JP4498078B2 - Color toner and full color image forming method using the color toner - Google Patents

Description

  The present invention relates to a toner 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 recent years, copying machines and printers are required to be smaller, lighter, faster, and more reliable due to demands for space saving and energy saving. As a result, the hardware configuration is configured with simple elements in various respects, whereas the performance required for the toner is higher. In other words, excellent hardware cannot be provided unless the toner performance can be improved. In particular, transfer performance is required for the performance of the toner. By improving the toner transfer capability, it is possible to obtain merits such as toner consumption reduction, high image quality, and simplification of the toner recovery system.

  Therefore, in recent years, as one of the techniques for improving the transfer capability of toner, it has been performed to make the shape of the toner close to a spherical shape. For example, a polymerized toner produced by a polymerization method such as suspension polymerization or emulsion polymerization is used, a pulverized toner is spheroidized in a solution, or spheroidized by hot air (for example, see Patent Document 1). And spheroidizing with a mechanical impact force (for example, see Patent Document 2). These techniques are very effective means for improving the transfer performance of the toner, but each has various problems. When a polymerized toner is used, the release agent is encapsulated in the toner. Therefore, if the pressure is not applied to the toner at the time of fixing, the release agent is less likely to come out on the toner surface and the fixing ability may be deteriorated. . In addition, when the pulverized toner is spheroidized by mechanical impact force, the more the spheronization is progressed, the more easily the release agent contained in the toner is eluted on the toner surface by heat, which adversely affects the electrophotographic characteristics. May affect. That is, when the release agent is eluted on the toner surface, the fluidity of the toner is deteriorated, and the adhesion between the toners and / or between the toner and the carrier is increased, so that the transfer ability is impaired. . Therefore, in the spheronization of the toner internally containing the release agent, it is important to select a toner constituent material that is easily spheroidized and to suppress the influence of the thermal history on the toner during the spheronization process. .

  As described above, in order to make full use of the toner having an improved sphericity and internally added with a release agent, for example, Patent Document 3 controls the average circularity and circularity distribution of the toner, and the transfer capability of the toner. It has also been proposed to control the charging ability. However, in Patent Document 3, a styrene-acrylic resin is used as the binder resin used in the toner, and no mention is made of a color toner containing polyester as a main component.

  Further, in the process of spheroidizing toner, particularly in the process of spheronizing toner by mechanical impact, very small fine powder (ultra fine powder) is likely to be generated, and these super fine powder reaggregates with the spheroidized toner. Even if a classification step is performed after the step of spheroidizing the toner, it is difficult to remove the ultrafine powder from the toner, and the toner is easily mixed into the product. The ultra fine powder is excessively charged in the developing process, and may contaminate the carrier in the sleeve or the two-component developing system due to electrostatic adhesion, thereby causing a charging failure of the toner supplied later.

  Many proposals have been made to reduce the amount of ultrafine powder. For example, Patent Document 4 and Patent Document 5 propose a method of driving ultrafine powder onto the toner surface by mechanical impact after the classification process. However, agitation in the developing section and the toner container due to long-term durability may cause peeling of the super fine powder hitting the toner surface, which may adversely affect the developability.

From the above, color toners having excellent transfer ability, durability and charging characteristics have been demanded for color toners containing a release agent.
JP 2000-029241 A Japanese Patent Application Laid-Open No. 07-181732 Japanese Patent Laid-Open No. 10-097095 Japanese Patent Laid-Open No. 10-232507 JP-A-11-149174

  An object of the present invention is to provide a toner that solves the above problems. That is, an object of the present invention is to provide a color toner excellent in transfer characteristics, development characteristics and durability stability by controlling the particle shape and surface properties of toner particles, and a full color image forming method using the toner. .

That is, an object of the present invention is a color toner having toner particles containing at least a binder resin, a colorant and a release agent, and inorganic fine particles.
(I) The average circularity of toner particles having an equivalent circle diameter of 3.00 μm or more in the toner particles is 0.920 or more and less than 0.950,
(Ii) The number frequency cumulative value with a circularity of 0.960 or more in the toner particles having an equivalent circle diameter of 3.00 μm or more in the toner particles is 35% or less,
(Iii) The number frequency cumulative value of circularity of 0.920 or less in toner particles having an equivalent circle diameter of 3.00 μm or more in the toner particles is 25% or less,
(Iv) In the particle size distribution of the equivalent circle diameter of the toner particles, the abundance A (number%) of toner particles having an equivalent circle diameter of 0.60 μm or more and less than 3.00 μm with respect to all toner particles is 0.1 ≦ A <. Meets 15.0,
(V) In the particle size distribution of the equivalent circle diameter of the toner particles, the abundance B (number%) of toner particles having an equivalent circle diameter of 0.60 μm or more and less than 2.00 μm with respect to all toner particles, and 2.00 μm or more and 3 The abundance C (number%) of toner particles having an equivalent circle diameter of less than 0.000 μm with respect to all toner particles satisfies 0.5 <B / C <4.0,
The average surface roughness measured with a scanning probe microscope of the toner particles, Ri 35.0nm less der than 5.0 nm, a binder resin is a polyester unit, the toner particles, surface modification step The surface modification step is performed using a batch-type surface modification device, and the batch-type surface modification device continuously discharges particles having a predetermined particle size or less to the outside of the device. Classifying means to be removed, surface treatment means using mechanical impact force, and guide means for partitioning a space between the classification means and the surface treatment means into a first space and a second space, The finely pulverized product is introduced into the first space, and fine particles having a predetermined particle diameter or less are continuously discharged out of the apparatus by the classifying means, and the mechanical impact force is used via the second space. Introduce into surface treatment means, perform surface modification treatment, and circulate again to the first space And the present invention is to provide a color toner characterized by step der Rukoto repeating the surface modification treatment using a predetermined time classification and a mechanical impact force.

Another object of the present invention is a full-color image forming method for forming an image using at least a magenta toner, a yellow toner, a cyan toner and a black toner,
At least one color toner selected from the group consisting of the magenta toner, the yellow toner, the cyan toner and the black toner is a toner particle containing at least a binder resin, a colorant and a release agent, and inorganic fine particles A color toner having
(I) The average circularity of toner particles having an equivalent circle diameter of 3.00 μm or more of the toner particles is 0.920 or more and less than 0.950,
(Ii) The number frequency cumulative value of circularity of 0.960 or more in toner particles having an equivalent circle diameter of 3.00 μm or more of the toner particles is 35% or less,
(Iii) a color toner in which the toner particle having an equivalent circle diameter of 3.00 μm or more of the toner particles has a circularity of 0.920 or less and a number frequency cumulative value of 25% or less;
(Iv) In the particle size distribution of the equivalent circle diameter of the toner particles, the abundance A (number%) of toner particles having an equivalent circle diameter of 0.60 μm or more and less than 3.00 μm with respect to all toner particles is 0.1 ≦ A <. Meets 15.0,
(V) In the particle size distribution of the equivalent circle diameter of the toner particles, the abundance B (number%) of toner particles having an equivalent circle diameter of 0.60 μm or more and less than 2.00 μm with respect to all toner particles, and 2.00 μm or more and 3 The abundance C (number%) of toner particles having an equivalent circle diameter of less than 0.000 μm with respect to all toner particles satisfies 0.5 <B / C <4.0,
The average surface roughness measured with a scanning probe microscope of the toner particles, Ri 35.0nm less der than 5.0 nm, a binder resin is a polyester unit, the toner particles, surface modification step The surface modification step is performed using a batch-type surface modification device, and the batch-type surface modification device continuously discharges particles having a predetermined particle size or less to the outside of the device. Classifying means to be removed, surface treatment means using mechanical impact force, and guide means for partitioning a space between the classification means and the surface treatment means into a first space and a second space, The finely pulverized product is introduced into the first space, and fine particles having a predetermined particle diameter or less are continuously discharged out of the apparatus by the classifying means, and the mechanical impact force is used via the second space. Introduce into surface treatment means, perform surface modification treatment, and circulate again to the first space And the present invention is to provide a full-color image forming method comprising the steps der Rukoto repeating the surface modification treatment using a predetermined time classification and a mechanical impact force.

  According to the present invention, a color toner having excellent transfer characteristics, development characteristics, and durability stability can be provided by using a toner in which the particle shape and surface properties of toner particles are controlled. In addition, since it has a sufficient fixable region, sufficient developability can be obtained even in continuous durability, and sufficient cleaning can be easily performed, so that a high-quality image can be formed.

  Hereinafter, the present invention will be described in more detail with reference to preferred embodiments.

  First, the toner used in the present invention will be described.

In the present invention, the toner is a color toner having toner particles containing at least a binder resin, a colorant and a release agent, and inorganic fine particles,
(I) The average circularity of toner particles having an equivalent circle diameter of 3.00 μm or more of the toner particles is 0.920 or more and less than 0.950,
(Ii) the number frequency cumulative value of circularity of 0.960 or more in toner particles having an equivalent circle diameter of 3.00 μm or more of the toner particles is 40% or less;
(Iii) A color toner characterized in that the toner particles having an equivalent circle diameter of 3.00 μm or more of the toner particles have a number frequency cumulative value with a circularity of 0.920 or less of 30% or less.

  Further, it is preferable that the average circularity of toner particles having an equivalent circle diameter of 3.00 μm or more in the flow type particle image measuring apparatus is 0.925 or more and 0.940 or less. It is preferable that the number frequency cumulative value having a circularity of 0.960 or more in toner particles having an equivalent circle diameter of 3.00 μm or more is 35% or less. It is preferable that the number frequency cumulative value with a circularity of 0.920 or less in toner particles having an equivalent circle diameter of 3.00 μm or more is 25% or less.

  In the present invention, the color toner includes black toner.

  Here, when the circularity of toner particles having an equivalent circle diameter of 3.00 μm or more in the flow type particle image measuring apparatus is less than 0.920, the contact area between the toner particles and between the toner and the carrier is increased, and the toner is separated. Is inhibited, leading to deterioration of transcription ability. On the contrary, if the circularity of toner particles having an equivalent circle diameter of 3.00 μm or more in the flow type particle image measuring apparatus is 0.950 or more, the shape of the toner particles approaches a spherical shape, and the cleaning blade passes through the cleaning blade. In addition, frictional charging between the toners and between the toner and the carrier becomes difficult, resulting in an unclear image with a lot of fog and scattering on the non-image area.

  Further, when the cumulative number frequency value of circularity of 0.960 or more in toner particles having an equivalent circle diameter of 3.00 μm or more exceeds 40%, toner near a sphere increases, which causes cleaning failure. Further, when the cumulative number frequency of circularity of 0.920 or less in toner particles having an equivalent circle diameter of 3.00 μm or more exceeds 30%, transfer efficiency is deteriorated. Further, when the number frequency cumulative value with a circularity of 0.960 or more in a toner particle having an equivalent circle diameter of 3.00 μm or more exceeds 40% and the number frequency cumulative value with a circularity of 0.920 or less exceeds 30%, the toner Since the surface shape of the particles becomes broad and the contact area between the toner particles and the developer carrier and / or the photoreceptor increases, the toner charge leaks to the developer carrier and / or the photoreceptor. It tends to occur through the part in contact with the toner, and as a result, the charge amount of the toner may decrease. Further, the contact area between the toner particles and the photoconductor is increased, and the adhesion force of the toner particles to the photoconductor is increased, so that it is difficult to obtain sufficient transfer efficiency.

  That is, by controlling the average circularity of toner particles having an equivalent circle diameter of 3.00 μm or more in the flow type particle image measuring device within a range of 0.920 or more and less than 0.950, toners and / or toners The contact area between the toner and the carrier can be reduced, and the transfer ability and charging ability of the toner can be improved. Further, the number frequency cumulative value with a circularity of 0.960 or more in toner particles having an equivalent circle diameter of 3.00 μm or more is controlled to 40% or less, and the number frequency cumulative value with a circularity of 0.920 or less is controlled to 30% or less. Charge stability can be improved. Further, by combining the above physical properties, the contact area between the toner particles and the photoconductor is reduced, and the adhesion force of the toner particles to the photoconductor due to van der Waals force and the like is reduced, thereby further increasing the transfer efficiency. It was.

  Further, according to the present invention, in the particle size distribution of the equivalent circle diameter of the toner particles, the abundance A (number%) of toner particles having an equivalent circle diameter of 0.60 μm or more and less than 3.00 μm with respect to all toner particles is 0.1. It is preferable to satisfy ≦ A <15.0, more preferably 0.5 ≦ A <12.0, and still more preferably 1.0 ≦ A <10.0. When the abundance A (number%) of toner particles having an equivalent circle diameter of 0.60 μm or more and less than 3.00 μm with respect to all toner particles is less than 0.1 (number%), it is substantially free of fine powder. means. When the abundance A (number%) of toner particles having an equivalent circle diameter of 0.60 μm or more and less than 3.00 μm with respect to all toner particles is 15.0 (number%) or more, the developing sleeve and / or two components are formed by fine powder. Contamination of the carrier in the development system tends to cause toner charging failure.

  Further, according to the present invention, in the particle size distribution of the equivalent circle diameter of the toner particles, the abundance B (number%) of toner particles having an equivalent circle diameter of 0.60 μm or more and less than 2.00 μm with respect to all toner particles; The abundance C (number%) of toner particles having an equivalent circle diameter of 00 μm or more and less than 3.00 μm with respect to all toner particles preferably satisfies 0.5 <B / C <4.0.

  Toner particles having a circle-equivalent diameter of less than 3.00 μm are likely to collect selectively at the cleaning blade edge portion of the cleaning portion, and toner particles having a smaller circle-equivalent diameter of less than 2.00 μm are likely to accumulate at the edge tip. Toner particles with a circle equivalent diameter of 3.00 μm form a layer with a certain width along the cleaning blade, thereby blocking waste toner and paper dust and dust generated in the machine with the cleaning blade edge. And can be recovered without slipping through.

  However, when the amount of toner particles having an equivalent circle diameter of less than 2.00 μm becomes excessive, the toner particles having an equivalent circle diameter of less than 2.00 μm slip through the cleaning blade edge, and the slipped toner particles cause exposure and charging of the photoreceptor. It may hinder or promote disturbance of the latent image. Also, if toner particles with an equivalent circle diameter of 2.00 μm or more and less than 3.00 μm become excessive, the supply of toner particles with an equivalent circle diameter of less than 2.00 μm to the tip of the edge portion becomes insufficient, resulting in a sparse state, Drowning is likely to occur. The abundance B (number%) of toner particles having an equivalent circle diameter of 0.60 μm or more and less than 2.00 μm with respect to all toner particles and the abundance of toner particles having an equivalent circle diameter of 2.00 μm or more and less than 3.00 μm to all toner particles. By causing C (number%) to exist at the above ratio, the occurrence of cleaning failure is suppressed even during long-term use.

  When B / C is 0.5 or less, the ratio of toner particles having an equivalent circle diameter of 2.00 μm or more and less than 3.00 μm increases, which tends to cause cleaning defects such as blade chatter and stagnation. Further, when B / C is 4.0 or more, it means that the amount of toner particles having an equivalent circle diameter of less than 2.00 μm is large, and it tends to cause a cleaning failure such as blade slippage.

  The abundance B (number%) of toner particles having an equivalent circle diameter of 0.60 μm or more and less than 2.00 μm with respect to all toner particles is preferably 0.1 ≦ B <10.0, more preferably It is 0.5 <= B <8.0. Further, the abundance C (number%) of toner particles having an equivalent circle diameter of 2.00 μm or more and less than 3.00 μm with respect to all toner particles is preferably 0.1 ≦ C <5.0, more preferably It is 0.5 <= C <3.0.

  When B is 10.0% by number or more, slipping out of the cleaning blade is likely to occur for the above reason. In addition, when C is 5.0% by number or more, chattering or twisting of the cleaning blade is likely to occur.

  In the present invention, the average surface roughness of the toner particles measured with a scanning probe microscope is preferably 5.0 nm or more and less than 35.0 nm, more preferably 10.0 nm or more and less than 30.0 nm. More preferably, it is 15.0 nm or more and less than 30.0 nm. Since the toner particles have an appropriate average surface roughness (smoothness), appropriate voids are created between the toners, and the fluidity of the toner can be improved, and better developability can be obtained. it can. In particular, in the toner particles having an average circularity of the present invention, excellent fluidity can be imparted to the toner particles by having the average surface roughness. If the average surface roughness of the toner particles is less than 5.0 nm, the surface of the toner particles becomes too smooth and it becomes difficult for inorganic fine particles to adhere to the toner particles, and the fluidity of the toner tends to decrease due to durability and the image density may decrease. is there. When the average surface roughness of the toner particles is 35.0 nm or more, the irregularities on the surface of the toner particles become large, and the voids between the toner particles are excessively increased, so that the toner is likely to be scattered.

  The particle shape and surface property of the toner particles of the present invention are also affected by the selection of the binder resin that occupies most of the toner particles. In particular, controlling the ease of cracking of toner particles in the toner pulverization process greatly affects the average circularity of the toner. When a styrene-acrylic resin is used, the toner surface shape is easily pulverized and the degree of unevenness is large, and in order to obtain the particle shape and surface property of the toner of the present invention, a surface shape operation such as heat treatment is required. Undesirable in terms. In that respect, if the resin having at least a polyester unit is used as the binder resin, the pulverization property is inferior, but since the degree of unevenness can be suppressed by the circulation of the toner in the pulverizing apparatus, the level of irregularities can be suppressed to a low level. It is preferable in order to obtain the particle shape and surface property.

  The binder resin used in the present invention includes (a) a polyester resin, (b) a hybrid resin having a polyester unit and a vinyl polymer unit, (c) a mixture of the hybrid resin and the vinyl polymer, (d) A resin selected from the group consisting of a mixture of a polyester resin and a vinyl polymer, (e) a mixture of a hybrid resin and a polyester resin, and (f) a mixture of a hybrid resin, a polyester resin, and a vinyl polymer. Preferably there is. Further, the ratio of the resin having a polyester unit contained in the binder resin is preferably 30% by mass or more, more preferably 40% by mass or more, and still more preferably 50% by mass with respect to the total binder resin. % Or more.

  The “polyester unit” used in the present invention means a part derived from polyester. Specifically, the components constituting the polyester unit include a divalent or higher valent alcohol monomer component and a divalent or higher carboxylic acid. Acid monomer components such as divalent or higher carboxylic acid anhydrides and divalent or higher carboxylic acid esters. The “vinyl polymer unit” refers to a portion derived from a vinyl polymer, and a component constituting the vinyl polymer unit is a monomer component having a vinyl group.

  The toner of the present invention is characterized in that a component having these polyester units is used as a part of a raw material and a resin having a condensation-polymerized portion is used.

  When a polyester resin is used, alcohol and carboxylic acid, carboxylic anhydride or carboxylic acid ester can be used as raw material monomers. Specifically, for example, as the dihydric alcohol component, polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (3.3) -2,2-bis ( 4-hydroxyphenyl) propane, polyoxyethylene (2.0) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (2.0) -polyoxyethylene (2.0) -2,2 -Alkylene oxide adducts of bisphenol A such as bis (4-hydroxyphenyl) propane and polyoxypropylene (6) -2,2-bis (4-hydroxyphenyl) propane, ethylene glycol, diethylene glycol, triethylene glycol, 1, 2-propylene glycol, 1,3-propylene glycol, 1,4-butanedio , Neopentyl glycol, 1,4-butenediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, bisphenol A and hydrogenated bisphenol A.

  Examples of the trivalent or higher alcohol component include sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane and 1,3,5-trihydroxymethylbenzene It is done.

  Divalent carboxylic acid monomers include aromatic carboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid or anhydrides thereof; alkyl dicarboxylic acids such as oxalic acid, adipic acid, sebacic acid and azelaic acid or anhydrides thereof; And succinic acid or anhydride thereof substituted with 6 to 12 alkyl groups or alkenyl groups; unsaturated dicarboxylic acids such as fumaric acid, maleic acid and citraconic acid or anhydrides thereof.

  Examples of the trivalent or higher carboxylic acid monomer component include trimellitic acid, pyromellitic acid, vinzophenone tetracarboxylic acid and polyvalent carboxylic acids such as anhydrides thereof.

  Examples of other monomers include polyhydric alcohols such as oxyalkylene ethers of novolak type phenol resins.

  Among them, in particular, a bisphenol derivative represented by the following formula (1) is used as a diol component, and a carboxylic acid component (for example, fumaric acid, a carboxylic acid having two or more valences or an acid anhydride thereof, or a lower alkyl ester thereof). A polyester resin obtained by condensation polymerization of maleic acid, maleic anhydride, phthalic acid, terephthalic acid, trimellitic acid or pyromellitic acid) as an acid component is preferable as a color toner because it has good charging characteristics.

  Furthermore, when a binder resin having a hybrid resin component is used, better wax dispersibility, low-temperature fixability and offset resistance are improved. The “hybrid resin component” used in the present invention means a resin in which a vinyl polymer unit and a polyester unit are chemically bonded. Specifically, a polyester unit and a vinyl polymer unit obtained by polymerizing a monomer having a carboxylic acid ester group such as acrylic acid ester or methacrylic acid ester are formed by a transesterification reaction. A graft copolymer (or block copolymer) in which a polymer is a trunk polymer and a polyester unit is a branch polymer is formed.

  Examples of the vinyl monomer for producing the vinyl polymer unit or vinyl polymer in the present invention include the following. Styrene; o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, p-phenylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p-tert- Butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p-methoxy styrene, p-chloro styrene, 3, Styrene and its derivatives such as 4-dichlorostyrene, m-nitrostyrene, o-nitrostyrene and p-nitrostyrene; styrene unsaturated monoolefins such as ethylene, propylene, butylene and isobutylene; unsaturated such as butadiene and isoprene Polyenes; vinyl chloride, vinylidene chloride, vinyl bromide Vinyl halides such as vinyl fluoride; vinyl esters such as vinyl acetate, vinyl propionate and vinyl benzoate; methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, methacryl Α-methylene aliphatic monocarboxylic esters such as n-octyl acid, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate; methyl acrylate; Ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate and Acrylic esters such as 2-chloroethyl acrylate, phenyl acrylate; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl isobutyl ether; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and methyl isopropenyl ketone; N -N-vinyl compounds such as vinylpyrrole, N-vinylcarbazole, N-vinylindole and N-vinylpyrrolidone; vinylnaphthalenes; acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile and acrylamide.

  In addition, unsaturated dibasic acids such as maleic acid, citraconic acid, itaconic acid, alkenyl succinic acid, fumaric acid and mesaconic acid; such as maleic anhydride, citraconic anhydride, itaconic anhydride and alkenyl succinic anhydride. Unsaturated dibasic acid anhydride; maleic acid methyl half ester, maleic acid ethyl half ester, maleic acid butyl half ester, citraconic acid methyl half ester, citraconic acid ethyl half ester, citraconic acid butyl half ester, itaconic acid methyl half ester, Unsaturated dibasic acid half esters such as alkenyl succinic acid methyl half ester, fumaric acid methyl half ester and mesaconic acid methyl half ester; Unsaturated dibasic acid esters such as dimethylmaleic acid and dimethylfumaric acid; Acrylic , Α, β-unsaturated acids such as methacrylic acid, crotonic acid and cinnamic acid; α, β-unsaturated acid anhydrides such as crotonic anhydride and cinnamic anhydride, the α, β-unsaturated acid and lower Anhydrides with fatty acids; monomers having a carboxyl group, such as alkenylmalonic acid, alkenylglutaric acid, alkenyladipic acid, acid anhydrides and monoesters thereof.

  In addition, acrylic or methacrylic esters such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate; 4- (1-hydroxy-1-methylbutyl) styrene and 4- (1-hydroxy-1 -Methylhexyl) Monomers having a hydroxy group such as styrene.

  The vinyl polymer or vinyl polymer unit in the present invention may have a crosslinked structure crosslinked with a crosslinking agent having two or more vinyl groups, but the crosslinking agent used in this case is aromatic. Examples of divinyl compounds include divinylbenzene and divinylnaphthalene; examples of diacrylate compounds linked by alkyl chains include ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6 hexanediol diacrylate, neopentyl glycol diacrylate, and those obtained by replacing acrylates of the above compounds with methacrylates; diacrylates linked by alkyl chains containing an ether bond As compounds For example, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 400 diacrylate, polyethylene glycol # 600 diacrylate, dipropylene glycol diacrylate and those obtained by replacing acrylates of the above compounds with methacrylate Examples of diacrylate compounds linked by a chain containing an aromatic group and an ether bond include polyoxyethylene (2) -2,2-bis (4-hydroxyphenyl) propane diacrylate, polyoxyethylene (4 ) -2,2-bis (4-hydroxyphenyl) propane diacrylate and those obtained by replacing the acrylate of the above compound with methacrylate.

  Polyfunctional cross-linking agents include pentaerythritol triacrylate, trimethylol ethane triacrylate, trimethylol propane triacrylate, tetramethylol methane tetraacrylate, oligoester acrylate, and acrylates of the above compounds replaced with methacrylate; triallylcia Examples include nurate and triallyl trimellitate.

  In this invention, it is preferable that the monomer component which can react with both resin components is contained in a vinyl polymer or a vinyl polymer unit and / or a polyester resin or a polyester unit. Among the monomers constituting the polyester resin or the polyester unit, those capable of reacting with the vinyl polymer or the vinyl polymer unit include, for example, unsaturated dicarboxylic acids such as phthalic acid, maleic acid, citraconic acid and itaconic acid or the like. An anhydride etc. are mentioned. Among the monomers constituting the vinyl polymer or the vinyl polymer unit, those capable of reacting with the polyester resin or the polyester unit include those having a carboxyl group or a hydroxy group, and acrylic acid or methacrylic acid esters.

  As a method for obtaining a reaction product of a vinyl polymer and a polyester resin, either a polymer or a resin containing a monomer component capable of reacting with each of the vinyl polymer and the polyester resin listed above is present. A method obtained by polymerizing one or both of the polymers or resins is preferred.

  Examples of the polymerization initiator used in producing the vinyl polymer or vinyl polymer unit of the present invention include 2,2′-azobisisobutyronitrile, 2,2′-azobis (4- Methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis (-2,4-dimethylvaleronitrile), 2,2′-azobis (-2methylbutyronitrile), dimethyl-2,2′- Azobisisobutyrate, 1,1′-azobis (1-cyclohexanecarbonitrile), 2- (carbamoylazo) -isobutyronitrile, 2,2′-azobis (2,4,4-trimethylpentane), 2- Phenylazo-2,4-dimethyl-4-methoxyvaleronitrile, 2,2′-azobis (2-methyl-propane), methyl ethyl ketone peroxide, acetyla Ketone peroxides such as ton peroxide and cyclohexanone peroxide, 2,2-bis (t-butylperoxy) butane, t-butyl hydroperoxide, cumene hydroperoxide, 1,1,3,3-tetramethyl Butyl hydroperoxide, di-t-butyl peroxide, t-butylcumyl peroxide, di-cumyl peroxide, α, α'-bis (t-butylperoxyisopropyl) benzene, isobutyl peroxide, octanoyl peroxide Decanoyl peroxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, benzoyl peroxide, m-trioyl peroxide, di-isopropyl peroxydicarbonate, di-2-ethyl Syl peroxydicarbonate, di-n-propyl peroxydicarbonate, di-2-ethoxyethyl peroxycarbonate, di-methoxyisopropyl peroxydicarbonate, di (3-methyl-3-methoxybutyl) peroxycarbonate, acetyl Cyclohexylsulfonyl peroxide, t-butyl peroxyacetate, t-butyl peroxyisobutyrate, t-butyl peroxyneodecanoate, t-butyl peroxy 2-ethylhexanoate, t-butyl peroxylaurate , T-butyl peroxybenzoate, t-butyl peroxyisopropyl carbonate, di-t-butyl peroxyisophthalate, t-butyl peroxyallyl carbonate, t-amyl peroxy 2-ethylhexanoate Di -t- butyl peroxy hexahydro terephthalate and di -t- butyl peroxy azelate and the like.

  As a manufacturing method which can prepare the hybrid resin used for the full-color toner of the present invention, for example, the manufacturing methods shown in the following (1) to (6) can be mentioned.

  (1) A method in which a vinyl polymer and a polyester resin are blended after production, and the blend is produced by dissolving and swelling in an organic solvent (for example, xylene) and then distilling off the organic solvent. The hybrid resin component is synthesized by separately producing a vinyl polymer and a polyester resin, dissolving and swelling in a small amount of an organic solvent, adding an esterification catalyst and an alcohol, and performing a transesterification reaction by heating. A hybrid resin having a polyester unit and a vinyl polymer can be obtained.

  (2) A method of producing a hybrid resin component having a polyester unit and a vinyl polymer unit by producing and reacting a polyester resin in the presence of the vinyl polymer after production. The hybrid resin component is produced by a reaction between a vinyl polymer (a vinyl monomer can be added if necessary) and a polyester monomer (alcohol, carboxylic acid) and / or polyester resin. Also in this case, an organic solvent can be appropriately used.

  (3) A method for producing a hybrid resin component having a polyester unit and a vinyl polymer unit by producing and reacting a vinyl polymer in the presence of the polyester resin after production. The hybrid resin component is produced by a reaction between a polyester resin (a polyester monomer can be added if necessary) and a vinyl monomer and / or a vinyl polymer.

  (4) After the vinyl polymer and the polyester resin are produced, the hybrid resin component is produced by adding a vinyl monomer and / or a polyester monomer (alcohol, carboxylic acid) in the presence of these polymer units. Also in this case, an organic solvent can be appropriately used.

  (5) After producing a hybrid resin component having a polyester unit and a vinyl polymer unit, by adding a vinyl monomer and / or a polyester monomer (alcohol, carboxylic acid) and performing an addition polymerization and / or a condensation polymerization reaction. A vinyl polymer and / or polyester resin, or further a hybrid resin component is produced. In this case, as the hybrid resin component having the polyester unit and the vinyl polymer unit, those produced by the production methods (2) to (4) can be used, and if necessary, by a known production method. What was manufactured can also be used. Furthermore, an organic solvent can be used as appropriate.

  (6) By mixing a vinyl monomer and a polyester monomer (alcohol, carboxylic acid, etc.) and continuously performing addition polymerization and condensation polymerization reaction, a vinyl polymer, a polyester resin, a polyester unit and a vinyl polymer unit are obtained. A hybrid resin component is produced. Furthermore, an organic solvent can be used as appropriate.

  In the production methods of (1) to (6) above, a polymer unit having a plurality of different molecular weights and crosslinking degrees can be used as the vinyl polymer unit and / or the polyester unit.

  In the present invention, the vinyl polymer or vinyl polymer unit means a vinyl homopolymer, a vinyl copolymer, a vinyl monopolymer unit, or a vinyl copolymer unit.

  The binder resin used in the toner of the present invention has a glass transition temperature (Tg) of 40 to 90 ° C. and a softening temperature (Tm) of 80 to 150 ° C., so that the storage stability, the dispersibility of the colorant, and the fixing can be achieved. It is preferable in order to balance the properties.

  The acid value of the binder resin is preferably 2 mgKOH / g or more and less than 50 mgKOH / g. When the acid value is less than 2 mgKOH / g, the polyester has a sufficient negative chargeability advantage and may be inferior in fixability and offset resistance. On the other hand, if it is 50 mgKOH / g or more, it is inferior in water resistance in a high-temperature and high-humidity environment, which may lead to problems such as fogging and toner scattering.

  Next, as a mold release agent used for this invention, the following are mentioned. Low molecular weight polyethylene, low molecular weight polypropylene, low molecular weight olefin copolymer, microcrystalline wax, aliphatic hydrocarbon wax such as Fischer-Tropsch wax and paraffin wax, oxide of aliphatic hydrocarbon wax such as oxidized polyethylene wax, Or block copolymers thereof; ester waxes such as behenate behenate and stearyl stearate, waxes based on fatty acid esters such as carnauba wax and montanate wax, and fatty acid esters such as deoxidized carnauba wax. The thing which deoxidized part or all is mentioned. Further, saturated linear fatty acids such as palmitic acid, stearic acid and montanic acid; unsaturated fatty acids such as brassic acid, eleostearic acid and valinalic acid; stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnauvyl alcohol, seryl alcohol And saturated alcohols such as melyl alcohol; polyhydric alcohols such as sorbitol; fatty acid amides such as linoleic acid amide, oleic acid amide and lauric acid amide; methylene bis stearic acid amide, ethylene biscapric acid amide, ethylene bis laurin Saturated fatty acid bisamides such as acid amides and hexamethylene bis stearic acid amides; ethylene bis oleic acid amides, hexamethylene bis oleic acid amides, N, N 'dioleyl adipic acid amides and Unsaturated fatty acid amides such as N, N′dioleyl sebacic acid amide; aromatic bisamides such as m-xylene bis-stearic acid amide and N, N ′ distearyl isophthalic acid amide; calcium stearate, calcium laurate, stearic acid Aliphatic metal salts such as zinc and magnesium stearate (commonly referred to as metal soaps); waxes grafted to aliphatic hydrocarbon waxes using vinylic monomers such as styrene and acrylic acid; behenic acid Examples include partially esterified products of fatty acids such as monoglycerides and polyhydric alcohols; methyl ester compounds having hydroxyl groups obtained by hydrogenation of vegetable oils and the like.

  The toner of the present invention has one or a plurality of endothermic peaks in the temperature range of 30 to 200 ° C. in the endothermic curve measured by a differential thermal analysis calorimeter (DSC) of the toner, and the maximum of the endothermic peaks. The temperature of the endothermic peak is preferably 60 to 110 ° C. More preferably, it exists in the range of 70-100 degreeC. When the peak temperature of the maximum endothermic peak is less than 60 ° C., the toner has poor blocking resistance, and conversely, when the peak temperature of the maximum endothermic peak exceeds 110 ° C., the fixability may deteriorate. is there. The release agent is preferably 0.5 to 10 parts by mass, more preferably 2 to 8 parts by mass per 100 parts by mass of the binder resin.

  The toner of the present invention preferably contains one or more release agents. Furthermore, in the toner of the present invention, the release agent is preferably a hydrocarbon wax, more preferably a paraffin wax, from the viewpoint of achieving both low-temperature fixability and blocking resistance.

  In the toner of the present invention, the light transmittance (%) at a wavelength of 600 nm with respect to a dispersion obtained by dispersing the toner in an aqueous solution of 45% by volume of methanol is preferably in the range of 10 to 80%, more preferably. 15 to 70%.

  The amount of the release agent in the vicinity of the toner surface can be determined by measuring the transmittance of light having a wavelength of 600 nm with respect to a dispersion in which the toner is dispersed in a 45 volume% methanol aqueous solution as a simple and accurate method. Can be grasped. This measurement method is to forcibly disperse the toner once in a mixed solvent to make the characteristics of the amount of the release agent present in each toner particle easy, and then measure the transmittance after a certain time, It is possible to accurately grasp the amount of the release agent present in the entire toner. That is, when a large amount of hydrophobic release agent is present on the surface of the toner, it is difficult to disperse in the solvent and aggregates and precipitates, resulting in a high transmittance. On the contrary, when a small amount of the release agent is present on the toner surface, since there are many binder resins that are hydrophilic, the dispersion is uniformly dispersed and the transmittance becomes a small value of less than 10%. In other words, the transmittance (%) of the toner in a 45% by volume aqueous solution of methanol indicates the presence state of the release agent component in the toner, and by controlling this, a wide fixing region is achieved, and the release agent. It is possible to prevent the component from being detached from the toner, and to produce a toner that does not contaminate the developing member even during long-term use.

  If the transmittance is less than 10%, the release agent on the toner surface is small and the releasing effect does not appear at the time of fixing. Therefore, low temperature fixing desired from the viewpoint of energy saving cannot be performed. The load which requires is required. On the other hand, if the transmittance is greater than 80%, the release agent on the toner surface is large, and the release agent is contaminated on the charge imparting member. Such an effect of the actual developing bias is lowered, which leads to a reduction in image density.

  Next, a known pigment or dye can be used as the colorant contained in the toner of the present invention. Although not particularly limited, examples of pigments include the following. Examples of the color pigment for magenta include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 39, 40, 41, 48, 49, 50, 52, 53, 54, 55, 57, 58, 60, 63, 64, 68, 112, 114, 119, 136, 147, 148, Azo pigments such as 150, 164, 170, 238, C.I. I. Pigment red 88, 122, 123, 202, 206, 207, 209, C.I. I. Pigment violet 19, C.I. I. Condensed polycyclic pigments such as Vat Red 23, 29 and 35; I. Pigment red 81, 83, C.I. I. Examples include lake pigments such as Vat Red 1 and 2. Of these pigments, azo pigments are preferred.

  Further, such a pigment may be used alone, but it is more preferable from the viewpoint of the image quality of a full color image to improve the sharpness by using a dye and a pigment together. Examples of the magenta dye include C.I. I. Solvent Red 1, 3, 8, 23, 24, 25, 27, 30, 49, 81, 82, 83, 84, 100, 109, 121, C.I. I. Disper thread 9, C.I. I. Solvent Violet 8, 13, 14, 21, 27, C.I. I. Oil-soluble dyes such as disperse violet 1, C.I. I. Basic Red 1, 2, 9, 12, 13, 14, 15, 17, 18, 22, 23, 24, 27, 29, 32, 34, 35, 36, 37, 38, 39, 40, C.I. I. Basic dyes such as basic violet 1,3,7,10,14,15,21,25,26,27,28 can be mentioned.

  As other coloring pigments, cyan pigments include C.I. I. Pigment blue 2, 3, 15, 16, 17, C.I. I. Bat Blue 6, C.I. I. Acid blue 45 or a copper phthalocyanine pigment having 1 to 5 phthalimidomethyl groups substituted on the phthalocyanine skeleton is preferred.

  Examples of the color pigment for yellow include C.I. I. Azo pigments such as C.I. Pigment Yellow 1, 2, 3, 5, 6, 12, 13, 14, 17, 49, 65, 73, 74, 128, 180; I. And condensed polycyclic pigments such as CI Pigment Yellow 110, 139, 147, 173, and 185. Of these pigments, azo pigments are preferred.

  As the black colorant, carbon black, those prepared as described above using the yellow colorant, the magenta colorant, and the cyan colorant described above, can be used.

  In addition, it is preferable that the usage-amount of a coloring agent is 0.1-20 mass parts with respect to 100 mass parts of binder resin, and it is more preferable that it is 0.5-15 mass parts.

In addition, a charge control agent can be added to the toner particles as necessary. Known charge control agents can be used, and examples thereof include aromatic carboxylic acid derivatives and aromatic carboxylic acid metal compounds. For example, the metal of the aromatic carboxylic acid metal compound is preferably a divalent or higher valent metal atom. Examples of the divalent metal include Mg ²⁺ , Ca ²⁺ , Sr ²⁺ , Pb ²⁺ , Fe ²⁺ , Co ²⁺ , Ni ²⁺ , Zn ²⁺ , and Cu ²⁺ . Of these, Zn ²⁺ , Ca ²⁺ , Mg ²⁺ and Sr ²⁺ are preferable. Examples of the trivalent or higher metal include Al ³⁺ , Cr ³⁺ , Fe ³⁺ , Ni ³⁺ , Ti ⁴⁺ , Zr ⁴⁺ and Si ³⁺ . Among these metals, Al ³⁺ and Cr ³⁺ are preferable, and Al ³⁺ is particularly preferable. In the present invention, an aluminum compound of 3,5-di-tert-butylsalicylic acid is particularly preferable as the charge control agent.

  When the charge control agent is used in an amount of 0.1 to 10% by mass based on the mass of the toner, the initial fluctuation of the toner charge amount is small, and an absolute charge amount necessary for development is easily obtained, resulting in a reduction in fog and image density. It is preferable that the image quality does not deteriorate.

  Further, the toner of the present invention has inorganic fine particles together with the toner particles in order to improve the image quality and improve the storage stability under a high temperature environment. As the inorganic fine particles, inorganic fine particles such as silica, titanium oxide and aluminum oxide are preferable. In particular, the inorganic fine particles are used from the viewpoint of suppressing the deterioration of the inorganic fine powder during development such as embedding in the toner particles and desorption from the toner particles with respect to the surface shape of the toner particles, and stabilizing the fluidity and charging stability. Titanium oxide is particularly preferable.

  The inorganic fine particles are preferably hydrophobized with a hydrophobizing agent such as a silane compound, silicone oil, or a mixture thereof. Examples of the hydrophobizing agent include coupling agents such as silane compounds, titanate coupling agents, aluminum coupling agents, and zircoaluminate coupling agents.

Specifically, for example, as a silane compound, the following formula RmSiYn
[In the formula, R represents an alkoxy group, m represents an integer of 1 to 3, Y represents an alkyl group, a vinyl group, a phenyl group, a methacryl group, an amino group, an epoxy group, a mercapto group, or a derivative thereof. , N represents an integer of 1 to 3. ]
The thing represented by these is preferable. For example, vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, isobutyltrimethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, trimethylmethoxysilane, hydroxypropyl Mention may be made of trimethoxysilane, phenyltrimethoxysilane, n-hexadecyltrimethoxysilane and n-octadecyltrimethoxysilane.

  The amount of the hydrophobic treatment is preferably 1 to 60 parts by mass, more preferably 3 to 50 parts by mass with respect to 100 parts by mass of the inorganic fine particles.

  Particularly preferred in the present invention is the compound represented by the general formula (8),

Is an alkylalkoxysilane represented by In the alkylalkoxysilane, when n is smaller than 4, the treatment becomes easy but the degree of hydrophobicity becomes low. When n is larger than 12, the hydrophobicity is sufficient, but the coalescence between the inorganic fine particles increases, and the fluidity imparting ability tends to decrease. When m is larger than 3, the reactivity of the alkylalkoxysilane coupling agent is lowered and it becomes difficult to perform hydrophobicity well. More preferable alkylalkoxysilane coupling agents have n of 4 to 8 and m of 1 to 2.

  The treatment amount of the alkylalkoxysilane coupling agent is also preferably 1 to 60 parts by mass, more preferably 3 to 50 parts by mass with respect to 100 parts by mass of the inorganic fine particles.

  The hydrophobizing treatment may be performed with one type of hydrophobizing agent alone, or two or more types of hydrophobizing agents may be used. For example, one type of hydrophobizing agent may be hydrophobized alone, or two hydrophobizing agents at the same time, or one hydrophobizing agent and another hydrophobizing agent. Hydrophobic treatment may be performed.

  The inorganic fine particles are preferably added in an amount of 0.01 to 5 parts by mass, more preferably 0.05 to 3 parts by mass with respect to 100 parts by mass of the toner particles.

  The toner of the present invention can be applied to a one-component developer and a two-component developer, and is not particularly limited, but when the toner of the present invention is used for a two-component developer, As the carrier used in combination, for example, surface oxidized or unoxidized iron, nickel, copper, zinc, cobalt, manganese, chromium, rare earth metals and their alloys or oxides and ferrite can be used.

  In particular, Mn—Mg—Fe three-element magnetic ferrite particles formed mainly of manganese, magnesium and iron components are preferred as carrier particles. The magnetic carrier particles are preferably coated with a resin, and examples of the resin include a silicone resin, a polyester resin, a styrene resin, an acrylic resin, polyamide, polyvinyl butyral, and an aminoacrylate resin, and a silicone resin is particularly preferable. Among them, the nitrogen-containing silicone resin or the modified silicone resin produced by the reaction of the nitrogen-containing silane coupling agent and the silicone resin is capable of imparting negative triboelectric charge to the toner of the present invention, environmental stability, carrier This is preferable in terms of suppression of surface contamination.

  As a coating method, a method in which a coating solution prepared by dissolving or suspending a coating material such as a resin in a solvent is adhered to the surface of the magnetic carrier core particle, and a method in which the magnetic carrier core particle and the coating material are mixed with powder. A conventionally known method can be applied.

  The magnetic carrier preferably has an average particle diameter of 15 to 60 μm (more preferably 25 to 50 μm) in relation to the weight average particle diameter of the toner. As a method for preparing the magnetic particles so as to have the above average particle size and specific particle size distribution, for example, classification can be performed by using a sieve. In particular, in order to classify with high accuracy, it is preferable to repeat a plurality of times using a sieve having an appropriate opening. It is also an effective means to use a mesh opening whose shape is controlled by plating or the like.

  When a two-component developer is prepared, good results are usually obtained when the mixing ratio is 2 to 15% by mass, preferably 4 to 13% by mass, as the toner concentration in the developer. If the toner concentration is less than 2%, the image density tends to be low, and if it exceeds 15% by mass, fogging and in-machine scattering tend to increase.

  The toner of the present invention is preferably a nonmagnetic toner.

  The toner of the present invention is preferably used in a full-color image forming method in which an image is formed using at least a magenta toner, a yellow toner, a cyan toner and a black toner. At this time, it is more preferable that all the toners used in the full-color image forming method are the toners of the present invention. In addition, when the toner of the present invention is used, it is preferable that an image forming method in which the toner is transferred to a recording material via an intermediate transfer member can obtain a good full color image faithfully reproducing the original.

  Next, a procedure for manufacturing toner will be described.

The toner particles of the present invention are:
A kneading step for obtaining a kneaded product by melt-kneading a mixture containing at least a binder resin and a colorant,
A cooling step for cooling the obtained kneaded product,
Coarse pulverization step of coarsely pulverizing the cooled kneaded product to obtain a coarsely pulverized product,
A fine pulverization step for producing a fine pulverized product by finely pulverizing the obtained coarse pulverization using airflow pulverization means;
A classification step of classifying the obtained finely pulverized product using a multi-division classifying means using the Coanda effect to obtain an intermediate powder, and surface modification of the obtained intermediate powder using a surface modification device It is preferable that the toner particles are obtained through a surface modification step of performing the above.

  First, in the kneading step, at least a binder resin and a colorant are weighed and blended, mixed, melted and kneaded to melt the binder resin, and a kneaded product in which the colorant is dispersed is obtained. obtain. Examples of the mixing device include a double-con mixer, a V-type mixer, a drum-type mixer, a super mixer, a Henschel mixer, and a Nauter mixer. In the kneading step, for example, a batch kneader such as a pressure kneader and a Banbury mixer or a continuous kneader can be used. In recent years, single-screw or twin-screw extruders have become mainstream due to the advantage that they can be produced continuously. For example, KTK type twin screw extruder manufactured by Kobe Steel, TEM type twin screw extruder manufactured by Toshiba Machine Co., Ltd., A twin-screw extruder manufactured by Kay C.K. and a co-kneader manufactured by Buss are generally used. Furthermore, the obtained kneaded material is rolled by a two-roll and cooled through a cooling step of cooling with water cooling.

  In general, the kneaded product obtained above is pulverized to a desired particle size in the pulverization step. In the pulverization step, first, coarse pulverization is performed with a crusher, a hammer mill or a feather mill, and further, pulverization is performed with a kryptron system manufactured by Kawasaki Heavy Industries, Ltd. and a super rotor manufactured by Nisshin Engineering Co., Ltd. After that, if necessary, the product is classified using an inertia class elbow jet (manufactured by Nippon Steel & Mining Co., Ltd.) and a centrifugal classifier turboplex (manufactured by Hosokawa Micron Co., Ltd.), and classified with a weight average particle size of 3 to 11 μm. (Toner particles) are obtained. If necessary, in the surface modification process, spheroidization (roundness adjustment) / smoothing (surface roughness adjustment), for example, a hybridization system manufactured by Nara Machinery Co., Ltd., a mechano-fusion system manufactured by Hosokawa Micron It can also be classified.

  In order to obtain the toner of the present invention, in the present invention, the cooled kneaded product is first roughly pulverized to obtain a coarsely pulverized product. The obtained coarsely pulverized product is repeatedly pulverized a plurality of times by an airflow pulverizing means such as an air jet pulverizer to produce a finely pulverized product. The obtained finely pulverized product is classified from coarse powder, medium powder and fine powder using a multi-division classifying means utilizing the Coanda effect such as an elbow jet classifier shown in FIG. . In FIG. 4, 241 and 242 are side walls, 243 and 244 are classification edge blocks, 245 is a Coanda block, 246 and 247 are classification edges, 248 and 249 are raw material supply pipes, 250 is a classification chamber upper wall, and 251 is an inlet. Reference numeral 252 and 253 are inlet pipes, reference numeral 255 is a gas introduction adjusting means, reference numerals 256 and 257 are static pressure gauges, reference numerals 258, 259 and 260 are outlets. The obtained intermediate powder is subjected to surface modification using a surface modification apparatus that simultaneously performs classification treatment and surface modification treatment using mechanical impact force as shown in FIGS. 2 and 3, and a weight average particle diameter of 3 It is preferable to obtain toner particles of 11 μm to 11 μm.

  Furthermore, as a method of externally adding an external additive such as inorganic fine particles, a predetermined amount of classified toner particles and various known external additives are mixed to give a shearing force to a powder such as a Henschel mixer or a super mixer. A toner can be obtained by stirring and mixing using a high-speed stirrer as an external additive.

  Here, the surface modification apparatus shown in FIG. 2 which is preferably used in the present invention will be described in detail. As shown in FIG. 2, in the surface modification device, the casing 30, a jacket (not shown) through which cooling water or antifreeze liquid can be passed, and surface modification means, which is in the casing 30 and attached to the central rotating shaft, Dispersion rotor 36, which is a rotating body on a disk that rotates at a high speed, and has a plurality of square disks or cylindrical pins 40 on the upper surface, and a surface that is arranged at a constant interval on the outer periphery of dispersion rotor 36 Liner 34 provided with a large number of grooves on the surface of the liner 34 (there is no need to have grooves on the liner surface), and further, a classification rotor 31 which is a means for classifying the surface-modified raw material into a predetermined particle size. Furthermore, a cold air introduction port 35 for introducing cold air, a raw material supply port 33 for introducing a raw material to be treated, and a surface modification time can be freely adjusted so that it can be opened and closed. The The space between the outlet valve 38, the powder discharge port 37 for discharging the processed powder, and the classification rotor 31 as the classification means, the dispersion rotor 36 as the surface modification means, and the liner 34 is classified. A cylindrical guide ring 39 which is a guide means for partitioning the first space 41 before being introduced into the means and the second space 42 for introducing the particles from which fine powder has been classified and removed by the classifying means into the surface treatment means. It consists of and. A gap portion between the dispersion rotor 36 and the liner 34 is a surface modification zone, and a classification rotor 4 and a rotor peripheral portion are classification zones.

  In the surface reforming apparatus configured as described above, when a finely pulverized product is introduced from the raw material supply port 33 with the discharge valve 38 closed, the charged finely pulverized product is firstly fed by a blower (not shown). Suctioned and classified by the classification rotor 31. At that time, the classified fine powder having a predetermined particle diameter or less is continuously discharged and removed out of the apparatus, and the coarse powder having a predetermined particle diameter or more passes along the inner periphery (second space 42) of the guide ring 39 by centrifugal force. The circulating flow generated by the dispersion rotor 36 is guided to the surface modification zone. The raw material guided to the surface modification zone is subjected to a surface modification treatment by receiving a mechanical impact force between the dispersion rotor 36 and the liner 34. The surface-modified particles having undergone surface modification are guided to the classification zone along the outer periphery (first space 41) of the guide ring 39 by the cold air passing through the inside of the machine. The coarse powder discharged to the outside of the machine is put into a circulating flow, returned to the surface modification zone again, and repeatedly subjected to the surface modification action. After a certain period of time, the discharge valve 38 is opened and the surface modified particles are recovered from the discharge port 37.

As a result of investigations by the present inventors, it has been found that the time until the discharge valve is opened (cycle time) and the rotational speed of the dispersion rotor are important in controlling the circularity and the surface roughness. In order to increase the sphericity and decrease the surface roughness, it is effective to increase the cycle time or increase the peripheral speed of the dispersion rotor. On the other hand, to increase the surface roughness, it is effective to shorten the cycle time or lower the peripheral speed. Among them, in particular, the peripheral speed of the distributed rotor cannot be efficiently spheroidized unless a certain speed is exceeded, so the cycle time must be increased and the spheroid must be spheroidized. The peripheral speed is 1.2 × 10 ⁵ mm / sec. The cycle time was effective for 15 to 60 seconds.

  Next, the measurement method in the present invention will be described.

(1) Measurement of equivalent circle diameter and average circularity of toner particles The equivalent circle diameter and average circularity of toner particles are measured using a flow type particle image measuring device “FPIA-2100 type” (manufactured by Sysmex Corporation). Calculated using the following formula.

  Here, the “particle projected area” is the area of the binarized toner particle image, and the “peripheral length of the particle projected image” is the length of the contour line obtained by connecting the edge points of the toner particle image. Define. The measurement uses the perimeter of the particle image when image processing is performed at an image processing resolution of 512 × 512 (pixels of 0.3 μm × 0.3 μm).

  The average circularity in the present invention is an index indicating the degree of unevenness of the toner particles. The average circularity is 1.000 when the toner particles are perfectly spherical, and the average circularity becomes smaller as the surface shape becomes more complicated. .

  The average circularity C, which means the average value of the circularity frequency distribution, is calculated from the following equation, where ci is the circularity (center value) at the dividing point i of the particle size distribution and m is the number of measured particles.

  In addition, “FPIA-2100”, which is a measuring apparatus used in the present invention, calculates the circularity of each particle, and then calculates the average circularity. 1.000 is divided into 0.010 equally divided classes, and the average circularity is calculated using the center value of the dividing points and the number of measured particles.

  Furthermore, “FPIA-2100”, which is a measuring apparatus used in the present invention, improves the magnification of the processed particle image as compared with “FPIA-1000” conventionally used for calculating the shape of toner particles. Further, the accuracy of the shape measurement is improved by improving the processing resolution of the captured image (256 × 256 → 512 × 512), thereby achieving more reliable capture of fine particles. Therefore, when it is necessary to measure the shape more accurately as in the present invention, the FPIA 2100 that can obtain information on the shape more accurately is more useful.

  As a specific method for measuring the average circularity using FPIA2100, 10 ml of ion-exchanged water from which impure solids are removed in advance is prepared in a container, and a surfactant, preferably an alkylbenzenesulfonic acid, is used as a dispersant therein. After the salt is added, 0.02 g of toner particles are further added and dispersed uniformly. As a means for dispersion, an ultrasonic disperser “Tetora 150 type” (manufactured by Nikka Ki Bios Co., Ltd.) is used, and dispersion treatment is performed for 2 minutes to obtain a dispersion for measurement. In that case, it cools suitably so that the temperature of the said dispersion liquid may not become 40 degreeC or more. In order to suppress variation in circularity, the installation environment of the apparatus is controlled at 23 ° C. ± 0.5 ° C. so that the temperature inside the flow type particle image analyzer FPIA-2100 is 26 to 27 ° C. Preferably, autofocus is performed using 2 μm latex particles every 2 hours. At the time of measurement, the dispersion concentration is adjusted so that the concentration of toner particles is 3000 to 10,000 / μl, and measurement is performed for 1000 or more particles. After the measurement, using this data, data having an equivalent circle diameter of less than 3.00 μm is cut to determine the average circularity of the toner particles.

  For the number frequency cumulative value of the circularity of the toner particles, the number frequency cumulative value of 0.960 or more and 0.920 or less is used, using the data divided into 61 classes from the circularity of 0.400 to 1.000. Calculated. In addition, the particle size distribution of the equivalent circle diameter of the toner particles is determined based on the particle diameter frequency data obtained by dividing the equivalent circle diameter by 226 in the range from 0.60 μm to 400 μm. Obtained in number%.

(2) Measurement of average surface roughness In the present invention, the average surface roughness of toner particles, the maximum height difference of toner particles, and the surface area are measured using a scanning probe microscope. Below, the example of a measuring method is shown.
Probe station: SPI3800N (manufactured by Seiko Instruments Inc.)
Measuring unit: SPA400
Measurement mode: DFM (resonance mode) shape image Cantilever: SI-DF40P
Resolution: Number of X data 256
Number of Y data 128
In the present invention, an area of 1 μm square on the surface of the toner particles is measured. The area to be measured is a 1 μm square area at the center of the toner particle surface measured with a scanning probe microscope. As the toner particles to be measured, toner particles equal to the weight average particle diameter (D4) measured by the Coulter counter method are selected at random, and the toner particles are measured. The measured data is subjected to secondary correction. Five or more different toner particles are measured, and the average value of the obtained data is calculated to obtain the average surface roughness of the toner particles.

In a toner in which an external additive such as an inorganic fine particle is externally added to the toner particle, it is necessary to remove the external additive when measuring the surface of the toner particle using a scanning probe microscope. For example, the following methods can be mentioned.
(1) Put 45 mg of toner into a sample bottle and add 10 ml of methanol.
(2) Disperse the sample for 1 minute with an ultrasonic cleaner to separate the external additive.
(3) Separating toner particles and external additives by suction filtration (10 μm membrane filter). In the case of a toner containing a magnetic material, the toner particles may be fixed by applying a magnet to the bottom of the sample bottle to separate only the supernatant.
(4) The above (2) and (3) are performed three times in total, and the obtained toner particles are sufficiently dried at room temperature with a vacuum dryer.

  The toner particles from which the external additive has been removed are observed with a scanning electron microscope, and after confirming that the external additive has disappeared, the surface of the toner particles can be observed with a scanning probe microscope. When the external additive has not been sufficiently removed, the surface of the toner particle is observed with a scanning probe microscope after repeating (2) and (3) until the external additive is sufficiently removed.

  As another method of removing the external additive in place of (2) and (3), there is a method of dissolving the external additive with an alkali. As the alkali, an aqueous sodium hydroxide solution is preferred.

  In the present invention, the average surface roughness (Ra) is a three-dimensional extension of the centerline average roughness Ra defined in JIS B0601 so that it can be applied to the measurement surface. The absolute value of the deviation from the reference plane to the specified plane is averaged and expressed by the following formula.

指定面とは、本発明においては１μｍ四方の測定エリアを意味する。

In the present invention, the designated surface means a measurement area of 1 μm square.

(3) Measurement of maximum endothermic peak of release agent and toner Temperature curve: Temperature increase I (30 ° C. to 200 ° C., temperature increase rate 10 ° C./min)
Temperature drop I (200 ° C-30 ° C, temperature drop rate 10 ° C / min)
Temperature increase II (30 ° C to 200 ° C, temperature increase rate 10 ° C / min)
The maximum endothermic peak of the toner is measured according to ASTM D3418-82 using DSC2920 (manufactured by TA Instruments Japan) as a differential scanning calorimeter (DSC measuring device).

  The sample to be measured is precisely weighed 5 to 20 mg, preferably 10 mg. It is put in an aluminum pan, and an empty aluminum pan is used as a reference, and measurement is performed at a measurement range of 30 to 200 ° C., a temperature increase rate of 10 ° C./min, and normal temperature and humidity. The maximum endothermic peak of the toner is determined in the process of temperature increase II, the one having the highest height from the baseline in the region above the endothermic peak of the resin Tg, or the endothermic peak of the resin Tg overlaps with another endothermic peak. If it is difficult, the maximum endothermic peak of the toner of the present invention is defined as the highest peak from the maximum peak of the overlapping peaks.

(4) Measurement of acid value Basic operation conforms to JIS K-0070.
1) A sample pulverized product of 0.5 to 2.0 (g) is precisely weighed, and the weight of the sample is defined as W (g).
2) A sample is put into a 300 (ml) beaker, and a mixed solution 150 (ml) of toluene / ethanol (4/1) is added and dissolved.
3) Titrate with 0.1 mol / l KOH ethanol solution using potentiometric titrator.
(For example, automatic titration using a potentiometric titrator AT-400 (winworkstation) manufactured by Kyoto Electronics Co., Ltd. and an ABP-410 electric burette can be used.)
4) The amount of KOH solution used at this time is S (ml), and a blank is measured at the same time. The amount of KOH solution used at this time is B (ml).
5) Calculate the acid value according to the following formula. f is a factor of KOH.
Acid value (mgKOH / g) = {(SB) × f × 5.61} / W
(5) Measurement of Glass Transition Temperature of Resin The glass transition temperature (Tg) of the resin is measured according to ASTM D3418-82 using DSC2920 (manufactured by TA Instruments Japan) as a differential scanning calorimeter (DSC measuring device). To do.

  The sample to be measured is precisely weighed 5 to 20 mg, preferably 10 mg. The sample is put in an aluminum pan, and an empty aluminum pan is used as a reference, and measurement is performed at a temperature rise rate of 10 ° C./min at room temperature and humidity in a measurement range of 30 to 200 ° C. In this temperature raising process, a specific heat change is obtained in the temperature range of 40 ° C to 100 ° C. At this time, the intersection of the intermediate point line of the baseline before and after the change in specific heat and the differential heat curve is defined as the glass transition temperature Tg of the resin of the present invention.

(6) Method for measuring softening point of resin This refers to the one measured by Koka-type flow tester in accordance with JIS K 7210. A specific measurement method is shown below. While a 1 cm ³ sample was heated at a heating rate of 6 ° C./min using a Koka type flow tester (manufactured by Shimadzu Corporation), a load of 1960 N / m ² (20 kg / cm ² ) was applied by a plunger, and the diameter was 1 mm. , A nozzle with a length of 1 mm is pushed out, thereby drawing a plunger descending amount (flow value) -temperature curve, where the height of the S-shaped curve is h, the temperature corresponding to h / 2 (resin Is the softening point (Tm) of the resin.

(7) Evaluation Method of Charging Stability FIG. 1 is an explanatory diagram of an apparatus for measuring the triboelectric charge amount. About 0.5 to 1.5 g of a two-component developer collected from the developing sleeve of a copying machine or printer is placed in a metal measuring container 52 having a screen 53 with a 30 μm opening (500 mesh) at the bottom. Cover 54. The total mass of the measurement container 52 at this time is weighed and is defined as W1 (g). Next, in the suction device 51 (at least the insulator is in contact with the measurement container 52), the pressure of the vacuum gauge 55 is set to 4 kPa by suctioning from the suction port 57 and adjusting the air volume control valve 56. In this state, the toner is removed by suction for 2 minutes. The potential of the electrometer 59 at this time is set to V (volt). Here, 58 is a capacitor, and the capacity is C (mF). Moreover, the mass of the whole measurement container after suction is weighed and is defined as W2 (g). The triboelectric charge amount (mC / kg) of this sample is calculated as follows.
Sample triboelectric charge (mC / kg) = C × V / (W1-W2)
(However, the measurement conditions are 23 ° C. and 50% RH)
Actually, using a remodeling machine with the oil application mechanism of the fixing unit of the color copier CLC-1000 (manufactured by Canon) removed, in a single color mode at room temperature and low humidity (23 ° C / 5%), under high temperature and high humidity ( A printing durability test of 50,000 sheets was performed using an original document with an image area ratio of 7% at 30 ° C./80%. The initial tribo on the sleeve in a normal temperature and low humidity environment (23 ° C./5%) and after endurance of 50,000 sheets were evaluated based on the following evaluation criteria.

(Evaluation criteria)
A: The difference in tribo between the initial stage and the endurance of 50,000 sheets is less than Δ5.
B: The difference in tribo between the initial stage and the endurance of 50,000 sheets is Δ5 or more and less than 10.
C: The difference in tribo between the initial stage and the endurance of 50,000 sheets is Δ10 or more and less than 15.
D: The difference in tribo between the initial stage and the endurance of 50,000 sheets is Δ15 or more.

(8) Molecular weight distribution by GPC measurement The molecular weight of the chromatogram of the binder resin by gel permeation chromatography (GPC) is measured under the following conditions.

The column was stabilized in a heat chamber at 40 ° C., and tetrahydrofuran (THF) as a solvent was passed through the column at this temperature at a flow rate of 1 ml / min, and the sample concentration was adjusted to 0.05 to 0.60% by mass. About 50 to 200 μl of THF sample solution is injected and measured. In measuring the molecular weight of a sample, the molecular weight distribution of the sample is calculated from the relationship between the logarithmic value of a calibration curve prepared from several types of monodisperse polystyrene standard samples and the number of counts (retention time). Examples of standard polystyrene samples for preparing a calibration curve include those manufactured by Tosoh Corporation or Pressure Chemical Co. The molecular weights manufactured are 6 × 10 ² , 2.1 × 10 ³ , 4 × 10 ³ , 1.75 × 10 ⁴ , 5.1 × 10 ⁴ , 1.1 × 10 ⁵ , 3.9 × 10 ⁵ , 8 It is suitable to use a standard polystyrene sample of at least about 10 points, using .6 × 10 ⁵ , 2 × 10 ⁶ , 4.48 × 10 ⁶ . An RI (refractive index) detector is used as the detector.

As a column, in order to accurately measure a molecular weight region of 10 ^{3 to} 2 × 10 ⁶ , it is preferable to combine a plurality of commercially available polystyrene gel columns. For example, shodex GPC KF-801, 802, 803 manufactured by Showa Denko KK , 804, 805, 806, and 807, and the combination of μ-styragel 500, 10 ³ , 10 ⁴ , and 10 ⁵ manufactured by Waters.

(9) Measurement of toner particle size distribution In the present invention, the average particle size and particle size distribution of toner particles are measured using a Coulter Counter TA-II type (manufactured by Coulter), but a Coulter Multisizer (manufactured by Coulter) is used. Is also possible. As the electrolytic solution, a 1% NaCl aqueous solution is prepared using primary sodium chloride. For example, ISOTON R-II (manufactured by Coulter Scientific Japan) can be used. As a measuring method, 0.1 to 5 ml of a surfactant, preferably alkylbenzene sulfonate, is added as a dispersant to 100 to 150 ml of the electrolytic aqueous solution, and 2 to 20 mg of a measurement sample is further added. The electrolytic solution in which the sample is suspended is subjected to a dispersion process for about 1 to 3 minutes with an ultrasonic disperser, and the volume and the number of toners of 2.00 μm or more are measured by using the 100 μm aperture as the aperture by the measuring device. Distribution and number distribution were calculated. Then, the weight average particle diameter (D4) obtained from the volume distribution according to the present invention (the median value of each channel is a representative value for each channel) was obtained.

  As channels, 2.00 to 2.52 μm; 2.52 to 3.17 μm; 3.17 to 4.00 μm; 4.00 to 5.04 μm; 5.04 to 6.35 μm; 6.35 to 8. 00 μm; 8.00 to 10.08 μm; 10.08 to 12.70 μm; 12.70 to 16.00 μm; 16.00 to 20.20 μm; 20.20 to 25.40 μm; 25.40 to 32.00 μm; 13 channels of 32.00-40.30 μm are used.

(10) Evaluation Method of Transfer Efficiency The toner transfer efficiency was evaluated based on the following evaluation method and evaluation criteria after enduring 50,000 sheets in a normal temperature and low humidity environment (23 ° C./5%). Using a color copying machine CLC-1000 (manufactured by Canon Inc.), adjusting the potential contrast of the photoconductor so that the applied amount is 0.6 mg / cm ² on the photoconductor, The image density of the transfer residue on the body was measured using a densitometer (X-rite 500Series). The amount of application was converted from the image density to determine the transfer efficiency onto the transfer paper. The transfer current used was adjusted to maximize transfer efficiency.

The density of the remaining transfer portion on the drum that is taped and pasted on the paper is D1, and the density that is transferred onto the paper and taped is D2.
Transfer efficiency (%) = D2 / (D1 + D2) × 100.

(Evaluation criteria)
A: Transfer efficiency after endurance of 50,000 sheets is 92% or more.
B: Transfer efficiency after endurance of 50,000 sheets is 87 or more and less than 92%.
C: Transfer efficiency after endurance of 50,000 sheets is 80 or more and less than 87%.
D: Transfer efficiency after endurance of 50,000 sheets is less than 80%.

(11) Fixable Area Using a laser jet 4100 (manufactured by Hewlett Packard) fixing machine, the fixing unit was subjected to a fixing test with the fixing unit modified so that the fixing temperature can be manually set. For the image, the development contrast was adjusted so that the applied amount of toner on paper was 1.2 mg / cm ² in a single color mode in a single color mode (23 ° C./60%) in CLC1000, and an unfixed image was created. An image is formed on A4 (TKCLA4 which is a CLC recommended paper) with an image area ratio of 25%. In a room temperature and normal humidity environment (23 ° C./60%), the temperature range was raised from 120 ° C. by 10 ° C., and the temperature range where no offset or wrapping occurred was defined as the fixable region.

(Evaluation criteria)
A: The fixing width is 50 ° C. or more.
B: The fixing width is 40 ° C. or more and less than 50 ° C.
C: The fixing width is 20 ° C. or more and less than 40 ° C.
D: The fixing width is less than 20 ° C.

(12) Anti-blocking property About 10 g of toner was put in a 100 ml polycup and allowed to stand at 50 ° C. for 3 days, and then visually evaluated.

(Evaluation criteria)
A: Aggregates are not seen.
B: Although aggregates are seen, they break apart easily.
C: Agglomerates are seen, but they collapse if shaken.
D: Aggregates can be grasped and do not collapse easily.

(13) Defective cleaning When the remaining toner's warp streaks and spots on the CLC1000 endured 10,000 sheets are visible on the image, a defective cleaning occurs.

(Evaluation criteria)
A: There are no image defects.
B: Two to three spots of spots.
C: Some spots or streaks appear.
D: Spots, streaks, and uneven density occur.

(14) Evaluation of toner spent property of carrier The toner is separated from the developer after copying 10,000 sheets with CLC-2150 using a cleaning agent, and only the carrier is taken out. The coated resin and spent toner components are extracted from 20 g of this cleaning carrier using 20 cc of methyl ethyl ketone. The same treatment was performed for unused carriers. This solution was diluted to 100 ml, and the transmittance was measured at 500 nm using a spectrophotometer. Evaluation was based on the difference in transmittance from unused carriers.
A: The difference in transmittance is less than 7%.
B: The difference in transmittance is 7% or more and less than 12%.
C: The difference in transmittance is 12% or more and less than 17%.
D: The difference in transmittance is 17% or more and less than 21%.
E: The difference in transmittance is 21% or more.

(15) Permeability in 45% by volume methanol aqueous solution (i) Preparation of toner dispersion An aqueous solution having a volume mixing ratio of methanol: water of 45:55 is prepared. 10 ml of this aqueous solution is placed in a 30 ml sample bottle (Nippon Denka Glass: SV-30), and 20 mg of toner is impregnated on the liquid surface to cover the bottle. Then, it is made to shake at 2.5S-1 for 5 seconds with a Yayoi type shaker (model: YS-LD). At this time, the angle of shaking is such that the shaking column moves 15 degrees forward and 20 degrees backward, assuming that the vertical (vertical) of the shaker is 0 degree. The sample bottle is fixed to a fixing holder (with the sample bottle lid fixed on the extension at the center of the column) attached to the tip of the column. After removing the sample bottle, the dispersion after 30 seconds is used as a dispersion for measurement.
(Ii) Transmittance measurement The dispersion obtained in (i) is placed in a 1 cm square quartz cell, and the transmittance at a wavelength of 600 nm of the dispersion after 10 minutes using a spectrophotometer MPS2000 (manufactured by Shimadzu Corporation) ( %).
Transmittance (%) = I / I0 × 100 (I... Transmitted light beam I0... Incident light beam)

  Examples of the present invention will be described below, but the present invention is not limited to these examples.

(Example of hybrid resin production)
As a vinyl polymer, 1.9 mol of styrene, 0.21 mol of 2-ethylhexyl acrylate, 0.15 mol of fumaric acid, 0.03 mol of α-methylstyrene dimer, and 0.05 mol of dicumyl peroxide are put into a dropping funnel. In addition, 7.0 mol of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene (2.2) -2,2-bis (4-hydroxyphenyl) propane; 0 mol, 3.0 mol of terephthalic acid, 2.0 mol of trimellitic anhydride, 5.0 mol of fumaric acid and 0.2 g of tin 2-ethylhexanoate were placed in a 4-liter 4-necked flask made of glass. A condenser and a nitrogen inlet tube were attached and placed in a mantle heater. Next, after the inside of the flask was replaced with nitrogen gas, the temperature was gradually increased while stirring, and while stirring at a temperature of 145 ° C., the monomer of the vinyl resin, the crosslinking agent and the polymerization initiator were added from the previous dropping funnel. It was dripped over 4 hours. Next, the temperature was raised to 200 ° C. and reacted for 4 hours to obtain a hybrid resin (Tm = 118 ° C., Tg = 63 ° C., acid value = 27 mgKOH / g). The obtained hybrid resin is referred to as Resin A. The results of molecular weight measurement by GPC are shown in Table 1.

(Example of polyester resin production)
3.6 mol of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, 1.6 mol of polyoxyethylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, 1.7 mol of terephthalic acid, 1.1 mol of trimellitic anhydride, 2.4 mol of fumaric acid, and 0.1 g of tin 2-ethylhexanoate are placed in a 4-liter four-necked flask made of glass, a thermometer, a stir bar, a condenser, A nitrogen inlet tube was installed and placed in the mantle heater. Under a nitrogen atmosphere, the reaction was carried out at 215 ° C. for 5 hours to obtain a polyester resin (Tm = 110 ° C., Tg = 52 ° C., acid value = 15 mgKOH / g). The obtained polyester resin is referred to as Resin B. The results of molecular weight measurement by GPC are shown in Table 1.

(Example of styrene-acrylic resin production)
-Styrene 70 parts by mass-N-butyl acrylate 24 parts by mass-Monobutyl maleate 6 parts by mass-G-tert-butyl peroxide 1 part by mass While stirring the above components in 200 parts by mass of xylene in a four-necked flask The inside of the container was sufficiently replaced with nitrogen, and the temperature was raised to 120 ° C., followed by dropwise addition over 3.5 hours. Further, the polymerization was completed under reflux of xylene, and the solvent was distilled off under reduced pressure to obtain a styrene-acrylic resin (Tm = 105 ° C., Tg = 60 ° C., acid value = 1.5 mgKOH / g). The obtained styrene-acrylic resin is referred to as Resin C. The results of molecular weight measurement by GPC are shown in Table 1.

  Table 2 shows the waxes used in the present invention.

<Example 1>
Cyan toner 1 was prepared by the following method.

(First kneading step)
-Resin A 70 parts by mass-C.I. I. A first paste-like pigment having a solid content of 30% by mass obtained by removing water to some extent from the pigment slurry containing Pigment Blue 15: 3, and having never passed through a drying step (the remaining 70% by mass is water) 100 parts by mass The above raw materials are first charged in a kneader-type mixer with the above-mentioned prescription, and the temperature is raised under no pressure while mixing. When the maximum temperature (necessarily determined by the boiling point of the solvent in the paste. In this case, about 90 to 100 ° C.) is reached, the pigment in the aqueous phase is distributed or transferred to the molten resin phase, and this is confirmed. After that, the mixture is further melted and kneaded for 30 minutes to sufficiently transfer the pigment in the paste. Then, once the mixer was stopped and the hot water was discharged, the temperature was further raised to 130 ° C., heated and kneaded for about 30 minutes, the pigment was dispersed and the water was distilled off, and the process was completed. The kneaded product was taken out and cooled to obtain a first kneaded product. The water content of the first kneaded product was about 0.5% by mass.

(Second kneading step)
The first kneaded product (pigment particle content 30% by mass) 10.0 parts by mass Resin A 100.0 parts by mass Wax (A) 5.0 parts by mass 3,5-di-tert-butyl 1.0 parts by weight of aluminum compound of salicylic acid (charge control agent) Preliminarily mixed with Henschel mixer with the above formulation, melt kneaded with a twin screw extruder kneader and melt kneaded, after cooling, using a hammer mill Coarsely pulverized to about 1 to 2 mm, and then repeatedly pulverized twice with a fine pulverizer using an air jet method to finely pulverize to a particle size of 20 μm or less. Further, the obtained finely pulverized product was classified with an elbow jet classifier to obtain an intermediate powder. The medium powder is classified and spheroidized by a surface modification apparatus that simultaneously performs classification and surface modification treatment using mechanical impact force, and the volume average particle size in the particle size distribution is 7.2 μm, the average circularity is 0.935, the average Cyan-based resin particles (classified product) that are toner particles having a surface roughness of 22.5 nm were obtained.

  Thereafter, 1.5 parts by mass of titanium oxide having a primary particle diameter of 50 nm surface-treated with isobutyltrimethoxysilane is added to 100 parts by mass of the cyan resin particles (toner particles), and cyan toner 1 is mixed. It was. The measurement results of the toner particle shape are shown in Table 3.

  Further, the cyan toner 1 and magnetic ferrite carrier particles (average particle diameter 45 μm) surface-coated with a silicone resin were mixed so that the toner concentration was 7% by mass to obtain a two-component cyan developer 1. As shown in Table 5, the transfer efficiency was good and the fixable area was also good. Further, even after the endurance of 50,000 sheets, there was little variation in charging from the initial stage, and there was no problem in cleaning performance, and a cyan image that faithfully reproduced the original was obtained.

<Example 2>
A cyan toner 2 was produced in the same manner as in Example 1 except that the wax (B) was used as a release agent, and a cyan developer 2 was obtained in the same manner. Various evaluations were made in the same manner as in Example 1, and the evaluation results are shown in Tables 3 and 4.

< Reference Example 1 >
A cyan toner 3 was produced in the same manner as in Example 1 except that the wax (C) was used as a release agent, and a cyan developer 3 was obtained in the same manner. Various evaluations were made in the same manner as in Example 1, and the evaluation results are shown in Tables 3 and 4.

<Example 4>
C.I. I. A magenta toner 1 was produced in the same manner as in Example 1 except that CI Pigment Red 57 was used, and a magenta developer 1 was obtained in the same manner. Various evaluations were made in the same manner as in Example 1, and the evaluation results are shown in Tables 3 and 4.

<Example 5>
C.I. I. A yellow toner 1 was produced in the same manner as in Example 1 except that CI Pigment Yellow 74 was used, and a yellow developer 1 was obtained in the same manner. Various evaluations were made in the same manner as in Example 1, and the evaluation results are shown in Tables 3 and 4.

< Reference Example 2 >
A black toner 1 was produced in the same manner as in Example 1 except that carbon black was used as the colorant, and a black developer 1 was obtained in the same manner. Various evaluations were made in the same manner as in Example 1, and the evaluation results are shown in Tables 3 and 4.

< Reference Example 3 >
In Example 4, wax (D) was used as the release agent, and C.I. I. Magenta toner 2 was produced in the same manner except that CI Pigment Red 122 was used, and magenta developer 2 was obtained in the same manner. The evaluation results are shown in Tables 3 and 4.

< Reference Example 4 >
In Example 5, wax (E) was used as the release agent, and C.I. I. A yellow toner 2 was prepared in the same manner except that CI Pigment Yellow 110 was used, and a yellow developer 2 was obtained in the same manner. The evaluation results are shown in Tables 3 and 4.

< Reference Example 5 >
In Example 1, a blended product of resin A and resin B (blend ratio = 50 parts / 50 parts) was used as the binder resin, and the same procedure as in Example 1 was used except that wax (D) was used as the release agent. Thus, cyan toner 4 was produced, and cyan developer 4 was obtained in the same manner. Various evaluations were made in the same manner as in Example 1, and the evaluation results are shown in Tables 3 and 4.

< Reference Example 6 >
In Example 1, cyan toner 5 was prepared in the same manner as in Example 1 except that resin B was used as the binder resin, wax (E) was used as the release agent, and titanium oxide and silica were used in combination as the inorganic fine particles. In the same manner, a cyan developer 5 was obtained. Various evaluations were made in the same manner as in Example 1, and the evaluation results are shown in Tables 3 and 4.

< Reference Example 7 >
In Example 1, a blended product of resin A and resin C (blend ratio = 50 parts / 50 parts) was used as a binder resin, wax (D) was used as a release agent, and titanium oxide and silica were used in combination as inorganic fine particles. Except for this, cyan toner 6 was prepared in the same manner as in Example 1, and cyan developer 6 was obtained in the same manner. Various evaluations were made in the same manner as in Example 1, and the evaluation results are shown in Tables 3 and 4.

<Comparative Example 1>
In Example 11, instead of using an apparatus that simultaneously performs classification and surface smoothing treatment using mechanical impact force, an elbow jet classifier was used as a classification apparatus, and titanium oxide alone was used as inorganic fine particles. Similarly, cyan toner 7 was produced, and cyan developer 7 was obtained in the same manner. In the elbow jet classifier, the average circularity did not increase and the transfer efficiency was extremely inferior. The evaluation results are shown in Tables 3 and 4.

<Comparative example 2>
In Example 10, cyan toner 8 was prepared in the same manner except that wax (F) was used as the release agent and silica alone was used as the inorganic fine particles, and cyan developer 8 was similarly obtained. The charging stability was greatly inferior due to intense embedding of silica in the toner. The evaluation results are shown in Tables 3 and 4.

<Comparative Example 3>
In Example 1, instead of using a surface modification device that simultaneously performs surface modification treatment using classification and mechanical impact force, resin C as the binder resin, wax (G) as the release agent, silica alone as the inorganic fine particles, and silica A cyan toner 9 was produced in the same manner as in Example 1 except that an elbow jet classification and a thermal spheronization apparatus were used, and a cyan developer 9 was obtained in the same manner. As shown in Tables 3 and 4, each evaluation item was significantly deteriorated.

<Comparative example 4>
In Example 1, cyan toner 10 was prepared in the same manner except that resin C was used as the binder resin, wax (G) was used as the release agent, and silica alone was used as the inorganic fine particles, and cyan developer 10 was similarly obtained. . As shown in Tables 4 and 5, the charge decreased due to poor cleaning, and all other evaluation items were significantly deteriorated.

<Example 12>
Using magenta developer 1, yellow developer 1, cyan developer 1 and black developer 1, image formation is performed using image forming apparatus CLC1000 (quadruple tandem type, no intermediate transfer member) shown in FIG. As a result, we were able to obtain a full-color image that faithfully reproduced the original. In addition, a full color image faithfully reproducing the original was obtained after the endurance of 50,000 sheets as in the initial stage. In FIG. 5, 1a, 1b, 1c and 1d are photosensitive drums, 2a, 2b, 2c and 2d are chargers, 3a, 3b, 3c and 3d are developing units, 4a, 4b, 4c and 4d are transfer blades, 5 is a recording material, 6 is a fixing device, 61 is a fixing roller, 62 is a pressure roller, 63 is a cleaning web, 64 is an oil application roller, 65 is fixing oil, 66 is a thermo switch, 67 is a heating body, and 7 is a recording medium. A material carrier, 8 is a transfer belt cleaning device, 9 is a driving roller, 10 is a belt remover, 11 is a registration roller, 12 is a separation charger, 13a, 13b, 13c and 13d are static removers, 14 is a polygon mirror, 15a , 15b, 15c and 15d are erase exposure units, and 16 is a recording material holder.

<Example 13>
Except for using an image forming apparatus modified to have an intermediate transfer member as shown in FIG. 6 for the CLC1000 used in Example 12, image output was performed in the same manner as in Example 12, and the original was faithfully reproduced. A full color image could be obtained. In addition, a full color image faithfully reproducing the original was obtained after the endurance of 50,000 sheets as in the initial stage. In FIG. 6, 101a, 101b, 101c and 101d are photosensitive drums, 102 is a tension roller, 103 is a driving roller, 104 is a secondary transfer counter roller, 105 is a secondary transfer roller, 106 is a belt cleaning unit, and 107 is an intermediate. A transfer belt (intermediate transfer member), 108 is a recording material, and 109 is a recording material storage portion.

It is explanatory drawing of the apparatus which measures a triboelectric charge amount. It is a schematic sectional drawing of an example of the surface modification apparatus used in the surface modification process of this invention. It is the schematic which shows an example of the top view of the dispersion | distribution rotor shown in FIG. It is a schematic sectional drawing of an example of the multi-division classification means used in the classification process of this invention. 1 is a schematic view of an image forming apparatus that performs an image forming method of the present invention. FIG. 2 is a schematic view of the vicinity of an intermediate transfer member of an image forming apparatus that performs an image forming method of the present invention.

Explanation of symbols

51 Suction Machine 52 Measuring Container 53 Screen 54 Lid 55 Vacuum Gauge 56 Air Volume Control Valve 57 Suction Port 58 Condenser 59 Electrometer 30 Casing 31 Classification Rotor 32 Fine Powder Recovery 33 Raw Material Supply Port 34 Liner 35 Cold Air Inlet 36 Dispersion Rotor 37 Powder Exhaust Outlet 38 Discharge valve 39 Guide ring 40 Pin 41 First space 42 Second space 241, 242 Side wall 243, 244 Classification edge block 245 Coanda block 246, 247 Classification edge 248, 249 Raw material supply pipe 250 Classification chamber upper wall 251 Enter Air edge 252, 253 Intake pipe 255 Gas introduction adjusting means 256, 257 Static pressure gauge 258, 259, 260 Discharge port 1a, 1b, 1c, 1d Photosensitive drum 2a, 2b, 2c, 2d Charger 3a, 3b, 3c, 3d Development 4a, 4 4c, 4d Transfer blade 5 Recording material 6 Fixing device 61 Fixing roller 62 Pressure roller 63 Cleaning web 64 Oil application roller 65 Fixing oil 66 Thermo switch 67 Heating body 7 Recording material carrier 8 Transfer belt cleaning device 9 Driving roller 10 Belt Electric discharger 11 Registration roller 12 Separation charger 13a, 13b, 13c, 13d Electric discharger 14 Polygon mirror 15a, 15b, 15c and 15d Erase exposure device 16 Recording material holder 101a, 101b, 101c, 101d Photosensitive drum 102 Tension roller 103 Driving roller 104 Secondary transfer counter roller 105 Secondary transfer roller 106 Belt cleaning means 107 Intermediate transfer belt (intermediate transfer member)
108 Recording material 109 Recording material storage

Claims (8)

In a color toner having toner particles containing at least a binder resin, a colorant and a release agent, and inorganic fine particles,
(I) The average circularity of toner particles having an equivalent circle diameter of 3.00 μm or more in the toner particles is 0.920 or more and less than 0.950,
(Ii) The number frequency cumulative value with a circularity of 0.960 or more in the toner particles having an equivalent circle diameter of 3.00 μm or more in the toner particles is 35% or less,
(Iii) The number frequency cumulative value of circularity of 0.920 or less in toner particles having an equivalent circle diameter of 3.00 μm or more in the toner particles is 25% or less,
(Iv) In the particle size distribution of the equivalent circle diameter of the toner particles, the abundance A (number%) of toner particles having an equivalent circle diameter of 0.60 μm or more and less than 3.00 μm with respect to all toner particles is 0.1 ≦ A <. Meets 15.0,
(V) In the particle size distribution of the equivalent circle diameter of the toner particles, the abundance B (number%) of toner particles having an equivalent circle diameter of 0.60 μm or more and less than 2.00 μm with respect to all toner particles, and 2.00 μm or more and 3 The abundance C (number%) of toner particles having an equivalent circle diameter of less than 0.000 μm with respect to all toner particles satisfies 0.5 <B / C <4.0,
The average surface roughness measured with a scanning probe microscope of the toner particles, Ri 35.0nm less der than 5.0 nm,
The binder resin has a polyester unit;
The toner particles are obtained through a surface modification step,
The surface modification step is performed using a batch type surface modification apparatus, and the batch type surface modification apparatus includes classification means for continuously discharging and removing fine particles having a predetermined particle size or less to the outside of the apparatus. Surface treatment means using mechanical impact force, and guide means for partitioning the space between the classification means and the surface treatment means into a first space and a second space, and Introduced to the surface treatment means using a mechanical impact force through the second space while introducing and removing fine particles having a predetermined particle size or less to the outside of the apparatus by the classification means. to perform surface modification treatment, the color toner again by circulating the first space, wherein the step der Rukoto repeating the surface modification treatment using a predetermined time classification and a mechanical impact force.   In the endothermic curve measured by a differential thermal analysis calorimeter (DSC) of the toner, the toner has one or a plurality of endothermic peaks in the range of 30 to 200 ° C., and the temperature of the maximum endothermic peak in the endothermic peak is The color toner according to claim 1, wherein the color toner is 60 to 110 ° C. The binder resin is (a) a polyester resin, (b) a hybrid resin having a polyester unit and a vinyl polymer unit, (c) a mixture of the hybrid resin and a vinyl polymer, (d) a polyester resin and a vinyl resin. It is a resin selected from the group consisting of a mixture with a polymer, (e) a mixture of a hybrid resin and a polyester resin, and (f) a mixture of a hybrid resin, a polyester resin, and a vinyl polymer. the color toner according to claim 1 or 2. The releasing agent is, the color toner according to any one of claims 1 to 3, characterized in that a hydrocarbon wax. Inorganic fine particles, a color toner according to any one of claims 1 to 4, characterized in that at least titanium oxide. The color toner according to any one of claims 1 to 5, characterized in that the color toners are nonmagnetic toners. The toner particles are
A kneading step for obtaining a kneaded product by melt-kneading a mixture containing at least a binder resin and a colorant,
A cooling step for cooling the obtained kneaded product,
Coarse pulverization step of coarsely pulverizing the cooled kneaded product to obtain a coarsely pulverized product,
A fine pulverization step for producing a fine pulverized product by finely pulverizing the obtained coarse pulverization using airflow pulverization means;
After the obtained finely pulverized product is classified using a multi-division classification means using the Coanda effect to obtain a middle powder ,
The color toner according to any one of claims 1 to 6, characterized in that the toner particles obtained through the surface modification step. A full-color image forming method for forming an image using at least magenta toner, yellow toner, cyan toner and black toner,
At least one color toner selected from the group consisting of the magenta toner, the yellow toner, the cyan toner and the black toner is a toner particle containing at least a binder resin, a colorant and a release agent, and inorganic fine particles A color toner having
(I) The average circularity of toner particles having an equivalent circle diameter of 3.00 μm or more of the toner particles is 0.920 or more and less than 0.950,
(Ii) The number frequency cumulative value of circularity of 0.960 or more in toner particles having an equivalent circle diameter of 3.00 μm or more of the toner particles is 35% or less,
(Iii) a color toner in which the toner particle having an equivalent circle diameter of 3.00 μm or more of the toner particles has a circularity of 0.920 or less and a number frequency cumulative value of 25% or less;
(Iv) In the particle size distribution of the equivalent circle diameter of the toner particles, the abundance A (number%) of toner particles having an equivalent circle diameter of 0.60 μm or more and less than 3.00 μm with respect to all toner particles is 0.1 ≦ A <. Meets 15.0,
(V) In the particle size distribution of the equivalent circle diameter of the toner particles, the abundance B (number%) of toner particles having an equivalent circle diameter of 0.60 μm or more and less than 2.00 μm with respect to all toner particles, and 2.00 μm or more and 3 The abundance C (number%) of toner particles having an equivalent circle diameter of less than 0.000 μm with respect to all toner particles satisfies 0.5 <B / C <4.0,
The average surface roughness measured with a scanning probe microscope of the toner particles, Ri 35.0nm less der than 5.0 nm,
The binder resin has a polyester unit;
The toner particles are obtained through a surface modification step,
The surface modification step is performed using a batch type surface modification apparatus, and the batch type surface modification apparatus includes classification means for continuously discharging and removing fine particles having a predetermined particle size or less to the outside of the apparatus. Surface treatment means using mechanical impact force, and guide means for partitioning the space between the classification means and the surface treatment means into a first space and a second space, and Introduced to the surface treatment means using a mechanical impact force through the second space while introducing and removing fine particles having a predetermined particle size or less to the outside of the apparatus by the classification means. to perform surface modification treatment, again by circulating the first space, the full-color image forming method comprising the steps der Rukoto repeating the surface modification treatment using a predetermined time classification and a mechanical impact force .

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