JP6762780B2 - Toner and developing equipment - Google Patents

Description

The present invention relates to a toner used in a recording method using an electrophotographic method, an electrostatic recording method, a toner jet recording method, or the like, and a developing device.

In recent years, copiers and printers using electrophotographic methods have come to be used in various countries and regions due to market expansion, so that stable high image quality is required even in a wide variety of environments.
In addition, there are various needs as the market scale expands, and for example, energy saving and miniaturization are considered as major technical issues.

As a means for miniaturization, it is effective to miniaturize the cartridge containing the developer. Therefore, the one-component developing method is preferable to the two-component developing method using a carrier, and at the same time, in order to obtain a high-quality image. , The contact development method is preferable. Therefore, in order to satisfy the above performance, the contact one-component developing method is an effective means.
In order to reduce the size of the contact one-component developing process cartridge, it is conceivable to reduce the diameter of the toner carrier or omit the supply roller that supplies the toner to the toner carrier. Here, when the supply roller is omitted, the transportability of the toner to the toner carrier is lowered, it becomes difficult to uniformly transport the toner to the regulation portion, and it becomes difficult to uniformly charge the toner.

Further, in order to save energy, there is an increasing need for so-called "low temperature fixability" in which toner can be melted and fused to paper with a low amount of heat.
As a method for enabling fixing at a low temperature, lowering the glass transition temperature (Tg) of the binder resin in the toner can be mentioned. However, lowering Tg causes the toner to lose its heat-resistant storage property, and leads to deterioration of the toner surface due to stress during exposure to various harsh environments and development. Therefore, it is difficult to suppress the deterioration of the toner when it is exposed to a harsh environment and when a large number of low print rate images are formed under the harsh environment while maintaining the low temperature fixability of the toner. Has been done.

Crystalline resins have been attracting attention in recent years as materials for binder resins to achieve both low-temperature fixability, heat-resistant storage stability, and environmental stability. Crystalline resins rapidly melt at the melting point. Has the property of causing a decrease in viscosity (sharp melt property). For this reason, toners in which a crystalline resin is added to an amorphous binder resin are being actively studied.
Further, as a method for further improving the low-temperature fixability while suppressing the heat-resistant storage property of the toner and the deterioration of the toner, studies are being made to disperse the crystalline resin in the amorphous binder resin.
In Patent Document 1, a toner in which a domain in which fine particles of a crystalline polyester resin are dispersed in an amorphous resin formed by chemically bonding an amorphous polyester segment and a vinyl polymerized segment is dispersed in a vinyl resin matrix is used. Proposed. It is described that the toner can achieve both low temperature fixability and heat storage property.

Japanese Unexamined Patent Publication No. 2014-235361

In the toner described in Patent Document 1, since the crystalline polyester resin is dispersed in the styrene acrylic resin, the compatibility is high when excessive heat is applied. However, when sufficient heat cannot be obtained, for example, when an image having a high printing rate is to be fixed on thick paper, the heat is taken away by the paper, so that the above compatibility is difficult to develop. Further, when the plasticization of the toner is insufficient, the effect of the release agent is less likely to be exhibited, and the releasability from the fixing film cannot be sufficiently obtained, so that there is room for improvement in the low temperature fixability.
Further, in the contact developing method in which the supply roller is omitted, there is room for improvement in durability and chargeability after use in a harsh environment.
The present invention provides a toner that solves the above problems. More specifically, a toner having low temperature fixability and environmental stability is provided. Another object of the present invention is to provide a developing apparatus having the above toner.

As a result of diligent studies, the present inventors have been able to solve the above problems by adjusting the plasticity and mold release property at the time of heat melting with respect to the crystalline polyester, the amorphous polyester and the mold release agent in the vinyl resin within a certain range. The present invention was completed.
That is, the toner of the present invention is a toner containing a vinyl resin, a colorant, a mold release agent, an amorphous polyester, and a crystalline polyester.
In the cross section of the toner observed with a transmission electron microscope,
The vinyl resin constitutes a matrix, and the amorphous polyester and the crystalline polyester form a domain.
In the measurement by a tacking tester having a terminal whose tip in contact with the toner is coated with polytetrafluoroethylene, the temperature of the terminal with respect to the toner pellet is set to 200 ° C. and the contact time with the pellet is set to 50 msec. When the integrated value of the toner stress is f1, the value of f1 is 5.9 g · m / sec or less.
When the glass transition temperature at the first temperature rise obtained by differential scanning calorimetry (DSC) of the toner is Tg1st (° C) and the glass transition temperature at the second temperature rise is Tg2nd (° C), the Tg1st value is at 50 ° C. or higher state, and are 5 ° C. or higher value of Tg1st-Tg2nd,
The amorphous polyester has a monomer unit derived from a linear aliphatic dicarboxylic acid having 6 to 12 carbon atoms and a monomer unit derived from a dialcohol.
The content of monomer units derived from carbon number 6 to 12 of the linear aliphatic dicarboxylic acid, a 50 mol% or less der Rukoto least 10 mol% based on all monomer units derived from carboxylic acids of the non-crystalline polyester the toner according to claim.

According to the present invention, a toner having both low temperature fixability and environmental stability can be obtained. Further, according to the present invention, it is possible to provide a developing apparatus having the above toner.

Schematic diagram of a tacking tester for measuring the integrated value of stress The figure which shows an example of a developing apparatus An example of an image forming apparatus with a built-in developing apparatus Schematic diagram of flow curve

In the present invention, the description of "○○ or more and XX or less" and "○○ to XX" indicating a numerical range means a numerical range including a lower limit and an upper limit which are end points, unless otherwise specified.
The toner of the present invention is a toner having toner particles containing a vinyl resin, an amorphous polyester, a crystalline polyester, a mold release agent, and a colorant, and is obtained at the first temperature rise of the DSC measurement of the toner. The glass transition temperature Tg1st and the glass transition temperature Tg2nd obtained at the second temperature rise are adjusted to a specific range, and the integrated value of stress is adjusted to a specific range in the measurement by a tacking tester using a specific terminal. It is characterized by that.

The present inventors consider the reason why the present invention has solved the above problems as follows.
First, in order to solve the problem of the present invention, it is important to have both amorphous polyester and crystalline polyester in the vinyl resin and to have domains of amorphous polyester and crystalline polyester in the vinyl resin. Is.
The vinyl resin, for example, tends to maintain the rigidity and viscosity of the toner, and tends to improve the stress resistance of the toner. Further, with respect to amorphous polyester and crystalline polyester, it is easy to improve the melting characteristics of the toner by changing the monomer composition of the resin.
That is, by controlling the domains of the vinyl resin, the amorphous polyester, and the crystalline polyester, it is possible to give the toner both low temperature fixability and environmental stability properties.

Further, by dispersing the amorphous polyester and the crystalline polyester as domains, the toner softens from the contact point of both domains, and it is easy to quickly improve the plasticity of the toner at the time of heat melting.
Furthermore, the domain of the crystalline polyester forms a path for the release agent to seep out in the toner, and can assist the release agent to seep out to the toner surface, so that the releaseability of the toner is likely to be improved. I'm guessing.
Therefore, in the toner of the present invention, it is preferable that the amorphous polyester and the crystalline polyester are present as domains in the vinyl resin, but are present in the vicinity of the surface to some extent. By controlling the vicinity of the surface layer, plasticization by heat at the time of fixing becomes easy.

Further, it is preferable that the crystalline polyester is finely dispersed while being present as a domain in the vinyl resin. By finely dispersing, the number of contacts with the amorphous polyester can be increased, and it becomes easy to properly form a path through which the release agent exudes.
Further, as a means for improving low-temperature fixability, for example, low-temperature fixability of a high-printability image on thick paper, the toner itself is thermoplasticized to promote deformation under pressure, and the number of contacts between resins and between resins and paper is increased. Therefore, it is important that it adheres to the paper properly.

In addition, it is important to control the glass transition temperature (Tg) of the toner when the heat resistance of the toner is taken into consideration. When the glass transition temperature at the first temperature rise obtained by differential scanning calorimetry (DSC) of the toner is Tg1st (° C) and the glass transition temperature at the second temperature rise is Tg2nd (° C), the Tg1st It is essential that the value is 50 ° C. or higher and the value of Tg1st-Tg2nd is 5 ° C. or higher. Tg1st indicates the heat resistance of the toner. Further, Tg2nd is Tg after heating and melting, and Tg1st-Tg2nd indicates how much the toner is plasticized by heating.
From the viewpoint of improving heat resistance, Tg1st needs to be 50 ° C or higher, and if it is lower than 50 ° C, the toner surface is deformed by stress in a harsh environment or stress due to contact development in a harsh environment, and the charging performance deteriorates. Therefore, the image density tends to decrease. Tg1st is preferably 53 ° C. or higher. On the other hand, the upper limit is not particularly limited, but is preferably 65 ° C. or lower, more preferably 60 ° C. or lower.

Further, from the viewpoint of the plasticity of the toner itself, when the difference between Tg2nd and Tg1st is 5 ° C. or more, the toners are easily deformed at the time of melting, and the adhesiveness between the toner papers and the toners is promoted. Further, if the difference between Tg2nd and Tg1st is less than 5 ° C., the above-mentioned effect is difficult to obtain, so that low temperature fixability is difficult to obtain. Tg1st-Tg2nd is preferably 8 ° C. or higher. The upper limit is not particularly limited, but is preferably 25 ° C. or lower, more preferably 20 ° C. or lower.
The Tg2nd is preferably 20 ° C. or higher and 50 ° C. or lower, and more preferably 30 ° C. or higher and 45 ° C. or lower. Tg can be measured by a differential scanning calorimeter (DSC).
The Tg1st and Tg2nd can be adjusted by the type and amount of crystalline polyester, the type and amount of vinyl resin, the type and amount of mold release agent, and the like.

Further, from the viewpoint of improving the peelability of the toner to the fixing film at the time of heat melting, it is necessary to reduce the instantaneous adhesive force in the tacking tester. Specifically, using a tacking tester having a terminal whose tip in contact with toner is coated with polytetrafluoroethylene (PTFE), the temperature of the terminal is set to 200 ° C. and the contact time between the terminal and the toner pellet is set to 50 msec. When the value of the integrated value of the stress measured in the above is f1, it is essential that the value of f1 is 5.9 g · m / sec or less.

Various methods have been proposed as methods for confirming the releasability of toner from a film, but the present invention is characterized in that measurement is performed with a tacking tester. The features of the tacking tester are that the tip of the contacting terminal can be heated to a high temperature, and the toner pellet can be instantly bonded and detached. As a result, the integrated value of the stress obtained by the tacking tester tends to have a higher correlation with the adhesion between the toner and the film generated in the actual fixing nip.
Further, in this measurement, by changing the tip of the terminal in contact with the toner to a material having high releasability, it is possible to obtain a result closer to the behavior for the fixing film.

Further, by setting the temperature of the tip of the terminal to 200 ° C., it can be confirmed at a temperature close to that of the actual fixing film, so that a result having a high correlation with the releasability of the actual film and the toner can be obtained. Further, by changing the contact time between the terminal and the toner to 50 msec, which is an instantaneous time, it is possible to measure the releasability in a system that does not give too much heat to the toner.
Further, it is a feature of this measurement that an instantaneous adhesiveness close to the passage of toner through the nip can be obtained by changing the toner in a short time.
If the value of f1 exceeds 5.9 g · m / sec, the adhesiveness to the film at the time of melting increases, which causes image peeling.
Further, the value of f1 is preferably 5.1 g · m / sec or less from the viewpoint of further improving the releasability from the fixing film and improving the fixing property. The lower limit is not particularly limited, but is preferably 0.5 g · m / sec or more, and more preferably 1.0 g · m / sec or more.
The value of f1 can be adjusted by the presence position and dispersion state of the amorphous polyester, the softening point, the softening point of the crystalline polyester, the dispersion state, and the type and amount of the release agent.

Hereinafter, preferred embodiments of the toner of the present invention will be described.
As described above, the toner of the present invention contains a vinyl resin, an amorphous polyester and a crystalline polyester.
Examples of the vinyl resin include the following.
Monopolymers of styrene such as polystyrene and polyvinyltoluene and their substitutes;
Styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalin copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, Octyl styrene-acrylate copolymer, dimethylaminoethyl styrene-acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-methacryl Dimethylaminoethyl acid copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene -Sterite copolymers such as maleic acid copolymers and styrene-maleic acid ester copolymers;
Polymethylmethacrylate, polybutylmethacrylate, polyvinyl acetate, polyethylene, polypropylene, polyvinyl butyral, and polyacrylic acid resin can be used, and these can be used alone or in combination of two or more. Among these, a styrene-based copolymer and further a styrene-butyl acrylate copolymer are particularly preferable from the viewpoint of easy control of development characteristics and fixability.

The crystalline polyester is preferably in a form in which the crystalline polyester has a polyester moiety and a vinyl polymer moiety from the viewpoint of improving the dispersibility of the crystalline polyester in the vinyl resin, and particularly in the polyester moiety. It is preferable to have a structure represented by the following formula (1).

式中、ｍは４〜１４の整数、ｎは６〜１６の整数を示す。

In the formula, m is an integer of 4 to 14, and n is an integer of 6 to 16.

It is shown that the polyester moiety has a structure in which a dicarboxylic acid having an alkylene group having 4 to 14 carbon atoms and a diol having an alkylene group having 6 to 16 carbon atoms are condensed as a repeating unit. The crystalline polyester preferably has a structure derived from the repeating unit in an amount of 90% by mass or more based on all the polyester units of the crystalline polyester. By adopting a structure having a carbon number lower limit or more of the formula (1), the dispersibility of the material and the chargeability of the toner are improved, and the change in image density after use in a harsh environment is suppressed.
Further, by making the structure equal to or less than the upper limit of the number of carbon atoms in the formula (1), crystallization is promoted, and sharp meltability can be exhibited while maintaining heat-resistant storage stability, so that low-temperature fixability is improved.

The structure represented by the above formula (1) can be obtained by condensation of a dicarboxylic acid and a diol.
As the dicarboxylic acid, adipic acid, suberic acid, sebacic acid, dodecanedioic acid, tetradecanedioic acid, hexadecanedioic acid and the like can be used.
Examples of the diol include 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, and 1,14-. Tetradecanediol, 1,16-hexadecanediol and the like can be used.

Next, the molecular weight of the vinyl polymer moiety of the crystalline polyester will be described.
The vinyl polymer moiety preferably has a certain length in order to exert a dispersion effect on the vinyl resin. Therefore, the weight average molecular weight (Mw) is preferably 4000 or more and 15000 or less. More preferably, it is 4000 or more and 12000 or less. When Mw is 4000 or more, the dispersibility of the crystalline polyester in the vinyl resin is improved and the fixability is improved. Further, when Mw is 15,000 or less, the increase in viscosity of the crystalline polyester tends to be suppressed, so that the fixability is excellent.
A known vinyl monomer such as styrene, methyl methacrylate or n-butyl acrylate can be used for the vinyl polymer moiety. Particularly preferably, when a polymer of styrene is used, it works effectively as a compatible site with the vinyl resin and more exhibits plasticity at the time of melting.

The mass-based ratio of the polyester moiety to the vinyl polymer moiety (polyester moiety: vinyl polymer moiety) of the crystalline polyester of the present invention is preferably 40:60 to 95: 5, and more preferably 40:60 to 80:20. is there. Within this range, sufficient low-temperature fixability can be obtained due to the sharp melt property, which is a characteristic of the polyester portion.

Further, the crystalline polyester is preferably a block polymer having a polyester moiety and a vinyl polymer moiety.
The crystalline polyester moiety facilitates a design that achieves both compatibility with the vinyl resin and maintenance of crystallinity in the toner. Further, by having an amorphous vinyl polymer moiety, it is possible to finely disperse the crystalline polyester in the vinyl resin, and the low temperature fixability is further improved. Further, in the case of a block polymer, since the crystalline part and the amorphous part are connected by a main chain and do not have a three-dimensional structure, the dispersed state with respect to the vinyl resin is uniform, and in use in a harsh environment. Also has excellent chargeability.
The definition of block polymer is a polymer composed of multiple blocks connected in a linear shape (a glossary of basic terminology of polymer science by the International Union of Pure and Applied Chemistry Polymer Naming Law Committee) Yes, the present invention also follows that definition.

The content of the crystalline polyester is preferably 2.0 parts by mass or more and 30.0 parts by mass or less with respect to 100 parts by mass of the vinyl resin. When it is 2.0 parts by mass or more, the fixability is improved. When it is 30.0 parts by mass or less, deterioration of the crystalline polyester in a harsh environment is suppressed, and the chargeability is excellent. The content of the crystalline polyester is more preferably 2.0 parts by mass or more and 15.0 parts by mass or less with respect to 100 parts by mass of the vinyl resin.
The weight average molecular weight of the crystalline polyester is preferably 12000 to 45000. Within this range, the dispersibility in the toner particles and the viscosity at the time of melting are excellent, which is preferable from the viewpoint of fixability.
The melting point of the crystalline polyester is preferably 55 ° C. or higher and 90 ° C. or lower from the viewpoint of developability and fixability.

The method for producing the crystalline polyester is not particularly limited, but since it contains a polyester moiety and a vinyl polymer moiety, a production method for obtaining a structure in which both are chemically bonded is preferable. The preferred manufacturing method is illustrated below.
Example 1: Polyester is obtained by polycondensation of a dicarboxylic acid and a diol. At this time, as the esterification catalyst, a known esterification catalyst such as a tin compound such as dibutyltin oxide, tin dioctylate, titanium (IV) isopropoxide, or a titanium compound may be used. Next, a monomer having an unsaturated group and having a functional group capable of undergoing an ester exchange reaction such as a carboxy group or an ester group and a vinyl monomer such as styrene, acrylic acid or methacrylic acid are added and polymerized. The desired polymer is obtained by advancing. When produced by such a production method, a reaction of cross-linking the polyester sites occurs during the production of the vinyl polymer, so that a graft polymer having a partially grafted structure can be obtained.

Example 2: A vinyl polymer having a carboxylic acid or a carboxylic acid ester at one end or both ends is produced, and a diol and a dicarboxylic acid are appropriately added to the vinyl polymer, and then the polycondensation reaction is carried out to obtain the desired polymer. For the polycondensation reaction, a known esterification catalyst can be used as in Example 1. Regarding the production of a vinyl polymer having a carboxylic acid or a carboxylic acid ester at one end or both ends, a method using a functional group-containing initiator and a method using a functional group-containing chain transfer agent can be mentioned as known methods.
Examples of the method using the functional group-containing initiator include Koji Ishizu and "Journal of Polymer Science Part A: Polymer Chemistry" (USA).
Examples of the method using the functional group-containing chain transfer agent include Toshiro Uchida, four others, and "Journal of Polymer Science Part A: Polymer Chemistry". The product produced by this production method takes the form of a block polymer as described above.

Example 3; Polyester is obtained in the same manner as in Example 1. Then, according to the ATRP method, a block copolymer of a polyester moiety and a vinyl polymer moiety is obtained. By using so-called precision radical polymerization, it is possible to prepare a polymer in which one block of polyester and one block of vinyl polymer are present in one molecule. The product produced by this production method takes the form of a block polymer as described above.

Examples of monomers having an unsaturated group and a functional group capable of transesterification reaction. Acrylic acid, fumaric acid, methacrylic acid, citraconic acid, maleic acid, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, glycidyl acrylate, glycidyl methacrylate, and anhydrides and alkyl (carbon number) of these carboxylic acids. 1-2) Derivatives such as esters can be mentioned. Among these, acrylic acid, methacrylic acid, fumaric acid, maleic acid and derivatives of these carboxylic acids are preferable from the viewpoint of reactivity.

Examples of the vinyl monomer include the following. Styrene, α-methylstyrene, α-ethylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, 3,4-dichlorostyrene, p -Ethyl styrene, 2,4-dimethyl styrene, pn-butyl styrene, p-tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn- Decylstyrene, pn-dodecylstyrene, ethylene, propylene, butylene, isobutylene, vinyl chloride, vinylidene chloride, vinylmethyl ether, vinyl ethyl ether, vinyl isobutyl ether, vinyl methyl ketone, vinyl hexyl ketone, methyl isopropenyl ketone, vinyl Examples thereof include naphthalin, acrylonitrile, methacrylonitrile, and acrylamide.

As the polymerization initiator used for polymerizing the vinyl polymer described above in the production of crystalline polyester, an oil-soluble initiator and / or a water-soluble initiator is appropriately used as long as the effect of the present invention is not impaired. It is possible. For example, as the oil-soluble initiator, an azo compound such as 2,2'-azobisisobutyronitrile; t-butylperoxyneodecanoate, t-hexylperoxypivalate, lauroyl peroxide, t- Examples thereof include peroxides such as butylperoxy2-ethylhexanoate, t-butylperoxyisobutyrate, dit-butylperoxyisophthalate and dit-butylperoxide.

Examples of the water-soluble initiator include ammonium persulfate, potassium persulfate, 2,2'-azobis (N, N'-dimethyleneisobutyroamidine) hydrochloride, and 2,2'-azobis (2-aminodinopropane) hydrochloric acid. Salt, azobis (isobutylamidine) hydrochloride, 2,2'-azobisisobutyronitrile sulfonate sodium, 2,2'-azobis {2-methyl-N- [1,1-bis (hydroxymethyl) -2 -Hydroxyethyl] propionamide}, 2,2'-azobis {2-methyl-N- [2- (1-hydroxybutyl)]-propionamide}, ferrous hydrochloride sulfate or hydrogen peroxide.

Amorphous polyester can utilize a condensate of any dicarboxylic acid and dialcohol. From the viewpoint of achieving both low-temperature fixability and environmental stability, it is preferable to control the presence state of the amorphous polyester in the toner within an appropriate range.
Specifically, in the cross section of the toner observed by a transmission electron microscope (TEM), it is preferable that the vinyl resin constitutes a matrix and the amorphous polyester constitutes a plurality of domains. Then, the domain of the amorphous polyester is within 25% of the distance between the contour and the center point of the cross section from the contour of the cross section, and is 30 area% or more and 70 area% or less based on the total area of the domain. It is preferable that it exists. More preferably, it is 45 area% or more and 70 area% or less.
From the contour of the toner cross section, the area ratio of the domain of the amorphous polyester existing within 25% of the distance between the contour and the center point of the cross section (hereinafter, also referred to as “25% area ratio”) is 30 areas. When it is% or more, the plasticity of the toner surface is increased and the low temperature fixability is improved. When it is 70 area% or less, the presence of low molecular weight components of crystalline polyester compatible with the vinyl resin in the vicinity of the surface is suppressed, exudation after a harsh environment is suppressed, and chargeability and fluidity are improved. By maintaining it, the concentration tends to be stable.

Next, the domain of the amorphous polyester is 80 area% or more and 100 area% based on the total area of the domain within 50% of the distance between the contour and the center point of the cross section from the contour of the cross section. It is preferable that the following exists. More preferably, it is 90 area% or more and 100 area% or less.
The area ratio of the amorphous polyester domain (hereinafter, also referred to as "50% area ratio") existing within 50% of the distance between the contour and the center point of the cross section from the contour of the toner cross section is 80 areas. When it is% or more, it can be melted instantly at the time of fixing, so that the low temperature fixing property is improved and image chipping is easily suppressed. Further, the presence of 80 area% or more of the domain can be rephrased as the abundance of the domain in the region from the center point of the toner to 50% of the contour of the toner cross section is 20 area% or less. In such a state, it is easy to maintain the fluidity during long-term use, and it is easy to suppress the decrease in image density.

Next, from the contour of the cross section, the area of the domain of the amorphous polyester existing within 25% of the distance between the contour and the center point of the cross section is, from the contour of the cross section, the contour and the center of the cross section. It is preferably 1.05 times or more the area of the domain of the amorphous polyester present at 25% to 50% of the distance between the points. This indicates that the domains are unevenly distributed on the toner surface. Since the domains are unevenly distributed on the toner surface, they can be melted instantly at the time of fixing, so that the low temperature fixing property is improved and image chipping can be easily suppressed.
(From the contour of the cross section of the toner, the area of the domain of the amorphous polyester existing within 25% of the distance between the contour and the center point of the cross section / from the contour of the cross section, between the contour and the center point of the cross section. The area of the amorphous polyester (hereinafter, also referred to as the area ratio of the domain) present at 25% to 50% of the distance is more preferably 1.20 times or more. On the other hand, the upper limit is not particularly limited, but is preferably 3.0 times or less, and more preferably 2.0 times or less.

Further, the average diameter of the number of domains of the amorphous polyester is preferably 0.3 μm or more and 3.0 μm or less, and more preferably 0.3 μm or more and 2.0 μm or less.
When the domain diameter is 0.3 μm or more, it becomes easy to be compatible with the crystalline polyester component at the time of heat melting. Further, when it is 3.0 μm or less, it becomes easy to control the existence state of the domain.

In order to form a domain in the vicinity of the toner surface and control the 25% area ratio, the 50% area ratio and the domain area ratio, and to control the domain diameter, for example, it is suspended. If it is a turbid polymerization method, it can be controlled by the acid value and the hydroxyl value of the amorphous polyester. In addition, the amorphous polyester has a lipophilic moiety (alkyl moiety) at the end of the molecular chain, which is a structure derived from a long-chain monomer described later, and the softening point of the amorphous polyester and the toner is controlled during toner production. It can be adjusted by controlling the annealing conditions of.
Next, when the peak intensity derived from the vinyl resin of the toner obtained by time-of-flight secondary ion mass spectrometry (TOF-SIMS) is S85 and the peak intensity derived from the amorphous polyester is S211, the following formula ( It is preferable to satisfy 1), and it is more preferable to satisfy the relationship of the following formula (1)'.
Equation (1) 0.30 ≤ S211 / S85 ≤ 3.00
Equation (1) '1.00 ≤ S211 / S85 ≤ 2.50
In time-of-flight secondary ion mass spectrometry (TOF-SIMS), information of several nm can be obtained from the surface of the toner particles, so that the constituent material of the outermost layer of the toner particles can be specified. The amorphous polyester preferably has a monomer unit derived from bisphenol A as an alcohol component, and S211 is a peak derived from the bisphenol A. Further, as the vinyl resin, as described above, a styrene-butyl acrylate copolymer is preferable, and S85 is a peak derived from the butyl acrylate.
When S211 / S85 is 0.30 or more, the amorphous polyester is contained in the vicinity of the toner surface, and the toner can be instantly melted at the time of fixing, which is preferable.
Further, when S211 / S85 is 3.00 or less, softening of the toner due to a harsh environment and exudation of crystalline polyester via amorphous polyester are easily suppressed, which is preferable.

The content of the amorphous polyester is preferably 5.0 parts by mass or more and 30.0 parts by mass or less with respect to 100 parts by mass of the vinyl resin. When it is 5.0 parts by mass or more, the domain state in the vinyl resin can be easily controlled, and by distributing it in the vicinity of the surface layer, the melting effect in the vicinity of the surface layer at the time of melting can be easily exhibited, and the low temperature fixability is improved. Further, when it is 30.0 parts by mass or less, it tends to lead to improvement of stress due to long-term use.
Further, the amorphous polyester has a monomer unit derived from a linear aliphatic dicarboxylic acid having 6 or more and 12 or less carbon atoms and a monomer unit derived from dialcohol from the viewpoint of durability of toner particles and low temperature fixability. However, the content ratio of the monomer unit derived from the linear aliphatic dicarboxylic acid having 6 or more and 12 or less carbon atoms is 10 mol% or more and 50 mol% or less with respect to all the monomer units derived from the carboxylic acid of the amorphous polyester. Is preferable.

In order to disperse the amorphous polyester in the vicinity of the surface layer and promote melting in the vicinity of the toner surface, it is preferable to use a low softening point material. As the control means, it is preferable to have a linear aliphatic dicarboxylic acid-derived moiety having 6 to 12 carbon atoms in the amorphous polyester.
When the number of carbon atoms is 6 or more, a pseudo-crystal state is easily formed, and the resin is easily plasticized, so that the low temperature fixability is easily improved. Further, when the number of carbon atoms is 12 or less, the softening point of the amorphous polyester tends to be lowered in a state where the peak molecular weight of the amorphous polyester is increased, so that the durability as a resin is maintained and at the time of fixing. Plasticization is possible. The number of carbon atoms is more preferably 6 or more and 10 or less.

Next, regarding the content of the monomer unit derived from the linear aliphatic dicarboxylic acid, if it is 10 mol% or more, the softening point tends to be lowered. On the other hand, when it is 50 mol% or less, it is difficult to reduce the peak molecular weight of the amorphous polyester, which is preferable from the viewpoint of improving the durability of the toner. The linear aliphatic dicarboxylic acid is more preferably 30 mol% or more and 50 mol% or less.

Examples of the carboxylic acid component for obtaining the amorphous polyester include a linear aliphatic dicarboxylic acid having 6 to 12 carbon atoms and other carboxylic acids. Examples of the linear aliphatic dicarboxylic acid having 6 or more and 12 or less carbon atoms include adipic acid, suberic acid, sebacic acid, and dodecanedioic acid.
Examples of the carboxylic acid other than the linear aliphatic dicarboxylic acid having 6 or more and 12 or less carbon atoms include the following. Examples of the divalent carboxylic acid component include maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, succinic acid, glutaric acid, n-dodecenyl succinic acid, and anhydrides of these acids, lower alkyl esters, and the like. Be done. Examples of the trivalent or higher valent carboxylic acid component include 1,2,4-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, pyromellitic acid, empol trimeric acid and their acid anhydrides, lower grades. Examples thereof include alkyl esters. Among these, terephthalic acid is preferable because it can maintain a high peak molecular weight and easily maintain durability.

Examples of the alcohol component for obtaining the amorphous polyester include the following in addition to the propylene oxide adduct of bisphenol A. Examples of the divalent alcohol component include ethylene oxide adduct of bisphenol A, ethylene glycol, 1,3-propylene glycol, neopentyl glycol and the like. Examples of the trihydric or higher alcohol component include sorbitol, pentaerythritol, dipentaerythritol and the like. The divalent alcohol component and the trihydric or higher polyhydric alcohol component can be used alone or in combination of a plurality of compounds. Among these, as the alcohol component, the alcohol component derived from bisphenol A is preferably used from the viewpoint of ease of controlling the presence state in the toner.

The amorphous polyester can be produced by an esterification reaction or a transesterification reaction using the above alcohol component and carboxylic acid component. In the case of polycondensation, a known esterification catalyst such as dibutyl tin oxide may be appropriately used in order to promote the reaction.
The molar ratio (carboxylic acid component / alcohol component) of the alcohol component and the carboxylic acid component, which are the raw material monomers of the amorphous polyester, is preferably 0.60 or more and 1.00 or less.

Further, the amorphous polyester preferably has an alkyl moiety at the end of the amorphous polyester from the viewpoint of facilitating the adjustment of the acid value and the hydroxyl value and promoting the crystallization of the crystalline polyester.
The amorphous polyester is an aliphatic monocarboxylic acid having a peak carbon number of 25 to 102 and an aliphatic monoalcohol having a peak carbon number of 25 to 102 (hereinafter, these two are collectively referred to as “long-chain monomer”. It is preferable to have a structure derived from at least one selected from the group consisting of (also referred to as) at the end. These long-chain monomers are preferably condensed at the ends. Specifically, when a carboxy group is present at the end of the amorphous polyester before the long-chain monomer is bonded, a condensation reaction with a monoalcohol occurs and a bond occurs. Further, when a hydroxy group is present at the end of the amorphous polyester before the long-chain monomer is bonded, a condensation reaction with a monocarboxylic acid occurs and a bond is generated.
Here, the "peak value of carbon number" is the carbon number calculated from the main peak molecular weight of the long-chain monomer.

Here, the "terminal" includes the end of the branched chain when the amorphous polyester has a branched chain. In the present invention, the amorphous polyester has a branched chain, and the form condensed at the end of the branched chain is one of the preferred embodiments.
By binding a long-chain monomer to the end of the amorphous polyester, an alkyl moiety can be introduced at the end of the amorphous polyester. As a result, it is presumed that the amorphous polyester can also take a pseudo-crystallized state by adopting a structure in which the alkyl moiety is easily folded. Furthermore, the effect of promoting the crystallization of the crystalline polyester existing in the toner is exhibited, and there is a tendency to suppress plasticization and exudation of low molecular weight components in a harsh environment.
Further, when the peak value of the carbon number of the aliphatic monocarboxylic acid and the aliphatic monoalcohol is 25 or more and 102 or less, the affinity with the crystalline polyester is enhanced, and the phase of the crystalline polyester to the vinyl resin is enhanced. It promotes the crystallinity of the dissolved component, and the above-mentioned low temperature fixability and charge stability in a harsh environment can be obtained.

The content ratio of the long-chain monomer is preferably 2.0 mol% or more and 10.0 mol% or less based on all the monomer units of the amorphous polyester. When it is 2.0 mol% or more, the affinity with the crystalline polyester is high, and the above-mentioned effect can be easily obtained. Further, when it is 10.0 mol% or less, the fluidity and chargeability are stable, and the concentration decrease in the heat cycle environment can be suppressed.

The long-chain monomer is industrially obtained by alcohol- or acid-denaturing an aliphatic hydrocarbon as a raw material. For example, in the case of alcohol-modified products, an aliphatic hydrocarbon having 25 or more and 102 or less carbon atoms is liquid-phase oxidized with a molecular oxygen-containing gas in the presence of a catalyst such as boric acid, anhydrous boric acid, or metaboric acid. It is known that it can be converted to alcohol. The amount of the catalyst added is preferably 0.01 to 0.5 mol with respect to 1 mol of the raw material aliphatic hydrocarbon.
As the molecular oxygen-containing gas to be blown into the reaction system, oxygen, air or a wide range of gas obtained by diluting them with an inert gas can be used, but an oxygen concentration of 3 to 20% is preferable. The reaction temperature is 100 ° C. or higher and 200 ° C. or lower.

Further, when the long-chain monomer is modified with alcohol or acid, each unmodified component may also be generated. In order to prevent the charge amount from being lowered by this unmodified component, the modification rate of the aliphatic hydrocarbon component is preferably in the range of 85% or more, more preferably 90% or more.
By optimizing the reaction conditions and performing purification work after the denaturation reaction, unmodified aliphatic hydrocarbon components can be removed and the denaturation rate can be controlled.

The peak molecular weight (Mp (AP)) of the amorphous polyester is preferably 8000 or more and 13000 or less, and the softening point is preferably 85 ° C. or more and 105 ° C. or less.
When the peak molecular weight (Mp (AP)) is 8000 or more, the toner durability during long-term use tends to be improved. Further, when the peak molecular weight (Mp (AP)) is 13000 or less, melting by heat occurs instantly, so that it becomes easy to control the low temperature fixability.
When the softening point of the amorphous polyester is 85 ° C. or higher, it becomes easy to improve the durability of the toner over a long period of use. Further, when the softening point is 105 ° C. or lower, melting by heat occurs instantaneously, so that the low temperature fixability is easily improved.
Further, as a means for controlling the peak molecular weight and the softening point of the amorphous polyester in a preferable range, a linear aliphatic dicarboxylic acid having 6 or more and 12 or less carbon atoms is contained in an amount of 10 mol% or more and 50 mol% or less based on the total carboxylic acid component. It is preferable to use the carboxylic acid component and the dialcohol component.

Next, the release agent will be described.
As the release agent, a known wax can be used as long as it is a wax for the purpose of imparting releasability and plasticity.
For example, petroleum waxes such as paraffin wax, microcrystalline wax, petrolactam and their derivatives;
Montan wax and its derivatives;
Hydrocarbon wax by Fischer-Tropsch method and its derivatives;
Polyolefin waxes such as polyethylene and their derivatives;
Examples thereof include natural waxes such as carnauba wax and candelilla wax and derivatives thereof. Derivatives include oxides, block copolymers with vinyl monomers, and graft modified products. Further, fatty acids such as higher fatty alcohols, stearic acid and palmitic acid, acid amide waxes, ester waxes, hardened castor oil and its derivatives, vegetable waxes, animal waxes and the like can also be used.
Among these waxes, paraffin wax is preferably used from the viewpoint of compatibility with vinyl resin and releasability.
The content of the release agent is preferably 1.0 part by mass or more and 30.0 parts by mass or less, and preferably 3.0 parts by mass or more and 25.0 parts by mass or less with respect to 100 parts by mass of the vinyl resin. More preferred.

Next, the colorant will be described.
As the black colorant, carbon black, magnetic fine particles, and those colored black using the yellow, magenta, and cyan colorants shown below are used.
When magnetic one-component development is adopted in the one-component development method, it is preferable to use magnetic fine particles having high transportability with respect to the toner carrier containing the magnet roller as the black colorant. Further, even when the supply roller for supplying the toner in the cartridge to the toner carrier is omitted, it is preferable to use magnetic fine particles having high transportability as the black colorant.

Further, in order to obtain uniform adhesion and high adhesiveness of the external additive, it is more preferable to use a magnetic toner using magnetic fine particles having a large specific gravity. We speculate that the reason for this high stickiness is as follows.
As a method of adhering the external additive to the toner particles, it is preferable to use a mixing device using a stirring blade or the like from the viewpoint of mixing property and shearing force. In such an external addition step, the portion mainly processed is in the vicinity of the stirring blade. It is considered that the magnetic toner having a large specific gravity has a larger load during the external addition treatment in the vicinity of the stirring blade than the non-magnetic toner, and the probability of being treated is higher. Therefore, it is considered that the magnetic toner can obtain higher adhesiveness than the non-magnetic toner.

The magnetic fine particles are mainly composed of magnetic iron oxide such as triiron tetraoxide and γ-iron oxide, and may contain elements such as phosphorus, cobalt, nickel, copper, magnesium, manganese, aluminum and silicon. These magnetic fine particles preferably have a BET specific surface area of ² to 30 m ² / g by the nitrogen adsorption method, and more preferably 3 to 28 m ² / g. Further, those having a Mohs hardness of 5 to 7 are preferable. The shape of the magnetic fine particles includes a polyhedron, an octahedron, a hexahedron, a sphere, a needle, and a scaly shape. Preferred above.
The number average particle size of the magnetic fine particles is preferably 0.10 μm or more and 0.40 μm or less. When the number average particle size is 0.10 μm or more, the magnetic fine particles are less likely to aggregate, and the uniform dispersibility of the magnetic fine particles in the toner is improved. Further, when the number average particle size is 0.40 μm or less, the coloring power of the toner is improved.

The number average particle diameter of the magnetic fine particles can be measured using a transmission electron microscope. Specifically, after the toner particles to be observed are sufficiently dispersed in the epoxy resin, the cured product is obtained by curing in an atmosphere at a temperature of 40 ° C. for 2 days. The obtained cured product is used as a flaky sample by a microtome, and the diameters of 100 magnetic fine particles in the field of view are measured with a photograph having a magnification of 10,000 to 40,000 times with a transmission electron microscope (TEM). Then, the number average particle diameter is calculated based on the equivalent diameter of the circle equal to the projected area of the magnetic fine particles. It is also possible to measure the particle size with an image analyzer.

The magnetic fine particles can be produced, for example, by the following method. An aqueous solution containing ferrous hydroxide is prepared by adding an alkali such as sodium hydroxide to the ferrous salt aqueous solution in an equivalent amount or equal to or more than the iron component. Air is blown while maintaining the pH of the prepared aqueous solution at pH 7 or higher, and the ferrous hydroxide oxidation reaction is carried out while heating the aqueous solution to 70 ° C. or higher to first form seed crystals that are the core of the magnetic iron oxide powder. Generate.
Next, an aqueous solution containing about 1 equivalent of ferrous sulfate is added to the slurry-like liquid containing seed crystals based on the amount of alkali added previously. While maintaining the pH of the liquid at 5 to 10, the reaction of ferrous hydroxide is promoted while blowing air, and the magnetic iron oxide powder is grown around the seed crystal. At this time, it is possible to control the shape and magnetic characteristics of the magnetic fine particles by selecting an arbitrary pH, reaction temperature, and stirring conditions. As the oxidation reaction progresses, the pH of the liquid shifts to the acidic side, but it is preferable that the pH of the liquid is not less than 5. Magnetic fine particles can be obtained by filtering, washing, and drying the magnetic fine particles thus obtained by a conventional method.

Further, when the toner is produced by the suspension polymerization method, it is very preferable to hydrophobize the surface of the magnetic fine particles because it is easy to enclose the magnetic fine particles in the toner. When surface treatment is performed by a dry method, the magnetic fine particles that have been washed, filtered, and dried are treated with a coupling agent. When the surface treatment is performed wet, the dried iron oxide is redispersed after the oxidation reaction is completed, or the iron oxide obtained by washing and filtering after the oxidation reaction is completed in another aqueous medium without drying. Is redistributed and the coupling process is performed. Specifically, the coupling treatment is performed by adding a silane coupling agent while sufficiently stirring the redispersion liquid to raise the temperature after hydrolysis, or by adjusting the pH of the dispersion liquid to an alkaline range after hydrolysis. .. Among these, from the viewpoint of performing a uniform surface treatment, it is preferable to perform surface treatment by reslurrying as it is without drying after completion of the oxidation reaction, filtration and washing.

In order to treat the surface treatment of the magnetic fine particles wet, that is, to treat the magnetic fine particles with a coupling agent in an aqueous medium, first sufficiently disperse the magnetic fine particles in the aqueous medium so as to have a primary particle size, and prevent sedimentation and aggregation. Stir with a stirring blade or the like. Next, an arbitrary amount of the coupling agent is added to the above dispersion, and the surface treatment is performed while hydrolyzing the coupling agent. At this time as well, the coupling agent is sufficiently stirred and not aggregated while using a device such as a pin mill or a line mill. It is more preferable to perform surface treatment while dispersing.
Here, the aqueous medium is a medium containing water as a main component. Specific examples thereof include water itself, water to which a small amount of surfactant is added, water to which a pH adjuster is added, and water to which an organic solvent is added. As the surfactant, a nonionic surfactant such as polyvinyl alcohol is preferable. The surfactant is preferably added in an amount of 0.1 to 5.0% by mass based on water. Examples of the pH adjuster include inorganic acids such as hydrochloric acid. Examples of the organic solvent include alcohols and the like.

Examples of the coupling agent that can be used in the surface treatment of the magnetic fine particles in the present invention include a silane coupling agent, a silane compound, and a titanium coupling agent. More preferably used are silane coupling agents and silane compounds, which are represented by the general formula (1).
R _m SiY _n general formula (1)
[In the formula, R represents an alkoxy group, m represents an integer of 1 to 3, Y represents a functional group such as an alkyl group, a phenyl group, a vinyl group, an epoxy group, or a (meth) acrylic group, and n is 1. Indicates an integer of ~ 3. However, m + n = 4. ]

Examples of the silane coupling agent and silane compound represented by the general formula (1) include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, and β- (3,4 epoxycyclohexyl) ethyltri. Methoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-methacryloxypropyltri Methoxysilane, vinyltriacetoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, diphenyldiethoxysilane, n-butyltri Methoxysilane, isobutyltrimethoxysilane, trimethylmethoxysilane, n-hexyltrimethoxysilane, n-octyltrimethoxysilane, n-octyltrimethoxysilane, n-decyltrimethoxysilane, hydroxypropyltrimethoxysilane, n-hexadecyl Examples thereof include trimethoxysilane and n-octadecyltrimethoxysilane.

Among these, from the viewpoint of imparting high hydrophobicity to the magnetic fine particles, it is preferable to use an alkyltrialkoxysilane coupling agent represented by the following general formula (2).
C _p H _{2p + 1} −Si− (OC _q H _{2q + 1} ) ₃ General formula (2)
[In the formula, p indicates an integer of 2 to 20, and q indicates an integer of 1 to 3. ]
When p in the above formula is 2 or more, it is easy to sufficiently impart hydrophobicity to the magnetic fine particles. Further, when p is 20 or less, the hydrophobicity becomes sufficient, and coalescence of magnetic fine particles can be prevented. When q is 3 or less, the reactivity of the silane coupling agent is good, and hydrophobization is sufficiently performed. Therefore, alkyltrialkoxysilanes in which p in the equation represents an integer of 2 to 20 (more preferably an integer of 3 to 15) and q represents an integer of 1 to 3 (more preferably an integer of 1 or 2). It is preferable to use a coupling agent.
When the above silane coupling agent is used, it can be treated alone or in combination of a plurality of types. When a plurality of types are used in combination, they may be treated individually with each coupling agent or may be treated at the same time.

In the present invention, other colorants may be used in combination with the magnetic fine particles. Examples of the colorant that can be used in combination include the above-mentioned known dyes and pigments, as well as magnetic or non-magnetic inorganic compounds. Specifically, ferromagnetic metal particles such as cobalt and nickel, or alloys obtained by adding chromium, manganese, copper, zinc, aluminum, rare earth elements, etc. to these. Particles such as hematite, titanium black, niglosin dye / pigment, carbon black, phthalocyanine and the like can be mentioned. These are also preferably used after surface treatment.
The content of the magnetic fine particles in the toner particles is preferably 20 to 200 parts by mass, more preferably 40 to 150 parts by mass with respect to 100 parts by mass of the polymerizable monomer or vinyl resin.

Examples of the yellow colorant include compounds typified by condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds. Specifically, the following C.I. I. Pigment Yellow 12, 13, 14, 15, 17, 62, 73, 74, 83, 93, 94, 95, 97, 109, 110, 111, 120, 128, 129, 138, 147, 150, 151, 154, 155, 168, 180, 185, 214 can be mentioned.
Examples of the magenta colorant include condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinone compounds, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds and perylene compounds. Specifically, the following C.I. I. Pigment Red 2, 3, 5, 6, 7, 23, 48: 2, 48: 3, 48: 4, 57: 1, 81: 1, 122, 146, 166, 169, 177, 184, 185, 202, 206, 220, 221 238, 254, 269, C.I. I. Pigment Bio Red 19.

Examples of the cyan colorant include a copper phthalocyanine compound and its derivative, an anthraquinone compound, and a basic dye lake compound. Specifically, C.I. I. Pigment Blue 1, 7, 15, 15: 1, 15: 2, 15: 3, 15: 4, 60, 62, 66.
These colorants can be used alone or in a mixed state and further in a solid solution state. The colorant is selected in terms of hue angle, saturation, lightness, light resistance, OHP transparency, and dispersibility in toner. The amount of the colorant added is preferably 1 to 20 parts by mass with respect to 100 parts by mass of the polymerizable monomer or vinyl resin that produces the vinyl resin.

In the present invention, the toner particles can be produced by any known method. First, a case of manufacturing by a pulverization method will be described.
When the toner particles are produced by the pulverization method, for example, toner components such as vinyl resin, colorant, mold release agent, amorphous polyester and crystalline polyester, and other additives are mixed with a mixer such as a Henschel mixer or a ball mill. Mix well. Then, it is melt-kneaded using a heat kneader such as a heating roll, a kneader, or an extruder to disperse or melt the above-mentioned materials, cool and solidify them, pulverize them, classify them, and perform surface treatment as necessary. Toner particles can be obtained. The order of classification and surface treatment may be either first. In the classification process, it is preferable to use a multi-division classifier from the viewpoint of production efficiency.

The crushing step can be performed by a method using various crushing devices such as a mechanical impact type and a jet type. Further, in order to obtain the toner (toner particles) having a preferable circularity used in the present invention, it is preferable to further apply heat to pulverize the toner or perform an auxiliary treatment of applying a mechanical impact. Further, a hot water bath method in which finely pulverized (classified if necessary) toner particles are dispersed in hot water, a method in which the toner particles are passed through a hot air stream, or the like may be used.
Examples of the method of applying the mechanical impact force include a method of using a mechanical impact type crusher such as a cryptron system manufactured by Kawasaki Heavy Industries, Ltd. or a turbo mill manufactured by Turbo Industries, Ltd. Another method is to apply a mechanical impact force to the toner by centrifugally pressing the toner inside the casing with blades that rotate at high speed, such as the method used by devices such as the Mechanofusion system manufactured by Hosokawa Micron. ..
In order to control the dispersed state of the vinyl resin and the amorphous polyester by the pulverization method, it is preferable to perform a treatment such as adding an amorphous polyester externally.

The toner particles used in the present invention can be produced by the pulverization method as described above, but in order to control the existence state of the domain of the amorphous polyester, a dispersion polymerization method, an association aggregation method, or dissolution It is preferable to produce toner particles in an aqueous medium such as a suspension method and a suspension polymerization method, and among them, the suspension polymerization method is more preferable.

In the suspension polymerization method, a polymerizable monomer that produces a vinyl resin, an amorphous polyester, a crystalline polyester, a mold release agent, and a colorant (and, if necessary, a polymerization initiator, a cross-linking agent, and a charge control agent) are used. , Other additives) are dissolved or dispersed to obtain a polymerizable monomer composition. After that, this polymerizable monomer composition is added to an aqueous medium (if necessary, a dispersion stabilizer may be contained). Then, particles of the polymerizable monomer composition are formed in an aqueous medium, and the polymerizable monomer contained in the particles is polymerized to obtain toner particles. Toners obtained by the suspension polymerization method (hereinafter, also referred to as "polymerized toners") have almost spherical shapes of individual toner particles, so that the fluidity at the regulation part is easily improved and uniform triboelectric charging is performed. Since it is easy to remove, the image quality is easily improved.

As a polymerizable monomer,
Styrene-based monomers such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, p-ethylstyrene;
Methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, n-propyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chlorethyl acrylate, Acrylic acid esters such as phenyl acrylate;
Methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, methacrylic acid Methacrylate esters such as dimethylaminoethyl and diethylaminoethyl methacrylate;
And so on. In addition, acrylonitrile, methacrylonitrile, acrylamide and the like can also be mentioned. These can be used alone or in combination of two or more.
Among the above-mentioned polymerizable monomers, styrene-based monomers, acrylic acid ester-based monomers, and methacrylic acid ester-based monomers can be preferably exemplified.
Further, the content of the styrene-based monomer in the polymerizable monomer is preferably 60% by mass or more and 90% by mass or less, and more preferably 65% by mass or more and 85% by mass or less. On the other hand, the content of the acrylic acid ester-based monomer or the methacrylic acid ester-based monomer is preferably 10% by mass or more and 40% by mass or less, and preferably 15% by mass or more and 35% by mass or less. More preferred.

It is preferable that the polymerizable monomer composition contains a polar resin. In the suspension polymerization method, since the toner particles are produced in an aqueous medium, the polar resin can be contained on the surface of the toner particles by containing the polar resin, so that the chargeability can be easily improved and the concentration decrease can be suppressed. It's easy to do.
As the polar resin, for example
Monopolymers of styrene such as polystyrene and polyvinyltoluene and their substitutes;
Styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalin copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, Styrene-octyl acrylate copolymer, dimethylaminoethyl styrene-acrylate copolymer, methyl styrene-methacrylic acid copolymer, ethyl styrene-ethyl methacrylate copolymer, butyl styrene-butyl methacrylate copolymer, Styrene-dimethylaminoethyl methacrylate copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer Styrene-based copolymers such as coalescence, styrene-maleic acid copolymer, styrene-maleic acid ester copolymer;
Examples thereof include polymethylmethacrylate, polybutylmethacrylate, polyvinyl acetate, polyethylene, polypropylene, polyvinylbutyral, silicone resin, polyamide resin, epoxy resin, polyacrylic acid resin, terpene resin, and phenol resin. These can be used alone or in combination of two or more. Further, functional groups such as an amino group, a carboxyl group, a hydroxyl group, a sulfonic acid group, a glycidyl group and a nitrile group may be introduced into these polymers.

The acid value Av of the amorphous polyester is preferably 1.0 mgKOH / g or more and 10.0 mgKOH / g or less. More preferably, it is 4.0 mgKOH / g or more and 8.0 mgKOH / g or less.
When the acid value Av is in the above range, it becomes easy to control the 25% area ratio, 50% area ratio and domain area ratio within the preferable ranges of the present invention.

Next, it is preferable that the hydroxyl value OHv of the amorphous polyester is 40.0 mgKOH / g or less. When the hydroxyl value OHv of the amorphous polyester is 40.0 mgKOH / g or less, the amorphous polyester easily forms a plurality of domains in the vicinity of the toner surface.
In order to control the acid value Av of the amorphous polyester to 1.0 mgKOH / g or more and 10.0 mgKOH / g or less and the hydroxyl value OHv to 40.0 mgKOH / g or less, as described above, the amorphous polyester It is preferable to have an alkyl moiety at the end of the molecular chain.

The polymerization initiator used in the production of the toner by the polymerization method used in the present invention preferably has a half-life of 0.5 hours or more and 30.0 hours or less during the polymerization reaction. Further, when the polymerization reaction is carried out by using an addition amount of 0.5 parts by mass or more and 20.0 parts by mass or less with respect to 100 parts by mass of the polymerizable monomer, the toner can be given desired strength and appropriate melting characteristics. it can.
Specific examples of polymerization initiators include 2,2'-azobis- (2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, and 1,1'-azobis (cyclohexane-1). -Carbonitrile), 2,2'-azobis-4-methoxy-2,4-dimethylvaleronitrile, azobisisobutyronitrile and other azo or diazo polymerization initiators, benzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl Peroxide-based polymerization initiators such as peroxycarbonate, cumenehydroperoxide, 2,4-dichlorobenzoyl peroxide, lauroyl peroxide, t-butylperoxy2-ethylhexanoate, and t-butylperoxypivalate. Can be mentioned.

When the toner used in the present invention is produced by a polymerization method, a cross-linking agent may be added. The preferable addition amount is 0.01 part by mass or more and 5.00 parts by mass or less with respect to 100 parts by mass of the polymerizable monomer.
Here, as the cross-linking agent, a compound having two or more polymerizable double bonds is mainly preferable. For example
Aromatic divinyl compounds such as divinylbenzene and divinylnaphthalene;
Carboxylate ester having two double bonds such as ethylene glycol diacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate;
Divinyl compounds such as divinylaniline, divinyl ether, divinyl sulfide, divinyl sulfone;
Compounds having three or more vinyl groups are used alone or as a mixture of two or more.

In the method for producing the toner used in the present invention by a polymerization method, if necessary, the above-mentioned toner composition or the like is added and uniformly dissolved or dispersed by a disperser to obtain a polymerizable monomer composition. Examples of the disperser include a homogenizer, a ball mill, and an ultrasonic disperser. The obtained polymerizable monomer composition is suspended in an aqueous medium containing a dispersion stabilizer. At this time, the particle size of the obtained toner particles becomes sharper when the desired toner particle size is set at once by using a high-speed disperser such as a high-speed stirrer or an ultrasonic disperser. The polymerization initiator may be added at the same time as the other additives are added to the polymerizable monomer, or may be mixed immediately before suspension in the aqueous medium. It is also possible to add a polymerization initiator immediately after granulation and before starting the polymerization reaction.
After granulation, a normal stirrer may be used to stir the particles to the extent that the state of the particles is maintained and the floating and sedimentation of the particles are prevented.

When producing the toner used in the present invention, various surfactants, organic dispersants and inorganic dispersants can be used as dispersion stabilizers. Among them, the inorganic dispersant can be preferably used because it does not easily generate ultrafine powder and has obtained dispersion stability due to its steric hindrance. Examples of such inorganic dispersants include tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, hydroxyapatite and other phosphate polyvalent metal salts, calcium carbonate, magnesium carbonate and other carbonates, calcium metasilicate, calcium sulfate and sulfuric acid. Examples thereof include inorganic salts such as barium, and inorganic compounds such as calcium hydroxide, magnesium hydroxide, and aluminum hydroxide.
The amount of these inorganic dispersants added is preferably 0.2 parts by mass or more and 20.0 parts by mass or less with respect to 100 parts by mass of the polymerizable monomer. Further, the dispersion stabilizer may be used alone or in combination of two or more. Further, a surfactant may be used in combination.

In the step of polymerizing the above-mentioned polymerizable monomer, the polymerization temperature is usually set to 40 ° C. or higher, preferably 50 ° C. or higher and 90 ° C. or lower.
In order to form the domain of amorphous polyester, it is preferable to carry out the following steps.
After the polymerization of the above-mentioned polymerizable monomer is completed to obtain colored particles, in a state where the colored particles are dispersed in an aqueous medium, the amorphous polyester is in the vicinity of the softening point (softening point to softening point + 10 ° C.), specifically. It is preferable to raise the temperature to about 100 ° C. and keep the temperature at that temperature for 30 minutes or more. The holding time is more preferably 60 minutes or more, and further preferably 120 minutes or more. The upper limit of the holding time is about 24 hours or less in relation to manufacturing efficiency.
Further, in order to achieve the dispersed state of the amorphous polyester as described above, it is preferable to perform the following operations in the subsequent cooling step. Specifically, it is preferable to cool the aqueous medium to Tg or less of the toner at a cooling rate of 5.00 ° C./min or more, more preferably at a cooling rate of 20 ° C./min or more, and a cooling rate of 100 ° C./min or more. It is more preferable to cool the above. The upper limit of the cooling rate is not particularly limited, but is preferably 500 ° C./min or less.
After cooling at the above cooling rate, it is preferable to keep at that temperature for 30 minutes or more. The holding time is more preferably 60 minutes or more, and further preferably 120 minutes or more. The upper limit of the holding time is about 24 hours or less in relation to manufacturing efficiency. In addition, Tg or less means from Tg to about Tg-5 ° C.
Toner particles are obtained by filtering, washing and drying the obtained polymer particles.

Toner can also be obtained by mixing inorganic fine particles with the toner particles, if necessary, and adhering them to the surface of the toner particles. It is also possible to add a classification step to the manufacturing process (before mixing the inorganic fine particles) to cut the coarse powder and fine powder contained in the toner particles.
Further, as the fluidizing agent, it is preferable that inorganic fine particles having a number average primary particle size of 4 nm or more and 80 nm or less, more preferably 6 nm or more and 40 nm or less, are added (externally added) to the toner particles. Further, it is more preferable to use inorganic fine particles having a number average primary particle size of more than 80 nm and 200 nm or less in combination. By doing so, the fluidity of the toner can be ensured through long-term use, uniform and stable triboelectric performance can be obtained, and the concentration can be easily improved. Inorganic fine particles are added to improve the fluidity of the toner and homogenize the charge of the toner particles. Functions such as adjusting the charge amount of the toner and improving the environmental stability by treating the inorganic fine particles with hydrophobic treatment are performed. Is also a preferable form.

In the present invention, the method for measuring the number average primary particle size of the inorganic fine particles is performed by using a photograph of the toner magnified by a scanning electron microscope.
As the inorganic fine particles, fine particles such as silica, titanium oxide, and alumina can be used. Examples of the silica fine particles include so-called dry silica produced by vapor phase oxidation of a silicon halide or dry silica called fumed silica, and so-called wet silica produced from water glass or the like.
However, fewer silanol groups on the inner surface and the silica fine particles and Na 2 _O, towards less dry silica of manufacture residues such as SO ₃ ^2-is preferable. Further, in dry silica, it is also possible to obtain composite fine particles of silica and other metal oxides by using other metal halogen compounds such as aluminum chloride and titanium chloride together with silicon halogen compounds in the manufacturing process. , Including them.
The amount of the inorganic fine particles added is preferably 0.1 to 3.0 parts by mass with respect to 100 parts by mass of the toner particles. The content of the inorganic fine particles can be quantified using a calibration curve prepared from a standard sample using fluorescent X-ray analysis.

In the present invention, it is preferable that the inorganic fine particles are hydrophobized because the environmental stability of the toner can be improved. Examples of the treatment agent used for the hydrophobic treatment of the inorganic fine particles include silicone varnish, various modified silicone varnishes, silicone oil, various modified silicone oils, silane compounds, and silane coupling agents. Further, other treatment agents such as organosilicon compounds and organotitanium compounds can be mentioned. These can be used alone or in combination of two or more.
Among the above treatment agents, those treated with silicone oil are preferable, and those treated with silicone oil at the same time or after treating the inorganic fine particles with a silane compound are more preferable. As a method for treating such inorganic fine particles, for example, as a first-stage reaction, a silylation reaction is carried out with a silane compound to eliminate silanol groups by chemical bonds, and then as a second-stage reaction, silicone oil is applied to the surface. A hydrophobic thin film can be formed.

The silicone oil is preferably a viscosity at 25 ° C. is 10 mm ² / s or more 200,000 mm ² / s or less things, more preferably the following 3,000 mm ² / s or more 80,000mm ² / s.
As the silicone oil used, for example, dimethyl silicone oil, methylphenyl silicone oil, α-methylstyrene modified silicone oil, chlorphenyl silicone oil, fluorine modified silicone oil and the like are particularly preferable.
Examples of the method of treating the inorganic fine particles with silicone oil include a method of directly mixing the inorganic fine particles treated with a silane compound and silicone oil using a mixer such as a Henshell mixer, or a method of spraying the inorganic fine particles with silicone oil. The method can be mentioned. Alternatively, a method may be used in which the silicone oil is dissolved or dispersed in an appropriate solvent, and then inorganic fine particles are added and mixed to remove the solvent. A method of spraying is more preferable because the formation of aggregates of inorganic fine particles is relatively small.

The treatment amount of the silicone oil is preferably 1 to 40 parts by mass, and more preferably 3 to 35 parts by mass with respect to 100 parts by mass of the inorganic fine particles. Within this range, good hydrophobicity can be easily obtained.
Inorganic fine particles used in the present invention, in order to impart good fluidity to the toner, the specific surface area measured by the BET method by nitrogen adsorption of preferably those in 20~350m ² / g range, 25~300m ² / The one of g is more preferable. The specific surface area is calculated by adsorbing nitrogen gas on the sample surface using the specific surface area measuring device Autosorb 1 (manufactured by Yuasa Ionics) according to the BET method and using the BET multipoint method.

The toner of the present invention includes still other additives, such as
Lubricants particles such as fluororesin particles, zinc stearate particles, polyvinylidene fluoride particles;
Abrasives such as cerium oxide particles, silicon carbide particles, strontium titanate particles;
Fluidity imparting agents such as titanium oxide particles and aluminum oxide particles;
Anti-caking agent;
It is also possible to use a small amount of opposite polar organic fine particles and inorganic fine particles as a developable improver. It is also possible to treat the surface of these additives with hydrophobic treatment before use.

The present invention relates to a developing apparatus having a toner for developing an electrostatic latent image formed on an image carrier and a toner carrier for carrying the toner and transporting the toner to the image carrier. The developing apparatus preferably used in the present invention will be described in detail with reference to the drawings.
FIG. 2 is a schematic cross-sectional view showing an example of a developing device. Further, FIG. 3 is a schematic cross-sectional view showing an example of an image forming apparatus incorporating a developing apparatus.
In FIG. 2 or 3, the electrostatic latent image carrier 45, which is an image carrier on which the electrostatic latent image is formed, is rotated in the direction of arrow R1. By rotating the toner carrier 47 in the direction of arrow R2, the toner 57 is conveyed to the developing region where the toner carrier 47 and the electrostatic latent image carrier 45 face each other. Further, the toner supply member 48 is in contact with the toner carrier, and the toner 57 is supplied to the surface of the toner carrier by rotating in the direction of arrow R3.

A charging roller 46, a transfer member (transfer roller) 50, a fixing device 51, a pickup roller 52, and the like are provided around the electrostatic latent image carrier 45. The electrostatic latent image carrier 45 is charged by the charging roller 46. Then, the laser light is irradiated to the electrostatic latent image carrier 45 by the laser generator 54 to perform exposure, and an electrostatic latent image corresponding to the target image is formed. The electrostatic latent image on the electrostatic latent image carrier 45 is developed with the toner in the developer 49 to obtain a toner image. The toner image is transferred onto the transfer material (paper) 53 by the transfer member (transfer roller) 50 that is in contact with the electrostatic latent image carrier 45 via the transfer material. The transfer material (paper) 53 on which the toner image is placed is carried to the fixing device 51 and fixed on the transfer material (paper) 53.

Next, a method for measuring each physical property according to the present invention will be described.
<Measurement method of softening point of toner and amorphous polyester>
The softening points of toner and amorphous polyester are measured using a constant load extrusion type thin tube rheometer "Flow Tester CFT-500D" (manufactured by Shimadzu Corporation) according to the manual attached to the device. In this device, while applying a constant load from the top of the measurement sample with a piston, the temperature of the measurement sample filled in the cylinder is raised and melted, and the melted measurement sample is pushed out from the die at the bottom of the cylinder, and the amount of piston drop at this time. A flow curve showing the relationship between and temperature can be obtained.
In the present invention, the softening point is the "melting temperature in the 1/2 method" described in the manual attached to the "flow characteristic evaluation device flow tester CFT-500D". The melting temperature in the 1/2 method is calculated as follows. First, 1/2 of the difference between the piston descent amount Smax at the time when the outflow ends and the piston descent amount Smin at the time when the outflow starts is obtained (this is defined as X. X = (Smax-Smin) / 2). Then, the temperature of the flow curve when the amount of descent of the piston is the sum of X and Smin in the flow curve is the melting temperature in the 1/2 method (a schematic diagram of the flow curve is shown in FIG. 4).
The measurement sample is about 60 g of toner or amorphous polyester at about 10 MPa in an environment of 25 ° C. using a tablet molding compressor (for example, NT-100H, manufactured by NPA System Co., Ltd.). A columnar product having a diameter of about 8 mm is used by compression molding for seconds.
The measurement conditions for the CFT-500D are as follows.
Test mode: Temperature rise method Start temperature: 50 ° C
Achieved temperature: 200 ° C
Measurement interval: 1.0 ° C
Heating rate: 4.0 ° C / min
Piston cross section: 1.000 cm ²
Test load (piston load): 10.0 kgf (0.9807 MPa)
Preheating time: 300 seconds Die hole diameter: 1.0 mm
Die length: 1.0 mm

<Measuring method of weight average particle size (D4)>
The weight average particle size (D4) of the toner is a precision particle size distribution measuring device "Coulter Counter Multisizer" by the pore electric resistance method equipped with an aperture tube of 100 μm.
3 ”(registered trademark, manufactured by Beckman Coulter) and the attached dedicated software“ Beckman Coulter Multisizer 3 Version 3.51 ”(manufactured by Beckman Coulter) for setting measurement conditions and analyzing measurement data. The measurement was performed with 25,000 effective measurement channels, and the measurement data was analyzed and calculated.
As the electrolytic aqueous solution used for the measurement, a special grade sodium chloride dissolved in ion-exchanged water so as to have a concentration of about 1% by mass, for example, "ISOTON II" (manufactured by Beckman Coulter) can be used.
Before the measurement and analysis, the dedicated software was set as follows.
In the dedicated software "Change standard measurement method (SOM) screen", set the total count number in the control mode to 50,000 particles, measure once, and set the Kd value to "standard particles 10.0 μm" (Beckman Coulter). The value obtained using (manufactured by) is set. By pressing the threshold / noise level measurement button, the threshold and noise level are automatically set. Also, set the current to 1600 μA, the gain to 2, and the electrolyte to ISOTON II, and check the flush of the aperture tube after measurement.
In the "pulse to particle size conversion setting screen" of the dedicated software, the bin spacing is set to logarithmic particle size, the particle size bin is set to 256 particle size bins, and the particle size range is set from 2 μm to 60 μm.

The specific measurement method is as follows.
(1) Approximately 200 ml of the electrolytic aqueous solution is placed in a 250 ml round bottom beaker made of glass dedicated to ultisizer 3, set on a sample stand, and the stirrer rod is stirred counterclockwise at 24 rpm. Then, the dirt and air bubbles in the aperture tube are removed by the "aperture flush" function of the dedicated software.
(2) Approximately 30 ml of the electrolytic aqueous solution is placed in a 100 ml flat-bottomed beaker made of glass, and "Contaminone N" (nonionic surfactant, anionic surfactant, and organic builder) as a dispersant is used as a dispersant for precise measurement of pH 7. Add about 0.3 ml of a diluted solution obtained by diluting a 10% by mass aqueous solution of a neutral detergent for cleaning a vessel, manufactured by Wako Pure Chemical Industries, Ltd.) with ion-exchanged water 3 times by mass.
(3) Two oscillators with an oscillation frequency of 50 kHz are built in with the phase shifted by 180 degrees, and are placed in the water tank of the ultrasonic disperser "Ultrasonic Dispersion System Tetora 150" (manufactured by Nikkaki Bios) with an electrical output of 120 W. A certain amount of ion-exchanged water is added, and about 2 ml of the contaminone N is added into the water tank.
(4) The beaker of (2) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. Then, the height position of the beaker is adjusted so that the resonance state of the liquid level of the electrolytic aqueous solution in the beaker is maximized.
(5) With the electrolytic aqueous solution in the beaker of (4) irradiated with ultrasonic waves, about 10 mg of toner is added little by little to the electrolytic aqueous solution and dispersed. Then, the ultrasonic dispersion processing is continued for another 60 seconds. In ultrasonic dispersion, the water temperature in the water tank is appropriately adjusted to be 10 ° C. or higher and 40 ° C. or lower.
(6) The (5) electrolytic aqueous solution in which toner is dispersed is dropped onto the (1) round-bottom beaker installed in the sample stand using a pipette, and the measured concentration is adjusted to about 5%. Then, the measurement is performed until the number of measurement particles reaches 50,000.
(7) The measurement data is analyzed by the dedicated software attached to the device, and the weight average particle size (D4) is calculated. The "arithmetic diameter" of the analysis / volume statistical value (arithmetic mean) screen when the graph / volume% is set by the dedicated software is the weight average particle diameter (D4).

<Measurement method of peak molecular weight Mp (AP) of crystalline polyester Mp (CP) and amorphous polyester>
The molecular weight distribution of the THF-soluble components of the crystalline polyester and the amorphous polyester is measured by gel permeation chromatography (GPC) as follows.
First, the toner is dissolved in tetrahydrofuran (THF) over 24 hours at room temperature. Then, the obtained solution is filtered through a solvent-resistant membrane filter "Maeshori Disc" (manufactured by Tosoh Corporation) having a pore diameter of 0.2 μm to obtain a sample solution. The sample solution is adjusted so that the concentration of the component soluble in THF is about 0.8% by mass. This sample solution is used for measurement under the following conditions.
Equipment: HLC8120 GPC (Detector: RI) (manufactured by Tosoh Corporation)
Column: 7 series of Shodex KF-801, 802, 803, 804, 805, 806, 807 (manufactured by Showa Denko KK)
Eluent: tetrahydrofuran (THF)
Flow velocity: 1.0 ml / min
Oven temperature: 40.0 ° C
Sample injection volume: 0.10 ml
In calculating the molecular weight of the sample, standard polystyrene resin (for example, trade name "TSK standard polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F-" 10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500 ”, manufactured by Tosoh Corporation) is used.

<Measurement method of 25% area ratio, 50% area ratio, and domain area ratio>
(25% area ratio)
Visible light curable resin (trade name, Aronix LCR series D-800; manufactured by Toagosei Co., Ltd.)
After the toner is sufficiently dispersed in it, it is cured by irradiating it with short wavelength light. The obtained cured product is cut out with an ultramicrotome equipped with a diamond knife to prepare a flaky sample of 250 nm. Next, the cut-out sample was magnified using a transmission electron microscope (JEM-2800 manufactured by JEOL Ltd.) (TEM-EDX) at a magnification of 40,000 to 50,000 times, the cross section of the toner particles was observed, and EDX was used. Element mapping is performed.
The toner cross section to be observed is selected as follows. First, the cross-sectional area of the toner is obtained from the toner cross-sectional image, and the diameter of a circle having an area equal to the cross-sectional area (diameter equivalent to the circle) is obtained. Only the toner cross-sectional image in which the absolute value of the difference between the equivalent circle diameter and the weight average particle size (D4) of the toner is within 1.0 μm is observed.
As the mapping conditions, the storage rate is 9000 to 13000, and the number of integrations is 120 times. Among the resin-derived domains confirmed from the observation images, the spectral intensity derived from the C element and the spectral intensity derived from the O element are measured, and the domain in which the spectral intensity of the C element with respect to the O element is 0.05 or more is found. It is a domain of amorphous polyester. After identifying the amorphous polyester domain, by binarization treatment, 25 of the distance between the contour and the center point of the cross section from the contour of the toner cross section with respect to the total area of the amorphous polyester domain existing in the toner cross section. Calculate the area ratio (area%) of the amorphous polyester domain present within%. Image Pro PLUS (manufactured by Nippon Roper Co., Ltd.) is used for the binarization treatment.
The calculation method is as follows. In the above TEM image, the contour and center point of the toner cross section are obtained. The contour of the toner cross section shall be along the surface of the toner observed in the TEM image. The center point of the toner cross section is the center of gravity of the toner cross section.
From the obtained center point, a line is drawn with respect to a point on the contour of the toner cross section. On the line, the position of 25% of the distance between the contour and the center point of the cross section is specified from the contour.
Then, this operation is performed for one round of the contour of the toner cross section, and a boundary line of 25% of the distance between the contour and the center point of the cross section is clearly indicated from the contour of the toner cross section.
Based on the TEM image in which the 25% boundary line is clearly shown, the area of the domain of the amorphous polyester existing in the region surrounded by the contour of the cross section of the toner and the 25% boundary line is measured. .. Then, the total area of the amorphous polyester domain existing in the toner cross section is measured, and the area% based on the total area is calculated.
(50% area ratio)
Similar to the above-mentioned measurement of the 25% area ratio, the boundary line of 50% of the distance between the contour and the center point of the cross section is specified from the contour of the toner cross section. The area of the domain of the amorphous polyester existing in the region surrounded by the contour of the cross section of the toner and the boundary line of 50% is measured, and the area% based on the total domain area is calculated.
(Domain area ratio)
Further, from the contour of the cross section of the toner, the area of the amorphous polyester domain existing within 25% of the distance between the contour and the center point of the cross section, and from the contour of the cross section of the toner, the contour and the center of the cross section. The ratio to the area of the amorphous polyester domain (domain area ratio) present at 25% to 50% of the distance between the points is obtained by the following formula using the calculated value obtained from the above.
Domain area ratio =
(25% area ratio (area%)) / [(50% area ratio (area%))-(25% area ratio (area%))]

<Measuring method of the number average diameter of amorphous polyester domains>
-Perform element mapping using EDX in the same manner as above to identify the amorphous polyester domain. The domain diameter is obtained by obtaining the circle-equivalent diameter from the area of the domain. The number of measurements is 100, and the arithmetic mean value of the circle-equivalent diameter of 100 domains is defined as the number average diameter of the domains. The domain for which the domain diameter is calculated is determined as follows.
First, the cross-sectional area of the toner is obtained from the toner cross-sectional image, and the diameter of a circle having an area equal to the cross-sectional area (diameter equivalent to the circle) is obtained. The domain diameter is calculated only for the toner cross-sectional image in which the absolute value of the difference between the equivalent circle diameter and the weight average particle diameter (D4) of the toner is 1.0 μm or less. Since the domain diameter may change depending on the particle size of the toner, the average domain diameter can be calculated by doing so.

<Measurement method of acid value Av of amorphous polyester>
The acid value is the number of mg of potassium hydroxide required to neutralize the acid contained in 1 g of the sample. The acid value of amorphous polyester is measured according to JIS K 0070-1992, but specifically, it is measured according to the following procedure.
(1) Preparation of Reagents 1.0 g of phenolphthalein is dissolved in 90 ml of ethyl alcohol (95% by volume), and ion-exchanged water is added to make 100 ml to obtain a phenolphthalein solution.
Dissolve 7 g of special grade potassium hydroxide in 5 ml of water and add ethyl alcohol (95% by volume) to make 1 L. Put it in an alkali-resistant container so as not to come into contact with carbon dioxide, leave it for 3 days, and then filter it to obtain a potassium hydroxide solution. The obtained potassium hydroxide solution is stored in an alkali-resistant container. The factor of the potassium hydroxide solution was that 25 ml of 0.1 mol / l hydrochloric acid was placed in a triangular flask, several drops of the phenolphthalein solution were added, titrated with the potassium hydroxide solution, and the hydroxylation required for neutralization was performed. Obtained from the amount of potassium solution. As the 0.1 mol / l hydrochloric acid, those prepared according to JIS K 8001-1998 are used.
(2) Operation (A) Main test 2.0 g of a crushed amorphous polyester sample is precisely weighed in a 200 ml Erlenmeyer flask, 100 ml of a mixed solution of toluene / ethanol (2: 1) is added, and the mixture is dissolved over 5 hours. To do. Then, a few drops of the phenolphthalein solution are added as an indicator, and titration is performed using the potassium hydroxide solution. The end point of the titration is when the light red color of the indicator continues for about 30 seconds. (B) Blank test Titration is performed in the same manner as above except that no sample is used (that is, only a mixed solution of toluene / ethanol (2: 1) is used).
(3) Substitute the obtained result into the following formula to calculate the acid value.
A = [(CB) x f x 5.61] / S
Here, A: acid value (mgKOH / g), B: addition amount of potassium hydroxide solution in blank test (ml), C: addition amount of potassium hydroxide solution in this test (ml), f: potassium hydroxide Solution factor, S: sample (g).

<Measurement method of hydroxyl value OHv of amorphous polyester and long chain monomer>
The hydroxyl value is the number of mg of potassium hydroxide required to neutralize acetic acid bonded to a hydroxyl group when 1 g of a sample is acetylated. The hydroxyl value of the amorphous polyester is measured according to JIS K 0070-1992, but specifically, it is measured according to the following procedure. The following method can be applied to long-chain monomers in the same manner.
(1) Preparation of Reagents 25 g of special grade acetic anhydride is placed in a 100 ml volumetric flask, pyridine is added to make the total volume 100 ml, and the mixture is sufficiently shaken to obtain an acetylation reagent. The obtained acetylation reagent is stored in a brown bottle so as not to come into contact with moisture, carbon dioxide, etc.
1.0 g of phenolphthalein is dissolved in 90 ml of ethyl alcohol (95% by volume), and ion-exchanged water is added to make 100 ml to obtain a phenolphthalein solution.
Dissolve 35 g of special grade potassium hydroxide in 20 ml of water and add ethyl alcohol (95% by volume) to make 1 L. Put it in an alkali-resistant container so as not to come into contact with carbon dioxide, leave it for 3 days, and then filter it to obtain a potassium hydroxide solution. The obtained potassium hydroxide solution is stored in an alkali-resistant container. The factor of the potassium hydroxide solution was that 25 ml of 0.5 mol / l hydrochloric acid was placed in a triangular flask, several drops of the phenolphthalein solution were added, titrated with the potassium hydroxide solution, and the hydroxylation required for neutralization was performed. Obtained from the amount of potassium solution. 0.5 mol / l
As hydrochloric acid, those prepared according to JIS K 8001-1998 are used.
(2) Operation (A) Main test 1.0 g of a crushed amorphous polyester sample is precisely weighed into a 200 ml round bottom flask, and 5.0 ml of the acetylation reagent is accurately added to this using a whole pipette. At this time, if the sample is difficult to dissolve in the acetylation reagent, a small amount of special grade toluene is added to dissolve the sample.
Place a small funnel on the mouth of the flask and immerse about 1 cm of the bottom of the flask in a glycerin bath at about 97 ° C. to heat it. At this time, in order to prevent the temperature of the neck of the flask from rising due to the heat of the bath, it is preferable to cover the base of the neck of the flask with thick paper having a round hole.
After 1 hour, remove the flask from the glycerin bath and allow to cool. After allowing to cool, add 1 ml of water from the funnel and shake to hydrolyze acetic anhydride. The flask is heated again in a glycerin bath for 10 minutes for further complete hydrolysis. After allowing to cool, wash the walls of the funnel and flask with 5 ml of ethyl alcohol.
A few drops of the phenolphthalein solution are added as an indicator and titrated with the potassium hydroxide solution. The end point of the titration is when the light red color of the indicator continues for about 30 seconds.
(B) Blank test Titration is performed in the same manner as described above except that an amorphous polyester sample is not used.
(3) Substitute the obtained result into the following formula to calculate the hydroxyl value.
A = [{(BC) x 28.05 x f} / S] + D
Here, A: hydroxyl value (mgKOH / g), B: addition amount of potassium hydroxide solution in blank test (ml), C: addition amount of potassium hydroxide solution in this test (ml), f: potassium hydroxide Factor of solution, S: sample (g), D: acid value of amorphous polyester (mgKOH / g).

<Measurement of toner glass transition temperatures Tg1st and Tg2nd (° C)>
The glass transition temperature Tg (° C.) of the toner is measured according to ASTM D3418-82 using a differential scanning calorimeter "Q1000" (manufactured by TA Instruments).
Here, the measurement of the glass transition temperature Tg (° C.) of the toner will be described first. The melting points of indium and zinc are used for temperature correction of the device detector, and the heat of fusion of indium is used for the correction of calorific value.
Specifically, about 4 mg of toner is precisely weighed, placed in an aluminum pan, and an empty aluminum pan is used as a reference, and the temperature rise rate is 10 ° C./in the measurement temperature range of 20 to 180 ° C. Measure in min (first temperature rise). The specific heat change is obtained in the temperature range of 40 ° C. to 100 ° C. in the first temperature raising process. The intersection of the line at the midpoint of the baseline before and after the specific heat change at this time and the differential thermal curve is defined as the glass transition temperature Tg1st of the toner.
In the measurement of Tg-2nd, the temperature is once raised to 180 ° C. at a heating rate of 10 ° C./min, then lowered to 10 ° C. at a temperature lowering rate of 10 ° C./min, and then the same as the first temperature rise. The temperature is raised again under the conditions of (second temperature rise). The specific heat change is obtained in the temperature range of 40 ° C. to 100 ° C. in the second temperature raising process. The intersection of the line at the midpoint of the baseline before and after the specific heat change at this time and the differential thermal curve is defined as the glass transition temperature Tg2nd of the toner.

<Measurement method of integrated toner stress>
(1) Preparation of Toner Pellet Approximately 3 g of toner (variable depending on the specific gravity of the sample) is placed in a vinyl chloride ring for measuring an inner diameter of 27 mm, and for example, a sample press molding machine "MAEKAWA Testing Machine" (MFG Co, LTD) Toner pellets are prepared by pressing at 200 kN for 60 seconds and molding a sample.
(2) Measurement of integrated value of stress The integrated value of toner stress is measured using a tacking tester "TAC-1000" (manufactured by Reska) according to the operation manual of the device. A schematic diagram of the tacking tester is shown in FIG. As for the probe, a fixing film material is assumed, and a polytetrafluoroethylene-coated probe having low adhesion to toner is used. Polytetrafluoroethylene coating is performed by the following method.
After degreasing and sandblasting the probe site, masking is performed and then preheating is performed, and polytetrafluoroethylene is applied to form a coating film. After the coating film is dried, masking is released, and then firing and cooling are performed to complete the coating. The roughness Ra of the surface coated by the above method was 0.5 μm. Further, it was confirmed that the value of the stress integral value measured in the range of Ra of 0.3 to 0.8 μm did not change in the error range.
As a specific measurement method, the toner pellet is placed on the sample holding plate 205, and the probe tip 203 is set to 200 ° C. using the probe unit 202.
Next, by adjusting the head portion 200, the probe tip is lowered until the probe tip can pressurize the toner pellet 204.
Next, the toner pellet is pressurized under the following conditions, and the stress value when the probe tip is pulled up is detected by the load sensor 201.
・ Pressing speed 5 mm / sec
・ Pressing load 19.7 kg ・ m / sec
・ Pressing holding time (contact time) 50 msec
・ Pulling speed 15mm / sec
The integrated value of stress is calculated by integrating the stress value detected by the load sensor.
Specifically, the stress value required for the time from the moment when the sensor pulls away from the pellet (the point where the stress value becomes 0 g ・ m / sec ² ) to the point where the sensor is completely separated from the pellet is integrated. Can be calculated with.

<Measurement of the intensity ratio (S211 / S85) of the peak intensity (S85) derived from vinyl resin and the peak intensity (S211) derived from amorphous polyester using time-of-flight secondary ion mass spectrometry (TOF-SIMS). Method>
The intensity ratio (S211 / S85) of the peak intensity (S85) derived from vinyl resin and the peak intensity (S211) derived from amorphous polyester using TOF-SIMS was measured by TRIFT-IV manufactured by ULVAC-PHI, Ltd. It was used.
The analysis conditions were as follows.
Sample preparation: Toner particles were attached to the indium sheet.
Sample pretreatment: None Primary ion: Au +
Acceleration voltage: 30kV
Charge neutralization mode: On
Measurement mode: Negative
Raster: 100 μm
Calculation of peak intensity (S85) derived from vinyl resin: According to ULVAC-PHI standard software (WinCadence), the total count number of mass numbers 84.5 to 85.5 was defined as peak intensity (S85).
Calculation of peak intensity (S211) derived from amorphous polyester: According to ULVAC-PHI standard software (WinCadence), the total count number of mass numbers 210.5 to 211.5 was defined as peak intensity (S211).
Calculation of strength ratio (S211 / S85): The strength ratio (S211 / S85) was calculated using S85 and S211 calculated as described above.

The basic configuration and features of the present invention have been described above, but the present invention will be specifically described below based on Examples. However, this does not limit any embodiment of the present invention. Parts and% in the examples are based on mass unless otherwise specified.

<Preparation of toner carrier 1>
(Preparation of substrate 1)
As the substrate 1, a SUS304 core metal having a diameter of 6 mm is coated with a primer (trade name, DY35-051; manufactured by Toray Dow Corning Co., Ltd.) and baked.
(Making elastic rollers)
The substrate 1 prepared as described above is placed in a mold, and an addition type silicone rubber composition mixed with the following materials is injected into a cavity formed in the mold.
・ Liquid silicone rubber material (trade name, SE6724A / B; manufactured by Toray Dow Corning) 100 copies ・ Carbon black (trade name, Toka Black # 4300; manufactured by Tokai Carbon Co., Ltd.)
15 parts ・ Silica particles as a heat resistance imparting agent 0.2 parts ・ Platinum catalyst 0.1 parts Next, the mold is heated and the silicone rubber is vulcanized and cured at a temperature of 150 ° C. for 15 minutes. After the substrate 1 having the cured silicone rubber layer formed on the peripheral surface is removed from the mold, the substrate 1 is further heated at a temperature of 180 ° C. for 1 hour to complete the curing reaction of the silicone rubber layer. In this way, an elastic roller having a silicone rubber elastic layer having a diameter of 12 mm formed so as to cover the outer peripheral surface of the substrate is produced.

(Preparation of surface layer 1)
(Synthesis of isocyanate group-terminated prepolymer 1)
Polypropylene glycol-based polyol (trade name: Excelol 4030; manufactured by Asahi Glass Co., Ltd.) 100 to 17.7 parts of toluene diisocyanate (TDI) (trade name: Cosmonate T80; manufactured by Mitsui Chemicals, Inc.) in a nitrogen atmosphere. .0 parts are gradually added dropwise while maintaining the temperature inside the reaction vessel at 65 ° C. After completion of the dropping, the reaction is carried out at a temperature of 65 ° C. for 2 hours. The obtained reaction mixture is cooled to room temperature to obtain an isocyanate group-terminated prepolymer 1 having an isocyanate group content of 3.8% by weight.

(Synthesis of Amino Compound 1)
In a reaction vessel equipped with a stirrer, a thermometer, a reflux tube, a dropping device and a temperature control device, 100.0 parts (1.67 mol) of ethylenediamine and 100 parts of pure water are heated to 40 ° C. while stirring. Next, 425.3 parts (7.35 mol) of propylene oxide is gradually added dropwise over 30 minutes while keeping the reaction temperature below 40 ° C. The reaction is carried out with stirring for another hour to obtain a reaction mixture. The obtained reaction mixture is heated under reduced pressure to distill off water to obtain 1: 426 parts of amino compound.
As a material for the surface layer
-Isocyanate group-terminated prepolymer 1 617.9 parts-Amino compound 1 34.2 parts-Carbon black (trade name, MA230; manufactured by Mitsubishi Chemical Corporation) 117.4 parts-Urethane resin fine particles (trade name, Artpearl C-400) ; Made by Negami Kogyo Co., Ltd.)
Stir 130.4 parts and mix.
Next, methyl ethyl ketone (hereinafter, also referred to as “MEK”) is added so that the total solid content ratio is 30% by mass, and then the mixture is mixed by a sand mill. Next, the viscosity is further adjusted to 10 cps or more and 13 cps or less with MEK to prepare a coating material for forming a surface layer.
The elastic roller 1 produced above is immersed in a paint for forming a surface layer to form a coating film of the paint on the surface of the elastic layer of the elastic roller 1 and dried. Further, by heat-treating at a temperature of 150 ° C. for 1 hour, a surface layer having a film thickness of 15 μm is provided on the outer periphery of the elastic layer to prepare the toner carrier 1.

<Production example of long-chain monomer 1>
1200 g of an aliphatic hydrocarbon having a peak carbon number of 35 is placed in a glass cylindrical reaction vessel, 38.5 g of boric acid is added at a temperature of 140 ° C., and immediately, the oxygen concentration of 50% by volume of air and 50% by volume of nitrogen is about. A mixed gas of 10% by volume is blown at a rate of 20 liters per minute and reacted at 200 ° C. for 3.0 hours, then warm water is added to the reaction solution, and hydrolysis is carried out at 95 ° C. for 2 hours. The reaction was taken. 20 parts of the modified product was added to 100 parts of n-hexane to dissolve and remove the unmodified component to obtain a long-chain monomer 1. Table 1 shows various physical properties of the obtained long-chain monomer 1. The long chain monomer 1 is a monohydric alcohol.

<Production examples of long-chain monomers 2 and 3>
The long-chain monomers 2 and 3 were produced in the same manner as in the production example of the long-chain monomer 1 except that the peak value of the carbon number of the aliphatic hydrocarbon used, the reaction time and the temperature were changed as shown in Table 1. The long chain monomers 2 and 3 are monohydric alcohols.

表中、炭素数は、炭素数のピーク値を示す。

In the table, the carbon number indicates the peak value of the carbon number.

<Production example of amorphous polyester 1>
After adjusting the amounts of raw material monomers shown in Table 2 so that the carboxylic acid component and alcohol component are shown in Table 2, they are placed in a reaction vessel equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple. , 1.5 parts of dibutyltin is added as a catalyst to 100 parts of the total amount of the monomer. Then, after rapidly raising the temperature to 180 ° C. under normal pressure under a nitrogen atmosphere, water is distilled off while heating at a rate of 10 ° C./hour from 180 ° C. to 210 ° C. to perform polycondensation. After reaching 210 ° C., the pressure inside the reaction vessel is reduced to 5 kPa or less, and polycondensation is performed under the conditions of 210 ° C. and 5 kPa or less to obtain amorphous polyester 1. At that time, the polymerization time is adjusted so that the peak molecular weight of the obtained amorphous polyester 1 becomes the value shown in Table 2. Table 2 shows the physical properties of the amorphous polyester 1.

<Production example of amorphous polyesters 2 to 16>
Amorphous polyesters 2 to 16 are obtained in the same manner as in amorphous polyester 1 except that the raw material monomer and the amount used are changed as shown in Table 2. Table 2 shows the physical properties of these amorphous polyesters.

表中のカルボン酸成分／アルコール成分のモル比とは、アルコール成分の合計（１００モル％）に対するカルボン酸成分の合計（１００モル％）のモル比を示す。原料モノマーの量はモル部を示す。

The molar ratio of the carboxylic acid component / alcohol component in the table indicates the molar ratio of the total carboxylic acid component (100 mol%) to the total alcohol component (100 mol%). The amount of the raw material monomer indicates the molar part.

<Production example of amorphous polyester 17>
100 mol part of bisphenol A ethylene oxide 2 mol addition, 173.6 mol part of bisphenol A propylene oxide 2 mol addition, 97.1 mol of terephthalic acid in a four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer and a thermocouple. 2 parts of esterification catalyst (tin octylate) was added to 100 parts of 166.2 mol of fumaric acid, 54.1 mol of adipic acid, and 2 mol of the bisphenol A ethylene oxide adduct, and shrunk at 230 ° C. for 8 hours. After the polymerization reaction was further reacted at 8 kPa for 1 hour and cooled to 160 ° C., 6 parts of acrylic acid, 70 parts of styrene, 31 parts of n-butyl acrylate and 20 parts of a polymerization initiator (di-t-butyl peroxide) were used. The mixture was added dropwise with a dropping funnel over 1 hour, and after the addition, the addition polymerization reaction was continued for 1 hour while being held at 160 ° C., the temperature was raised to 200 ° C., and the mixture was held at 10 kPa for 1 hour. By removing unreacted acrylic acid, styrene and butyl acrylate, an amorphous polyester 17 which is a composite resin formed by bonding a vinyl polymerized segment and a polyester polymerized segment was obtained.

<Manufacturing example of processed magnetic material>
In a ferrous sulfate aqueous solution, 1.00 to 1.10 equivalents of caustic soda solution with respect to iron element, P ₂ O ₅ with an amount of 0.15% by mass in terms of phosphorus element with respect to iron element, and iron element On the other hand, SiO ₂ in an amount of 0.50% by mass in terms of silicon element is mixed to prepare an aqueous solution containing ferrous hydroxide. The pH of the aqueous solution is set to 8.0, and an oxidation reaction is carried out at 85 ° C. while blowing air to prepare a slurry liquid having seed crystals.
Next, ferrous sulfate aqueous solution was added to this slurry liquid so that the amount was 0.99 to 1.20 equivalents with respect to the initial alkali amount (sodium component of caustic soda), the slurry liquid was maintained at pH 7.6, and air was introduced. The oxidation reaction is promoted while blowing to obtain a slurry liquid containing magnetic iron oxide. After filtering and washing, this hydrous slurry liquid is once taken out. At this time, a small amount of a water content sample is taken and the water content is measured. Next, this water-containing sample is put into another aqueous medium without being dried, and the slurry is redispersed with a pin mill while being stirred and the slurry is circulated to adjust the pH of the redispersed liquid to about 4.8. Then, while stirring, 1.6 parts of the n-hexyltrimethoxysilane coupling agent was added to 100 parts of magnetic iron oxide (the amount of magnetic iron oxide was calculated as the value obtained by subtracting the water content from the water content sample), and water was added. Disassemble. After that, the mixture is sufficiently stirred to adjust the pH of the dispersion to 8.6 and surface-treated. The produced hydrophobic magnetic material is filtered with a filter press, washed with a large amount of water, dried at 100 ° C. for 15 minutes and 90 ° C. for 30 minutes, and the obtained particles are crushed to have a volume average particle size of 0. A processed magnetic material of .21 μm is obtained.

<Manufacturing method of vinyl polymer 1>
A reaction vessel equipped with a stirrer, a thermometer, a nitrogen introduction tube, and a decompression device was heated with 100.0 parts of xylene substituted with nitrogen, and refluxed at a liquid temperature of 140 ° C. A mixture of 100.0 parts of styrene and 6.0 parts of Dimethyl-2,2'-azobis (2-methylpropionate) was added dropwise to the solution over 3 hours, and the solution was stirred for 3 hours after completion of the addition. Then, xylene and residual styrene were distilled off at 160 ° C. and 1 kPa to obtain a vinyl polymer 1. The Mw of the vinyl polymer 1 was 6000.

<Manufacturing method of vinyl polymers 2-5>
Vinyl polymers 2 to 5 were obtained in the same manner as in the method for producing vinyl polymer 1 except that the production conditions were changed as shown in Table 1. The physical properties are shown in Table 3.

<Manufacturing method of crystalline polyester 1>
The following was placed in a reaction vessel equipped with a stirrer, a thermometer, a nitrogen introduction tube, a dehydration tube, and a decompression device, and reacted at 160 ° C. for 5 hours under a nitrogen atmosphere.
・ Vinyl polymer 1 159.1 parts ・ Xylene 127.3 parts ・ 1,10-decanediol 105.3 parts ・ Titanium (IV) isopropoxide 0.56 parts Then, 100.0 parts of sebacic acid is added and 160 ° C. The reaction was carried out at 180 ° C. for 4 hours. Further, the reaction was carried out at 180 ° C. and 1 kPa until a desired Mw was obtained to obtain a crystalline polyester 1 as a block polymer. Table 4 shows the physical properties of the obtained crystalline polyester 1.

<Manufacturing method of crystalline polyester 2>
Add 100.0 parts of sebacic acid and 106.5 parts of 1,12-dodecanediol to a reaction vessel equipped with a stirrer, a thermometer, a nitrogen introduction pipe, a dehydration pipe, and a decompression device, and adjust the temperature while stirring. It was heated to 130 ° C. After adding 0.7 part of titanium (IV) isopropoxide, the temperature is raised to 160 ° C. and polycondensation is carried out over 5 hours. 15.0 parts of acrylic acid and 140.0 parts of styrene were added dropwise over 1 hour. After continuing stirring for 1 hour while maintaining the temperature at 160 ° C., the monomer of the styrene resin component was removed at 8.3 kPa for 1 hour. Then, the temperature was raised to 210 ° C. and the reaction was carried out until the desired molecular weight was obtained to obtain crystalline polyester 2 as a graft polymer. Table 4 shows the physical properties of the obtained crystalline polyester 2.

<Manufacturing method of crystalline polyester 3-9>
Crystalline polyesters 3 to 9 were obtained in the same manner as in the production methods of crystalline polyesters 1 and 2, except that the raw materials and production conditions were changed as shown in Table 4. The physical properties are shown in Table 4.

<Production example of toner particles 1>
450 parts of 0.1 mol / L-Na ₃ PO ₄ aqueous solution was added to 720 parts of ion-exchanged water and heated to 60 ° C., and then 67.7 parts of 1.0 mol / L-CaCl ₂ aqueous solution was added. , Obtain an aqueous medium containing a dispersion stabilizer.
・ 75.0 parts of styrene ・ 25.0 parts of n-butyl acrylate ・ 10.0 parts of amorphous polyester 1 5.0 parts of crystalline polyester ・ 0.6 parts of divinylbenzene ・ Iron complex of monoazo dye (T- 77: Hodogaya Chemical Co., Ltd.) 1.5 parts, treated magnetic material 65.0 parts The above formulation was uniformly dispersed and mixed using an attritor (Mitsui Miike Kakoki Co., Ltd.) to obtain a monomer composition. .. This monomer composition is heated to 63 ° C., and 15 parts of paraffin wax (melting point 78 ° C.) is added and mixed therein to dissolve it. Then, 5.0 parts of the polymerization initiator tert-butylperoxypivalate is dissolved.
The aqueous medium of the above monomer composition was charged in, 60 ° C., and stirred at 12000 rpm 10 min at TK Homomixer (Tokushu Kika Kogyo Co., Ltd.) under _{N 2} atmosphere and granulated.
Then, the reaction is carried out at 70 ° C. for 4 hours while stirring with a paddle stirring blade. After completion of the reaction, it is confirmed that the colored particles are dispersed in the aqueous medium obtained here, and that calcium phosphate is attached to the surface of the colored particles as an inorganic dispersant.
At this point, hydrochloric acid was added to the aqueous medium to wash and remove calcium phosphate, and then the particles were filtered and dried to analyze the colored particles. As a result, the glass transition temperature Tg of the vinyl resin was 55 ° C.
Subsequently, the water-based medium in which the colored particles are dispersed is heated to 100 ° C. and held for 120 minutes. Then, 5 ° C. water is added to the aqueous medium, and the mixture is cooled from 100 ° C. to 50 ° C. at a cooling rate of 100 ° C./min. Subsequently, the aqueous medium was held at 50 ° C. for 120 minutes.
Then, hydrochloric acid is added to the aqueous medium to wash and remove calcium phosphate, which is then filtered and dried to obtain toner particles 1. Table 5 shows the production conditions of the toner particles 1.

<Production example of toner particles 2-39>
In the production of the toner particles 1, the toner particles 2 to 39 are produced in the same manner except that the amorphous polyester, the crystalline polyester, the mold release agent, the colorant, and the production conditions are changed. Table 5 shows the production conditions of the obtained toner particles.

<Manufacturing example of toner particles 40>
<< Preparation of each dispersion >>
-Resin particle dispersion (1)-
・ Styrene (manufactured by Wako Junyaku Co., Ltd.): 325 parts ・ n Butyl acrylate (manufactured by Wako Junyaku Co., Ltd.): 100 parts ・ Acrylic acid (manufactured by Rhodia Nikka Co., Ltd.): 13 parts ・ 1,10-decanediol diacrylate (new Nakamura Kagaku Co., Ltd.): 1.5 parts, Dodecanthiolu (Wako Junyaku Co., Ltd.): 3.0 parts The above components are mixed in advance and dissolved to prepare a solution, and an anionic surfactant (Dow Chemical). A surfactant solution prepared by dissolving 9 parts of Doufax A211) in 580 parts of ion-exchanged water is placed in a flask, and 400 parts of the above solution is added to disperse and emulsify, and the mixture is slowly stirred for 10 minutes. While mixing, 50 parts of ion-exchanged water in which 6 parts of ammonium persulfate was dissolved was added.
Next, after the inside of the flask was sufficiently replaced with nitrogen, the inside of the flask was heated with an oil bath while stirring until the inside of the flask reached 75 ° C., and emulsion polymerization was continued as it was for 5 hours to obtain a resin particle dispersion liquid (1). It was.
When the physical properties of the resin particles were examined by separating them from the resin particle dispersion liquid (1), the number average particle size was 195 nm, the solid content in the dispersion liquid was 42%, the glass transition point was 51.5 ° C., and the weight average molecular weight Mw. Was 32000.
-Resin particle dispersion (2)-
The amorphous polyester 17 and the crystalline polyester 4 were charged with Cavitron CD1010 (manufactured by Eurotec Limited) at a ratio of 2: 1 and dispersed using a disperser modified to a high temperature and high pressure type. Specifically, the composition ratio is 79% of ion-exchanged water, 1% of anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen RK) (as an active ingredient), and 20% of solid content, and ammonia. The pH was adjusted to 8.5, the Cavitron was operated under the conditions of a rotor rotation speed of 60 Hz, a pressure of 5 kg / cm ² , and heating by a heat exchanger at 140 ° C., and resin fine particles having a number average particle size of 200 nm. The dispersion liquid (2) was obtained.
-Colorant dispersion-
-Carbon black 20 parts-Anionic surfactant (Neogen R, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 2 parts-Ion-exchanged water 78 parts Using a homogenizer (IKA, Ultratarax T50) at 3000 rpm Soak the pigment in water for 2 minutes, disperse it at 5000 rpm for 10 minutes, stir it with a normal stirrer for 1 day and night to defoam, and then use the high-pressure impact disperser Ultimateizer Co., Ltd., manufactured by Sugino Machine Co., Ltd. Using HJP30006), the mixture was dispersed at a pressure of 240 MPa for about 1 hour to obtain a colorant dispersion. Further, the pH of the dispersion was adjusted to 6.5.
-Release release agent dispersion-
-45 parts of hydrocarbon wax (Fischer-Tropsch wax, maximum endothermic peak = 78 ° C, Mw = 750)
・ Cationic surfactant (Neogen RK, Dai-ichi Kogyo Seiyaku) 5 parts ・ Ion-exchanged water 200 parts Heat the above components to 95 ° C and disperse them sufficiently with a homogenizer (Ultratarax T50 manufactured by IKA). The dispersion treatment was carried out with a pressure-discharging type Gorin homogenizer to obtain a release agent dispersion having an average number diameter of 190 nm and a solid content of 25%.

<< Manufacturing example of toner particles >>
-Ion-exchanged water 400 parts-Resin particle dispersion (1) 620 parts (resin particle concentration: 42%)
-Resin particle dispersion (2) 279 parts (resin particle concentration: 20%)
-Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd., Neogen RK, active ingredient amount: 60%)
1.5 parts (0.9 parts as active ingredient)
The above components were placed in a 3 liter reaction vessel equipped with a thermometer, a pH meter, and a stirrer, and kept at a temperature of 30 ° C. and a stirring rotation speed of 150 rpm for 30 minutes while controlling the temperature from the outside with a mantle heater. Then, 88 parts of the colorant dispersion and 60 parts of the release agent dispersion were added and held for 5 minutes. As it was, a 1.0% aqueous nitric acid solution was added to adjust the pH to 3.0. Next, the stirrer and mantle heater were removed, and while dispersing at 3000 rpm with a homogenizer (manufactured by IKA Japan: Ultratarax T50), 0.33 parts of polyaluminum chloride and 37.5 parts of 0.1% nitric acid aqueous solution were added. After adding 1/2 of the mixed solution, the dispersion speed was set to 5000 rpm, the remaining 1/2 was added over 1 minute, and the dispersion speed was set to 6500 rpm for 6 minutes.
A stirrer and a mantle heater are installed in the reaction vessel, and the temperature is raised to 42 ° C. at 0.5 ° C./min while appropriately adjusting the rotation speed of the stirrer so that the slurry is sufficiently agitated, and at 42 ° C. After holding for 15 minutes, the particle size was measured with a Coulter Multisizer every 10 minutes while raising the temperature at 0.05 ° C./min, and when the weight average particle size was 7.8 μm, 5% water was used. The pH was adjusted to 9.0 using an aqueous sodium oxide solution. Then, while adjusting the pH to 9.0 every 5 ° C., the temperature was raised to 96 ° C. at a heating rate of 1 ° C./min and maintained at 96 ° C. When the particle shape and surface properties were observed with an optical microscope and a scanning electron microscope (FE-SEM) every 30 minutes, the particles became almost spherical in the second hour, so the temperature was lowered to 20 ° C. at 1 ° C./min to cool the particles. It was solidified.
After that, the reaction product is filtered and washed with ion-exchanged water, and when the conductivity of the filtrate becomes 50 mS or less, the cake-shaped particles are taken out and the amount of ion-exchanged water is 10 times the particle weight. The particles were charged, stirred with a three-one motor, and when the particles were sufficiently loosened, the pH was adjusted to 3.8 with a 1.0% aqueous nitrate solution and held for 10 minutes. After that, it was filtered and washed with water again, and when the conductivity of the filtrate became 10 mS or less, the water flow was stopped and solid-liquid separation was performed. The obtained cake-like particles were crushed with a sample mill and dried in an oven at 40 ° C. for 24 hours. Further, the obtained powder was crushed by a sample mill and then vacuum dried in an oven at 40 ° C. for 5 hours to obtain toner particles 40.

<Example 1>
<Making toner>
<Manufacturing example of toner 1>
100 parts of toner particles 1 and silica having a primary particle size of 12 nm are treated with hexamethyldisilazane and then treated with silicone oil, and the treated hydrophobic silica fine particles 1.2 have a BET specific surface area value of 120 m ² / g. The particles were mixed using a Henschel mixer (Mitsui Miike Kakoki Co., Ltd.) to prepare toner 1. Table 6 shows the physical properties of the toner 1.

<Manufacturing examples of toners 2-34 and comparison toners 1-6>
In the production of the toner 1, the toner particles were changed as shown in Table 5 to obtain toners 2-34 and comparative toners 1-6. The physical properties are shown in Table 6.

<Example 1 (evaluation of toner 1)>
The printer LBP7700C was modified and used for image output evaluation. As a modification point, the toner carrier is changed to the toner carrier 1, the toner supply member of the developing device is removed from the toner supply roller: 48 shown in FIG. 2, and the voltage application to the toner supply member is turned off. did. The contact pressure was adjusted so that the width of the contact portion between the toner carrier and the electrostatic latent image carrier was 1.1 mm, and the process speed was further modified to be 35 ppm.
In this way, by removing the supply roller and increasing the process speed, the transportability of the toner to the carrier is tightened, and the area of the contact portion between the toner carrier and the electrostatic latent image carrier is reduced, so that the process can be performed. Increasing the speed can increase the stress on the toner during long-term use, allowing it to be evaluated in a rigorous electrophotographic process.
The developing apparatus modified as described above was filled with 100 g of toner 1 and image evaluation was performed. As the durable printed image, a horizontal line having a printing rate of 1% was used, and as a durable condition, a test was conducted using two sheets of intermittent paper. The evaluation results are shown in Table 7.

Each evaluation method and its judgment criteria are described below.
[Low temperature fixability (solid image missing)]
The toner-filled developing apparatus is left to stand in a normal temperature and humidity environment (23 ° C./50% RH) for 48 hours.
After that, the developing device is set, the fixing device is temporarily removed from the image forming device, and the unfixed image is modified so that it can flow. After that, the applied voltage is adjusted so that the toner loading amount of the solid image is 0.8 mg / cm ² .
The evaluation paper used at this time is GF-C157 (manufactured by Canon Inc.) having a basis weight of 157 g / m ² .
Then, in an environment of a temperature of 23 ° C. and a relative humidity of 50%, the fixing property was evaluated while changing the set temperature control every 5 ° C. in the temperature range of the sleeve surface temperature of the fuser from 170 ° C. to 210 ° C. , A to D were ranked according to the following criteria.
The lack of solid image (white spots) was visually evaluated.
A: Chips (white spots) occur at 175 ° C or lower.
B: Chips (white spots) occur at 180 ° C to 185 ° C.
C: Chips (white spots) occur at 190 ° C to 195 ° C.
D: Chips (white spots) occur at 200 ° C or higher.

[Low temperature fixability (rubbing)]
The developing apparatus was prepared in the same manner as in the evaluation of solid image chipping described above.
After that, a fixed image of an image pattern in which 9 points of 10 mm × 10 mm square images were evenly arranged on the entire paper was output on the evaluation paper, and the image density (measured using a Macbeth reflection densitometer (manufactured by Macbeth)). The halftone image density is adjusted so that the image density is 0.75 or more and 0.80 or less, and image printing is performed at a fixing temperature of 150 ° C. The evaluation paper used at this time is GF-C157 (manufactured by Canon Inc.) having a basis weight of 157 g / m ² .
Then, the halftone fixed image was rubbed 10 times with Sylbon paper loaded with 55 g / cm ² . From the halftone image density before and after rubbing, the density decrease rate at 150 ° C. was calculated using the following formula.
Density reduction rate = (image density before rubbing-image density after rubbing) / image density before rubbing x 100 (%)
Similarly, the fixing temperature was increased by 5 ° C., and the concentration decrease rate was calculated in the same manner up to 210 ° C. From the evaluation results of the fixing temperature and the concentration decrease rate obtained by a series of operations, the temperature at which the concentration decrease rate was 15% was calculated, and the temperature was set as the lower limit temperature for fixing indicating the threshold value at which the low temperature fixability was good. .. They were ranked A to D according to the following criteria.
A: Lower limit temperature for fixing is 175 ° C or lower B: Lower limit temperature for fixing is 180 ° C to 185 ° C or lower C: Lower limit temperature for fixing is 185 ° C to 190 ° C or lower D: Lower limit temperature for fixing is 195 ° C or higher

[Solid concentration in high temperature and high humidity environment]
After initial image output evaluation was performed in a high temperature and high humidity environment (32.5 ° C., 85% RH), a solid image (FFH) was printed. The density was measured by a densitometer X-Rite (manufactured by X-Rite, 500 series, density measurement mode), and the average value of 6 points was taken to obtain the image density. The initial concentrations were ranked A to D according to the following criteria:
A: 1.45 or more B: 1.35 or more and less than 1.45 C: 1.25 or more and less than 1.35 D: less than 1.25

[Solid concentration at the beginning of long-term use and after long-term use in a high-temperature and high-humidity environment after being left in a harsh environment]
The developing device was left in a harsh environment (40 ° C./95% RH) for 168 hours. Then, the developing apparatus was further left in a high temperature and high humidity environment (32.5 ° C./85% RH) for 24 hours.
Then, the initial concentration for long-term use was measured in a high temperature and high humidity environment (32.5 ° C., 85% RH) and evaluated according to the following criteria. Further, after long-term use image output evaluation (3000 sheets), a solid image (FFH) was printed. Densitometer X-Rite (X-Rite, 500 series,
The density was measured in the density measurement mode), and the average value of 6 points was taken to obtain the image density. The difference between the initial density of long-term use and the image density after long-term use image output was ranked A to D according to the following criteria.
(Early endurance)
A: 1.45 or more B: 1.35 or more and less than 1.45 C: 1.25 or more and less than 1.35 D: less than 1.25 (after durability)
A: Concentration difference is less than 0.05 B: Concentration difference is 0.05 or more and less than 0.10 C: Concentration difference is 0.10 or more and less than 0.15 D: Concentration difference is 0.15 or more

<Examples 2-37>
The toner was changed according to Table 7, and image drawing evaluation was performed in the same manner as in Example 1. The evaluation results are shown in Table 7.

<Comparative Examples 1 to 5>
The toner was changed according to Table 7, and image drawing evaluation was performed in the same manner as in Example 1. The evaluation results are shown in Table 7.

47: Toner carrier, 48: Toner supply member, 49: Developer, 55: Toner regulation member, 56: Metal plate, 57: Toner, 58: Stirring member 200: Head part, 201: Load sensor, 202: Probe unit , 203: (terminal) probe tip, 204: toner pellet, 205: sample holding plate

Claims (10)

In toners having toner particles containing vinyl resin, colorants, mold release agents, amorphous polyesters, and crystalline polyesters,
In the cross section of the toner observed with a transmission electron microscope, the vinyl resin constitutes a matrix, and the amorphous polyester and the crystalline polyester form a domain.
In the measurement by a tacking tester having a terminal whose tip in contact with toner is coated with polytetrafluoroethylene, the temperature of the terminal with respect to the toner pellet is set to 200 ° C. and the contact time with the pellet is set to 50 msec. When the integrated value of the toner stress is f1, f1 is 5.9 g · m / sec or less.
When the glass transition temperature at the first temperature rise obtained by the differential scanning calorimetry of the toner is Tg1st (° C.) and the glass transition temperature at the second temperature rise is Tg2nd (° C.), the value of Tg1st is 50. ° C. not less than state, and are 5 ° C. or higher value of Tg1st-Tg2nd,
The amorphous polyester has a monomer unit derived from a linear aliphatic dicarboxylic acid having 6 to 12 carbon atoms and a monomer unit derived from a dialcohol.
The content of monomer units derived from carbon number 6 to 12 of the linear aliphatic dicarboxylic acid, a 50 mol% or less der Rukoto least 10 mol% based on all monomer units derived from carboxylic acids of the non-crystalline polyester Characteristic toner. The toner according to claim 1, wherein f1 is 5.1 g · m / sec or less. The crystalline polyester has a polyester moiety and a vinyl polymer moiety.
The polyester moiety has a structure represented by the following formula (1).
The toner according to claim 1 or 2, wherein the weight average molecular weight (Mw) of the vinyl polymer moiety is 4000 or more and 15000 or less.

In the formula, m is an integer of 4 to 14, and n is an integer of 6 to 16. The toner according to any one of claims 1 to 3, wherein the crystalline polyester is a block polymer having a polyester moiety and a vinyl polymer moiety. In the cross section of the toner observed with a transmission electron microscope,
The domain of the amorphous polyester is present within 25% of the distance between the contour and the center point of the cross section from the contour of the cross section, based on the total area of the domain, 30 area% or more and 70 area% or less. The toner according to any one of claims 1 to 4. In the cross section of the toner observed with a transmission electron microscope,
The domain of the amorphous polyester exists within 50% of the distance between the contour and the center point of the cross section from the contour of the cross section, and is 80 area% or more and 100 area% or less based on the total area of the domain. The toner according to any one of claims 1 to 5. In the cross section of the toner observed with a transmission electron microscope,
The area of the amorphous polyester domain present within 25% of the distance between the contour of the cross section and the center point of the cross section is from the contour of the cross section to the center point of the contour The toner according to any one of claims 1 to 6, which is 1.05 times or more the area of the domain of the amorphous polyester present at 25% to 50% of the distance. The toner according to any one of claims 1 to 7, wherein the number average diameter of the domains of the amorphous polyester is 0.3 μm or more and 3.0 μm or less. The toner according to any one of claims 1 to 8, wherein the acid value of the amorphous polyester is 1.0 mgKOH / g or more and 10.0 mgKOH / g or less. Toner that develops the electrostatic latent image formed on the image carrier,
A developing apparatus having a toner carrier that supports the toner and conveys the toner to the image carrier.
The developing apparatus according to any one of claims 1 to 9 , wherein the toner is the toner according to any one of claims 1 to 9 .

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