JP5578923B2 - toner - Google Patents

Description

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

  In recent years, with the development of computers and multimedia, there is a demand for means for outputting further high-definition full-color images in a wide range of fields from offices to homes. A heavy user demands high durability that does not deteriorate image quality even when a large number of copies or prints are made, while a small office or home demands that a high-quality image be obtained. Furthermore, improvement in low-temperature fixability is required for energy saving.

  In general, when the fixing temperature is set low, the amount of heat of fusion of the toner becomes insufficient, the image glossiness and color reproducibility tend to decrease, and the fixed image has poor scratch resistance and peeling resistance. Therefore, the toner corresponding to the low-temperature fixing process is required to have a performance that melts instantaneously even at a low heat quantity and exhibits sufficient fixability.

  In recent years, a wax having a relatively low molecular weight has been proposed in order to obtain low-temperature fixability and high releasability (Patent Document 1). However, the toner containing these waxes (Patent Document 2) is excellent in low-temperature fixability, but also contains volatile components, so that the inside of the machine is contaminated with volatile components generated at the time of fixing, causing image defects and malfunction of the main body. I understood it. On the other hand, a toner using a wax having a small volatile component has been proposed in order to suppress in-machine contamination and odor (Patent Document 3). Although this has certainly reduced the volatile components, it has been found that waxes with less volatile components are relatively hard and thus deteriorate the cleaning properties in a low temperature environment.

  Further, it is disclosed that a toner having a certain storage elastic modulus for improving the durability of the toner is excellent in durability stability at the time of temperature rise (Patent Documents 4 and 5). Although these toners certainly improved the fixing and developing characteristics compared to conventional toners, there is room for improvement in cleaning properties when printing more sheets in a low temperature environment. It has also been found that component contamination occurs.

  As described above, there is a demand for a toner that does not contaminate the inside of the apparatus and satisfies the durability stability and the cleaning property that maintain high image quality even when a large number of printouts are performed.

JP 2001-051445 A JP 2001-281976 A JP 2005-266832 A JP 2007-183382 A JP 2008-033210 A

  The problem to be solved by the present invention is to provide a toner having developability that prevents in-machine contamination, has excellent cleanability in a low temperature environment, and maintains high image quality even when a large number of printouts are made. .

The present invention provides a toner particle containing a binder resin, a polyester resin, a colorant and a hydrocarbon wax ;
Inorganic fine powder ,
A toner having
The toner has an average circularity of 0.970 or more and 0.995 or less;
In the DSC curve at the time of temperature rise measured by a differential scanning calorimetry (DSC) apparatus, the maximum endothermic peak temperature of the hydrocarbon wax is 70 ° C. or more and 120 ° C. or less,
In the hydrocarbon desorption-GC / MS analysis of the hydrocarbon wax, the concentration in terms of hexadecane based on the hydrocarbon wax mass with respect to volatile components detected after the peak detection time of hexadecane at a heating temperature of 200 ° C. for a heating time of 10 minutes. There is less than or equal to 1100ppm,
Wherein in a dynamic viscoelasticity test of the toner, the storage elastic modulus at a temperature of 70 ° C. is (G _'70), is in the range of 1.0 × 10 ⁵ (Pa) or 1.0 × 10 ⁸ (Pa) or less, 110 storage modulus at ℃ (G _'110) is directed to toner lies in the range of 1.0 × 10 ⁴ (Pa) or 2.0 × 10 ⁵ (Pa) or less.

  According to the present invention, it is possible to obtain a toner that is free from contamination in the apparatus, has excellent cleaning properties, and can maintain developability even when a large number of sheets are printed out.

It is an enlarged view of the developing unit of the electrophotographic apparatus. 1 is a cross-sectional view of an electrophotographic apparatus using an image forming method of the present invention.

  Hereinafter, the present invention will be described in detail.

The toner of the present invention is a toner having toner particles containing at least a binder resin, a polyester resin, a colorant and a hydrocarbon wax and an inorganic fine powder, and the average circularity of the toner is 0.970 or more and 0.995. It is characterized by the following. Further, in the above thermal desorption / GC / MS analysis of the hydrocarbon waxes, for volatile components detected after hexadecane peak detection time at 10 minutes heating temperature 200 ° C. The heating time, hexadecane conversion relative to the said hydrocarbon wax mass The concentration of is 1100 ppm or less. Furthermore, in the dynamic viscoelasticity test of the toner, the storage elastic modulus (G ′ ₇₀ ) at a temperature of 70 ° C. is in the range of 1.0 × 10 ⁵ (Pa) to 1.0 × 10 ⁸ (Pa). The storage elastic modulus (G ′ ₁₁₀ ) at 110 ° C. is in the range of 1.0 × 10 ⁴ (Pa) to 2.0 × 10 ⁵ (Pa).

In the present invention, volatile components detected after the peak detection time of hexadecane at a heating temperature of 200 ° C. and a heating time of 10 minutes in GC / MS analysis of hydrocarbon wax contained in the toner are based on the wax mass. By setting the concentration in terms of hexadecane to 1100 ppm or less, internal contamination can be prevented. In addition, the average circularity of the toner is 0.970 or more and 0.995 or less, and the storage elastic modulus (G ′ ₇₀ ) at ₇₀ ° C. and the storage elastic modulus (G ′ ₁₁₀ ) at 110 ° C. are defined as described above. As a result, it is possible to obtain a toner having excellent cleaning properties, excellent durability and charging uniformity, and further suppressing member contamination.

  The measurement of the volatile component of the wax can be measured by holding at 200 ° C. near the fixing temperature for 10 minutes, whereby the volatile component generated in the fixing process can be measured, and the value does not change even if the wax is held for 10 minutes or more.

Although the detailed reason why the effects of the present invention can be obtained by setting the volatile components of wax, G ′ ₇₀ and G ′ ₁₁₀ and the average circularity as described above is not clear, the inventors have I think so. That is, by using a hydrocarbon wax with a small amount of volatile components in the toner of the present invention, it is possible to prevent in-machine contamination due to volatile components generated by heating during fixing.

On the other hand, since hydrocarbon wax with a small amount of volatile components is hard, it becomes hard as a toner. Therefore, the deformation of the toner is reduced particularly in a low temperature environment, and the toner remaining on the photosensitive member is difficult to be removed by the cleaning blade and the cleaning property is deteriorated. Therefore, the cleaning is performed by defining G ′ ₇₀ as described above. The property can be kept good. Here, since G ′ ₇₀ is lower than the melting point of the wax, it represents the elasticity of the binder resin. Since the binder resin has elasticity, it can be removed from the photoreceptor without slipping through the cleaning blade.

Further, by defining G ′ ₁₁₀ as described above, the toner is not completely crushed, and deterioration and member contamination caused by sliding between the toner and various members can be suppressed. Here, G ′ ₁₁₀ represents the elasticity of the toner, and it is considered that the durability is improved because the hard hydrocarbon wax exists in the toner and the toner has elasticity.

  Here, regarding the volatile component of the wax measured above, if the concentration in terms of hexadecane based on the wax mass exceeds 1100 ppm, malfunction caused by the volatile component adhering to the machine and soiling the sensor, Deterioration of the image due to adhesion occurs.

Further, if G ′ ₇₀ is less than 1.0 × 10 ⁵ (Pa), the hardness of the binder resin is insufficient, and the toner is liable to be crushed by a stress such as rubbing against various members, so that developability and transfer Sex is reduced. On the other hand, when G ′ ₇₀ exceeds 1.0 × 10 ⁸ (Pa), the elasticity of the binder resin is lowered, so that the deformation of the toner is reduced and it becomes difficult to remove with a cleaning blade, and the cleaning property is deteriorated.

On the other hand, if G ′ ₁₁₀ is less than 1.0 × 10 ⁴ (Pa), the hardness of the toner becomes low, and toner fusing due to rubbing with the member occurs, causing contamination of the member. If G ′ ₁₁₀ exceeds 2.0 × 10 ⁵ (Pa), the hardness of the toner becomes high and the brittleness may occur, so that it may be rubbed against various members and the like, resulting in a decrease in durability.

  Further, when the average circularity of the present invention is less than 0.970, not only the deterioration of the toner cannot be suppressed, but also the toner charging characteristics become non-uniform.

The values of G ′ ₇₀ and G ′ ₁₁₀ can satisfy the above range by adjusting, for example, the glass transition temperature of the binder resin constituting the binder resin or the addition amount of the crosslinking agent.

  Hereinafter, further preferred embodiments of the toner of the present invention will be described.

  As a method for producing the toner particles contained in the present invention, a suspension polymerization method is particularly preferable. In this suspension polymerization method, a polymerizable monomer is uniformly dissolved or dispersed in a polymerizable monomer by dissolving or dispersing a wax and a colorant (and, if necessary, a polymerization initiator, a crosslinking agent, a charge control agent, and other additives). A meter composition is defined. Thereafter, the polymerizable monomer composition is dispersed in an aqueous medium containing a dispersion stabilizer using an appropriate stirrer, and a polymerization reaction is performed to obtain toner particles having a desired particle size. is there. After the polymerization is completed, the toner of the present invention can be obtained by filtering, washing and drying by a known method, mixing a fluidity improver if necessary, and adhering it to the surface.

  By obtaining the toner of the present invention by the suspension polymerization method, the wax is present in the vicinity of the center of the toner particles, and the outer surface of the binder resin has a core-shell structure, so that development is possible even when a large number of printouts are made. Properties and cleaning properties can be maintained, and contamination of members can be suppressed. This is presumably because the wax does not easily exist in the vicinity of the surface, and the binder resin layer tends to have elasticity and the cleaning property and durability are improved.

The toner particles contained in the present invention further contain a styrenic polar resin, and when the molecular weight of the main peak in the GPC chromatogram of the styrenic polar resin is Mp, the Mp is 1.0 × 10 ⁴ or more and 3.0. × is 10 ⁴ or less, the acid value of the low molecular weight component (the region of molecular weight of less than peak molecular weight Mp) α (mgKOH / g) , the acid value of the high molecular weight component (region molecular weight is more than the peak molecular weight Mp) beta ( When mgKOH / g), α / β preferably satisfies 0.80 or more and 1.20 or less.

  By producing a toner in an aqueous medium using a styrene polar resin, the polar resin functions as an outer layer of the toner.

  Many of the capsule type toners are separated into an inner layer and an outer layer. In this type of capsule toner, the inner layer is protected by the outer layer. However, when the adhesion between the inner layer and the outer layer is weak, if the toner is continuously stressed with continuous output, the outer layer may be peeled off or scraped, and the toner particle surface may change abruptly at a certain point.

  On the other hand, although the mechanism is not clear, it is considered that the adhesion to the inner layer is improved by using the styrene polar resin in the present invention. Specifically, when producing toner particles in an aqueous medium, the outer layer is formed while sufficiently adhering to the inner layer by using a styrene polar resin that has polarity and is easily compatible with the binder resin. I think it is possible. In addition, since the polar resin has polarity and compatibility with the binder resin at the same time, the inventors consider that a concentration gradient of the resin having a polar group occurs in the toner particles.

  That is, the present inventors consider that the development characteristics are improved due to the high adhesion between the inner layer and the outer layer of the toner particles and the high toughness against external factors when the toner is pressed.

  The peak molecular weight Mp of the styrenic polar resin is preferably in the above range, since the storage stability of the toner is improved and the cleaning property and durability under a lower temperature environment can be compatible.

  Further, by setting α / β within the above range, the durability is further improved as compared with the conventional toner. When a toner is produced in an aqueous medium, a component having a high acid value tends to be unevenly distributed on the surface of the toner because of its higher affinity with water. Therefore, among the polymer chains in the polar resin, the polymer chain having a high acid value is more unevenly distributed toward the toner surface.

  From the above, it is preferable that the styrene polar resin used in the present invention has a low molecular weight component acid value and a high molecular weight component acid value close to each other.

In order to make the value of α / β within the above range, for example, the following production method can be mentioned.
(1) Raise the polymerization temperature under pressure.
(2) A large amount of styrene is dropped in the initial stage of polymerization, and a large amount of methacrylic acid or acrylic acid is dropped in the latter half of the polymerization.
(3) Two types of polar resins having the same acid value with a narrow molecular weight distribution but different peak molecular weights are mixed.

  The acid value of the styrenic polar resin used in the present invention is preferably 5 mgKOH / g or more and 40 mgKOH / g or less. Moreover, it is preferable that content of a styrenic polar resin is 1 to 30 mass parts with respect to 100 mass parts of polymerizable monomers, More preferably, it is 8 to 30 mass parts. By setting the acid value and the content of the styrenic polar resin in the above ranges, the outer layer of the toner has an appropriate hardness, so that the durability and cleaning properties of the toner are further improved.

  Below, the material used by this invention is demonstrated.

  Examples of the binder resin used in the present invention include polystyrene; a styrene-substituted homopolymer such as poly-p-chlorostyrene and polyvinyltoluene; a styrene-p-chlorostyrene copolymer, a styrene-vinyltoluene copolymer, Styrene-vinyl naphthalene copolymer, styrene-acrylic acid ester copolymer, styrene-methacrylic acid ester copolymer, styrene-α-chloromethacrylic acid methyl copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ether Styrene copolymer such as copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer Coalescence; acrylic resin; methacrylic tree ; Polyvinyl acetate; silicone resins; polyester resins; polyamide resin; furan resins, epoxy resins, xylene resins. These resins are used alone or in combination.

  The comonomer for the styrene monomer of the styrene copolymer includes acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, doditer acrylate, octyl acrylate, 2-ethylhexyl acrylate, phenyl acrylate, methacrylic acid, methacrylic acid. Monocarboxylic acid having a double bond such as methyl acid, ethyl methacrylate, butyl methacrylate, octyl methacrylate, acrylonitrile, methacrylonitrile, acrylamide or a substituted product thereof; maleic acid, butyl maleate, methyl maleate, maleate Dicarboxylic acids having a double bond such as dimethyl acid and its substitutes; vinyl esters such as vinyl chloride, vinyl acetate and vinyl benzoate; ethylene-based olefins such as ethylene, propylene and butylene; Sulfonyl methyl ketone, vinyl ketones such as vinyl hexyl ketone, vinyl methyl ether, vinyl ethyl ether, vinyl ethers such as vinyl isobutyl ether. These vinyl monomers are used alone or in combination of two or more.

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

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

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

  In the present invention, the polyester resin has a tendency to easily separate layers as the polymerization proceeds in a dispersoid oil droplet mainly composed of styrene or an acrylate monomer, so that a stable outermost shell layer is formed. . Formation of a uniform shell layer is excellent in durability.

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

（式中、Ｒはエチレンまたはプロピレン基であり、ｘ，ｙはそれぞれ１以上の整数であり、かつｘ＋ｙの平均値は２乃至１０である。）

(In the formula, R is an ethylene or propylene group, x and y are each an integer of 1 or more, and the average value of x + y is 2 to 10.)

  Or a hydrogenated product of the compound of the general formula (1), a diol represented by the following general formula (2),

  Or the diol of the hydrogenated compound of the compound of the formula (2), and polyhydric alcohols such as glycerin, pentaerythritol, sorbit, sorbitan, oxyalkylene ethers of novolac type phenol resins, and the like.

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

  In the present invention, the content of the polyester resin is preferably 1 to 10 parts by mass with respect to 100 parts by mass of the polymerizable monomer. When the polyester resin is contained in an amount of 1 part by mass or more, a uniform shell layer can be formed. Moreover, when it contains within 10 mass parts, the production | generation of an emulsified particle etc. will be suppressed and the stable developability can be shown.

  Specific examples of the styrenic polar resin used in the present invention include a copolymer of a polymerizable monomer composed of vinyl benzoic acid and its derivatives and styrene; dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, and the like. Polymer of nitrogen-containing monomer or copolymer of nitrogen-containing monomer, styrene-unsaturated carboxylic acid ester and styrene; copolymer of nitrile monomer such as acrylonitrile and styrene; such as vinyl chloride Copolymer of halogen-containing monomer and styrene; copolymer of unsaturated carboxylic acid such as acrylic acid and methacrylic acid; copolymer of styrene; copolymer of unsaturated dibasic acid and styrene; unsaturated dibasic And a copolymer of an acid anhydride and styrene; a copolymer of a nitro monomer and a styrene monomer.

  In the present invention, a styrene resin containing at least one polymerizable monomer from a polymerizable monomer composed of methacrylic acid, methacrylic acid ester, acrylic acid, and acrylic acid ester in order to improve chargeability. Preferably there is.

  For the purpose of adjusting the molecular weight, a known polyfunctional polymerizable monomer or chain transfer agent may be added to these polymerizable monomers.

  Specific examples of the hydrocarbon wax used in the present invention include paraffin wax, microcrystalline wax, petroleum wax such as petrolactam and derivatives thereof, hydrocarbon wax and derivatives thereof by Fischer-Tropsch method, and polyethylene. Examples thereof include polyolefin wax and derivatives thereof.

  Among these, when the hydrocarbon wax by the Fischer-Tropsch method is used, it is possible to maintain good developability for a long period of time and to maintain good offset resistance to the fixing member. These hydrocarbon waxes may contain an antioxidant within a range that does not affect the chargeability of the toner.

  The content of the wax used in the present invention is preferably 1.0 to 15.0 parts by mass, more preferably 6.0 to 15 parts by mass with respect to 100.0 parts by mass of the polymerizable monomer. 0.0 part by mass.

  Further, the wax preferably has a maximum endothermic peak temperature in a range of 70 ° C. to 120 ° C. in a DSC curve at the time of temperature rise measured by a differential scanning calorimetry (DSC) apparatus.

  As the black colorant used in the present invention, carbon black, a magnetic material, and a toned color of each color using the following yellow / magenta / cyan colorant are used. In particular, since dyes and carbon black have many polymerization-inhibiting properties, care must be taken when using them.

  Examples of the yellow colorant used in the present invention include compounds typified by condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds. Specifically, the following C.I. I. Pigment Yellow 12, 13, 14, 15, 17, 62, 73, 74, 83, 93, 94, 95, 97, 109, 110, 111, 120, 128, 129, 138, 147, 150, 151, 154, Examples include 155, 168, 180, 185, 214 and the like.

  Examples of the magenta colorant used in the present invention include condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, and perylene compounds. Specifically, the following C.I. I. Pigment Red 2, 3, 5, 6, 7, 23, 48: 2, 48: 3, 48: 4, 57: 1, 81: 1, 122, 146, 166, 169, 177, 184, 185, 202, 206, 220, 221, 238, 254, 269, C.I. I. Pigment Bio Red 19 and the like can be exemplified.

  Examples of the cyan colorant used in the present invention include copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds, basic dye lake compounds, and the like. Specifically, C.I. I. Pigment blue 1, 7, 15, 15: 1, 15: 2, 15: 3, 15: 4, 60, 62, 66, and the like.

  These colorants can be used alone or in combination and further in the form of a solid solution. The colorant is selected from the viewpoints of hue angle, saturation, brightness, light resistance, OHP transparency, and dispersibility in the toner. The colorant is added in an amount of 1 to 20 parts by mass with respect to 100 parts by mass of the polymerization.

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

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

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

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

  Examples of the monomer having a sulfonic acid group for producing the polymer include styrene sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, 2-methacrylamide-2-methylpropane sulfonic acid, vinyl sulfonic acid, methacrylic acid. A sulfonic acid can be illustrated.

  The polymer containing a sulfonic acid group and the like used in the present invention may be a homopolymer of the above monomer, but is a copolymer of the above monomer and another monomer. It doesn't matter. As a monomer that forms a copolymer with the above monomer, there is a vinyl polymerizable monomer, and a monofunctional polymerizable monomer or a polyfunctional polymerizable monomer can be used.

  Monofunctional polymerizable monomers include the following 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 Styrene-based polymerizable monomers such as p-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 Acrylic polymerizable monomers such as polyacrylate, 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 Mer: 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 Methacrylic polymerizable monomers such as til methacrylate and dibutyl phosphate ethyl methacrylate; methylene aliphatic monocarboxylic acid ester; vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate and vinyl formate; vinyl methyl ether And vinyl ethers such as vinyl ethyl ether and vinyl isobutyl ether; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and vinyl isopropyl ketone.

  The following polyfunctional polymerizable monomers include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, triethylene glycol diacrylate, Propylene glycol diacrylate, polypropylene glycol diacrylate, 2,2'-bis (4- (acryloxy-diethoxy) phenyl) propane, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, tri Ethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol Coal dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, polypropylene glycol dimethacrylate, 2,2'-bis (4- (methacryloxy-diethoxy) phenyl) propane 2,2′-bis (4-methacryloxy-polyethoxy) phenyl) propane, trimethylolpropane trimethacrylate, tetramethylolmethane tetramethacrylate, divinylbenzene, divinylnaphthalene, divinyl ether and the like.

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

  In addition to the polymer having a sulfonic acid group in the side chain, a charge control agent may be blended in the toner of the present invention in order to stabilize charging characteristics. As the charge control agent, known ones can be used, and in particular, a charge control agent that has a high charging speed and can stably maintain a constant charge amount is preferable. Further, when the toner is produced by a direct polymerization method, a charge control agent having a low polymerization inhibition property and substantially free from a solubilized product in an aqueous dispersion medium is particularly preferable.

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

  On the other hand, examples of the charge control agent that control the toner to be positively charged include the following. Nigrosine modified products with nigrosine and fatty acid metal salts; guanidine compounds; imidazole compounds; quaternary ammonium salts such as tributylbenzylammonium-1-hydroxy-4-naphthosulfonate, tetrabutylammonium tetrafluoroborate, and the like Some onium salts such as phosphonium salts and their lake pigments; triphenylmethane dyes and their lake pigments (as rake agents, phosphotungstic acid, phosphomolybdic acid, phosphotungsten molybdic acid, tannic acid, lauric acid, gallic acid , Ferricyanides, ferrocyanides); metal salts of higher fatty acids; resin-based charge control agents.

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

  Among these charge control agents, a salicylic acid-based compound containing a metal is preferable, and the metal is particularly preferably aluminum or zirconium. The most preferred charge control agent is an aluminum 3,5-di-tert-butylsalicylate compound.

  A preferable blending amount of the charge control agent is 0.01 parts by mass or more and 20 parts by mass or less, more preferably 0.5 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the binder resin. However, it is not essential to add a charge control agent to the toner of the present invention, and the toner does not necessarily contain a charge control agent by actively utilizing frictional charging with the toner layer thickness regulating member or the toner carrier. There is no need to let it.

  Examples of the method for producing toner particles in an aqueous medium include the following methods. An emulsion aggregation method in which an emulsion composed of essential toner components is aggregated in an aqueous medium; a suspension granulation method in which the essential toner components are dissolved in an organic solvent and then the organic solvent is volatilized after granulation in the aqueous medium. A suspension polymerization method or an emulsion polymerization method in which a polymerizable monomer in which an essential toner component is dissolved is directly granulated in an aqueous medium and then polymerized; a method in which an outer layer is then formed on the toner by using seed polymerization; A microcapsule method represented by drying in liquid.

  Among these, the suspension polymerization method is particularly preferable as the one that easily exhibits the effects of the present invention. In this suspension polymerization method, a polymerizable monomer is uniformly dissolved or dispersed with a wax and a colorant (and a polymerization initiator, a crosslinking agent, a charge control agent, and other additives as necessary) to achieve polymerization. A monomer composition is used. Thereafter, the polymerizable monomer composition is dispersed in an aqueous medium containing a dispersion stabilizer using a suitable stirrer, and a polymerization reaction is performed to obtain toner particles having a desired particle size. is there. After the polymerization, the toner particles are filtered, washed and dried by a known method, and if necessary, a fluidity improver is mixed and adhered to the surface to obtain the toner of the present invention.

  In the case of producing toner by this suspension polymerization method, since the shape of individual toner particles is almost spherical, the charge amount distribution is relatively uniform. Further, it is easy to obtain a toner that maintains a high transferability with little dependence on external additives.

  Examples of the polymerizable monomer for producing the toner by the suspension polymerization method include the monofunctional polymerizable monomer and the polyfunctional polymerizable monomer.

  As the crosslinking agent, a compound having two or more polymerizable double bonds is mainly used. The following 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 can be used alone or as a mixture. A preferable addition amount is 0.001 to 15 parts by mass with respect to 100 parts by mass of the binder resin.

  As the polymerization initiator used in the present invention, an oil-soluble initiator and / or a water-soluble initiator is used. Preferably, the half-life at the reaction temperature during the polymerization reaction is 0.5 to 30 hours. When the polymerization reaction is carried out at an addition amount of 0.5 to 20 parts by mass with respect to 100 parts by mass of the polymerizable monomer, a polymer having a maximum between 10,000 and 100,000 is usually obtained. A toner having strength and melting characteristics can be obtained.

  As polymerization initiators, the following 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile, 1,1′-azobis (cyclohexane-1-carbohydrate) were used. Nitrile), 2,2′-azobis-4-methoxy-2,4-dimethylvaleronitrile, azo or diazo polymerization initiators such as azobisisobutyronitrile; benzoyl peroxide, t-butylperoxy 2- Ethyl hexanoate, t-butyl peroxypivalate, t-butyl peroxyisobutyrate, t-butyl peroxyneodecanoate, methyl ethyl ketone peroxide, diisopropyl peroxycarbonate, cumene hydroperoxide, 2,4- Peroxidation such as dichlorobenzoyl peroxide and lauroyl peroxide System polymerization initiators and the like.

  A dispersion stabilizer is added to the aqueous medium. The following inorganic compounds used as dispersion stabilizers are calcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, calcium carbonate, magnesium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, sulfuric acid. Examples include calcium, barium sulfate, bentonite, silica, alumina and the like.

  Examples of the organic compound include polyvinyl alcohol, gelatin, methyl cellulose, methyl hydroxypropyl cellulose, ethyl cellulose, sodium salt of carboxymethyl cellulose, polyacrylic acid and its salt, starch and the like. These dispersion stabilizers are preferably used in an amount of 0.2 to 20 parts by mass with respect to 100 parts by mass of the polymerizable monomer.

  Further, 0.001 to 0.1 parts by mass of a surfactant may be used for fine dispersion of these dispersion stabilizers. This is to promote the initial action of the dispersion stabilizer. Specific examples include sodium dodecylbenzene sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, sodium laurate, potassium stearate, calcium oleate and the like.

  When an inorganic compound is used as the dispersion stabilizer, a commercially available one may be used as it is, but in order to obtain finer particles, the inorganic compound may be generated and used in an aqueous medium.

  For example, in the case of calcium phosphate, a sodium phosphate aqueous solution and a calcium chloride aqueous solution may be mixed under high stirring.

  Furthermore, in the toner of the present invention, a fluidity improver may be added to the toner particles for the purpose of improving the fluidity of the toner particles. As the fluidity improver, the following fluororesin powders such as fine vinylidene fluoride powder and polytetrafluoroethylene fine powder; fatty acid metal salts such as zinc stearate, calcium stearate and lead stearate; titanium oxide powder, oxidation Metal powder such as aluminum powder and zinc oxide powder, or powder obtained by hydrophobizing the above metal oxide; and silica fine powder such as wet process silica and dry process silica, or silica with silane coupling agent and titanium coupling Examples thereof include surface-treated silica fine powder that has been surface-treated with a treating agent such as an agent and silicone oil.

  The fluidity improver is preferably used in an amount of 0.01 to 5 parts by mass with respect to 100 parts by mass of the toner particles.

  The physical property value measuring method of the present invention will be described below.

<Measurement of Wax Volatile Component Concentration Using Heat Desorption Device>
The volatile component concentration of the wax in the present invention is measured by the following method.

  The following measuring devices are used as measuring devices.

Thermal desorption device: TurboMatrixATD (manufactured by PerkinElmer)
GC / MS: TRACE DSQ (manufactured by Thermo Fisher Scientific)

(Production of glass tube with internal standard)
A glass tube for a heat desorption apparatus in which 10 mg of TenaxTA adsorbent is sandwiched between glass wools in advance is prepared, and a glass tube that has been conditioned at 300 ° C. for 3 hours in a state of flowing an inert atmosphere gas is prepared. Thereafter, 5 μL of a 100 ppm methanol solution of deuterated hexadecane (hexadecane D34) is adsorbed on TenaxTA to obtain a glass tube containing an internal standard.

(Measurement of wax)
About 1 mg of wax is wrapped in aluminum foil previously baked out at 300 ° C., and put in a special tube prepared in (Preparation of glass tube with internal standard). The sample is covered with a Teflon (registered trademark) cap for a heat desorption apparatus and set in the apparatus.

  This sample is measured under the following conditions, and the total peak area of the internal standard peak and the peak after deuterated hexadecane is calculated.

・ Heat desorption equipment tube temperature: 200 ° C
Transfer temperature: 300 ° C
Valve temperature: 300 ° C
Column pressure: 150 kPa
Inlet split: 25 ml / min.
Outlet split: 10 ml / min.
Secondary adsorption tube material: TenaxTA
Holding time: 10 min.
Secondary adsorption tube temperature during desorption: -30 ° C
Secondary adsorption tube desorption temperature: 300 ° C

GC / MS conditions Column: Ultra alloy (metal column) UT-5 (inner diameter 0.25 mm, liquid phase 0.25 μm, length 30 m)
Column heating conditions: 60 ° C. (3 min), 350 ° C. (20.0 ° C./min), 350 ° C. (10 min)

  The transfer line of the heat desorption apparatus and the GC column are directly connected, and the GC inlet is not used.

(analysis)
Of the peaks obtained by the above operation, all peaks after the retention time of deuterated hexadecane, which is an internal standard, are integrated, the total value of all peaks is calculated, and the volatile component concentration of wax is calculated from the following formula. At this time, care should be taken not to add a noise peak or the like different from the peak to the integrated value.

Volatile component concentration of wax (ppm)
= (A1 / B1 × 0.0005 × 0.77) / C1 × 1000000
A1 ... Total peak area after deuterated hexadecane B1 ... Peak area C1 of deuterated hexadecane (internal standard) ... Weight of weighed wax (mg)

<Measurement of storage modulus>
Storage modulus temperature 70 ° C. in the present invention 'and _(70, storage elastic modulus at _{110 ℃ (G G)' 110} ) is measured by the following method.

  As a measuring apparatus, a rotating plate type rheometer “ARES” (manufactured by TA INSTRUMENTS) is used. As a measurement sample, a sample obtained by press molding a toner into a disk shape having a diameter of 7.9 mm and a thickness of 2.0 ± 0.3 mm using a tablet molding machine in an environment of 25 ° C. is used.

  The sample is mounted on a parallel plate, heated from room temperature (25 ° C.) to 120 ° C. over 15 minutes to adjust the shape of the sample, then cooled to the measurement start temperature of viscoelasticity, and measurement is started. At this time, it is important to set the sample so that the initial normal force becomes zero. Further, as described below, in the subsequent measurement, the effect of normal force can be canceled by performing automatic tension adjustment (Auto Tension Adjustment ON).

The measurement is performed under the following conditions.
(1) A parallel plate having a diameter of 7.9 mm is used.
(2) The frequency (Frequency) is 1.0 Hz.
(3) The applied strain initial value (Strain) is set to 0.1%.
(4) Measure between 30 and 200 ° C. at a ramp rate of 2.0 ° C./min. In the measurement, the following automatic adjustment mode setting conditions are used. Measurement is performed in an automatic strain adjustment mode (Auto Strain).
(5) The maximum strain (Max Applied Strain) is set to 20.0%.
(6) The maximum torque (Max Allowed Torque) is set to 200.0 g · cm, and the minimum torque (Min Allowed Torque) is set to 0.2 g · cm.
(7) Set distortion adjustment (Strain Adjustment) as 20.0% of Current Strain. In the measurement, an automatic tension adjustment mode (Auto Tension) is adopted.
(8) The automatic tension direction (Auto Tension Direction) is set as the compression (Compression).
(9) The initial static force (Initial Static Force) is set to 10.0 g, and the automatic tension sensitivity (Auto Tension Sensitivity) is set to 40.0 g.
(10) The operating condition of automatic tension (Sample Tension) is 1.0 × 103 (Pa) or more.
The storage elastic modulus G ′ at a temperature of 70 ° C. when the storage elastic modulus G ′ is measured in the temperature range of 30 ° C. or more and 200 ° C. or less by the above method is G ′ ₇₀ , and the storage elastic modulus G ′ at 110 ° C. the value was G _'110.

<Measurement of average circularity of toner>
The average circularity of the toner particles is measured by a flow type particle image analyzer “FPIA-3000” (manufactured by Sysmex Corporation) under the measurement and analysis conditions during the calibration operation.

  A specific measurement method is as follows. First, about 20 ml of ion-exchanged water from which impure solids are removed in advance is put in a glass container. In this, "Contaminone N" (nonionic surfactant, anionic surfactant, 10% by weight aqueous solution of neutral detergent for pH7 precision measuring instrument cleaning, made by organic builder, manufactured by Wako Pure Chemical Industries, Ltd. About 0.2 ml of a diluted solution obtained by diluting the solution with ion exchange water about 3 times by mass. Further, about 0.02 g of a measurement sample is added, and dispersion treatment is performed for 2 minutes using an ultrasonic disperser to obtain a dispersion for measurement. In that case, it cools suitably so that the temperature of a dispersion liquid may become 10 to 40 degreeC. As the ultrasonic disperser, a desktop type ultrasonic cleaner disperser (for example, “VS-150” (manufactured by VervoCrea)) having an oscillation frequency of 50 kHz and an electric output of 150 W is used. Ion exchange water is added, and about 2 ml of the above-mentioned Contaminone N is added to this water tank.

  For the measurement, the above-mentioned flow type particle image analyzer equipped with “UPlanApro” (magnification 10 times, numerical aperture 0.40) as an objective lens is used, and the particle sheath “PSE-900A” (manufactured by Sysmex Corporation) is used as the sheath liquid. It was used. The dispersion prepared in accordance with the above procedure is introduced into the flow type particle image analyzer, and 3000 toner particles are measured in the HPF measurement mode and in the total count mode. Then, the binarization threshold at the time of particle analysis is set to 85%, the analysis particle diameter is limited to the circle equivalent diameter of 1.985 μm or more and less than 39.69 μm, and the average circularity of the toner particles is obtained.

  In the measurement, automatic focus adjustment is performed using standard latex particles (eg, “RESEARCH AND TEST PARTICLES Latex Microsphere Suspensions 5200A” manufactured by Duke Scientific) diluted with ion-exchanged water before starting the measurement. Thereafter, it is preferable to perform focus adjustment every two hours from the start of measurement.

  In the examples of the present application, a flow-type particle image analyzer that has been issued a calibration certificate issued by Sysmex Corporation, which has been calibrated by Sysmex Corporation, was used. Measurement was performed under the measurement and analysis conditions when the calibration certificate was received, except that the analysis particle diameter was limited to a circle equivalent diameter of 1.985 μm or more and less than 39.69 μm.

  The measurement principle of the flow-type particle image analyzer “FPIA-3000” (manufactured by Sysmex Corporation) is to capture flowing particles as a still image and perform image analysis. The sample added to the sample chamber is fed into the flat sheath flow cell by a sample suction syringe. The sample fed into the flat sheath flow is sandwiched between sheath liquids to form a flat flow. The sample passing through the flat sheath flow cell is irradiated with strobe light at 1/60 second intervals, and the flowing particles can be photographed as a still image. Further, since the flow is flat, the image is taken in a focused state. The particle image is captured by a CCD camera, and the captured image is subjected to image processing at an image processing resolution of 512 × 512 (0.37 × 0.37 μm per pixel), and the contour of each particle image is extracted, The projected area S, the peripheral length L, etc. are measured.

Next, the equivalent circle diameter and the circularity are obtained using the area S and the peripheral length L. The equivalent circle diameter is the diameter of a circle having the same area as the projected area of the particle image, and the circularity C is a value obtained by dividing the circumference of the circle obtained from the equivalent circle diameter by the circumference of the projected particle image. And is calculated by the following formula.
Circularity C = 2 × (π × S) 1/2 / L

  When the particle image is circular, the degree of circularity is 1, and the degree of unevenness on the outer periphery of the particle image increases, and the degree of circularity decreases. After calculating the circularity of each particle, the range of the circularity of 0.200 to 1.000 is divided into 800, the arithmetic average value of the obtained circularity is calculated, and the value is defined as the average circularity.

<Physical properties of polar resin>
The peak molecular weight Mp in the GPC chromatogram in the present invention was measured as follows.

  First, a measurement sample was prepared as follows.

  Polar resin and THF were mixed at a concentration of 5 mg / ml, and left at room temperature for 24 hours. Then, what passed the sample processing filter (Maishori disk H-25-2 Tosoh company make, Excro disk 25CR Gelman Science Japan company make) was prepared as a sample of GPC.

  Next, it measured on the following measurement conditions according to the operation manual of the said apparatus using the GPC measuring apparatus (HLC-8120G PC Tosoh Corporation make).

(Measurement condition)
Equipment: High-speed GPC “HLC8120 GPC” (manufactured by Tosoh Corporation)
Column: Seven series of Shodex KF-801, 802, 803, 804, 805, 806, 807 (Showa Denko)
Eluent: THF
Flow rate: 1.0 ml / min
Oven temperature: 40.0 ° C
Sample injection volume: 0.10 ml

  In calculating the molecular weight of the sample, a calibration curve was obtained from standard polystyrene resin (TSK Standard Polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F- manufactured by Tosoh Corporation). 20, F-10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500), and the peak molecular weight Mp is calculated. did.

  The fractionation method of the low molecular weight component and the high molecular weight component of the polar resin was carried out as follows.

<Preparation of each component>
[Device configuration]
LC-908 (manufactured by Nippon Analysis Industry Co., Ltd.)
JRS-86 (Company; repeat injector)
JAR-2 (Company; Autosampler)
FC-201 (Gilson, Hula cushion collector)

[Column structure]
JAIGEL-1H to 5H (20φ × 600mm: preparative column)

[Measurement condition]
Temperature: 40 ° C
Solvent: THF
Flow rate: 5 ml / min.
Detector: RI

  A fractionation method measures the elution time used as the peak molecular weight Mp of polar resin beforehand, and fractionates a low molecular weight component and a high molecular weight component before and after that. The solvent is removed from the collected sample to prepare a sample for acid value measurement.

  In the present invention, the acid value of the polar resin, the acid value α of the low molecular weight component, and the acid value β of the high molecular weight component are measured by the following methods.

The acid value is obtained from the following calculation formula.
Acid value = [(sample end point−blank end point) × 1.009 × 56 × 1/10] / sample mass

(Sample preparation)
Weigh accurately 1.0 g of sample in a 200 ml beaker, dissolve in 120 ml of toluene while stirring with a stirrer, and add 30 ml of ethanol.

(apparatus)
As an apparatus, for example, an automatic potentiometric titrator AT-400WIN (manufactured by Kyoto Electronics Industry Co., Ltd.) is used.

  The setting of the apparatus is intended for a sample dissolved in an organic solvent. The glass electrode and the comparative electrode to be used should be compatible with organic solvents.

  For example, product code # 100-H112 is used as the pH glass electrode. The tip is never dried.

  Cork type reference electrode uses product code # 100-R115. The tip is never dried. Check if the internal liquid is filled up to the internal liquid replenishment port. As the internal solution, a 3.3 mol / KCl solution is used.

(procedure)
The adjusted sample is set in the autosampler of the apparatus, and the electrode is immersed in the sample solution. Next, a titrant (1/10 N KOH (ethanol solution)) is set on the sample solution, and 0.05 ml is added dropwise by automatic intermittent titration to calculate the acid value.

  The glass transition temperature Tg of the polar resin in the present invention is measured under the following conditions and determined from the peak position of the DSC curve at the first temperature increase.

(Measurement condition)
・ Equilibrium at 20 ° C. for 5 minutes ・ Modulation of 1.0 ° C./min is applied and the temperature is increased to 140 ° C. at 1 ° C./min. ・ Equilibration is maintained at 140 ° C. for 5 minutes.

  A differential scanning calorimeter (DSC measuring apparatus) is measured as follows according to ASTM D3418-82 using DSC-7 (manufactured by PerkinElmer), DSC2920 (manufactured by TA Instruments Japan) and the like. The sample to be measured is precisely weighed from 2 to 5 mg, preferably 3 mg. It is put in an aluminum pan, and an empty aluminum pan is used as a control, and measurement is performed at a temperature rising rate of 1 ° C./min between a measurement range of 20 to 140 ° C.

  The glass transition temperature here is a value determined by the midpoint method.

  Next, an example of an image forming method using the toner of the present invention will be described with reference to FIGS.

  FIG. 2 shows the configuration of the image forming apparatus including the image forming method used in the present embodiment. The image forming apparatus shown in FIG. 2 is a laser beam printer using a transfer type electrophotographic process. In particular, FIG. 2 shows a cross-sectional view of a tandem color LBP (color laser printer).

  In FIG. 2, reference numeral 101 (101a to 101d) denotes a drum-type electrophotographic photosensitive member (hereinafter referred to as a photosensitive drum) as a latent image carrier that rotates in a direction indicated by an arrow (counterclockwise) at a predetermined process speed. . The photosensitive drums 101a, 101b, 101c, and 101d sequentially share the yellow (Y) component, magenta (M) component, cyan (C) component, and black (Bk) component of the color image.

  Hereinafter, the Y, M, C, and Bk image forming apparatuses are referred to as a unit a, a unit b, a unit c, and a unit d, respectively.

  These photosensitive drums 101a to 101d are rotationally driven by a drum motor (DC servo motor) (not shown), but independent driving sources may be provided for the respective photosensitive drums 101a to 101d. The rotational drive of the drum motor is controlled by a DSP (digital signal processor) (not shown), and other controls are performed by a CPU (not shown).

  The electrostatic adsorption conveyance belt 109a is stretched around a driving roller 109b, fixed rollers 109c and 109e, and a tension roller 109d. The electrostatic adsorption conveyance belt 109a is rotationally driven by the driving roller 109b in the direction of the arrow in the figure to adsorb and convey the recording medium S. To do.

  Hereinafter, unit a (yellow) of the four colors will be described as an example.

  The photosensitive drum 101a is uniformly charged to a predetermined polarity and potential by the primary charging means 102a during its rotation. The photosensitive drum 101a is exposed to a light image by a laser beam exposure means (hereinafter referred to as a scanner) 103a, and an electrostatic latent image of image information is formed on the photosensitive drum 101a.

  Next, a toner image is formed on the photosensitive drum 101a by the developing unit 104a, and the electrostatic latent image is visualized. Similar steps are performed for the other three colors (magenta (B), cyan (C), and black (Bk)).

  Thus, the four color toner images are synchronized with the photosensitive drums 101a to 101d by the registration rollers 108c that stop and re-transport the recording medium S conveyed by the paper feed roller 108b at a predetermined timing. The toner images are sequentially transferred onto the recording medium S at the nip portion with the belt 109a. At the same time, the photosensitive drums 101a to 101d after the transfer of the toner image to the recording medium S are subjected to repeated image formation by removing residual deposits such as transfer residual toner by the cleaning means 106a, 106b, 106c and 106d. .

  The recording medium S on which the toner images are transferred from the four photosensitive drums 101a to 101d is separated from the surface of the electrostatic attraction / conveyance belt 109a by the driving roller 109b and sent to the fixing device 110, and the toner image is fixed by the fixing device 110. Then, the sheet is discharged to the discharge tray 113 by the discharge roller 110c.

  Next, a specific example of an image forming method using a non-magnetic one-component contact developing method that can be applied to the present invention will be described with reference to an enlarged view of the developing portion (FIG. 1). In FIG. 1, the developing unit 13 is located in a developer container 23 containing a nonmagnetic toner 17 as a one-component developer, and an opening extending in the longitudinal direction in the developer container 23. A photosensitive drum) 10 and a toner carrier 14 disposed opposite to each other, and the electrostatic latent image on the latent image carrier 10 is developed and visualized. The latent image carrier contact charging member 11 is in contact with the latent image carrier 10. The bias of the latent image carrier contact charging member 11 is applied by a power source 12.

  The toner carrier 14 is horizontally provided with the substantially right half-periphery surface shown in the drawing through the opening into the developer container 23 and the left substantially half-periphery surface exposed outside the developer container 23. The surface exposed to the outside of the developer container 23 is in contact with the latent image carrier 10 located on the left side of the developing unit 13 as shown in FIG.

  The toner carrier 14 is rotationally driven in the direction of arrow B, the peripheral speed of the latent image carrier 10 is 50 to 170 mm / s, and the peripheral speed of the toner carrier 14 is 1 to 2 with respect to the peripheral speed of the latent image carrier 10. It is rotating at twice the peripheral speed.

  At a position above the toner carrier 14, a metal plate such as SUS, a rubber material such as urethane or silicone, a metal thin plate of SUS or phosphor bronze having spring elasticity, and a contact surface side to the toner carrier 14. A restricting member 16 made of a rubber material and the like is supported on the restricting member support metal plate 24 and is provided so that the vicinity of the free end side is in contact with the outer peripheral surface of the toner carrying member 14 by surface contact. The contact direction is a so-called counter direction in which the tip side with respect to the contact portion is located upstream of the rotation direction of the toner carrier 14. As an example of the regulating member 16, a plate-like urethane rubber having a thickness of 1.0 mm is bonded to the regulating member support sheet metal 24, and the contact pressure (linear pressure) with respect to the toner carrier 14 is appropriately set. is there. The contact pressure is preferably 20 to 300 N / m. The measurement of the contact pressure is converted from a value obtained by inserting three metal thin plates with known friction coefficients into the contact portion and pulling out the central one with only a spring. The regulating member 16 having a rubber material or the like bonded to the abutting surface is desirable in terms of adhesion to the toner, and can suppress the fusion and fixing of the toner to the regulating member in long-term use. Further, the restricting member 16 may be in contact with the toner carrier 14 by edge contact in which the tip is contacted. 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.

  The toner supply roller 15 is in contact with the contact portion of the regulating member 16 with the surface of the toner carrier 14 on the upstream side in the rotation direction of the toner carrier 14 and is rotatably supported. The contact width of the toner supply 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 charging roller 29 is not essential for the image forming method of the present invention, but is preferably installed. The 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 charging roller 29 on the toner carrier 14 by the suppressing member 30 is set to 0.49 to 4.9N. Due to the contact of the charging roller 29, the toner layer on the toner carrier 14 is finely filled and uniformly coated. The longitudinal positional relationship between the regulating member 16 and the charging roller 29 is preferably arranged so that the charging roller 29 can reliably cover the entire contact area of the regulating member 16 on the toner carrier 14.

  Further, for the driving of the charging roller 29, a driven or the same peripheral speed is indispensable between the charging roller 29 and the toner carrier 14, and if a peripheral speed difference occurs between the charging roller 29 and the toner carrier 14, the toner coat becomes uneven. This is not preferable because unevenness occurs on the image.

  The bias of the charging roller 29 is applied by a power source 27 between the toner carrier 14 and the latent image carrier 10 in a direct current (27 in FIG. 1), and the nonmagnetic toner 17 on the toner carrier 14 is charged by the charging roller. From 29, charge is applied by discharge.

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

  After being charged by the charging roller 29, the toner layer formed as a thin layer on the toner carrier 14 is uniformly conveyed to a developing unit that is a portion facing the latent image carrier 10.

  In this developing unit, the toner layer formed as a thin layer on the toner carrier 14 is transferred to the latent image by a DC bias applied between the toner carrier 14 and the latent image carrier 10 by the power source 27 shown in FIG. The electrostatic latent image on the carrier 10 is developed as a toner image.

  The present invention will be specifically described with reference to the following examples. In the following, the method for producing wax, styrenic polar resin and toner will be described. In the examples and comparative examples, all parts are based on mass unless otherwise specified.

(Wax Production Example 1)
Vacuum distillation is performed at 0.2 mmHg and 250 ° C. using HNP-51 (manufactured by Nippon Seiki Co., Ltd.). When the low molecular weight component is distilled off 20% of the whole, the distillation is stopped and the wax A is obtained by cooling. Obtained.

(Wax Production Example 2)
In Wax Production Example 1, wax B was obtained in the same manner except that 5% of the low molecular weight component was cut.

(Wax Production Example 3)
Wax C was obtained by the same method except that HNP-9 (manufactured by Nippon Seiki Co., Ltd.) was used in Wax Production Example 1 and the low molecular weight component was cut by 10%.

  HNP-51 is referred to as wax D.

  Table 1 shows physical property values of the waxes A to D.

(Production Example 1 of Styrenic Polar Resin)
300 parts of xylene (boiling point 144 ° C.) is put into a flask capable of being pressurized and depressurized, and the inside of the container is sufficiently replaced with nitrogen while stirring, and then heated to reflux.

Under this reflux,
-Styrene 95.8 parts-Methyl methacrylate 2.5 parts-Methacrylic acid 1.7 parts-Di-tert-butyl peroxide 2.0 parts mixed solution, and then the polymerization temperature is 175 ° C, during the reaction The polymerization was carried out at a pressure of 0.100 MPa for 5 hours. Then, the solvent removal process was performed for 3 hours under reduced pressure, xylene was removed, and the polar resin A was obtained by grinding.

(Production Example 2 of Styrenic Polar Resin)
In Production Example 1 of Styrenic Polar Resin, Production was conducted in the same manner except that the polymerization temperature was changed to 198 ° C. to obtain Polar Resin B.

(Production Example 3 of Styrenic Polar Resin)
In the production example 1 of the styrenic polar resin, a polar resin C was obtained in the same manner except that the polymerization temperature was changed to 165 ° C.

(Production Example 4 of Styrenic Polar Resin)
A polar resin D was obtained in the same manner as in Production Example 1 of Styrenic Polar Resin except that the addition amount of di-tert-butyl peroxide was changed to 1.0 part.

(Production Example 5 of Styrenic Polar Resin)
A polar resin E was obtained in the same manner as in Production Example 1 of Styrenic Polar Resin except that the addition amount of di-tert-butyl peroxide was changed to 3.5 parts.

(Production Example 6 of Styrenic Polar Resin)
In Production Example 1 of Styrenic Polar Resin, Production was performed in the same manner except that the polymerization temperature was changed to 210 ° C., and Polar Resin F was obtained.

(Production Example 7 of Styrenic Polar Resin)
In Production Example 1 of Styrenic Polar Resin, Production was performed in the same manner except that the polymerization temperature was changed to 145 ° C., and Polar Resin G was obtained.

(Production Example 8 of Styrenic Polar Resin)
In the production example 1 of the styrenic polar resin, the polymerization temperature was changed to 165 ° C., and the polar resin was produced in the same manner except that the addition amount of di-tert-butyl peroxide was changed to 0.5 part. H was obtained.

(Production Example 9 of Styrenic Polar Resin)
Produced in the same manner except that the polymerization temperature was changed to 165 ° C. and the addition amount of di-tert-butyl peroxide was changed to 4.0 parts in the production example 1 of the styrenic polar resin. I was obtained.

  Table 2 shows the physical properties of the polar resins A to I.

[Example 1]
-Styrene 42.0 parts-C.I. I. Pigment Blue 15: 3 7.0 parts / sulfonic acid group-containing resin (acrylic base FCA-1001-NS, manufactured by Fujikura Kasei)
1.0 part The said material was disperse | distributed for 3 hours using the star mill LMZ type 2 (made by Ashizawa Finetech), and the pigment dispersion composition was prepared.

Moreover, the following material was melt | dissolved with the propeller type stirring apparatus with another container, and the resin solution was prepared.
-Styrene 30.0 parts-n-Butyl acrylate 28.0 parts-Polar resin A 20.0 parts-Polyester resin 5.0 parts (Terephthalic acid-propylene oxide modified bisphenol A (2 mole adduct) -ethylene oxide modified bisphenol A (2 mol adduct) (molar ratio 50:30:20); acid value 9; glass transition point 60 ° C. Mw = 10000, Mw / Mn = 3.20)

  Further, 900 parts of ion-exchanged water heated to 60 ° C., 2.5 parts of tricalcium phosphate, 11 parts of 10% hydrochloric acid are added to a separate container, and 10 parts are added using a TK homomixer (made by Special Machine Industries). The mixture was stirred at 1,000 rpm to obtain an aqueous medium.

  Next, after adding the pigment dispersion composition, the resin solution, 9.0 parts of wax A and 0.075 part of divinylbenzene, the temperature was raised to 60 ° C., and dispersion and mixing were performed for 30 minutes.

  The polymerization initiator tert-butyl peroxy 2-ethylhexanoate 8.0 part was melt | dissolved in this, and the polymerizable monomer composition was prepared. The polymerizable monomer composition is charged into the aqueous medium, and stirred at 10,000 rpm for 10 minutes with a TK homomixer at a temperature of 60 ° C. in a nitrogen atmosphere to prepare the polymerizable monomer composition. After granulation, the temperature was raised to 70 ° C. while stirring with a paddle stirring blade. After reacting for 5 hours, the temperature was further raised to 80 ° C. and reacted for 3 hours. After cooling, hydrochloric acid was added to adjust the pH to 1.4 and stirred for 3 hours. The toner particles were separated by filtration, washed with water, and dried at a temperature of 40 ° C. for 48 hours to obtain toner particles.

  To toner particles (100.0 parts), 1.5 parts of hydrophobic silica fine powder (number average primary particle size: 16 nm) surface-treated with dimethyl silicone oil is mixed for 10 minutes with a Henschel mixer (Mitsui Mining Co., Ltd.). Thus, toner (A) was obtained.

[Example 2]
A toner (B) was obtained in the same manner as in Example 1 except that the wax A was changed to the wax B.

Example 3
In Example 1, the same method except that the amount of styrene added in adjusting the resin solution was changed to 32.0 parts, the amount of n-butyl acrylate added was changed to 26.0 parts, and wax A was changed to wax C. Thus, toner (C) was obtained.

Example 4
A toner (D) was obtained in the same manner as in Example 1 except that the amount of styrene added when preparing the resin solution was changed to 28.0 parts and the amount of n-butyl acrylate added was changed to 32.0 parts.

Example 5
A toner (E) was obtained in the same manner as in Example 1 except that the addition amount of divinylbenzene was changed to 0.10 parts.

Example 6
A toner (F) was obtained in the same manner as in Example 1 except that the addition amount of divinylbenzene was changed to 0.050 part.

Example 7
A toner (G) was obtained in the same manner as in Example 1 except that the amount of 10% hydrochloric acid added to obtain an aqueous medium was 13 parts.

Example 8
In Example 1, a toner (H) was obtained in the same manner except that the amount of 10% hydrochloric acid added to obtain an aqueous medium was 9 parts.

Example 9
A toner (I) was obtained in the same manner as in Example 1 except that the polar resin A was changed to the polar resin B.

Example 10
A toner (J) was obtained in the same manner as in Example 1 except that the polar resin A was changed to the polar resin C.

Example 11
A toner (K) was obtained in the same manner as in Example 1 except that the polar resin A was changed to the polar resin D.

Example 12
A toner (L) was obtained in the same manner as in Example 1 except that the polar resin A was changed to the polar resin E.

Example 13
A toner (M) was obtained in the same manner as in Example 1 except that the polar resin A was changed to the polar resin F.

Example 14
A toner (N) was obtained in the same manner as in Example 1 except that the polar resin A was changed to the polar resin G.

Example 15
A toner (O) was obtained in the same manner as in Example 1 except that the polar resin A was changed to the polar resin H.

Example 16
A toner (P) was obtained in the same manner as in Example 1 except that the polar resin A was changed to the polar resin I.

Example 17
A toner (Q) was obtained in the same manner as in Example 1 except that the polar resin A was not used.

Example 18
In Example 18, a toner was produced by the emulsion aggregation method described below.

<Preparation of resin fine particle dispersion>
・ Styrene 72.0 parts ・ n-butyl acrylate 28.0 parts ・ Polar resin A 20.0 parts ・ Sulphonic acid group-containing resin (Acrybase FCA-1001-NS, manufactured by Fujikura Kasei))
1.0 parts The above components are mixed and dissolved, while 6 parts of nonionic surfactant (Nonipol 400, manufactured by Kao) and 10 parts of anionic surfactant (Neogen SC, manufactured by Daiichi Kogyo Seiyaku) are ion-exchanged. What was dissolved in 500 parts of water was placed in a flask, and the above mixed solution was added and dispersed and emulsified, and 50 parts of an ion exchange solution in which 4 parts of ammonium persulfate was dissolved while slowly stirring and mixing for 10 minutes. Was introduced. Next, after sufficiently replacing the inside of the system with nitrogen, the flask was heated with an oil bath until the temperature reached 70 ° C. while stirring, and emulsion polymerization was continued for 5 hours. Thereby, an anionic resin fine particle dispersion was obtained.

<Preparation of colorant particle dispersion>
・ C. I. Pigment Blue 15: 3 7.0 parts, nonionic surfactant (Nonipol 400, manufactured by Kao) 1.0 part, ion-exchanged water 100.0 parts The above ingredients are mixed and dissolved, and a homogenizer (Ultra Turrax manufactured by IKA). Was dispersed for 10 minutes to obtain a colorant particle dispersion.

<Preparation of release agent particle dispersion>
-Wax A 9.0 parts-Cationic surfactant (Sanisol B50, manufactured by Kao) 5.0 parts-Ion-exchanged water 200.0 parts The above ingredients are heated to a temperature of 95 ° C, and the IKA Ultra Turrax T50 is used. After sufficiently dispersing, dispersion treatment was performed with a pressure discharge homogenizer to obtain a release agent particle dispersion.

<Preparation of fine particle dispersion for shell formation>
5.0 parts of the polyester resin used in Example 1 was dissolved in 50.0 parts of ethyl acetate. The emulsified solution was emulsified with IKA Ultra Turrax T50, and the solvent was removed by heating at 80 ° C. and holding for 6 hours to obtain a shell-forming fine particle dispersion.

<Production of toner particles>
The resin fine particle dispersion, the colorant particle dispersion, the release agent particle dispersion, and 1.2 parts of polyaluminum chloride are mixed, and an IKA Ultra Turrax T50 is used in a round stainless steel flask. After sufficiently mixing and dispersing, the flask was heated to a temperature of 51 ° C. with stirring in an oil bath for heating. After maintaining at a temperature of 51 ° C. for 60 minutes, the above-mentioned fine particle dispersion for shell formation was added thereto. Then, after adjusting the pH in the system to 6.5 using a sodium hydroxide aqueous solution having a concentration of 0.5 mol / L, the stainless steel flask was sealed, and the stirring shaft seal was magnetically sealed while stirring was continued. Heated to a temperature of 97 ° C. and held for 3 hours. After completion of the reaction, the mixture was cooled, filtered and thoroughly washed with ion exchange water, and then solid-liquid separation was performed by suction filtration. This was further redispersed using ion-exchanged water at a temperature of 40 ° C., and stirred and washed at 300 rpm for 15 minutes. This washing operation was further repeated 5 times, and then solid-liquid separation was performed by suction filtration. Subsequently, it was dried at a temperature of 40 ° C. for 48 hours to obtain toner particles.

  To toner particles (100.0 parts), 1.5 parts of hydrophobic silica fine powder (number average primary particle size: 16 nm) surface-treated with dimethyl silicone oil is mixed for 10 minutes with a Henschel mixer (Mitsui Mining Co., Ltd.). Thus, toner (R) was obtained.

[Comparative Example 1]
A toner (a) was obtained in the same manner as in Example 1 except that the wax A was changed to the wax D and the polar resin A was changed to the polar resin F.

[Comparative Example 2]
In Example 1, the amount of styrene added to adjust the resin solution was changed to 34.0 parts, the amount of n-butyl acrylate added was changed to 24.0 parts, the polar resin A was changed to the polar resin F, and the amount of divinylbenzene added. Was changed to 0.12 parts. Further, a toner (b) was obtained by the same method except that 10% hydrochloric acid which was added when obtaining an aqueous medium was not added.

[Comparative Example 3]
In Example 1, the amount of styrene added in preparing the resin solution was changed to 28.0 parts, the amount of n-butyl acrylate added was changed to 30.0 parts, the polar resin A was changed to the polar resin G, and divinylbenzene was added. A toner (c) was obtained in the same manner except that the amount was changed to 0.03 parts.

[Comparative Example 4]
In Example 1, the amount of styrene added in preparing the resin solution was changed to 26.0 parts, the amount of n-butyl acrylate added was changed to 32.0 parts, the polar resin A was changed to the polar resin G, and divinylbenzene was added. A toner (d) was obtained in the same manner except that the amount was changed to 0.03 parts.

  Table 3 shows the toner physical properties of Examples 1 to 18 and Comparative Examples 1 to 4.

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

<Evaluation for developability>
As an image forming apparatus, a commercially available laser printer LBP-5400 (made by Canon) is used, and an A4 color laser is used at a temperature of 15 ° C., a relative humidity of 10% and a temperature of 0 ° C., a relative humidity of 5%. Copier paper (manufactured by Canon, 80 g / m ² ) was used. A schematic diagram of the developing device is shown in FIGS.

The remodeling points of the evaluation machine are as follows.
(1) The process speed was set to 190 mm / sec by changing the gear and software of the evaluation machine main body.
(2) A commercially available cyan cartridge was used as the cartridge for evaluation, and the contact pressure between the cleaning blade and the photosensitive member was changed to 85% of the normal pressure.

  The product toner was extracted from this commercially available cyan cartridge, the inside was cleaned by air blow, and then 200 g of the toner according to the present invention was filled for evaluation. In addition, the product toner was extracted from each of the magenta, yellow, and black stations, and evaluation was performed by inserting magenta, yellow, and black cartridges in which the toner remaining amount detection mechanism was disabled.

  Printing was performed continuously on a chart with a printing ratio of 2%, and evaluation was performed at the initial stage (first sheet) and at the time of 6000 sheets, and image density / filming / cleanability was confirmed by the following method.

(Image density)
The image density was measured by using a “Macbeth reflection densitometer RD918” (manufactured by Macbeth) to measure a relative density with respect to an image of a white background portion having a document density of 0.00.

Evaluation criteria A: 1.40 or more B: 1.30 or more and less than 1.40 C: 1.20 or more and less than 1.30 D: 1.10 or more and less than 1.20

(Parts contamination)
The member contamination was evaluated based on the following criteria by visually observing the state of toner and external additives adhering to the surface of the developer carrying member and the effect on the obtained image.
Evaluation criteria A: Not generated (no sticking)
B: Although sticking occurs slightly, the influence on the image is small. C: Sticking occurs, and image unevenness is slightly caused by this, but there are few problems in practical use.
D: There is a large amount of fixation, resulting in image unevenness. There are also practical problems.

(Cleaning failure)
For the evaluation of the cleaning property, the degree of dirt on the solid white image and the degree of dirt on the electrostatic image bearing member after the solid white image was produced were evaluated.

Evaluation criteria A: A clear image quality with no problem on the image, and no stain on the image carrier.
B: A cleaning property in which an image having no problem on the image can be obtained, but the image carrier is slightly stained.
C: Cleanability with no problem in practical use.
D: Dirt is observed on the image and the image bearing member, and cleaning properties which are not preferable for practical use.

<Evaluation on in-flight contamination>
In-machine contamination was evaluated by printing 6000 sheets in a normal temperature and humidity environment (25 ° C, 50%), replacing the newly prepared cyan cartridge, printing 6000 sheets again, and repeating this three times. The extent of the surrounding dirt was evaluated.

Evaluation Criteria A: The image quality is clear with no problem on the image, and no dirt is seen in the entire machine.
B: Image quality with no problem on the image can be obtained, but dirt is seen around the fixing device.
C: Dirt is observed on the fixing roller, which causes slight image unevenness, but there are few problems in practical use.
D: Dirt is seen in the fixing roller and the sensor around the fixing device, and there is a problem in practical use.

<Evaluation on storage stability>
(Blocking test)
10 g of toner was placed in a 50 cc polycup. The state of the toner when left in a constant temperature bath at 55 ° C. for 72 hours was visually judged as follows.

Evaluation criteria A: No blocking at all, almost the same as the initial state.
B: Slightly agglomerated, but collapsed by the rotation of the polycup, and there is no particular problem.
C: Although it looks agglomerated, it is in a state where it is broken by hand and has few problems in practical use.
D: Aggregation is intense (solidification).

  Table 4 shows the results of evaluating the toners (A) to (R) and the toners (a) to (d) by the above evaluation method.

  10 latent image carrier (photosensitive drum), 11 latent image carrier contact charging member, 12 power supply, 13 developing unit, 14 toner carrier, 15 toner supply roller, 16 regulating member, 17 non-magnetic toner, 23 developer container, 24 regulating member support sheet metal, 27 power source, 29 charging roller, 30 suppression member, 101a to d photosensitive drum, 102a to d primary charging unit, 103a to d scanner, 104a to d developing unit, 106a to d cleaning unit, 108b Roller, 108c Registration roller, 109a Electrostatic adsorption conveyance belt, 109b Driving roller, 109c Fixed roller, 109d Tension roller, 110 Fixing device, 110c Discharge roller, 113 Discharge tray, S Recording medium

Claims (3)

Toner particles containing a binder resin, a polyester resin, a colorant and a hydrocarbon wax ;
Inorganic fine powder ,
A toner having
The toner has an average circularity of 0.970 or more and 0.995 or less;
In the DSC curve at the time of temperature rise measured by a differential scanning calorimetry (DSC) apparatus, the maximum endothermic peak temperature of the hydrocarbon wax is 70 ° C. or more and 120 ° C. or less,
In the hydrocarbon desorption-GC / MS analysis of the hydrocarbon wax, the concentration in terms of hexadecane based on the hydrocarbon wax mass with respect to volatile components detected after the peak detection time of hexadecane at a heating temperature of 200 ° C. for a heating time of 10 minutes. There is less than or equal to 1100ppm,
Wherein in a dynamic viscoelasticity test of the toner, the storage elastic modulus at a temperature of 70 ° C. is (G _'70), is in the range of 1.0 × 10 ⁵ (Pa) or 1.0 × 10 ⁸ (Pa) or less, 110 toner storage modulus (G _'110), characterized in that in the range of 1.0 × 10 ⁴ (Pa) or 2.0 × 10 ⁵ (Pa) or less at ° C.. The toner particles add a polymerizable monomer composition containing a polymerizable monomer to an aqueous medium, and form particles of the polymerizable monomer composition in the aqueous medium. the toner according to claim 1, wherein the toner particles obtained by polymerizing the polymerizable monomer contained in the particles of the composition. The toner particles further comprises a styrene-based polar resin,
When the Mp a peak molecular weight of the styrene polar resin, Mp is, it is 1.0 × 10 ⁴ or more 3.0 × 10 ⁴ or less,
The acid value of the low molecular weight component (region where the molecular weight is less than the peak molecular weight Mp) is α (mg KOH / g), and the acid value of the high molecular weight component (the region where the molecular weight is the peak molecular weight Mp or more) is β (mg KOH / g). when, alpha / beta is, toner according to claim 2 satisfying 0.80 to 1.20.

Images