slightly different charging ability, color tone in the visible region, light absorption ability, and reactivity with a charge controlling agent depending on the anionic species, and these may be used in combination as appropriate. As a result, it is found that a toner satisfying the charging ability, the light absorbing ability and the color tone can be obtained as in the case where the compounds of the general formulas (1) and (2) are used in combination.

Means (viii) The present inventors have studied and found that a compound represented by the general formula (1), an aminium salt compound represented by the general formula (2) and a compound represented by the general formulas (4) to (8) Quaternary ammonium salt-based charge control for toner by using in combination with ammonium salts of aromatic dithiol and mercaptophenol and diamine-based metal complexes, and compounds having infrared light absorption such as polyenylidenebisbenzoquinones and phthalocyanine. When an agent is added, the compounds represented by the general formulas (4) to (8) that do not react with the quaternary ammonium salt-based charge control agent lose the light absorption ability of the aminium salt-based compound lost by the reaction with the quaternary ammonium salt. It has been found that good light absorbing ability can be imparted to the color toner in order to compensate for the problem.

The compound of the general formula (4) is a dithiol compound, the compound of the general formula (5) is a mercaptophenol and a mercaptonaphthol compound, the compound of the general formula (6) is a diamine compound, and the compound of the general formula (7) is Polyenylidenebisbenzoquinone-based compound of general formula (8) is phthalocyanine,
It is a naphthalocyanine type. When using an aromatic dithiol, an ammonium salt of a mercaptophenol or a diamine-based metal complex or a polyenylidenebisbenzoquinone as an infrared light absorber to be used in combination, the influence on the generated fixing odor and the color tone of the color toner is 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 does not cause much problem, but the color tone of these phthalocyanine compounds in the visible region is strong blue to green. In many cases, even when a small amount is added to the toner, the effect on the toner color tone is large.
When it is added to a toner having a color tone different from the color tone inherent to the phthalocyanine-based 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]

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[In the equations (9) and (10), l, m and n are 0
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. ]

[0085]

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[In the formula (11), l and m are positive integers, and R ⁵
To R ⁷ are the same as defined above. By externally adding an appropriate amount of an 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. Was found.

It is presumed that the following phenomenon occurs as a mechanism showing this effect. First, in this toner, the amide compound as an externally added resin is melted slightly before the entire toner is melted. The molten amide compound has large polar sites such as amide groups (including amide bonds) and hydroxyl groups in the molecular structure, has a very high affinity for paper fibers, and forms a toner. Since the binder resin has a lower melting point and lower melt viscosity than the binder resin, it quickly penetrates between the paper fibers. By this effect, the wettability of the molten binder resin to the paper fibers is enhanced, and the binder resin (toner base) having a somewhat high melt viscosity penetrates between the fibers of the paper, thereby exhibiting strong fixing properties. For this reason, the amount of light absorbed by the toner is not sufficient, and good fixability can be imparted even when the binder resin has a low melt viscosity due to a low temperature.

The amide compound having such properties can be found in 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 desirably 500 or more and 3000 or less. This is because if the molecular weight is below this range, the amide compound becomes soft, so that drum filming is liable to occur. On the other hand, if the molecular weight is 3,000 or more, the viscosity upon melting is often high, and it is difficult to exhibit the effect. .

In order to exhibit the effect well,
The amide resin must melt faster than the toner matrix,
In addition, the viscosity at the time of melting must be low. For this reason, the melting temperature of the externally added amide compound is lower by at least 10 ° C. than the melting temperature of the binder resin forming the toner matrix, and
This is the melting temperature range of the molten toner near the recording paper. 100
It is necessary that the melt viscosity in the region of about 150 ° C. be lower than the melt viscosity of the binder resin forming the toner base.

The same effect can be obtained in a toner in which an amide compound is internally added (melted and kneaded together with a binder resin) to the toner, 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, the amide compound to be used is relatively soft and brittle, and when a large amount of the amide compound having such characteristics is added to the toner, a long-term printing forms a thin film of the amide compound on the photosensitive drum. So-called drum filming occurs and causes printing troubles such as background fogging. In order to prevent drum filming even during long-term use, the amount of the amide compound in the total amount of the toner is at least 2% by weight or less, preferably 1% by weight or less.
% By weight or less. In order to exhibit the above-mentioned good fixing effect with the added amount of such an amide compound,
The amide compound is preferably added to the toner by external addition.

It is desirable that the amide compound to be externally added has an average particle size of 2 μm or less and a maximum particle size of 5 μm or less. If the particle diameter of the amide compound to be added exceeds the above range, the amide compound is not uniformly attached to the toner surface and easily detached from the toner, so that problems such as accumulation of the amide compound in the developing device are likely to occur. That's why. In addition,
It is noted that this embodiment is effective not only in the case of combining with the means (i) to (viii) but also for any flash fixing toner.

Method for Producing Toner The method for producing the color toner for flash fixing of the present invention described in each of the above-mentioned means is provided by the present invention in both a general production method and a special production method. The specific description is as described above and will not be repeated, but especially the manufacturing method described in the claims is unique.

[0093]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

Light absorption wave of binder resin added with infrared light absorber
The strongest emission wavelength of the xenon lamp for long measurement flash fixing is 800-1000 nm. Therefore, various types to which 1 wt% of an aminium salt-based compound represented by the general formula (1) and whose anion is a perchlorate ion (this aminium salt-based compound was used unless otherwise specified in the following Examples) were added. For the resin, put the evaluation resin powder and the aminium salt compound into a stainless steel dish, gently melt and mix on a hot plate at 150 ° C (in this case, confirm the color tone). However, the light absorption characteristics were examined using an infrared absorption spectrometer.

Table 1 shows the results.

[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, as the binder resin 1-2, styrene-
Acrylic resin (styrene-methyl methacrylate-n-butyl methacrylate copolymer) was used, 1% of a quaternary ammonium salt was added as a positive charge control agent 3, and 2% of brominated copper phthalocyanine was used as a coloring agent 4 to fix the toner. As an agent 5, 1% of a polypropylene wax is added and melt-kneaded. This kneaded product is called B.

When the difference between the solubility parameters of the used polyester resin and the styrene-acrylic resin was calculated, the value was about 0.8. Then, after roughly kneaded products of the kneaded products A and B were blended at a ratio of 7: 3, they were further melt-kneaded, and then pulverized and classified to obtain a toner C. This toner C was used as a developer in combination with a ferrite carrier, mounted on a printer (product name: F6718K, manufactured by Fujitsu), and the flash fixability and the charging ability in a high-temperature, high-humidity environment were investigated.

As a result, an excellent fixing property with a fixing rate of 90% (tape peeling test) was exhibited. Regarding the charging ability, the developer was exposed to an environment at 35 ° C. and 80% RH for 12 hours, and then the developing device was stirred for 3 minutes under the same environment.
After stirring for 3 minutes, the toner showed a charge recovery up to about 80% of the charge amount in a normal temperature and normal humidity state (hereinafter, this value is referred to as a charge recovery rate), and it was confirmed that it had excellent charging ability. Was.

It should be noted that, in place of the polyester resin used in this embodiment, a polyester resin and / or a polyamide resin, and a styrene-butadiene resin instead of a styrene-acrylic resin were used. The effect can be obtained. Polyester resin and styrene-
The effects of combinations of binder resins other than acrylic resins are shown in the table below.

Binder resin 1-1 Binder resin 1-2 Fixing rate% Charge recovery rate% Polyester styrene-acryl 90 80 polyester styrene-acryl 85 95 polyester styrene-butadiene 80 95 epoxy styrene-acryl 100 80 polyamide styrene-acryl 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 is used. On the other hand, 2% of an aminium salt compound and 2% of brominated copper phthalocyanine are used.
% And 1% of a polypropylene wax and melt-kneaded. This kneaded product is called D.

The kneaded product D and an amine-modified styrene-acrylic binder resin 1-2 containing dimethylaminoethyl methacrylate as an essential monomer are melt-kneaded at a ratio of 9: 1 and then pulverized and classified to form a toner E. I got The toner E was examined for fixability and charging ability in the same manner as in Example 1. As a result, excellent characteristics with 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 a fine particle having a submicron particle size having a melting point of 200 ° C. or more. The toner F was examined for fixability and charging ability by the same method as described in Example 1.
% And a charge recovery rate of 90%.

Example 4 A 7: 3 mixture of 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 during resin synthesis was used. And then pulverized and classified to obtain toner G. When the toner G was examined for fixability and charging ability in the same manner as in Example 1, excellent properties such as a fixing rate of 85% and a charge recovery rate of 70% were obtained.

[Example 5] A bisphenol A type epoxy resin (epoxy equivalent: 900) was melt-kneaded with 3% of an aminium salt-based compound, and then finely pulverized with a jet mill to 2 µm or less to obtain a pulverized product H. . In addition, 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 ground product H, brominated copper phthalocyanine,
The mixture was heated to 20 ° C., aggregated, and fixed to obtain a toner I.

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

[Example 6] The bisphenol A type epoxy resin formed in Example 5 was changed to a polyester resin having a weight average molecular weight of about 6000 containing 1,2-propylene glycol, neopentyl glycol and terephthalic acid as essential constituent monomers. Other than the above, the toner J
I got

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

Example 7 Toner K was 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. was added and the heating temperature was 90 ° C. Was. The toner K was examined for fixability and charging ability in the same manner as described in Example 1.
Excellent characteristics of 0% and a charge recovery rate of 85% were obtained.

[Comparative Example 1] As a 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 fixability and charging ability in the same manner as in Example 1.
However, the charge recovery rate was 30% or less. In this comparative example, the chargeability was extremely low because the positive charge control agent was not added.

Comparative Example 2 Chemical as a positive charge control agent
The formula [(C₁₄H₂₉)_Two(CH_Three)_TwoN⁺]_FourMo₈O₂₆ ^Four-In table
Except that 1% of quaternary ammonium salt was added
In the same manner as in Comparative Example 1, a toner M was obtained. This toner
M was measured in the same manner as described in Example 1 to determine the fixing property and the charging ability.
According to the investigation, the fixing rate was 20% or less, and the charge recovery rate was 40%.
The light absorption and charging characteristics are both low.
Also, the color tone of the toner changes from green to brown, the color tone of the colorant.
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 disadvantageous results were obtained.

Comparative Example 3 A kneaded product A was obtained in the same manner as in Example 1. Further, a carboxylic acid-modified styrene-acryl resin having methacrylic acid as an essential constituent monomer is used, and a quaternary ammonium salt is used as a positive charge control agent in an amount of 1%.
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 between the solubility parameters of the acrylic resin was calculated, the value was about 0.2. The kneaded product A and the kneaded product N were melt-kneaded at a ratio of 8: 2, and then pulverized and classified to obtain a toner O.

When the fixing property and the charging ability of this toner were examined in the same manner as in Example 1, the fixing rate was 45%.
%, The charge recovery rate was 60%, and did not reach the target performance. Further, when the state of dispersion of the kneaded product A and the kneaded product N in the toner O was examined, no clear "sea-island structure" was found, although they were not completely compatible.

Comparative Example 4 As a resin in which an aminium salt compound is dispersed, a polyester resin having bisphenol A type epoxy resin as a main diol component with an ethylene oxide adduct of bisphenol A and terephthalic acid as a main dicarboxylic acid component is used. Except for the above, the production of the toner was attempted in the same manner as in Example 5.

However, the resin in which the aminium salt compound was dispersed in Comparative Example 4 had a particle size of 4 to 6 in ordinary jet pulverization.
It was only possible to pulverize to about μm, and it was not possible to obtain a toner of about 10 to 12 μm by using this pulverized product to aggregate and fix in an aqueous phase.

Means (ii) [Example 8] Toner L of Comparative Example 1
Styrene-dimethylaminoethyl methacrylate copolymer resin powder (copolymerization ratio: divinylbenzene: styrene:
Dimethylaminoethyl methacrylate = 5: 75: 20
(Average particle size: 0.1 μm) was mixed and stirred using a Henschel mixer to obtain a toner P to which divinylbenzene-styrene-dimethylaminoethyl methacrylate copolymer resin powder was externally added.

When the amount of charge in combination with the Mn—Zn ferrite carrier coated with methyl methacrylate was measured, the amount of charge of the toner P in a normal temperature and normal humidity environment was 20 μC / g. Then, at 35 ° C., 80%
After exposing the developer to the environment under RH for 12 hours, the developing device was stirred for 3 minutes in the same environment. When the developer was stirred for 3 minutes, the charge amount was increased to about 75% of the charge amount in a normal temperature and normal humidity state. Recovery (hereinafter, this value is referred to as a charge recovery rate), and it was confirmed that the toner had excellent charging ability.

Further, the above-mentioned methyl methacrylate-coated ferrite carrier and toner P were combined to form 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 9 [(C ₁₄ H ₂₉ ) ₂ (CH ₃ ) ₂ N
^+] ₄ Mo ₈ O ₂₆ ^4-formula styrene -n-butyl acrylate copolymer resin powder was incorporated with a quaternary ammonium salt polymerization process represented by (copolymerization ratio; styrene: n-
Butyl acrylate = 75: 25 / average particle size 0.1 μ
m) was externally added to the toner L of Comparative Example 1 by mixing and stirring using a Henschel mixer to obtain a toner Q.

When the charge amount was measured in combination with a Mn-Zn 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, at 35 ° C., 80%
After exposing the developer to the environment under the RH for 12 hours, the developer was stirred for 3 minutes in the same environment. When the developer was stirred for 3 minutes, the charge amount was increased to about 90% of the charge amount at room temperature and normal humidity. It showed recovery and was confirmed to have excellent charging ability.

Further, the combination of the methyl methacrylate coated ferrite carrier and the toner Q
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 The quaternary ammonium salt-containing styrene-n-butyl acrylate copolymer resin powder used in Example 2 (copolymerization ratio: styrene: n-butyl acrylate = 75: 25 / average particle diameter of 0.1%). 1 μm) at 4 wt%,
The 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 Kikai), and the surface of the toner L was subjected to pressure and impact. A toner R coated with the resin was obtained.

When the charge amount was measured in combination with a Mn-Zn 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, at 35 ° C., 80%
After exposing the developer to the environment under RH for 12 hours, the developing device was stirred for 3 minutes in the same environment. When the developer was stirred for 3 minutes, the charge amount was increased to about 85% of the charge amount at room temperature and normal humidity. It showed recovery and was confirmed to have excellent charging ability.

Further, the above-mentioned methyl methacrylate-coated ferrite carrier and toner R were combined to form 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 Toner L of Comparative Example 1 was mixed with styrene-methyl methacrylate-dimethylaminoethyl methacrylate copolymer resin powder (copolymerization ratio: styrene: methyl methacrylate: dimethylaminoethyl methacrylate = 75: 10). : 15 / average particle size 0.1μ
m) was added in an amount of 4 wt%, and a toner S having a surface layer coated with a styrene-methyl methacrylate-dimethylaminoethyl methacrylate copolymer resin was obtained in the same manner as in Example 10.

When the charge amount was measured in combination with a Mn-Zn 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, at 35 ° C., 80%
After exposing the developer to the environment under the RH for 12 hours, the developer was stirred for 3 minutes in the same environment. When the developer was stirred for 3 minutes, the charge amount was increased to about 90% of the charge amount at room temperature and normal humidity. It showed recovery and was confirmed to have excellent charging ability.

Further, the combination of the methyl methacrylate coated ferrite carrier and the toner S
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, and the amount of charge in a normal temperature and normal humidity environment was 12 μm.
C / g. Next, after the developer was exposed to an environment at 35 ° C. and 80% RH for 12 hours, the developing device was stirred for 3 minutes in the same environment. When the developer was stirred for 3 minutes, the charge amount in a normal temperature and normal humidity state was obtained. Of about 40%, and it was found that charge recovery was difficult.

Further, the above-mentioned methyl methacrylate-coated ferrite carrier and toner L were combined to obtain F6718.
The printer was mounted on a K printer (manufactured by Fujitsu) and its printing characteristics were investigated. In a continuous running test at room temperature, excellent printing characteristics were shown over 100,000 sheets, but after stopping the printer for two days or more. In a running test at the time of re-driving or in a high-temperature and high-humidity environment, ground fogging and excessive development occurred due to insufficient recovery of the charge amount of the developer, and satisfactory printing characteristics were not obtained.

[Comparative Example 6] A resin fine powder to be externally added was mixed with styrene-methyl methacrylate-dimethylaminoethyl methacrylate copolymer resin powder (copolymerization ratio: styrene: methyl methacrylate: dimethylaminoethyl methacrylate = 75: 10: 15 / A resin externally added toner T was obtained in the same manner as in Example 8 except that the average particle size was changed to 1.0 μm.

When the charge amount of the toner T 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 22 μC / g. Then, at 35 ° C,
After the developer was exposed to an environment under 80% RH for 12 hours, the developing device was stirred for 3 minutes in the same environment. When the developer was stirred for 3 minutes, about 80% of the charge amount in a normal temperature and normal humidity state was reduced. It was confirmed that the toner had excellent charging ability.

Also, the above-mentioned methyl methacrylate-coated ferrite carrier and toner T were combined to form F6718.
When installed on a K printer (manufactured by Fujitsu) and examined the printing characteristics, it showed excellent printing characteristics over about 20,000 sheets from the beginning, but after that, the printing showed that the charge amount suddenly increased and faded. Became. Investigation into the cause revealed that the externally added resin powder was not sufficiently retained on the toner surface, and the resin powder gradually desorbed from the toner surface over a long period of use and accumulated in the developing device. .

Means (iii) [Example 12] Bisphenol A was used as the binder resin.
Using a polyester resin containing ethylene oxide adduct as a main diol component and terephthalic acid as a main dicarboxylic acid component, adding 1% of a quaternary ammonium salt as a charge controlling agent, and fixing 2% of a brominated phthalocyanine as a coloring agent. 1% polypropylene wax as auxiliary agent
The resulting mixture was melt-kneaded, pulverized to a particle size of 5 to 20 μm to obtain a base toner U.

Further, a bisphenol A type epoxy resin was used as a binder resin, an aminium salt-based compound was added to the mixture in an amount of 20 wt%, and the mixture was 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, 3 wt% of the aminium salt compound-containing resin fine powder V was externally added to the base toner U using a super mixer to obtain a toner W.

The toner W was used as a developer in combination with a ferrite carrier, mounted on an F6718K printer (manufactured by Fujitsu), and the flash fixability and the charging ability in a high-temperature, high-humidity environment were investigated. As a result, an excellent fixing property with a fixing rate of 75% (tape peeling test) was exhibited. Regarding the charging ability, the developer was exposed to an environment at 35 ° C. and 80% RH for 12 hours, and then the developing device was stirred for 3 minutes in the same environment. About 75
% Charge recovery (hereinafter, this value is called the charge recovery rate)
And it was confirmed that it had an excellent charging ability.

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

Next, 4 wt% of the resin fine powder X containing the 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, and F
It was mounted on a 6718K printer (manufactured by Fujitsu), and its flash fixability and charging ability in a high-temperature, high-humidity environment were investigated. As a result, an excellent fixing property with a fixing rate of 80% (tape peeling test) was exhibited. In addition, the charging ability showed a charge recovery rate of about 85%, and it was confirmed that the toner had excellent charging ability.

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

The toner α was used as a developer in combination with a ferrite carrier, mounted on an F6718K printer (manufactured by Fujitsu), and the flash fixability and the charging ability in a high-temperature, high-humidity environment were investigated. As a result, an excellent fixing property with a fixing rate of 90% (tape peeling test) was exhibited. In addition, the charging ability showed a charge recovery rate of about 90%, and it was confirmed that the toner had excellent charging ability.

[Comparative Example 7] With respect to the base toner U exemplified in Example 12, the fixability and the charging ability of the toner were examined in the same manner as in Example 12, and the charge recovery rate was 80%. Was not fixed at all and was unsatisfactory.

Comparative Example 8 A polyester resin containing a bisphenol A ethylene oxide adduct as a main diol component and terephthalic acid as a main dicarboxylic acid component was used, and an aminium salt-based compound was added thereto in an amount of 20 wt% and melt-kneaded. 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.
A powder of only about μm was obtained (external 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 a toner γ. Did not electrostatically adhere to the base toner γ, the externally added resin powder scattered in the printer device, and was not practical.

Means (iv) According to the knowledge of the present inventors, when an aminium salt-based compound is kneaded and added to a binder resin, if there is no reactivity between the binder resin and the aminium salt-based compound, the kneaded product is treated with an aminium salt-based compound. 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 black brown color tone.

Using this phenomenon, prior to toner production,
An aminium salt compound is melt-added to a mixture of a binder resin containing an acidic functional group and a positively chargeable resin and / or a positive charge control agent to investigate the reactivity between the binder resin and the aminium salt compound. did. Table 1 shows the results. Further, the produced toner is combined with a Mn-Zn based ferrite carrier coated with methyl methacrylate to form a developer, and an F6718K printer (manufactured by Fujitsu)
We investigated the flash fixability and charging ability in a high-temperature, high-humidity environment. Table 2 shows the results. The criteria in Table 2 are as follows: も の: excellent fixability with a fixing rate of 95% or more (tape peeling test); ○: 90% to 80% with a fixing rate of 90% or less; And x was given.
As for the charging ability in a high-temperature and high-humidity environment, three
After being exposed to an environment at 5 ° C. and 80% RH for 12 hours, the developing device is stirred for 3 minutes in the same environment, and the charge recovery of 80% or more of the charge amount at room temperature and normal humidity is performed by stirring for 3 minutes. ◎ indicates that the charge recovery was 70 to 80%, and X indicates that the charge recovery rate was lower than that.

Example 15 A polyester resin having an acid value of 48 mg / KOH was used as a binder resin at 80% of the total amount of the binder resin, and a styrene-dimethylaminoethyl methacrylate copolymer (styrene: dimethylaminoethyl methacrylate = 66:34), 20% by weight of the total amount of the binder resin, 2% of an aminium salt (infrared light absorbing agent) added thereto, 2% of a brominated phthalocyanine (coloring agent), and 1 part of a polypropylene wax as a fixing aid. %, Melt-kneaded, and pulverized and classified to obtain a toner δ.

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

Example 17 As a binder resin, a polyester resin having an acid value of 48 mg / KOH was used as 80% of the total amount of the binder resin, and a styrene-dimethylaminoethyl methacrylate copolymer (styrene: dimethylaminoethyl methacrylate = 66:34) was used in an amount of 20% by weight of 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 a polypropylene wax as a fixing aid are added to the melt-kneaded resin, melt-kneaded, and pulverized and classified. I got

Example 18 As a positively charged binder resin, a styrene-dimethylaminoethyl methacrylate copolymer (styrene: dimethylaminoethyl methacrylate =
66:34), which was introduced during the process of synthesizing a styrene-acrylic acid copolymer having an acid value of 25 mg / KOH, thereby obtaining styrene-dimethylaminoethyl methacrylate copolymer particles. Was obtained to obtain a styrene-acrylic acid copolymer. The weight ratio between 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 prepared by adding 80% of the total amount of the binder resin, 1,3 propane glycol,
Acid value 15mg / KO with terephthalic acid as the main constituent monomer
A total amount of 20% polyester resin of H is used, 2% of an aminium salt compound, 2% of a brominated phthalocyanine (coloring agent) and 1% of a polypropylene wax as a fixing aid are melt-kneaded, and then crushed and classified. Thus, a toner η was obtained.

Comparative Example 9 An acid value of 3 was used as the binder resin.
mg / KOH of polyester resin to 7 of total binder resin
0%, a styrene-dimethylaminoethyl methacrylate copolymer (styrene: dimethylaminoethyl methacrylate = 66: 34) was used as a positively charged binder resin at 30% by weight of the total amount of the binder resin, and an aminium salt-based compound was used at 2% based on this. Then, 2% of a brominated phthalocyanine (coloring agent) and 1% of a polypropylene wax as a fixing aid were added, melt-kneaded, and then pulverized and classified to obtain a toner θ.

[0153]

[Table 2]

Means (v) The reactivity of the binder resin with the aminium salt-based compound and the properties of the produced toner were evaluated in the same manner as described in the examples of the 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 at 50% by weight of the total amount of the binder resin, and terephthalic acid and bisphenol A ethylene oxide were further used. 50% by weight of polyester resin containing adduct as main monomer component based on the total amount of binder resin
2% of an aminium salt compound, 2% of a brominated phthalocyanine (coloring agent), and 1% of a polypropylene wax as a fixing aid were melt-kneaded, and the mixture was pulverized and classified. Obtained.

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

Example 21 A methyl methacrylate-dimethylacrylamide copolymer (methyl methacrylate: 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 further used. A polyester resin containing an ethylene oxide adduct as a main monomer component is 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 a brominated phthalocyanine (colorant), and a fixing aid are used. 1% of a polypropylene wax was added, melt-kneaded, and further crushed and classified to obtain a toner λ.

Example 22 Amide-modified polyester obtained by reacting a carboxylic acid of a polyester with an amine as a positively chargeable binder resin (amine monomer: 15 mol%)
And an aminium salt-based compound is used in an amount of 2%,
2% of a brominated phthalocyanine (coloring agent) and 1% of a polypropylene wax as a fixing aid were added, melt-kneaded, and pulverized and classified to obtain a toner μ.

Example 23 A urethane-modified polyester (about 30% of the terminal OH groups contained urethane was obtained by reacting isocyanate with hydroxyl groups of a polyester resin containing terephthalic acid and bisphenol A ethylene oxide adduct as essential monomer components as a binder resin). And 2% of an aminium salt-based compound, 2% of a brominated phthalocyanine (colorant), and 1% of a polypropylene wax as a fixing aid, melt-kneading, and pulverizing and classifying. As a result, a toner ν was obtained.

Example 24 As a positively chargeable binder resin, an amine-crosslinked epoxy resin obtained by crosslinking bisphenol A type epoxy with N-aminoethylpiperazine was used in an amount of 30% by weight based on the total amount of the binder resin. Further, terephthalic acid and bisphenol A ethylene were used. A polyester resin containing an oxide adduct as a main monomer component is used in an amount of 70% by weight based on the total amount of the binder resin, based on which 2% of an aminium salt compound, 2% of a brominated phthalocyanine (colorant), and polypropylene as a fixing aid 1% of wax was added, melt-kneaded, and further crushed and classified to obtain a toner ξ.

Example 25 As a positively chargeable binder, propylene bishydroxyarachinamide was used in an amount of 20% by weight based on the total amount of the binder resin, and a polyester resin containing terephthalic acid and bisphenol A ethylene oxide adduct as main monomer components was used as the binder. 80% by weight of the total amount of the resin, 2% of an aminium salt-based compound, 2% of a brominated phthalocyanine (coloring agent), and 1% of a polypropylene wax as a fixing aid were melt-kneaded, followed by pulverization and classification. Thus, a toner π was obtained.

Comparative Example 10 A styrene-2ethylhexyl acrylate copolymer (styrene: 2ethylhexyl acrylate = 75: 25) was used as a binder resin at 50% by weight of the total amount of the binder resin, and terephthalic acid and bisphenol A ethylene oxide were further added. 50% by weight of the total amount of the binder resin is used as the main monomer component, 2% of the aminium salt-based compound, 2% of the brominated phthalocyanine (coloring agent), and polypropylene wax as the fixing aid. 1% was added, melt-kneaded, and further pulverized and classified to obtain a toner ρ.

Comparative Example 11 A styrene-dimethylaminoethyl methacrylate copolymer (styrene: dimethylaminoethyl methacrylate = 90: 1) was used as an alternative to the positively chargeable binder shown in Examples 19 to 21.
A 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 of the total amount of the binder resin.

Comparative Example 12 A styrene-methyl methacrylate dimethyl acrylamide copolymer (styrene: methyl methacrylate: dimethyl acrylamide = 35:30:35) was used as a binder instead of the positively chargeable binder shown in Examples 19 to 21. 20 of the total amount
A toner τ was obtained in the same manner as in Examples 19 to 21 except that the toner τ was used in a percentage by weight.

Comparative Example 13 The procedure of Examples 19 to 21 was repeated except that the positively chargeable binder was not used and a quaternary ammonium salt-based charge control agent (P-51: Orient Chemical) was added at 2% by weight. In the same manner as in Examples 19 to 21, a toner υ was obtained. The evaluation results are summarized in Table 3. The positive charge was given to the toner by using a binder composed of dimethylaminoethyl methacrylate as a monomer, or the positive charge was obtained by using a quaternary ammonium salt-based charge control agent. When the property is imparted, the aminium salt is affected and the fixability is extremely reduced.

On the other hand, a toner that does not use a positive charge control agent or a binder having a positive charge imparting property has poor charge recovery ability when re-stirred after standing, and thus has many practical problems. In order to achieve both of these problems, 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 represents 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 with a binder molecular chain, a specific polyester, epoxy, or amide resin is required.

[0167]

[Table 3]

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

The toner φ was combined with a ferrite carrier to form a developer, mounted on an F6718K printer (manufactured by Fujitsu), and examined for flash fixability and charging ability in a high-temperature, high-humidity environment. As a result, an excellent fixing property with a fixing rate of 85% (tape peeling test) was exhibited. Regarding the charging ability, the developer was exposed to an environment at 35 ° C. and 80% RH for 12 hours, and then the developing device was stirred for 3 minutes in the same environment. About 80
%, Indicating that the toner had excellent charging ability.

Example 27 Using the same binder resin as in Example 26, 3% of an aminium salt compound having a common anion as perchloric acid, 1% of a quaternary ammonium salt, and furthermore, molybdate 4 Melt kneading is performed by adding 0.2% of a quaternary ammonium salt, 2% of a brominated phthalocyanine, and 1% of a polypropylene wax. Next, a toner χ was obtained by pulverizing and classifying.

The toner χ was examined for fixability and charging ability in the same manner as in Example 26.
% And a charge recovery rate of 90%.

Means (vii) [Example 28] 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. 1.5% by weight of the compound of the structural formula (1), 0.5% by weight of the compound of the structural formula (2) using perchloric acid as an anion, and quinacridone red pigment as a coloring agent.
5 wt%, 1 polypropylene wax as fixing aid
%, And the mixture was melt-kneaded and pulverized and classified to obtain a toner having a highly saturated red color tone.

This toner】 was combined with a ferrite carrier to form a developer, and was mounted on an F6718K printer (manufactured by Fujitsu), and its flash fixability and charging ability in a high-temperature, high-humidity environment were investigated. As a result, an excellent fixing property with a fixing rate of 85% (tape peeling test) was exhibited. Regarding the charging ability, the developer was exposed to an environment at 35 ° C. and 80% RH for 12 hours, and then the developing device was stirred for 3 minutes in the same environment. About 80
%, Indicating that the toner had excellent charging ability.

Example 29 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 a structural formula using perchloric acid as an anion was used. 1.5% by weight of the compound of (1), 0.5% by weight of the compound of structural formula (1) having hexafluoroantimonic acid as an anion, 2.5% by weight of a quinacridone red pigment as a coloring agent, and a fixing aid 1% of polypropylene wax, melt-kneaded, and then pulverized and classified to obtain a toner ω having a highly saturated red color tone.

The toner ω was used as a developer in combination with a ferrite carrier, mounted on an F6718K printer (manufactured by Fujitsu), and the flash fixability and the charging ability in a high-temperature, high-humidity environment were investigated. As a result, an excellent fixing property with a fixing rate of 85% (tape peeling test) was exhibited. In addition, as for the charging ability, the charging recovery rate was about 80%, and it was confirmed that the toner had excellent charging ability.

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 a structural formula using perchloric acid as an anion was used. 2.0% by weight of the compound of (1), 2.5% by weight of a quinacridone-based red pigment as a coloring agent, and 1% of polypropylene wax as a fixing aid, melt kneading, and pulverizing and classifying to obtain high chroma. A toner a having a red color tone was obtained.

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

Comparative Example 15 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 a structural formula using perchloric acid as an anion was used. 2.0% by weight of the compound (2), 2.5% by weight of a quinacridone red pigment as a coloring agent, and 1% of a polypropylene wax as a fixing aid, melt-kneading, followed by pulverization and classification to obtain toner b Was. The color tone of this toner b was reddish brown, which was not suitable as a red toner (color quality was deteriorated).

Means (viii) [Example 30] Bisphenol A was used as the binder resin.
A polyester resin containing ethylene oxide as the main diol component and terephthalic acid as the main dicarboxylic acid component is used. 0.5% by weight of a quaternary ammonium salt containing molybdic acid as an anion as a charge control agent and a coloring agent Infrared light using 2.5% by weight of a quinacridone-based red pigment, 1% of a 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,
0.5 wt% of (2 dithiophenolate) nickel / tetra-n-butylammonium salt was added, melt-kneaded, and pulverized and classified to obtain a toner d.

This toner d was used as a developer in combination with a ferrite carrier, mounted on an F6718K printer (manufactured by Fujitsu), and its flash fixability and charging ability in a high-temperature, high-humidity environment were investigated. As a result, an excellent fixing property with a fixing rate of 85% (tape peeling test) was exhibited. Regarding the charging ability, the developer was exposed to an environment at 35 ° C. and 80% RH for 12 hours, and then the developing device was stirred for 3 minutes in the same environment. About 80
%, Indicating that the toner had excellent charging ability.

Example 31 Toner e was prepared in the same manner as in Example 30, except that 1.0% by weight of bis (1 mercaptolate 2 naphtholate) platinum tetra-n-butylammonium salt was used as an infrared light absorbing agent. Obtained. The toner e was used as a developer in combination with a ferrite carrier, mounted on an F6718K printer (manufactured by Fujitsu), and the flash fixability and the charging ability in a high-temperature, high-humidity environment were investigated.
As a result, an excellent fixing property 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 toner had excellent charging ability.

Example 32 A toner f was obtained in the same manner as in Example 30, except that 0.5% by weight of bithienylidenebisbenzoquinone was used as the infrared light absorber used in combination. The toner f was used as a developer in combination with a ferrite carrier, mounted on an F6718K printer (manufactured by Fujitsu), and the flash fixability and the charging ability in a high-temperature, high-humidity environment were investigated.
As a result, an excellent fixing property with a fixing rate of 90% (tape peeling test) was exhibited. The charge recovery rate was 85%, and it was confirmed that the toner had excellent charging ability.

Example 33 A toner g was obtained in the same manner as in Example 30, except that vanadyloxyhexadecamethylphthalocyanine was used in an amount of 0.3% by weight as the infrared light absorber used in combination. This toner is combined with a ferrite carrier to form a developer, and an F6718K printer (manufactured by Fujitsu)
We investigated the flash fixability and charging ability in a high-temperature, high-humidity environment. As a result, an excellent fixing property with a fixing rate of 90% (tape peeling test) was exhibited. The charge recovery rate is 85
%, Which indicates that the toner has an excellent charging ability.

Example 34 Toner C was obtained by the method exemplified in Example 1. 0.8% of propylene bishydroxyaraquinamide powder (average particle size: 1.5 μm) was externally added to Toner C using a Henschel mixer to obtain Toner h. When the fixing ability and the charging ability of the toner h were examined by the same method as that shown in Example 1, the toner h showed a fixing ability of 95% and a charging recovery ability of 90%. 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. After dye and carbon were added and melt-kneaded, the mixture was pulverized by a jet mill to an average particle size of about 10 μm to obtain a base toner j. To this base toner j, propylene bishydroxyaraquinamide powder (average particle size: 1.5 μm) was externally added using a 0.5 wt% Henschel mixer to obtain a toner l.

This toner 1 was combined with a ferrite carrier to form a developer, and an F6700 printer (manufactured by Fujitsu)
The results were investigated for changes in the toner's flash fixability, anti-blocking properties, toner filming properties for photocon drums, and printing properties in long-term running tests. As a result, no blocking occurred even when left in a 60 ° C. environment for 24 hours, and the flash fixing rate was 90%.
(Tape peel test). further,
Even after continuous printing of 1 million sheets, toner filming on the photo-con drum did not occur, and excellent printing characteristics were maintained for a long time.

Example 36 An amide oligomer powder (weight average molecular weight 2000, average particle size 1 μm) having malic acid and methylenediamine as essential constituent monomers was used for a base toner j similar to that of Example 34, using a Henschel mixer. To obtain a toner m. This toner m is combined with a ferrite carrier to form a developer, and F67
00 printer; manufactured by Fujitsu), and the flash fixing property of toner, anti-blocking property, toner filming property for photo-con drum, and printing property in long-term running test were investigated.

As a result, no blocking occurred even when left in an environment of 60 ° C. for 24 hours, and a flash fixing rate of 8
Excellent fixability of 5% (tape peel test) was exhibited. Further, even after continuous printing of one million sheets, toner filming on the photo-con drum did not occur, and the printing characteristics were maintained for a long time.

[Reference Example] Example 34 except that propylene bishydroxyaraquinamide powder was not externally added.
In the same manner as in the above, changes in the toner's flash fixing property, anti-blocking property, toner filming property for a photo-con drum, and printing properties in a long-term running test were investigated.

As a result, although blocking did not occur even when left in an environment of 60 ° C. 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 red having a high efficiency of absorbing infrared light and having a pale color in the visible light region (does not interfere with the color tone of the colorant). It uses an external light absorber and generally uses a positive charge control agent that reacts with the aminium salt-based infrared light absorber to inhibit its light absorption ability. Since the reaction with the agent is physically or chemically prevented, suppressed, or supplemented, all of the color tone, charging characteristics, and flash fixing properties of the color toner for flash fixing can be satisfied. The effect is obtained.

[Brief description of the drawings]

FIG. 1 is a schematic diagram illustrating a configuration of a toner according to a mode (i) of the present invention.

[Explanation of symbols]

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

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[Procedure amendment]

[Submission date] July 1, 1998

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Full text

[Correction method] Change

[Correction contents]

[Document Name] Statement

[Title of the Invention] Flash fixing toner

[Claims]

Embedded image [In the formulas (1) and (2), 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. ]

Embedded image [In the formula (3), l and m are positive integers, and R ^{5 to} R ⁷ are the same as defined above. ]

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flash fixing color toner used for visualizing an electrostatic latent image in electrophotography and the like, and a method of manufacturing the same. The present invention relates to a method for improving fixing characteristics of a light fixing toner for fixing a toner by irradiating light energy.

[0002]

2. Description of the Related Art Conventionally, as an electrophotographic method, US Pat.
Although the method described in No. 297691 is well known,
This is generally done by using a photoconductive insulator (such as a photo-condrum), applying a uniform electrostatic charge to the photoconductive insulator by corona discharge or the like, and applying various means to the photoconductive insulator. An electrostatic latent image is formed by irradiating a light image thereon, and the latent image is developed and visualized using a fine powder called toner.

[0003] If necessary, the toner image is transferred onto a recording medium such as paper, and then the toner image is melted by pressurization, heating, solvent vapor, light, or the like, and is fixed on the recording medium. Is what you get. As a toner for developing these electrostatic latent images, a toner in which an additive such as a colorant and, if necessary, a charge control agent is dispersed in a binder resin composed of a natural or synthetic polymer substance is conventionally used. 30 μm
Finely pulverized particles are used.

In the electrophotographic two-component developing method, such a toner is usually mixed with a ferromagnetic material such as iron powder and a carrier material (carrier) such as glass beads and used for developing an electrostatic latent image. In the case of the magnetic brush developing method using ferromagnetic particles such as iron powder or ferrite as a carrier, a developer composed of a toner and a carrier is triboelectrically charged by being mixed and stirred in a developing device, and furthermore, a developer in a developing device. The magnetic brush is held by the 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 electric attraction. By doing so, development is performed.

Here, the binder resin constituting the toner must be quickly melted in the process of fixing to the recording medium and exhibit good fixability. Therefore, the binder resin is generally referred to as an oligomer having a low melt viscosity and a low molecular weight. Polymer resins are widely used. On the other hand, the fixing is to fuse the toner on the recording paper surface by pressurizing, heating, solvent vapor, light or the like and fix the toner on the recording paper. Among these fixing methods, the following characteristics are provided. The light fixing method being used is attracting attention.

(1) Since non-contact fixing is performed, the resolution of an image is not degraded during the fixing process. (2) Quick start is possible without waiting time after the apparatus is turned on. (3) No ignition occurs even if recording paper is jammed in the fixing unit due to the system down. (4) Fixing is possible regardless of the material and thickness of the recording paper, such as glued paper, preprinted paper, and paper of different thicknesses.

Incidentally, the flash fixing method using xenon flash light as a light source is currently the most common method as the light fixing method.

[0008]

The light fixing toner must absorb instantaneous flash light energy of several milliseconds or less and quickly melt and fix it. And a binder resin having a low melting temperature of about 10 to 40 ° C. In recent years, studies on reducing the energy consumption of printers have been actively pursued, and as a part of this, toner having a higher melting temperature has been demanded because of the need to reduce flash fixing energy.
However, if the melting temperature of the binder is lowered as a method for further imparting low-temperature fixability to the flash fixing toner, the thermal stability of the toner itself is impaired, and problems such as blocking easily occur even in an environment at about room temperature. Also, in order to improve the melt viscoelasticity at the time of melting the toner by kneading a large amount of low-viscosity components such as polypropylene wax in order to impart low-temperature fixability by lowering the melt viscosity of the toner, the toner becomes soft. Problems such as filming on the photosensitive drum are likely to occur.

[0009]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and it is intended to externally add a small amount of an amide compound powder represented by the general formulas (1) to (3) as an essential constituent of a toner. Accordingly, it is an object of the present invention to provide a toner which does not cause toner blocking or filming on a photosensitive drum, reduces the melt viscosity of the toner at the time of melting, and improves the flash fixing ability under low energy.

[0010]

Embedded image

[In the formulas (1) and (2), l, m and n are 0 to 0]
The integer 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. ]

[0012]

Embedded image

[In the formula (3), l and m are positive integers, and R ⁵ to
R ⁷ is the same as defined above. Preferred embodiments are as follows. The toner for flash fixing according to the toner, wherein the weight average molecular weight of the amide compound powder to be externally added is 500 or more and 3000 or less. In the toner, the average particle size of the amide compound powder to be externally added is 2 μm or less and the maximum particle size is 5 μm or less, and the external addition weight of the amide compound is 0.2% by weight to 1.0% by weight.
% By weight.

In the toner, the melting temperature of the amide compound powder to be externally added is 10 to 30 ° C. lower than the melting temperature of the binder resin constituting the toner, and 100 ° C. to
A flash fixing toner characterized in that in a temperature range of 150 ° C., the melt viscosity of the binder resin constituting the toner> the melt viscosity of the amide compound powder to be externally added. 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 an externally added resin is melted slightly before the entire toner is melted. The molten amide compound has large polar sites such as amide groups (including amide bonds) and hydroxyl groups in the molecular structure, has a very high affinity for paper fibers, and forms a toner. Since the binder resin has a lower melting point and lower melt viscosity than the binder resin, it quickly penetrates between the paper fibers. By this effect, the wettability of the molten binder resin to the paper fibers is enhanced, and the binder resin (toner base) having a somewhat high melt viscosity penetrates between the fibers of the paper, thereby exhibiting strong fixing properties. For this reason, the amount of light absorbed by the toner is not sufficient, and good fixability can be imparted even when the binder resin has a low melt viscosity due to a low temperature.

The amide compound having such properties can be found in hydroxy fatty acid monoamides, hydroxy fatty acid bisamides, and low molecular weight hydroxyl-containing polyamide oligomers. The weight average molecular weight of the amide compound is desirably 500 or more and 3000 or less. This is because if the molecular weight is below this range, the amide compound becomes soft, so that drum filming is liable to occur. On the other hand, if the molecular weight is 3,000 or more, the viscosity upon melting is often high, and it is difficult to exhibit the effect. .

Further, in order to exert the effect well,
The amide resin must melt faster than the toner matrix,
In addition, the viscosity at the time of melting must be low. For this reason, the melting temperature of the externally added amide compound is lower by at least 10 ° C. than the melting temperature of the binder resin forming the toner matrix, and
This is the melting temperature range of the molten toner near the recording paper. 100
It is necessary that the melt viscosity in the region of about 150 ° C. 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 an amide compound is internally added (melted and kneaded together with a binder resin) to the toner, but in this case, the amide compound contains at least 5% by weight. As described above, it is desirable to add 20% by weight or more. However, the amide compound to be used is relatively soft and brittle, and when a large amount of the amide compound having such characteristics is added to the toner, a long-term printing forms a thin film of the amide compound on the photosensitive drum. So-called drum filming occurs and causes printing troubles such as background fogging. In order to prevent drum filming even during long-term use, the amount of the amide compound in the total amount of the toner is at least 2% by weight or less, preferably 1% by weight or less.
% By weight or less. In order to exhibit the above-mentioned good fixing effect with the added amount of such an amide compound,
The amide compound is preferably added to the toner by external addition.

It is desirable that the amide compound to be externally added has an average particle diameter of 2 μm or less and a maximum particle diameter of 5 μm or less. If the particle diameter of the amide compound to be added exceeds the above range, the amide compound is not uniformly attached to the toner surface and easily detached from the toner, so that problems such as accumulation of the amide compound in the developing device are likely to occur. That's why.

[0020]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

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

The toner 1 is combined with a ferrite carrier to form a developing agent, and an F6700 printer (manufactured by Fujitsu)
The results were investigated for changes in the toner's flash fixability, anti-blocking properties, toner filming properties for photocon drums, and printing properties in long-term running tests. As a result, no blocking occurred even when left in a 60 ° C. environment for 24 hours, and the flash fixing rate was 90%.
(Tape peel test). further,
Even after continuous printing of 1 million sheets, toner filming on the photo-con drum did not occur, and excellent printing characteristics were maintained for a long time.

Example 2 An amide oligomer powder containing malic acid and methylenediamine as essential constituent monomers (weight average molecular weight 20
(00, average particle size 1 μm) Using a Henschel mixer, 1.0 wt% was externally added to obtain a toner m. This toner m is combined with a ferrite carrier to form a developer, and F670
0 printer; manufactured by Fujitsu), and the flash fixing property of toner, anti-blocking property, toner filming property for photo-con drum, and printing property in long-term running test were investigated.

As a result, no blocking occurred even when left in an environment of 60 ° C. for 24 hours, and the flash fixing rate was 8%.
Excellent fixability of 5% (tape peel test) was exhibited. Further, even after continuous printing of one million sheets, toner filming on the photo-con drum did not occur, and the printing characteristics were maintained for a long time.

COMPARATIVE EXAMPLE The same procedure as in Example 1 was carried out except that propylene bishydroxyaraquinamide powder was not externally added, and the flash fixing property of the toner, the anti-blocking property, the toner filming property for a photo-condrum, The change of printing characteristics in the long-term running test was investigated.

As a result, no blocking occurred even when left in an environment of 60 ° C. for 24 hours, but the flash fixation rate was low at 60% (tape peel test).

[Procedure amendment 2]

[Document name to be amended] Drawing

[Correction target item name] Fig. 1

[Correction method] Deleted

Claims (15)

[Claims] 1. A binder resin having the following general formula (1) and / or (2): An infrared light absorber of an aminium salt compound represented by
A colorant and a positive charge control agent or / and a positive charge control resin (hereinafter, the positive charge control agent and the positive charge control resin are collectively referred to as a positive charge control agent),
And the reaction between the infrared light absorber and the positive charge control agent is suppressed by any of the following (i) to (vi), or by the reaction between the infrared light absorber and the positive charge control agent. (Vii) or (vii)
A color toner for flash fixing, wherein the color toner is supplemented by means of i). (I) A mixture of plural kinds of resins is used as a binder resin, and an infrared light absorber is selectively dispersed or melted in one part of the specific resin. (Ii) A positive charge control agent and / or a binder resin containing a positive charge control agent is coated on the outer peripheral portion of the toner containing the infrared light absorber, the colorant, and the binder resin, or is attached as fine particles. . (Iii) An infrared light absorbing agent and / or a binder resin containing the infrared light absorbing agent is coated on the outer peripheral portion of the toner containing the colorant and the positive charge control agent, or is attached as fine particles. (Iv) As the binder resin, an amine-containing functional group resin containing a secondary amine and / or a tertiary amine and / or a quaternary amine functional group, and / or a quaternary ammonium salt and a resin containing an acidic functional group And blocking the amine-containing functional group resin and / or the quaternary ammonium salt with a resin containing an acidic functional group. (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,
One or more of a urethane-modified polyester resin and an amine-modified epoxy resin crosslinked with a diamine are used. (Vi) A positive charge control agent represented by the general formula (3): Is used. (Vii) The compound represented by the general formula (1) and the compound represented by the general formula (2) are used in combination as the infrared light absorber, and the anion X ⁻ is commonly used, or the compound represented by the general formula (1) is used. Two or more compounds represented by the formula are used. (Viii) As the infrared light absorber, one or more compounds represented by formulas (4) to (8) are further mixed and used. Embedded image Embedded image Embedded image Embedded image Embedded image 2. The toner according to claim 1, wherein when the means (i) is employed, 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 solubility parameter of the binder resin in which the infrared light absorbing agent is dispersed or melted and the solubility parameter of the binder resin in which the positive charge control agent is dispersed or melted are 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 containing an acidic functional group is a polyester resin having a carboxylic acid and / or a sulfonic acid, and the resin containing an amine-based functional group is a copolymer of styrene and amino acrylate. The toner according to claim 1, which is a polymer. 6. The method according to claim 6, wherein the common anion between 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 2. The composition of claim 1, which is one of acid ions.
The toner described in the above. 7. The toner according to claim 1, wherein another quaternary ammonium salt having an anion different from the 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 employed, the anion of the aminium salt compound represented by the general formula (1) is perchlorate ion. 9. A flash fixing toner comprising amide compound fine particles represented by the general formulas (9) to (11) adhered to the toner surface. Embedded image [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. Embedded image [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 an aminium salt-based compound represented by or dispersed therein and a second binder resin different from the first binder resin in which a 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 and pulverizing a second binder resin to obtain a toner. 11. General formulas (1) and / or (2) And a first fine powder of a first binder resin in which an aminium salt compound represented by the following formula is dispersed or melted, and a positive charge control agent and / or a positive charge control resin (hereinafter referred to as a positive charge control agent and a positive charge The control resin is collectively referred to as a positive charge control agent.) Dispersed or melted second binder resin and / or amine-containing functional group containing secondary amine and / or tertiary amine and / or quaternary amine functional groups Base resin and / or secondary quaternary ammonium salt
And a process of aggregating and fixing tens to tens of thousands of fine powders in a liquid phase to obtain a toner. 12. A first fine powder, together with a second fine powder,
After aggregating 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 in the liquid phase, the first and second fine powders do not melt. The method according to claim 11, wherein the liquid phase is heated to a temperature at which the third fine powder melts to fix the fine powders together. 13. A compound of the general formula (1) and / or (2) After electrostatically adhering the fine particles of the second binder resin containing the positive charge control agent 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 a step of forming a second binder resin into a film on a toner surface by a fusion method. 14. The flash fixing toner according to claim 9, wherein the weight average molecular weight of the amide compound powder to be externally added is 500 or more and 3000 or less. 15. The toner according to claim 15, wherein the amide compound powder to be externally added has an average particle diameter of 2 μm or less and a maximum particle diameter of 5 μm.
15. The flash fixing toner according to claim 9, wherein the amide compound is 0.2 μm or less, and the external addition weight of the amide compound is 0.2% by weight to 1.0% by weight.