JP6113001B2 - Toner production method - Google Patents

Description

The present invention relates to a method for producing a toner used in an image forming method such as an electrophotographic method, an electrostatic recording method, and a toner jet method.

  In today's multifunctional copiers and printers, there is a need for a toner with excellent durability and low durability that can reduce power consumption and increase copying speed and printing speed. It has been. On the other hand, for output to thick paper such as gloss paper performed in a low-speed process, a toner that exhibits uniform and high gloss is desired. As described above, in order to cope with various fixing conditions and perform good image formation even in a high-speed process, the binder resin and wax used in the toner have been improved.

  In order to fix the toner at a lower fixing temperature, it is necessary to melt the binder resin at a lower temperature. As a method for melting the binder resin at a low temperature, a method for designing a low glass transition temperature of the resin and a method for designing a low molecular weight of the resin are generally known. However, if these designs are excessively carried out, the toner will change when exposed to high temperatures in the printer or copying machine, or in the course of physical distribution, causing various image problems. Therefore, these designs are naturally limited.

  On the other hand, as another method for melting the binder resin at a low temperature, a method is known in which the toner contains a wax having a large effect of plasticizing the resin near the fixing temperature. Hydrocarbon waxes with a low molecular weight and polar waxes with polar groups are known as waxes with a large resin plasticizing effect, but hydrocarbon waxes with a low molecular weight have a narrow temperature range showing a mold release effect and melt at the time of fixing. A so-called offset phenomenon is easily generated in which the toner adheres to the surface of the fixing roller and stains subsequent paper.

  In that respect, ester waxes containing ester groups are easily compatible with the resin due to the action of polar groups and have a large resin plasticizing effect, so that the molecular weight of the wax can be designed to be large, and the effect of preventing offset when the fixing temperature is high. Also excellent.

  However, ester wax has many compatible components in the binder resin and has a high affinity with the processing agent of the external additive added to the surface of the toner particles. The dissolved component oozes out on the surface of the toner particles, contaminates the members in the developing machine, and easily causes various image defects.

  In order to solve this problem, a technique is known in which an ester wax and a hydrocarbon wax are used in combination to suppress the exudation of the wax component over time.

  Patent Document 1 proposes a toner having an excellent balance of toner storage stability, hot offset resistance, and low-temperature fixability by containing an eutectic wax of ester wax and petroleum wax. In Patent Document 2, by including a monoester compound and a hydrocarbon compound having a branched chain structure and / or a cyclic structure, fixing can be performed with sufficient fixing strength at a low fixing temperature, and strip-like or stripe-like image defects can be obtained. There has been proposed a toner capable of suppressing the occurrence of this.

  However, although the toner described in Patent Document 1 is excellent in low-temperature fixability on general plain paper, when a solid image is output on plain paper with high smoothness, a blister is included in a part of the fixed image. It has been found that a new problem arises in which the so-called small blister-like image defect appears. Further, the toner described in Patent Document 2 still has room for improvement in the developability of the toner after long-term storage in a printer having a high-speed process.

  For this reason, it is necessary to develop a toner that enables stable low-temperature fixing on various types of paper, does not cause an offset phenomenon, and can maintain stable image quality over a long period of time even if a large amount of printing is performed in a high-speed process. ing.

JP 2008-299010 A JP 2007-206179 A

  The object of the present invention is to show good fixability even in a high-speed process, there is no occurrence of blisters even on printing on smooth paper, and contamination of members in the developing device even during long-term use or use after long-term storage. It is an object of the present invention to provide a toner capable of suppressing image quality and maintaining image quality over a long period.

The present invention adds a polymerizable monomer composition containing a polymerizable monomer, a microcrystalline wax, an ester wax, and a colorant to an aqueous medium, and particles of the polymerizable monomer composition in the aqueous medium. granulation step, and the polymerizable monomer and polymerizable monomer is polymerized included in particles of the composition to obtain toner particles with polymer to form a
A method for producing a toner comprising:
The toner contains 5.0% by mass or less of tetrahydrofuran (THF) insoluble matter derived from a resin component;
The weight average molecular weight of the absolute molecular weight measured by GPC-MALS viscometer analysis at 40 ° C. of the THF soluble component of the toner is 2.5 × 10 ⁴ or more and 2.5 × 10 ⁵ or less. The slope (a) when the common logarithm (log [M]) of absolute molecular weight (M) is plotted on the horizontal axis and the common logarithm (log [Iv]) of viscosity (Iv) is plotted on the vertical axis is 0. 50 or more and 0.80 or less,
A method for producing a toner , wherein the ester wax is a mono-functional or tetra-functional ester wax.

  According to the present invention, good fixability is exhibited even in a high-speed process, no blisters are generated even on printing on smooth paper, and contamination of members in the developing device even during long-term use or use after long-term storage. Thus, it is possible to provide a toner capable of suppressing image quality and maintaining image quality over a long period of time.

In the 40 ° C. GPC-MALS viscometer analysis of the toner, the common logarithm (log [Iv]) of viscosity (Iv) was plotted against the common logarithm of absolute molecular weight (M) (log [M]). It is a figure which shows inclination. FIG. 2 is a system diagram in which a stirring device preferably used in the present invention is incorporated in a circulation path. It is explanatory drawing of the stirring apparatus which has a stator and a rotor.

  The present inventors diligently studied about a toner capable of achieving both low-temperature fixability and development stability corresponding to various paper types even in a high-speed process in a copying machine or a printer.

  As a result, it was found that the dispersion state of the wax in the toner particles is related to the low-temperature fixability and the bleeding suppression property. By controlling the branching characteristics of the binder resin in the toner containing the ester wax and the microcrystalline wax, a finely dispersed state of the wax component in the binder resin can be achieved. The present inventors have invented a toner that improves the blisters generated and has a high effect of suppressing the seepage of toner particles to the surface.

  Hereinafter, the wax dispersion state of the conventional toner and the mechanism of blister generation on smooth paper will be described, and then the action of the branching characteristics of the binder resin on the wax dispersibility in the present invention and the toner of the present invention will be described in detail.

  In a suspension polymerization method toner obtained by making droplets of monomer particles containing toner materials such as wax and pigment in an aqueous medium and polymerizing them, in the case of a conventional toner using ester wax and hydrocarbon wax, the wax is It exists in a state of being collected at the center of the toner particles. This is considered to be due to the property that when the toner particles are produced in an aqueous medium having a high polarity, a highly polar component is oriented toward the interface of the toner particles and a low component is oriented toward the center of the toner particles. Therefore, in the process of producing toner particles, most of the non-polar hydrocarbon wax tends to collect at the center of the toner particles in a phase-separated state from the binder resin. In addition, the ester wax having polarity is mostly collected in the center of the toner particles in a phase-separated state due to the influence of the long-chain hydrocarbon group, but a part thereof is present in a form compatible with the binder resin. When two types of waxes are used in combination, the ester wax exhibits the property of being attracted to the hydrocarbon wax having high affinity, so that the amount of compatibility in the binder resin is reduced, and it is possible to maintain a state where it is difficult to exude over time.

  The presence state of such a wax contributes to plasticization of the binder resin at the time of low-temperature fixing, and exhibits an effect of suppressing the seepage of toner particles to the surface during toner storage.

  However, it has been found that when a solid image is output on plain paper having a high smoothness, a new problem occurs in which blisters are generated in a part of the fixed image.

  As a result of detailed analysis of the blister image, the present inventors have found that the fixing toner surface adheres to the fixing roller at a minute portion where the supply of the wax component is insufficient on the contact surface between the fixing image and the fixing roller, and is bonded. I found out that it was causing a small blister of the resin.

  When low-temperature fixing is performed using smooth paper, the unevenness of the paper surface is eliminated as compared with general plain paper, and the contact area between the paper surface and the fixing toner surface and between the fixing toner surface and the fixing roller surface increases. Therefore, in order to satisfactorily perform low-temperature fixing using smooth paper, it is necessary to supply a uniform and sufficient amount of the wax component to the surface of the fixing roller. In conventional toners using ester wax and hydrocarbon wax, since the wax exists in the center of the toner, it is suggested that it is disadvantageous to uniformly supply the wax component to every corner of the fixed toner surface. .

  The present inventors examined the resin composition, the wax type, and the presence state of the wax that can sufficiently and uniformly supply the wax component to the fixing roller even during low-temperature fixing and that do not cause development problems even under severe use conditions. As a result, by containing microcrystalline wax and ester wax and controlling the branching characteristics of the binder resin, the microcrystalline wax can be uniformly dispersed in the toner particles, and the toner of the present invention satisfying the above effects can be obtained. To achieve.

  Microcrystalline wax, unlike paraffin wax consisting of general linear hydrocarbon components, has a large amount of microparaffins due to the large amount of isoparaffin having a branched chain structure and cycloparaffin having a cyclic structure. It is a wax characterized by crystal growth.

  When microcrystalline wax is added to a conventional suspension polymerization toner, the microcrystalline wax is present in the center of the toner by forming a large number of fine crystals.

  According to the study by the present inventors, in a toner containing microcrystalline wax and ester wax, when the binder resin has a certain branch composition, the wax is finely dispersed and grown in the binder resin constituting the toner particles. I found out.

  The reason why the finely dispersed state can be achieved in the binder resin is not necessarily clear, but the present inventors believe that the reason is as follows.

  The production process of the suspension polymerization method includes a distillation process for removing residual monomers at a high temperature above the melting point of the wax. The wax component in the binder resin exists in a molten state in the distillation step, but crystal growth starts with a certain trigger when the wax crystallization temperature is reached in the cooling step of the next step. At this time, the crystal growth is considered to depend on the amount of compatible components in the resin and the presence of crystal nuclei that are the starting point of crystal growth. It is considered that the ester wax before crystallizing has a large amount of compatibility with the binder resin, and microcrystalline wax having high affinity with the ester wax exists in a state of sufficiently penetrating into the binder resin.

  When toner particles are cooled in such an atmosphere, it is thought that molecular entangled parts due to the branching and crosslinking structure of the resin present in the binder resin act as crystal nuclei, and fine crystal growth starts from there. As a result, it is considered that a uniform wax fine dispersion state has been achieved.

  In the toner of the present invention, it is essential to control the absolute molecular weight of a tetrahydrofuran (THF) -soluble component measured by GPC-MALS-viscosity analysis at 40 ° C. and the slope that serves as an index representing the degree of branching. .

  Conventionally, molecular weight measurement by GPC using a THF solvent, which has been generally measured, only yields an equivalent molecular weight based on the molecular size. For this reason, information such as the molecular weight and the degree of branching of the polymer contained in the toner cannot be obtained accurately. On the other hand, the molecular weight obtained by GPC-MALS-viscosity analysis of the tetrahydrofuran (THF) soluble component in the present invention indicates the absolute molecular weight of the resin component. Moreover, the branch information contained in the resin component is also obtained.

The toner of the present invention contains 5.0 mass% or less of a tetrahydrofuran (THF) insoluble component derived from a resin component, and the tetrahydrofuran (THF) soluble component has a weight average molecular weight of 2.5 × 10 ⁴ or more and 2 in absolute molecular weight. 5 × 10 ⁵ or less, and the composition of the resin component of the toner is relatively low molecular weight, and the branching degree distribution contained in the resin component in this molecular weight region is highly controlled to the state described below. is there.

  The resin component insoluble in THF is a polymer gel component having a high degree of crosslinking. In the present invention, the resin component soluble in THF is intentionally branched to improve the fine dispersion of the wax, and the resin microcrosslinking structure is specialized in the low temperature fixing region due to its elasticity. It also has the effect of offset suppression. Therefore, in the present invention, there is no need for a THF-insoluble matter that may hinder the low-temperature fixability. In the toner of the present invention, it is essential that the content of the THF-insoluble matter is 5.0% by mass or less based on the toner. is there.

  By setting the THF-insoluble content to 5.0% by mass or less, stable low-temperature fixing characteristics can be obtained even in a high-speed process.

When the weight average molecular weight of the THF soluble component is less than 2.5 × 10 ⁴ , the viscosity of the resin component at the time of fixing becomes too low, resulting in poor anti-offset performance. In addition, the effect of suppressing the exudation of wax on the surface of the toner particles with time is weakened. On the other hand, when the absolute molecular weight of the THF-soluble component exceeds 2.5 × 10 ⁵ , the low-temperature fixing property is deteriorated.

  In GPC-MALS-viscosity analysis, as described above, distribution information of linear polymers and branched polymers can be obtained. In general, as the molecular weight of a polymer increases, the viscosity increases due to the bulky structure. Further, when comparing the viscosities of polymers having the same molecular weight and different degrees of branching, the higher the degree of branching, the smaller the molecular spread and the smaller the radius of rotation. The above relationship shows a linear linear relationship specific to the constituent monomer when the common logarithm (log [Iv]) of viscosity Iv is plotted against the common logarithm (log [M]) of absolute molecular weight (M). It has been known. In addition, a distribution containing more components having a higher degree of branching exhibits a lower viscosity than a distribution of a polymer composed only of linear components, and thus the slope of this straight line becomes smaller.

  The present inventors paid attention to this relationship, and intensively studied the effect of the molecular weight and branching degree of the resin component constituting the toner on the wax dispersibility. As a result, the inventors have found that when the absolute molecular weight is controlled to be small and the degree of branching of the resin component is increased at a certain rate, excellent characteristics are exhibited.

  In the toner of the present invention, the common logarithm (log [M]) of the absolute molecular weight (M) measured by the GPC-MALS viscometer analysis is plotted on the horizontal axis, and the common logarithm (log [Iv) of the viscosity (Iv) is plotted. ]) Is plotted on the vertical axis, the slope (a) is 0.50 or more and 0.80 or less.

  In the present invention, precisely controlling the branched structure of the resin represented by the inclination (a) is a particularly important factor for exerting the effects of the present invention.

  In the present invention, the slope (a) when plotting the common logarithm (log [Iv]) of viscosity (Iv) against the common logarithm (log [M]) of absolute molecular weight (M) is as follows: By performing Mark-Houwink-Sakurada Plots with the analysis software attached to the main body, and specifying the analysis range corresponding to all resin components of the chromatogram detected by the viscometer in the GPC-MALS-viscosity analysis ternary simultaneous output profile It is calculated | required (refer FIG. 1).

  When the slope (a) is less than 0.50, the proportion of the polymer having a high degree of branching becomes excessive and the elastic modulus increases, so that the low-temperature fixing characteristics tend to be inferior. On the other hand, when the slope (a) exceeds 0.80, the proportion of the linear polymer increases, so that the branch point of the resin that becomes the wax crystal nucleus decreases and the finely dispersed state of the wax becomes worse.

  In order to control the molecular weight and branching degree distribution of the resin component constituting the toner of the present invention and to adjust the above (a), in the case of producing toner particles by polymerizing monomers by suspension polymerization, Examples thereof include a method of controlling the degree of branching by selecting an initiator having a high pulling effect and adjusting the addition method and active conditions to control the crosslinking reaction and graft polymerization. It can also be controlled by selecting monomer types, adding a crosslinking agent, and adding a plurality of types of resin components whose branching degree is controlled.

  The ester wax used in the present invention is a monofunctional or tetrafunctional ester wax, and a bifunctional or tetrafunctional ester wax is more preferable.

  Specifically, saturated fatty acid monoesters such as stearyl stearate and behenyl behenate; diesters of saturated aliphatic dicarboxylic acids and saturated fatty alcohols such as dibehenyl sebacate, distearyl dodecanedioate and distearyl octadecanedioate A diesterified product of a saturated aliphatic diol such as nonanediol dibehenate or dodecanediol distearate and a saturated fatty acid; a triesterified product of a trialcohol such as glycerin tribehenate or glycerin tristearate and a saturated fatty acid; Partially esterified products of trialcohols such as glycerin monobehenate and glycerin dibehenate and saturated fatty acids; tetraethers of tetrahydric alcohols such as pentaerythritol tetrapalmitate and pentaerythritol tetrastearate and saturated fatty acids Ether compound; pentaerythritol monostearate, pentaerythritol distearate, partial ester of tetravalent alcohol and a saturated fatty acid such as pentaerythritol tristearate; and the like.

  An ester wax having more than four functionalities satisfying a desired melting point has a high molecular weight, and therefore the resin plasticity is weakened. Therefore, it is difficult to effectively exhibit the low-temperature fixing property.

  The ester wax used in the present invention is more preferably a bifunctional or tetrafunctional ester wax. Although the clear reason is not necessarily clarified, the present inventors consider the reason as follows.

  Since the molecular structure of the bifunctional or tetrafunctional ester wax is easily compatible with the binder resin, and exhibits a characteristic that is easily compatible with the microcrystalline wax, the affinity is further increased and more uniform fine dispersion is achieved. It is considered that the wax component can be uniformly supplied to the surface of the fixing toner at the time of low-temperature fixing, and the effect of suppressing seepage during long-term storage has been enhanced.

  The microcrystalline wax used in the present invention preferably has an extrapolated melting start temperature (Tim) of 52 ° C. or higher and 70 ° C. or lower in a DSC curve measured by a differential scanning calorimeter.

  By setting the extrapolated melting start temperature (Tim) to 52 ° C. or more and 70 ° C. or less, the melting start temperature of the wax and the glass transition temperature of the binder resin approach, so the resin plastic effect at the time of fixing works more effectively, A sufficient amount of wax can be supplied to the surface of the fixing toner, and stable low-temperature fixing characteristics can be exhibited regardless of the type of paper.

  When the extrapolated melting start temperature (Tim) is less than 52 ° C., the wax tends to ooze out on the toner surface over time, and the durability after long-term storage is poor. On the other hand, when the extrapolated melting start temperature (Tim) exceeds 70 ° C., it becomes difficult to supply a sufficient amount of wax to the surface of the fixing toner at the time of low-temperature fixing, resulting in poor low-temperature fixability.

  The microcrystalline wax used in the present invention preferably has a maximum endothermic peak temperature (Tpm) of 60 ° C. or higher and 90 ° C. or lower in a DSC curve measured by a differential scanning calorimeter.

  By setting the peak temperature (Tpm) of the maximum endothermic peak to 60 ° C. or higher and 90 ° C. or lower, blisters generated when outputting a solid image to smooth paper in low-temperature fixing can be improved, and solid paper such as gloss paper in a low-speed process can be improved. Also in the image output, an offset is suppressed and a high gloss image can be obtained.

  When the peak temperature (Tpm) of the maximum endothermic peak is less than 60 ° C., it is difficult to exert a release effect during high-temperature fixing, resulting in poor hot offset properties. On the other hand, when the peak temperature (Tpm) of the maximum endothermic peak exceeds 90 ° C., it becomes difficult to instantaneously supply wax to the surface of the fixed image during low-temperature fixing, resulting in poor low-temperature fixability.

  The ratio of the ester wax to the total amount (additional total amount) of the microcrystalline wax and the ester wax used in the present invention is preferably 30% by mass or more and 96% by mass or less.

  By setting the proportion of the ester wax to be 30% by mass or more and 96% by mass or less, it exhibits good fixing characteristics regardless of the paper type in a wide temperature range, and prevents the wax from exuding on the toner surface over time. Excellent.

  When the addition ratio of the ester wax is less than 30% by mass, it is difficult to obtain a resin plasticizing effect by the ester wax and a releasing effect at low temperature fixing, and the low temperature fixing property is inferior. On the other hand, when the addition ratio of the ester wax exceeds 96% by mass, the fine dispersion property of the wax becomes insufficient, and the blister suppressing effect when the solid image is output to the smooth paper, the offset preventing effect, It is inferior in the effect of suppressing the exudation of wax.

  The total amount of microcrystalline wax and ester wax used in the present invention is preferably 4 to 16 parts by mass, more preferably 7 to 14 parts by mass, with respect to 100 parts by mass of the binder resin. It is.

  By adding the total amount of the microcrystalline wax and the ester wax to 4 parts by mass or more and 16 parts by mass or less, the effect of the present invention can be more effectively exhibited, and low temperature fixability corresponding to various paper types can be obtained. Excellent development characteristics after long-term storage.

  Below, the material used by this invention is demonstrated.

  As the polymerizable monomer used in producing the toner of the present invention, a vinyl polymerizable monomer capable of radical polymerization is used. As the vinyl polymerizable monomer, a monofunctional polymerizable monomer or a polyfunctional polymerizable monomer can be used. Monofunctional polymerizable monomers include styrene; α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, pn-butyl. Styrene, p-tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p-methoxy styrene, p A styrene derivative such as phenylstyrene; 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 accelerator Acrylic polymerizable monomers such as N-octyl acrylate, n-nonyl acrylate, cyclohexyl acrylate, benzyl acrylate, dimethyl phosphate ethyl acrylate, diethyl phosphate ethyl acrylate, dibutyl phosphate ethyl acrylate, 2-benzoyloxyethyl acrylate Body; 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 meta Methacrylic polymerizable monomers such as relate and dibutyl phosphate ethyl methacrylate; methylene aliphatic monocarboxylic acid esters; vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate and vinyl formate; vinylmethyl And vinyl ethers such as ether, vinyl ethyl ether and vinyl isobutyl ether; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and vinyl isopropyl ketone.

  As polyfunctional polymerizable monomers, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol Diacrylate, polypropylene glycol diacrylate, 2,2′-bis (4- (acryloxydiethoxy) phenyl) propane, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol Dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol Dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, polypropylene glycol dimethacrylate, 2,2'-bis (4- (methacryloxy-diethoxy) phenyl) propane, Examples include 2,2′-bis (4- (methacryloxy / polyethoxy) phenyl) propane, trimethylolpropane trimethacrylate, tetramethylolmethane tetramethacrylate, divinylbenzene, divinylnaphthalene, and divinyl ether.

  In the present invention, the above-described monofunctional polymerizable monomers are used alone or in combination of two or more, or the above-described monofunctional polymerizable monomers and polyfunctional polymerizable monomers are used in combination. . Since the polyfunctional polymerizable monomer also acts as a crosslinking agent, it is effective for controlling the degree of branching of the present invention.

  In the production of the toner of the present invention, it is preferable to use a crosslinking agent during the synthesis of the binder resin as a means for controlling the molecular weight and branching degree of the binder resin component.

  Examples of the crosslinking agent used in the present invention include the following as the bifunctional crosslinking agent. 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 Nippon Kayaku), and dimethacrylate instead of the above diacrylate Thing was.

  The following are mentioned as a polyfunctional crosslinking agent. Pentaerythritol triacrylate, trimethylol ethane triacrylate, trimethylol propane triacrylate, tetramethylol methane tetraacrylate, oligoester acrylate and methacrylate, 2,2-bis (4-methacryloxypolyethoxyphenyl) propane, diallyl phthalate, tri Allyl cyanurate, triallyl isocyanurate and triallyl trimellitate. The addition amount of these crosslinking agents is preferably 0.02 parts by mass or more and 5 parts by mass or less, and more preferably 0.05 parts by mass or more and 2 parts by mass or less with respect to 100 parts by mass of the monomer.

  An oil-soluble initiator and / or a water-soluble initiator is used as a polymerization initiator that can be used by the toner of the present invention to control the molecular weight and branching degree of the binder resin. Preferably, the half-life at the reaction temperature during the polymerization reaction is from 0.5 hours to 30 hours. Further, when the polymerization reaction is carried out at an addition amount of 0.5 to 20 parts by mass with respect to 100 parts by mass of the polymerizable monomer, a polymer having a maximum between usually 10,000 and 100,000 is obtained. Therefore, a toner having appropriate strength and melting characteristics can be obtained.

  As polymerization initiators, 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile, 1,1′-azobis (cyclohexane-1-carbonitrile), 2,2′-azobis-4-methoxy-2,4-dimethylvaleronitrile, azo or diazo polymerization initiator such as azobisisobutyronitrile; benzoyl peroxide, t-butylperoxy 2-ethylhexa Noate, t-butyl peroxypivalate, t-butyl peroxyisobutyrate, t-butyl peroxyneodecanoate, methyl ethyl ketone peroxide, diisopropyl peroxycarbonate, cumene hydroperoxide, 2,4-dichlorobenzoyl Peroxides such as peroxide and lauroyl peroxide Initiator and the like.

  In the present invention, the most preferable initiator selection and conditions for controlling the degree of branching of the binder resin include a method in which an initiator having a high hydrogen abstraction effect is used in an active state at the initial stage of the polymerization reaction. As the initiator having a high hydrogen abstraction ability, an organic peroxide-based initiator is preferable, and a perbutyl-based organic peroxide that generates a t-butoxy radical is most preferable. Moreover, the preferable atmosphere of the active state of the initiator in the present invention includes, for example, a polymerization state at a temperature higher by 10 ° C. or more than the 10-hour half-life temperature of the initiator.

  In the present invention, in order to control the degree of polymerization of the polymerizable monomer constituting the binder resin, a known chain transfer agent, polymerization inhibitor and the like can be further added and used.

  When the toner of the present invention is used in a printer or copying machine having a high process speed, it is preferable to add a resin having a polar group for the purpose of improving durability stability. When a resin having a polar group is added to the suspension polymerization method toner of the present invention, the toner particles have high robustness because the polar group tends to exist at a gradient concentration on the interface side of the toner particles. Rise. The resin having a polar group that can be preferably used in the present invention is a polyester resin capable of forming a strong shell layer by phase separation from the binder resin, or an excellent sloped shell layer that is compatible with the binder resin. A vinyl resin containing the same composition as the binder resin that can be formed is preferable.

  As the resin having a polar group, either one or both of a polyester resin and a vinyl resin can be appropriately selected and used.

  As the polyester resin that can be used in the present invention, either one or both of a saturated polyester resin and an unsaturated polyester resin can be appropriately selected and used.

  The alcohol component and acid component which comprise a polyester resin are illustrated below. As alcohol components, ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol, 1,5-pentanediol, 1,6-hexane Diol, neopentyl glycol, 2-ethyl-1,3-hexanediol, cyclohexanedimethanol, butenediol, octenediol, cyclohexenedimethanol, hydrogenated bisphenol A, and bisphenol derivatives represented by the following general formula (1),

（式中、Ｒはエチレンまたはプロピレン基であり、ｘ，ｙはそれぞれ１以上の整数であり、かつｘ＋ｙの平均値は２〜１０である。）
あるいは一般式（１）の化合物の水添物、また、下記一般式（２）で示されるジオール、

(In the formula, R is an ethylene or propylene group, x and y are each an integer of 1 or more, and the average value of x + y is 2 to 10.)
Or a hydrogenated product of the compound of the general formula (1), a diol represented by the following general formula (2),

あるいは式（２）の化合物の水添物のジオール、さらには、グリセリン、ペンタエリスリトール、ソルビット、ソルビタン、ノボラック型フェノール樹脂のオキシアルキレンエーテルのような多価アルコール等、が挙げられる。

Or the diol of the hydrogenated product of the compound of Formula (2), Furthermore, polyhydric alcohol like the oxyalkylene ether of glycerol, pentaerythritol, sorbit, sorbitan, a novolak-type phenol resin, etc. are mentioned.

  Examples of the divalent carboxylic acid include the following. Benzene dicarboxylic acid or its anhydride such as phthalic acid, terephthalic acid, isophthalic acid, phthalic anhydride, alkyl dicarboxylic acid such as succinic acid, adipic acid, sebacic acid, azelaic acid or its anhydride, and further 6 carbon atoms Succinic acid or its anhydride substituted with an alkyl or alkenyl group of -18, unsaturated dicarboxylic acid such as fumaric acid, maleic acid, citraconic acid, itaconic acid or its anhydride, and trimellitic acid, pyromellitic Acid, polyvalent carboxylic acid such as 1,2,3,4-butanetetracarboxylic acid and benzophenonetetracarboxylic acid and its anhydride.

  When the resin having a polar group is a polyester resin, the addition amount is preferably 0.5 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the binder resin.

  As the resin having a vinyl polar group that can be used in the present invention, a styrene-based acrylic acid copolymer, a styrene-based methacrylic acid copolymer, a styrene-based maleic acid copolymer, and the like are preferable. A styrene-acrylic-acrylic acid copolymer is preferable because the charge amount can be easily controlled. Moreover, it is more preferable that the resin having a polar group of the present invention contains a monomer having a primary or secondary hydroxyl group.

  Specifically, styrene-2-hydroxyethyl methacrylate-methacrylic acid-methyl methacrylate copolymer, styrene-n-butyl acrylate-2-hydroxyethyl methacrylate-methacrylic acid-methyl methacrylate copolymer, styrene-α- Examples thereof include methylstyrene-2-hydroxyethyl methacrylate-methacrylic acid-methyl methacrylate copolymer. A resin containing a monomer having a primary or secondary hydroxyl group has a large polarity and has a better long-term storage stability.

  When the resin having a polar group is a vinyl resin, the addition amount is preferably 2 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the binder resin.

  A preferable method for adding the resin having a polar group is a method in which the polar group-containing resin is dissolved in a monomer constituting the binder resin in the process of producing a toner by a suspension polymerization method.

  In the present invention, a polymer having a sulfonic acid group, a sulfonic acid group or a sulfonic acid ester group in the side chain is preferably used mainly for charge control and stabilization of granulation in an aqueous dispersion medium. Among them, it is particularly preferable to use a polymer or copolymer of a sulfonic acid group, a sulfonic acid group, or a sulfonic acid ester group.

  Monomers having a sulfonic acid group, a sulfonic acid group or a sulfonic acid ester group for producing this polymer are styrenesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-methacrylamide-2-methyl. There are propane sulfonic acid, vinyl sulfonic acid, methacryl sulfonic acid and their alkyl esters.

  The polymer containing a sulfonic acid group, a sulfonic acid group or a sulfonic acid ester group used in the present invention may be a homopolymer of the above monomer. And a copolymer thereof. As the monomer that forms a copolymer with the above monomer, there is a vinyl polymerizable monomer, and the monofunctional polymerizable monomer or polyfunctional polymerization exemplified in the description of the binder resin component above. Sex monomers can be used.

  The polymer having a sulfonic acid group or the like preferably contains 0.01 part by mass or more and 5.0 parts by mass or less with respect to 100 parts by mass of the polymerizable monomer or the binder resin. More preferably, it is 0.1 to 3.0 parts by mass.

  When the polymer having a sulfonic acid group or the like is 0.01 parts by mass or more and 5.00 parts by mass or less, a sufficient charging stability effect of the toner particles is exhibited, and therefore, environmental characteristics and durability characteristics are excellent. Furthermore, in the granulation step in an aqueous dispersion medium using a dispersion stabilizer having a positive component, a sharp distribution of toner particle size can be obtained in order to enhance the formation of the electric double layer.

  In the production of the toner of the present invention, it is preferable to add a low molecular weight polymer in order to obtain a preferable molecular weight distribution of the toner of the present invention. The low molecular weight polymer can be added to the polymerizable monomer composition during the production process of the suspension polymerization toner. The low molecular weight polymer has a weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) in the range of 2,000 to 5,000 and Mw / Mn of less than 4.5, preferably Is preferably less than 3.0.

  Examples of the low molecular weight polymer include low molecular weight polystyrene, low molecular weight styrene-acrylic acid ester copolymer, and low molecular weight styrene-acrylic copolymer.

  The toner of the present invention contains a colorant as an essential component in order to impart coloring power. Examples of the colorant preferably used in the present invention include the following organic pigments or dyes and inorganic pigments.

  As an organic pigment or organic dye as a cyan colorant, a copper phthalocyanine compound and a derivative thereof, an anthraquinone compound, or a basic dye lake compound can be used. Specific examples include the following. C. I. Pigment blue 1, C.I. I. Pigment blue 7, C.I. I. Pigment blue 15, C.I. I. Pigment blue 15: 1, C.I. I. Pigment blue 15: 2, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 60, C.I. I. Pigment blue 62, C.I. I. Pigment Blue 66.

  Examples of the organic pigment or organic dye as the magenta colorant include the following. Condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, perylene compounds. Specific examples include the following. C. I. Pigment red 2, C.I. I. Pigment red 3, C.I. I. Pigment red 5, C.I. I. Pigment red 6, C.I. I. Pigment red 7, C.I. I. Pigment violet 19, C.I. I. Pigment red 23, C.I. I. Pigment red 48: 2, C.I. I. Pigment red 48: 3, C.I. I. Pigment red 48: 4, C.I. I. Pigment red 57: 1, C.I. I. Pigment red 81: 1, C.I. I. Pigment red 122, C.I. I. Pigment red 144, C.I. I. Pigment red 146, C.I. I. Pigment red 150, C.I. I. Pigment red 166, C.I. I. Pigment red 169, C.I. I. Pigment red 177, C.I. I. Pigment red 184, C.I. I. Pigment red 185, C.I. I. Pigment red 202, C.I. I. Pigment red 206, C.I. I. Pigment red 220, C.I. I. Pigment red 221, C.I. I. Pigment Red 254.

  As the organic pigment or organic dye as the yellow colorant, compounds represented by condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds are used. Specific examples include the following. C. I. Pigment yellow 12, C.I. I. Pigment yellow 13, C.I. I. Pigment yellow 14, C.I. I. Pigment yellow 15, C.I. I. Pigment yellow 17, C.I. I. Pigment yellow 62, C.I. I. Pigment yellow 74, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 93, C.I. I. Pigment yellow 94, C.I. I. Pigment yellow 95, C.I. I. Pigment yellow 97, C.I. I. Pigment yellow 109, C.I. I. Pigment yellow 110, C.I. I. Pigment yellow 111, C.I. I. Pigment yellow 120, C.I. I. Pigment yellow 127, C.I. I. Pigment yellow 128, C.I. I. Pigment yellow 129, C.I. I. Pigment yellow 147, C.I. I. Pigment yellow 151, C.I. I. Pigment yellow 154, C.I. I. Pigment yellow 155, C.I. I. Pigment yellow 168, C.I. I. Pigment yellow 174, C.I. I. Pigment yellow 175, C.I. I. Pigment yellow 176, C.I. I. Pigment yellow 180, C.I. I. Pigment yellow 181, C.I. I. Pigment yellow 191, C.I. I. Pigment Yellow 194.

  As the black colorant, carbon black, a magnetic material, and a color toned to black using the yellow / magenta / cyan colorant are used.

  In the present invention, since toner particles are obtained by using the suspension polymerization method, it is necessary to pay attention to the polymerization inhibition property and water phase migration property of the colorant, and preferably, there is no surface modification, for example, polymerization inhibition. It is better to apply a hydrophobic treatment to the colorant with a substance. In particular, dyes and carbon blacks have many polymerization inhibiting properties, so care must be taken when using them. A preferable method for surface-treating the dye system includes a method in which a polymerizable monomer is polymerized in the presence of these dyes in advance, and the obtained colored polymer is added to the monomer system.

  Moreover, about carbon black, you may process with the substance which reacts with the surface functional group of carbon black other than the process similar to the said dye, for example, polyorganosiloxane.

  These colorants can be used alone or mixed and further used in the form of a solid solution. The colorant used in the toner of the present invention is selected from the viewpoints of hue angle, saturation, brightness, light resistance, OHP transparency, and dispersibility in the toner.

  The colorant is preferably used in an amount of 1 part by mass or more and 20 parts by mass or less based on 100 parts by mass of the binder resin.

  Furthermore, the toner of the present invention can be a magnetic toner containing a magnetic material as a colorant. In this case, the magnetic material can also serve as a colorant. Magnetic materials include iron oxides such as magnetite, hematite and ferrite; metals such as iron, cobalt and nickel or aluminum, cobalt, copper, lead, magnesium, tin, zinc, antimony and beryllium of these metals And alloys of metals such as bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten and vanadium, and mixtures thereof.

  The magnetic material is more preferably a surface-modified magnetic material. When a magnetic toner is prepared by a polymerization method, it is preferable to apply a hydrophobic treatment with a surface modifier, which is a substance that does not inhibit polymerization. Examples of such surface modifiers include silane coupling agents and titanium coupling agents.

  These magnetic materials have a number average particle diameter of 2 μm or less, preferably 0.1 μm or more and 0.5 μm or less. The amount contained in the toner particles is 20 parts by mass or more and 200 parts by mass or less with respect to 100 parts by mass of the polymerizable monomer or binder resin, and particularly preferably 40 parts by mass or more and 150 parts by mass with respect to 100 parts by mass of the binder resin. The following is good.

  In the toner of the present invention, a charge control agent can be mixed with toner particles as needed, separately from or in addition to the polymer having a sulfonic acid group in the side chain described above. . By adding a charge control agent, the charge characteristics can be stabilized, and the optimum triboelectric charge amount can be controlled according to the development system.

  As the charge control agent, known ones can be used, and in particular, a charge control agent that has a high frictional charging speed and can stably maintain a constant triboelectric charge amount is preferable. Further, when the toner is produced by a direct polymerization method, a charge control agent having a low polymerization inhibitory property and substantially free from a solubilized product in an aqueous dispersion medium is particularly preferable.

  Examples of charge control agents include those that control the toner to be negatively charged, such as organometallic compounds and chelate compounds. Examples thereof include monoazo metal compounds, acetylacetone metal compounds, aromatic oxycarboxylic acids, aromatic dicarboxylic acids, oxycarboxylic acids, and dicarboxylic acid-based metal compounds. Others include aromatic oxycarboxylic acids, aromatic mono- and polycarboxylic acids and their metal salts, anhydrides, esters, phenol derivatives such as bisphenols. Further examples include urea derivatives, metal-containing salicylic acid compounds, metal-containing naphthoic acid compounds, boron compounds, quaternary ammonium salts, calixarene, and resin charge control agents.

  Examples of charge control agents include those that control the toner to be positively charged. Nigrosine-modified products with nigrosine and fatty acid metal salts; guanidine compounds; imidazole compounds; quaternary ammonium salts such as tributylbenzylammonium-1-hydroxy-4-naphthosulfonate, tetrabutylammonium tetrafluoroborate, and analogs thereof Phosphonium salts and other onium salts and their lake pigments; triphenylmethane dyes and their lake pigments (as rake agents, phosphotungstic acid, phosphomolybdic acid, phosphotungsten molybdic acid, tannic acid, lauric acid, gallic acid Acid, ferricyanide, ferrocyanide); metal salt of higher fatty acid; resin charge control agent.

  The toner of the present invention can contain these charge control agents alone or in combination of two or more.

  Among these charge control agents, a metal-containing salicylic acid-based compound is preferable in order to sufficiently exhibit the effects of the present invention, and the metal is particularly preferably aluminum or zirconium. The most preferred charge control agent is an aluminum 3,5-di-tert-butylsalicylate compound.

  A preferable blending amount of the charge control agent is 0.01 parts by mass or more and 5 parts by mass or less, more preferably 0.2 parts by mass or more and 3 parts by mass or less with respect to 100 parts by mass of the binder resin. However, it is not essential to add a charge control agent to the toner of the present invention, and the toner does not necessarily contain a charge control agent by actively utilizing frictional charging with the toner layer thickness regulating member or the toner carrier. There is no need to let it.

  The method for producing the toner of the present invention will be described below.

  The toner of the present invention is produced by a suspension polymerization method. In this suspension polymerization method, a polymerizable monomer is polymerized by uniformly dissolving or dispersing a wax and a colorant (and, if necessary, a polymerization initiator, a crosslinking agent, a charge control agent, and other additives). A monomer composition is used. Thereafter, the polymerizable monomer composition is dispersed in an aqueous dispersion medium containing a dispersion stabilizer using an appropriate stirrer, and a polymerization reaction is performed to obtain toner particles having a desired particle size. It is. The toner particles of the present invention can be obtained by subjecting the toner particles to distillation, filtration, washing, and drying by a known method after the polymerization is completed, and if necessary, mixing a fluidity improver and adhering it to the surface.

  As the dispersant used for preparing the aqueous dispersion medium, known inorganic and organic dispersants can be used.

  Specifically, examples of the inorganic dispersant include the following. Tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, magnesium carbonate, calcium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate, bentonite, silica, alumina Is mentioned. Examples of the organic dispersant include polyvinyl alcohol, gelatin, methyl cellulose, methyl hydroxypropyl cellulose, ethyl cellulose, carboxymethyl cellulose sodium salt, and starch.

  Commercially available nonionic, anionic and cationic surfactants can also be used. Examples of such surfactants include the following. Sodium dodecylbenzenesulfonate, sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, sodium laurate, potassium stearate, calcium oleate.

  As the dispersant used in preparing the aqueous dispersion medium used in the toner of the present invention, an inorganic, poorly water-soluble dispersant is preferable, and a poorly water-soluble inorganic dispersant that is soluble in an acid is preferably used.

  In the present invention, when preparing an aqueous dispersion medium using a poorly water-soluble inorganic dispersant, the amount of these dispersants used is 0.2 with respect to 100 parts by mass of the polymerizable vinyl monomer. It is preferable that it is not less than 2.0 parts by mass. In the present invention, it is preferable to prepare an aqueous dispersion medium using 300 to 3,000 parts by mass of water with respect to 100 parts by mass of the polymerizable monomer composition.

  In the present invention, when preparing an aqueous dispersion medium in which the poorly water-soluble inorganic dispersant as described above is dispersed, a commercially available dispersant may be used as it is. Further, in order to obtain dispersant particles having a fine and uniform particle size, a water-based dispersion medium is prepared by generating a poorly water-soluble inorganic dispersant as described above in a liquid medium such as water under high-speed stirring. Also good. For example, when tricalcium phosphate is used as a dispersant, a preferred dispersant can be obtained by mixing aqueous sodium phosphate solution and aqueous calcium chloride solution at high speed to form fine particles of tricalcium phosphate. .

  In the present invention, a granulating step of adding a polymerizable monomer composition to an aqueous medium and forming particles of the polymerizable monomer composition in the aqueous medium includes a stirrer having a high shearing force. Even in the method performed by batch operation in the container, between the first container (hereinafter referred to as tank 1) provided with a stirrer and the second container (hereinafter referred to as tank 2) provided with a stirrer having high shearing force. Any method of granulating by providing a circulation line and circulating and circulating may be used, but the method of circulating and circulating that can prevent a short pass and achieve a more uniform particle size distribution is more preferable.

  FIG. 2 is an example of a system that can be used in the granulation process in the present invention. FIG. 3 is an example of a high shear stirrer that can be used in the granulation step in the present invention. The dissolution tank (reference numeral 1) and the tank 1 (reference numeral 2), and the tank 1 and the polymerization tank (reference numeral 7) are connected to each other by a discharge line. In addition, a circulation line (reference numeral 4) is connected to the tank 1, and in the circulation line, a pump (reference numeral 5), a tank 2 (reference numeral 6) provided with a high shear stirrer (not shown), and a necessity Corresponding equipment (not shown) such as a pressure gauge, a thermometer, and a flow meter is installed accordingly.

  When the granulation process is carried out by batch operation, after preparing an aqueous dispersion medium containing a poorly water-soluble inorganic dispersant in the tank 1 (reference numeral 2), a polymerizable monomer and a wax are prepared from the dissolution tank (reference numeral 1). And a polymerizable monomer composition containing at least a colorant, and forming a droplet of the polymerizable monomer composition with a high shear stirrer (reference numeral 3), discharging it to the polymerization tank (reference numeral 7), The reaction proceeds in the polymerization tank to form toner particles.

  When the granulation step is performed by a circulation method, after the polymerizable monomer composition is received, the droplet formation of the polymerizable monomer composition is performed by the high shear stirrer (reference numeral 3). The high shear stirrer in the pump (symbol 5) and the tank 2 (symbol 6) is activated, and the aqueous medium containing the polymerizable monomer composition is circulated and circulated through the circulation line (symbol 4). The droplet formation of the monomer composition is performed.

  In the present invention, at the time of circulation and circulation, the ring-shaped projections having a plurality of slits are coaxially arranged so that the stators having the same shape as the rotor formed in multiple stages on the concentric circles maintain a constant interval and mesh with each other. It is preferable to have the process of processing the said polymerizable monomer composition using the stirring apparatus installed on the top.

  In the granulation step for circulation, by performing the treatment using the stirring device, the high melting point component of the microcrystalline wax having a relatively low monomer solubility can be uniformly dispersed in the monomer droplets, Performance stability at the time of fixing can be improved.

  In addition, when the above stirring device is used, the chance of shearing and coalescence of the droplet particles increases, so that the initiator and the cross-linking agent that function to control the degree of branching are uniformly dispersed among the droplet particles. Therefore, since the branching and micro-crosslinking structure work in the process of polymerization of the toner particles, the micro-dispersion of the microcrystalline can be improved.

  Subsequently, a rotor in which ring-shaped protrusions having a plurality of slits are formed in multiple stages on a concentric circle and a stator having the same shape are placed on the same axis so as to mesh with each other while maintaining a constant interval. An example of an apparatus is given. FIG. 3A is a general view of the stirring device, FIG. 3B is a side view of the stirring device, and FIG. 3C is a cross-sectional view taken along line AA ′ in FIG. FIG. 3D is a sectional view taken along the line BB ′ of FIG. 3B, FIG. 3E is a perspective view of the rotor, and FIG. 3F is a perspective view of the stator. . An aqueous medium in which a poorly water-soluble inorganic dispersant such as calcium phosphate is dispersed in advance is prepared in the holding tank 158. Subsequently, a solution of the polymerizable monomer composition containing a polymerizable monomer, microcrystalline wax, ester wax and a colorant prepared in a separate container is put into an aqueous medium in the holding tank 158 to prepare Use granulated liquid. The charged granulation liquid is supplied from the inlet of the stirring device through the circulation pump 160, and in the stirring device, passes through the slits of the rotor 175 and the stator 171 provided in the casing 152, It is discharged in the centrifugal direction. When the granulation liquid passes through the stirrer, it is polymerizable in the aqueous medium by compression in the centrifugal direction caused by displacement of the rotor and stator slits, impact by discharge, and impact by shear between the rotor and stator. A droplet of the monomer composition is formed.

  The shape of the rotor and the stator is a shape in which ring-shaped protrusions having a plurality of slits are formed in multiple stages on concentric circles, and are arranged on the same axis so as to mesh with each other at a constant interval. It is preferable.

  The shape in which the rotor and the stator are installed so as to mesh with each other reduces the short path and sufficiently forms droplets of the polymerizable monomer composition. In addition, since the rotor and stator are alternately arranged in multiple stages in the concentric direction, when the granulation liquid proceeds in the centrifugal direction, it receives a lot of shearing and impact, so that more uniform droplets can be formed. It can be carried out. Since the holding tank 158 has a jacket structure, the granulating liquid can be cooled and heated. As the above-described stirring device, for example, Cavitron (manufactured by Eurotech) can be suitably used.

  In the present invention, in order to remove volatile impurities such as remaining unreacted polymerizable monomers and by-products, a part of the aqueous medium may be distilled off by distillation step after the completion of the polymerization step. The distillation step can be performed under normal pressure or reduced pressure.

  In the present invention, when the distillation step is performed after completion of the reaction step, the production method preferably includes a cooling step in which the aqueous medium containing toner particles is cooled while stirring after the distillation step. . The cooling step is a cooling of 0.70 ° C./min or less in the temperature range from the glass transition temperature (Tg) to the peak temperature (Tpc) of the maximum exothermic peak in the DSC curve measured by the differential scanning calorimeter of the toner. It is preferable that the production method is cooled at a speed.

  In addition, a manufacturing method having a so-called annealing step in which the temperature is kept constant for a certain time within the temperature region in the cooling step is also preferable.

  In the temperature range from the glass transition temperature (Tg) of the toner to the peak temperature (Tpc) of the maximum exothermic peak, the resin component constituting the toner particles is soft, and the wax component is a temperature range in which the wax component can grow relatively freely. When slow cooling is performed in this temperature range, the crosslinking and branching points in the binder resin are more likely to be the starting point of crystal nuclei of microcrystalline wax, and the finely dispersed cluster-like wax domains tend to grow greatly. Indicates. Such a dispersion state of the wax makes it easy to supply a sufficient amount of molten wax to the toner fixing surface during low-temperature fixing, and the compatible components derived from the ester wax in the resin are relatively reduced, so that the leaching out. The suppression effect increases.

  In the present invention, an aqueous medium containing particles of the polymerizable monomer composition can be treated with an acid or an alkali for the purpose of removing the dispersion stabilizer adhering to the toner particle surface. Thereafter, the toner particles are separated from the liquid phase by a general solid-liquid separation method, but in order to completely remove the acid or alkali and the dispersant dissolved therein, water is added again to wash the toner particles. This process is repeated several times, and after sufficient washing, solid-liquid separation is performed again to obtain toner particles. The obtained toner particles are dried by a known drying means if necessary.

  The toner particles of the present invention are externally added with inorganic fine powder as a fluidizing agent. As the inorganic fine powder added to the toner particles of the present invention, silica is preferable, and silica fine powder having a number average primary particle size of 4 nm to 80 nm is preferable. In the present invention, when the number average primary particle size is in the above range, the fluidity of the toner is improved and the storage stability of the toner is also improved.

  The number average primary particle size of the inorganic fine powder is obtained by observing with a scanning electron microscope and measuring the particle size of 100 inorganic fine powders in the field of view to determine the average particle size.

  Silica and fine powders such as titanium oxide, alumina or their double oxides can be used in combination. Among the inorganic fine powders used in combination with silica, titanium oxide is preferable.

Examples of the silica of the inorganic fine powder include both dry silica produced by vapor phase oxidation of silicon halide or dry silica called fumed silica, and wet silica produced from water glass. As the inorganic fine powder, dry silica having less silanol groups on the surface and inside the silica fine powder and less production residue of Na ₂ O and SO ₃ ²⁻ is preferable. In addition, dry silica can also be used to produce composite fine powders of silica and other metal oxides by using other metal halogen compounds such as aluminum chloride and titanium chloride together with silicon halogen compounds in the production process. . Silica also includes them.

  The inorganic fine powder is added to improve the fluidity of the toner and to make the triboelectric charge of the toner base particles uniform. Hydrophobic treatment of inorganic fine powder can provide functions such as adjustment of triboelectric charge amount of toner, improvement of environmental stability, improvement of characteristics under high humidity environment, etc. It is preferable to use inorganic fine powder. When the inorganic fine powder added to the toner absorbs moisture, the triboelectric charge amount as the toner decreases, and the developability and transferability tend to decrease.

  Examples of the treatment agent for the hydrophobic treatment of the inorganic fine powder include the following. Unmodified silicone varnish, various modified silicone varnishes, unmodified silicone oil, various modified silicone oils, silane compounds, silane coupling agents, other organosilicon compounds, and organotitanium compounds. These treatment agents may be used alone or in combination.

  Among these, inorganic fine powder treated with silicone oil is preferable. More preferably, the inorganic fine powder is hydrophobized with a coupling agent at the same time or after the treatment, and the silicone oil-treated hydrophobized inorganic fine powder is treated with silicone oil. Is kept high and the selective developability is reduced.

  The toner of the present invention can be used as a two-component developer in combination with a carrier as a magnetic or non-magnetic one-component developer. As the carrier for use in the two-component development method, a conventionally known carrier can be used. Specifically, particles having an average particle diameter of 20 to 300 μm of metals such as iron, nickel, cobalt, manganese, chromium, rare earth, and alloys or oxides thereof are used. Also preferably used are a magnetic material-dispersed carrier in which a magnetic material is dispersed in a resin, a low specific gravity carrier in which a resin is embedded in porous iron oxide, and the like.

  Further, those obtained by adhering or coating a resin such as a styrene resin, an acrylic resin, a silicone resin, a fluorine resin, or a polyester resin on the surface of the carrier particles are preferably used.

  Below, the measuring method of the physical-property value concerning this invention is demonstrated.

[1] GPC-MALS viscometer analysis at 40 ° C. (i) Pretreatment 0.1 g of toner is put into a dedicated filtration container (for example, Tosoh dissolution filter, pore size: 10 μm) and put into a 15 ml test tube together with 10 ml of THF. This is dissolved at 40 ° C. for 24 hours using a solution filtration device (for example, DF-8020 manufactured by Tosoh Corporation).

  After 24 hours, a sample processing filter (pore size 0.2 to 0.5 μm, for example, Mysori Disc H-25-2 (manufactured by Tosoh Corporation) can be used) is used as a measurement sample, and the following apparatus is used. ,Analysis was carried out.

(Ii) [Analysis conditions]
Apparatus: HLC-8121GPC / HT (manufactured by Tosoh Corporation)
DAWN EOS (manufactured by Wyatt Technology)
High temperature differential pressure viscosity detector (Viscotek)
Column: KF-807, 806M, 805, 803 (Showa Denko Co., Ltd.) quadruple column detector 1: Multi-angle light scattering detector Wyatt DAWN EOS
Detector 2: High temperature differential pressure viscosity detector Detector 3: Bryce type dual flow differential refractometer Temperature: 40 ° C
Solvent: THF
Flow rate: 1.0 ml / min
Injection volume: 400 μl

  In this measurement, the molecular weight distribution and intrinsic viscosity based on the absolute molecular weight are directly output, and the measurement theory is as follows.

[Measurement theory]
M ₉₀ = R (θ ₉₀ ) / KC... Rayleigh equation M ₉₀ : molecular weight R (θ ₉₀ ) at 90 °: Rayleigh ratio at a scattering angle of 90 ° K: optical constant (= 2π ² n ² / λ ₀ ⁴ N _A · (dn / dc) ² )
C: Solution concentration Rg = (1/6) ^1/2 ([η] M ₉₀ / φ) ^1/3 ... Froly Fox formula Rg: radius of inertia η: intrinsic viscosity φ: shape element absolute molecular weight: M = R (Θ ₀ ) / KC
R (θ ₀ ) = R (θ ₉₀ ) / P (θ ₉₀ )
P (θ ₉₀ ) = 2 / X ² · (e ^−X − (1−X)) (X = 4πn / λ · Rg)
λ: Wavelength (dn / dc): In the present invention, since the binder resin is a styrene-acrylic resin, it was set to 0.185 ml / g.

  In the present invention, the weight average molecular weight of the absolute molecular weight and the slope when the common logarithm (log [Iv]) of the viscosity Iv representing the degree of branching is plotted against the common logarithm (log [Mw]) of the absolute molecular weight (Mw) ( a) was determined using the dedicated software “TriSEC GPC Software GPC-LS-Viscometry Module Version 3.0 Rev. B.05.15” (manufactured by Viscotek).

  In calculating the absolute molecular weight, a standard polystyrene resin (for example, trade name “TSK Standard Polystyrene F-10”, manufactured by Tosoh Corporation) is used, and a known molecular weight and intrinsic viscosity (for example, when F-10 is used, the weight is used). The average molecular weight (Mw) was 96400 and the intrinsic viscosity was 0.411 dl / g).

  The slope (a) was calculated by performing Mark-Houwink-Sakurada Plots with the dedicated software attached to the apparatus and designating the analysis range.

  The definition of the total resin component (a) of the toner in the present invention corresponds to the total resin component of the chromatogram detected by the viscometer in the ternary simultaneous output profile of GPC-MALS-viscosity analysis at 40 ° C. Based on domain analysis.

[2] Amount of THF Insoluble Content of Resin Component of Toner The amount of THF insoluble content of the resin component in the toner is measured as follows.

  About 1.0 g of toner is weighed (W1 g), put in a pre-weighed cylindrical filter paper (for example, trade name No. 86R (size 28 × 100 mm), manufactured by Advantech Toyo Co., Ltd.), and set in a Soxhlet extractor. Then, extraction is performed for 16 hours using 200 ml of tetrahydrofuran (THF) as a solvent. At this time, extraction is performed at a reflux rate such that the solvent extraction cycle is about once every 5 minutes.

  After the extraction is completed, the cylindrical filter paper is taken out and air-dried, and then vacuum-dried at 40 ° C. for 8 hours. The mass of the cylindrical filter paper including the extraction residue is weighed, and the mass of the extraction residue is subtracted from the mass of the cylindrical filter paper ( W2g) is calculated.

And a THF insoluble content can be calculated | required by subtracting content (W3g) of components other than a resin component like following formula (1).
THF insoluble matter (mass%) = {(W2-W3) / (W1-W3)} × 100 (1)

  Content of components other than a resin component can be measured by a well-known analysis means. When the analysis is difficult, the content of components other than the resin component (incineration residual ash content (W3′g)) in the toner is estimated as follows, and the THF-insoluble content is obtained by subtracting the content. be able to.

The incineration residual ash content in the toner is obtained by the following procedure. About 2 g of toner is weighed (Wag) into a 30 ml magnetic crucible weighed in advance. Put the crucible in an electric furnace, heat at about 900 ° C for about 3 hours, let cool in the electric furnace, let it cool in a desiccator at room temperature for more than 1 hour, weigh the mass of the crucible containing the incineration residual ash, and crucible The incineration residual ash content (Wbg) is calculated by subtracting the mass of. And the mass (W3'g) of the incineration residual ash content in sample W1g is computed by following formula (2).
W3 ′ = W1 × (Wb / Wa) (2)

In this case, the THF-insoluble matter is obtained by the following formula (3).
THF-insoluble matter (mass%) = {(W2-W3 ′) / (W1-W3 ′)} × 100 (3)

[3] Extrapolated melting start temperature (Tim) of wax / peak temperature of maximum endothermic peak (Tpm)
The extrapolated melting start temperature (Tim) and the peak endothermic peak temperature (Tpm) of the wax are measured according to ASTM D3418-82 using a differential scanning calorimeter “Q1000” (manufactured by TA Instruments).

  The temperature correction of the device detection unit uses the melting points of indium and zinc, and the correction of heat uses the heat of fusion of indium.

  Specifically, about 4 mg of wax is precisely weighed, placed in an aluminum pan, and an empty aluminum pan is used as a reference. Measurement is performed at ° C / min. In the measurement, the temperature is once raised to 150 ° C., subsequently lowered to 20 ° C., and then the temperature is raised again. The extrapolated melting start temperature and the maximum endothermic peak temperature of the DSC curve in the temperature range of 20 to 150 ° C. in the second temperature increase process are the extrapolated melting start temperature (Tim) and the maximum endothermic temperature of the wax of the present invention. The peak temperature (Tpm) is assumed.

  Here, extrapolated melting start temperature (Tim) is defined in Japanese Industrial Standard (JIS) K7121 9.1 (Established date: October 01, 1987, confirmed date: February 04, 2013) The extrapolated melting start temperature (Tim), and in the DSC curve measured by the above measurement method, the gradient is maximized between the straight line obtained by extending the low-temperature base line to the high-temperature side and the low-temperature curve of the melting peak. The temperature at the intersection of the tangent lines drawn with.

  However, if the melting peak has a shoulder or multi-stage peak, the melting peak leaves the low-temperature base line and the first gradient is maximized (if the shoulder has a low-temperature shoulder, the shoulder gradient is maximized). The temperature at the intersection of the tangent lines drawn at

[4] Glass Transition Temperature of Toner The glass transition temperature of the toner in the present invention is measured as follows using a differential scanning calorimeter “Q1000” (manufactured by TA Instruments) according to ASTM D3418-82.

  Specifically, using the modulated mode of the differential scanning calorimeter, the measurement is performed under the following conditions, and is obtained from the peak position of the DSC curve at the first temperature increase. About 5 mg of the measurement sample is accurately weighed. It is put in an aluminum pan, an empty aluminum pan is used as a control, and the measurement is performed between 20 ° C. and 140 ° C.

<Measurement conditions>
• Equilibrate at a temperature of 20 ° C for 5 minutes.
・ Modulation of 1.0 ° C / min was applied, and the temperature was increased to 140 ° C at 1 ° C / min.
• Equilibrate at 140 ° C for 5 minutes.
・ Temperature drop to 20 ℃.

Here, the glass transition temperature is a mid-point glass transition temperature defined in Japanese Industrial Standard (JIS) K7121 9.3 (Establishment date October 01, 1987, confirmation date February 02, 2013). is there.

[5] Peak temperature (Tpc) of maximum heat generation peak of toner
The peak temperature (Tpc) of the maximum exothermic peak of the toner is measured according to ASTM D3418-82 using a differential scanning calorimeter “Q1000” (manufactured by TA Instruments).

  The temperature correction of the device detection unit uses the melting points of indium and zinc, and the correction of heat uses the heat of fusion of indium.

  Specifically, about 5 mg of toner is precisely weighed, put in an aluminum pan, an empty aluminum pan is used as a reference, and the temperature rising rate is 10 to 150 ° C. Measurement is performed at a temperature of 10 ° C./min. In the measurement, in the process of raising the temperature to 150 ° C. and then lowering to 20 ° C., the peak temperature of the maximum exothermic peak of the DSC curve in the temperature range of 20 to 150 ° C. is the toner of the present invention. The peak temperature (Tpc) of the maximum exothermic peak.

[6] Weight average particle diameter of toner (D4)
The weight average particle diameter (D4) of the toner is calculated as follows. As a measuring device, a precision particle size distribution measuring device “Coulter Counter Multisizer 3” (registered trademark, manufactured by Beckman Coulter, Inc.) using a pore electrical resistance method is used. For setting of measurement conditions and analysis of measurement data, attached dedicated software “Beckman Coulter Multisizer3 Version 3.51” (manufactured by Beckman Coulter, Inc.) is used. The measurement is performed with 25,000 effective measurement channels.

  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 screen for changing the standard measurement method (SOM) of the dedicated software, set the total count in the control mode to 50000 particles, set the number of measurements once, and the Kd value is “standard particles 10.0 μm” (manufactured by Beckman Coulter) 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 special software pulse to particle size conversion setting screen, 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, the dirt and bubbles in the aperture tube are removed by the “aperture flush” function of the dedicated software.
(2) About 30 ml of the electrolytic aqueous solution is put into a glass 100 ml flat bottom beaker. In this, "Contaminone N" (nonionic surfactant, anionic surfactant, 10% by weight aqueous solution of neutral detergent for pH7 precision measuring instrument cleaning, made by organic builder, manufactured by Wako Pure Chemical Industries, Ltd. About 0.3 ml of a diluted solution obtained by diluting 3) with ion-exchanged water is added.
(3) Two oscillators with an oscillation frequency of 50 kHz are incorporated with the phase shifted by 180 degrees, and an ultrasonic disperser “Ultrasonic Dissipation System Tetora 150” (manufactured by Nikki Bios Co., Ltd.) having an electrical output of 120 W is prepared. A predetermined amount of ion-exchanged water is placed in a water tank of an ultrasonic disperser, and about 2 ml of the contamination N is added to the water tank.
(4) The beaker of (2) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. And the height position of a beaker is adjusted so that the resonance state of the liquid level of the electrolyte solution 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 ultrasonic dispersion, the water temperature in 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%. . 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) is calculated. The “average diameter” on the analysis / volume statistics (arithmetic average) screen when the graph / volume% is set with the dedicated software is the weight average particle diameter (D4).

  The present invention will be specifically described with reference to the following examples. However, this does not limit the present invention in any way. In the examples and comparative examples, all parts are based on mass unless otherwise specified.

[Microcrystalline wax]
Table 1 shows the physical properties of the microcrystalline wax used in the toner production examples determined by DSC measurement.

[Ester wax]
Table 2 shows the physical properties of the ester wax used in the toner production example obtained by DSC measurement.

(Toner Production Example 1)
A suspension polymerization toner was prepared according to the following procedure.

  Using the system of the embodiment shown in FIG. 2, the aqueous dispersion medium was adjusted and the granulation step was performed using the stirring means having a high shear force shown in FIG.

(Preparation of aqueous dispersion medium)
850 parts of a 0.1 mol / L-Na3PO4 aqueous solution and 8.0 parts by mass of 10% hydrochloric acid in a tank 1 (container 2 shown in FIG. 2) equipped with a high-speed stirring device TK type homomixer (made by Tokushu Kika Kogyo) Was added, the rotational speed was adjusted to 10,000 r / min, and the mixture was heated to 60 ° C.

  Next, a part of this liquid was extracted from the bottom of the tank 1, and a high shearing stirrer: Cavitron (manufactured by Eurotech) was continuously installed from the circulation line using a rotary pump (reference numeral 5 in FIG. 2). Liquid was fed to the inlet of tank 2 (container 6 in FIG. 2). The aqueous medium is subjected to high shear treatment inside the tank 2, and then returns to the tank 1 through the circulation line again from the discharge port. At this time, the flow rate of the aqueous medium in the circulation line was 0.5 m / s. The rotor peripheral speed of the Cavitron was 40 m / s.

Next, while the above operation was continued, the inside of the tank 1 was replaced with nitrogen, and 68 parts of a 1.0 mol / L CaCl ₂ aqueous solution was added to the tank 1, and the stirring was continued for 30 minutes to give a slightly poor water-insoluble property. An aqueous medium containing the dispersant Ca ₃ (PO ₄ ) ₂ was prepared.

(Preparation of dissolution solution)
Moreover, the following material was melt | dissolved at 100 r / min with the propeller-type stirring apparatus, and the solution was prepared.
・ Styrene ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 31.0 parts ・ n-butyl acrylate ・ ・ ・ ・ ・ ・ ・ ・ ・・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 30.0 parts ・ Styrene-methacrylic acid-methyl methacrylate-methacrylic acid 2-hydroxyethyl copolymer ... ... 15.0 parts (styrene / methacrylic acid / methyl methacrylate / 2-hydroxyethyl methacrylate = 91.7 / 3.3 / 2.5 /2.5, Mp = 20,000, Mn = 8,000, Mw = 15,000, Mw / Mn = 1.9, Tg = 92.0 ° C., acid value = 20.0 mgKOH / g, hydroxyl value = 10.0mgKOH / g)
・ Saturated polyester resin ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 5.0 parts (addition of 2 mol of isophthalic acid / terephthalic acid / trimellitic anhydride / bisphenol A propylene oxide) Product / bisphenol A propylene oxide 3 mol adduct = produced from 50 mol% / 50 mol% / 0.1 mol% / 88 mol% / 22 mol%, acid value 10 mg KOH / g, peak molecular weight 10,000, weight average molecular weight: 9,900, Tg = 72 ° C)
・ Sulfonic acid group-containing copolymer FCA-1001-NS (manufactured by Fujikura Kasei Co., Ltd.) ・ 0.3 parts

(Preparation of polymerization monomer composition)
Next, in the above solution, styrene, 30.0 parts, colorant, C.I. I. Pigment Blue 15: 3 ········ 6.5 parts · Charge control agent Bontron E-88 (manufactured by Orient Chemical Co., Ltd.) ······· 0.5 parts · Microcrystalline wax 1 ·・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 3.0 parts ・ Ester wax 1-1 ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・・ 9.0 parts ・ 1,6-hexanediol diacrylate ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 0.25 parts is added, and then the mixture is heated to a temperature of 60 ° C. With a homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), the mixture was stirred, dissolved and dispersed at 9,000 r / min to obtain a polymerizable monomer composition.

[Preparation of toner particles (granulation process)]
Subsequently, the polymerizable monomer composition is charged into the aqueous dispersion medium, and as a polymerization initiator, perbutyl PV (10-hour half-life temperature 54.6 ° C. (manufactured by NOF Corporation)). 0 parts were added, and granulated by stirring at 60 ° C. with a TK homomixer of 10,000 r / min and a Cavitron at a rotor peripheral speed of 40 m / s and a circulation flow rate of 0.5 m / s for 30 minutes.

  Thereafter, the mixture was transferred to a propeller type stirring device and reacted at 70 ° C. for 5 hours while stirring at 100 r / min, then heated to 80 ° C. and further reacted for 2 hours to produce toner particles. After completion of the polymerization reaction, steam was blown into the reaction vessel, the temperature was raised to 98 ° C., and a distillation operation was performed for 5 hours. After the distillation step, the slurry containing the particles is cooled from 98 ° C. to 20 ° C. at a rate of 0.2 ° C./min. After the cooling step, diluted hydrochloric acid is added to make the pH of the aqueous medium less than 3.0. Soluble dispersant was dissolved. Further, it was washed with 10 times the amount of water as the slurry, filtered and dried, and then the particle size was adjusted by classification to obtain toner particles. In addition, by measuring the amount of the polymerizable monomer in the filtrate obtained by filtering the slurry, it was confirmed that 100.0% by mass of the added polymerizable monomer was a binder resin.

To 100 parts of the toner particles, a hydrophobic silica fine powder (primary particle diameter: treated with 20% by mass of dimethyl silicone oil based on silica fine powder as a fluidity improver and triboelectrically charged negatively. 1.7 parts of 7 nm, BET specific surface area: 130 m ² / g) were mixed with a Henschel mixer (manufactured by Mitsui Miike) at 3000 r / min for 15 minutes to obtain toner 1 having a weight average particle diameter (D4) of 6.5 μm. Obtained. Table 4 shows the physical properties of Toner 1.

(Toner Production Examples 2-35)
In Toner Production Example 1, the types, addition amounts, and polymerization temperatures of the initiator, the cross-linking agent, and the chain transfer agent were changed to those described in Table 3, and the wax types, addition amounts, and toner particle production methods were changed to Table 4. Toners 2 to 35 were obtained in the same manner as in Toner Production Example 1 except that the toners were changed to those described above. In the toners 2 to 35, it was confirmed that 100.0% by mass of the added polymerizable monomer was a binder resin. Table 4 shows the physical properties of Toner 2 to 35.

  The wax content in Table 4 is the wax content relative to 100.0 parts of the binder resin.

  The image evaluation method and evaluation criteria of the present invention will be described below.

(1) Low-temperature fixability Using an LBP9200C (manufactured by Canon Inc.) modified so that the fixing temperature control can be freely changed, a solid whole area image (tip margin: 5 mm, toner applied amount 0.50 mg / cm ² ) manufactured by Xerox The image was output on Business 4200 (75 g / m ² ), and the lowest fixable temperature at which a stable fixed image was obtained was evaluated according to the following criteria. The stable fixed image of the present invention refers to the obtained fixed image density and the fixed image after rubbing the fixed image 5 times with Sylbon paper applied with a load of 50 g / cm ² (0.49 N / cm ² ). The image density is measured and defined as a fixed state with a density reduction rate of 10% or less.
A: A stable fixed image can be obtained when the minimum fixable temperature is 150 ° C. or more and 160 ° C. or less. B: A stable fixed image can be obtained when the minimum fixable temperature is higher than 160 ° C. but not more than 170 ° C. C: Minimum fixable A stable fixed image can be obtained when the temperature is higher than 170 ° C. and lower than 190 ° C. D: The minimum fixing temperature is higher than 190 ° C. or has no fixing temperature.

(2) Blister test Using LBP9200C (manufactured by Canon Inc.) with a process speed adjusted to 270 mm / sec and a fixing temperature control adjusted to 190 ° C., a solid full-color image (tip margin: 5 mm, toner applied amount 0) .90 mg / cm ² ) was output on plain paper GF-C081 (manufactured by Canon Inc.) (81.4 g / m ² ) with high smoothness, and the blister generation level on the fixed image was visually evaluated. A blister is a blister-like image defect in which a part of a fixed image is peeled off by a fixing roller in a fixing process.
A: Not generated B: Generated slightly C: Generated D: Remarkably generated

(3) Thick paper gloss stability Using LBP9200C (manufactured by Canon Inc.) modified so that the fixing temperature control and process speed can be freely changed, a solid full-color image (tip margin: 5 mm, toner loading) 0.90 mg / cm ² ) on HP Color Laser Photo Paper, glossy (220 g / m ² ) manufactured by HP, at a fixing temperature of 200 ° C., 210 ° C. and 230 ° C. under cardboard fixing conditions (process speed 100 mm / sec). Output at each temperature of ° C. The five-point average value of 75 ° gloss in the fixed image of each output image was measured, and the average gloss value in each condition and the maximum gloss difference between the conditions were determined, and the stability of the fixing gloss was evaluated according to the following criteria.

The output is performed in a low-temperature and low-humidity environment (temperature 15 ° C., humidity 10% RH), and the gloss is measured using PG-3D (incident angle θ = 75 °) manufactured by Nippon Denshoku Industries Co., Ltd. The standard surface was black glass having a gloss level of 96.9.
A: Gloss 70 or more under all conditions and gross difference less than 2.0% B: Gloss 70 or more under all conditions and gross difference 2.0% or more and less than 5.0% C: Gloss 70 or more under all conditions , And gloss difference of 5.0% or more and less than 10.0% D: There is a condition of less than gloss 70, or gloss 70 or more under all conditions, but gloss difference of 10.0% or more

[Evaluation of durable developability]
Using a commercially available laser beam printer LBP9200C (manufactured by Canon Inc.) modified as described below, a durability test of 25,000 sheets was performed. As conditions for remodeling the printer, the process speed in the plain paper mode was changed to 270 mm / sec, and the fixing temperature control was set to 190 ° C. As the durability evaluation chart, an original chart having a printing rate of 2% was used, and the toner cartridge 322II (cyan) (manufactured by Canon Inc.) was refilled with the evaluation toner and mounted on the cyan station for printing.

  Further, as a sample for evaluation of developability after long-term storage, another cartridge refilled with the above-mentioned evaluation toner is prepared and left in a harsh environment (temperature 40 ° C., humidity 95% RH) for 30 days, and long-term storage toner is stored. Used for evaluation.

The conditions of the durability test are as follows: normal temperature and humidity environment (temperature 23 ° C., humidity 50% RH) as a normal evaluation, and high temperature and high humidity environment (temperature 30 ° C., humidity 80% RH) as a long-term storage toner evaluation. A total of 25,000 print tests were performed using paper having a basis weight of 75 g / m ² (LETTER size) in the plain paper mode.

(4) Halftone image reproducibility (development streaks)
In order to confirm the presence or absence of vertical streaks on the image due to the toner or free external additive fusion to the toner regulating member, and the visual evaluation by the halftone image, and to confirm the occurrence of streaks earlier and strictly, A halftone image without dithering (an image in which the halftone was reproduced only by adjusting the laser light amount without performing pseudo halftone expression) was output, and the presence or absence of vertical stripes was evaluated by visual confirmation.

Note that the sampling timing was evaluated according to the following criteria by outputting halftone images and halftone images not subjected to dithering every 1,000 sheets in the durability test, and using the worst image through the durability test.
A: Both halftone images are good with no vertical stripes.
B: No streaks are observed in the halftone image, but there are portions where the streaks are slightly seen in the halftone image where the dither processing is not performed.
C: Although vertical stripes are difficult to see in halftone images, clear vertical stripes are recognized in halftone images that are not subjected to dithering.
D: Conspicuous vertical streaks are also observed in halftone images.

(5) Density stability An original image in which nine 20 mm square solid black patches are arranged in the development area is output, and the maximum density difference of the image density during the endurance test is compared with the initial image density of the nine-point average density. Thus, the concentration stability was evaluated. The image density was measured using a “Macbeth reflection densitometer RD918” (manufactured by Macbeth Co., Ltd.) to measure the relative density with respect to an image of a white background portion having a document density of 0.00.

The sampling timing was evaluated by outputting an original image every 1,000 sheets in the same manner as the halftone image reproducibility evaluation.
A: Maximum density difference less than 0.15 B: Maximum density difference 0.15 or more, less than 0.25 C: Maximum density difference 0.25 or more, less than 0.30 D: Maximum density difference 0.30 or more

[Examples 1 to 29, Comparative Examples 1 to 5]
The toners produced in Toner Production Examples 1 to 35 were evaluated in accordance with the criteria for the items described above. The toners of Examples 1 to 29 exhibited excellent effects in low temperature fixing characteristics and development durability characteristics, whereas the toners of Comparative Examples 1 to 5 had poor balance between low temperature fixing characteristics and development durability characteristics. there were. The evaluation results are shown in Table 5.

  DESCRIPTION OF SYMBOLS 1 Dissolution tank, 2 Tank 1, 3 Tank 1 stirrer, 4 Circulation line, 5 Pump, 6 Tank 2, 7 Polymerization tank, 151 Motor, 152 Main body casing (dispersing device), 158 Holding tank, 159 Pressure gauge, 160 Circulation Pump, 161 Cooling means, 162 Thermometer, 163 Stirring motor, 164 Cooling water inlet, 165 Cooling water outlet, 166 Cooling water inlet, 167 Cooling water outlet, 168 Cooling jacket, 170 Three-way valve, 171 Stator, 172 Stator protrusion, 173 Stator circumferential groove, 174 Stator protrusion slit, 175 Rotor, 176 Rotor circumferential groove, 177 Rotor protrusion, 178 Rotor protrusion, 179 Treatment liquid inlet, 180 Drive shaft

Claims (6)

Polymerizable monomers, forming to form particles of adding microcrystalline wax, ester wax and a polymerizable monomer composition containing a colorant in an aqueous medium, the polymerizable monomer composition in aqueous medium grain step, and polymerizable monomer a polymerizable monomer is polymerized included in particles of the composition to obtain toner particles with the polymerization step,
A method for producing a toner comprising:
The toner contains 5.0% by mass or less of tetrahydrofuran (THF) insoluble matter derived from a resin component;
The weight average molecular weight of the absolute molecular weight measured by GPC-MALS viscometer analysis at 40 ° C. of the THF soluble component of the toner is 2.5 × 10 ⁴ or more and 2.5 × 10 ⁵ or less. The slope (a) when the common logarithm (log [M]) of absolute molecular weight (M) is plotted on the horizontal axis and the common logarithm (log [Iv]) of viscosity (Iv) is plotted on the vertical axis is 0. 50 or more and 0.80 or less,
A method for producing a toner , wherein the ester wax is a mono-functional or tetra-functional ester wax. The toner production method according to claim 1, wherein an extrapolated melting start temperature (Tim) of the microcrystalline wax in a DSC curve measured by a differential scanning calorimeter is 52 ° C. or higher and 70 ° C. or lower. The method for producing a toner according to claim 1, wherein a peak temperature (Tpm) of the maximum endothermic peak in the DSC curve of the microcrystalline wax measured by a differential scanning calorimeter is 60 ° C. or higher and 90 ° C. or lower. The method for producing a toner according to claim 1, wherein a ratio of the ester wax to a total amount of the microcrystalline wax and the ester wax is 30% by mass or more and 96% by mass or less. The method for producing a toner according to claim 1, wherein the ester wax is a bifunctional or tetrafunctional ester wax. The granulation step, a first container stirring means is installed, a step of performing by circulating flow between the second container stirring means is installed with a high shear force,
The stirring means having a high shearing force is coaxial so that a stator having a shape similar to a rotor in which ring-shaped protrusions having a plurality of slits are concentrically formed are maintained at regular intervals and mesh with each other. The toner manufacturing method according to claim 1, further comprising a stirring chamber installed on the top.

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