JP2007193253A - Emulsion aggregation toner - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an emulsion aggregation toner capable of achieving expansion of a fixing region, improvement of image glossiness and improvement of developing performance after allowed to stand in a high temperature and high humidity environment. <P>SOLUTION: The emulsion aggregation toner is obtained by sticking or fixing polymer fine particles (B) on particle aggregates comprising at least polymer fine particles (A), colorant fine particles and a wax, wherein a tetrahydrofuran-insoluble component of the polymer fine particles (B) is larger than a tetrahydrofuran-insoluble component of the polymer fine particles (A) by ≥5.0%, the wax is an ester wax having a DSC peak temperature of 50.0-100.0°C and a tangent departure temperature of 45.0-95.0°C, and when a total peak area in a molecular weight distribution of the wax measured by GC is considered to be 100, the highest peak area is 50.0-99.0%. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

The present invention relates to a toner particle used in an image forming method such as an electrophotographic method, an electrostatic recording method, an electrostatic printing method, and a toner jet method. In particular, the present invention relates to an emulsion aggregation method toner.

  In the conventional electrophotographic method, after charging on a photosensitive drum by various means, an electrical latent image is formed, then toner is developed on the latent image, and the toner image is transferred to a transfer material such as paper. Then, the toner image is fixed by means of heating, pressurizing or the like to obtain a toner image (for example, see Non-Patent Document 1).

  In recent years, in printers and copiers based on the above method, there is an increasing demand for images that are the same as the initial images even if they are printed over a long period of time, and high image quality and high reliability have become indispensable for machine design. . Here, high image quality and high reliability indicate that the initial print image is maintained even after printing over a long period of time. Specifically, sufficient fixing area (low-temperature fixability and hot offset resistance compatible), image glossiness (gloss uniformity between pages), developability after leaving at high temperature and high humidity (streak-like image, photosensitivity) (Fusing to the drum) is to continue outputting a good image.

  In response to this need, the material selectivity for improving the fixing characteristics is wider than that of the conventional pulverization method, and the toner structure is diverse. Is growing.

  For the purpose of improving hot offset resistance and ensuring a sufficient fixing area, in the emulsion aggregation method toner, resin fine particles are adhered or fixed to the surface of the particle aggregate containing the polymer primary particles, and the surface resin particle physical properties and the wax melting point are fixed. (For example, refer to Patent Document 1). Specifically, in a toner for developing an electrostatic charge image in which resin fine particles are adhered or fixed to particle aggregates containing at least polymer primary particles, the tetrahydrofuran insoluble content of the resin fine particles is 5 to 70%, and The toner contains a wax having a melting point of 30 to 100 ° C.

  However, Patent Document 1 does not disclose the present case because there is no sufficient logical development in the description relating to the present developability.

  For the purpose of improving low-temperature fixability and hot offset resistance and ensuring a sufficient fixing area, in the emulsion aggregation method toner, resin fine particles are adhered or fixed to the surface of the particle aggregate containing the polymer primary particles, and the There is a proposal that defines the physical properties and wax melting point of coalesced primary particles (see, for example, Patent Document 2). Specifically, in a toner for developing an electrostatic charge image in which resin fine particles are adhered or fixed to a particle aggregate containing at least polymer primary particles, the tetrahydrofuran insoluble content of the polymer primary particles is 15% to 80%. The toner has a melting point of 30 to 100 ° C.

  However, Patent Document 2 does not have a sufficient logical development in the description relating to the present developability. In addition, this matter is not disclosed because there is no description in the Examples about the insoluble content of resin fine particles in tetrahydrofuran.

JP 2002-156780 A JP 2002-156781 A The Electrophotographic Society of Japan "Basics and Applications of Electrophotographic Technology" Corona Co., Ltd. June 15, 1988, P46-79

  Problems to be solved by the present invention are improvement of the fixing region, improvement of image glossiness, and improvement of developability after leaving at high temperature and high humidity.

  An object of the first aspect of the present invention is to solve the improvement of the fixing region, the improvement of the image glossiness, and the improvement of the developability after being left at high temperature and high humidity.

  The object of the second invention according to the present invention is to solve the improvement of the fixing region and the improvement of the developability after leaving at high temperature and high humidity.

  The object of the third invention according to the present invention is to solve the improvement in developability after standing at high temperature and high humidity.

  An object of the fourth invention according to the present invention is to solve the improvement in developability especially after leaving at high temperature and high humidity.

  An object of the fifth aspect of the present invention is to solve the improvement of the fixing area and the improvement of the image glossiness.

  An object of the sixth invention according to the present invention is to solve the improvement in developability especially after leaving at high temperature and high humidity.

  An object of the seventh invention of the present invention is to solve the improvement of the fixing area and the improvement of the image glossiness.

In order to achieve the above object, the first invention according to the present application further attaches or fixes the polymer fine particles (B) to the particle aggregates containing at least the polymer fine particles (A), the colorant fine particles and the wax. In the emulsion aggregation method toner comprising:
The tetrahydrofuran insoluble content of the polymer fine particles (B) is 5.0% or more larger than the tetrahydrofuran insoluble content of the polymer fine particles (A),
The DSC peak temperature of the wax is 50.0 to 100.0 ° C., the tangential desorption temperature is 45.0 to 95.0 ° C., and the total peak area in the molecular weight distribution of GC measurement of the wax is 100. It is an emulsion aggregation method toner containing an ester wax having a maximum peak area of 50.0 to 99.0%.

  According to a second invention of the present application, in the emulsion aggregation method toner, the polymer fine particles (A) of the present invention have a tetrahydrofuran insoluble content of 1.0 to 50.0%, and the polymer fine particles (B) of the present invention. The insoluble content of tetrahydrofuran is 6.0 to 75.0%.

A third invention according to the present application is an emulsion aggregation method toner having a particle size of 0.6 to 2.0 μm by a flow particle image analyzer when the toner of the present invention is irradiated for 1 minute. The relationship between the measured value X1 of the particle and the measured value X2 when irradiated for 5 minutes is as follows.
5.0 ≦ X1 ≦ 50.0% by number 1.0 ≦ X2 / X1 ≦ 3.0

  According to a fourth aspect of the present invention, in the emulsion aggregation toner, the wax of the present invention has a DSC maximum peak half width of 2.0 to 10.0 ° C.

  According to a fifth aspect of the present invention, in the emulsion aggregation method toner, the wax of the present invention is an ester wax containing 1 to 6 ester groups.

  According to a sixth aspect of the present invention, in the emulsion aggregation toner, the penetration of the wax of the present invention is 0.1 to 5.0.

  A seventh invention according to the present application is characterized in that, in the emulsion aggregation toner, the weight average particle diameter of the wax of the present invention is 0.01 to 3.00 μm.

  In a toner as described in the above-mentioned patent document, that is, an emulsion polymerization toner in which resin fine particles are attached or fixed to particle aggregates such as polymer primary particles, colorant fine particles, and charge control agent fine particles, What defines the melting point can be said to be specialized for fixing. Although the fixing area and OHP transparency are excellent, for users who require high-quality images, image glossiness (uniformity of gloss between pages), development characteristics under various environments, especially high temperature Sufficient effects are not expected for long-term use in wet environments.

  In contrast, the present invention relates to an emulsion aggregation method toner obtained by further attaching or fixing polymer fine particles (B) to particle aggregates containing at least polymer fine particles (A), colorant fine particles and wax. The relationship between the insoluble content of tetrahydrofuran in the polymer fine particles (A) and the insoluble content of tetrahydrofuran in the fine polymer particles (B), and a particle size of 0.6-2 by the flow particle image analyzer of the toner (Flow Particle Image Analyzer). Proportion due to difference in irradiation time of particle measurement value of 0 μm, wax GC measurement peak temperature, wax DSC measurement tangential separation temperature, wax DSC measurement half width, purity in molecular weight distribution of wax GC method measurement, wax type, wax By optimizing the needle penetration and the particle size of the wax, Image gloss, found a result of intensive studies to those compatible all the developing characteristics after leaving the high temperature and high humidity.

  Detailed description will be given below.

  The present inventors consider that it is important how to effectively exude wax from the inside of the toner to the toner surface in order to achieve both low-temperature fixability and hot offset resistance in order to obtain a sufficient fixing area. It was.

  For that purpose, it was necessary to optimize the tetrahydrofuran-insoluble content of the polymer fine particle (B) layer existing outside the toner so that the effect of the present invention can be exhibited.

  By doing so, it is considered that a sufficient fixing region can be achieved without causing adverse effects on the speed of the wax that affects the low-temperature fixability while having an insoluble component that maintains hot offset resistance.

  Further, in order to improve image glossiness (uniformity between pages), it was considered important to make the wax that exudes to the toner surface during fixing uniform.

  For that purpose, it was necessary to optimize the type, half width, particle diameter, existence state, etc. of the wax fine particles so that the effects of the present invention can be exhibited.

  By doing so, it is believed that the wax exudes uniformly and quickly at the time of fixing, and image gloss can be achieved.

  Furthermore, in order to improve the development characteristics after leaving at high temperature and high humidity (streaky image, fusion to a photosensitive drum), the wax exudes to the toner surface even when subjected to a long-term heat history in the environment, It was considered important to prevent the polymer particles (A) in the toner and the polymer particles (B) in the outer layer from being plasticized.

  For that purpose, the insoluble content difference between the polymer fine particles (A) and (B), the physical properties of wax (purity, melting point, tangential separation temperature, penetration), toner glass transition point, and flow type particle image analyzer (Flow) It was necessary to optimize the ratio of particle measurement values of particle diameters of 0.6 to 2.0 μm by Particle Image Analyzer) due to the difference in irradiation time so that the effect of the present case can be exhibited.

  In this way, even if it receives a heat history, it is believed that plasticization by a substance that adversely affects the developability can be prevented, and development characteristics after being left at high temperature and high humidity can be achieved.

  The present inventors consider that the problems of the present invention have been solved for the above reasons.

  The appropriate range of the present invention will be described below.

  The tetrahydrofuran insoluble content of the polymer fine particles (B) is preferably 5.0% or more larger than the tetrahydrofuran insoluble content of the polymer fine particles (A). More preferably, it is 5.0 to 70.0%, and still more preferably 10.0 to 50.0%. If it is less than 5.0%, the image on the streak of development characteristics after leaving at high temperature and high humidity deteriorates.

  An ester wax having a maximum peak area of 50.0 to 99.0% when the total peak area is 100 in the molecular weight distribution measured by gas chromatography (GC method) of the wax is preferable. More preferably, it is 55.0 to 95.0%, and further preferably 60.0 to 95.0%.

  The differential scanning calorimeter (DSC) peak temperature of the wax is preferably 50.0 to 100.0 ° C. More preferably, it is 55.0-90.0 degreeC. The tangential separation temperature of the wax is preferably 45.0 to 95.0 ° C. More preferably, it is 50.0-90.0 degreeC, More preferably, it is desired that it is 50.0-80.0 degreeC.

  When the GC maximum peak area is less than 50.0%, the DSC peak temperature is less than 50.0 ° C, and the tangential desorption temperature is less than 45.0 ° C, the purity is low, and low purity components are left at high temperature and high humidity. The image on the streak of the bleeding development characteristic is deteriorated.

  When the GC maximum peak area exceeds 99.0%, it is difficult to obtain a stable product. When the DSC peak temperature exceeds 100.0 ° C. and the tangential separation temperature exceeds 95.0 ° C., the balance between low-temperature fixability and developability is lost, and the fixing area is not satisfied with the present case.

  The penetration of the wax is preferably 0.1 to 5.0. More preferably, it is 0.5 to 5.0, and still more preferably 0.5 to 3.0. If it is less than 0.1, the low-temperature fixability becomes weak, and the fixing region is not satisfactory in the present case. If it exceeds 5.0, wax exudes when left at high temperature and high humidity, which promotes liberation of external additives and deteriorates drum fusion.

  Relationship between measured value X1 of particles having a particle size of 0.6 to 2.0 μm and a measured value X2 when irradiated with toner for 5 minutes when the toner is irradiated for 1 minute with a flow type particle image analyzer (Flow Particle Image Analyzer) X1 is preferably 5.0 to 50.0% by number. More preferably, it is 5.0 to 40.0% by number, and still more preferably 5.0 to 30.0% by number. When X1 is less than 5.0% by number, tact-up is promoted in the production process when the aggregates of the respective polymer fine particles are fixed. When X1 exceeds 50.0% by number, the amount of fine particles is large, so that the streak-like image is remarkably deteriorated, or the free fine particles themselves cause drum fusion.

  X2 / X1 is preferably 1.0 to 3.0. More preferably, it is 1.0 to 2.5, and further preferably 1.0 to 2.0. When X2 / X1 exceeds 3.0, fine particles are produced due to some stress, and the functional parts related to development are contaminated, and the action and effect required in this case cannot be obtained.

  It is preferable that the tetrahydrofuran insoluble content of the polymer fine particles (A) is 1.0 to 50.0%. More preferably, it is 1.0 to 40.0%, and still more preferably 1.0 to 30.0%. If it is less than 1.0%, the characteristics at high temperature and high humidity are weakened, and the streak image and the drum fusion are also unacceptable. When it exceeds 50.0%, the desired effect of the present case cannot be obtained in image uniformity.

  It is desired that the tetrahydrofuran insoluble content of the polymer fine particles (B) is 6.0 to 75.0%, more preferably 10.0 to 55.0%, and still more preferably 10.0 to 50.0%. If it is less than 6.0%, the developability at high temperature and high humidity is weak and the hot offset resistance is also deteriorated, so that a desired effect cannot be obtained. If it exceeds 75.0%, the developability is strong, but the desired effect of the present case cannot be obtained in image uniformity.

  The full width at half maximum of the DSC maximum peak of the wax is preferably 2.0 to 10.0 ° C, more preferably 2.0 to 9.0 ° C. If it is less than 2.0, it is difficult to obtain a stable product. If it exceeds 10.0, the effect obtained by the present invention in the uniformity between pages in image glossiness cannot be obtained.

  The weight average particle diameter of the wax fine particles is preferably 0.01 to 3.00 μm, more preferably 0.10 to 2.00 μm, and further preferably 0.10 to 1.50 μm. If it is less than 0.01 μm, it is difficult to prevent reaggregation of the wax, and a problem is likely to occur in the aggregation property with other fine particles. When the particle size exceeds 3.00 μm, it is difficult to obtain a uniform particle size distribution and a small particle size as the aggregated toner.

  For the polymer fine particles (A) and (B) used in the present invention, the following polymerizable monomers are used.

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

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

  In the present invention, the above monofunctional polymerizable monomers are used alone or in combination of two or more, or the above monofunctional polymerizable monomers and polyfunctional polymerizable monomers are used in combination. . The polyfunctional polymerizable monomer can also be used as a crosslinking agent.

  As the crosslinking agent for the polymer fine particles (A) and (B) used in the present invention, a compound having two or more polymerizable double bonds is used. For example, aromatic divinyl compounds such as divinylbenzene and divinylnaphthalene; carboxylic acid esters having two double bonds such as ethylene glycol diacrylate, ethylene glycol dimethacrylate, and 1,3-butanediol dimethacrylate; divinylaniline; And divinyl compounds such as divinyl ether, divinyl sulfide, and divinyl sulfone; and compounds having three or more vinyl groups. These are used alone or as a mixture.

  In order to make an insoluble difference, a crosslinking reaction is performed with a crosslinking agent when the polymer fine particles are produced. The amount of the crosslinking agent may be 0.01 to 5.00 parts by mass, more preferably 0.03 to 3.00 parts by mass, per 100 parts by mass of the binder resin.

  An example of the colorant used in the present invention is given, but other colorants may be used.

  As the black colorant, carbon black, which is toned to black using the yellow / magenta / cyan colorant shown below, is used.

  As the colorant used in the present invention, known pigments can be used, and those shown below are representative.

  As the yellow colorant, compounds represented by condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complex methine compounds, and allylamide compounds are used. Specifically, C.I. I. Pigment Yellow 3, 7, 10, 12, 13, 14, 15, 17, 23, 24, 60, 62, 74, 75, 83, 93, 94, 95, 99, 100, 101, 104, 108, 109, 110 111, 117, 123, 128, 129, 138, 139, 147, 148, 150, 166, 168, 169, 177, 179, 180, 181, 183, 185, 191: 1, 191, 192, 193, 199 Etc. are preferably used.

  As the magenta colorant, condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, and perylene compounds are used. Specifically, C.I. I. Pigment Red 2, 3, 5, 6, 7, 23, 48; 2, 48; 3, 48; 4, 57; 1, 81; 1, 122, 146, 150, 166, 169, 177, 184, 185, 202, 206, 220, 221, 254, C.I. I. Pigment Bio Red 19 is particularly preferable.

  As the cyan colorant, phthalocyanine compounds and derivatives thereof, anthraquinone compounds, basic dye lake compounds, and the like can be used. Specifically, C.I. I. Pigment Blue 1, 7, 15, 15: 1, 15: 2, 15: 3, 15: 4, 60, 62, 66 and the like are particularly preferably used.

  The wax used in the present invention is an ester wax having a structural formula having 1 to 6 ester groups having moderate polarity.

  In order to improve the effect on the image glossiness of the present invention, an ester wax having 1 to 4 ester groups belonging to the following (I) to (V) is preferable.

（式中、ａ及びｂは０〜４の整数であり、ａ＋ｂは４である。Ｒ₁及びＲ₂は炭素数が１〜４０の有機基である。ｍ及びｎは０〜４０の整数であり、ｍとｎは同時に０になることはない。）

(In the formula, a and b are integers of 0 to 4 and a + b is 4. R ₁ and R ₂ are organic groups having 1 to 40 carbon atoms. M and n are integers of 0 to 40. Yes, m and n are not 0 at the same time.)

（式中、ａ及びｂは０〜３の整数であり、ａ＋ｂは１〜３である。Ｒ₁及びＲ₂は炭素数が１〜４０の有機基である。Ｒ₃は水素原子または炭素数が１以上の有機基である。ｋは１〜３の整数であり、ａ＋ｂ＋ｋ＝４である。ｍ及びｎは０〜４０の整数であり、ｍとｎが同時に０になることはない。）

(In the formula, a and b are integers of 0 to 3, a + b is 1 to _3. R ₁ and R ₂ are organic groups having 1 to 40 carbon atoms. R ₃ is a hydrogen atom or a carbon number. Is an organic group of 1 or more, k is an integer of 1 to 3, and a + b + k = 4, m and n are integers of 0 to 40, and m and n are not 0 at the same time.)

（式中、Ｒ₁及びＲ₃は炭素数１〜４０の有機基であり、Ｒ₁とＲ₃は同じものであっても異なっていても良い。Ｒ₂は炭素数１〜４０の有機基を示す。）

(In the formula, R ₁ and R ₃ are organic groups having 1 to 40 carbon atoms, and R ₁ and R ₃ may be the same or different. R ₂ is an organic group having 1 to 40 carbon atoms. Is shown.)

（式中、Ｒ₁及びＲ₃は炭素数１〜４０の有機基であり、Ｒ₁とＲ₃は同じものであってもなくてもよい。Ｒ₂は炭素数１〜４０の有機基を示す。）

(In the formula, R ₁ and R ₃ are organic groups having 1 to 40 carbon atoms, and R ₁ and R ₃ may or may not be the same. R ₂ represents an organic group having 1 to 40 carbon atoms. Show.)

（式中、ａは０〜４の整数であり、ｂは１〜４の整数であり、ａ＋ｂは４である。Ｒ₁は炭素数１〜４０の有機基である。ｍ及びｎは０〜４０の整数であり、ｍとｎが同時に０になることはない）

(In the formula, a is an integer of 0 to 4, b is an integer of 1 to 4, and a + b is 4. R ₁ is an organic group having 1 to 40 carbon atoms. (It is an integer of 40, and m and n cannot be 0 at the same time.)

  The wax fine particles used in the present invention are obtained by emulsifying the wax in the presence of at least one emulsifier selected from known cationic surfactants, anionic surfactants, and nonionic surfactants.

  The added amount of the wax is 1.00 to 40.00 parts by mass, more preferably 3.00 to 30.00 parts by mass, per 100 parts by mass of the binder resin.

  Examples of the method for producing the ester wax used in the present invention include a synthesis method by oxidation reaction, synthesis from carboxylic acid and its derivatives, ester group introduction reaction represented by Michael addition reaction, and the like. A particularly preferred method for producing the ester wax used in the present invention is shown below from the variety of raw materials and the ease of reaction. A method using a dehydration condensation reaction from a carboxylic acid compound and an alcohol compound or a reaction from an acid halide and an alcohol compound is particularly preferred.

〔式中、Ｒ₃及びＲ₄は有機基を示す〕

[Wherein R ₃ and R ₄ represent an organic group]

  In order to transfer the above ester equilibrium reaction to the production system, the reaction is carried out using a large excess of alcohol or using a Dean-Stark water separator in an aromatic organic solvent capable of azeotropy with water. preferable. An ester may be synthesized by adding a base as an acid acceptor by-produced in an aromatic organic solvent using an acid halogen compound.

  The ester wax used in the present invention is generally synthesized from a higher carboxylic acid component as well as a higher alcohol component. These higher alcohol and higher carboxylic acid components are usually obtained from natural products and are generally composed of a mixture having an even number of carbon atoms. When these mixtures are esterified as they are, by-products having various similar structures in addition to the target ester compound are produced as a by-product, which tends to adversely affect the properties of the toner. Therefore, a structural ester wax having 1 to 6 ester groups used in the present invention can be obtained by purifying raw materials and products using solvent extraction or vacuum distillation operation.

  The toner of the present invention may be used in combination with a charge control agent (charge control agent). The following substances are used for controlling the toner to be negatively charged. Although an example is given, things other than these may be used.

  For example, organometallic compounds and chelate compounds are effective, and there are monoazo metal compounds, acetylacetone metal compounds, aromatic oxycarboxylic acids, aromatic dicarboxylic acids, oxycarboxylic acids, and dicarboxylic acid-based metal compounds. Other examples include aromatic oxycarboxylic acids, aromatic mono- and polycarboxylic acids and their metal salts, anhydrides, esters, and phenol derivatives such as bisphenol. Furthermore, urea derivatives, metal-containing salicylic acid compounds, metal-containing naphthoic acid compounds, boron compounds, quaternary ammonium salts, calixarene, and the like can be mentioned.

  The following substances are used to control the toner to be positively charged. An example is given, but other examples may be used.

  Modified products of nigrosine, such as nigrosine and fatty acid metal salts, guanidine compounds, imidazole compounds, quaternary ammonium salts such as tributylbenzylammonium-1-hydroxy-4-naphthosulfonate, tetrabutylammonium tetrafluoroborate; analogs thereof Onium salts such as phosphonium salts and lake pigments thereof; triphenylmethane dyes and lake pigments thereof (as rake agents, phosphotungstic acid, phosphomolybdic acid, phosphotungsten molybdic acid, tannic acid, lauric acid, Gallic acid, ferricyanide, ferrocyanide, etc.); metal salts of higher fatty acids; diorganotin oxides such as dibutyltin oxide, dioctyltin oxide, dicyclohexyltin oxide; Over DOO, dioctyl tin borate, diorgano tin borate such as dicyclohexyl tin borate, and the like. These can be used alone or in combination of two or more. Particularly preferred are oxycarboxylic acids, which are suitable for the present invention.

  The charge control agent is used in an amount of 0.01 to 10.00 parts by mass, more preferably 0.50 to 5.00 parts by mass, per 100 parts by mass of the binder resin.

  The charge control agent is also used as an emulsion (charge control agent fine particles) having an average particle diameter of 0.01 to 3 μm in water.

  In the present invention, the polymer fine particles (A) are co-aggregated with the wax fine particles and the colorant fine particles, and then the polymer fine particles (B) are further adhered or fixed to produce an emulsion aggregation toner. In addition, you may take the aggregation method other than this.

  Examples of the cationic surfactant used as the emulsifier of the present invention include dodecyl ammonium chloride, dodecyl ammonium bromide, dodecyl trimethyl ammonium bromide, dodecyl pyridinium chloride, dodecyl pyridinium bromide, hexadecyl trimethyl ammonium bromide and the like. Examples of the anionic surfactant include fatty acid soaps such as sodium stearate and sodium dodecanoate, sodium dodecyl sulfate, sodium dodecylbenzenesulfonate, and sodium lauryl sulfate.

  Nonionic surfactants include dodecyl polyoxyethylene ether, hexadecyl polyoxyethylene ether, nonylphenyl polyoxyethylene ether, lauryl polyoxyethylene ether, sorbitan monooleate polyoxyethylene ether, monodecanoyl sucrose, etc. Can be mentioned.

  The external additives used in the present invention include inorganic fine powders such as silica, silicone resin, titanium oxide (anatase type, rutin type, non-crystalline), aluminum oxide, strontium titanate, cerium oxide, magnesium oxide, silicon nitride. Nitrides such as silicon carbide, carbides such as silicon carbide, metal salts such as calcium sulfate, barium sulfate, and calcium carbonate, carbon fluoride, hydrotalcite, and the like. Examples of the organic fine powder include PMMA resin and charge control agent.

  Among them, silica needs to be hydrophobized and silicone oil is essential as a hydrophobizing agent, but a silane coupling agent may be used in combination.

  The inorganic fine powder other than silica may or may not be hydrophobized. More preferably, the hydrophobizing treatment is good, and when the hydrophobizing treatment is performed, either a wet method or a dry method may be used.

  The amount of the external additive is 0.40 to 5.00 parts by mass in total per 100 parts by mass of the colored particles, and more preferably 0.60 to 3.00 parts by mass.

  The tetrahydrofuran insoluble content of the polymer particles used in the present invention is measured by the following measuring method.

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

  About 1 g of the polymer was weighed (W1 g), placed in a cylindrical filter paper (for example, No. 86R manufactured by Toyo Roshi), passed through a Soxhlet extractor, extracted for 6 hours using 100 to 200 ml of THF as a THF solvent, and extracted with a THF solvent. After evaporation of the soluble component, vacuum drying is performed at 100 ° C. for several hours, and the amount of the THF soluble polymer component is weighed (W2 g). The THF-insoluble content of the polymer is calculated from the following formula.

  The particle diameter of the toner used in the present invention is 0.6 to 2.0 μm and is measured by the following measuring method.

  Using a flow type particle image measuring device “FPIA-1000 type” (manufactured by Toa Medical Electronics Co., Ltd.), the concentration of the dispersion is readjusted so that the toner concentration at the time of measurement is 3000 to 10,000 particles / μl. 1000 or more are measured, and the number based on the equivalent circle diameter distribution and the ratio (number%) of particles having a prescribed equivalent circle diameter are measured. As shown in Table 1, the results (frequency% and cumulative%) can be obtained by dividing the particle size range of 0.06 to 400 μm into 226 channels (divided into 30 channels per octave). After the measurement, the ratio of particles having a particle diameter of 0.6 to 2.0 μm is obtained using this data.

  The purity of the wax used in the present invention can be measured by a gas chromatography (GC) method. The gas chromatography method (GC method) is measured using GC-17A (manufactured by Shimadzu Corporation). As a sample, a solution previously dissolved in toluene at a concentration of 1% by weight is injected into a GC apparatus equipped with 1 μl of an on-column injector. As the column, 0.5 mm diameter × 10 m long Ultra Alloy-1 (HT) is used. The column is initially 40 ° C. to 40 ° C./min. The temperature was increased to 200 ° C. at a temperature increase rate of 15 ° C./min. At 350 ° C. and then 7 ° C./min. The temperature is raised to 450 ° C. at a temperature raising speed of As the carrier gas, He gas is allowed to flow under a pressure condition of 50 kPa. The identification of the compound species involves identifying the structure by separately injecting an alkane having a known carbon number and comparing the same outflow times or introducing a gasification component into mass spectrochromatography. The ester compound content is calculated by determining the ratio of the peak area to the total peak area of the chromatogram.

  The DSC peak of the wax used in the present invention is the maximum endothermic peak value in the DSC endothermic curve, and the endothermic peak value, tangential desorption temperature, and half-value width are measured in accordance with ASTM D3418-82.

  The penetration of the wax used in the present invention is measured according to JIS K2235. The measurement temperature is 25 ° C.

  The particle size of the fine particles used in the present invention was measured with a laser diffraction type particle size distribution meter, Coulter counter TA-II type, or Coulter Multisizer (manufactured by Coulter Co.).

  The volume particle size distribution is measured by a laser diffraction particle size distribution meter in the present invention by the method described later, and the measuring device is a Coulter LS-230 type particle size distribution meter (manufactured by Coulter). The measurement solvent was ethanol, and the measurement temperature was 20 ° C to 25 ° C.

  Alternatively, when a Coulter Counter TA-II type or Coulter Multisizer (manufactured by Coulter Inc.) is used, the measurement can be performed with a measuring device connected to an interface for outputting the number distribution and volume distribution and a personal computer. In this measurement, an electrolytic solution is used. As this electrolytic solution, for example, a 1% NaCl aqueous solution prepared using primary sodium chloride or ISOTON R-II (manufactured by Coulter Scientific Japan) can be used.

  The toner of the present invention may be used in any form of a two-component developer or a non-magnetic one-component developer. When used as a two-component developer, the carrier may be a magnetic substance such as iron powder, magnetite powder, ferrite powder, or a known material such as a mono or magnetic carrier having a resin coating on the surface thereof. 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.

  In the toner production method of the present invention, an emulsion aggregation toner is used.

  In the present invention, the polymer particles (A), the colorant fine particles, the wax fine particles, the charge control agent fine particles and the like are co-aggregated. If necessary, the wax, pigment, and charge control agent may be seed-polymerized in advance. In the coaggregation, the other fine particles may be coaggregated simultaneously with the polymer particles (A), or may be coaggregated separately. In order to sufficiently exhibit the effects of the present invention, it is preferable to co-aggregate the polymer fine particles (A) and the colorant fine particles, and then co-aggregate the wax fine particles and the charge control agent fine particles.

  The toner of the present invention is produced by adding a step of attaching or fixing the polymer particles (B) to the surface of the particle aggregate. The polymer particles (B) can be dispersed in water or a liquid mainly composed of water with an emulsifier and used as an emulsion, or polymer particles (B) obtained by an emulsion polymerization method can be used. . The latter is preferred.

  Prior to coating the particle aggregate with resin fine particles, the particle aggregate may be fused at a temperature equal to or higher than the glass transition point of the polymer particles (A).

  Next, an example of a developing device and an image forming method for outputting an image of the toner produced in the present invention will be described. Note that the present invention is not limited to this.

  The developing device of the present invention uses the developing device of FIG.

As an example of the toner carrier 14, an elastic roller having a diameter of 16 mm, a surface roughness Rz of ³ to 10 μm, and a resistance of 10 ⁴ to 10 ⁸ Ω, which is a NBR base layer coated with ether urethane, can be used. The peripheral speed of the photosensitive drum 10 is 50 to 170 mm / s, and the peripheral speed of the toner carrier 14 is rotated at a peripheral speed that is 1 to 2 times the peripheral speed of the photosensitive drum 10. Reference numeral 11 denotes a photosensitive drum charging member.

  As an example of the toner regulating member 16, a plate-like urethane rubber having a thickness of 1.0 mm is bonded to the blade support metal plate 24, and the contact pressure against the toner carrier 14 is appropriately set. The linear pressure was converted from a value obtained by inserting three metal thin plates having a known friction coefficient into the abutting portion and pulling out the central one with only a spring. The restricting member 16 can also be brought into contact with the toner carrier 14 by edge contact with which the tip contacts. In the case of edge contact, it is more desirable in terms of toner layer regulation to set the contact angle of the regulating member with respect to the tangent of the toner carrying body at the contact with the toner carrying body to be 40 degrees or less.

  As an example of the elastic roller 15, an elastic roller 15 having a diameter of 12 mm in which a polyurethane foam is provided on the core metal 15a is used. The contact width of the elastic roller 15 with respect to the toner carrier 14 is preferably 1 to 8 mm, and it is preferable that the toner carrier 14 has a relative speed at the contact portion.

  The toner charging roller 29 is an elastic body such as NBR or silicone rubber, and is attached to the suppression member 30. The contact load of the toner charging roller 29 on the toner carrier 14 by the suppressing member 30 was set to 0.49 to 4.9N.

  The bias of the toner charging roller 29 is a bias equal to or higher than the discharge start voltage having the same polarity as the toner, and is set so that a potential difference of 1000 to 2000 V occurs with respect to the toner carrier 14.

  The toner of the present invention can also be used in full color image formation. As an example of the full-color image forming method, the image forming method shown in FIG. 2 will be described.

  Note that the full-color image forming method is not limited to the configuration shown in FIG.

  In the apparatus system shown in FIG. 2, a developer having cyan toner, a developer having magenta toner, a developer having yellow toner, and a black are respectively added to the developing devices 4-1, 4-2, 4-3, and 4-4. A developer having toner is introduced, and the electrostatic image formed on the photosensitive drum 1 is developed by a contact one-component developing system, and each color toner image is formed on the photosensitive drum 1. The photosensitive drum 1 is a photosensitive drum or a photosensitive belt having a photoconductive insulating material layer. The photosensitive drum 1 is rotated in the direction of the arrow by a driving device (not shown).

  The charging roller 2 is basically composed of a central core metal 2b and a surface layer 2a that forms the outer periphery thereof. The charging roller 2 is pressed against the surface of the photosensitive drum 1 with a pressing force, and is driven to rotate as the photosensitive drum 1 rotates.

  The toner image on the photosensitive drum is transferred to the intermediate transfer member 5 to which a voltage (for example, ± 0.1 to ± 5 kV) is applied. The surface of the photosensitive drum after the transfer is cleaned by a cleaning unit 9 having a cleaning blade 8.

  The intermediate transfer member 5 includes a pipe-shaped conductive core 5b and a medium-resistance elastic layer 5a formed on the outer peripheral surface thereof. The core 5b may be a plastic pipe with conductive plating.

Medium resistance elastic layer 5a is made of elastic material such as silicone rubber, fluorine rubber, chloroprene rubber, urethane rubber, EPDM (terpolymer of ethylene propylene diene), carbon black, zinc oxide, tin oxide, silicon carbide. A solid or foamed meat layer in which the electrical conductivity value (volume resistivity) is adjusted to a medium resistance of 10 ⁵ to 10 ¹¹ Ω · cm by blending and dispersing the conductivity imparting material as described above.

  The intermediate transfer member 5 is disposed in parallel with the photosensitive drum 1 and is in contact with the lower surface portion of the photosensitive drum 1, and rotates in the counterclockwise direction indicated by an arrow at the same peripheral speed as the photosensitive drum 1.

  The first color toner image formed and supported on the surface of the photosensitive drum 1 passes through the transfer nip where the photosensitive drum 1 and the intermediate transfer member 5 are in contact with each other, and is applied to the transfer nip region by the applied transfer bias to the intermediate transfer member 5. The intermediate transfer is sequentially performed on the outer surface of the intermediate transfer body 5 by the formed electric field.

  If necessary, the surface of the intermediate transfer member 5 is cleaned by the removable cleaning means 3 after the transfer of the toner image onto the transfer material.

  When there is a toner image on the intermediate transfer member, the cleaning means 3 is separated from the surface of the intermediate transfer member so as not to disturb the toner image.

  A transfer unit is disposed in parallel with the intermediate transfer member 5 and brought into contact with the lower surface of the intermediate transfer member 5. The transfer unit 7 is a transfer roller or a transfer belt, for example, and has the same circumference as the intermediate transfer member 5. Rotates clockwise at the speed of the arrow. The transfer unit 7 may be disposed so as to be in direct contact with the intermediate transfer member 5, or a belt or the like may be disposed between the intermediate transfer member 5 and the transfer unit 7.

  In the case of a transfer roller, the basic configuration is a central core 7b and a surface layer 7a forming the outer periphery thereof.

  The transfer unit 7 is rotated with a difference in speed or peripheral speed from the intermediate transfer body 5. The transfer material 6 is conveyed between the intermediate transfer body 5 and the transfer means 7 and at the same time, a bias having a polarity opposite to the frictional charge of the toner is applied to the transfer means 7 from the transfer bias means. The toner image is transferred to the surface side of the transfer material 76.

  As the material of the transfer rotator, the same material as that of the charging roller can be used. As a preferable transfer process condition, the contact pressure of the roller is 4.9 to 490 N / m (5 to 500 g / cm). The DC voltage is ± 0.2 to ± 10 kV.

  Next, the transfer material 6 is conveyed to a fixing device H, which basically includes a heating roller incorporating a heating element such as a halogen heater and an elastic pressure roller that is pressed against the heating roller. By passing between the pressure rollers, the toner image is fixed to the transfer material by heating and pressing. A method of fixing with a heater through a film may be used.

  In the case of evaluation of only a single color, four same toners are set for each developer, and continuous paper printing is performed.

  The present invention will be specifically described with reference to the following examples. However, this does not limit the present invention in any way. A method for producing toner particles will be described below. Incidentally, all parts and percentages in the examples and comparative examples are based on mass unless otherwise specified.

(Method for producing polymer fine particle A)
A mixture of the following monomers / aqueous emulsifier solution was added over 5 hours from the start of polymerization, and an aqueous initiator solution was added over 6 hours from the start of polymerization, and the mixture was further maintained for 30 minutes.
[Monomers]
Styrene 80.0 parts butyl acrylate 20.0 parts acrylic acid 3.0 parts bromotrichloromethane 0.5 part 2-mercaptoethanol 0.01 part divinylbenzene 0.15 part [emulsifier aqueous solution]
10% sodium dodecylbenzenesulfonate 4.0 parts demineralized water 100.0 parts [initiator aqueous solution]
8% hydrogen peroxide aqueous solution 9.0 parts 8% ascorbic acid aqueous solution 9.0 parts

  After completion of the polymerization reaction, the mixture was cooled to prepare a polymer fine particle dispersion A (THF insoluble matter 5.0%).

(Method for producing polymer fine particle B)
A mixture of the following monomers / aqueous emulsifier solution was added over 5 hours from the start of polymerization, and an aqueous initiator solution was added over 6 hours from the start of polymerization, and the mixture was further maintained for 30 minutes.
[Monomers]
Styrene 80.0 parts butyl acrylate 20.0 parts acrylic acid 3.0 parts bromotrichloromethane 0.5 part 2-mercaptoethanol 0.01 part divinylbenzene 0.80 part [emulsifier aqueous solution]
10% sodium dodecylbenzenesulfonate 4.0 parts demineralized water 100.0 parts [initiator aqueous solution]
8% hydrogen peroxide aqueous solution 9.0 parts 8% ascorbic acid aqueous solution 9.0 parts

  After completion of the polymerization reaction, the mixture was cooled to prepare polymer fine particles B-1 (THF insoluble content: 30.0%).

  Moreover, polymer fine particle dispersion B-2 was prepared by making 1.00 part of divinylbenzene (THF insoluble content: 40.0%).

  Furthermore, polymer fine particle dispersion liquid B-3 was prepared by making 2.00 parts of divinylbenzene (THF insoluble content 80.0%).

(Method for producing wax dispersion)
25.0 parts of pentaerythritol behenate (GC method peak area ratio 83.0%) listed in Table 2, 2.5 parts of an anionic surfactant (Neogen SC Daiichi Kogyo Seiyaku Co., Ltd.), 100.0 demineralized water The part was heated to 90 ° C. and stirred with a disper for 15 minutes. Next, this dispersion was emulsified using a homogenizer (15-M-8PA type Gorin Co., Ltd.) under the conditions of high pressure shearing 95 ° C. and 4900 kPa (50 kg / cm ² ) to obtain wax dispersion 1.

The wax dispersion 2 is a 1,9 nonanediol behenic acid ester (GC method peak area ratio 86.0%) described in Table 2 as a wax component.
As the wax dispersion 3, the dipentaerythritol behenate ester (GC method peak area ratio 80.0%) described in Table 2 is used as a wax component.
The wax dispersion 4 contains stearic acid diglyceride (GC method peak area ratio 68.0%) described in Table 2 as a wax component.
The wax dispersion 5 contains pentaerythritol behenic acid (peak area ratio of GC method 55.0%) described in Table 2 as a wax component.
The wax dispersion 6 contains normal paraffin (GC method peak area ratio 51.0%) as a wax component,
The wax dispersion 7 contains dipentaerythritol behenate ester (peak area ratio of GC method 48.5%) described in Table 2 as a wax component.
The wax dispersions 2 to 7 were prepared in the same manner using each.

  As a method for producing the wax of the ester wax dispersion 1, 300.0 parts of benzene, 450.0 parts of behenic acid, 100.0 parts of pentaerythritol were installed in a reactor equipped with a Dimroth reflux apparatus, a Dean-Stark water separator, and a thermometer. Further, 10.0 parts of p-toluenesulfonic acid was added and sufficiently stirred and dissolved. After refluxing for 6 hours, the water separator valve was opened and azeotropic distillation was performed. After azeotropic distillation, the residue was thoroughly washed with sodium hydrogen carbonate and dried to remove benzene. The obtained product was recrystallized, washed and purified to obtain an ester wax.

  Each ester wax produced waxes 2, 3, 4, 5, and 7 of an ester wax dispersion by controlling the type and amount of carboxylic acid shown in Table 2, the type and amount of alcohol, and the reflux time.

  In addition, the normal paraffin of the wax dispersion liquid 6 used the commercial item.

(Method for producing colorant fine particle dispersion)
To 100.0 parts of demineralized water, C.I. I. 25.0 parts of Pigment Blue 15: 3 and 6.0 parts of polyoxyethylene nonylphenyl ether were added and dispersed with a ball mill to obtain a cyan colorant fine particle dispersion.

  Similarly, C.I. I. Pigment Red 122, a magenta colorant fine particle dispersion, C.I. I. Pigment YELLOW 180 was used to prepare a yellow colorant fine particle dispersion, and carbon black was used to prepare a black colorant fine particle dispersion.

(Method for producing charge control agent fine particle dispersion)
To 100.0 parts of demineralized water, 25.0 parts of a charge control agent 4,4′-methylenebis [2- [N- (4-chlorophenyl) amide] -3-hydroxynaphthalene], and an alkylnaphthalene sulfonate 5.0 Was dispersed by a ball mill in the presence of a part to obtain a charge control agent fine particle dispersion.

(Toner production method)
<Cyan Toner No. 1>
-Polymer fine particle A dispersion 410.0 parts (as solid content)
-Colorant fine particle dispersion 40.0 parts (as solid content)
・ 1.0 parts of charge control agent fine particle dispersion (as solid content)
The above was put into a reaction vessel for coagulation aging equipped with a stirrer, a cooling tube and a thermometer and stirred. The mixture was adjusted to pH = 5.1 using 1.0N aqueous potassium hydroxide solution.

  As a flocculant, 180.0 parts of a 20.0% sodium chloride aqueous solution is dropped into the above mixed solution over 20 minutes, and the reaction vessel is heated to 50 ° C. with stirring in an oil bath for heating, and then at 50 ° C. for 1 hour. Then, the temperature was raised to 55 ° C. and held for 1 hour to prepare an aggregate (polymer fine particles + colorant fine particles + charge control agent fine particles).

In the aggregate dispersion,
-Wax dispersion 1 75.0 parts (as solid content)
As a flocculant, 500.0 parts of a 20.0% sodium chloride aqueous solution was added dropwise, and (polymer fine particles + colorant fine particles + charge control agent fine particles + wax dispersion 1) Aggregates were made.

Furthermore, in the aggregate dispersion liquid,
-Polymer fine particle B-1 dispersion 50.0 parts (as solid content)
As a flocculant, 500.0 parts of a 20.0% sodium chloride aqueous solution was added dropwise, and (polymer fine particles + colorant fine particles + charge control agent fine particles + wax dispersion 1 + polymer) Agglomerates of fine particles B) were prepared.

Finally in the aggregate dispersion,
-Polymer fine particle B-1 dispersion 35.0 parts (as solid content)
As a flocculant, 500.0 parts of a 20.0% sodium chloride aqueous solution was added dropwise, and (polymer fine particles + colorant fine particles + charge control agent fine particles + wax dispersion 1 + polymer) Agglomerates of fine particles B) were prepared. After adding 5.0 parts of an anionic surfactant (Daiichi Kogyo Seiyaku: Neogen SC), the reaction vessel was sealed and heated to 95 ° C. while continuing to stir using a magnetic seal for 5 hours. Retained. The slurry was cooled, washed with 10 times the amount of water as the slurry, and dried to obtain cyan particles.

To 100 parts of the obtained toner particles, 1.2 parts of silica (number average diameter 30 nm, BET 38 m ^{2 /} g) was added, and cyan toner No. 1 was added using a Henschel mixer (Mitsui Miike Chemical Co., Ltd.). 1 was obtained. Table 3 shows the physical properties.

<Cyan Toner No. 2>
Except for changing the wax dispersion 1 to the wax dispersion 2, cyan toner no. In the same manner as in No. 1, cyan toner no. 2 was obtained. Table 3 shows the physical properties.

<Cyan Toner No. 3>
Except for changing the wax dispersion 1 to the wax dispersion 3, cyan toner no. In the same manner as in No. 1, cyan toner no. 3 was obtained. Table 3 shows the physical properties.

<Cyan Toner No. 4>
Except for changing the addition amount of the polymer fine particles B-1 added to the second stage from 35.0 parts to 50.0 parts, the cyan toner No. In the same manner as in No. 1, cyan toner no. 4 was obtained. Table 3 shows the physical properties.

<Cyan Toner No. 5>
Except for changing the polymer fine particle B-1 to the polymer fine particle B-2, cyan toner No. In the same manner as in No. 1, cyan toner no. 5 was obtained. Table 3 shows the physical properties.

<Cyan Toner No. 6>
Except for changing the wax dispersion 1 to the wax dispersion 4, cyan toner no. In the same manner as in No. 1, cyan toner no. 6 was obtained. Table 3 shows the physical properties.

<Cyan Toner No. 7>
Except for changing the wax dispersion 1 to the wax dispersion 5, cyan toner no. In the same manner as in No. 1, cyan toner no. 7 was obtained. Table 3 shows the physical properties.

<Cyan Toner No. 8>
Except for changing the wax dispersion 1 to the wax dispersion 6, cyan toner no. In the same manner as in No. 1, cyan toner no. 8 was obtained. Table 3 shows the physical properties.

<Cyan Toner No. 9>
Except for changing the addition amount of the polymer fine particles B-1 added to the second stage from 35.0 parts to 70.0 parts, cyan toner No. In the same manner as in No. 1, cyan toner no. 9 was obtained. Table 3 shows the physical properties.

<Cyan Toner No. 10>
Except for changing the polymer fine particle B-1 to the polymer fine particle A, cyan toner no. In the same manner as in No. 1, cyan toner no. 10 was obtained. Table 3 shows the physical properties.

<Cyan Toner No. 11>
Except for changing the polymer fine particle B-1 to the polymer fine particle B-3 and changing the wax dispersion 1 to the wax dispersion 7, the cyan toner no. In the same manner as in No. 9, cyan toner no. 11 was obtained. Table 3 shows the physical properties.

<Cyan Toner No. 12>
Except for changing the polymer fine particle B-1 to the polymer fine particle A, cyan toner no. In the same manner as in No. 11, cyan toner no. 12 was obtained. Table 3 shows the physical properties.

<Magenta Toner No. 1>
C. I. Pigment Blue 15: 3 to C.I. I. Except for changing to Pigment Red 122, cyan toner No. 1 and magenta toner no. 1 was obtained. Table 3 shows the physical properties.

<Yellow Toner No. 1>
C. I. Pigment Blue 15: 3 to C.I. I. Except for changing to Pigment YELLOW180, cyan toner no. In the same manner as in yellow toner No. 1 1 was obtained. Table 3 shows the physical properties.

<Black Toner No. 1>
C. I. Pigment Blue 15: 3 except for changing to carbon black, cyan toner No. In the same manner as in No. 1 1 was obtained. Table 3 shows the physical properties.

<Magenta Toner No. 2>
C. I. Pigment Blue 15: 3 to C.I. I. Except for changing to Pigment Red 122, cyan toner No. In the same manner as in Magenta Toner No. 2 was obtained. Table 3 shows the physical properties.

<Yellow Toner No. 2>
C. I. Pigment Blue 15: 3 to C.I. I. Except for changing to Pigment YELLOW180, cyan toner no. In the same manner as in No. 12, yellow toner no. 2 was obtained. Table 3 shows the physical properties.

<Black Toner No. 2>
C. I. Pigment Blue 15: 3 except for changing to carbon black, cyan toner No. No. 12 and black toner No. 2 was obtained. Table 3 shows the physical properties.

  The fixing property evaluation method and evaluation criteria will be described below.

(1) Fixing area In the image forming apparatus of the contact single component development system shown in FIG. 2, the developer shown in FIG. 20 ° C./60% RH: A environment) After a margin of 5 mm at the leading edge, 50 mm of an unfixed image with a monochrome toner loading of 0.5 to 0.8 mg / cm ² is taken, and a fixing start temperature for judging low-temperature fixability The fixing end temperature for judging the hot offset resistance was evaluated.

For the evaluation of the fixing area, Xerox 4024 (75 g / cm ² ) was used as the paper type. The fixing machine was an external fixing capable of controlling the temperature of a 45 mmφ heat roller without an oil application function, and measurement was performed under a fixing condition of 120 mm / sec. In addition, as a roller material at this time, the fluorine-type thing was used for both the upper part and the lower part. The nip width was 8 mm.

The determination of the start of fixing is performed by rubbing a fixed image (including an image with a low temperature offset) on a sylbon with a load of 50 g / cm ² [Lenz Cleaning Paper “dasper (R)” (Ozu Paper Co. Ltd)] The temperature at which the density reduction rate before and after rubbing was less than 10% was defined as the fixing start point. The fixing end point was defined as the end point of the fixing temperature at which high temperature offset was not visually observed.

(2) Image Glossiness In the image forming apparatus of the contact one-component development system shown in FIG. 2, the developer shown in FIG. At 20 ° C./60% RH: A environment), an unfixed image with a monochromatic toner loading of 0.5 to 0.8 mg / cm ² is sampled on the entire surface after a margin of 5 mm at the leading edge. Next, using the fixed image at the maximum gloss temperature in the fixing area test, the inter-page gloss uniformity was confirmed at five points. The five sampling points were the center of the image and the four corners of the image, and the gloss was measured. The gloss measuring instrument used was PG-3D (incident angle θ = 75 °) manufactured by Nippon Denshoku Industries Co., Ltd., and the standard surface was black glass with a glossiness of 96.9.

(3) Developability after leaving at high temperature and high humidity (Striped image, fusion to photosensitive drum)
In the image forming apparatus of the contact one-component developing system shown in FIG. 2, the developing device shown in FIG. After leaving in a high temperature and high humidity environment (32 ° C./85% RH: B environment) for 14 days in the above state, 100 character images with a printing ratio of 5% were continuously fed, and a solid white image and a toner loading amount of 0.1. ~0.4mg / cm ² halftone whole images to two sampling respectively. The determination of the streak state and fusion to the photosensitive drum was made from the output image and the toner coat state on the toner carrier. Evaluation was made into A, B, C, and D.

Judgment criteria A for streaky images: There is no streak-like image in the sheet passing direction on the toner carrier and the entire halftone image, and there is no practical problem at all.
B: Although there are two or less minor streaks on the toner carrier, there is no streak-like image in the entire halftone image, and there is no practical problem.
C: Although there are 5 or less minor streaks on the toner carrying member and 2 or less minor streaks on the entire halftone image, the level is less likely to cause a practical problem.
D: The half-tone whole area image is on the entire surface of the streak-like image in the sheet passing direction and has a high possibility of causing a practical problem.

Photosensitive drum fusion criterion A: No solid fused image and no halftone image, and no practical problem at all.
B: Although there are 2 or less fused objects having a length of 1 to 5 mm only in a solid white image, it is a level that causes no problem in practical use.
C: A solid white image and a halftone image, which have 10 or less fused materials having a length of 1 to 5 mm, have a low possibility of causing a practical problem.
D: There is a high possibility that there are more than 10 fusion objects having a length of 1 to 5 mm in a solid white image and a halftone image, causing a practical problem.

[Examples 1-13, Comparative Examples 1-6]
The toner particles listed in Table 3 were evaluated according to the combinations listed in Table 4.

  The results are listed in Table 5.

It is the schematic of the image development apparatus which performs nonmagnetic one-component contact development. It is the schematic of the image forming method which performs nonmagnetic one-component contact development.

Explanation of symbols

10 Latent image carrier (photosensitive drum)
11 Photosensitive drum charging member (elastic roller)
13 Developing Device 14 Toner Carrier 15 Elastic Roller 16 Elastic Blade (Regulating Member)
17 Toner 24 Blade support sheet metal 25 Stirrer 26 Toner leakage preventing member 27 Power supply 29 Toner charging member (pressure contact elastic member)
30 Suppressing member 31 Cleaning member

Claims (7)

In the emulsion aggregation method toner obtained by further attaching or fixing the polymer fine particles (B) to the particle aggregate containing at least the polymer fine particles (A), the colorant fine particles and the wax,
The tetrahydrofuran insoluble content of the polymer fine particles (B) is 5.0% or more larger than the tetrahydrofuran insoluble content of the polymer fine particles (A),
The differential scanning calorimeter (DSC) peak temperature of the wax is 50.0 to 100.0 ° C., the tangential desorption temperature is 45.0 to 95.0 ° C., and the gas chromatography method (GC method) of the wax is measured. An emulsion aggregation method toner comprising an ester wax having a maximum peak area of 50.0 to 99.0% when the total peak area in the molecular weight distribution is 100.0.   The polymer fine particles (A) have a tetrahydrofuran insoluble content of 1.0% to 50.0%, and the polymer fine particles (B) have a tetrahydrofuran insoluble content of 6.0 to 75.0%. The emulsion aggregation method toner according to claim 1. A measured value X1 of particles having a particle diameter of 0.6 to 2.0 μm and a measured value X2 when irradiated with the toner for 5 minutes when the toner is irradiated for 1 minute, using a flow particle image analyzer (Flow Particle Image Analyzer). The emulsion aggregation method toner according to claim 1, wherein the relationship is as follows.
5.0 ≦ X1 ≦ 50.0% by number 1.0 ≦ X2 / X1 ≦ 3.0   4. The emulsion aggregation method toner according to claim 1, wherein the DSC maximum peak half-width of the wax is 2.0 to 10.0 ° C. 5.   5. The emulsion aggregation method toner according to claim 1, wherein the wax is an ester wax containing 1 to 6 ester groups.   The emulsion aggregation method toner according to any one of claims 1 to 5, wherein the penetration of the wax is 0.1 to 5.0.   The emulsion aggregation method toner according to claim 1, wherein the wax is fine particles and has a weight average particle diameter of 0.01 to 3.00 μm.

Images