JP2009300719A - Method for manufacturing toner - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a toner which is excellent in prevention of contamination in members of an apparatus, cleaning property, low temperature fixability and offset resistance, and provides a fixed image with high gloss upon fixing and a toner image of high picture qualities with excellent durability. <P>SOLUTION: A method for manufacturing a toner includes granulating a monomer composition containing a polymerizable monomer, a colorant, a polymer having a sulfonic acid functional group in an aqueous medium and polymerizing the particles, wherein the composition is polymerized with an oil-soluble initiator and further polymerized by adding a water-soluble initiator when a conversion rate reaches 97.500 to 99.990% at the pH of the aqueous medium equal to or less than 7.00. The polymer having a sulfonic acid functional group is a polymer or a copolymer having a sulfonic acid group, a sulfonate group or a sulfonic acid ester group. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a toner manufacturing method for developing an electrostatic image or a toner jet toner manufacturing method in an image forming method such as electrophotography and electrostatic printing.

  In order to visualize an electric or magnetic latent image on a recording medium, there is an image forming method in which the latent image is visualized using toner. A typical example is electrophotography. In this electrophotographic method, a latent image is electrically formed on a photosensitive member by various means, and then the latent image is developed with toner to form a toner image, and if necessary, transferred to paper or the like. After the toner image is transferred to the material, the toner image is fixed to the transfer material by using a fixing method such as heating, pressurization, heat pressurization, or solvent vapor to obtain an image.

  Considering the recent demands for miniaturization, weight reduction, energy saving, and high reliability, the toner performance cannot be met without further improvement in toner performance such as fixing property, offset resistance, and high durability.

  Conventionally, a toner used for these purposes is generally obtained by a method in which a colorant is melt-mixed in a thermoplastic resin, uniformly dispersed, and then finely pulverized by a fine pulverizer to obtain a toner having a desired particle size by a classifier. Has been used.

  Although these manufacturing methods can produce fairly good toners, there are certain limitations. For example, the colorant-dispersed resin composition must be sufficiently brittle and capable of being finely pulverized with an economically possible production apparatus. However, if the colorant-dispersed resin composition is made brittle, the particle size range of the particles formed when actually pulverized at high speed tends to be widened, and in particular, there is a problem that relatively large particles are included therein.

  Furthermore, such a highly brittle material is more easily pulverized during development. In this method, it is difficult to uniformly and satisfactorily disperse solid fine particles such as a colorant in the resin. Depending on the degree of dispersion, the fog increases, the image density decreases, the toner color mixing property, or the transparency. Cause a drop in Further, exposure of the colorant to the fracture surface of the toner particles may cause fluctuations in the development characteristics of the toner.

  On the other hand, in order to overcome the problems of the toner produced by the pulverization method, a toner production method by a suspension polymerization method has been proposed. In the suspension polymerization method, a monomer composition is obtained by uniformly dissolving or dispersing a polymerizable monomer, a colorant, a polymerization initiator, and, if necessary, a crosslinking agent, a charge control agent, and other additives. Thereafter, the toner is dispersed in an aqueous medium containing a dispersion stabilizer using an appropriate stirrer, and a polymerizable monomer is polymerized to obtain toner particles having a desired particle size (see, for example, Patent Document 1). ).

  Since this method does not include a pulverization step, the toner particles do not need to be brittle, and a soft material can be used, and the colorant is not exposed to the surface of the toner particles. It has characteristics that have sex. In addition, since the classification process can be omitted, the cost reduction effect such as saving energy, shortening the manufacturing time, and improving the process yield is great.

  However, even with such a manufacturing method, unless the surface properties of the toner are further improved, the durability, the resistance to contamination of members, and the charging property that can cope with the recent increase in speed, size, and on-demand cannot be satisfied. It was observed.

  Therefore, a method for producing a suspension-polymerized toner obtained by adding a water-soluble initiator after toner particle generation to have a polyester resin layer on the toner surface and surface-treating with the water-soluble initiator is disclosed. (For example, Patent Document 2).

  However, the toner has some problems as a toner excellent in low temperature fixability, high gloss, wide fixable temperature range, member contamination, and long-term development durability which are currently required.

  In addition, as a toner that achieves both low-temperature fixability and storability of the toner, a water-soluble initiator is added at a specific polymerization conversion rate in the polymerization process, and the toner surface is further coated with a polymer layer (shell) for encapsulation. A method for producing a suspension polymerization toner is disclosed (for example, Patent Document 3).

  However, in these methods, since a water-soluble initiator is added when the polymerization conversion rate is low, there are some problems as a toner excellent in member contamination and environmental stability due to generation of emulsified particles.

Japanese Patent Publication No. 51-14895 Japanese Patent Laid-Open No. 09-50150 JP-A-11-160909

  An object of the present invention is to provide a toner production method that solves the above problems.

  More specifically, a toner manufacturing method that is excellent in member contamination, cleaning property, low-temperature fixing property and offset resistance, can obtain a high gloss fixed image at the time of fixing, and can form a high-quality toner image excellent in durability. It is to provide.

  As a result of intensive studies, the present inventors have found that the above problem can be solved by adopting the following configuration. Specifically, it is excellent in member contamination, cleaning properties, low-temperature fixability and offset resistance, and a high gloss fixed image can be obtained at the time of fixing, and a toner capable of forming a high-quality toner image excellent in durability can be obtained. As a result, the present invention has been completed.

That is, the present invention relates to a toner produced by granulating and polymerizing a monomer composition containing at least a polymerizable monomer, a colorant, and a polymer having a sulfonic acid functional group in an aqueous medium. In the manufacturing method,
Polymerized with an oil-soluble initiator, and polymerized by adding a water-soluble initiator at a pH of the aqueous medium of 7.00 or less when the conversion rate was 97.500 to 99.990%,
The polymer having a sulfonic acid functional group is a polymer or copolymer having a sulfonic acid group, a sulfonic acid group, or a sulfonic acid ester group.

  According to the present invention, a toner manufacturing method that is excellent in member contamination resistance, cleaning property, low-temperature fixing property, and offset resistance, can obtain a high gloss fixed image at the time of fixing, and can form a high-quality toner image excellent in durability. Can be provided.

  Hereinafter, the present invention will be described in detail.

  It is known that environmental stability is improved by using a toner containing a polymer having a sulfonic acid functional group. Conventional techniques have attempted to stabilize the environment by incorporating a polymer having a sulfonic acid functional group into the toner.

  Under high temperature and high humidity, it is preferable to incorporate a resin component having a sulfonic acid functional group in the toner, since the rise of frictional charging is accelerated, and the stability in development is increased. However, there are still some problems with the rising performance of triboelectric charging that can cope with the recent increase in speed, miniaturization, and on-demand, and the photosensitive drum fusing and charging member contamination due to poor cleaning.

  Furthermore, if a large amount of a resin component having a sulfonic acid functional group is contained, the resin component having a sulfonic acid functional group is likely to be segregated or separated in the toner when trying to achieve environmental stability. The segregation of the release agent causes the fixing property to deteriorate. Furthermore, toner materials such as waxes and colorants are difficult to enter into the toner in which the resin component having a sulfonic acid functional group is segregated or separated without being uniformly mixed, which deteriorates development.

  In the present invention, a polymer having a sulfonic acid functional group is contained, polymerized with an oil-soluble initiator (such as an organic peroxide initiator described later), and the conversion rate of the monomer composition is 97.500 to 99. When it is 990%, a water-soluble initiator (such as a persulfate-based initiator described later) is added at a pH of 7.0 or lower to perform polymerization. When the conversion rate of the monomer composition is 97.500 to 99.990% and the pH of the aqueous medium is 7.00 or less, a water-soluble initiator is added to precipitate in the vicinity of the toner surface in the aqueous medium. It is possible to uniformly fix a polymer having a sulfonic acid functional group that is easy to be fixed on the toner surface. Thereby, an effect excellent in environmental stability and cleanability is exhibited.

  The pH when the water-soluble initiator is added to the aqueous medium is 7.00 or less. The pH is preferably 3.00 to 6.50, particularly preferably 4.00 to 6.00. By adding it to an aqueous medium having a pH of 7.00 or less, the salphenyl ion radical easily reacts with the oil-soluble monomer, and the polymer having a sulfonic acid functional group can be uniformly fixed. A toner having excellent fog is obtained. On the other hand, when the pH is higher than 7.00, environmental stability and fogging are deteriorated. When the pH is less than 3.00, the toner tends to agglomerate and the development streak tends to deteriorate. In addition, in this invention, pH when adding the said water-soluble initiator to an aqueous medium can be adjusted with the following acids and bases. As the acid, hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid and the like are used. Examples of the base include ammonium hydroxide, potassium hydroxide, sodium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, ammonium carbonate, ammonium hydrogen carbonate, sodium hydrogen carbonate, sodium phosphate, and other alkaline substances and hydrates thereof. The aqueous solution is mentioned. These substances can be diluted as necessary and used as an aqueous solution having a specific concentration.

  The conversion rate of the monomer composition when the water-soluble initiator is added to the aqueous medium is 97.500 to 99.990%. The conversion rate of the preferable monomer composition is 97.750 to 99.950%, and the conversion rate of the particularly preferable monomer composition is 98.000% to 99.500%. When the conversion rate of the monomer composition is less than 97.500%, environmental stability, photosensitive drum contamination, and development streaks are deteriorated. Probably because of the increased number of emulsified particles. When the conversion rate of the monomer composition is larger than 99.990%, it is considered that the effect of uniformly fixing the polymer having a sulfonic acid functional group on the toner surface is reduced, and the environmental stability is lowered. .

  The polymer having a sulfonic acid functional group used in the present invention is a polymer or copolymer having a sulfonic acid group, a sulfonic acid group, or a sulfonic acid ester group.

  Examples of the polymer or copolymer having a sulfonic acid group, a sulfonic acid group or a sulfonic acid ester group include a polymer compound having a sulfonic acid group in the side chain. In particular, styrene and / or styrene (meta) containing a sulfonic acid group-containing (meth) acrylamide monomer in a copolymerization ratio of 2% by mass or more, preferably 5% by mass or more and having a glass transition temperature (Tg) of 40 to 90 ° C. ) It is preferable to use a polymer compound composed of an acrylate copolymer because the synergistic effect with the water-soluble initiator is further improved.

  As said sulfonic-acid-group-containing (meth) acrylamide type monomer, what can be represented by the following general formula (1) is preferable, and 2-acrylamide-2-methylpropanoic acid and 2-methacrylamide-2-methyl are specifically mentioned. And propanoic acid.

［上記一般式（１）中、Ｒ₁は水素原子、又はメチル基を示し、Ｒ₁とＲ₃は、それぞれ水素原子、Ｃ１乃至Ｃ１０のアルキル基、アルケニル基、アリール基、又はアルコキシ基を示し、ｎは１乃至１０の整数を示す。］

[In the general formula (1), R ₁ represents a hydrogen atom or a methyl group, and R ₁ and R ₃ represent a hydrogen atom, a C1 to C10 alkyl group, an alkenyl group, an aryl group, or an alkoxy group, respectively. , N represents an integer of 1 to 10. ]

  When the polymer having a sulfonic acid group according to the present invention is contained in the toner particles in an amount of 0.1 to 10 parts by mass with respect to 100 parts by mass of the binder resin, the toner is charged in combination with the water-soluble initiator. The state can be made even better.

  The viscosity at 100 ° C. is 5000 Pa · s to 100000 Pa · s, preferably 7000 Pa · s to 45000 Pa · s, more preferably 10,000 Pa · s to 39000, and is excellent in low temperature fixability and image glossiness, and is preferable for low temperature fixability. Is obtained. If it is less than 5000 Pa · s, the gloss is lowered due to the penetration of toner into the medium, which is not preferable. Specifically, as a long-term use, the inorganic fine powder added as an external additive is embedded in the surface of the toner particles, and the toner particles are deformed and the triboelectric charge characteristics become non-uniform. This is not preferable because a phenomenon in which toner adheres to the image portion (hereinafter referred to as fogging) is likely to occur. If it is 100,000 Pa · s or more, the toner particles cannot be sufficiently deformed during the fixing step in high-speed and low-temperature printing, and the toner image is likely to be peeled off when the surface of the fixed image is rubbed. In the present invention, the viscosity at 100 ° C. can be adjusted by the monomer composition ratio, reaction temperature and addition amount during the production of the low molecular weight resin, and the initiator amount, monomer composition ratio and reaction temperature during the production of the binder resin. .

  The viscosity at 100 ° C. correlates with toner fixing properties (gross). By reducing the viscosity change due to the temperature change, it is possible to reduce the gloss unevenness due to the temperature change of the fixing device and the environmental change during use such as temperature and humidity.

  Examples of molecular weight distribution charts measured for the THF soluble content of the preferred toner in the present invention are shown in FIGS.

  In the molecular weight distribution chart measured by GPC-RI of the THF soluble part of the toner, the molecular weight distribution when the molecular weight at the main peak is Mr1 and the height of the peak at that time is h (Mr1) [mV] It was shown in FIG. In the molecular weight distribution chart of FIG. 1, the horizontal axis represents the common logarithm of molecular weight M, and the vertical axis represents the peak height (mV).

  In the molecular weight distribution chart measured by GPC-RI of the THF soluble part of the toner shown in FIG. 1, the molecular weight distribution chart when the peak height is converted as hr1 [mV] = 1.00 is shown in FIG. It was shown to. Accordingly, in FIG. 2, the peak height is expressed in%.

  In FIG. 3, the height of the main peak (the molecular weight of the main peak is Mr1) is indicated by H (Mr1).

  FIG. 3 shows the same molecular weight distribution chart as in FIG. 2. The integrated value in the region where the molecular weight is 300 to 2000 is S1, the integrated value in the region where the molecular weight is 2000 to 15000 is S2, and the molecular weight is 15000 to 1,000,000. The integrated value in the region is indicated by S3.

  In the molecular weight distribution chart measured by GPC-RI of the THF soluble content of the toner, the toner containing a component having a molecular weight in the range of 2000 to 15000 is effective in low-temperature fixability and has a low melt viscosity and a high gloss. An image is obtained.

  In the present invention, in the molecular weight distribution measured by GPC of the THF soluble content in the toner, the integrated value (S1) in the region having a molecular weight of 300 to 2000 and the integrated value (S2) in the region having a molecular weight of 2000 to 15000. ) And the integral value (S3) of the region having a molecular weight of 15,000 to 1,000,000 is S1: S2: S3 = (0.01 to 0.95): 1.00: (1.00 to 8.00) Preferably there is. Since S1: S2: S3 = (0.01 to 0.95): 1.00: (1.00 to 8.00), the components contained in the toner are contained in a well-balanced state. Further improvement in fixing property, offset resistance and high gloss of a fixed image can be achieved. In the present invention, the above S1: S2: S3 can be adjusted by the amount of the low molecular weight resin, the amount of the initiator at the time of producing the binder resin, and the reaction temperature.

  When S2 is 1.00 and S1 is less than 0.01 or S3 exceeds 8.00, the low-temperature fixability may be deteriorated. Conversely, when S1 exceeds 0.95 or S3 is less than 1.00, the offset resistance may be deteriorated.

  More preferably, S1: S2: S3 = (0.15 to 0.80): 1.00: (1.00 to 5.00). If S2 is 1.00 and S1 is less than 0.15 or S3 exceeds 5.00, the low-temperature fixability may be deteriorated. Conversely, when S1 exceeds 0.80 or S3 is less than 1.00, offset resistance and member contamination may deteriorate.

  The toner of the present invention has an endothermic main peak in the range of 40 to 130 ° C. in the endothermic chart measured by differential scanning calorimetry (DSC), and the calorific integral value represented by the peak area of the endothermic main peak. Q is preferably 10 to 35 J per gram of toner. In the present invention, the endothermic main peak can be adjusted by the wax type and the amount of wax.

  As described above, when the polymer having a sulfonic acid functional group is contained and the conversion rate of the monomer composition is 97.500 to 99.990%, the water-soluble initiator is adjusted to pH 7 of the aqueous medium. It is preferable to use a method for producing a toner that is added and polymerized at 0.000 or less. As a result, it is possible to obtain a toner having high performance in terms of cleaning properties, low-temperature fixability, high-temperature offset resistance and environmental stability. Of the configurations defined in the present invention, the endothermic main peak is in the range of 40 to 130 ° C., and the integral value Q expressed by the peak area of the endothermic main peak is 10 to 35 J per 1 g of toner. By containing the amount of the agent, good releasability can be exhibited even at low temperature fixing. Further, a water-soluble initiator is added when a polymer having a highly polar sulfonic acid functional group is contained, the pH of the aqueous medium is 7.00 or less, and the polymerization conversion is 97.500 to 99.990%. By doing so, it is possible to prevent uneven distribution of a release agent having low polarity near the toner surface.

  The calorie integral value Q represented by the peak area of the endothermic main peak can be adjusted by appropriately selecting the type of wax, its content, and the like. The endothermic main peak is more preferably in the range of 50 to 110 ° C., particularly preferably 60 to 90 ° C. Further, the heat quantity integral value Q expressed by the peak area of the endothermic main peak is more preferably 15 to 35 J per 1 g of toner.

  Note that when the heat quantity integral value Q represented by the peak area of the endothermic main peak is less than 10 J per 1 g of toner, the fixability is deteriorated and the gloss of the fixed image is lowered. Further, it is not expected to suppress the fixing member or the like from being scraped or scratched. On the other hand, when the heat quantity integral value Q represented by the peak area of the endothermic main peak exceeds 35 J per 1 g of toner, the plastic effect of the wax becomes too great, and the offset resistance deteriorates and the wax penetrates into the toner surface. Occurrence of member contamination and durability is reduced.

  A production method for producing the toner of the present invention is a method for producing a toner directly in a medium (hereinafter also referred to as a polymerization method) such as a suspension polymerization method, an interfacial polymerization method and a dispersion polymerization method. preferable. The toner obtained by this polymerization method (hereinafter also referred to as “polymerized toner”) has high transferability because the shape of individual toner particles is almost spherical and the distribution of charge amount is relatively uniform. In particular, among the above polymerization methods, a suspension polymerization method is preferable as a production method for producing the toner of the present invention.

  The suspension polymerization method will be described below.

In the present invention, the suspension polymerization method is a method in which a polymerizable monomer composition containing at least a polymerizable monomer and a colorant is dispersed in an aqueous medium to produce droplets of the polymerizable monomer composition. A polymerization method for producing toner particles through at least a granulation step of polymerizing and a polymerization step of polymerizing the polymerizable monomer in the droplets. As will be described later, a wax, a polar resin, and a low molecular weight resin can be added to the polymerizable monomer composition as desired. Further, the weight average molecular weight (Mw) of the THF-soluble component of the low molecular weight resin determined by GPC is preferably 2000 to 6000 from the viewpoint of low-temperature fixability and blocking resistance.

  In the toner of the present invention, the resin component may have a reactive functional group for the purpose of improving the viscosity change of the toner at a high temperature. For example, a double bond, an isocyanate group, etc. are raised.

  In the production of the toner of the present invention, a polar resin may be added to the polymerizable monomer composition for the purpose of improving the shape of the toner particles, the dispersibility and fixing properties of the material, or the image characteristics. it can. For example, hydrophilic functions such as amino groups, carboxylic acid groups, hydroxyl groups, sulfonic acid groups, glycidyl groups, and nitrile groups cannot be used because monomers are water-soluble and dissolve in aqueous suspension to cause emulsion polymerization. When it is desired to introduce a monomer component containing a group into the toner, a random copolymer of these and a vinyl compound such as styrene or ethylene, a copolymer such as a block copolymer, and a graft copolymer, a polyester, and a polyamide Can be used in the form of polycondensates such as, or addition polymers such as polyethers and polyimines.

  In addition to the above, low molecular weight resins that can be added to the polymerizable monomer composition include, for example, styrene such as polystyrene and polyvinyltoluene, and homopolymers of substituted products thereof; styrene-propylene copolymer, styrene- Vinyl toluene copolymer, styrene-vinyl naphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, Styrene-dimethylaminoethyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-dimethylaminoethyl methacrylate copolymer, styrene -Vinyl methyl ether copolymer, styrene-bi Styrene-based copolymers such as ruethyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-maleic acid copolymer, styrene-maleic acid ester copolymer Copolymer: polymethyl methacrylate, polybutyl methacrylate, polyvinyl acetate, polyethylene, polypropylene, polyvinyl butyral, silicone resin, polyester resin, polyamide resin, epoxy resin, polyacrylic resin, rosin, modified rosin, terpene resin, phenolic resin, Aliphatic or alicyclic hydrocarbon resins, aromatic petroleum resins and the like can be used alone or in combination.

  Among the low molecular weight resins, the glass transition point of the low molecular weight resin is preferably 40 to 100 ° C. When the glass transition point is less than 40 ° C., the strength of the entire toner particles is lowered, and the transferability and development characteristics are liable to be lowered during a multi-endurance test. Further, the toner particles are aggregated in a high-temperature and high-humidity environment, resulting in a problem that storage stability is lowered. On the other hand, if the glass transition point exceeds 100 ° C., the problem of poor fixing tends to occur.

  The glass transition point of the low molecular weight resin is more preferably 40 to 70 ° C., particularly preferably 40 to 65 ° C., from the viewpoint of low temperature fixability and high gloss image.

  The addition amount of the low molecular weight resin is preferably 0.1 to 75 parts by mass in 100 parts by mass of the binder resin in the toner particles. When the amount is less than 0.1 part by mass in 100 parts by mass of the binder resin in the toner particles, the effect of adding the low molecular weight resin is small.

The toner of the present invention preferably contains an addition reactive resin having a double bond. In producing the toner of the present invention, an addition reactive resin having a double bond is preferably used. As the addition-reactive resin having a double bond, a styrene resin is preferable. For example, in a styrene resin produced by polymerization at a high temperature of 180 ° C. or more, double bonds of 4.6 to 4.9 ppm and 5.0 to 5.2 ppm are measured in ¹ H-NMR measurement using a deuterated chloroform solvent. A peak derived from is observed. That is, the addition-reactive resin obtained as described above has double bonds, and these double bonds are crosslinked during the production of toner particles. Thus, by introducing a small amount of a crosslinked structure in the toner particles, the rate of change in the viscosity of the toner at a high temperature can be reduced more effectively. Furthermore, when the weight average molecular weight of the addition-reactive resin is 1500 to 5000, the molecular weight is higher and the reactivity is milder than a conventionally used low-molecular crosslinking agent such as divinylbenzene. By finely cross-linking, a toner having a thermal characteristic with a low viscosity and a small viscosity change rate depending on temperature can be obtained.

  The number-average molecular weight of the addition-reactive resin having a double bond is preferably 500 or more and less than 3000. When the number average molecular weight of the addition-reactive resin is smaller than 500, there are many components having a small molecular weight, and the storage stability deteriorates due to the oozing out. On the other hand, when the number average molecular weight is larger than 3000, the low-temperature fixability is lowered. In the present invention, the number average molecular weight of the addition-reactive resin can be measured by GPC. In the present invention, the number average molecular weight of the addition-reactive resin can be adjusted by the amount of solvent, the type of solvent, the reaction temperature, and the amount of initiator when the addition-reactive resin is produced.

  The glass transition point of the addition-reactive resin is preferably 40 to 100 ° C. When the glass transition point is less than 40 ° C., the strength of the whole toner particles is lowered, and the transferability and development characteristics are liable to be lowered during a multi-endurance test. Further, the toner particles are aggregated in a high-temperature and high-humidity environment, resulting in a problem that storage stability is lowered. On the other hand, if the glass transition point exceeds 100 ° C., the problem of poor fixing tends to occur.

  The glass transition point of the addition-reactive resin is more preferably 40 to 70 ° C., particularly preferably 40 to 65 ° C., from the viewpoints of low temperature fixability and high gloss image.

  The addition amount of the addition reactive resin is preferably 0.1 to 75 parts by mass in 100 parts by mass of the binder resin in the toner particles. When the amount is less than 0.1 part by mass in 100 parts by mass of the binder resin in the toner particles, the effect of adding the addition reactive resin is small.

  The toner of the present invention is preferably a toner containing toner particles having at least a core portion and a shell portion and an inorganic fine powder. The toner particles have a shell portion so as to cover the core portion. By adopting such a structure, it is possible to prevent charging failure and blocking in each environment due to deposition of the core portion on the toner surface. The presence of this surface layer portion can improve environmental stability, durability, and blocking resistance.

  The material constituting the surface layer portion preferably has a molecular chain polar structure. In the present invention, the molecular chain polar structure refers to a molecular structure in which atoms in the molecule have many δ + or δ− electron density states.

  Resin molecules are composed of a plurality of types of atoms, and the constituent atoms have inherent electronegativity, and the values differ greatly depending on the atoms. Due to this difference in electronegativity, electrons are localized in the molecule. In this localization, the state changes depending on the type, number, and bonding mode of the atoms to be configured, and the polarity of the molecular chain changes.

  What is preferable as the molecular chain polar structure is, for example, a bond structure formed by condensation polymerization or addition polymerization. Specifically, ester bonds (—COO—), ether bonds (—O—), amide bonds (—CONH—), imine bonds (—NH—), urethane bonds (—NHCOO—), urea bonds ( -NHCONH-).

For example, in an ether chain (—CH ₂ —O—CH ₂ —) or the like, electrons on the carbon atom are slightly deficient (δ ⁺ ), and electrons on the oxygen atom are slightly excessive (δ ⁻ ). Furthermore, a bond angle with an oxygen atom as a vertex is in a state. Thus, if there are many polarized molecular chains, the polarity of the molecule, that is, the resin will increase, and if there are few polarized molecular chains, it will decrease. In general, molecules composed of hydrocarbons have low polarity.

  When the surface layer portion has a molecular chain polar structure, charging stability is improved. In addition, when toner particles are produced in a polar solvent such as an aqueous or hydrophilic medium, the surface layer portion having a molecular chain polar structure is more uniformly formed in the vicinity of the toner surface. Underlying charging stability and durability during high-speed printing are improved.

  The toner of the present invention preferably contains a polyester resin. As the polyester resin, a styrene-modified polyester resin is preferably used.

  Examples of the surface layer portion that is particularly preferably used in the present invention include a polyester resin or a derivative thereof.

  Preferred examples of the polymerizable monomer that can be used to produce the toner particles of the present invention include vinyl-based polymerizable monomers. For example, styrene; α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p-tert-butylstyrene, p Styrene derivatives such as -n-hexyl styrene, pn-octyl, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p-methoxy styrene, p-phenyl styrene; methyl acrylate, Ethyl acrylate, n-propyl acrylate, iso-propyl acrylate, n-butyl acrylate, iso-butyl acrylate, tert-butyl acrylate, n-amyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, n- Acrylic polymerizable monomers such as nonyl acrylate, cyclohexyl acrylate, benzyl acrylate, dimethyl phosphate ethyl acrylate, diethyl phosphate ethyl acrylate, dibutyl phosphate ethyl acrylate, 2-benzoyloxyethyl acrylate; methyl methacrylate, ethyl methacrylate, n -Propyl methacrylate, iso-propyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, tert-butyl methacrylate, n-amyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, n-nonyl methacrylate, diethyl Phosphate ethyl methacrylate, dibutyl phosphate Methacrylic polymerizable monomers such as methyl methacrylate; methylene aliphatic monocarboxylic acid esters; vinyl acetate, vinyl propionate, vinyl benzoate, vinyl butyrate, vinyl benzoate, vinyl formate; vinyl methyl ether; And vinyl ethers such as vinyl ethyl ether and vinyl isobutyl ether; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and vinyl isopropyl ketone.

  The shell portion of the toner of the present invention is composed of a vinyl polymer formed from these vinyl polymerizable monomers and an added resin. Among these vinyl polymerizable monomers, a styrene polymer, a styrene-acrylic copolymer, or a styrene-methacrylic copolymer is used from the viewpoint of efficiently covering the wax mainly forming the inside or the central portion. Is preferred.

  The material constituting the core of the toner of the present invention is preferably wax. The wax component usable in the toner according to the present invention includes paraffin wax, microcrystalline wax, petroleum wax such as petrolatum and derivatives thereof, montan wax and derivatives thereof, hydrocarbon wax and derivatives thereof according to the Fischer-Tropsch method, polyethylene, Polyolefin waxes such as polypropylene and derivatives thereof, natural waxes such as carnauba wax and candelilla wax and derivatives thereof, and the like include oxides, block copolymers with vinyl monomers, and graft modified products. In addition, fatty acids such as higher aliphatic alcohols, stearic acid and palmitic acid, or compounds thereof, acid amide waxes, ester waxes, ketones, hydrogenated castor oil and derivatives thereof, plant waxes, animal waxes, and silicone resins. Can be used.

  In particular, ester waxes having at least one long-chain ester moiety having 10 or more carbon atoms represented by the following formulas (2) to (7) can improve transparency of an overhead projector transparency film (OHP film). It is preferable without inhibition.

（式中、ａ及びｂは独立して０乃至４の整数を示し、ａ＋ｂは４であり、Ｒ¹及びＲ²は独立して炭素数が１乃至４０の有機基を示し、ｎ及びｍは独立して０乃至１５の整数を示し、ｎとｍが同時に０になることはない。）

(Wherein, a and b independently represent an integer of 0 to 4, a + b is 4, R ¹ and R ² independently represent an organic group having 1 to 40 carbon atoms, and n and m are Independently represents an integer of 0 to 15, and n and m are not 0 at the same time.)

（式中、ａ及びｂは独立して１乃至３の整数を示し、ａ＋ｂは４であり、Ｒ¹は炭素数が１乃至４０の有機基を示しｎ及びｍは独立して０乃至１５の整数を示し、ｎとｍが同時に０になることはない。）

(Wherein, a and b independently represent an integer of 1 to 3, a + b is 4, R ¹ represents an organic group having 1 to 40 carbon atoms, and n and m independently represent 0 to 15) Indicates an integer, and n and m are not 0 at the same time.)

（式中、ａ及びｂは独立して０乃至３の整数を示し、ａ＋ｂは２または３であり、Ｒ¹及びＲ²は独立して炭素数が１乃至４０の有機基を示し、且つＲ¹とＲ²との炭素数差が１０以上である基を示し、Ｒ³は炭素数が１以上の有機基を示し、ｃは２または１であり、ａ＋ｂ＋ｃ＝４であり、ｎ及びｍは独立して０乃至１５の整数を示し、ｎとｍが同時に０になることはない。）

(Wherein, a and b independently represent an integer of 0 to 3, a + b is 2 or 3, R ¹ and R ² independently represent an organic group having 1 to 40 carbon atoms, and R ¹ and the number of carbon atoms difference between R ² represents a group of 10 or more, R ³ represents one or more organic groups having a carbon number, c is 2 or 1, a + b + c = a 4, n and m are Independently represents an integer of 0 to 15, and n and m are not 0 at the same time.)

（式中、Ｒ¹及びＲ²は炭素数が１乃至４０の炭化水素基を示し、且つＲ¹及びＲ²は、お互いに同じでも異なる炭素数でもよい。）

(Wherein R ¹ and R ² represent a hydrocarbon group having 1 to 40 carbon atoms, and R ¹ and R ² may be the same or different from each other.)

（式中、Ｒ¹及びＲ²は炭素数が１乃至４０の炭化水素基を示し、ｎは２乃至２０の整数であり、且つＲ¹及びＲ²は、お互いに同じでも異なる炭素数でもよい。）

(Wherein R ¹ and R ² represent a hydrocarbon group having 1 to 40 carbon atoms, n is an integer of 2 to 20, and R ¹ and R ² may be the same or different from each other) .)

（式中、Ｒ¹及びＲ²は炭素数が１乃至４０の炭化水素基を示し、ｎは２乃至２０の整数であり、且つＲ¹及びＲ²は、お互いに同じでも異なる炭素数でもよい。）

(Wherein R ¹ and R ² represent a hydrocarbon group having 1 to 40 carbon atoms, n is an integer of 2 to 20, and R ¹ and R ² may be the same or different from each other) .)

  As the molecular weight of the wax, those having a weight average molecular weight (Mw) of 300 to 1500 are preferable. If it is less than 300, the wax is likely to be exposed to the toner particle surface, and if it exceeds 1500, the low-temperature fixability is deteriorated. Particularly preferred is a range of 400 to 1250. Furthermore, when the ratio of the weight average molecular weight / number average molecular weight (Mw / Mn) is 1.5 or less, the peak of the DSC endothermic curve of the wax becomes sharper, and the mechanical strength of the toner particles at room temperature is improved. Particularly excellent toner characteristics exhibiting sharp melting characteristics upon fixing can be obtained.

  Specific examples of the ester wax include compounds represented by the following formula.

  In recent years, the need for full-color double-sided images has increased, and when a double-sided image is formed, the toner image on the transfer material first formed on the front surface is also used when the next image is formed on the back surface. In this case, it is necessary to sufficiently consider the high-temperature offset resistance of the fixed image of the toner. Specifically, it is preferable to add 2 to 30% by mass of wax in the toner particles. When the content is less than 2% by mass, the high temperature offset resistance is lowered, and further, the image on the back surface may show an offset phenomenon when fixing a double-sided image. When the amount is more than 30% by mass, toner particles are likely to be coalesced during granulation in the production by the polymerization method, and those having a wide particle size distribution are likely to be generated.

  In the toner of the present invention, the average circularity of toner particles of 2 μm or more in a number-based equivalent circle diameter-circularity scattergram measured by a flow type particle image measuring apparatus is 0.970 or more and 1.000 or less. -The circularity is preferably 0.98 or more and 1.00 or less.

  Here, “circularity” in the present invention is used as a simple method for quantitatively expressing the shape of the particles. In the present invention, flow type particle image analyzer FPIA-2100 manufactured by Toa Medical Electronics is used. The value obtained from the following equation is defined as circularity.

（Ｌ₀；粒子像と同じ投影面積をもつ円の周囲長、Ｌ；粒子の投影像の周囲長）

(L ₀ : Perimeter of a circle having the same projected area as the particle image, L: Perimeter of the projected image of the particle)

  The circularity in the present invention is an index of the degree of unevenness of the toner, and when the toner is a perfect sphere, the circularity is 1.00, and the circularity becomes smaller as the surface shape becomes more complicated.

  A toner having an average circularity of 0.970 to 1.000 is preferred because it has excellent transferability. This is presumably because the contact area between the toner and the photoconductor is small and the adhesion force of the toner to the photoconductor due to mirror image force, van der Waals force, etc. is reduced. Therefore, if such a toner is used, the transfer rate is high and the residual toner is greatly reduced. Therefore, the toner in the pressure contact portion between the charging member and the photosensitive member is very little, toner fusion is prevented, and image defects are prevented. It is considered to be significantly suppressed.

  These effects are more prominent in an image forming method including a contact transfer process in which transfer loss is likely to occur.

  In the circularity distribution of the toner, when the mode circularity is 0.98 to 1.00, it means that most of the toner particles have a shape close to a true sphere. The decrease in the adhesion force of the toner to the photoreceptor due to the mirror image force, van der Waals force, etc. becomes more remarkable, and the transfer efficiency becomes very high, which is preferable.

  Here, the mode circularity is a circularity from 0.40 to 1.00, 0.40 or more and less than 0.41, 0.41 or more and less than 0.42,... Or more and less than 1.00 and It is divided into 61 every 0.01 as 1.00, and the measured circularity of each particle is assigned to each divided range, and the circularity of the divided range where the frequency value is maximum in the circularity frequency distribution is said.

  In the present invention, it is preferable to add a charge control agent to the toner for the purpose of controlling the chargeability of the toner.

  Of these known charge control agents, those having little polymerization inhibition and aqueous phase transfer are preferred. Examples of the positive charge control agent include nigrosine dyes, triphenylmethane dyes, quaternary ammonium salts, guanidine derivatives, imidazole derivatives, amine compounds, and the like. Examples of the negative charge control agent include metal-containing monoazo dye compounds and urea derivatives.

  The addition amount of these charge control agents is preferably 0.1 to 10% by mass of the binder resin or polymerizable monomer.

  In the present invention, it is preferable to add a negative charge control resin to the toner for the purpose of controlling the chargeability of the toner. Examples of the negative charge control resin include a polymer having a sulfonic acid functional group, a metal-containing salicylic acid copolymer, a styrene-acrylic acid copolymer, and a styrene-methacrylic acid copolymer.

  The addition amount of these charge control resins is preferably 0.1 to 10% by mass of the binder resin or polymerizable monomer.

  Examples of the polymerization initiator used when the toner particles are produced by a polymerization method include 2,2′-azobis- (2,4-divaleronitrile), 2,2′-azobisisobutyronitrile, 1,1 ′. -Azo- or diazo-based polymerization initiators such as azobis (cyclohexane-1-carbonitrile), 2,2'-azobis-4-methoxy-2,4-dimethylvaleronitrile, azobisisobutyronitrile; benzoyl peroxide And organic peroxide polymerization initiators such as methyl ethyl ketone peroxide, diisopropyloxycarbonate, cumene hydroperoxide, 2,4-dichlorobenzoyl peroxide and lauroyl peroxide. These polymerization initiators are preferably added in an amount of 0.5 to 20% by mass relative to the polymerizable monomer, and may be used alone or in combination.

  Further, the toner of the present invention is preferably polymerized with a polymerizable monomer composition using, as an initiator, an organic peroxide having a 10-hour half-life temperature exceeding 50 ° C. as an oil-soluble initiator. When an organic peroxide having a temperature of 50 ° C. or lower is used as an initiator, the reaction is difficult to control due to the remarkable decomposition rate of the initiator. For this reason, there is a strong tendency for the toner particles to have ultra-low molecular weight components locally, which may cause deterioration of charging uniformity and the occurrence of fusion of the photosensitive drum, particularly in a high temperature and high humidity environment.

  Further, the oil-soluble initiator is t-butyl peroxypivalate (10-hour half-life temperature 54.6 ° C.), t-butyl peroxy-2-ethylhexanoate (10-hour half-life temperature 72.1 ° C. ), T-butyl peroxyisobutyrate (10 hour half-life temperature 77.3 ° C.).

  This is presumably because these oil-soluble initiators are decomposed and part of them generate t-butanol by the hydrogen abstraction reaction, thereby being more uniformly dispersed in the toner binder resin.

  Water-soluble initiators include ammonium persulfate, potassium persulfate, 2,2′-azobis (N, N′-dimethyleneisobutyroamidine) hydrochloride, 2,2′-azobis (2-aminodinopropane) hydrochloric acid Salts, sodium azobis (isobutylamidine) hydrochloride, sodium 2,2′-azobisisobutyronitrile sulfonate, ferrous sulfate or hydrogen peroxide. In particular, potassium persulfate is preferable.

  This is because the decomposition product of the initiator is an ionic sulfonyl ion, and when the pH is 7.0 or less in an aqueous medium, the sulfenyl ion radical easily reacts with the oil-soluble monomer. Conceivable.

  The binder resin for the toner particles is preferably a vinyl resin. The vinyl resin is produced by polymerization of the vinyl polymerizable monomer described above.

  In order to control the molecular weight of the binder resin of the toner particles, a chain transfer agent may be added. A preferable addition amount is 0.001 to 15% by mass of the polymerizable monomer.

  In order to control the molecular weight of the binder resin of the toner particles, a crosslinking agent may be added. For example, as a crosslinkable monomer, bifunctional crosslinking agents include divinylbenzene, bis (4-acryloxypolyethoxyphenyl) propane, ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol. Diacrylate, 1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 200, # 400 , # 600 diacrylate, dipropylene glycol diacrylate, polypropylene glycol diacrylate, polyester type diacrylate (MANDA Japan Drugs), and those that were changed to methacrylate or acrylate.

  Polyfunctional crosslinkable monomers include pentaerythritol triacrylate, trimethylol ethane triacrylate, trimethylol propane triacrylate, tetramethylol methane tetraacrylate, oligoester acrylate and its methacrylate, 2,2-bis (4-methacryloxy polyethoxy Phenyl) propane, diacrylphthalate, triallyl cyanurate, triallyl isocyanurate, triallyl trimellitate, diaryl chlorendate and the like. A preferable addition amount is 0.001 to 15% by mass of the polymerizable monomer.

  In the case of an aqueous dispersion medium, as a dispersion stabilizer for particles of the polymerizable monomer composition, for example, tricalcium phosphate, magnesium phosphate, zinc phosphate, aluminum phosphate, calcium carbonate, magnesium carbonate, hydroxide Fine powders of inorganic compounds such as calcium, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate, bentonite, silica, and alumina may be added.

In the present invention, various additives shown below can be included in addition to the above for the purpose of imparting various properties. The additive preferably has a particle size of 1/10 or less of the weight average particle size of the toner particles in view of durability when added to the toner particles. The particle size of the additive means the average particle size obtained by observing the surface of the toner particles with an electron microscope. As additives for the purpose of imparting these characteristics, for example, the following are used.
1) Fluidity imparting agent: metal oxide (for example, silica, alumina, titanium oxide), carbon black and carbon fluoride. Each of them is more preferably hydrophobized.
2) Abrasive: metal oxide (eg strontium titanate, cerium oxide, alumina, magnesium oxide, chromium oxide), nitride (eg silicon nitride), carbide (eg silicon carbide), metal salt (eg calcium sulfate, barium sulfate) , Calcium carbonate).
3) Lubricant: Fluorine resin powder (for example, vinylidene fluoride, polytetrafluoroethylene), fatty acid metal salt (for example, zinc stearate, calcium stearate).
4) Charge controllable particles: metal oxides (for example, tin oxide, titanium oxide, zinc oxide, silica, alumina), carbon black.

  These additives are preferably used in an amount of 0.1 to 10.0 parts by weight, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the toner particles. These additives may be used alone or in combination.

  The toner of the present invention preferably has a weight average particle diameter (D4) of 2.0 to 12.0 μm, and more preferably has a weight average particle diameter (D4) of 4.0 to 9.0 μm. More preferably, it has a weight average particle diameter (D4) of 5.0 to 8.0 μm.

  The glass transition point (Tg) of the toner of the present invention is 40 to 100 ° C., preferably 40 to 80 ° C. More preferably, it is 45 to 70 ° C. When the glass transition point is lower than 40 ° C., the blocking resistance of the toner is lowered. When the glass transition point exceeds 100 ° C., the low temperature offset resistance of the toner and the transparency of the transmitted image of the overhead projector film are deteriorated.

  The THF-insoluble content of the toner of the present invention is 0.0% by mass or more and less than 16.0% by mass, more preferably 0.0% by mass or more and 10% by mass with respect to toner components other than the toner colorant and inorganic fine powder. Less than 0.0% by mass, most preferably 0.0% by mass or more and less than 5.0% by mass. When it is larger than 16.0% by mass, the low-temperature fixability is lowered.

  The THF-insoluble content of the toner refers to the mass ratio of the ultra-high molecular weight polymer component (substantially crosslinked polymer) that has become insoluble in the THF solvent. The THF-insoluble content of the toner is defined by the values measured as follows.

1.0 g of toner is weighed (W1 g), placed in a cylindrical filter paper (for example, No. 86R manufactured by Toyo Filter Paper), passed through a Soxhlet extractor, and extracted for 20 hours using 200 ml of THF as a solvent. After the soluble component extracted by the solvent is evaporated, it is vacuum-dried at 40 ° C. for several hours, and the amount of the THF-soluble resin component is weighed (W2 g). The weight of a component other than the resin component such as a pigment in the toner is (W3 g). The THF-insoluble content can be obtained from the following formula.
THF insoluble matter (mass%) = (W1− (W3 + W2)) / (W1−W3) × 100

  The THF insoluble content of the toner can be adjusted by the degree of polymerization and the degree of crosslinking of the binder resin.

  In the present invention, the weight average molecular weight (Mw) in gel permeation chromatography (GPC) of the soluble portion of tetrahydrofuran (THF) in the toner is 15000 to 80000. Such toner exhibits good environmental stability and durability stability. Further, it is preferable that the weight average molecular weight in gel permeation chromatography (GPC) of the soluble portion of tetrahydrofuran (THF) in the toner is 20,000 to 50,000. If the weight average molecular weight in the gel permeation chromatography (GPC) of the soluble content of tetrahydrofuran (THF) in the toner is less than 15000, the blocking resistance and durability tend to be poor. And high gloss images are difficult to obtain.

  In the present invention, the ratio Mw / Mn of the weight average molecular weight and the number average molecular weight in gel permeation chromatography (GPC) of the soluble portion of tetrahydrofuran (THF) in the toner is preferably 5 to 100. When Mw / Mn is less than 5, the fixable temperature range is narrow, and when it exceeds 100, the low-temperature fixability is deteriorated.

  In the present invention, polyvinyl alcohol, gelatin, methylcellulose, methylhydroxypropylcellulose, ethylcellulose, sodium salt of carboxymethylcellulose, polyacrylic acid, and salts thereof as dispersion stabilizers used when a toner is manufactured using a polymerization method, An organic compound such as polymethacrylic acid, a salt thereof, and starch may be used. These dispersion stabilizers are preferably used in an amount of 0.2 to 20.0 parts by mass with respect to 100 parts by mass of the polymerizable monomer.

  When an inorganic compound is used in the dispersion stabilizer, a commercially available one may be used as it is, but the inorganic compound may be produced in an aqueous dispersion medium in order to obtain fine particles. For example, in the case of calcium phosphate, a sodium phosphate aqueous solution and a calcium chloride aqueous solution may be mixed with high stirring.

  For fine dispersion of the dispersion stabilizer, 0.001 to 0.1 parts by mass of a surfactant may be used with respect to 100 parts by mass of the polymer monomer. This is to promote the initial action of the dispersion stabilizer. Specific examples include sodium dodecylbenzene sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, sodium laurate, sodium octylate, sodium stearate, and calcium oleate.

  As the colorant used in the present invention, a known colorant can be used.

  For example, examples of the black pigment include carbon black, aniline black, nonmagnetic ferrite, and magnetite.

  Examples of yellow pigments include condensed iron azo compounds such as yellow iron oxide, navel yellow, naphthol yellow S, hanzer yellow G, hanzer yellow 10G, benzidine yellow G, benzidine yellow GR, quinoline yellow lake, permanent yellow NCG, tartrazine lake, Isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds are used. Specifically, C.I. I. Pigment Yellow 12, 13, 14, 15, 17, 62, 74, 83, 93, 94, 95, 109, 110, 111, 128, 129, 147, 155, 168, 180, etc. are preferably used.

  Examples of the orange pigment include permanent orange GTR, pyrazolone orange, vulcan orange, benzidine orange G, indanthrene brilliant orange RK, and indanthrene brilliant orange GK.

  Red pigments include Bengala, Permanent Red 4R, Resol Red, Pyrazolone Red, Watching Red Calcium Salt, Lake Red C, Lake D, Brilliant Carmine 6B, Brilliant Carmine 3B, Eoxin Lake, Rhodamine Lake B, Alizarin Lake, etc. Examples include azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, and perylene compounds. Specifically, C.I. I. Pigment Red 2, 3, 5, 6, 7, 23, 48: 2, 48: 3, 48: 4, 57: 1, 81: 1, 122, 144, 146, 166, 169, 177, 184, 185, 202, 206, 220, 221, 254 are particularly preferred.

  Blue pigments include alkali blue lake, Victoria blue lake, phthalocyanine blue, metal-free phthalocyanine blue, phthalocyanine blue partial chloride, first sky blue, indanthrene blue BG and other copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds, basic dyes Examples include lake compounds. Specifically, C.I. I. Pigment Blue 1, 7, 15, 15: 1, 15: 2, 15: 3, 15: 4, 60, 62, 66 and the like are particularly preferable.

  Examples of purple pigments include fast violet B and methyl violet lake.

  Examples of the green pigment include Pigment Green B, Malachite Green Lake, and Final Yellow Green G. Examples of white pigments include zinc white, titanium oxide, antimony white, and zinc sulfide.

  These colorants can be used alone or in combination, and further in a solid solution state.

  In the present invention, in order to produce toner particles using a polymerization method, it is necessary to pay attention to the polymerization inhibitory property and dispersion medium transferability of the colorant. If necessary, the surface may be modified by subjecting the colorant to a surface treatment with a substance that does not inhibit polymerization. In particular, since dyes and carbon black often have polymerization inhibiting properties, care must be taken when using them.

  As a preferred method for treating the dye, a polymerizable monomer is previously polymerized in the presence of these dyes, and the resulting colored polymer is added to the polymerizable monomer composition. Moreover, about carbon black, you may process with the substance (for example, organosiloxane etc.) which reacts with the surface functional group of carbon black besides the process similar to the said dye.

  The toner of the present invention can be used for both non-magnetic toner and magnetic toner. When the toner of the present invention is used as a magnetic toner, magnetic powder may be contained therein. As such magnetic powder, a substance that is magnetized in a magnetic field is used. For example, a powder of a ferromagnetic metal such as iron, cobalt, or nickel, or a powder of magnetic iron oxide such as magnetite or ferrite is used. is there.

  When obtaining magnetic toner particles using a polymerization method, it is necessary to pay attention to the polymerization inhibitory property and dispersion medium transferability of the magnetic material. If necessary, surface modification (for example, surface treatment with a material that does not inhibit polymerization) ) Is preferable.

  During the production process of the toner particles, the temperature may be raised in the latter half of the polymerization reaction, or a part of the dispersion medium may be distilled off from the reaction system in the latter half of the reaction or after the completion of the polymerization reaction. After completion of the reaction, the produced toner particles are washed, collected by filtration, and dried.

  In the suspension polymerization method, it is preferable to use 300 to 3,000 parts by weight of water as a dispersion medium with respect to 100 parts by weight of the polymerizable monomer composition.

  In the fixing of the toner of the present invention, the fixable temperature region is a temperature region between the low temperature offset end temperature and the high temperature offset start temperature.

A method for measuring and evaluating physical properties relating to the toner of the present invention will be described below.
<Measurement of molecular weight>
The chart of the molecular weight distribution of the THF soluble content of the toner of the present invention is measured under the following measurement conditions using a GPC measuring apparatus (HLC-8120 GPC manufactured by Tosoh Corporation).

<Measurement conditions>
Column (manufactured by Showa Denko KK): Shodex GPC KF-801, Shodex GPC KF-802, Shodex GPC KF-803, Shodex GPC KF-804, Shodex GPC KF-805, Shodex GPC KF-806, G 807 (diameter 8.0mm, length 30cm) 7 stations ・ Temperature: 40 ℃
・ Flow rate: 0.6ml / min
・ Detector: RI
Sample concentration: 10 μl of 0.1% by mass sample

  Sample preparation is performed by placing a toner sample to be measured in tetrahydrofuran (THF), allowing it to stand for 6 hours, and then shaking it sufficiently (until the sample is no longer integrated), and then allowing it to stand for 1 day or longer. And let what passed the sample processing filter (pore size 0.45 micrometer) be a sample for GPC measurement. The calibration curve uses a molecular weight calibration curve created with a monodisperse polystyrene standard sample.

<DSC measurement>
In the present invention, M-DSC (trade name, manufactured by TA Instruments) was used as a differential scanning calorimeter (DSC). Weigh accurately 6 mg of the toner sample to be measured. This is put in an aluminum pan, and an empty aluminum pan is used as a reference, and measurement is performed at a temperature increase rate of 1 ° C./min and normal temperature and humidity in a measurement temperature range of 20 ° C. to 200 ° C. Measurement is performed at a modulation amplitude of ± 0.5 ° C. and a frequency of 1 / min. The maximum glass transition point Tg (° C.) is calculated from the obtained reversing heat flow curve. Tg is obtained as Tg (° C.) as the center value of the intersection of the baseline before and after endotherm and the tangent of the curve due to endotherm.

  In addition, in the endothermic chart at the time of temperature rise measured by DSC, the calorific value integrated value Q (J / g) obtained by converting the endothermic amount (J) represented by the peak area of the endothermic main peak into the amount of heat per 1 g of toner is measured. did. An example of a reversing heat flow curve obtained by DSC measurement of the toner is shown in FIG. The calorie integral value Q (J / g) is obtained using the reversing heat flow curve obtained from the above measurement. For the calculation, analysis software Universal Analysis Ver. Using 2.5H (manufactured by TA Instruments) and using the function of Integral PeakLinear, the heat value integral value Q (J / g) from the region surrounded by the straight line connecting the measurement points at 35 ° C and 135 ° C and the endothermic curve Ask for.

<Measurement of polymerization conversion>
The amount of residual styrene monomer in the toner is measured by gas chromatography (GC) as follows.

  For the measurement, a polymerization inhibitor was added to 1 g of suspension (exactly), and measurement was performed by gas chromatography using an internal standard method.

  Weigh accurately about 1 g of the suspension into a sample bottle. About 10 g of acetone and 0.01 g of toluene precisely weighed are added to this, and the mixture is well mixed. A desktop ultrasonic cleaner with an oscillation frequency of 42 kHz and an electric output of 125 W (for example, trade name “B2510J- MTH ”(manufactured by Branson) is irradiated with ultrasonic waves for 30 minutes. Thereafter, filtration is performed using a solvent-resistant membrane filter “Maesori Disc” (manufactured by Tosoh Corporation) having a pore diameter of 0.2 μm, and 2 μl of the filtrate is analyzed by gas chromatography. And the residual amount of a residual styrene monomer is computed with the analytical curve created beforehand using styrene and toluene.

The measurement apparatus and measurement conditions are as follows.
GC: HP 6890GC
Column: HP INNOWax (200 μm × 0.40 μm × 25 m)
Carrier gas: He (constant pressure mode: 20 psi)
Oven: (1) Hold at 50 ° C. for 10 minutes, (2) Increase to 200 ° C. at 10 ° C./min, (3) Hold at 200 ° C. for 5 minutes Inlet: 200 ° C., pulsed splitless mode (20 → 40 psi, until 0.5 min)
Split ratio: 5.0: 1.0
Detector: 250 ° C. (FID)
Sample volume: 2 μl
Marking substance: Toluene (exact balance)

<Measurement Method of Toner Viscosity at 100 ° C.>
The viscosity value at 100 ° C. of the toner in the present invention is determined by the following method.

  The viscosity of the toner at 100 ° C. is measured using a constant-load extrusion type capillary rheometer “Flow Characteristic Evaluation Apparatus Flow Tester CFT-500D” (manufactured by Shimadzu Corporation) according to the manual attached to the apparatus. In this device, while applying a constant load from the top of the measurement sample by the piston, the measurement sample filled in the cylinder is heated and melted, and the molten measurement sample is extruded from the die at the bottom of the cylinder, and the temperature at this time And measure the relationship between the amount of piston descent.

  In the present invention, measurement is performed from 50 ° C. to 200 ° C., and the apparent viscosity calculated at 100 ° C. is defined as the viscosity (Pa · s) of the toner at 100 ° C.

The apparent viscosity η (Pa · s) at 100 ° C. is calculated as follows. First, the flow rate Q (cm3 / s) is calculated from the following equation (1). In the formula, the sectional area of the piston is A (cm 2), and the time required for the piston to descend between 0.10 mm up and down (0.20 mm as the interval) with respect to the position of the piston at 100 ° C. is Δt ( Seconds).
Q = (0.20 × A) / (10 × Δt) (1)

And the apparent viscosity (eta) in 100 degreeC is computed from the following formula (2) using the obtained flow rate Q. In the formula, the piston load is P (Pa), the diameter of the hole of the die is B (mm), and the length of the die is L (mm).
η = (π × B4 × P) / (128000 × L × Q) (2)

As a measurement sample, about 1.0 g of toner is compression-molded at about 10 MPa using a tablet molding compressor (for example, NT-100H, manufactured by NPA System) in an environment of 25 ° C. for about 60 seconds. A cylindrical shape having a diameter of about 8 mm is used. The measurement conditions of CFT-500D are as follows.
Test mode: Temperature rising start temperature: 50 ° C
Achieving temperature: 200 ° C
Measurement interval: 1.0 ° C
Temperature increase rate: 4.0 ° C./min
Piston cross-sectional area: 1.000cm2
Test load (piston load): 10.0 kgf (0.9807 MPa)
Preheating time: 300 seconds Die hole diameter: 1.0 mm
Die length: 1.0mm

  By the above method, the viscosity (Pa · s) of the toner at 50 ° C. to 200 ° C. is measured to obtain the viscosity (Pa · s) at 100 ° C.

<PH measurement method>
The pH measurement was performed as follows. 20 ml of an aqueous dispersion medium containing the polymerizable monomer composition during the reaction was collected in a 30 ml glass bottle, cooled to 25.0 ± 0.2 ° C. within 5 minutes after collection, and pH was measured. HM-30G (manufactured by Toa Denpa Kogyo) was used as the pH measuring device, and GST-5721C (manufactured by Toa Denpa Kogyo) was used as the pH electrode. The calibration was performed using pH standard solutions of pH 4.01 and pH 6.86 (manufactured by Toa Denpa Kogyo).

  Aqueous dispersion containing a polymerizable monomer composition when the addition rate of the polymerizable monomer composition is 5%, 10%, 25%, 50%, 75%, 99.9%, 99.900% The pH of the medium was measured by adding the polymerizable monomer composition at a rate of 5.0 ± 0.5%, 10.0 ± 0.5%, 25.0 ± 0.5%, 50.0 ± 0, respectively. 0.5%, 75.0 ± 0.5%, 99.9 ± 0.05%, more than 99.950 and 99.990 or less.

<Measuring method of weight average particle diameter (D4) and number average particle diameter (D1)>
The weight average particle diameter (D4) and number average particle diameter (D1) of the toner are measured by a fine particle size distribution measuring apparatus “Coulter Counter Multisizer 3” (registered trademark, Beckman 2) Effective measurement channel number 25,000 using “Beckman Coulter Multisizer 3 Version 3.51” (manufactured by Beckman Coulter, Inc.) and attached dedicated software “Beckman Coulter Multisizer 3 Version 3.51” for measurement condition setting and measurement data analysis Measurement was performed on the channel, and the measurement data was analyzed and calculated.

  As the electrolytic aqueous solution used for the measurement, special grade sodium chloride is dissolved in ion-exchanged water so as to have a concentration of about 1% by mass, for example, “ISOTON II” (manufactured by Beckman Coulter, Inc.) can be used.

  Prior to measurement and analysis, the dedicated software was set as follows.

  In the “Standard Measurement Method (SOM) Change Screen” of the dedicated software, set the total count in the control mode to 50000 particles, set the number of measurements once, and set the Kd value to “standard particles 10.0 μm” (Beckman Coulter, Inc.) Set the value obtained using The threshold and noise level are automatically set by pressing the threshold / noise level measurement button. Also, the current is set to 1600 μA, the gain is set to 2, the electrolyte is set to ISOTON II, and the aperture tube flash after measurement is checked.

  In the “pulse to particle size conversion setting screen” of the dedicated software, the bin interval is set to logarithmic particle size, the particle size bin is set to 256 particle size bin, and the particle size range is set to 2 μm to 60 μm.

The specific measurement method is as follows.
(1) About 200 ml of the electrolytic solution is placed in a glass 250 ml round bottom beaker exclusively for Multisizer 3, set on a sample stand, and the stirrer rod is stirred counterclockwise at 24 rpm. Then, dirt and bubbles in the aperture tube are removed by the “aperture flush” function of the analysis software.
(2) About 30 ml of the electrolytic aqueous solution is put in a glass 100 ml flat bottom beaker, and "Contaminone N" (nonionic surfactant, anionic surfactant, organic builder pH 7 precision measurement is used as a dispersant therein. About 0.3 ml of a diluted solution obtained by diluting a 10% by weight aqueous solution of a neutral detergent for washing a vessel (made by Wako Pure Chemical Industries, Ltd.) 3 times with ion-exchanged water is added.
(3) Two oscillators with an oscillation frequency of 50 kHz are incorporated in a state where the phases are shifted by 180 degrees, and are placed in a water tank of an ultrasonic dispersion device “Ultrasonic Disposition System Tetora 150” (manufactured by Nikkiki Bios Co., Ltd.) having an electrical output of 120 W. A fixed amount of ion-exchanged water is added, and about 2 ml of the above-mentioned Contaminone N is added to this water tank.
(4) The beaker of (2) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. And the height position of a beaker is adjusted so that the electrolytic solution liquid surface resonance state in a beaker may become the maximum.
(5) In a state where the electrolytic aqueous solution in the beaker of (4) is irradiated with ultrasonic waves, about 10 mg of toner is added to the electrolytic aqueous solution little by little and dispersed. Then, the ultrasonic dispersion process is continued for another 60 seconds. In the ultrasonic dispersion, the temperature of the water tank is appropriately adjusted so as to be 10 ° C. or higher and 40 ° C. or lower.
(6) To the round bottom beaker of (1) installed in the sample stand, the electrolyte solution of (5) in which the toner is dispersed is dropped using a pipette, and the measurement concentration is adjusted to about 5%. . Then, measurement is performed until the number of measured particles reaches 50,000.
(7) The measurement data is analyzed with the dedicated software attached to the apparatus, and the weight average particle diameter (D4) and the number average particle diameter (D1) are calculated. When the graph / volume% is set with the dedicated software, the “average diameter” on the analysis / volume statistics (arithmetic average) screen is the weight average particle size (D4), and the graph / number% is set with the dedicated software. The “average diameter” on the analysis / number statistic (arithmetic average) screen is the number average particle diameter (D1).

<Measurement of ¹ H-NMR (nuclear magnetic resonance) spectrum>
The measurement was performed under the following conditions.

Measuring apparatus: FT NMR apparatus JNM-EX400 (manufactured by JEOL Ltd.)
Measurement frequency: 400MHz
Pulse condition: 5.0μs
Data points: 32768
Frequency range: 10500Hz
Integration count: 10000 times Measurement temperature: 60 ° C
Sample: 50 mg of a measurement sample is put in a sample tube having a diameter of 5 mm, CDCl3 is added as a solvent, and this is dissolved in a 60 ° C. constant temperature bath.

Determination of proton abundance ratio of methine group (—CH═CH—) derived from double bond by ¹ H-NMR measurement:
Intensity ratio between 4.6 ppm to 4.9 ppm of methine group hydrogen (corresponding to 1H each) and 5.0 ppm to 5.2 ppm of methine group hydrogen (corresponding to 1H each) in ¹ H-NMR spectrum, S _{4.6 to 4.9} / S _{5.0 to 5.2} are obtained.
A: With peak B: Without peak

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

Production Example of Styrenic Resin (1) [Synthesis Example of Addition Reactive Resin Having Double Bond]
38 mass parts of xylene was put into a pressure resistant reactor equipped with a dropping funnel, a Liebig condenser and a stirrer, and the temperature was raised to 200 ° C. The pressure at this time was 0.3 MPa. A mixture of 100 parts by mass of styrene monomer, 0.1 part by mass of n-butyl acrylate and 3.7 parts by mass of di-tert-butyl peroxide was charged into a dropping funnel, and the mixture was pressurized with xylene at 200 ° C. over 2 hours ( 0.3 MPa). After the dropping, the reaction was further carried out at 200 ° C. for 2 hours to complete the solution polymerization, and xylene was removed. The obtained styrene resin had a weight average molecular weight of 2900 and Tg of 58 ° C. This is designated as styrene resin (1).

Production Example of Styrene Resin (2) A reactor equipped with a dropping funnel, a Liebig cooler, a nitrogen sealed tube (nitrogen flow rate 100 ml / min) and a stirrer was charged with 610 parts by mass of xylene and heated to 135 ° C. A mixture of 100 parts by mass of styrene monomer, 0.1 part by mass of n-butyl acrylate and 18 parts by mass of di-tert-butyl peroxide was charged into a dropping funnel and dropped into xylene at 135 ° C. over 2 hours at normal pressure. Further, the reaction was carried out for 2 hours under reflux of xylene (137 ° C. to 145 ° C.) to complete solution polymerization, and xylene was removed. The resulting styrene resin had a weight average molecular weight of 3200 and a Tg of 56 ° C. This is designated as styrene resin (2).

  Table 2 shows the physical properties of the styrene resins (1) and (2) obtained above.

Example of production of negatively charged control agent resin 1 In a pressurizable reaction vessel equipped with a reflux tube, a stirrer, a thermometer, a nitrogen introduction tube, a dropping device and a decompression device, 250 parts by mass of methanol as a solvent, 150 2-butanone While stirring by adding 100 parts by mass and 100 parts by mass of 2-propanol, 88 parts by mass of styrene as a monomer, 6.5 parts by mass of 2-ethylhexyl acrylate, and 4.8 parts by mass of 2-acrylamido-2-methylpropanesulfonic acid. Heated to reflux temperature. A solution obtained by diluting 1 part by mass of 2,2′-azobisisobutyronitrile as a polymerization initiator with 20 parts by mass of 2-butanone was added dropwise over 30 minutes, and stirring was continued for 5 hours. -A solution obtained by diluting 1 part by mass of azobisisobutyronitrile with 20 parts by mass of 2-butanone was added dropwise over 30 minutes, and the mixture was further stirred for 5 hours to complete the polymerization.

  Next, the polymer obtained after the polymerization solvent was distilled off under reduced pressure was coarsely pulverized to 100 μm or less by a cutter mill equipped with a 150 mesh screen, and further finely pulverized by a jet mill. The fine powder was classified with a 250 mesh sieve to obtain particles of 60 μm or less. Next, the particles were dissolved by adding MEK to a concentration of 10%, and the above solution was gradually poured into 20 times the amount of MEK in methanol for reprecipitation. The resulting precipitate was washed with one-half the amount of methanol used for reprecipitation, and the filtered particles were vacuum dried at 35 ° C. for 48 hours.

  Further, MEK was added and redissolved so that the particles after the vacuum drying had a concentration of 10%, and the above solution was gradually poured into n-hexane 20 times the amount of MEK for reprecipitation. The obtained precipitate was washed with half the amount of n-hexane used for reprecipitation, and the filtered particles were vacuum dried at 35 ° C. for 48 hours. The polar polymer thus obtained had a Tg of about 83 ° C. and a main peak molecular weight (Mp) of 215000, Mn 11900, and Mw 31500. Further, the composition measured by 1H-NMR (EX-400: 400 MHz manufactured by JEOL Ltd.) was as charged. The obtained resin is referred to as negative charge control resin 1.

(Example of production of polyester resin (1))
・ Terephthalic acid: 11.1 mol
・ Bisphenol A-propylene oxide 2-mol adduct (PO-BPA)
: 10.1 mol
The above polyester monomer is charged into an autoclave together with an esterification catalyst, and a pressure reducing device, a water separation device, a nitrogen gas introducing device, a temperature measuring device, and a stirring device are attached to the autoclave, and the pressure is reduced under a nitrogen atmosphere at 198 ° C. The reaction was carried out until the Tg reached 68 to 70 ° C. to obtain a polyester resin 1. Table 3 shows the physical properties.

(Example of production of polyester resin (2))
・ Terephthalic acid: 9.8 mol
・ Bisphenol A-propylene oxide 2-mol adduct (PO-BPA)
: 10.0 mol
The polyester monomer is charged into an autoclave together with an esterification catalyst, and a decompression device, a water separation device, a nitrogen gas introduction device, a temperature measurement device, and a stirring device are attached to the autoclave and reduced pressure in a nitrogen atmosphere at 198 ° C. according to a conventional method. The reaction was carried out until Tg reached 66 to 68 ° C. to obtain polyester resin A (Mw 8, 400, Mw / Mn 2.9, Tg 68 ° C.).

  Next, the polyester resin A (9.80 mol of terephthalic acid, 10.00 mol of bisphenol A-propylene oxide 2-mol adduct (PO-BPA) 10.00 mol) was added to 25.00 mol of xylene, and this mixed solution was added at 135 ° C. Heated. A solution obtained by dissolving 15.31 mol of styrene, 1.54 mol of acrylic acid and 1.96 mol of tert-butylperoxybenzoate as a radical polymerization initiator in 1.00 mol parts of xylene in a nitrogen atmosphere in the above mixed solution. The solution was added dropwise over about 30 minutes. The mixture was held at 135 ° C. for another 5 hours to complete the radical polymerization reaction. Further, the mixed solution was depressurized while being heated to remove the solvent, thereby obtaining a polyester resin (2). Table 3 shows the physical properties.

[Example 1]
While adding 720 parts by weight of ion-exchanged water and 935 parts by weight of a 0.1 mol / liter Na ₃ PO ₄ aqueous solution in a four-necked container, while stirring at 11,000 rpm using a high-speed stirring device TK-homomixer, Maintained at 60 ° C. To this, 75 parts by mass of 1.0 mol / liter-CaCl ₂ aqueous solution was gradually added to prepare an aqueous dispersion medium containing a fine hardly water-soluble dispersion stabilizer Ca ₃ (PO ₄ ) ₂ .

Styrene monomer 64 parts by mass n-butyl acrylate 16 parts by mass Copper phthalocyanine pigment (Pigment Blue 15: 3) 6.5 parts by mass Styrenic resin (1) 20 parts by mass (Mw = 2900, Mw / Mn = 1.67)
Polyester resin (1) 5 parts by mass Negative charge control agent 1 (aluminum compound of 3,5-di-tert-butylsalicylic acid)
0.5 parts by mass Negatively charged control agent resin 1 0.5 parts by mass Wax [Fischer-Tropsch wax (1), endothermic main peak temperature 78.2 ° C.] 10 parts by mass A polymerizable monomer composition in which 5.6 parts by mass of t-butyl peroxypivalate as a polymerization initiator was added to the monomer mixture dispersed in time was charged into the aqueous dispersion medium. Next, granulation was performed for 5 minutes while maintaining the rotation speed of the stirrer at 10,000 rpm. Thereafter, the high-speed stirrer is changed to a propeller stirrer, and the aqueous dispersion medium containing the obtained polymerizable monomer composition is heated to an internal temperature of 70 ° C., and the conversion is 97. At 512% (conversion rate (Ck) of polymerizable monomer composition when water-soluble initiator is added), 0.5 part by weight of potassium persulfate, which is a water-soluble initiator, is added to 19.5 parts by weight of distilled water. The dissolved aqueous solution was added dropwise and maintained at 70 ° C. Furthermore, the conversion rate was 97.712% (when the conversion rate (Cp) of the polymerizable monomer composition at the time of adding the pH adjusting agent was reached, 0.15 parts by mass of sodium carbonate was changed to 3.0 parts by mass as the pH adjusting agent. The dissolved aqueous solution was added dropwise, and the reaction at 70 ° C. was performed for a total of 5 hours.

  Also, the addition rate of the polymerizable monomer composition is 5%, 10%, 25%, 50%, 75%, 99.9%, 99.950% immediately before the addition of the water-soluble initiator and immediately before the addition of the pH adjuster. The pH of the aqueous dispersion medium containing the polymerizable monomer composition at the time of less than 99.999 was measured. The raw materials and polymerization conditions are shown in Table 1-1 and Table 4, the physical properties of the styrene resin are shown in Table 2, and the physical properties of the polyester resin are shown in Table 3.

  Subsequently, the inside of a container was heated up to 80 degreeC and reaction was performed for 3 hours. Thereafter, the slurry was gradually cooled to 30 ° C. at a cooling rate of 1 ° C. per minute to obtain slurry 1. Dilute hydrochloric acid was added to the container containing the slurry 1 to remove the dispersion stabilizer. Further, filtration, washing and drying were performed to obtain polymer particles (toner particles 1) having a weight average particle diameter (D4) of 5.8 μm.

The obtained toner particles 1 (100 parts by weight), titanium oxide specific surface area by BET method specific surface area by 1.8 parts by mass of hydrophobic silica and a BET method is 200 meters ² / g is 100 m ² / g Toner (1-1) was obtained by externally adding 0.1 part by mass. Other physical properties of the toner (1-1) were measured, and the results are shown in Table 1-2.

  The measurement results of a chart of molecular weight distribution measured by GPC of the THF soluble part of the toner (1-1) are shown in Table 1-2.

<Fixing test>
The fixing unit of the full color laser beam printer (LBP-2510, manufactured by Canon) has been modified so that the fixing temperature and the process speed can be adjusted, and the fixing temperature can be adjusted within a range of 100 to 250 ° C. at a process speed of 180 mm / sec. An unfixed toner image (0.4 mg / cm ² ) was heated and pressed without oil on an image receiving paper (75 g / m ² ) at intervals of 5 ° C. to form a fixed image on the image receiving paper.

<Evaluation of low temperature fixability and high temperature offset resistance>
For a 1 cm square fixed image, three Kimwipes (trade name S-200, manufactured by Crecia Co., Ltd.) are rubbed 10 times with a load of 75 g / cm ² applied, and the density of the fixed image before and after the rub is lowered. The temperature at which the rate was less than 5% was defined as the toner fixing temperature, the lowest fixing temperature was used as the low temperature fixing property evaluation criterion, and the highest fixing temperature was used as the high temperature offset resistance evaluation criterion.

<Image density measurement>
Regarding the image density, using a Macbeth densitometer (RD-914; manufactured by Macbeth), using an SPI auxiliary filter, low temperature and low humidity (L / L) (15 ° C./15% RH), normal temperature and normal humidity (N / N) ) The image density of the fixed image portion was measured for an image output in an environment of (25 ° C./60% RH) and high temperature and high humidity (H / H) (32 ° C./80% RH). The output image is fixed at a fixing temperature of 170 ° C and a process speed of 180 mm / sec by a modified fixing device that has been modified so that the fixing temperature and process speed of the full-color laser beam printer (LBP-2510, manufactured by Canon) can be adjusted. did.

<Durable image density measurement>
Using a full color laser beam printer (LBP-2510, manufactured by Canon), low temperature and low humidity (15 ° C / 15% RH), normal temperature and normal humidity (25 ° C / 60% RH), high temperature and high humidity (32 ° C / 80 % RH), 200 g of toner is set in the process cartridge, and an image with a printing ratio of 2% is printed up to 10,000 sheets using recording paper (75 mg / cm ² ), and the initial and 10,000 sheets are output. The solid image density at the time was evaluated according to the following evaluation criteria. The durability image density measurement conditions were the same as the image density measurement.
Rank A: 1.45 or higher Rank B: 1.44 to 1.40
Rank C: 1.39 to 1.35
Rank D: 1.34 to 1.30
Rank E: 1.29 to 1.25
Rank F: 1.24 or less

<Development streak evaluation>
The development streak was evaluated according to the following criteria from a halftone image (toner applied amount of 0.30 mg / cm ² ) obtained after printing 10,000 sheets.
A: A vertical streak in the paper discharge direction, which appears as a development streak, is not seen on the developing roller or the halftone image. There is no problem in practical use.
B: Although there are 1 to 5 thin circumferential streaks at both ends of the developing roller, no vertical streak in the paper discharge direction, which appears as a developing streak, is seen on the halftone image. There is no problem in practical use.
C: There are several thin circumferential streaks at both ends of the developing roller, and several fine developing streaks can be seen on the halftone image. However, there is no practical problem at the level that can be erased by image processing.
D: Many development streaks are seen on the developing roller and the halftone image, and cannot be erased by image processing.

<Evaluation of charging member contamination>
The charging member contamination evaluation was carried out by visual evaluation of the charging member after enduring 10,000 sheets from the following criteria.
A: No charging member contamination.
B: There is almost no contamination of the charging member.
C: Charging member is slightly contaminated.
D: There is a lot of contamination of the charging member.

<Photosensitive drum fusion evaluation>
After the 10,000-sheet continuous print test is completed, halftone images are printed on 75 g / m ² paper of A4 size that has been sufficiently conditioned in the test environment, and the photosensitive drum used remains on the drum by air blow. Microscopic observation was performed after removing the weak deposits, and evaluation was performed according to the following criteria.
A: No toner fusion is observed when a 50 × microscope observation is performed at positions approximately 5 cm from the center of the drum and both ends of the image forming area. B: Approximately from the center of the drum and both ends of the image forming area. When a 50 × microscope observation is performed at a position of 5 cm, toner fusion is confirmed, but image omission due to adhesion does not occur.
C: When observed with a microscope, toner fusing was confirmed, and three or less image omission due to fusing per drum circumference.
D: When observed with a microscope, toner fusion was confirmed, and there were four or more image omissions due to fusion per drum circumference.

<Fog>
The fog density (%) is calculated from the difference between the whiteness of the white portion of the printed image and the whiteness of the transfer paper measured by “Reflectometer” (manufactured by Tokyo Denshoku Co., Ltd.), and the image fog is evaluated according to the following criteria. did.
A: Very good (less than 1.5%)
B: Good (1.5% or more, less than 2.5%)
C: Practical use possible (2.5% or more, less than 4.0%)
D: Not practical (4% or more)

  200 g of toner (1-1) is filled in a process cartridge, and low temperature and low humidity (15 ° C./15% RH), normal temperature and normal humidity (25 ° C./60% RH), high temperature and high humidity (32 ° C./80% RH) In this environment, images with a printing ratio of 2% were printed up to 10,000 sheets, and the solid image density at the initial stage and when outputting 10,000 sheets was evaluated. The results are shown in Table 5. Next, fixing evaluation was performed, and the results are also shown in Table 5.

[Example 2]
0.25 part by mass of divinylbenzene, 0 part by mass of styrene-based resin (1), 0 part by mass, and 5.6 parts by mass of t-butyl peroxypivalate are added to the monomer of Example 1 (styrene monomer and n-butyl acrylate). The amount was changed to 2.8 parts by mass, and the conversion rate (Ck) of the polymerizable monomer composition when the water-soluble initiator was added was changed from 97.512% to 97.540%.

  Further, the toner particles 2 were prepared in the same manner as in Example 1 except that the conversion ratio (Cp) of the polymerizable monomer composition upon addition of the pH adjuster of Example 1 was changed from 97.712% to 98.018%. Obtained. Raw materials and polymerization conditions are shown in Tables 1-1 and 4.

For toner particles 2 (100 parts by mass), 1.8 parts by mass of hydrophobic silica having a specific surface area of 200 m ² / g by the BET method and 0.1 m of titanium oxide having a specific surface area of 100 m ² / g by the BET method A toner (2-1) was obtained by externally adding parts by mass. Table 1-2 shows the physical properties of Toner (2-1).

  Measurement of the molecular weight distribution of the obtained toner (2-1) was performed in the same manner as in Example 1. The measurement results are shown in Table 1-2.

  In the same manner as in Example 1, the toner (2-1) was set in a process cartridge of a modified laser beam printer (Canon: LBP-2510), and the same image evaluation as in Example 1 was performed. Next, the same fixing evaluation as in Example 1 was performed, and the results are also shown in Table 5.

Example 3
While adding 720 parts by weight of ion-exchanged water and 935 parts by weight of a 0.1 mol / liter Na ₃ PO ₄ aqueous solution in a four-necked container, while stirring at 11,000 rpm using a high-speed stirring device TK-homomixer, Maintained at 60 ° C. To this, 75 parts by mass of 1.0 mol / liter-CaCl ₂ aqueous solution was gradually added to prepare an aqueous dispersion medium containing a fine hardly water-soluble dispersion stabilizer Ca ₃ (PO ₄ ) ₂ .

Styrene monomer 64 parts by mass n-butyl acrylate 16 parts by mass Copper phthalocyanine pigment (Pigment Blue 15: 3) 6.5 parts by mass Styrenic resin (1) 20 parts by mass (Mw = 2900, Mw / Mn = 1.67)
Polyester resin (2) 5 parts by mass Negative charge control agent 1 (aluminum compound of 3,5-di-tert-butylsalicylic acid)
5 parts by weight Negatively charged control agent resin 1 0.5 parts by weight Wax [Fischer-Tropsch wax (1), endothermic main peak temperature 78.2 ° C.] 10 parts by weight The above monomer mixture is dispersed by an attritor for 3 hours. A polymerizable monomer composition obtained by adding 4.0 parts by mass of 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate as a polymerization initiator to the monomer mixture obtained above Charged into dispersion medium. Next, granulation was performed for 5 minutes while maintaining the rotation speed of the stirrer at 10,000 rpm. Thereafter, the high-speed stirrer was changed to a propeller stirrer, and the aqueous dispersion medium containing the obtained polymerizable monomer composition was heated to an internal temperature of 70 ° C., and slowly stirred at 70 ° C. for 5 hours. Reaction was performed. The raw materials and polymerization conditions are shown in Table 1-1 and Table 4, the physical properties of the styrene resin are shown in Table 2, and the physical properties of the polyester resin are shown in Table 3.

  Next, an aqueous solution in which 0.50 part by mass of potassium persulfate, which is a water-soluble initiator, was dissolved in 19.50 parts by mass of distilled water when the inside of the container was heated to a temperature of 80 ° C. and the conversion rate was 99.902%. Dropped and maintained at 70 ° C. Further, when the conversion rate reached 99.952%, an aqueous solution in which 0.15 parts by mass of sodium carbonate was dissolved in 3.00 parts by mass as a pH adjuster was dropped. The reaction at 80 ° C. was performed for a total of 3 hours. Thereafter, the slurry was gradually cooled to 30 ° C. at a cooling rate of 1 ° C. per minute to obtain slurry 3. Dilute hydrochloric acid was added to the container containing the slurry 3 to remove the dispersion stabilizer. Further, filtration, washing and drying were performed to obtain polymer particles (toner particles 3) having a weight average particle diameter (D4) of 5.8 μm.

The toner particles 3 (100 parts by weight), titanium oxide 0.1 specific surface area by BET method specific surface area by hydrophobic silica 1.8 parts by weight and the BET method is 200 meters ² / g is 100 m ² / g A toner (3-1) was obtained by externally adding parts by mass. Table 1-2 shows the physical properties of Toner (3-1).

  Measurement of the molecular weight distribution of the obtained toner (3-1) was performed in the same manner as in Example 1. The measurement results are shown in Table 1-2.

  In the same manner as in Example 1, the toner (3-1) was set in a process cartridge of a modified laser beam printer (Canon: LBP-2510), and the same image evaluation as in Example 1 was performed. Next, the same fixing evaluation as in Example 1 was performed, and the results are also shown in Table 5.

Example 4
While adding 720 parts by weight of ion-exchanged water and 935 parts by weight of a 0.1 mol / liter Na ₃ PO ₄ aqueous solution in a four-necked container, while stirring at 11,000 rpm using a high-speed stirring device TK-homomixer, Maintained at 60 ° C. To this, 75 parts by mass of 1.0 mol / liter-CaCl ₂ aqueous solution was gradually added to prepare an aqueous dispersion medium containing a fine hardly water-soluble dispersion stabilizer Ca ₃ (PO ₄ ) ₂ .

Styrene monomer 64 parts by mass n-butyl acrylate 16 parts by mass Copper phthalocyanine pigment (Pigment Blue 15: 3) 6.5 parts by mass Styrenic resin (2) 20 parts by mass (Mw = 3200, Mw / Mn = 1.76)
Polyester resin (1) 5 parts by mass Negative charge control agent 1 (aluminum compound of 3,5-di-tert-butylsalicylic acid)
0.5 parts by mass Negatively charged control agent resin 1 0.5 parts by mass Wax [Fischer-Tropsch wax (1), endothermic main peak temperature 78.2 ° C.] 10 parts by mass A polymerizable monomer composition in which 5.6 parts by mass of t-butyl peroxypivalate as a polymerization initiator was added to the monomer mixture dispersed in time was charged into the aqueous dispersion medium. Next, granulation was performed for 5 minutes while maintaining the rotation speed of the stirrer at 10,000 rpm. Thereafter, the high-speed stirrer was changed to a propeller stirrer, and the aqueous dispersion medium containing the obtained polymerizable monomer composition was heated to an internal temperature of 70 ° C., and slowly stirred at 70 ° C. for 5 hours. Next, the temperature inside the container was raised to 80 ° C. and reacted for 3 hours. When the conversion rate was 97.524%, 0.15 parts by mass of sodium carbonate as a pH adjuster was dissolved in 3.00 parts by mass. An aqueous solution was added dropwise. Further, when the conversion rate reached 98.012%, an aqueous solution in which 0.50 parts by mass of potassium persulfate as a water-soluble initiator was dissolved in 19.50 parts by mass of distilled water was added dropwise. The raw materials and polymerization conditions are shown in Table 1-1 and Table 4, the physical properties of the styrene resin are shown in Table 2, and the physical properties of the polyester resin are shown in Table 3.

  Thereafter, the slurry was gradually cooled to 30 ° C. at a cooling rate of 1 ° C. per minute to obtain slurry 4. Dilute hydrochloric acid was added to the container containing the slurry 4 to remove the dispersion stabilizer. Further, filtration, washing, and drying were performed to obtain polymer particles (toner particles 4) having a weight average particle diameter (D4) of 5.8 μm.

The toner particles 3 (100 parts by weight), titanium oxide 0.1 specific surface area by BET method specific surface area by hydrophobic silica 1.8 parts by weight and the BET method is 200 meters ² / g is 100 m ² / g The toner (4-1) was obtained by externally adding parts by mass. Table 1-2 shows the physical properties of this toner (4-1).

  Measurement of the molecular weight distribution of the obtained toner (4-1) was performed in the same manner as in Example 1. The measurement results are shown in Table 1-2.

  In the same manner as in Example 1, the toner (4-1) was set in a process cartridge of a laser beam printer (Canon: LBP-2510) modified machine, and the same image evaluation as in Example 1 was performed. Next, the same fixing evaluation as in Example 1 was performed, and the results are also shown in Table 5.

Example 5
While adding 720 parts by weight of ion-exchanged water and 935 parts by weight of a 0.1 mol / liter Na ₃ PO ₄ aqueous solution in a four-necked container, while stirring at 11,000 rpm using a high-speed stirring device TK-homomixer, Maintained at 60 ° C. To this, 75 parts by mass of 1.0 mol / liter-CaCl ₂ aqueous solution was gradually added to prepare an aqueous dispersion medium containing a fine hardly water-soluble dispersion stabilizer Ca ₃ (PO ₄ ) ₂ .

Styrene monomer 54 parts by mass n-butyl acrylate 16 parts by mass Copper phthalocyanine pigment (Pigment Blue 15: 3) 6.5 parts by mass Styrenic resin (1) 30 parts by mass (Mw = 2900, Mw / Mn = 1.67)
Polyester resin (1) 5 parts by mass Negative charge control agent 1 (aluminum compound of 3,5-di-tert-butylsalicylic acid)
0.5 parts by weight Negatively charged control agent resin 1 1.0 part by weight Wax [Fischer-Tropsch wax (1), endothermic main peak temperature 78.2 ° C.] 10 parts by weight A polymerizable monomer composition in which 8.0 parts by mass of t-butyl peroxypivalate as a polymerization initiator was added to the monomer mixture dispersed in time was added to the aqueous dispersion medium. Next, granulation was performed for 5 minutes while maintaining the rotation speed of the stirrer at 10,000 rpm. Thereafter, the high-speed stirrer was changed to a propeller stirrer, and the aqueous dispersion medium containing the obtained polymerizable monomer composition was heated to an internal temperature of 70 ° C., and slowly stirred at 70 ° C. for 5 hours. Next, the temperature in the vessel was raised to 80 ° C. and reacted for 3 hours. When the conversion rate reached 98.214%, 0.50 parts by mass of potassium persulfate was dissolved in 19.50 parts by mass of distilled water. The aqueous solution and the aqueous solution which dissolved 0.15 mass part of sodium carbonate in 3.00 mass part were dripped. The raw materials and polymerization conditions are shown in Table 1-1 and Table 4, the physical properties of the styrene resin are shown in Table 2, and the physical properties of the polyester resin are shown in Table 3.

  Thereafter, the slurry was gradually cooled to 30 ° C. at a cooling rate of 1 ° C. per minute to obtain slurry 5. Dilute hydrochloric acid was added to the container containing the slurry 5 to remove the dispersion stabilizer. Further, filtration, washing and drying were performed to obtain polymer particles (toner particles 5) having a weight average particle diameter (D4) of 5.8 μm.

The toner particles 5 (100 parts by weight), titanium oxide 0.1 BET specific surface area is the specific surface area due to hydrophobic silica 1.8 parts by weight and the BET method is 200 meters ² / g is 100 m ² / g A toner (5-1) was obtained by externally adding parts by mass. Table 1-2 shows the physical properties of Toner (5-1).

  Measurement of the molecular weight distribution of the obtained toner (5-1) was performed in the same manner as in Example 1. The measurement results are shown in Table 1-2.

  In the same manner as in Example 1, the toner (5-1) was set in a process cartridge of a laser beam printer (Canon: LBP-2510) modified machine, and the same image evaluation as in Example 1 was performed. Next, the same fixing evaluation as in Example 1 was performed, and the results are also shown in Table 5.

Example 6
The negative charge control agent resin 1 of Example 1 was changed from 0.5 parts by mass to 0.1 parts by mass, and the conversion rate (Ck) of the polymerizable monomer composition when the water-soluble initiator was added was 97.512. % Was changed to 97.508%.

  Further, toner particles 6 in Example 1 were prepared in the same manner as in Example 1 except that the conversion ratio (Cp) of the polymerizable monomer composition upon addition of the pH adjusting agent was changed from 97.712% to 97.722%. The raw materials and polymerization conditions are shown in Table 1-1 and Table 4.

The toner particles 6 (100 parts by weight), titanium oxide 0.1 specific surface area by BET method specific surface area by hydrophobic silica 1.8 parts by weight and the BET method is 200 meters ² / g is 100 m ² / g A toner (6-1) was obtained by externally adding parts by mass. Table 1-2 shows the physical properties of Toner (6-1).

  Measurement of the molecular weight distribution of the obtained toner (6-1) was performed in the same manner as in Example 1. The measurement results are shown in Table 1-2.

  In the same manner as in Example 1, the toner (6-1) was set in a process cartridge of a laser beam printer (Canon: LBP-2510) modified machine, and the same image evaluation as in Example 1 was performed. Next, the same fixing evaluation as in Example 1 was performed, and the results are also shown in Table 5.

Example 7
When the conversion ratio (Ck) of the polymerizable monomer composition at the time of addition of the water-soluble initiator of Example 1 was 97.512%, 97.524%, and potassium persulfate 0.50 parts by mass was 19.50 parts by mass. Part of the aqueous solution dissolved in distilled water was changed from 5.00 parts by mass of potassium persulfate to an aqueous solution dissolved in 195.00 parts by mass of distilled water.

  Furthermore, the conversion rate (Cp) of the polymerizable monomer composition at the time of addition of the pH adjuster of Example 1 was changed from 97.712% to 97.723%, and sodium carbonate 0.15 parts by mass was 3.00 parts by mass Toner particles 7 were obtained in the same manner as in Example 1 except that the dissolved aqueous solution was changed from 1.50 parts by mass to 30.00 parts by mass of sodium carbonate to obtain toner particles 7. Raw materials and polymerization conditions are shown in Table 1- 1 and Table 4.

The toner particles 7 (100 parts by weight), titanium oxide 0.1 specific surface area by BET method specific surface area by hydrophobic silica 1.8 parts by weight and the BET method is 200 meters ² / g is 100 m ² / g A toner (7-1) was obtained by externally adding parts by mass. Table 1-2 shows the physical properties of Toner (7-1).

  Measurement of the molecular weight distribution of the obtained toner (7-1) was performed in the same manner as in Example 1. The measurement results are shown in Table 1-2.

  In the same manner as in Example 1, the toner (7-1) was set in a process cartridge of a laser beam printer (Canon: LBP-2510) modified machine, and the same image evaluation as in Example 1 was performed. Next, the same fixing evaluation as in Example 1 was performed, and the results are also shown in Table 5.

Example 8
97.824% when the conversion ratio (Ck) of the polymerizable monomer composition at the time of addition of the water-soluble initiator of Example 1 was 97.512%, and 19.50 mass by 0.50 parts by mass of potassium persulfate. Part of the aqueous solution dissolved in distilled water was changed from 0.20 part by weight of potassium persulfate to an aqueous solution dissolved in 7.80 parts by weight of distilled water, and 0.15 part by weight of sodium carbonate in Example 1 was changed to 0. Toner particles 8 were obtained in the same manner as in Example 1 except for changing to 0.000 parts by mass. The raw materials and polymerization conditions are shown in Table 1-1 and Table 4.

The toner particles 8 (100 parts by weight), titanium oxide 0.1 specific surface area by BET method specific surface area by hydrophobic silica 1.8 parts by weight and the BET method is 200 meters ² / g is 100 m ² / g A toner (8-1) was obtained by externally adding parts by mass. Table 1-2 shows the physical properties of Toner (8-1).

  Measurement of the molecular weight distribution of the obtained toner (8-1) was performed in the same manner as in Example 1. The measurement results are shown in Table 1-2.

  In the same manner as in Example 1, the toner (8-1) was set in a process cartridge of a laser beam printer (Canon: LBP-2510) modified machine, and the same image evaluation as in Example 1 was performed. Next, the same fixing evaluation as in Example 1 was performed, and the results are also shown in Table 5.

Example 9
6.5 parts by mass of copper phthalocyanine of Example 1 was changed to 6.5 parts by mass of carbon black (primary particle size 35 nm).

    The conversion rate (Ck) of the polymerizable monomer composition at the time of addition of the water-soluble initiator in Example 1 was changed to 99.910% from 97.512%.

  Furthermore, the conversion ratio (Cp) of the polymerizable monomer composition at the time of adding the pH adjuster of Example 1 was 97.712% to 99.910%, 0.15 parts by mass of sodium carbonate was 0.10 parts by mass of potassium hydroxide. Toner particles 9 were obtained in the same manner as in Example 1 except that the amount of the toner particles 9 was changed. The raw materials and polymerization conditions are shown in Table 1-1 and Table 4.

The toner particles 9 (100 parts by weight), titanium oxide 0.1 specific surface area by BET method specific surface area by hydrophobic silica 1.8 parts by weight and the BET method is 200 meters ² / g is 100 m ² / g A toner (9-1) was obtained by externally adding parts by mass. Table 1-2 shows the physical properties of Toner (9-1).

  Measurement of the molecular weight distribution of the obtained toner (9-1) was performed in the same manner as in Example 1. The measurement results are shown in Table 1-2.

  In the same manner as in Example 1, the toner (9-1) was set in a process cartridge of a laser beam printer (Canon: LBP-2510) modified machine, and the same image evaluation as in Example 1 was performed. Next, the same fixing evaluation as in Example 1 was performed, and the results are also shown in Table 5.

[Comparative Example 1]
In Example 1, 64.0 parts by mass of styrene is 70.0 parts by mass, 20.0 parts by mass of n-butyl acrylate is 20.0 parts by mass, 0.007 parts by mass of divinylbenzene is 0.25 parts by mass, and a styrene resin. (1) 10.0 parts by mass of 20.0 parts by mass, 0.5 parts by mass of negative charge control agent resin 1 0.0 parts by mass, 5.6 parts by mass of t-butyl peroxypivalate 2.1 Changed to parts by mass.

  The conversion rate (Ck) of the polymerizable monomer composition at the time of addition of the water-soluble initiator in Example 1 was changed from 99.512% to 99.999%.

  Furthermore, the conversion rate (Cp) of the polymerizable monomer composition at the time of addition of the pH adjuster of Example 1 was changed from 97.712% to 99.999%, and the polymerization time at 80 ° C. was changed from 3 hours to 10 hours. Produced toner particles 10 in the same manner as in Example 1. The raw materials and polymerization conditions are shown in Table 1-1 and Table 4.

  In the same manner as in Example 1, the toner (10-1) was set in a process cartridge of a laser beam printer (Canon: LBP-2510) modified machine, and the same image evaluation as in Example 1 was performed. Next, the same fixing evaluation as in Example 1 was performed, and the results are also shown in Table 5.

[Comparative Example 2]
In Example 1, 64.0 parts by mass of styrene is 83.0 parts by mass, 16.0 parts by mass of n-butyl acrylate is 17.0 parts by mass, 0 part by mass of divinylbenzene is 0.25 parts by mass, styrene resin (1 ) 20 parts by mass was changed to 0 parts by mass, and 5.6 parts by mass of t-butyl peroxypivalate was changed to 2.1 parts by mass.

    The conversion rate (Ck) of the polymerizable monomer composition when adding the water-soluble initiator in Example 1 was changed from 90.512% to 90.125%.

  Further, the toner particles 11 were prepared in the same manner as in Example 1 except that the conversion ratio (Cp) of the polymerizable monomer composition at the time of addition of the pH adjuster of Example 1 was changed from 97.712% to 96.307%. Obtained. The raw materials and polymerization conditions are shown in Table 1-1 and Table 4.

For toner particles (100 parts by mass), 1.8 parts by mass of hydrophobic silica having a specific surface area of 200 m ² / g by the BET method and 0.1 parts by mass of titanium oxide having a specific surface area of 100 m ² / g by the BET method The toner (11-1) was obtained by externally adding parts. Table 1-2 shows the physical properties of Toner (11-1).

  Measurement of the molecular weight distribution of the obtained toner (11-1) was performed in the same manner as in Example 1. The measurement results are shown in Table 1-2.

  In the same manner as in Example 1, the toner (11-1) was set in a process cartridge of a laser beam printer (Canon: LBP-2510) modified machine, and the same image evaluation as in Example 1 was performed. Next, the same fixing evaluation as in Example 1 was performed, and the results are also shown in Table 5.

[Comparative Example 3]
(3-1) Preparation of Release Agent Dispersion Solution 90 parts by mass of styrene and 10 parts by mass of a release agent (made by Nippon Seiwa Co., Ltd., trade name “paraffin wax 155”, melting point 70 ° C.) are put into a media type wet pulverizer. Then, wet pulverization was performed to prepare a dispersion (solid content concentration 10%) in which the release agent was uniformly dispersed in styrene. The weight average particle diameter (D4) of the release agent in this dispersion was 2.9 μm.

(3-1) Preparation of toner In an aqueous solution in which 10.2 parts by mass of magnesium chloride (water-soluble polyvalent metal salt) is dissolved in 250 parts by mass of ion-exchanged water, sodium hydroxide (alkali hydroxide) is added to 50 parts by mass of ion-exchanged water. An aqueous solution in which 6.2 parts by mass of metal was dissolved was gradually added with stirring to prepare a magnesium hydroxide colloid (hardly water-soluble metal hydroxide colloid) dispersion.

Release agent dispersion 40 parts by mass (including 36 parts by mass of styrene and 4 parts by mass of release agent)
Styrene 47 parts by mass n-butyl acrylate 17 parts by mass Carbon black 6.5 parts by mass Divinylbenzene 0.3 part by mass t-dodecyl mercaptan 1.0 part by mass The above monomer mixture was dispersed by an attritor for 3 hours. A polymerizable monomer composition in which 4 parts by mass of t-butyl peroxyneodecanoate (trade name “Perbutyl ND”, manufactured by NOF Corporation), which is a polymerization initiator, is added to an aqueous dispersion medium. Then, granulation was performed for 5 minutes while maintaining the rotation speed of the stirrer at 10,000 rpm. Thereafter, the high-speed stirrer is changed to a propeller-type stirrer, and the aqueous dispersion medium containing the obtained polymerizable monomer composition is heated to an internal temperature of 70 ° C., while the conversion rate is 80.degree. When it reached 213%, an aqueous solution in which 5.00 parts by mass of ammonium persulfate as a water-soluble polymerization initiator was dissolved in 65 parts by mass of distilled water was added, and the reaction was performed at 70 ° C. for a total of 5 hours. Raw materials and polymerization conditions are shown in Table 1-1 and Table 4.

  Next, the temperature inside the container was raised to 80 ° C. and maintained at 70 ° C., and the reaction was performed for 3 hours. Thereafter, the slurry was gradually cooled to 30 ° C. at a cooling rate of 1 ° C. per minute to obtain a slurry 12. Dilute hydrochloric acid was added to the container containing the slurry 12 to remove the dispersion stabilizer. Further, filtration, washing and drying were performed to obtain polymer particles (toner particles 12) having a weight average particle diameter (D4) of 7.0 μm. Table 4 shows the reaction conditions.

The toner particles 12 (100 parts by weight), titanium oxide 0.1 specific surface area by BET method specific surface area by hydrophobic silica 1.8 parts by weight and the BET method is 200 meters ² / g is 100 m ² / g A toner (12-1) was obtained by externally adding parts by mass. Table 1-2 shows the physical properties of Toner (12-1).

  Measurement of the molecular weight distribution of the obtained toner (12-1) was performed in the same manner as in Example 1. The measurement results are shown in Table 1-2.

  As in Example 1, the toner (12-1) was set in the process cartridge of a modified laser beam printer (manufactured by Canon: LBP-2510), and the same image evaluation as in Example 1 was performed. Next, the same fixing evaluation as in Example 1 was performed, and the results are also shown in Table 5.

[Comparative Example 4]
4.0 parts by mass of t-butyl peroxyneodecanoate (trade name “Perbutyl ND”, manufactured by Nippon Oil & Fats Co., Ltd.) in Comparative Example 3 was 8.0 parts by mass, and the conversion reached 80.213%. When an aqueous solution in which 5.00 parts by mass of ammonium persulfate as a water-soluble polymerization initiator was dissolved in 65 parts by weight of distilled water was added, when the conversion reached 75.247%, 5.00 ammonium persulfate as a water-soluble polymerization initiator. Toner particles 13 were obtained in the same manner as in Comparative Example 3, except that an aqueous solution in which parts by mass were dissolved in 65 parts by mass of distilled water was added.

To the toner particles 13 (100 parts by mass), 1.8 parts by mass of hydrophobic silica having a specific surface area of 200 m ² / g by BET method and titanium oxide 0.1 having a specific surface area of 100 m ² / g by BET method A toner (13-1) was obtained by externally adding parts by mass. Table 1-2 shows the physical properties of Toner (13-1).

  Measurement of the molecular weight distribution of the obtained toner (13-1) was performed in the same manner as in Example 1. The measurement results are shown in Table 1-2.

  In the same manner as in Example 1, the toner (13-1) was set in a process cartridge of a laser beam printer (Canon: LBP-2510) modified machine, and the same image evaluation as in Example 1 was performed. Next, the same fixing evaluation as in Example 1 was performed, and the results are also shown in Table 5.

[Comparative Example 5]
When the conversion rate of Comparative Example 3 reached 80.213%, the conversion rate became 97.20% when an aqueous solution in which 5 parts by mass of ammonium persulfate as a water-soluble polymerization initiator was dissolved in 65 parts by mass of distilled water was added. Incidentally, toner particles 14 were obtained in the same manner as in Comparative Example 3, except that an aqueous solution in which 5.00 parts by mass of ammonium persulfate as a water-soluble polymerization initiator was dissolved in 65 parts by mass of distilled water was added.

The obtained toner particles 14 (100 parts by weight), titanium oxide specific surface area by BET method specific surface area by 1.8 parts by mass of hydrophobic silica and a BET method is 200 meters ² / g is 100 m ² / g Toner (14-1) was obtained by externally adding 0.1 part by mass. Table 1-2 shows the physical properties of Toner (14-1).

  Measurement of the molecular weight distribution of the obtained toner (14-1) was performed in the same manner as in Example 1. The measurement results are shown in Table 1-2.

  In the same manner as in Example 1, the toner (14-1) was set in a process cartridge of a laser beam printer (Canon: LBP-2510) modified machine, and the same image evaluation as in Example 1 was performed. Next, the same fixing evaluation as in Example 1 was performed, and the results are also shown in Table 5.

[Comparative Example 6]
When the conversion rate of Comparative Example 3 reached 80.213%, the conversion rate was 80.020% when an aqueous solution in which 5 parts by mass of ammonium persulfate as a water-soluble polymerization initiator was dissolved in 65 parts by mass of distilled water was added. When an aqueous solution in which 0.50 part by mass of ammonium persulfate as a water-soluble polymerization initiator was dissolved in 65 parts by mass of distilled water was added, 0.50 part by mass of sodium bicarbonate was distilled when the conversion was 85.297%. Toner particles 15 were obtained in the same manner as in Comparative Example 3 except that an aqueous solution dissolved in 65 parts by mass of water was added.

The obtained toner particles 15 (100 parts by weight), titanium oxide specific surface area by BET method specific surface area by 1.8 parts by mass of hydrophobic silica and a BET method is 200 meters ² / g is 100 m ² / g Toner (15-1) was obtained by externally adding 0.1 part by mass. Table 1-2 shows the physical properties of Toner (15-1).

  Measurement of the molecular weight distribution of the obtained toner (15-1) was performed in the same manner as in Example 1. The measurement results are shown in Table 1-2.

  In the same manner as in Example 1, the toner (15-1) was set in a process cartridge of a laser beam printer (Canon: LBP-2510) modified machine, and image evaluation similar to that in Example 1 was performed. Next, the same fixing evaluation as in Example 1 was performed, and the results are also shown in Table 5.

[Comparative Example 7]
When the conversion rate of Comparative Example 3 reached 80.213%, the conversion rate was 95.010 when an aqueous solution in which 5.00 parts by mass of ammonium persulfate as a water-soluble polymerization initiator was dissolved in 65 parts by mass of distilled water was added. Comparative Example 3 except that an aqueous solution in which 0.01 part by weight of potassium persulfate as a water-soluble polymerization initiator was dissolved in 65 parts by weight of distilled water was added and 10 parts by weight of styrene was added. Similarly, toner particles 16 were obtained.

The obtained toner particles 16 (100 parts by weight), titanium oxide specific surface area by BET method specific surface area by 1.8 parts by mass of hydrophobic silica and a BET method is 200 meters ² / g is 100 m ² / g Toner (16-1) was obtained by externally adding 0.1 part by mass. Table 1-2 shows the physical properties of Toner (16-1).

  Measurement of the molecular weight distribution of the obtained toner (16-1) was performed in the same manner as in Example 1. The measurement results are shown in Table 1-2.

  In the same manner as in Example 1, the toner (16-1) was set in a process cartridge of a laser beam printer (Canon: LBP-2510) modified machine, and the same image evaluation as in Example 1 was performed. Next, the same fixing evaluation as in Example 1 was performed, and the results are also shown in Table 5.

It is a figure which shows the chart of the molecular weight distribution measured by GPC of the THF soluble part of the toner of this invention. In the chart of FIG. 1, it is a figure which shows the chart of molecular weight distribution when converting the height of a peak into h (M1) [mV] = 1.00. In the chart of FIG. 2, integrated values S1, S2, and S3 of three molecular weight regions are shown.

Claims (7)

In a method for producing a toner produced by granulating and polymerizing a monomer composition containing at least a polymerizable monomer, a colorant, and a polymer having a sulfonic acid functional group in an aqueous medium,
Polymerized with an oil-soluble initiator, and polymerized by adding a water-soluble initiator at a pH of the aqueous medium of 7.00 or less when the conversion rate was 97.500 to 99.990%,
The method for producing a toner, wherein the polymer having a sulfonic acid functional group is a polymer or copolymer having a sulfonic acid group, a sulfonic acid group, or a sulfonic acid ester group.   The toner manufacturing method according to claim 1, wherein the water-soluble initiator is a persulfate-based initiator.   3. The method for producing a toner according to claim 1, wherein the oil-soluble initiator is an organic peroxide initiator.   4. The toner production method according to claim 1, wherein the toner has a 100 ° C. viscosity of 5000 Pa · s to 100,000 Pa · s. 5.   The method for producing a toner according to claim 1, wherein the toner has a THF-insoluble content of less than 16.0% by mass.   6. The method for producing a toner according to claim 1, wherein an organic peroxide having a 10-hour half-life temperature exceeding 50 ° C. of the oil-soluble initiator is used.   7. The oil-soluble initiator is selected from t-butyl peroxypivalate, t-butyl peroxy-2-ethylhexanoate, and t-butyl peroxyisobutyrate. The method for producing a toner according to any one of the above.

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