JP6074904B2 - Magenta toner for electrostatic image development - Google Patents

Description

  The present invention relates to a magenta toner for developing an electrostatic image containing a specific wax and a colorant, and in particular, it suppresses dust generated during fixing and secures fixability and anti-blocking properties, and can be used for repeated printing over a long period of time. In particular, the present invention relates to a magenta toner for developing an electrostatic image that maintains good charging characteristics and provides a stable and good image quality.

In an image forming apparatus such as an electrophotographic apparatus or an electrostatic recording apparatus, an electrostatic latent image formed on a photoreceptor is developed with toner. Next, the formed toner image is transferred onto a transfer material such as paper as necessary, and then fixed by heating, pressing, or the like.
In such image forming apparatuses, digital full-color copying machines and digital full-color printers have been put into practical use.

  In a digital color copying machine, a color image original is color-separated by blue (B), green (G) and red (R) filters, and then a static image having a dot diameter of 20 to 70 μm corresponding to the original color original. A full-color image is formed by using a subtractive color mixing method using yellow, magenta, cyan, and black toners as an electrostatic latent image.

  Conventionally, quinacridone colorants, thioindigo colorants, xanthene colorants, monoazo colorants, perylene colorants, diketopyrrolopyrrole colorants, and the like have been used as colorants for magenta toners.

  For example, Japanese Patent Publication No. 49-46951 proposes a 2,9-dimethylquinacridone pigment, Japanese Patent Publication No. 55-26574 proposes a thioindigo pigment, and Japanese Patent Publication No. 59-57256 discloses A xanthene dye is proposed, a diketopyrrolopyrrole pigment is proposed in Japanese Patent Application Laid-Open No. 2-210459, and an anthraquinone dye is proposed in Japanese Patent Publication No. 55-42383.

  These magenta colorants have good affinity with the binder resin and light resistance, and can provide magenta toners with excellent tribocharging properties and color tone, but they can be printed repeatedly over a long period in copiers and printers. When it did, there existed a difficulty which image degradation will produce. This is due to the deterioration of the charging characteristics, such as the amount of charge changing and the amount of reversely charged toner increasing due to repeated printing, and good charging characteristics are maintained for repeated printing over a long period of time. There is a need for a magenta toner that can provide stable and good image quality.

  Furthermore, with the recent spread of copiers and printers, in addition to the demand for further improvement in image quality, a toner that is particularly excellent in high-speed printing and low-energy fixability has been desired, and the low-temperature fixability of the toner has been increased. Improvements are being attempted. At the same time, environmental standards centered on Europe have been established to deal with the impact on the human body in the office environment, and countermeasures are becoming essential in electrophotographic fixing systems.

In particular, in recent years, it has become essential to obtain the most stringent “Blue Angel” certification. In electrophotographic fixing systems, substances that are generated during high-temperature fixing and diffused outside the device, specifically, “Dust and organic volatile substances” due to sublimation substances and the like are required to be less than or equal to the regulation values defined in ECMA-328 / RAL-UZ122.
In Japan, the standard values of RAL-UZ122 have been adopted as they were since the re-revision in 2008 as the Eco Mark certification standards for copiers and multifunction machines. It has been demanded.

For the purpose of fixing toner at low temperature, low melting point wax is used (Patent Documents 1 to 6).
However, since the low melting point wax is easily dissolved and sublimated at a low temperature, it becomes a causative substance of dust and it is difficult to achieve a reduction in the sublimation substance.

On the other hand, although it is possible to reduce sublimation substances by using a wax having a high melting point, low-temperature fixability and glossiness are required as toner performance, and simply selecting a high melting point wax These toner performances are significantly impaired.
In addition, the wax tends to be poorly dispersed in the toner as the melting point becomes higher. For this reason, the chargeability and fluidity of the toner are impaired, and image quality deterioration such as fog is likely to occur.

  In other words, environmental safety and toner performance are in a trade-off relationship, and no one that can meet both requirements has been provided.

Japanese Patent Laid-Open No. 06-123999 JP 07-199538 A JP-A-11-249331 JP 11-288124 A JP 2001-209209 A Japanese Patent Laid-Open No. 2005-266753

  The object of the present invention is to suppress dust generated at the time of fixing, reduce the degree of toner aggregation, secure fixing property and anti-blocking property, maintain good charging characteristics for long-term repeated printing, and stable The present invention provides a magenta toner for developing an electrostatic charge image that exhibits good image quality.

  The present inventor has repeatedly studied to solve the above problems, and has found that the above problems can be solved by using a specific wax and colorant in combination.

［構造式（１）中、Ｒ^１は２〜８価のネオペンチルポリオール残基、Ｒ^２は炭素数１３〜２５の直鎖アルキル基、ｍは２〜８の整数である。］

［構造式（２）中、Ｒ^１１およびＲ^１２は、それぞれ独立にＨまたはＣＨ_３を表す。］

［構造式（３）中、Ｒ^１３はＣＨ_３またはＯＣＨ_３を表し、Ｒ^１４はＨまたはＣｌを表し、Ｒ^１５はＯＣＨ_３またはＣｌを表す。］

［構造式（４）中、Ｒ^１６はＣｌまたはＳＯ_３ ⁻を表し、Ｒ^１７はＨ、ＣＨ_３またはＣｌを表し、Ｒ^１８はＨまたはＳＯ_３ ⁻を表し、ただしＲ^１６とＲ^１８の何れか一方のみはＳＯ_３ ⁻を表す。Ｍ^２＋は２価の金属イオンを表す。］ That is, the present invention contains at least a colorant, a binder resin, and a wax, and the wax is “a component having 40 or more carbon atoms is 80% by mass or more and is a non-component among components having 40 or more carbon atoms”. A hydrocarbon-based wax whose normal body component is 10% by mass or more and 50% by mass or less with respect to the whole component having 40 or more carbon atoms and / or a neopentyl polyol ester represented by the structural formula (1), and The electrostatic image development, wherein the colorant is a compound represented by Structural Formula (2) and / or a compound represented by Structural Formula (3), and a compound represented by Structural Formula (4) A magenta toner is provided.

[In Structural Formula (1), R ¹ is a divalent to octavalent neopentyl polyol residue, R ² is a linear alkyl group having 13 to 25 carbon atoms, and m is an integer of 2 to 8. ]

[In Structural Formula (2), R ¹¹ and R ¹² each independently represent H or CH ₃ . ]

[In the structural formula (3), R ¹³ represents CH ₃ or OCH ₃ , R ¹⁴ represents H or Cl, and R ¹⁵ represents OCH ₃ or Cl. ]

[In Structural Formula (4), R ¹⁶ represents Cl or SO ₃ ^— , R ¹⁷ represents H, CH ₃ or Cl, R ¹⁸ represents H or SO ₃ ^— , and any one of R ¹⁶ and R ¹⁸ or the other only SO ₃ ^- represents a. M ²⁺ represents a divalent metal ion. ]

  According to the present invention, while suppressing dust generated during fixing, fixing property and anti-blocking property are ensured, toner cohesion degree is small, good charging characteristics are maintained for repeated printing over a long period, and stable. An electrostatic image developing magenta toner exhibiting good image quality can be provided. In particular, an electrostatic image developing toner excellent in the performance can be provided even with a low-temperature fixing toner.

It is a longitudinal cross-sectional view of the wet bead mill which is an example of the apparatus used in preparation of a coloring agent dispersion liquid. It is the schematic which shows an example of a structure of the dispersion | distribution process used in preparation of a coloring agent dispersion liquid.

  The magenta toner for developing an electrostatic image of the present invention contains a wax having a specific structure, two or three kinds of colorants having a specific structure, and a resin, and other charge control agents, external additives and the like as required. May be contained. Hereinafter, “magenta toner for developing an electrostatic image” may be simply abbreviated as “toner” or “magenta toner”. Further, the toner before external addition is referred to as “toner mother particles”.

  According to the study of the present inventor, most of the causative substances of dust generated at the time of heat fixing and diffused outside the apparatus are wax components contained in the toner. The heated fixing device that passes when the toner transferred onto the paper is fixed not only dissolves the wax in the toner and exerts a releasing action, but also a part of the toner sublimates to generate “dust”. It has occurred. Therefore, since dust is the result of the physical sublimation phenomenon of the wax component, a method for suppressing the sublimation of the wax itself is required.

  Here, “dust” in the present invention refers to a substance collected by a filter in accordance with a measurement method (RAL-UZ122-2006) certified by Blue Angel Mark and collected on the filter. Therefore, “dust” in the present invention is not limited to solids such as dust, dust, and debris, but refers to all substances other than gas collected on the filter by the measurement method. The “dust” in the present invention includes those dusts that have been emitted from the toner, once converted into a gas or liquid, and collected on the filter as a liquid or solid.

When non-polar wax is used as the wax of the toner, a high release effect is obtained without being familiar with the binder resin, and since it is highly hydrophobic, it is advantageous in terms of environmental resistance, but the intermolecular force is low. Therefore, it may be difficult to suppress dust. In addition, when a method of suppressing the dust by increasing the molecular weight is used, the melting point is increased and the low-temperature fixability may not be achieved.
In addition, in the wet method, since non-polar wax is handled in an aqueous medium, sufficient dispersion stability is required, and the wax incorporated during the production is uniformly dispersed in the toner, and is added to the resin. It must also be well wrapped. That is, the nonpolar wax tends to improve the toner performance but is difficult to manufacture.

  On the other hand, there is a method of suppressing sublimation by increasing the intermolecular force between wax molecules or between a wax and a resin component. A typical example is an ester wax having a polar group, but these have low sublimation even at a relatively low melting point, and are useful for suppressing dust without deteriorating fixing performance. However, the familiarity with the resin and the introduction of polar groups make it possible to manufacture wax relatively easily by preventing the leakage of wax, but at the same time chargeability under high temperature and high humidity and long-term storage stability. Since the toner may be damaged greatly, there may be a problem in the toner performance itself.

Also, the relationship between the wax dispersion state and the toner charging characteristics is not always clear, but the charging characteristics change directly or indirectly due to differences in toner fluidity due to different wax dispersion states. I think that.
That is, controlling the dispersion state of the wax is an important means for controlling the charging characteristics of the toner.

That is, in order to optimize the charging characteristics, it is necessary to optimize the dispersion state of the colorant and the wax.
It is also known that the dispersibility of the colorant and wax in the toner varies greatly depending on the type and combination.
For this reason, the optimal combination of colorant and wax optimizes each dispersion state, provides good charging characteristics, maintains good charging characteristics for repeated printing over a long period of time, and provides stable and good image quality It is expected that a magenta toner that can be obtained will be obtained.

The present invention has been completed on the basis of these findings, and even with a low-temperature fixing toner, while suppressing dust generated during fixing, the fixing property and blocking resistance are ensured, and the degree of aggregation of the toner is improved. A small magenta toner for developing an electrostatic image having excellent image quality can be provided.
Further, by using a specific colorant in combination, it is possible to provide a magenta toner for developing an electrostatic image that has excellent charging characteristics, maintains good charging characteristics for long-term repeated printing, and exhibits stable and good image quality.

The wax used in the toner of the present invention is a hydrocarbon wax and / or a neopentyl polyol ester represented by the following structural formula (1). “Containing other waxes” is not excluded from the present invention, but the wax used in the toner of the present invention contains only hydrocarbon wax and / or neopentyl polyol ester represented by the following structural formula (1). It is preferable to contain.
The “hydrocarbon wax” in the present invention refers to a wax substantially consisting of carbon and hydrogen.

  The average carbon number of the hydrocarbon wax used in the present invention is preferably 30 or more and 60 or less, more preferably 35 or more and 55 or less, and particularly preferably 40 or more and 50 or less. When the number of carbon atoms is too large, the low-temperature fixability of the toner may not be achieved. On the other hand, when the number of carbon atoms is too small, the storage stability may deteriorate, and dust may be generated during fixing.

  Regarding the hydrocarbon wax used in the present invention, it is essential that the component of the hydrocarbon wax having 40 or more carbon atoms is 80% by mass or more with respect to the entire hydrocarbon wax, but it is 82% by mass or more. More preferably, it is particularly preferably 84% by mass or more. The upper limit of the content ratio of the component having 40 or more carbon atoms is not particularly limited, but in order to achieve low-temperature fixability of the toner, the component having 40 or more carbon atoms is used depending on the amount of the non-normal component described below. However, 95 mass% or less is preferable with respect to the whole hydrocarbon wax, and 90 mass% or less is especially preferable.

When there are too few components having 40 or more carbon atoms relative to the entire hydrocarbon wax, the generation of dust cannot be suppressed, the aggregation degree of the toner becomes large, the storage stability deteriorates, the production stability May get worse. On the other hand, if there are too many components having 40 or more carbon atoms relative to the entire hydrocarbon wax, the fixing lower limit temperature of the obtained toner will rise, so the fixing temperature range will be higher, and energy saving and high-speed printing performance will be reduced. May end up.
When the component having 40 or more carbon atoms is approximately 100% by mass, the above-described problems may occur. Further, even if the following non-normal component is within the following range, the above-described problems may occur because the minimum fixing temperature of the obtained toner increases.

  Further, in the hydrocarbon wax in the present invention, in order to further suppress the generation of dust, the component having 30 or more carbon atoms is preferably 90% by mass or more, particularly preferably 95% by mass or more in the total amount of the hydrocarbon wax. . Moreover, 100 mass% may be sufficient. If there are too few components having 30 or more carbon atoms relative to the entire hydrocarbon wax, the generation of dust may not be suppressed.

  Among hydrocarbon waxes, non-normal bodies such as isoforms and cyclic bodies are preferably 5% by mass or more and 50% by mass or less, and preferably 10% by mass or more and 45% by mass or less, based on the total amount of hydrocarbon wax. It is more preferable that the content is 15% by mass or more and 40% by mass or less. If the ratio of non-normal bodies in the entire hydrocarbon wax is not within the above range, the same problems as those described below with respect to the "ratio of non-normal bodies in hydrocarbon wax having 40 or more carbon atoms" May occur.

  In the present invention, among the components having 40 or more carbon atoms in the hydrocarbon-based wax, the non-normal component such as an iso form or a cyclic product is 10% by mass with respect to the entire hydrocarbon wax having 40 or more carbon atoms. The above is essential, but it is preferably 15% by mass or more, and particularly preferably 20% by mass or more.

  In the present invention, from the viewpoint of suppressing the generation of dust, as described above, it is essential that the component having 40 or more carbon atoms is 80% by mass or more with respect to the entire hydrocarbon wax, but the number of carbons is increased. This means that the molecular weight is high. When the molecular weight is high, the crystallinity is high and the melt viscosity is increased only with the normal form. Therefore, if the ratio of the non-normal body is too small, the melting point of the wax is increased and the melt viscosity of the toner is increased, and the fixing lower limit temperature of the toner is increased and the fixing temperature range is moved to the high temperature side, thereby saving energy. Or high-speed printing performance may be degraded.

In addition, among the components having 40 or more carbon atoms of the hydrocarbon wax, it is essential that the non-normal body is 50% by mass or less of the total components having 40 or more carbon atoms of the hydrocarbon wax, but 40% by mass. The following is preferable, and 30% by mass or less is particularly preferable.
When the proportion of the non-normal body is too large, the wax oozes out during granulation, and the fluidity of the toner may be deteriorated, and the degree of aggregation of the toner may be increased.

  Further, since the fluidity of the toner tends to deteriorate as the particle diameter of the toner decreases, the hydrocarbon wax in the present invention is suitable for a small particle diameter toner having a volume median diameter (Dv50) of 8 μm. It is particularly suitable for a toner having a small particle diameter of 4 to 7 μm.

  In the present invention, the carbon number of the wax is measured by a high temperature gas chromatography with FID (high temperature GC) and a mass spectrometer (MS). The linear carbon number is obtained by measuring the peak and carbon number of each chromatogram in advance using a linear polyethylene wax as a standard, and grasping the peak position of each linear carbon. The molecular weight of the peak is determined by mass identification of each carbon component separated by high temperature GC using MS directly connected. Since peaks with the same molecular weight appear at different positions from the peak derived from straight-chain carbon, they are identified as non-normal components such as iso-forms and cyclic forms, and normal and non-normal forms are identified from the area of each peak. The composition ratio (mass ratio) is calculated.

  Specific examples of the hydrocarbon wax include graft polymer wax, star polymer wax, microcrystalline wax; paraffin wax and the like that contain a lot of branched or cyclic hydrocarbon components. In order to achieve both reductions, microcrystalline waxes are preferable, and microcrystalline waxes that satisfy the requirements such as the number of carbon atoms and the composition ratio of normal bodies are preferable.

  The hydrocarbon wax in the present invention may be one type or two or more types. A plurality of hydrocarbon waxes having different types and composition ratios may be mixed and used so as to satisfy the requirements of the present invention. In the case of using a mixture of a plurality of hydrocarbon waxes having different composition ratios, the ranges of the essential content mass% and the preferred content mass% are those of the composition after mixing.

  The wax used in the toner of the present invention is the above-described hydrocarbon wax and / or neopentyl polyol ester represented by the following structural formula (1).

［構造式（１）中、Ｒ^１は２〜８価のネオペンチルポリオール残基、Ｒ^２は炭素数１３〜２５の直鎖アルキル基、ｍは２〜８の整数である。］

[In Structural Formula (1), R ¹ is a divalent to octavalent neopentyl polyol residue, R ² is a linear alkyl group having 13 to 25 carbon atoms, and m is an integer of 2 to 8. ]

R ¹ in the above structural formula (1) is a divalent to octavalent neopentyl polyol residue, which is obtained by removing a hydroxyl group from neopentyl polyol. Specific examples of the neopentyl polyol include neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol, and tripentaerythritol.

R ² in the structural formula (1) is a linear alkyl group having 13 to 25 carbon atoms. R ² preferably has substantially no carbon-carbon double bond. Further, it preferably has no substituent. That is, R ² is preferably a linear saturated alkyl group.

R ² is preferably a linear alkyl group having 15 to 23 carbon atoms, and particularly preferably a linear alkyl group having 17 to 21 carbon atoms. If the carbon number of R ² is too small, when it is a fatty acid ester, the melting temperature becomes low, and the storage stability and chargeability of the toner may deteriorate. On the other hand, if R ² has too many carbon atoms, when it is a fatty acid ester, the melting temperature becomes high, the low-temperature fixability is impaired, and the fixing temperature region may be narrowed.

  M in the structural formula (1) is an integer of 2 to 8, and preferably an integer of 3 to 8. If m is too large, the melting temperature becomes high and the low-temperature fixability is impaired, and the fixing temperature range may be narrowed. If it is too small, the melting temperature becomes low and the storage stability and chargeability of the toner deteriorate. May end up.

The acid value of the neopentyl polyol ester represented by the structural formula (1) is preferably 5 mgKOH / g or less, particularly preferably 1 mgKOH / g or less. The hydroxyl value is preferably 10 mgKOH / g or less, particularly preferably 4 mgKOH / g or less.
The hue (Gardner) is preferably 6 or less, and particularly preferably 3 or less.
The transparent melting point is preferably from 60 ° C. to 95 ° C., particularly preferably from 65 ° C. to 85 ° C.

  One type of neopentyl polyol ester represented by the structural formula (1) may be used, or a plurality of different types may be mixed.

  Since the fluidity of the toner tends to deteriorate as the particle size of the toner decreases, the neopentyl polyol ester represented by the structural formula (1) in the present invention has a volume median diameter (Dv50) of 4 to 7 μm. It is particularly suitable for small particle size toners.

  In the present invention, the total amount of wax is preferably 1 part by mass or more per 100 parts by mass of toner, more preferably 2 parts by mass or more, and particularly preferably 5 parts by mass or more. Moreover, it is preferable that it is 40 mass parts or less, More preferably, it is 35 mass parts or less, Most preferably, it is 30 mass parts or less. When the wax content in the toner is less than the above range, performance such as low-temperature fixability, glossiness, high-temperature offset property may not be sufficient, and when it exceeds the above range, blocking resistance may not be sufficient. In some cases, the wax may leak from the toner and contaminate the device.

  In the present invention, the content of the hydrocarbon wax and / or the neopentyl polyol ester represented by the structural formula (1) is 3 parts by mass in total regardless of whether it is used alone or in combination. -30 mass parts is preferable. A more preferable range is 5 to 20 parts by mass, and a most preferable range is 5 to 15 parts by mass. If the addition amount is less than the preferred range, the charging property is deteriorated such that the charge amount is lowered and the charge amount distribution is deteriorated. Moreover, when there is more addition amount than the preferable range, the fluidity | liquidity will deteriorate too much, and the same charging characteristic deterioration will be caused.

When the content of the wax is less than the preferred range, there may be a case where the low temperature fixability is deteriorated and the charging characteristics are deteriorated such as a decrease in the charge amount and an increase in the reverse polarity toner in repeated printing.
Further, when the wax content is larger than the preferred range, the fluidity and charging characteristics of the toner may be deteriorated. In addition, there may be a problem that a large amount of dust is generated during fixing.
When the wax in the toner is in the above range, both “suppression of dust generated during fixing” and “coexistence of low-temperature fixing property and blocking resistance” can be achieved.

  The polyglycerin fatty acid ester also exhibits an effect as a dispersion aid for hydrocarbon waxes. For example, combining polyglycerin fatty acid ester with hydrocarbon wax improves the dispersion stability of the wax during the production process and in water, and improves the dispersibility of the wax in the toner. The polyglycerol fatty acid ester is preferably blended by mixing and dispersing in the above-described hydrocarbon wax by a known method.

  The polyglycerin fatty acid ester can improve the stability of wax particles and other particles in water during the toner production process and the dispersibility of the final toner wax. By improving the dispersibility of the wax, exposure of the wax to the toner surface and release from the toner are suppressed. Wax exposed on the toner surface or loose wax causes image quality degradation such as fogging, PC contamination, dirt, afterimage (ghost), blurring (solid followability), and cleaning properties by contaminating various parts of the image forming apparatus. Or the toner being stored is blocked, or the external additive on the surface of the toner base particles is gradually buried in the toner base particles, which tends to cause deterioration of the fluidity, storage stability, and chargeability of the toner.

  The polyglycerol fatty acid ester used in the present invention preferably has a hydroxyl value of 1.0 mgKOH / g or more. 5 mgKOH / g or more is more preferable, 10 mgKOH / g or more is more preferable, 20 mgKOH / g or more is more preferable, and 25 mgKOH / g or more is particularly preferable. The upper limit is preferably 500 mgKOH / g or less, more preferably 300 mgKOH / g or less, and still more preferably 150 mgKOH / g or less.

  The hydroxyl value is determined by a conventional method and refers to the number of mg of potassium hydroxide required to neutralize acetic acid necessary for acetylating a free hydroxyl group contained in 1 g. If the hydroxyl value is too low, the ability to control the dispersion / aggregation balance of the raw material, intermediate product and final toner base particles in an aqueous solvent tends to be poor throughout the entire process from raw material storage to particle production. On the other hand, if the hydroxyl value is too high, the hydrophilicity tends to be affected by humidity in the air, and the environmental resistance as a toner tends to be lost. Also, in the manufacturing process, the affinity to the manufacturing container and the inner wall surface of the pipe is increased and adhesion occurs, which may affect the dispersion / aggregation balance of the particles, making it difficult to obtain a toner with stable performance. .

  The polyglycerol fatty acid ester preferably has an acid value of 1 mgKOH / g or more, and more preferably 20 mgKOH / g or less. The acid value refers to the number of mg of potassium hydroxide required to neutralize the acidic component contained in 1 g. When the acid value is within the above range, high particle control ability in an aqueous solvent can be obtained.

  Polyglycerol fatty acid ester is at least one glycerol multimeric component such as diglycerol, triglycerol, tetraglycerol, hexaglycerol, decaglycerol, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid An ester compound produced by reaction with at least one of higher saturated and unsaturated fatty acid components having 12 to 30 carbon atoms such as erucic acid is preferable. Specifically, decaglycerin decabehenate, decaglycerin heptaster Rate, decaglycerin tetrabehenate, octaglycerin octapalinate, octaglycerin tetrabehenate, hexaglycerin hexabehenate, tetraglycerin pentastearate, tetraglycerin tetrabehenate, etc. Even in kind, may be used in multiple species.

  The content of the polyglycerol fatty acid ester is preferably 0.01 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the toner. More preferably, it is 5 mass parts or less, More preferably, it is 4.5 mass parts or less, Most preferably, it is 4 mass parts or less. If the content is too low, sufficient effects may not be obtained. If the content is too high, it becomes susceptible to the humidity in the air due to an increase in hydrophilicity, and the environment resistance such as toner solidification and storage stability. May cause loss of sex. In addition, it tends to be difficult to obtain a toner with stable performance, such as significantly increasing the viscosity of the emulsion and dispersion formed in the manufacturing process.

［構造式（２）中、Ｒ^１１およびＲ^１２は、それぞれ独立にＨまたはＣＨ_３を表す。］

［構造式（３）中、Ｒ^１３はＣＨ_３またはＯＣＨ_３を表し、Ｒ^１４はＨまたはＣｌを表し、Ｒ^１５はＯＣＨ_３またはＣｌを表す。］

［構造式（４）中、Ｒ^１６はＣｌまたはＳＯ_３ ⁻を表し、Ｒ^１７はＨ、ＣＨ_３またはＣｌを表し、Ｒ^１８はＨまたはＳＯ_３ ⁻を表し、ただしＲ^１６とＲ^１８の何れか一方のみはＳＯ_３ ⁻を表す。Ｍ^２＋は２価の金属イオンを表す。］ In the toner of the present invention, the colorant includes “a compound represented by the structural formula (2) and / or a compound represented by the structural formula (3)” and “a compound represented by the structural formula (4)”. It is characterized by that. That is, the colorant used in the present invention is a combination of the “compound of structural formula (2) and / or (3)” and the compound of structural formula (4).

[In Structural Formula (2), R ¹¹ and R ¹² each independently represent H or CH ₃ . ]

[In the structural formula (3), R ¹³ represents CH ₃ or OCH ₃ , R ¹⁴ represents H or Cl, and R ¹⁵ represents OCH ₃ or Cl. ]

[In Structural Formula (4), R ¹⁶ represents Cl or SO ₃ ^— , R ¹⁷ represents H, CH ₃ or Cl, R ¹⁸ represents H or SO ₃ ^— , and any one of R ¹⁶ and R ¹⁸ or the other only SO ₃ ^- represents a. M ²⁺ represents a divalent metal ion. ]

It is essential to use either one or both of the compound represented by the structural formula (2) and the compound represented by the structural formula (3).
When both are used, they can be used in any ratio.

As the colorant, the compound represented by the structural formula (4) is essential. The content ratio of “the compound represented by Structural Formula (2) and the compound represented by Structural Formula (3)” and “the compound represented by Structural Formula (4)” is not particularly limited, The range of 97: 3 to 5:95 is preferable, more preferably 95: 5 to 50:50, and particularly preferably 93: 7 to 60:40.
If the total content of the compound represented by the structural formula (2) and the compound represented by the structural formula (3) is too large, the change in the charge amount during repeated printing is large, causing deterioration in image quality. There is a case. On the other hand, if the content of the compound represented by the structural formula (4) is too large, image quality may be deteriorated due to deterioration of charging characteristics under high temperature and high humidity.

  Further, the content of the colorant is preferably 2 parts by mass to 20 parts by mass with respect to the entire magenta toner. More preferably, they are 3 mass parts-15 mass parts, Especially preferably, they are 4 mass parts-10 mass parts.

  The magenta toner for developing an electrostatic charge image of the present invention preferably has a core / shell structure. The core / shell structure can be prepared by a known method, but the emulsion polymerization aggregation method or a modified method thereof is most preferable.

  In the case of using the emulsion polymerization aggregation method or a modified method thereof, the method of blending the wax includes a method of dispersing or containing the resin in the resin particle dispersion in advance, a method of emulsifying the wax to obtain a dispersion, a colorant dispersion, and resin particles. There is a method of coagulating and fusing together with a raw material dispersion such as a dispersion.

  As the former method, a method using so-called seed emulsion polymerization in which wax is added as a seed during emulsion polymerization, a method using so-called mini-emulsion polymerization in which emulsion polymerization is performed in a state where wax is dissolved or finely dispersed in a monomer, vinyl A method of dispersing a wax in a resin particle in a resin particle dispersion by emulsifying the resin after a wax is previously dispersed in a binder resin such as a resin or a polyester resin by kneading or the like can be used.

  As the latter, there is a method in which wax is emulsified and dispersed by a known method, and agglomerated and fused together with a raw material dispersion such as a colorant dispersion or a resin particle dispersion. At this time, the hydrocarbon wax and the ester wax may be used by being melt-mixed in advance, or may be separately dispersed and used, but it is more preferable to use them after being melt-mixed in advance. .

  Among these, the former method, that is, a method using a wax that is previously dispersed or contained in the resin particles of the resin particle dispersion is preferable from the viewpoint that the wax can be uniformly dispersed.

The emulsion polymerization agglomeration method is to prepare a resin particle dispersion, a colorant dispersion, etc., which are dispersions of polymer primary particles obtained by emulsion polymerization, and prepare a wax dispersion if necessary. In this method, the toner base particles are obtained by dispersing these in an aqueous medium and performing heating or the like, followed by an aggregation step and a ripening step of fusing the particles.
In emulsion polymerization, wax or the like can be contained in polymer primary particles (resin particles in a resin particle dispersion) by seed emulsion polymerization or miniemulsion polymerization.

“Modification of emulsion polymerization aggregation method” means that a resin particle dispersion is obtained by emulsifying a vinyl resin, a polyester resin or the like polymerized in advance by a known method to obtain a resin particle dispersion, and at least a colorant In this method, toner mother particles are obtained through a process of aggregating and fusing the dispersion and the resin particle dispersion.
In a modification of the emulsion polymerization aggregation method, a toner can be produced in the same manner as the emulsion polymerization aggregation method except that a raw material such as wax can be dispersed in the resin in advance.

  In the present invention, as the binder resin contained in the toner and the resin constituting the resin particles in the resin particle dispersion, resins conventionally used as the binder resin for the toner can be appropriately used.

For example, among the binder resins, monomers used for the vinyl resin include the following.
Styrene; o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, 3,4-dichlorostyrene, p-ethylstyrene, 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, etc. Styrene derivatives of ethylene; ethylenically unsaturated monoolefins such as ethylene, propylene, putylene, isobutylene; unsaturated polyenes such as butadiene; vinyl halides such as vinyl chloride, vinylidene chloride, vinyl bromide, and vinyl fluoride; vinyl acetate , Vinyl esters such as vinyl propionate and vinyl benzoate, Methyl acrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, behenyl methacrylate, phenyl methacrylate, Methacrylic acid esters such as dimethylaminoethyl methacrylate and dimethylaminoethyl methacrylate; methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, behenyl acrylate, phenyl acrylate, 2-chloroethyl acrylate, dimethylaminoethyl acrylate, dimethyl acrylate Acrylic esters such as Noethyl; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl isobutyl ether; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and methyl isopropenyl ketone; N-vinyl pyrrole, N-vinyl carbazole N-vinyl compounds such as N-vinylindole and N-vinylpyrrolidone; vinyl naphthalenes; and acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile, and acrylamide.
These vinyl monomers are used alone or as two or more copolymers, but are not limited thereto.

  Among these, a combination of vinyl monomers forming a styrene copolymer, a styrene-acrylic copolymer, and a styrene-methacrylic copolymer is preferable.

Furthermore, it is preferable that a monomer having two or more polymerizable double bonds is mainly used as the crosslinkable monomer.
Examples of such compounds include aromatic divinyl compounds such as divinylbenzene and divinylnaphthalene; ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, and 1,5-pentanediol. Diacrylates linked by alkyl chains such as diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, etc .; dimethacrylates in which the acrylate of the above compound is replaced by methacrylate; diethylene glycol diacrylate, triethylene glycol diacrylate Diacrylates linked with alkyl chains containing ether linkages such as acrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, dipropylene glycol diacrylate, etc. Acrylates; dimethacrylates in which the acrylate of the above compound is replaced by methacrylate; polyoxyethylene (2) -2,2-bis (4-hydroxyphenyl) propane diacrylate, polyoxyethylene (4) -2,2- Aromatic groups such as bis (hydroxyphenyl) propane diacrylate; dimethacrylate in which the acrylate of the above compound is replaced by methacrylate; polyester-type diacrylate compounds, pentaerythritol triacrylate, trimethylol ethane triacrylate, trimethylol propane tri Acrylate, tetramethylol methane tetraacrylate, oligoester acrylate; acrylate of the above compound replaced with methacrylate; triallyl cyanurate; triallyl trimellite DOO; Although the like can be exemplified, but the invention is not limited thereto.

  From the viewpoint of fixability and offset resistance, those that are preferably used include aromatic divinyl compounds and diacrylate compounds linked by a chain containing an aromatic group or an ether bond.

  These crosslinking agents are preferably used in an amount of 0 to 5% by mass, particularly preferably 0.03 to 3% by mass, relative to 100% by mass of other monomer components.

  These binder resins may be formed into a resin particle dispersion by emulsion polymerization, or may be polymerized by a known method and then emulsified and dispersed by a known method to obtain a resin particle dispersion.

  Among the binder resins, as the polyester resin, a polyester resin obtained by condensing a polyvalent carboxylic acid component and a polyhydric alcohol component can be used.

  Among the polyvalent carboxylic acid components, examples of the divalent carboxylic acid component include maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, phthalic acid, isophthalic acid, terephthalic acid, cyclohexanedicarboxylic acid, oxalic acid, and succinic acid. Acid, glutaric acid, adipic acid, pemelic acid, azelinic acid, sebacic acid, azelaic acid, malonic acid, 1,9-nonanedicarboxylic acid, 1,10-decanedicarboxylic acid, 1,11-undecanedicarboxylic acid, 1,12 -Dodecanedicarboxylic acid, 1,13-tridecanedicarboxylic acid, 1,14-tetradecanedicarboxylic acid, 1,16-hexadecanedicarboxylic acid, 1,18-octadecanedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 4, 4'-biphenyldicarboxylic acid, n-dodecenyl succinic acid, isododecenyl Examples include succinic acid, n-dodecyl succinic acid, isododecyl succinic acid, n-octenyl succinic acid, isooctenyl succinic acid, n-octyl succinic acid, isooctyl succinic acid, anhydrides or lower alkyl esters of these acids, etc. It is not limited to.

  Among the polyhydric alcohol components, examples of the divalent alcohol component include polyoxypropylene (2,2) -2,2-bis (4-hydroxyphenyl) propane and polyoxypropylene (3,3) -2,2 -Bis (4-hydroxyphenyl) propane, polyoxypropylene (6) -2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene (2,0) -2,2-bis (4-hydroxyphenyl) Bisphenol A alkylene oxide adducts such as propane, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol 1,4-butenediol, 1,5-pentanedio 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol 1,13-tridecanediol, 1,14-tetradecanediol, 1,18-octadecanediol, 1,20-eicosanediol, 1,4-cyclohexanedimethanol, dipropylene glycol, polyethylene glycol, polytetramethylene glycol , Bisphenol A, hydrogenated bisphenol A and the like, but are not limited thereto.

As the crosslinking agent, a trivalent or higher carboxylic acid component and / or a trivalent or higher alcohol component is used.
Examples of the trivalent or higher carboxylic acid component include 1,2,4-benzenetricarboxylic acid (trimellitic acid), 1,2,5-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, and 1,2 , 4-Naphthalenetricarboxylic acid, 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methyl-2-methylenecarboxypropane, 1,2,4- Examples include cyclohexanetricarboxylic acid, tetra (methylenecarboxyl) methane, 1,2,7,8-octanetetracarboxylic acid, pyromellitic acid, embol dimer acid, acid anhydrides thereof, and lower alkyl esters.

  Examples of the trivalent or higher alcohol component include sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol. 1,2,5-pentanetriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimetroleethane, trimethylolpropane, 1,3,5-trihydroxymethylbenzene, etc. However, it is not limited to these.

  The trivalent or higher carboxylic acid component and / or the trivalent or higher alcohol component used as the crosslinking agent is preferably 0 to 10% by mass, particularly preferably 0.03 to 5% by mass with respect to 100% by mass of the monomer component. % Used.

  These resins are polymerized by a known method, then emulsified and dispersed by a known method, and used as a resin particle dispersion.

A crystalline resin can also be used.
Examples of the crystalline resin include vinyl resins that are obtained by copolymerizing long-chain alkyl acrylates such as stearyl acrylate and behenyl acrylate and long-chain alkyl methacrylates alone or with other vinyl monomers. However, it is not limited to these.

  These resins may be formed into a resin particle dispersion by emulsion polymerization, or may be polymerized by a known method and then emulsified and dispersed by a known method to obtain a resin particle dispersion.

  In the polyester resin, as the polyvalent carboxylic acid component, for example, oxalic acid, malonic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelic acid, sebacic acid, 1,9-nonanedicarboxylic acid, 1,10 -Decanedicarboxylic acid, 1,11-undecanedicarboxylic acid, 1,12-dodecanedicarboxylic acid, 1,13-tridecanedicarboxylic acid, 1,14-tetradidecanedicarboxylic acid, 1,16-hexadecanedicarboxylic acid, 1,18 -Octadecanedicarboxylic acid, terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, or the like, or acid anhydrides or lower alkyl esters thereof are used. For example, ethylene glycol, 1,3-propanediol, 1,4-butane 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecane Diols, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1,18-octadecanediol, 1,20-eicosanediol and the like are used, but are not limited thereto. is not.

  These resins are polymerized by a known method, then emulsified and dispersed, and used as a resin particle dispersion.

In the present invention, it is preferable to use one or more types of crosslinked resin particle dispersions and, if necessary, one or more types of non-crosslinked resin particle dispersions. It is particularly preferable that the resin particle dispersion is a particle dispersion of a crosslinked resin and a non-crosslinked resin. That is, it is particularly preferable to use one or more types of crosslinked resin particle dispersions and one or more types of non-crosslinked resin particle dispersions in combination.
For example, a plurality of types of crosslinked resin dispersions having different monomer compositions may be used, and a plurality of types of non-crosslinked resin particle dispersions having different monomer compositions may be used in combination as necessary. Moreover, you may use the crosslinked resin particle dispersion which has 2 or more types of different crosslinking degree as a crosslinked resin particle dispersion. Furthermore, one or more types of crosslinked resin particle dispersions having different molecular weights or molecular weight distributions and one or more types of non-crosslinked resin particle dispersions having different molecular weights or molecular weight distributions may be used.

In the present invention, the “crosslinked resin” does not necessarily mean only a resin that is crosslinked so that the THF-insoluble matter is substantially the entire amount, but a resin that is synthesized using a crosslinkable unit. . Here, the “crosslinkable unit” means, for example, a crosslinkable monomer (mainly a monomer having two or more polymerizable double bonds) in a vinyl resin, and a trivalent in a polyester resin. The above carboxylic acid components or trihydric or higher alcohol components are used.
In the present invention, “non-crosslinked resin” refers to a resin synthesized without using a crosslinkable unit.

  The THF-insoluble content of the toner is determined by the degree of cross-linking of the cross-linked resin (ratio of use of cross-linkable units) or the ratio of the cross-linked resin and the non-cross-linked resin. Preferably, the content is 15% by mass or more, and more preferably 20% by mass or more. Further, the upper limit is preferably 40% by mass or less, more preferably 35% by mass or less, and particularly preferably 30% by mass or less. If the THF-insoluble content in the toner is small, a hot offset phenomenon tends to occur, and if the THF-insoluble content is large, the low-temperature fixability and gloss may be impaired.

The content of the non-crosslinked resin particles is preferably 0.1 to 30% by mass, more preferably 3 to 25% by mass, and particularly preferably 5 to 20% by mass with respect to the entire resin particles.
That is, the content of the non-crosslinked resin is preferably 0.1 to 30% by mass, more preferably 3 to 25% by mass, and particularly preferably 5 to 20% by mass with respect to the entire binder resin.

  Further, the resin design is such that the tetrahydrofuran (THF) insoluble content with respect to only the binder resin component in the toner is preferably 3 to 35% by mass, more preferably 5 to 30% by mass, and particularly preferably 10 to 20% by mass. It is preferable to do. If the THF-insoluble content of the binder resin component in the toner is too small, the hot offset phenomenon tends to occur, and if the THF-insoluble content is too large, the low-temperature fixability and gloss may be impaired.

The weight-average molecular weight of the toner soluble matter in THF as measured by gel permeation chromatography (GPC) is preferably 30,000 to 100,000, and the molecular weight peak is 10,000 to 60,000. It is more preferable. More preferably, the weight average molecular weight is 30,000 to 80,000, and the weight molecular weight peak is particularly preferably 10,000 to 50,000.
“Molecular weight peak of weight” refers to a molecular weight peak when the vertical axis represents weight instead of the number of molecules. In the GPC measurement, when the infrared absorption or refractive index is taken along the vertical axis, it becomes a “weight molecular weight peak”.

  The above-mentioned “THF soluble matter of toner” includes THF soluble components such as the above-mentioned wax and a resin having a sulfonic acid group and / or a sulfonic acid salt described later.

The resin particle dispersion, the colorant dispersion, and, if necessary, the wax dispersion are separately prepared as emulsified dispersions, and are contained in the toner by aggregation and fusion.
Furthermore, a core / shell structure can be obtained by using one or more types of resin particle dispersions as a core and one or more types of resin particle dispersions as a shell.

The resin particle dispersion for core preparation preferably contains at least one kind of crosslinked resin particle dispersion. Moreover, it is preferable that the resin particle dispersion for shell preparation contains at least one kind of non-crosslinked resin particle dispersion.
That is, the binder resin for core preparation preferably contains at least one kind of cross-linked resin, and the binder resin for shell preparation preferably contains at least one kind of non-cross-linked resin.
The binder resin that forms the core preferably includes a crosslinked resin, and the binder resin that forms the shell preferably includes a non-crosslinked resin.
Furthermore, it is preferable that the binder resin for core preparation is all cross-linked resin, and the binder resin for shell preparation is preferably all non-cross-linked resin.

  The binder resin component forming the shell is preferably 0.5 to 40% by mass, particularly preferably 1 to 20% by mass of the total binder resin component.

Even in the case of a toner having a core / shell structure, as described above, the content of the non-crosslinked resin is preferably 0.1 to 30% by mass and more preferably 3 to 25% by mass with respect to the entire binder resin. 5 to 20% by mass is preferable.
Looking only at the shell, the content of the non-crosslinked resin is preferably 50 to 100% by mass, more preferably 60 to 100% by mass, and particularly preferably 70 to 100% by mass with respect to the entire binder resin contained in the shell. preferable.
On the other hand, when only the core is viewed, the content of the crosslinked resin is preferably 50 to 100% by mass, more preferably 60 to 100% by mass, and 70 to 100% by mass with respect to the entire binder resin contained in the core. Particularly preferred.

  In the present invention, by designing the wax, the crosslinked resin and the non-crosslinked resin as described above, excellent low-temperature fixability, high glossiness, excellent offset resistance and blocking resistance, and dust is suppressed. Toner can be obtained.

By using a combination of crosslinked resin particles and non-crosslinked resin particles, a toner having a better balance in terms of low-temperature fixability, glossiness, offset resistance, blocking resistance, and dust suppression than using crosslinked resin particles alone is obtained. be able to.
This seems to be because in the emulsion polymerization aggregation method and its modified method, the crosslinked resin particles and the non-crosslinked resin particles are not completely compatible with each other and are in an appropriate phase separation state.
The non-crosslinked resin particles are preferably present as close to the toner surface as possible. For this reason, when designing a core / shell structure, it is preferable to contain many non-crosslinked resin components in a shell part.

  In this invention, it is preferable to contain resin which has a sulfonic acid group and / or a sulfonate. By containing these resins, the chargeability can be improved, and thereby high image quality of the toner can be realized. In addition, it has excellent environmental characteristics and can provide stable image quality even for long-term repeated live action, and in combination with the wax in the present invention, while suppressing dust generated during fixing, It is possible to provide a toner for developing an electrostatic charge image that ensures blocking resistance and is excellent in image quality.

  The resin having a sulfonic acid group and / or a sulfonate is not particularly limited, and examples thereof include monomers having a sulfonic acid group and / or a sulfonate represented by the following structural formula (5) or the following structural formula (6). Examples thereof include resins obtained by copolymerizing other vinyl monomers that can be copolymerized.

［構造式（５）中、Ｒ^３はＨまたはＣＨ_３を表わし、Ｒ^４はＣ_２Ｈ_４またはＣ_３Ｈ_６を表わし、Ｍ^１はＨ、Ｎａ、ＫおよびＮＨ_４からなる群より選ばれる１種を表わす。］

[In the structural formula (5), R ³ represents H or CH ₃ , R ⁴ represents C ₂ H ₄ or C ₃ H ₆ , and M ¹ is selected from the group consisting of H, Na, K and NH _4. Represents one type. ]

［構造式（６）中、Ｒ^５はＨまたはＣＨ_３を表わし、Ｒ^６はＣ_２Ｈ_４またはＣ_３Ｈ_６を表わし、Ｍ^２はＣａまたはＭｇを表わし、ｐは１または２であり、ｑは２−ｐである。］

[In the structural formula (6), R ⁵ represents H or CH ₃ , R ⁶ represents C ₂ H ₄ or C ₃ H ₆ , M ² represents Ca or Mg, p is 1 or 2, q is 2-p. ]

Although the copolymerization ratio of the monomer having a sulfonic acid group and / or sulfonate represented by the structural formula (5) or the structural formula (6) with other vinyl monomers copolymerizable is not particularly limited, The monomers having a sulfonic acid group and / or a sulfonate are preferably 1% by mass or more and 30% by mass or less based on the entire resin.
If the copolymerization ratio of monomers having sulfonic acid groups and / or sulfonates is too small, it may be difficult to accumulate a sufficient amount of charge in the resulting toner, and the toner may scatter and be unusable. . On the other hand, if the amount is too large, the electric resistance value of the resulting toner will be low, the stability over time of the change in charge amount will be poor, the compatibility with the binder will be poor, and the transparency may be impaired.

  When the “resin having sulfonic acid and / or sulfonate” is used in combination with the above-described combination of waxes in the present invention, the gloss can be increased while maintaining a favorable fixing temperature range. When using a resin with few crosslinking components in an attempt to increase gloss, the high-temperature offset property decreases. However, when the above-mentioned “resin having sulfonic acid and / or sulfonate” is used in combination, it increases gloss while maintaining a good fixing temperature range. Is possible.

  Specific examples of monomers having a sulfonic acid group and / or a sulfonate represented by the above structural formula (5) that can be used in the present invention include, for example, sulfoethylacrylic acid, sulfoethylmethacrylic acid, sulfoethyl Sodium acrylate, sulfoethyl methacrylate, ammonium sulfoethyl acrylate, ammonium sulfoethyl methacrylate, potassium sulfoethyl acrylate, potassium sulfoethyl methacrylate, potassium sulfopropyl acrylate, potassium sulfopropyl methacrylate, etc. Specific examples of monomers represented by the structural formula (6) include, for example, calcium sulfoethyl acrylate, calcium sulfoethyl methacrylate, magnesium sulfoethyl acrylate, sulfoethyl methacrylate Neshiumu and the like, these monomers singly or can be used in combination of two or more thereof.

  Among the monomers having a sulfonic acid group and / or a sulfonate salt exemplified above, the reason is that it is easy to copolymerize and a copolymer having a softness that is preferable as a component of an electrophotographic toner is easily obtained. And at least one selected from the group consisting of sodium sulfoethyl acrylate, sodium sulfoethyl methacrylate, ammonium sulfoethyl acrylate, ammonium sulfoethyl methacrylate, potassium sulfopropyl acrylate and potassium sulfopropyl methacrylate Is preferred.

  Other vinyl monomers that can be used as a copolymer component with monomers having the sulfonic acid group and / or sulfonate are not particularly limited, and may be those having a polymerizable unsaturated bond. Any of them can be used. Specific examples include styrene, o, m, p-chlorostyrene, α-methylstyrene, vinyltoluene, (meth) acrylic acid, maleic acid, itaconic acid, methyl (meth) acrylate, ethyl (meth) acrylate, (Meth) acrylic acid propyl, (meth) acrylic acid butyl, (meth) acrylic acid-2-ethylhexyl, (meth) acrylic acid amyl, (meth) acrylic acid cyclohexyl, (meth) acrylic acid lauryl, (meth) acrylic acid Examples include stearyl, (meth) acrylic acid behenyl, acrylamide, vinyl chloride, vinyl acetate, etc. Among these vinyl monomers, at least one selected from the group consisting of styrene and (meth) acrylic acid alkyl esters is used. It is preferable that the (meth) acrylic acid alkyl ester is It is preferable to use with an atom number 1 to 18 alkyl groups (meth) acrylic acid alkyl ester.

  In the present invention, as the above sulfoalkyl (meth) acrylic acid monomer, at least one selected from the group consisting of ammonium sulfoethyl methacrylate, sodium sulfoethyl methacrylate and potassium sulfopropyl methacrylate is used. A copolymer obtained by copolymerizing at least one selected from the group consisting of styrene and (meth) acrylic acid alkyl ester as a system monomer is well compatible in a transparent state in a binder, and is at high temperature and high humidity. This is preferable because the toner characteristics can be stabilized even under such a severe environment.

These resins having a sulfonic acid group and / or a sulfonate may be formed into a resin particle dispersion by emulsion polymerization, or are polymerized by a known method and then emulsified and dispersed by a known method. It is good.
Moreover, the addition amount is preferably 0.1 to 20% by mass, and particularly preferably 1 to 10% by mass. If the added amount is small, the effect of charge control is reduced, and if it is too large, the charge amount may be lowered or the charge amount distribution may be deteriorated.

  The addition method may be included in the entire toner particles together with other resin particle dispersions, or may be added alone or together with other resin particle dispersions as a shell and contained in the vicinity of the toner surface. The effect can be exhibited in a smaller amount by incorporating it into.

  Furthermore, by using a non-crosslinked resin having a sulfonic acid group and / or a sulfonate, the low-temperature fixability and the gloss can be improved as well as the chargeability. If low-temperature fixability and gloss can be improved, it will be easier to secure a balance between dust suppression and low-temperature fixability and blocking resistance during fixing, and a synergistic effect with the wax described above will be achieved, resulting in excellent electrostatic charge. An image developing toner can be provided.

In the case of using a non-crosslinked resin having a sulfonic acid group and / or a sulfonate, the weight average molecular weight is preferably 10,000 to 50,000, more preferably, in the gel permeation chromatography (GPC) measurement of THF-soluble matter. It is desirable that it is 15,000-40,000. A non-crosslinked resin having a sulfonic acid group and / or a sulfonate salt can provide a toner having an excellent balance of low-temperature fixability / gloss and offset / blocking resistance as compared with non-crosslinked resin particles not containing these. This is presumed to be because non-crosslinked resin particles containing sulfonic acid groups and / or sulfonates form a network due to loose interaction different from the covalently crosslinked structure.
By incorporating a non-crosslinked resin having a sulfonic acid group and / or a sulfonic acid salt in the vicinity of the toner surface, the effect of improving low-temperature fixability and gloss can be exhibited in a small amount.

  When preparing a resin particle dispersion by emulsion polymerization in the present invention, for example, as a monomer, a polymerizable monomer having an acidic group (hereinafter sometimes simply referred to as “acidic monomer”), A polymerizable monomer having a basic group (hereinafter sometimes simply referred to as “basic monomer”), a polymerizable monomer having neither an acidic group nor a basic group (hereinafter referred to as “other monomers”). Any polymerizable monomer (sometimes abbreviated as “monomer”) can be used.

  In the emulsion polymerization step, the polymerizable monomer is usually polymerized in an aqueous medium in the presence of an emulsifier. At this time, when supplying the polymerizable monomer to the reaction system, each monomer is added separately. Alternatively, a plurality of types of monomers may be mixed in advance and added simultaneously. Further, the monomer may be added as it is, or may be added as an emulsified liquid previously mixed and adjusted with water or an emulsifier.

  As the acidic monomer, a polymerizable monomer having a carboxyl group such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, cinnamic acid, a polymerizable monomer having a sulfonic acid group such as sulfonated styrene, Examples thereof include polymerizable monomers having a sulfonamide group such as vinylbenzenesulfonamide. Examples of the basic monomer include aromatic vinyl compounds having an amino group such as aminostyrene, nitrogen-containing heterocyclic-containing polymerizable monomers such as vinylpyridine and vinylpyrrolidone, dimethylaminoethyl acrylate, diethylaminoethyl methacrylate, etc. And (meth) acrylic acid ester having an amino group. These acidic monomers and basic monomers may be used alone or in combination as a mixture, or may exist as a salt with a counter ion. Among these, it is preferable to use an acidic monomer, more preferably acrylic acid and / or methacrylic acid.

  The total amount of the acidic monomer and the basic monomer in 100 parts by mass of the total polymerizable monomers constituting the binder resin is preferably 0.05 parts by mass or more, more preferably 0.5 parts by mass. As mentioned above, More preferably, it is 1 mass part or more, Preferably it is 10 mass parts or less, More preferably, it is 5 mass parts or less.

  As the other polymerizable monomer, the known vinyl monomers mentioned above can be used, and they may be used alone or in combination.

  Further, when the binder resin is a cross-linked resin, the above-mentioned polymerizable monomer and the above-mentioned polyfunctional monomer can be used alone or in combination.

  In the emulsion polymerization of the present invention, a known polymerization initiator can be used as necessary, and the polymerization initiators can be used alone or in combination of two or more. For example, persulfates such as potassium persulfate, sodium persulfate, ammonium persulfate, and the like, and redox initiators combining these persulfates as a component with a reducing agent such as acidic sodium sulfite, hydrogen peroxide, 4,4 Water-soluble polymerization initiators such as' -azobiscyanovaleric acid, t-butyl hydroperoxide, cumene hydropeoxide, etc., and these water-soluble polymerization initiators as a component combined with a reducing agent such as ferrous salt Redox initiator systems, benzoyl peroxide, 2,2′-azobis-isobutyronitrile, and the like are used. These polymerization initiators may be added to the polymerization system before, simultaneously with the addition of the monomer, or after the addition, and these addition methods may be combined as necessary.

  Furthermore, a known chain transfer agent can be used as necessary. Specific examples of the chain transfer agent include t-dodecyl mercaptan, 2-mercaptoethanol, diisopropyl xanthogen, carbon tetrachloride, trichlorobromomethane, and the like. The chain transfer agent may be used alone or in combination of two or more, and is used in an amount of 0 to 5% by mass based on the polymerizable monomer.

  Moreover, a well-known suspension stabilizer can be used as needed. Specific examples of the suspension stabilizer include calcium phosphate, magnesium phosphate calcium hydroxide, magnesium hydroxide and the like. These may be used alone or in combination of two or more, and may be used in an amount of 1 part by mass or more and 10 parts by mass or less based on 100 parts by mass of the polymerizable monomer.

Both the polymerization initiator and the suspension stabilizer may be added to the polymerization system at any time before, simultaneously with, and after the addition of the polymerizable monomer. You may combine.
In addition, a pH adjuster, a polymerization degree adjuster, an antifoaming agent, and the like can be appropriately added to the reaction system.

  In the present invention, when the binder resin is polymerized by emulsion polymerization, known emulsifiers can be used, but one kind selected from a cationic surfactant, an anionic surfactant and a nonionic surfactant Alternatively, two or more emulsifiers can be used in combination.

  Examples of the cationic surfactant include dodecyl ammonium chloride, dodecyl ammonium bromide, dodecyl trimethyl ammonium bromide, dodecyl pyridinium chloride, dodecyl pyridinium bromide, hexadecyl trimethyl ammonium bromide, and examples of the anionic surfactant include And fatty acid soap such as sodium stearate and sodium dodecanoate, sodium dodecyl sulfate, sodium dodecylbenzenesulfonate, sodium lauryl sulfate and the like. Nonionic surfactants include, for example, polyoxyethylene dodecyl ether, polyoxyethylene hexadecyl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene lauryl ether, polyoxyethylene sorbitan monooleate ether, monodecanoyl sucrose, etc. Is mentioned.

  In this invention, it is preferable that the usage-amount of an emulsifier is used by 0.1 to 10 mass parts with respect to 100 mass parts of polymerizable monomers. These emulsifiers can be used as protective colloids, for example, one or two or more of partially or completely saponified polyvinyl alcohols such as polyvinyl alcohol and cellulose derivatives such as hydroxyethyl cellulose.

  In the present invention, the volume average particle size of the polymer primary particles obtained by emulsion polymerization is usually 0.02 μm or more, preferably 0.05 μm or more, more preferably 0.1 μm or more, and usually 1 μm or less, preferably 0. 0.8 μm or less, more preferably 0.5 μm or less. If the particle size is too small, it may be difficult to control the aggregation rate in the aggregation process. If it is too large, the particle size of the toner particles obtained by aggregation tends to be large, and a toner having the target particle size is obtained. May be difficult.

  The blending of the colorant in the emulsion polymerization aggregation method is usually performed in an aggregation step. A dispersion of polymer primary particles and a dispersion of colorant particles are mixed to form a mixed dispersion, which is then aggregated to form a particle aggregate. The colorant is preferably used in the state of being dispersed in water in the presence of an emulsifier, and the volume average particle size of the colorant particles is 0.01 μm or more, more preferably 0.05 μm or more, and more preferably 2 μm or less. 1 μm or less.

  When a charge control agent is used in the present invention, any known one can be used alone or in combination. For example, as a positively chargeable charge control agent, a quaternary ammonium salt, a basic / electron-donating agent can be used. Examples of negative charge control agents include metal chelates, metal salts of organic acids, amide group-containing compounds, phenol compounds, naphthol compounds and their metal salts, urethane bond-containing compounds, acidic or electron-withdrawing compounds. Organic substances are mentioned.

  It is preferable to use a charge control agent that is colorless or light and does not impair the color tone of the toner. For example, a quaternary ammonium salt compound is used as a positive charge control agent, and salicylic acid or alkyl salicylic acid is used as a negative charge control agent. Metal salts with chromium, zinc, aluminum, etc., metal complexes, metal salts of benzylic acid, metal complexes, amide compounds, phenol compounds, naphthol compounds, phenolamide compounds, 4,4′-methylenebis [2- [N- ( Hydroxynaphthalene compounds such as 4-chlorophenyl) amido] -3-hydroxynaphthalene] are preferred.

  In the present invention, when the charge control agent is contained in the toner using the emulsion polymerization aggregation method, the charge control agent is added together with the polymerizable monomer or the like during the emulsion polymerization, or the charge control agent is The dispersion liquid dispersed in is added in the agglomeration step together with the polymer primary particles and the colorant, or is added after the polymer primary particles and the colorant are agglomerated to almost the target particle size. Can be blended. Among these, it is preferable to disperse the charge control agent in water by a known method and add it as a dispersion having a volume average particle size of 0.01 μm or more and 3 μm or less to the aggregation step.

  In the emulsion polymerization aggregation method, the aggregation is usually carried out in a tank equipped with a stirrer, but there are a heating method, a method of adding an electrolyte, and a method of combining them. When polymer primary particles are agglomerated with stirring to obtain particle aggregates of the desired size, the particle size of the particle aggregates is controlled based on the balance between the agglomeration force between the particles and the shearing force due to agitation. However, the cohesive force can be increased by heating or adding an electrolyte.

In the present invention, the electrolyte in the case of performing aggregation by adding an electrolyte may be either an organic salt or an inorganic salt. Specifically, NaCl, KCl, LiCl, Na ₂ SO ₄ , K ₂ SO ₄ , Li ₂ SO ₄ , MgCl ₂ , CaCl ₂ , MgSO ₄ , CaSO ₄ , ZnSO ₄ , Al ₂ (SO ₄ ) ₃ , Fe ₂ (SO ₄ ) ₃ , CH ₃ COONa, C ₆ H ₅ SO ₃ Na, etc. It is done. Of these, inorganic salts having a divalent or higher polyvalent metal cation are preferred.

  In the present invention, the amount of electrolyte added varies depending on the type of electrolyte, target particle size, etc., but is preferably 0.05 parts by mass or more, and 0.1 parts by mass with respect to 100 parts by mass of the solid component of the mixed dispersion. Part or more is more preferable. Further, it is preferably 25 parts by mass or less, more preferably 15 parts by mass or less, and particularly preferably 10 parts by mass or less. If the amount added is too small, the progress of the agglomeration reaction will be slow, and there will be problems such as a fine powder of 1 μm or less remaining after the agglomeration reaction or the average particle size of the obtained particle aggregate will not reach the target particle size. In some cases, when the amount is larger than the above range, rapid aggregation tends to occur and it is difficult to control the particle size, and the obtained aggregated particles may cause problems such as inclusion of coarse powder or irregular shapes. .

The aggregation temperature in the case of performing aggregation by adding an electrolyte is preferably 20 ° C. or higher, particularly preferably 30 ° C. or higher. Moreover, 70 degrees C or less is preferable and 60 degrees C or less is especially preferable.
The aggregation temperature in the case of performing aggregation only by heating without using an electrolyte is preferably (Tg-20) ° C. or higher, and more preferably (Tg-10) ° C. or higher, where Tg is the glass transition temperature of the polymer primary particles. . Moreover, Tg or less is preferable and (Tg-5) degree C or less is preferable.

  The time required for agglomeration is optimized depending on the shape of the apparatus and the processing scale, but in order for the toner particle size to reach the target particle size, it is usually held at the predetermined temperature for at least 30 minutes. desirable. The temperature rise until reaching the predetermined temperature may be raised at a constant rate, or may be raised stepwise.

  If necessary, particles having resin fine particles attached or fixed thereto may be formed on the surface of the particle aggregate after the above-described aggregation treatment. By attaching or fixing resin fine particles whose properties are controlled to the surface of the particle aggregate, the chargeability and heat resistance of the obtained toner may be improved, and the effect of the present invention can be further enhanced. .

  When resin fine particles having a glass transition temperature higher than the glass transition temperature of the polymer primary particles are used as the resin fine particles, it is preferable because blocking resistance can be further improved without impairing fixability. The volume average particle size of the resin fine particles is preferably 0.02 μm or more, and more preferably 0.05 μm or more. Moreover, 1 micrometer or less, Furthermore 0.6 micrometer or less are preferable. As the resin fine particles, those obtained by emulsion polymerization of monomers similar to the polymerizable monomers used for the above-described polymer primary particles can be used.

  The resin fine particles are usually used as a dispersion dispersed in water or a liquid mainly composed of water using a surfactant. However, when a charge control agent is added after the aggregation treatment, charge control is performed on the dispersion containing particle aggregates. It is preferable to add resin fine particles after adding the agent.

  In order to increase the stability of the particle aggregate obtained in the aggregation step, it is preferable to perform fusion in the aggregated particles in the aging step after the aggregation step. The temperature of the ripening step is preferably not less than Tg of the polymer primary particles, more preferably not less than 5 ° C higher than Tg, and preferably not more than 80 ° C higher than Tg, more preferably not less than 50 ° C higher than Tg. It is as follows. The time required for the ripening step varies depending on the shape of the target toner, but is usually 0.1 to 10 hours, preferably 0.5 to 5 hours after reaching the glass transition temperature or higher of the polymer primary particles. It is desirable to do.

  In addition, it is preferable to add a surfactant or raise the pH value after the aggregation process, preferably before the aging process or at a stage during the aging process. As the surfactant used here, one or more emulsifiers can be selected from the emulsifiers that can be used when producing the polymer primary particles. In particular, the emulsifiers used when producing the polymer primary particles. It is preferable to use the same. Although the addition amount in the case of adding surfactant is not limited, Preferably it is 0.1 mass part or more with respect to 100 mass parts of solid components of a mixed dispersion liquid, More preferably, it is 1 mass part or more, More preferably, it is 3 masses. It is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and still more preferably 10 parts by mass or less. After the aggregation process, before the completion of the ripening process, by adding a surfactant or raising the pH value, it is possible to suppress aggregation of the particle aggregates aggregated in the aggregation process, In some cases, the generation of coarse particles can be suppressed.

  By heat treatment in the aging step, the polymer primary particles in the aggregate are fused and integrated, and the toner particle shape as the aggregate becomes close to a spherical shape. The particle aggregate before the aging step is considered to be an aggregate due to electrostatic or physical aggregation of the polymer primary particles, but after the aging step, the polymer primary particles constituting the particle aggregate are fused to each other. In addition, the shape of the toner particles can be made nearly spherical. According to such an aging process, by controlling the temperature and time of the aging process, the primary shape of the polymer primary particles is agglomerated, a potato type with advanced fusion, and a spherical shape with further fusion For example, various shapes of toner can be manufactured according to the purpose.

The toner mother particles are subjected to a step of filtering and washing the toner mother particles from a dispersion containing the toner mother particles and a dispersion medium using a centrifuge.
In the step of filtering and washing, for example, the toner base particle collecting property, clogging resistance, cake forming property, water permeability, simplicity when replacing the filter cloth, and the like are required. It is not easy to satisfy these required characteristics at the same time. In particular, toner base particles obtained by a wet method are particles having a small particle size, and it is difficult to satisfy them simultaneously.

Further, in the toner base particle dispersion (slurry) processed in the step of filtering and washing, it is derived not only from the toner base particles but also from raw materials, surfactants, additives, etc. used in each manufacturing process. Since impurities such as various by-products and contaminants are present, when effective filtration and washing that appropriately removes these impurities in the filtration and washing process is not performed, the finally obtained electrostatic charge image developing toner Performance will be poor. That is, toner obtained from toner base particles from which impurities are not properly removed tends to be inferior in terms of storage stability, and when image formation is performed, the image is fogged. Temperature and humidity changes during image formation Image quality changes such as image density, toner scattering in the image forming apparatus, and images with a constant image quality cannot be obtained when used for a long period of time. Become. Therefore, filtration cleaning that can sufficiently remove impurities is desired.
The technique of the present invention realizes filtration and cleaning satisfying each of these required characteristics.

  To the toner of the present invention, an external additive can be added as necessary to improve the fluidity and charge control of the toner. Examples of such an external additive include various inorganic or organic fine particles. It can be appropriately selected and used.

  Examples of inorganic fine particles include silicon carbide, boron carbide, titanium carbide, zirconium carbide, hafnium carbide, vanadium carbide, tantalum carbide, niobium carbide, tungsten carbide, chromium carbide, molybdenum carbide, calcium carbide, and other carbides, boron nitride, titanium nitride. , Various nitrides such as zirconium nitride, various borides such as zirconium boride, various oxides such as titanium oxide, calcium oxide, magnesium oxide, zinc oxide, copper oxide, aluminum oxide, cerium oxide, silica, colloidal silica, titanium Various titanate compounds such as calcium oxide, magnesium titanate and strontium titanate, phosphate compounds such as calcium phosphate, sulfides such as molybdenum disulfide, fluorides such as magnesium fluoride and fluorocarbon, aluminum stearate, stearin Calcium, zinc stearate, can be used various metal soaps such as magnesium stearate, talc, bentonite, various carbon black or conductive carbon black, magnetite, ferrite or the like. As the organic fine particles, fine particles such as styrene resin, acrylic resin, epoxy resin, and melamine resin can be used.

  Among these external additives, silica, titanium oxide, alumina, zinc oxide, various carbon blacks, conductive carbon blacks, and the like are preferably used. In addition, the external additive, the surface of the inorganic or organic fine particles, silane coupling agent, titanate coupling agent, silicone oil, modified silicone oil, silicone varnish, fluorine silane coupling agent, fluorine silicone oil, What has been subjected to surface treatment such as hydrophobization by a treating agent such as a coupling agent having an amino group or a quaternary ammonium base can also be used. Two or more kinds of the treatment agents can be used in combination.

The external additive preferably has an average particle size of 0.001 μm or more, more preferably 0.005 μm or more. Moreover, 3 micrometers or less are preferable, More preferably, it is 1 micrometer. Also, a plurality of types having different particle sizes can be blended. The average particle diameter of the external additive can be determined by observation with an electron microscope.
In addition, the external additive can be used in combination of two or more different types, can be used in combination with those that have not been surface-treated and those that have been surface-treated, A positively chargeable one and a negatively chargeable one can be used in appropriate combination.

  The content of the external additive in the present invention is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, preferably 5 parts by mass or less, based on 100 parts by mass of the toner base particles. Preferably it is 3 mass parts or less.

  Examples of the method for adding the external additive include a method using a high-speed stirrer such as a Henschel mixer, a method using an apparatus capable of applying a compressive shear stress, and the like.

  Further, inorganic fine powders such as magnetite, ferrite, cerium oxide, strontium titanate, and conductive titania can be added. The amount of these additives used may be appropriately selected depending on the desired performance, and is usually preferably 0.05 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the toner particles.

The toner for developing an electrostatic charge image of the present invention preferably has a volume median diameter (Dv50) of 7 μm or less, more preferably 6.5 μm or less, and particularly preferably 6 μm or less. Moreover, it is preferable that it is 4 micrometers or more, and it is especially preferable that it is 4.5 micrometers or more.
If the volume median diameter (Dv50) is too large, it may not be suitable for high-resolution image formation. In addition, toner consumption during continuous actual shooting may increase, or toner deterioration such as burying of an external additive may easily occur. On the other hand, if it is too small, the wax tends to be liberated during production, and as a result, the chargeability and fluidity of the toner may be deteriorated, and handling as a powder may be difficult.

Hydrocarbon waxes (particularly microcrystalline waxes) are likely to be liberated and difficult to uniformly disperse in the toner.
In addition, since ester wax has good compatibility with the resin for toner, there are cases where storage stability is deteriorated and charging characteristics are deteriorated. This tendency was remarkable in a high temperature and high humidity environment.

However, in the present invention, by using a colorant having a specific structure, this defect can be solved, and a toner having a small amount of free wax and good wax dispersibility can be obtained. Further, it is excellent in storage stability and chargeability, and a toner excellent in these performances can be obtained not only at normal temperature / normal humidity but also at high temperature / high humidity and low temperature / low humidity.
As a result, it is possible to provide a toner for developing an electrostatic image having excellent image quality while ensuring the fixing property and blocking resistance while suppressing the generation of dust during fixing.

  A value (Dv50 / Dn50) obtained by dividing the volume median diameter (Dv50) of the toner by the number median diameter (Dn50) is referred to as “particle size distribution”, and the “particle size distribution” is preferably close to 1, and 1.1 or less. Preferably, 1.09 or less is more preferable. Since the electrostatic charge image developing toner has a sharper particle size distribution, the chargeability between the particles tends to be uniform. Therefore, the particle size distribution (Dv50) of the electrostatic image developing toner for achieving high image quality and high speed. / Dn50) is preferably in the above range.

On the other hand, in order to sharpen the particle size distribution, it is important that the wax is uniformly dispersed in the toner resin and that no free wax is generated during production.
In order to achieve high speed, it is necessary that the toner melts in a short time and is resistant to heat generated by high-speed stirring in the developing machine. In order to satisfy these contradictory performances, it is important that the wax is uniformly dispersed in the toner resin and that no free wax is generated during production.
In the present invention, an electrostatic charge image developing toner having excellent image quality with a sharp particle size distribution while ensuring fixing property and blocking resistance, while suppressing dust generated during fixing, depending on the type and mixing ratio of the wax described above. Can be provided.

  The volume median diameter (Dv50) and the number median diameter (Dn50) of the toner base particles and the toner are measured and defined by the method described in the examples.

In addition, the shape of the toner for developing an electrostatic charge image is preferably as close to a sphere as possible. In the scattergram based on the number-of-circle-based equivalent diameter-circularity scattergram measured by the flow type particle image measuring device, the average circularity is preferably Is 0.95 or more, more preferably 0.96 or more, and particularly preferably 0.97 or more. The closer to a sphere, the less the amount of charge is localized in the particles, and the developability tends to be uniform. On the other hand, a perfect spherical toner is a toner in the cleaning process on the photoreceptor in electrostatic image development. The average circularity is preferably 0.995 or less, more preferably 0.990 or less.
The circularity standard deviation is preferably less than 0.10, and more preferably less than 0.05.

  “Average circularity” and “circularity standard deviation” are defined as values obtained by measuring by the method described in the Examples and measuring in such a manner. The “average circularity” and “circularity standard deviation” of the toner for developing an electrostatic charge image are equal to the “average circularity” and “circularity standard deviation” of the toner base particles before external addition. Further, the toner base particles were measured, and they were defined as “average circularity” and “circularity standard deviation” of the electrostatic image developing toner, respectively.

  The electrostatic image developing magenta toner obtained by the production method of the present invention is used in any form of a two-component developer using the toner together with a carrier, or a magnetic or non-magnetic one-component developer using no carrier. Also good. When used as a two-component developer, the carrier may be a magnetic substance such as iron powder, magnetite powder, ferrite powder or the like, or a known material such as a resin-coated surface or a magnetic carrier. As the coating resin of the resin coating carrier, generally known styrene resin, acrylic resin, styrene acrylic copolymer resin, silicone resin, modified silicone resin, fluororesin, or a mixture thereof can be used.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist. Hereinafter, “part” means “part by mass”, and “%” simply means “% by mass” in terms of concentration and the like.

Measurement Example The particle size, circularity, electrical conductivity, wax carbon number, and the like were measured as follows.

<Measurement method and definition of volume average diameter (Mv)>
The volume average diameter (Mv) of the particles having a volume average diameter (Mv) of less than 1 μm is a model Microtrac Nanotrac 150 (hereinafter abbreviated as “Nanotrack”) manufactured by Nikkiso Co., Ltd. .2-019EE, using ion-exchanged water with an electric conductivity of 0.5 μS / cm as a solvent, solvent refractive index: 1.333, measurement time: 600 seconds, number of measurements: 1 It was measured by the method described in the document. Other setting conditions were particle refractive index: 1.59, transparency: transmission, shape: true sphere, density: 1.04.

<Measurement method and definition of volume median diameter of wax dispersion>
Measurement was performed using Partica LA-950V2 (hereinafter abbreviated as “LA950”) manufactured by HORIBA, Ltd., which is a laser diffraction scattering type particle size distribution measuring apparatus capable of high-speed measurement. The end point particle size for determining the end point during wax emulsification was set as the median diameter.
The solvent used was ion-exchanged water having an electric conductivity of 0.5 μS / cm, and the measurement was performed by adjusting the sample amount in a concentration range of solvent refractive index: 1.333 and visible light transmittance of 70% to 90%.

<Measurement Method and Definition of Volume Median Diameter Dv1 of Colorant Premix Liquid and Colorant Dispersion>
The volume median diameter Dv1 (μm) is as follows using an ultrafine particle size distribution measuring apparatus (manufactured by Nikkiso Co., Ltd., UPA-EX150, hereinafter abbreviated as “UPA”) using a dynamic light scattering method. It is defined as measured by the following settings.

Measurement upper limit: 6.54 μm
Measurement lower limit: 0.0008 μm
Number of channels: 52
Measurement time: 100 seconds Particle permeability: Absorption Particle refractive index: N / A (not applicable)
Particle shape: non-spherical density: 1 (g / cm ³ )
Dispersion medium type: WATER
Dispersion medium refractive index: 1.333

At the time of measurement, the colorant dispersion is diluted with pure water so that the sample concentration index is in the range of 0.01 to 0.1, and the measurement is performed with a sample that has been subjected to dispersion treatment with an ultrasonic cleaner or the like.
In the present invention, the volume median diameter Dv1 (μm) is obtained by accumulating the above volume particle size distribution results from the small particle diameter side to obtain a volume cumulative distribution (curve), and measuring it as a particle diameter at a point of 50% by volume. It is what is done.

<Measurement method and definition of volume median diameter (Dv50) and number median diameter (Dn50)>
The toner finally obtained through the external addition process was subjected to the following pre-measurement treatment.
That is, in a cylindrical polyethylene (PE) beaker having an inner diameter of 47 mm and a height of 51 mm, 0.100 g of toner using a spatula and 20% by weight DBS aqueous solution using a syringe (Daiichi Kogyo Seiyaku Co., Ltd., Neogen S-) 20A) (hereinafter abbreviated as “20% DBS aqueous solution”) was added in an amount of 0.15 g. At this time, toner and a 20% DBS aqueous solution were added only to the bottom of the beaker so that the toner would not scatter on the edges of the beaker.
Next, the mixture was stirred for 3 minutes using a spatula until the toner and 20% DBS aqueous solution became a paste. At this time, the toner was prevented from being scattered on the edge of the beaker.

  Subsequently, 30 g of dispersion medium Isoton II was added, and the mixture was stirred for 2 minutes using a spatula to obtain a uniform solution as a whole. Next, a fluororesin-coated rotor having a length of 31 mm and a diameter of 6 mm was placed in a beaker and dispersed using a stirrer at 400 rpm for 20 minutes. At this time, macroscopic particles visually observed at the gas-liquid interface and the edge of the beaker were dropped into the beaker at a rate of once every 3 minutes so as to form a uniform dispersion. Subsequently, this was filtered through a mesh having an opening of 63 μm, and the obtained filtrate was designated as “toner dispersion”.

  Regarding the measurement of the particle diameter during the production process of the toner base particles, the filtrate obtained by filtering the agglomerated slurry with a 63 μm mesh was used as the “slurry liquid”.

The median diameter (Dv50 and Dn50) of the particles is Bocman Coulter's Multisizer III (aperture diameter 100 μm) (hereinafter abbreviated as “Multisizer”), the dispersion medium is Isoton II, and the above-mentioned The “toner dispersion liquid” or “slurry liquid” was diluted to a dispersoid concentration of 0.03% by mass, and measured with Multisizer III analysis software at a KD value of 118.5.
The measurement particle diameter range is from 2.00 μm to 64.00 μm, and this range is discretized into 256 divisions so as to be equally spaced on a logarithmic scale, and those calculated based on statistical values on the basis of the volume are “ The volume median diameter (Dv50) ”and the value calculated based on the statistical value on the basis of the number were referred to as“ number median diameter (Dn50) ”.

<Measurement method and definition of toner particle size distribution>
The volume median diameter (Dv50) was divided by the number median diameter (Dn50) to obtain Dv50 / Dn50 as the “particle size distribution”.

<Measuring method and definition of average circularity and circularity standard deviation of toner>
The “average circularity” in the present invention was measured as follows and defined as follows.
That is, the toner is dispersed in a dispersion medium (Isoton II, manufactured by Beckman Coulter, Inc.) so as to be in the range of 5720-7140 particles / μL, and the toner is obtained using a flow-type particle image analyzer (manufactured by Sysmex Corporation, FPIA 3000). The number-based circle equivalent diameter-circularity scattergram was measured under the following apparatus conditions, and the value was defined as the “average circularity” of the toner. In the present invention, the same measurement was performed three times at different locations, and an arithmetic average value of three “average circularity” was adopted as the “average circularity”.

・ Mode: HPF
-HPF analysis amount: 0.35 μL
-Number of HPF detected: 8,000-10,000 The following are measured by the above device and automatically calculated and displayed in the above device, but "roundness" is defined by the following formula The
[Circularity] = [Perimeter of a circle with the same area as the projected particle area] / [Perimeter of projected particle image]
Then, the number of HPF detected is 8,000 to 10,000, and the arithmetic average (arithmetic mean) of the circularity of each particle is displayed on the apparatus as “average circularity”.

The standard deviation of 8,000 to 10,000 circularities measured as described above is defined as “circularity standard deviation”.
In the present invention, the same measurement was performed three times at different locations, and an arithmetic average value of three “circularity standard deviations” was adopted as the “circularity standard deviation”.

<Measurement method and definition of insoluble content of tetrahydrofuran (THF)>
1 g of a sample is added to 50 g of tetrahydrofuran, dissolved by standing at 25 ° C. for 24 hours, filtered using 10 g of Celite, the solvent of the filtrate is distilled off to determine the amount of tetrahydrofuran (THF) soluble, and the amount of sample charged ( By subtracting from 1 g), “tetrahydrofuran (THF) insoluble matter (mass%)” was calculated.
As a sample, it is applied to a toner, a resin in a resin particle dispersion, and the like.

<Method for measuring weight average molecular weight and molecular weight peak>
The THF soluble content of toner and polymer primary particles (resin particles) was measured by gel permeation chromatography (GPC) under the following conditions.

Apparatus: GPC apparatus HLC-8020 manufactured by Tosoh Corporation
Column: Polymer Laboratory, PL-gel Mixed-B 10 μm
Solvent: tetrahydrofuran (THF)
Sample concentration: 0.1% by mass
Calibration curve creation: Standard polystyrene

As the THF soluble content of the toner, the “tetrahydrofuran (THF) soluble content” obtained by the above “Method for measuring tetrahydrofuran (THF) insoluble content” was used.
Further, the THF soluble content of the polymer primary particles (resin particles) is obtained by adding 1 g of the polymer primary particles (resin particles) to 50 g of THF and allowing to stand at 25 ° C. for 24 hours, followed by filtration and evaporation of the solvent. Prepared.

<Measurement method and structure identification of carbon number of wax>
Gas chromatography Agilent 6890 (manufactured by Agilent Technologies) with a programmable temperature vaporization inlet was used to measure the carbon number of the wax and the structure, and as a separation column, a capillary column (inner diameter of 100% dimethylpolysiloxane in the liquid phase) was used. 0.25 mm / film thickness 0.10 μm / length 30 m), column temperature was 50 to 420 ° C. (temperature increase of 10 ° C./min), and carrier gas was measured using helium (flow rate 1 mL / min).
Moreover, Agilent5973 (made by the company) was used for the mass spectrometry.

Table 1 shows the values of the wax used and the carbon number composition of each wax.

P: Ratio (mass%) of the hydrocarbon-based wax in the hydrocarbon-based wax with respect to the entire hydrocarbon-based wax.
Q: Ratio (% by mass) of the normal form of the hydrocarbon wax having 40 or more carbon atoms in the hydrocarbon wax having 40 or more carbon atoms.
R: The proportion of non-normal components in the hydrocarbon-based component having 40 or more carbon atoms in the hydrocarbon wax (% by mass)
S: Ratio of non-normal body to the entire hydrocarbon wax among the components of hydrocarbon wax having 40 or more carbon atoms (mass%)
T: The proportion (mass%) of the hydrocarbon wax in which the component having 30 or more carbon atoms occupies the entire hydrocarbon wax.

Example 1
<Preparation of wax dispersion W1>
Add 30.0 parts of HI-Mic-1090 (manufactured by Nippon Seiwa), a microcrystalline wax, 2.8 parts of 20% DBS aqueous solution and 67.3 parts of demineralized water, heat to 100 ° C., and pressurize circulation line The primary circulation emulsification was performed under a pressure condition of 10 MPa using a homogenizer (manufactured by Gorin, LAB60-10TBS type) attached.
The particle diameter was measured every few minutes with LA950, and when the median diameter decreased to around 500 nm, the pressure condition was further increased to 25 MPa, followed by secondary circulation emulsification. A wax dispersion W1 was prepared by dispersing until the median diameter became 230 nm or less.
The volume median diameter of this wax dispersion was 220 nm.

<Preparation of wax dispersion W2>
Microcrystalline wax Hi-Mic-1090 (Nippon Seiwa Co., Ltd.) 25.0 parts, Decaglycerin decabehenate (acid value 3.2 mgKOH / g, hydroxyl value 27 mgKOH / g) 5.0 parts, 20% dodecyl 2.8 parts of sodium benzenesulfonate aqueous solution (Daiichi Kogyo Seiyaku Co., Ltd., Neogen S20D) (hereinafter abbreviated as “20% DBS aqueous solution”) and 67.3 parts of demineralized water were added and heated to 100 ° C. Primary circulation emulsification was performed under a pressure condition of 10 MPa using a homogenizer with a pressure circulation line (manufactured by Gorin, LAB 60-10TBS type).

The particle diameter was measured every few minutes with LA950, and when the median diameter decreased to around 500 nm, the pressure condition was further increased to 25 MPa, followed by secondary circulation emulsification. A wax dispersion W2 was produced by dispersing until the median diameter became 230 nm or less.
The volume median diameter of this wax dispersion was 210 nm.

<Preparation of wax dispersion W3>
Nissan Electol WEP-6 (manufactured by NOF), which is a neopentyl polyol ester wax (R ¹ in the structural formula (1) is a pentaerythritol residue, R ² is an icosyl group, m is 4, and an acid value of 0.6 mgKOH / g, hydroxyl value 2.6 mg KOH / g) 30.0 parts, 20% DBS aqueous solution 2.7 parts, demineralized water 67.3 parts, heated to 100 ° C., homogenizer with pressure circulation line (manufactured by Gorin) LAB60-10TBS type) was used for primary circulation emulsification under a pressure of 10 MPa.

The particle diameter was measured every few minutes with LA950, and when the median diameter decreased to around 500 nm, the pressure condition was further increased to 25 MPa, followed by secondary circulation emulsification. A wax dispersion W3 was prepared by dispersing until the median diameter became 230 nm or less.
The volume median diameter of the wax dispersion was 225 nm.

<Preparation of wax dispersion W4>
21.4 parts of Hi-Mic-1090 (manufactured by Nippon Seiwa) which is microcrystalline wax, Nissan Electol WEP-4 (manufactured by NOF) which is neopentyl polyol ester (R ¹ in the structural formula (1) is penta Erythritol residue, R ² is stearyl group, m is 4, acid value 0.2 mgKOH / g, hydroxyl value 1.1 mgKOH / g) 5.3 parts and decaglycerin decabehenate (acid value 3.2 mgKOH / g, (Hydroxyl value 27 mgKOH / g) 0.3 parts by heating at 90 ° C., 2.8 parts of 20% DBS aqueous solution and 67.3 parts of demineralized water were added and heated to 100 ° C., and a homogenizer with a pressure circulation line The primary circulation emulsification was performed under a pressure condition of 10 MPa using (LAB 60-10TBS type, manufactured by Gorin).

The particle diameter was measured every few minutes with LA950, and when the median diameter decreased to around 500 nm, the pressure condition was further increased to 25 MPa, followed by secondary circulation emulsification. A wax dispersion W4 was produced by dispersing until the median diameter became 230 nm or less.
The volume median diameter of this wax dispersion was 210 nm.

<Preparation of wax dispersion W5>
A wax dispersion W5 was prepared in the same manner as the wax dispersion W1, except that HI-Mic-1090 (manufactured by Nippon Seiwa), which is a microcrystalline wax, was replaced with HNP-9 (manufactured by Nippon Seiwa), a paraffin wax.
The volume median diameter of this wax dispersion was 220 nm.

<Preparation of wax dispersion W6>
A wax dispersion W6 was prepared in the same manner as the wax dispersion W3 except that WEP-6 (manufactured by NOF) was replaced with behenyl behenate.
The volume median diameter of this wax dispersion was 220 nm.

<Preparation of wax dispersion W7>
A wax dispersion W7 was produced in the same manner as the wax dispersion W3 except that WEP-6 (manufactured by NOF Corporation) was replaced with stearyl stearate.
The volume median diameter of this wax dispersion was 210 nm.

<Preparation of colorant dispersion>
In a stirrer vessel equipped with a propeller blade, 20 parts of a colorant in which R ¹¹ and R ¹² in the structural formula (2) are both CH ₃ , a nonionic surfactant (manufactured by Kao Corporation, 1204 parts of Emulgen (colorant) 20 parts), and 76 parts of ion-exchanged water having an electric conductivity of 2 μS / cm was added and predispersed to obtain a colorant premix solution, and the volume median diameter of the colorant particles in the colorant premix solution. Dv1 was about 90 μm.

The colorant premix solution was used as a raw material slurry and supplied to a wet bead mill equipped with a rotating screen (bead separation mesh separator) as shown in FIG. 1, and circulated and dispersed in the configuration shown in FIG. Note that zirconia beads (true density of 6.0 g / cm ³ ) having a diameter of 120 mmφ, a separator having a diameter of 60 mmφ, and a diameter of 100 μm (0.1 mm) were used as a dispersion medium. The effective internal volume of the stator is about 0.5 L, and the media filling volume is 0.35 L, so the media filling rate is 70%.

The premix slurry was supplied from the supply port at a supply speed of about 54 L / hr by a non-pulsating metering pump with the rotor rotating speed kept constant (the peripheral speed at the rotor tip was about 7 m / sec). During the operation, cooling water of about 10 ° C. was circulated from the jacket to obtain a colorant dispersion C1 having a volume median diameter Dv1 of 0.15 μm.
Similarly, colorant dispersions C1 to C10 shown in Table 2 were obtained.

In addition, a colorant in which R ¹¹ and R ¹² in Structural Formula (2) are both CH ₃ , R ¹⁶ in Structural Formula (4) is Cl, R ¹⁷ is CH ₃ , R ¹⁸ is SO ₃ ⁻ , M ^A colorant in which ²⁺ is Sr ²⁺ mixed in a mass ratio of 7: 3 was similarly dispersed in water to obtain a colorant dispersion C11 having a volume median diameter Dv1 of 0.16 μm. .

<Preparation of polymer primary particle dispersion D1>
In a reactor equipped with a stirrer (three blades), a heating / cooling device, a concentrating device, and a raw material / auxiliary charging device, 1.2 parts (24 g) of 20% DBS aqueous solution and 315.0 parts (6300 g) of demineralized water Then, 3.5 parts (70 g) of an 8% by mass hydrogen peroxide aqueous solution and 3.5 parts (70 g) of an 8% by mass L (+)-ascorbic acid aqueous solution were added, and the temperature was raised to 90 ° C.
Further, a mixture of the following “polymerizable monomers” and “emulsifier aqueous solution” was added over 5 hours. The time at which this mixture was started to be dropped was designated as “polymerization start”, and the following “initiator aqueous solution” was added over 4.5 hours from 30 minutes after the start of polymerization. Further, after 5 hours from the start of polymerization, the following “additional start” The agent aqueous solution ”was added over 2 hours, and the internal temperature was maintained at 90 ° C. for 1 hour while continuing stirring.

[Polymerizable monomers, etc.]
Styrene: 76.8 parts Butyl acrylate: 23.2 parts Acrylic acid: 1.5 parts Hexanediol diacrylate: 0.7 parts Dodecyl mercaptan: 3.0 parts

[Emulsifier aqueous solution]
20% DBS aqueous solution: 1.0 part demineralized water: 67.1 parts [initiator aqueous solution]
8% by mass aqueous hydrogen peroxide solution: 15.5 parts 8% by mass L (+)-ascorbic acid aqueous solution: 15.5 parts [additional aqueous initiator solution]
8% by mass L (+)-ascorbic acid aqueous solution: 14.2 parts

After completion of the polymerization reaction, the mixture was cooled to obtain a milky white polymer primary particle dispersion D1.
The volume average diameter (Mv) measured using Nanotrac was 275 nm, and the solid content concentration was 22.6% by mass.
The weight average molecular weight Mw by GPC measurement was 72000.

<Preparation of polymer primary particle dispersion D2>
A primary polymer particle dispersion D2 was obtained in the same manner as the primary polymer particle dispersion D1, except that butyl acrylate was changed to 2-ethylhexyl acrylate and the monomer composition ratio was changed as follows.

[Polymerizable monomers, etc.]
Styrene: 79.8 parts Diethylhexyl acrylate: 20.3 parts Acrylic acid: 1.5 parts Hexanediol diacrylate: 0.7 parts Trichlorobromomethane: 1.0 parts

The volume average particle size (Mv) was 255 nm, and the solid content concentration was 22.8% by mass.
The weight average molecular weight Mw by GPC measurement was 70000.

<Preparation of polymer primary particle dispersion D3>
A reactor equipped with a stirrer (three blades), a heating / cooling device, a concentrating device, and each raw material / auxiliary charging device was charged with 100 parts (3000 g) of demineralized water and 1 part of a 20% DBS aqueous solution as an emulsifier. Then, the atmosphere was replaced with nitrogen for 30 minutes. Next, 2.0 parts of potassium peroxodisulfate (KPS) was dissolved, and then heated to 70 ° C. under a nitrogen stream.
Thereafter, the following “polymerizable monomers” and an aqueous solution in which 4 parts of 2-acrylamido-2-methylpropanesulfonic acid were dissolved in 60 parts of demineralized water were added dropwise over 3 hours while the stirring of the liquid was continued. Thereafter, the temperature was raised to 80 ° C. and polymerization was carried out for 5 hours to obtain a polymer primary particle dispersion D3.

[Polymerizable monomers]
Styrene: 28 parts 2-ethylhexyl acrylate: 8 parts

The volume average particle size (Mv) was 260 nm, and the solid content concentration was 23.0% by mass.
The weight average molecular weight Mw by GPC measurement was 55000.

<Preparation of polymer primary particle dispersion E1>
A reactor equipped with a stirring device (three blades), a heating / cooling device, a concentrating device, and each raw material / auxiliary charging device was charged with 36.3 parts of wax dispersion W2 and 218 parts of demineralized water while stirring. The temperature was raised to 90 ° C. under a nitrogen stream.
Thereafter, the mixture of the following “polymerizable monomers and the like” and “emulsifier aqueous solution” was added to the solution over 5 hours while continuing to stir the liquid. The time at which this mixture was started to be dropped was designated as “polymerization start”, and the following “initiator aqueous solution” was added over 4.5 hours from 30 minutes after the start of polymerization. Further, after 5 hours from the start of polymerization, the following “additional start” The agent aqueous solution ”was added over 2 hours, and the internal temperature was maintained at 90 ° C. for 1 hour while continuing stirring.

[Polymerizable monomers, etc.]
Styrene: 76.8 parts Butyl acrylate: 23.2 parts Acrylic acid: 1.5 parts Hexanediol diacrylate: 0.7 parts Dodecyl mercaptan: 4.0 parts

[Emulsifier aqueous solution]
20% DBS aqueous solution: 1.0 part demineralized water: 67.1 parts [initiator aqueous solution]
8% by mass aqueous hydrogen peroxide solution: 20.0 parts 8% by mass L (+)-ascorbic acid aqueous solution: 20.0 parts [additional aqueous initiator solution]
8% by mass L (+)-ascorbic acid aqueous solution: 14.2 parts

After completion of the polymerization reaction, the mixture was cooled to obtain a milky white polymer primary particle dispersion E1.
The volume average diameter (Mv) measured using Nanotrac was 265 nm, and the solid content concentration was 22.6% by mass.
The weight average molecular weight Mw by GPC measurement was 68,000.

<Preparation of polymer primary particle dispersion E2>
A reactor equipped with a stirring device (three blades), a heating / cooling device, a concentrating device, and each raw material / auxiliary charging device was charged with 36.3 parts of wax dispersion W3 and 218 parts of demineralized water while stirring. The temperature was raised to 90 ° C. under a nitrogen stream.
Thereafter, the mixture of the following “polymerizable monomers and the like” and “emulsifier aqueous solution” was added to the solution over 5 hours while continuing to stir the liquid. The time at which this mixture was started to be dropped was designated as “polymerization start”, and the following “initiator aqueous solution” was added over 4.5 hours from 30 minutes after the start of polymerization. Further, after 5 hours from the start of polymerization, the following “additional start” The agent aqueous solution ”was added over 2 hours, and the internal temperature was maintained at 90 ° C. for 1 hour while continuing stirring.

[Polymerizable monomers, etc.]
Styrene: 76.8 parts Butyl acrylate: 23.2 parts Acrylic acid: 1.5 parts Hexanediol diacrylate: 0.7 parts Trichlorobromomethane: 1.0 parts

[Emulsifier aqueous solution]
20% DBS aqueous solution: 1.0 part demineralized water: 67.1 parts [initiator aqueous solution]
8% by mass aqueous hydrogen peroxide solution: 15.5 parts 8% by mass L (+)-ascorbic acid aqueous solution: 15.5 parts [additional aqueous initiator solution]
8% by mass L (+)-ascorbic acid aqueous solution: 14.2 parts

After completion of the polymerization reaction, the mixture was cooled to obtain a milky white polymer primary particle dispersion E2.
The volume average diameter (Mv) measured using Nanotrac was 260 nm, and the solid content concentration was 22.8% by mass.
The weight average molecular weight Mw by GPC measurement was 76000.

<Preparation of polymer primary particle dispersion E3>
A reactor equipped with a stirring device (three blades), a heating / cooling device, a concentrating device, and each raw material / auxiliary charging device was charged with 36.3 parts of wax dispersion W4 and 218 parts of demineralized water while stirring. The temperature was raised to 90 ° C. under a nitrogen stream.
Thereafter, the mixture of the following “polymerizable monomers and the like” and “emulsifier aqueous solution” was added to the solution over 5 hours while continuing to stir the liquid. The time at which this mixture was started to be dropped was designated as “polymerization start”, and the following “initiator aqueous solution” was added over 4.5 hours from 30 minutes after the start of polymerization. Further, after 5 hours from the start of polymerization, the following “additional start” The agent aqueous solution ”was added over 2 hours, and the internal temperature was maintained at 90 ° C. for 1 hour while continuing stirring.

[Polymerizable monomers, etc.]
Styrene: 79.8 parts Diethylhexyl acrylate: 20.3 parts Acrylic acid: 1.5 parts Hexanediol diacrylate: 0.7 parts Trichlorobromomethane: 1.0 parts

[Emulsifier aqueous solution]
20% DBS aqueous solution: 1.0 part demineralized water: 67.1 parts [initiator aqueous solution]
8% by mass hydrogen peroxide aqueous solution: 25.0 parts 8% by mass L (+)-ascorbic acid aqueous solution: 25.0 parts [additional initiator aqueous solution]
8% by mass L (+)-ascorbic acid aqueous solution: 14.2 parts

After completion of the polymerization reaction, the mixture was cooled to obtain a milky white polymer primary particle dispersion E3. The volume average diameter (Mv) measured using Nanotrac was 270 nm, and the solid content concentration was 23.0% by mass.
The weight average molecular weight Mw by GPC measurement was 63000.

<Manufacture of toner mother particles F1>
By using the following components, toner base particles F1 were produced by carrying out the following aggregation process (core material aggregation process / shell coating process) / rounding process.

Wax Dispersion W1 8 parts as solids Polymer Primary Particle Dispersion D1 100 parts as Solids Colorant Dispersion C1 3.5 parts as Colorant Solids C6 Colorant Dispersion C6 1.5 parts as Colorant Solids 20 % DBS aqueous solution In the rounding process, the solid content is 6 parts.

○ Core material agglomeration step A wax dispersion W1 and a polymer primary particle dispersion D1 were placed in a mixer (volume 1000 L, inner diameter 850 mm) equipped with a stirrer (double helical blade), a heating / cooling device, and each raw material / auxiliary charging device. Was mixed uniformly at an internal temperature of 10 ° C. for 10 minutes. Then at an internal temperature of 10 ° C., allowed to stir at 101Rpm, a 5 wt% aqueous solution of potassium sulfate _from continuously added over 1 minute 0.12 parts as K 2 SO _4, and colorant dispersion C1 coloring The agent dispersion C6 was continuously added over 5 minutes and mixed uniformly at an internal temperature of 10 ° C.

  Thereafter, 0.3 part by weight of an aqueous solution of 0.5% by mass of aluminum sulfate was continuously added over 30 minutes, and the internal temperature was raised to 48.0 ° C. over 70 minutes while maintaining the rotation speed at 101 rpm ( 0.5 ° C./min). Subsequently, after raising the temperature by 1 ° C. every 30 minutes (0.03 ° C./min), the temperature was maintained at 54.0 ° C., the volume median diameter was measured using a multisizer, and grown to 5.5 μm.

○ Circularization process Subsequently, a mixed aqueous solution of 20% DBS aqueous solution (6 parts as solids) and 0.04 part of water was added over 30 minutes with the same rotation speed, and the temperature was raised to 90 ° C. The temperature was raised by 1 ° C. every 30 minutes, raised to 95 ° C., and heating and stirring were continued under these conditions until the average circularity became 0.968 over 2.5 hours. Thereafter, the mixture was cooled to 20 ° C. over 50 minutes to obtain a slurry of toner base particles C1.
At this time, the volume median diameter of the particles was 5.6 μm, the number median diameter was 5.2 μm, the distribution Dv50 / Dn50 was 1.08, the average circularity was 0.968, and the circularity standard deviation was 0.014. It was.

○ Washing and drying process Using a wet electromagnetic sieve shaker (AS200 / Lecche Co., Ltd.) equipped with a sieve with a mesh size of 24μm, the resulting slurry is filtered for the purpose of removing coarse particles and equipped with a stirrer Once stored in the tank. Thereafter, this slurry was subjected to a horizontal centrifuge (HZ40Si type / Mitsubishi Chemical Corporation) equipped with a filter cloth (polyester TR815C, Nakao filter industry / thickness 0.3 mm / air permeability 48 (cc / cm ² / min)). Then, centrifugal dehydration washing was performed under the condition of acceleration 800G.
When ion-exchanged water having an electric conductivity of 1 μS / cm was added at a rate not to overflow from the rim at about 50 times the amount of slurry solids, the electric conductivity of the filtrate was 2 μS / cm. Finally, water was thoroughly shaken off, and the cake was recovered with a scraping device.
The obtained cake was spread on a stainless steel vat so as to have a height of 20 mm, and dried in a blow dryer set at 40 ° C. for 48 hours to obtain toner mother particles F1.

<Manufacture of developing toner G1: external addition process>
The toner base particle F1 2500 g is mixed with 50 g of Clariant H05TD silica and 15 g H30TD silica as external additives, mixed with a Henschel mixer (Mitsui Mine), sieved with 150 mesh, and developing toner G1. Got.

<Manufacture of toner mother particles F2>
Wax dispersion W2 7 parts as a solid content Polymer primary particle dispersion D2 100 parts as a solid content Colorant dispersion C1 4.0 parts as a colorant solid content C7 1.0 parts as a colorant solid content Wax Toner base particles F2 were obtained in the same manner as F1, except that the dispersion, polymer primary particle dispersion, and colorant dispersion were all changed to the above.

  Volume median diameter (Dv) was 5.8 μm, number median diameter (Dn) was 5.4 μm, Dv50 / Dn50 was 1.07, average circularity was 0.970, and circularity standard deviation was 0.012. It was.

<Manufacture of developing toner G2: external addition process>
The toner base particle F2 (2,500 g) is mixed with 50 g of Clariant H05TD silica and 15 g H30TD silica (external additive), mixed with a Henschel mixer (Mitsui Mine), sieved with 150 mesh, and developing toner G2 Got.

<Manufacture of toner mother particles F3>
Wax dispersion W1 6.5 parts as solids Wax dispersion W3 2.5 parts as solids Polymer primary particle dispersion D1 100 parts as solids Colorant dispersion C1 4.0 parts as colorant solids Dispersion C8 1.0 parts as a colorant solid content Toner base particles F3 were obtained in the same manner as F1, except that all of the wax dispersion, polymer primary particle dispersion, and colorant dispersion were changed as described above.

  The volume median diameter (Dv) was 5.5 μm, the number median diameter (Dn) was 5.2 μm, Dv50 / Dn50 was 1.06, the average circularity was 0.970, and the circularity standard deviation was 0.011. It was.

<Manufacture of developing toner G3: external addition process>
To the obtained toner base particle F16 2500 g, 50 g of Clariant H05TD silica and 15 g H30TD silica manufactured as external additives are mixed, mixed with a Henschel mixer (Mitsui Mine), sieved with 150 mesh, and developing toner G15. Got.

<Manufacture of toner mother particles F4>
Polymer primary particle dispersion E1 100 parts colorant dispersion C1 as solids colorant 4.0 parts colorant dispersion C9 as colorant solids 1.0 parts as colorant solids Wax dispersion, polymer primary particle dispersion Toner mother particles F4 were obtained in the same manner as F1, except that all of the colorant dispersion was changed to the above.

  Volume median diameter (Dv) was 5.9 μm, number median diameter (Dn) was 5.4 μm, Dv50 / Dn50 was 1.09, average circularity was 0.969, and circularity standard deviation was 0.011. It was.

<Manufacture of developing toner G4: external addition process>
The toner base particle F4 (2,500 g) thus obtained is mixed with 50 g of Clariant H05TD silica and 15 g of H30TD silica (external additive), mixed with a Henschel mixer (Mitsui Mine), sieved with 150 mesh, and developing toner G4. Got.

<Manufacture of toner mother particles F5>
Wax Dispersion W2 Solid Part 6 Part Polymer Primary Particle Dispersion D1 Solid Part 100 Part Colorant Dispersion C1 Colorant Solid Part 2.4 Part Colorant Dispersion C10 Colorant Solid Part 1.6 Part Wax Toner base particles F5 were obtained in the same manner as F1 except that all of the dispersion, polymer primary particle dispersion, and colorant dispersion were changed as described above.

  Volume median diameter (Dv) was 5.6 μm, number median diameter (Dn) was 5.1 μm, Dv50 / Dn50 was 1.10, average circularity was 0.970, and circularity standard deviation was 0.012. It was.

<Manufacture of developing toner G5: external addition process>
The toner base particle F5 (2,500 g) is mixed with 50 g of Clariant H05TD silica and 15 g H30TD silica (external additive), mixed with a Henschel mixer (Mitsui Mine), sieved with 150 mesh, and developing toner G5. Got.

<Manufacture of toner mother particles F6>
Polymer primary particle dispersion E2 80 parts colorant dispersion C1 as solids 2.4 parts colorant dispersion C2 as colorants solids 0.4 parts colorant dispersion C9 as colorants solids As colorant solids 1.2 parts Aggregation was carried out in the same manner as in F1 except that the wax dispersion, polymer primary particle dispersion, and colorant dispersion were all changed to the above.
Furthermore, when the internal temperature was 54.0 ° C. and the volume median diameter (Dv50) was 5.2 μm, 20 parts of the polymer primary particle dispersion E3 was added as a solid material as a shell material and held at that temperature for 60 minutes. .
After that, the toner mother particles F6 were obtained by rounding, washing and drying in the same manner as F1.

  Volume median diameter (Dv) was 5.5 μm, number median diameter (Dn) was 5.2 μm, Dv50 / Dn50 was 1.06, average circularity was 0.967, and circularity standard deviation was 0.014. It was.

<Manufacture of developing toner G6: external addition process>
The toner base particle F6 (2,500 g) was mixed with 50 g of Clariant H05TD silica and 15 g of H30TD silica (external additive), mixed with a Henschel mixer (Mitsui Mine), sieved with 150 mesh, and developing toner G6. Got.

<Manufacture of toner mother particles F7>
Polymer primary particle dispersion E1 95 parts colorant dispersion C3 as solid content 3.6 parts colorant dispersion C10 as colorant solids 0.4 part as colorant solids Wax dispersion, polymer primary particle dispersion Aggregation was carried out in the same manner as F1 except that all of the colorant dispersion was changed to the above.
Furthermore, when the internal temperature was 54.0 ° C. and the volume median diameter (Dv50) was 5.4 μm, 5 parts of the polymer primary particle dispersion D3 was added as a solid material as a shell material and held at that temperature for 60 minutes. .
Thereafter, toner mother particles F7 were obtained by rounding, washing and drying in the same manner as in F1.

  The volume median diameter (Dv) was 5.6 μm, the number median diameter (Dn) was 5.2 μm, Dv50 / Dn50 was 1.08, the average circularity was 0.968, and the circularity standard deviation was 0.014. It was.

<Manufacture of developing toner G7: external addition process>
The toner base particle F7 (2,500 g) thus obtained is mixed with 50 g of Clariant H05TD silica and 15 g of H30TD silica (external additive), mixed with a Henschel mixer (Mitsui Mine), sieved with 150 mesh, and developing toner G7. Got.

<Manufacture of toner mother particles F8>
Polymer primary particle dispersion E1 100 parts colorant dispersion C4 as solids 3.6 parts colorant dispersion C8 as colorants solids 0.4 parts as colorant solids Wax dispersion, polymer primary particle dispersion Toner mother particles F8 were obtained in the same manner as F4 except that all of the colorant dispersion was changed to the above.

  Volume median diameter (Dv) was 5.8 μm, number median diameter (Dn) was 5.3 μm, Dv50 / Dn50 was 1.09, average circularity was 0.970, and circularity standard deviation was 0.011. It was.

<Manufacture of developing toner G8: external addition process>
To 2500 g of the obtained toner base particles F8, 50 g of H05TD silica manufactured by Clariant and 15 g of H30TD silica manufactured as external additives are mixed, mixed with a Henschel mixer (manufactured by Mitsui Mining), sieved with 150 mesh, and developing toner G8. Got.

<Manufacture of toner mother particles F9>
Polymer primary particle dispersion E2 100 parts colorant dispersion C1 as solids 2.2 parts colorant dispersion C4 as colorant solids 0.6 parts colorant dispersion C10 as colorant solids As colorant solids 1.2 parts Toner base particles F9 were obtained in the same manner as F1, except that the wax dispersion, the polymer primary particle dispersion, and the colorant dispersion were all changed to the above.

  The volume median diameter (Dv) was 5.6 μm, the number median diameter (Dn) was 5.1 μm, Dv50 / Dn50 was 1.10, the average circularity was 0.970, and the circularity standard deviation was 0.011. It was.

<Manufacture of developing toner G9: external addition process>
The toner base particle F9 (2,500 g) was mixed with 50 g of Clariant H05TD silica and 15 g H30TD silica (external additive), mixed with a Henschel mixer (Mitsui Mine), sieved with 150 mesh, and developed toner G9. Got.

<Manufacture of toner mother particles F10>
Wax dispersion W4 8 parts as a solid content Polymer primary particle dispersion D2 95 parts as a solid content Colorant dispersion C1 6.3 parts as a colorant solids C9 Colorant dispersion C9 0.7 parts as a colorant solids Wax Aggregation was carried out in the same manner as in F1 except that all of the dispersion, polymer primary particle dispersion, and colorant dispersion were changed to the above.
Further, when the internal temperature was 54.0 ° C. and the volume median diameter (Dv50) was 5.3 μm, 5 parts of the polymer primary particle dispersion D3 was added as a solid material as a shell material, and held at that temperature for 60 minutes. .
Thereafter, toner mother particles F10 were obtained by rounding, washing and drying in the same manner as in F1.

  Volume median diameter (Dv) was 5.5 μm, number median diameter (Dn) was 5.2 μm, Dv50 / Dn50 was 1.06, average circularity was 0.967, and circularity standard deviation was 0.014. It was.

<Manufacture of developing toner G10: external addition process>
To the toner base particle F10 obtained, 50 g of H05TD silica manufactured by Clariant and 15 g of H30TD silica manufactured by Clariant are mixed as external additives, mixed with a Henschel mixer (Mitsui Mine), sieved with 150 mesh, and developing toner G10. Got.

<Manufacture of toner mother particles F11>
Polymer primary particle dispersion E1 90 parts colorant dispersion C1 as solids colorant 3.5 parts colorant dispersion C5 as colorant solids 0.5 parts colorant dispersion C8 as colorant solids As colorant solids 1.0 part Aggregation was carried out in the same manner as F1 except that the wax dispersion, polymer primary particle dispersion, and colorant dispersion were all changed to the above.
Furthermore, when the internal temperature was 54.0 ° C. and the volume median diameter (Dv50) was 5.2 μm, 10 parts of the polymer primary particle dispersion E1 was added as a solid material as a shell material, and held at that temperature for 60 minutes. .
Thereafter, toner mother particles F11 were obtained by rounding, washing and drying in the same manner as in F1.

  Volume median diameter (Dv) was 5.6 μm, number median diameter (Dn) was 5.2 μm, Dv50 / Dn50 was 1.08, average circularity was 0.966, and circularity standard deviation was 0.014. It was.

<Manufacture of developing toner G11: external addition process>
To the toner base particle F11 obtained 2500 g, 50 g of Clariant H05TD silica and 15 g H30TD silica as external additives are mixed, mixed with a Henschel mixer (Mitsui Mine), sieved with 150 mesh, and developing toner G11. Got.

<Manufacture of toner mother particles F12>
Polymer primary particle dispersion E1 80 parts colorant dispersion C1 as solids 5.6 parts colorant dispersion C8 as colorants solids 1.4 parts as colorant solids Wax dispersion, polymer primary particle dispersion Aggregation was carried out in the same manner as F1 except that all of the colorant dispersion was changed to the above.
Furthermore, when the internal temperature was 54.0 ° C. and the volume median diameter (Dv50) was 5.2 μm, 20 parts of polymer primary particle dispersion E2 was added as a solid material as a shell material, and the temperature was maintained for 60 minutes. .
Thereafter, toner mother particles F12 were obtained by rounding, washing and drying in the same manner as in F1.

  The volume median diameter (Dv) was 5.5 μm, the number median diameter (Dn) was 5.1 μm, Dv50 / Dn50 was 1.08, the average circularity was 0.971, and the circularity standard deviation was 0.014. It was.

<Manufacture of developing toner G12: external addition process>
To the toner base particle F12 obtained 2500 g, 50 g of Clariant H05TD silica and 15 g H30TD silica as external additives are mixed, mixed with a Henschel mixer (Mitsui Mine), sieved with 150 mesh, and developing toner G12. Got.

<Manufacture of toner mother particles F13>
Polymer primary particle dispersion E2 90 parts colorant dispersion C1 as solids 5.6 parts colorant dispersion C9 as colorant solids 1.4 parts as colorant solids Wax dispersion, polymer primary particle dispersion Aggregation was carried out in the same manner as F1 except that all of the colorant dispersion was changed to the above.
Furthermore, when the internal temperature was 54.0 ° C. and the volume median diameter (Dv50) was 5.3 μm, 10 parts of the polymer primary particle dispersion E3 was added as a solid material as a shell material, and held at that temperature for 60 minutes. .
Thereafter, toner mother particles F13 were obtained by rounding, washing and drying in the same manner as in F1.

  The volume median diameter (Dv) was 5.5 μm, the number median diameter (Dn) was 5.2 μm, Dv50 / Dn50 was 1.06, the average circularity was 0.966, and the circularity standard deviation was 0.014. It was.

<Manufacture of developing toner G13: external addition process>
Toner toner particle F13 obtained by mixing 50 g of H05TD silica manufactured by Clariant Co., Ltd. and 15 g of H30TD silica manufactured by Co., Ltd. as an external additive, is mixed with 2500 g of the obtained toner base particle F13 using a Henschel mixer (Mitsui Mine Co., Ltd.). Got.

<Manufacture of toner mother particles F14>
Polymer primary particle dispersion E3 95 parts colorant dispersion C11 as solid content 7.0 parts as colorant solid content Except for changing all of wax dispersion, polymer primary particle dispersion, and colorant dispersion to the above. Aggregation was carried out as in F1.
Further, when the internal temperature was 54.0 ° C. and the volume median diameter (Dv50) was 5.2 μm, 5 parts of the polymer primary particle dispersion D3 was added as a solid material as a shell material, and held at that temperature for 60 minutes. .
Thereafter, toner mother particles F14 were obtained by rounding, washing and drying in the same manner as in F1.

  Volume median diameter (Dv) was 5.6 μm, number median diameter (Dn) was 5.3 μm, Dv50 / Dn50 was 1.06, average circularity was 0.967, and circularity standard deviation was 0.012. It was.

<Manufacture of developing toner G14: external addition process>
To the toner base particle F14 obtained 2500 g, 50 g of Clariant H05TD silica and 15 g H30TD silica as external additives are mixed, mixed with a Henschel mixer (Mitsui Mine), sieved with 150 mesh, and developing toner G14. Got.

<Manufacture of toner mother particles F15>
Wax dispersion W1 8 parts polymer primary particle dispersion D1 as solids 100 parts colorant dispersion C1 as solids 5.0 parts as colorant solids Wax dispersion, polymer primary particle dispersion, colorant dispersion A toner mother particle F15 was obtained in the same manner as F1 except that all of the above were changed to the above.

  Volume median diameter (Dv) was 5.8 μm, number median diameter (Dn) was 5.4 μm, Dv50 / Dn50 was 1.07, average circularity was 0.970, and circularity standard deviation was 0.012. It was.

<Manufacture of developing toner G15: external addition process>
To the toner base particle F15 thus obtained, 50 g of H05TD silica manufactured by Clariant Co., Ltd. and 15 g of H30TD silica manufactured by the same company are mixed as external additives, mixed with a Henschel mixer (Mitsui Mine Co., Ltd.), sieved with 150 mesh, and developing toner G15. Got.

<Manufacture of toner mother particles F16>
Colorant dispersion C3 4.0 parts as colorant solids Same as F2, except that all of the colorant dispersion (in the case of F2, only the colorant dispersion C1 and the colorant dispersion C7) was changed to the above. Thus, toner mother particles F16 were obtained.

  Volume median diameter (Dv) was 5.7 μm, number median diameter (Dn) was 5.2 μm, Dv50 / Dn50 was 1.10, average circularity was 0.970, and circularity standard deviation was 0.012. It was.

<Manufacture of developing toner G16: external addition process>
To 2500 g of the obtained toner base particles F16, 50 g of H05TD silica manufactured by Clariant Co., Ltd. and 15 g of H30TD silica manufactured by the same company are mixed as external additives, mixed with a Henschel mixer (manufactured by Mitsui Mine), sieved with 150 mesh, and developing toner G16. Got.

<Manufacture of toner mother particles F17>
Colorant dispersion C4 4.0 parts as colorant solids Same as F1 except that only all of the colorant dispersion (in the case of F1, colorant dispersion C1 and colorant dispersion C6) was changed to the above. Thus, toner mother particles F17 were obtained.

  Volume median diameter (Dv) was 5.8 μm, number median diameter (Dn) was 5.3 μm, Dv50 / Dn50 was 1.09, average circularity was 0.972, and circularity standard deviation was 0.014. It was.

<Manufacture of developing toner G17: external addition process>
To 2500 g of the obtained toner base particles F17, 50 g of H05TD silica manufactured by Clariant Co., Ltd. and 15 g of H30TD silica manufactured by the company are mixed as external additives, mixed with a Henschel mixer (Mitsui Mine Co., Ltd.), sieved with 150 mesh, and developing toner G17. Got.

<Manufacture of toner mother particles F18>
Colorant dispersion C5 4.0 parts as the colorant solid content In the same manner as F4 except that only the colorant dispersion (in the case of F4, only the colorant dispersion C1 and the colorant dispersion C9) was changed to the above. Toner mother particles F18 were obtained.

  Volume median diameter (Dv) was 5.9 μm, number median diameter (Dn) was 5.4 μm, Dv50 / Dn50 was 1.09, average circularity was 0.970, and circularity standard deviation was 0.012. It was.

<Manufacture of developing toner G18: external addition process>
To the toner base particle F18 thus obtained, 50 g of H05TD silica manufactured by Clariant and 15 g of H30TD silica manufactured by Clariant are mixed as external additives, mixed with a Henschel mixer (manufactured by Mitsui Mine), sieved with 150 mesh, and developing toner G18. Got.

<Manufacture of toner mother particles F19>
Colorant dispersion C6 4.0 parts as colorant solid content Toner base particles F19 were obtained in the same manner as F9 except that only the entire colorant dispersion was changed to the above.

  Volume median diameter (Dv) was 6.0 μm, number median diameter (Dn) was 5.5 μm, Dv50 / Dn50 was 1.09, average circularity was 0.968, and circularity standard deviation was 0.015. It was.

<Manufacture of developing toner G19: external addition process>
Toner toner particle F19 obtained by mixing 50 g of H05TD silica manufactured by Clariant Co., Ltd. and 15 g of H30TD silica manufactured by Co., Ltd., as an external additive, is mixed with 2500 g of the toner base particle F19 obtained, mixed with a Henschel mixer (Mitsui Mine Co., Ltd.), and sieved with 150 mesh. Got.

<Manufacture of toner mother particles F20>
Colorant dispersion C7 4.0 parts as colorant solid content Toner base particles F20 were obtained in the same manner as F2, except that only the entire colorant dispersion was changed to the above.

  Volume median diameter (Dv) was 5.8 μm, number median diameter (Dn) was 5.2 μm, Dv50 / Dn50 was 1.12, average circularity was 0.970, and circularity standard deviation was 0.016. It was.

<Manufacture of developing toner G20: external addition process>
To the toner base particle F20 thus obtained, 50 g of Clariant H05TD silica and 15 g of H30TD silica manufactured as external additives are mixed, mixed with a Henschel mixer (Mitsui Mine), sieved with 150 mesh, and developing toner G20. Got.

<Manufacture of toner mother particles F21>
Colorant dispersion C8 4.0 parts as colorant solid content Toner base particles F19 were obtained in the same manner as F2, except that only the entire colorant dispersion was changed to the above.

  Volume median diameter (Dv) was 5.8 μm, number median diameter (Dn) was 5.1 μm, Dv50 / Dn50 was 1.14, average circularity was 0.970, and circularity standard deviation was 0.012. It was.

<Manufacture of developing toner G21: external addition process>
The toner base particle F21 obtained is mixed with 50 g of Clariant H05TD silica and 15 g H30TD silica as an external additive, mixed with a Henschel mixer (Mitsui Mine), sieved with 150 mesh, and developing toner G21. Got.

<Manufacture of toner mother particles F22>
Wax dispersion W5 7 parts polymer primary particle dispersion D1 as solids 100 parts colorant dispersion C3 as solids 4.0 parts as colorant solids Wax dispersion, polymer primary particle dispersion, colorant dispersion A toner mother particle F22 was obtained in the same manner as F1, except that all of the above were changed to the above.

  The volume median diameter (Dv) was 5.7 μm, the number median diameter (Dn) was 5.1 μm, Dv50 / Dn50 was 1.12, the average circularity was 0.971, and the circularity standard deviation was 0.014. It was.

<Manufacture of developing toner G22: external addition process>
The toner base particle F22 (2,500 g) thus obtained is mixed with 50 g of Clariant H05TD silica and 15 g of H30TD silica (external additive), mixed with a Henschel mixer (Mitsui Mine), sieved with 150 mesh, and developing toner G22. Got.

<Manufacture of toner mother particles F23>
Wax dispersion W6 7 parts polymer primary particle dispersion D1 as solids 100 parts colorant dispersion C3 as solids 4.0 parts as colorant solids Wax dispersion, polymer primary particle dispersion, colorant dispersion A toner mother particle F22 was obtained in the same manner as F1, except that all of the above were changed to the above.

  Volume median diameter (Dv) was 5.8 μm, number median diameter (Dn) was 5.3 μm, Dv50 / Dn50 was 1.09, average circularity was 0.967, and circularity standard deviation was 0.012. It was.

<Manufacture of developing toner G23: external addition process>
To 2500 g of the obtained toner base particles F23, 50 g of H05TD silica manufactured by Clariant and 15 g of H30TD silica manufactured as external additives are mixed, mixed with a Henschel mixer (manufactured by Mitsui Mine), sieved with 150 mesh, and developing toner G23. Got

<Manufacture of toner mother particles F24>
Wax dispersion W5 7 parts polymer primary particle dispersion D1 as solid content 100 parts colorant dispersion C10 as solid content 4.0 parts as colorant solid content Wax dispersion, polymer primary particle dispersion, colorant dispersion A toner mother particle F24 was obtained in the same manner as F1 except that all of the above were changed to the above.

  Volume median diameter (Dv) was 5.9 μm, number median diameter (Dn) was 5.4 μm, Dv50 / Dn50 was 1.09, average circularity was 0.971, and circularity standard deviation was 0.012. It was.

<Manufacture of developing toner G24: external addition process>
To 2500 g of the obtained toner base particles F24, 50 g of H05TD silica manufactured by Clariant Co., Ltd. and 15 g of H30TD silica manufactured by the same company are mixed as external additives, mixed with a Henschel mixer (Mitsui Mine Co., Ltd.), sieved with 150 mesh, and developing toner G24. Got.

<Manufacture of toner mother particles F25>
Wax dispersion W5 Toner base particle F25 was obtained in the same manner as F1 except that the solid content was changed to 8 parts except for the wax dispersion.

  Volume median diameter (Dv) was 5.8 μm, number median diameter (Dn) was 5.3 μm, Dv50 / Dn50 was 1.09, average circularity was 0.970, and circularity standard deviation was 0.014. It was.

<Manufacture of developing toner G25: external addition process>
The toner base particle F25 (2,500 g) was mixed with 50 g of Clariant H05TD silica and 15 g H30TD silica (external additive), mixed with a Henschel mixer (Mitsui Mine), sieved with 150 mesh, and developing toner G24. <Production of toner mother particles F26>
Wax dispersion W6 Toner base particles F26 were obtained in the same manner as F2, except that the 8 parts component was changed to the above as the solid content.

  The volume median diameter (Dv) was 5.9 μm, the number median diameter (Dn) was 5.3 μm, Dv50 / Dn50 was 1.11, the average circularity was 0.971, and the circularity standard deviation was 0.012. It was.

<Manufacture of developing toner G26: external addition process>
To the toner base particle F26 thus obtained, 50 g of H05TD silica manufactured by Clariant Co., Ltd. and 15 g of H30TD silica manufactured by the same company are mixed as an external additive, mixed with a Henschel mixer (Mitsui Mine Co., Ltd.), sieved with 150 mesh, and developing toner G26. Got.

<Manufacture of toner mother particles F27>
Wax dispersion W7 7 parts as solid content Toner base particles F27 were obtained in the same manner as F3 except that only the wax dispersion was changed to the above.

  The volume median diameter (Dv) was 5.7 μm, the number median diameter (Dn) was 5.1 μm, Dv50 / Dn50 was 1.12, the average circularity was 0.971, and the circularity standard deviation was 0.012. It was.

<Manufacture of developing toner G27: external addition process>
The toner base particle F27 (2,500 g) thus obtained is mixed with 50 g of Clariant H05TD silica and 15 g of H30TD silica (external additive), mixed with a Henschel mixer (Mitsui Mine), sieved with 150 mesh, and developing toner G27. Got.

Evaluation example <fixing test>
<< Measurement method and definition of low-temperature fixability >>
Further, in the above measurement method, the actual image test was performed with the roller temperature set at 130 ° C., the obtained fixed image was rubbed under a certain load, the density drop before and after rubbing was visually compared, and the following criteria were used. The “low temperature fixability” was determined.
◎ (Good): No decrease in concentration ○ (Practical use possible): Slight decrease in concentration is observed Δ (Inadequate): Concentration decrease is conspicuous × (Unusable): Almost peeled off

<< Measurement method and definition of fixing temperature range >>
When recording paper carrying an unfixed toner image is prepared, the surface temperature of the heating roller is changed from 100 ° C. to 215 ° C. in increments of 5 ° C., conveyed to the fixing nip, and discharged at a speed of 150 mm / sec. The fixing state of was observed.
A temperature region in which toner on the heating roller or paper wrapping does not occur at the time of fixing and the toner on the recording paper after fixing is sufficiently adhered to the recording paper is defined as a “fixing temperature region”. The heating roller of the fixing machine has a release layer made of PFA (tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer), and was evaluated without application of silicone oil. The “fixing temperature region” was determined according to the following criteria.

“Surface temperature” in the determination criteria refers to the surface temperature of the heating roller described above.
Further, although the “fixing temperature” varies depending on the toner, the “fixing temperature region” is determined for each toner as follows based on the “fixing temperature different for each toner”. Accordingly, for example, a toner having a low fixing temperature is determined to have a good fixing temperature region if there is a sufficient fixing temperature range even if the offset generation temperature is low.

A (good): Offset occurs when the surface temperature is [fixing temperature + 50 ° C.] or more.
○ (Practical use possible): Offset occurs when the surface temperature is [fixing temperature + 40 ° C.] or more and less than [fixing temperature + 50 ° C.].
Δ (insufficient): Offset occurs when the surface temperature is [fixing temperature + 30 ° C.] or more and less than [fixing temperature + 40 ° C.].
X (Unusable): Offset occurs when the surface temperature is lower than [fixing temperature + 30 ° C.].

<Measurement method and definition of toner aggregation degree>
The degree of aggregation of the toner was confirmed by a vibration sieve measurement method using a three-stage mesh.
Using a powder tester manufactured by Hosokawa Micron Co., Ltd., three types of sieves are stacked and fixed, and a sample is placed on the shaking table.

The measurement conditions are as follows.
Mesh opening (top): 250 μm (60 mesh)
Mesh opening (medium): 150 μm (100 mesh)
Mesh opening (bottom): 75 μm (200 mesh)
Swing scale: 1.0mm
Sampling amount: 2.0 g
Vibration time: 90 seconds

After the measurement, the degree of aggregation was determined from the following calculation.
(Mass of powder remaining in upper mesh / sampled amount) × 100
(Mass of powder remaining in the middle mesh / amount of sample collected) × 100 × 0.6
(Mass of powder remaining in lower mesh / sampled amount) × 100 × 0.2
The total of the above three calculated values is defined as the degree of aggregation (%).

The determination of “toner aggregation degree” is as follows.
○ (Practical use possible): Aggregation degree is less than 10% Δ (Insufficient): Aggregation degree is 10% or more and less than 20% × (Unusable): Aggregation degree is 20% or more

<Measurement method and definition of blocking resistance>
10 g of toner is put into a cylindrical container having an inner diameter of 3 cm and a height of 6 cm, and a load of 20 g is put on it and left in an environment of 50 ° C. and 40% RH for 24 hours. The degree of solidification of the toner was confirmed by applying, and “blocking resistance” was determined according to the following criteria.

◎ (Good): Even if no load is applied, it collapses and does not solidify.
○ (Practical use possible): Solidified but collapsed with a load of less than 50 g.
Δ (insufficient): solidified and collapsed with a load of 50 g or more and less than 200 g.
X (Unusable): It is consolidated and does not collapse unless a load of 200 g or more is applied.

<Dust generation measurement method and definition>
Put all four development toners into the cartridge of the color page printer ML9600PS (Oki Data Co., Ltd.) and write “Dust” in RAL-UZ122-2006 according to the measurement method (RAL-UZ122-2006) certified by Blue Angel Mark. The “dissipation rate (mg / h) described in RAL-UZ122-2006” was determined from the mass measurement of the substance collected on the filter.
The “emission rate (mg / h) described in RAL-UZ122-2006” was defined as the “dust generation amount (mg / h)” of the present invention. The definition of “dust” is as described above, and is not limited to “dust”.
As described above, the substance derived from wax is actually dominant.

  Specifically, after the blanking measurement was performed by baking the emission test chamber (VOC-010 / Volume 1000L / Espec Corp.) in advance, the printer and the dust measurement filter were installed, and the tank was for 60 minutes. After waiting for the temperature and humidity to be within the specified value (23 ± 2 ° C / 50 ± 5%), the printer is operated by remote control and at the same time, suction from the filter is started, and the specified number of sheets is printed for 2 hours. Suction collection was performed until later. Note that VE110-7, Version 2006-06-01 (RAL-UZ122 / RALC00.PDF) was used as the print pattern.

The emission rate (mg / h), that is, “dust generation amount (mg / h)” was obtained from the following equation.
(1) Dust mass after temperature / humidity correction m _St (mg)
_{m St (mg) = (m} MF brutto -m MF tara) + (m RF1 -m RF2)
m _{MF tara} : Mass of measurement filter with stable mass before collecting dust sample (mg)
m _{MF brutto} : Mass of measurement filter with stable mass after dust sampling (mg)
m _RF1 : Mass of reference filter before test (mg)
m _RF2 : Mass of the reference filter after the test (mg)

(2) _Emission rate EF _uSt (mg / h)
= (M _St × n × V × t _o ) / (V _S × t _p )
n: Number of ventilations (h ^-1 )
t _o : Total sampling time (min)
t _p : Printing time (min)
V: chamber volume (m ³ )
V _S : volume of air sucked through the filter (m ³ )

<Repeated printing evaluation method>
Printing was repeated using Microline 9600 manufactured by Oki Data Co., Ltd., and the initial image and image quality evaluation after printing 30,000 sheets were performed as follows.
A: Image defects including image density and fog are hardly observed.
○: A fine image defect is recognized, but there is no major problem.
(Triangle | delta): Although an image defect is recognized, it is within an allowable limit.
X: An unacceptable image defect is recognized.

  Table 3 shows the toner composition, Table 3 shows the toner physical properties, and Table 4 shows the evaluation results of the toner.

  The electrostatic image developing magenta toner using the specific wax and the specific colorant of the present invention suppresses dust generated during fixing, has low toner aggregation, secures fixing property and blocking resistance, and lasts for a long time. It retains good charging characteristics with respect to repeated printing, and provides a stable and good image quality. Therefore, it is widely used in the fields of copying machines, printers, printing machines, and the like.

1 Raw material tank 2 Raw material pump 3 Wet mill (bead mill)
4 Rotating screen 5 Shaft 6 Jacket 7 Stator 8 Discharge path 9 Rotor 10 Raw material slurry supply 11 Raw material slurry inlet 12 Valve 13 Valve 14 Valve 15 Valve 16 Product tank

Claims (7)

It contains at least a colorant, a binder resin, and a wax, and the wax contains 80% by mass or more of a component having 40 or more carbon atoms, and a non-normal component among the components having 40 or more carbon atoms is 40 carbon atoms. The hydrocarbon-based wax and / or neopentyl polyol ester represented by the structural formula (1) is 10% by mass or more and 50% by mass or less with respect to the whole of the above components, and the colorant has the structural formula ( 2) and / or a compound represented by Structural Formula (3), and a compound represented by Structural Formula (4), and having a core / shell structure, For magenta toner.

[In Structural Formula (1), R ¹ is a divalent to octavalent neopentyl polyol residue, R ² is a linear alkyl group having 13 to 25 carbon atoms, and m is an integer of 2 to 8. ]

[In Structural Formula (2), R ¹¹ and R ¹² each independently represent H or CH ₃ . ]

[In the structural formula (3), R ¹³ represents CH ₃ or OCH ₃ , R ¹⁴ represents H or Cl, and R ¹⁵ represents OCH ₃ or Cl. ]

[In the structural formula (4), R ¹⁶ represents Cl 2 , SO ₃ ^— or H , R ¹⁷ represents H, CH ₃ or Cl, R ¹⁸ represents H or SO ₃ ^— , provided that R ¹⁶ and R ¹⁸ It is one of only SO ₃ ^- represents a. M ²⁺ represents a divalent metal ion. ]   Carbonization in which the component having 40 or more carbon atoms is 80% by mass or more, and among the components having 40 or more carbon atoms, the non-normal component is 10% by mass or more and 50% by mass or less with respect to the entire component having 40 or more carbon atoms. The magenta toner for developing an electrostatic charge image according to claim 1, comprising a hydrogen wax. Carbonization in which the component having 40 or more carbon atoms is 80% by mass or more, and among the components having 40 or more carbon atoms, the non-normal component is 10% by mass or more and 50% by mass or less with respect to the entire component having 40 or more carbon atoms. The magenta toner for developing an electrostatic image according to claim 1, comprising a hydrogen wax and a neopentyl polyol ester represented by the structural formula (1).

[In Structural Formula (1), R ¹ is a divalent to octavalent neopentyl polyol residue, R ² is a linear alkyl group having 13 to 25 carbon atoms, and m is an integer of 2 to 8. ]   The binder resin that forms the core includes a crosslinked resin, and the binder resin that forms the shell includes a non-crosslinked resin. Magenta toner for developing electrostatic images.   The weight-average molecular weight in gel permeation chromatography of tetrahydrofuran-soluble matter is 30,000 to 100,000, and the molecular weight peak of weight is 20,000 to 60,000. The magenta toner for developing an electrostatic charge image according to the item.   The volume median diameter (Dv50) is 4 μm or more and 7 μm or less, and the particle size distribution Dv50 / Dn50 represented by the ratio of the volume median diameter to the number median diameter (Dn50) is 1.1 or less. The magenta toner for developing an electrostatic charge image according to any one of claims 1 to 5.   In the toner-based circle equivalent diameter-circularity scattergram measured by the flow type particle image measuring device, the average circularity is 0.950 to 0.990, and the circularity standard deviation is less than 0.05. The magenta toner for developing an electrostatic charge image according to any one of claims 1 to 6.

Images