JP4698425B2 - Yellow toner for image formation and developer for developing electrostatic latent image - Google Patents

Description

  The present invention relates to a toner used for developing an electrostatic latent image formed on a photoreceptor, and particularly relates to a yellow toner. The present invention also relates to a developer for developing a one-component or two-component electrostatic latent image using such a toner.

  Conventionally, in an electrophotographic apparatus, an electrostatic recording apparatus, or the like, an electrical or magnetic latent image is visualized with toner. For example, in electrophotography, an electrostatic charge image (latent image) is formed on a photoreceptor, and then the latent image is developed with toner to form a toner image. The toner image is usually transferred onto a transfer material such as paper and then fixed by a method such as heating. Toner used for electrostatic image development is generally colored particles in which a binder, a colorant, a charge control agent, and other additives are contained in a binder resin. There is a suspension polymerization method. In the pulverization method, a colorant, a charge control agent, an offset preventing agent and the like are melt-mixed in a thermoplastic resin and uniformly dispersed, and the resulting composition is pulverized and classified to produce a toner. According to the pulverization method, a toner having some excellent characteristics can be produced, but there is a limitation in the selection of the toner material. For example, the composition obtained by melt mixing must be capable of being pulverized and classified by economically usable equipment.

  From this requirement, the melt-mixed composition must be made sufficiently brittle. For this reason, when the above composition is actually pulverized into particles, a wide range of particle size distribution is likely to be formed, and when attempting to obtain a copy image with good resolution and gradation, for example, a particle size of 5 μm The following fine powder and coarse powder of 20 μm or more must be removed by classification, which has the disadvantage that the yield becomes very low. Further, in the pulverization method, it is difficult to uniformly disperse the colorant, the charge control agent, and the like in the thermoplastic resin. In addition, since the colorant added to the toner is exposed on the surface of the obtained toner, there is a problem that the toner surface is non-uniformly charged, the toner charge distribution is expanded, and the development characteristics are deteriorated. Therefore, because of these problems, the kneading and pulverizing method cannot sufficiently meet the demand for high performance.

  In recent years, in order to overcome these problems in the pulverization method, a toner production method by a suspension polymerization method has been proposed and implemented. A technique for producing a toner for developing an electrostatic latent image by a polymerization method is known. For example, toner particles are obtained by a suspension polymerization method. However, the toner particles obtained by the suspension polymerization method are spherical and have a drawback of poor cleaning properties. Development / transfer with a low image area ratio results in a small amount of residual toner, and poor cleaning does not pose a problem. However, images with a high image area ratio, such as photographic images, and untransferred images formed due to poor paper feed, etc. Toner may be generated on the photoconductor as untransferred toner, and if accumulated, the image may be soiled. In addition, the charging roller that contacts and charges the photosensitive member is contaminated, and the original charging ability cannot be exhibited. For this reason, a method for obtaining irregularly shaped toner particles by associating resin fine particles obtained by an emulsion polymerization method is disclosed (see Patent Document 1).

  However, in the toner particles obtained by the emulsion polymerization method, a large amount of the surfactant remains not only on the surface but also inside the particles even after the water washing step, and the environmental stability of the toner charging is impaired. The amount distribution is widened, and the background stain of the obtained image becomes poor. Further, the remaining surfactant contaminates the photoreceptor, the charging roller, the developing roller, etc., and the original charging ability cannot be exhibited. In addition, even in the emulsion polymerization method in which the colorant component is hardly exposed on the toner surface, the colorant easily aggregates, so that it is difficult to add and disperse the colorant uniformly in the toner. Due to the difference, there is a problem that the non-uniformity of charging occurs and the stability when used for a long time is lowered. In the case of color output, a slight deterioration in developability and transferability causes a problem in color balance and gradation. Furthermore, since the colorant in the toner is generally incompatible with the resin, the transmitted light is irregularly reflected at the interface, and the transparency of OHP or the like is hindered. Therefore, if the dispersion of the colorant is poor, there is also a problem that the transparency with OHP deteriorates.

  Furthermore, in particular, in color output machines, oil-less toner that eliminates the need for an oil supply device for the fixing device and adds a release agent that replaces the oil into the toner has become common sense. Further, since it cannot be atomized as much as the colorant, it is difficult to add and disperse more uniformly, and if the dispersion of the release agent is poor, there is a problem that charging property, developability, storage property and OHP permeability are inhibited.

  Conventionally, as a yellow toner, a toner containing a dichlorobenzidine pigment such as pigment yellow 17 as a colorant has been used, but dichlorobenzidine is one of the regulations of Blue Angel in the German Eco Mark. Therefore, the development of a yellow toner using a colorant containing no dichlorobenzidine is expected. Examples of yellow pigments that do not contain dichlorobenzidine include PY155, PY180, PY93, and PY74. However, in the above polymerization method, when the pigment is dispersed in the solvent, the structural viscosity of the dispersion may be too high to be granulated. In addition, since water is used at the time of granulation, a phenomenon that the pigment is lost to the aqueous phase side occurs depending on the pigment. Furthermore, polymerized toners obtained by methods other than the above emulsion polymerization method often have a shape close to a true sphere, and have a smaller adhesion force to a photoreceptor or the like than an irregular shaped toner obtained by a kneading and pulverization method. Good releasability from the body, so high transfer rate is obtained, adhesion between toner particles is small, and it is easy to be affected by the lines of electric force, so transfer faithful to the latent image along the lines of electric force is made. On the other hand, in the unfixed state after transfer onto the transfer paper, the adhesive force between the toners is small as described above, so that the toner easily rolls in contact with the fixing member in the fixing step, and the image is disturbed. Further, toner close to a true sphere tends to roll on the surface of the photosensitive member and slips through the gap between the photosensitive member and the cleaning blade, so that there is a problem that it is difficult to clean by blade cleaning.

Various proposals have been made for controlling the shape of spherical and small-diameter toners. For example, shape factors SF-1 and SF-2 are used (see, for example, Patent Documents 2 to 4). This is to control the shape of the toner by defining one or both of the shape factors SF-1 and SF-2 as an index representing the shape of the toner. It is intended to achieve both charging properties, developing properties, transfer properties, and cleaning properties.
In the technique described in Patent Document 5, the range of the shape factor of the toner particles is defined, and the surface area ratio represented by the following formula is defined. Surface area ratio = ρ × D50p × S where ρ is the specific gravity (g / m ³ ) of the toner particles, D50p is the number average particle diameter (m) of the toner particles, and S is the BET specific surface area (m ³ / g of the toner particles). ). This surface area ratio represents the unevenness of the toner particles on a scale different from the above-described shape factor. When the surface area ratio exceeds the specified range, the degree of unevenness on the surface of the toner particles increases, and external additives added to the toner particles gradually enter the recesses of the toner particles over time, and chargeability is maintained over a long period of time. The transferability cannot be maintained.
As described above, an electrophotographic toner that can sufficiently meet the demand for higher performance has not yet been obtained.

Japanese Patent No. 2537503 JP-A-9-179331 JP-A-10-142835 JP 11-327197 A JP 2001-51444 A

  Therefore, an object of the present invention is to provide a yellow toner that uses an environmentally-friendly pigment as a yellow pigment in a polymerization method toner, and does not escape to the aqueous phase during granulation and uses a pigment having excellent heat resistance. In addition, by adopting a toner shape that does not cause poor cleaning of the toner, in order to meet the demand for higher performance, it has excellent offset property, charging property, storage property, good color development property, and OHP permeability. It is to provide a yellow toner having.

As a result of intensive studies, the present inventors have found that the colorant contains formula (I):
By using an acrylic copolymer having an N, N-disubstituted amino group and an acidic group in the main chain or side chain as a dispersant for the colorant, and further using a pigment derivative in combination The inventors have found that the granulation property is satisfactory, the heat resistance is excellent, and the shape of the toner can be controlled, and the present invention has been completed. The configuration of the present invention is as follows.

(1) In a toner produced in an aqueous medium and comprising at least a binder resin, a colorant, a dispersant for dispersing the colorant, and a pigment derivative for dispersing the colorant, the colorant Is the formula (I):

And the dispersant is an acrylic copolymer having an N, N-disubstituted amino group and an acidic group in the main chain or side chain, and the toner is represented by the following formula (1): And a shape factor SF-1 represented by (2) is 135 or more and 138 or less, and SF-2 is 125 or more and 130 or less.
SF-1 = {L ² / A} × (100π / 4) (1)
SF-2 = {C ² / A} × (100 / 4π) (2)
(L is the major axis length of the projected particles to be measured, C is the perimeter, and A is the projected area)

(2) The colorant is C.I. I. The yellow toner for image formation according to (1), which is CI Pigment Yellow 93.
(3) The yellow toner for image formation according to (1) or (2), wherein the dispersant has an acid value of 1 to 30 mgKOH / g or less and an amine value of 1 to 100.
(4) The yellow toner for image formation according to any one of (1) to (3), wherein 50 to 100% by weight of the binder resin is a polyester resin.

(5) The yellow toner for image formation according to any one of (1) to (4), wherein the method of producing in an aqueous medium is a suspension polymerization method.
(6) The yellow toner for image formation according to any one of (1) to (4), wherein the method of producing in an aqueous medium is a dissolution suspension method.
(7) The method of producing in the aqueous medium dissolves or disperses a polymer and a colorant which are binder resins having a site capable of reacting with at least a compound having an active hydrogen group in an organic solvent, A method in which the organic solvent is removed, washed and dried after the dispersion is dispersed in an aqueous medium and the binder resin having a site capable of reacting with the compound having an active hydrogen group is reacted or reacted. The yellow toner for image formation according to any one of (1) to (4), wherein
(8) The binder resin having a site capable of reacting with the compound having an active hydrogen group is a modified polyester resin and a non-modified polyester resin, and a weight ratio of the modified polyester resin to the non-modified polyester resin. 5/95 to 75/25, The yellow toner for image formation according to (7).
(9) The yellow toner for image formation according to (8), wherein the acid value of the modified polyester resin and the non-modified polyester resin is 0 to 30 mg KOH / g.
(10) The image forming method according to any one of (1) to (9), wherein the method of producing in the aqueous medium includes a step of containing resin fine particles and attaching them to the toner surface. For yellow toner.
(11) The yellow toner for image formation according to (10), wherein the resin fine particles have an average particle size of 5 to 500 nm.

(12) The yellow toner for image formation according to any one of (1) to (8), wherein the dispersant is compatible with a binder resin.
(13) The yellow toner for image formation according to any one of (1) to (9), wherein the dispersant has a weight average molecular weight of 2,000 to 100,000.
(14) The yellow toner for image formation according to any one of (1) to (10), wherein the addition amount of the dispersant is 1 to 50 parts by weight with respect to 100 parts by weight of the colorant.
(15) The yellow toner for image formation according to any one of (1) to (11), wherein the dispersant is contained in the toner in a proportion of 0.1 to 10% by weight.
(16) The yellow toner for image formation according to any one of (1) to (12), wherein a release agent is contained in the image formation toner.
(17) The image forming yellow toner according to any one of (1) to (13), wherein the releasing agent has a melting point of 40 to 160 ° C.

(18) The image forming toner according to any one of (1) to (17), wherein a blending ratio of the colorant and the organic solvent is in a range of 5:95 to 50:50.
(19) The volume average particle diameter Dv of the yellow toner is 3.0 to 8.0 μm, and the ratio Dv / Dn of the volume average particle diameter Dv to the number average particle diameter Dn is 1.00 to 1.30. (1) -Yellow toner for image formation in any one of (18).
(20) A one-component developer for developing an electrostatic latent image, wherein the yellow toner for image formation according to any one of (1) to (19) is used.
(21) A two-component developer for developing an electrostatic latent image, comprising the yellow toner for image formation according to any one of (1) to (19) and a carrier.

The colorant used in the present invention has a drawback that it becomes only spherical when the toner is produced by a polymerization method other than the emulsion polymerization method. Even if a method of controlling the shape of the toner base particles in the production process by using an inorganic filler as a so-called deforming agent in the vicinity of the surface of the toner base particles, the yellow pigment used in the present invention is used. Was not effective. For this reason, the problem that it is difficult to clean by blade cleaning cannot be avoided, and the colorant represented by the formula (I) cannot be used. However, the shape of the toner can be controlled by adding an acrylic copolymer having an N, N-disubstituted amino group and an acidic group in the main chain or side chain as a dispersant for the colorant, and further using a pigment derivative in combination. found.
In other words, by making the acid value and amine value of the dispersant used in the present invention within a certain range, the affinity between the dispersant and the binder can be increased, and the balance between the polar part and the nonpolar part can be improved. I can take it well. As a result, when the dispersant used in the present invention is added, the amine site of the dispersant is adsorbed on the acid site on the pigment surface via the pigment derivative, and the acid site of the dispersant comes out on the toner surface side. It is presumed that when granulating in the aqueous phase, the arrangement of the colorant in the toner is controlled, and the shape of the toner can be controlled while exhibiting high dispersibility in the colorant, resin and solvent.

  That is, in the electrophotographic toner of the present invention, the dispersibility of the colorant is improved by adsorbing the pigment derivative on the surface of the colorant and using the dispersant having an acid value and an amine value in a certain range, The coloring property of the toner and the optical transparency of the OHP are improved, and the colorant can be stably dispersed for a long time even during production, so that the particle production efficiency is improved. Furthermore, it is possible to control the chargeability, which is a harmful effect when using a dispersant.

  In the present invention, 50 to 100% by weight of the binder resin of the toner is a polyester resin. By setting the polyester resin in the toner binder resin to 50 to 100% by weight, the excellent fixing performance and color suitability obtained by the conventional kneading and pulverization method can be expressed, and it can sufficiently cope with speeding up and colorization. be able to. Examples of the polyester resin include all polyester resins such as a modified polyester resin, a non-modified polyester resin, and a low molecular weight polyester resin, and the total of them is 50 to 100% by weight in the binder resin, more preferably 75 to 100% by weight. It is.

As described above, according to the present invention, the colorant contains the formula (I):
By using the compound represented by the formula, it is possible to obtain a yellow toner having clear heat resistance and a blue angel regulation item in the German Eco Mark.

  Further, when the toner is produced by a polymerization method other than the emulsion polymerization method, there is a defect that even if the inorganic filler is present in the vicinity of the surface of the toner base particles, it becomes a perfect sphere. Alternatively, an acrylic copolymer having an N, N-disubstituted amino group and an acidic group in the side chain is contained, the acid value and amine value of the dispersant are set within a certain range, and a pigment derivative is used in combination, so that Since the shape can be arbitrarily controlled, it is possible to avoid a cleaning failure that is a problem with the spherical toner. Further, since the dispersibility of the colorant is also improved, by applying this colorant to the developer, an image forming method for forming a latent image can form an image having excellent image quality and excellent light transmission in OHP. be able to.

Hereinafter, embodiments of the present invention will be described in detail, but the present invention is of course not limited thereto.
(Organic solvent)
The organic solvent in the present invention is not particularly limited as long as it can dissolve and / or disperse the toner composition. As a preferable thing, it is preferable that the boiling point of this solvent is less than 150 degreeC from the point of being easy to remove. Examples of the solvent include toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, methyl acetate, ethyl acetate, methyl ethyl ketone, acetone. , Tetrahydrofuran and the like can be used alone or in combination of two or more. The amount of solvent used is usually 40 to 300 parts, preferably 60 to 140 parts, and more preferably 80 to 120 parts with respect to 100 parts of the toner composition.

The binder resin used in the toner of the present invention is made of, for example, the following constituent materials in addition to the polyester resin as described above.
(Binder resin)
Polymers of styrene such as polystyrene, poly-p-chlorostyrene, and polyvinyltoluene and substituted products thereof; styrene-p-chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene Copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene -Ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer Coalesce, styrene-isoprene Styrene copolymers such as polymers, styrene-acrylonitrile-indene copolymers, styrene-maleic acid copolymers, styrene-maleic acid ester copolymers; polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate , Polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, polyacrylic acid resin, rosin, modified rosin, terpene resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin Chlorinated paraffin, paraffin wax and the like can be used, and these can be used alone or in combination.

For the binder resin of the toner of the present invention, modified polyester resins and non-modified polyester resins can be preferably used. Among these, modified polyester resins will be described.
(Modified polyester resin)
Any group capable of reacting with active hydrogen can be used as long as it is known, and is preferably an isocyanate group, an epoxy group, a carboxylic acid, or an acid chloride group, more preferably an isocyanate group. Therefore, a particularly preferred resin used in the present invention is a polyester resin (RMPE) modified with a group capable of urea bonding. Examples thereof include a polyester prepolymer (A) having an isocyanate group. Examples of the prepolymer (A) include a polycondensate of a polyol (PO) and a polycarboxylic acid (PC) and a polyisocyanate (PIC) reacted with a polyester having active hydrogen. Examples of the group containing active hydrogen in the polyester include a hydroxyl group (alcoholic hydroxyl group and phenolic hydroxyl group), an amino group, a carboxyl group, a mercapto group, and the like. Among these, an alcoholic hydroxyl group is preferable.

  Modified polyester (MPE) such as urea-modified polyester is easy to adjust the molecular weight of its polymer component, and is a dry toner, especially oil-less low-temperature fixing characteristics (extensive releasability without a mechanism for applying a release oil to a fixing heating medium) And fixing property). Particularly, a polyester prepolymer whose end is modified with urea can suppress adhesion to a heating medium for fixing while maintaining high fluidity and transparency in the fixing temperature range of the unmodified polyester resin itself.

Examples of the polyol (PO) include diol (DIO) and trivalent or higher polyol (TO), and DIO alone or a mixture of DIO and a small amount of TO is preferable.
Examples of the diol include alkylene glycol (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, etc.); alkylene ether glycol (diethylene glycol, triethylene glycol, Dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc.); alicyclic diols (1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.); bisphenols (bisphenol A, bisphenol F, bisphenol S, etc.) ); Alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adduct of the alicyclic diol; bisphenol Alkylene oxide classes (ethylene oxide, propylene oxide, butylene oxide, etc.), etc. adducts. Among them, preferred are alkylene glycols having 2 to 12 carbon atoms and alkylene oxide adducts of bisphenols, and particularly preferred are alkylene oxide adducts of bisphenols and alkylene glycols having 2 to 12 carbon atoms. It is a combined use. Examples of the trivalent or higher polyol (TO) include 3 to 8 or higher polyhydric aliphatic alcohols (glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, etc.); trivalent or higher phenols (Tris) Phenol PA, phenol novolak, cresol novolak, etc.); alkylene oxide adducts of the above trivalent or more polyphenols.

  Examples of the polycarboxylic acid (PC) include dicarboxylic acid (DIC) and trivalent or higher polycarboxylic acid (TC), and DIC alone or a mixture of DIC and a small amount of TC is preferable. Dicarboxylic acids include alkylene dicarboxylic acids (succinic acid, adipic acid, sebacic acid, etc.); alkenylene dicarboxylic acids (maleic acid, fumaric acid, etc.); aromatic dicarboxylic acids (phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, etc.) ) And the like. Of these, preferred are alkenylene dicarboxylic acids having 4 to 20 carbon atoms and aromatic dicarboxylic acids having 8 to 20 carbon atoms. Examples of the trivalent or higher valent polycarboxylic acid include aromatic polycarboxylic acids having 9 to 20 carbon atoms (such as trimellitic acid and pyromellitic acid). In addition, as polycarboxylic acid, you may make it react with a polyol using the acid anhydride or lower alkyl ester (methyl ester, ethyl ester, isopropyl ester, etc.) of the above-mentioned thing. The ratio of the polyol (PO) and the polycarboxylic acid (PC) is usually 2/1 to 1/1, as the equivalent ratio [OH] / [COOH] of the hydroxyl group [OH] and the carboxyl group [COOH], preferably 1.5 / 1 to 1/1, more preferably 1.3 / 1 to 1.02 / 1.

  As polyisocyanate (PIC), aliphatic polyisocyanate (tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-diisocyanatomethylcaproate, etc.); alicyclic polyisocyanate (isophorone diisocyanate, cyclohexylmethane diisocyanate, etc.); aromatic Diisocyanates (tolylene diisocyanate, diphenylmethane diisocyanate, etc.); araliphatic diisocyanates (α, α, α ′, α′-tetramethylxylylene diisocyanate, etc.); isocyanurates; polyisocyanates such as phenol derivatives, oximes, caprolactams, etc. And a combination of two or more of these.

  The ratio of the polyisocyanate (PIC) is usually 5/1 to 1/1, preferably 4 /, as an equivalent ratio [NCO] / [OH] of the isocyanate group [NCO] and the hydroxyl group [OH] of the polyester having a hydroxyl group. 1 to 1.2 / 1, more preferably 2.5 / 1 to 1.5 / 1. When [NCO] / [OH] exceeds 5, low-temperature fixability deteriorates. When the molar ratio of [NCO] is less than 1, in the case of a urea-modified polyester, the urea content in the polyester becomes low and the hot offset resistance deteriorates. The content of the polyisocyanate (PIC) component in the polyester prepolymer (A) having an isocyanate group at the terminal is usually 0.5 to 40% by weight, preferably 1 to 30% by weight, more preferably 2 to 20% by weight. %. If it is less than 0.5% by weight, the hot offset resistance deteriorates, and it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability. On the other hand, if it exceeds 40% by weight, the low-temperature fixability deteriorates. The number of isocyanate groups contained per molecule in the polyester prepolymer (A) having an isocyanate group is usually 1 or more, preferably 1.5 to 3 on average, more preferably 1.8 to 2.5 on average. It is a piece. If it is less than 1 per molecule, the molecular weight of the modified polyester will be low, and the hot offset resistance will deteriorate.

  In the present invention, a urea-modified polyester that is preferably used as a binder resin can be obtained by a reaction between a polyester prepolymer (A) having an isocyanate group and amines (B). As amines (B), diamine (B1), trivalent or higher polyamine (B2), aminoalcohol (B3), aminomercaptan (B4), amino acid (B5), and amino acids B1-B5 blocked (B6) etc. are mentioned. Examples of the diamine (B1) include aromatic diamines (phenylenediamine, diethyltoluenediamine, 4,4′diaminodiphenylmethane, etc.); alicyclic diamines (4,4′-diamino-3,3′dimethyldicyclohexylmethane, diaminecyclohexane, Isophorone diamine etc.); and aliphatic diamines (ethylene diamine, tetramethylene diamine, hexamethylene diamine etc.) and the like. Examples of the trivalent or higher polyamine (B2) include diethylenetriamine and triethylenetetramine. Examples of amino alcohol (B3) include ethanolamine and hydroxyethylaniline. Examples of amino mercaptan (B4) include aminoethyl mercaptan and aminopropyl mercaptan. Examples of the amino acid (B5) include aminopropionic acid and aminocaproic acid. Examples of the block (B6) in which the amino group of B1 to B5 is blocked include ketimine compounds and oxazolidone compounds obtained from the amines of B1 to B5 and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.). Among these amines (B), preferred are B1 and a mixture of B1 and a small amount of B2.

  Furthermore, the molecular weight of a modified polyester such as urea-modified polyester can be adjusted using an elongation terminator. Examples of the elongation terminator include monoamines (diethylamine, dibutylamine, butylamine, laurylamine, etc.), and those obtained by blocking them (ketimine compounds). The ratio of amines (B) is the equivalent ratio [NCO] / [NHx] of isocyanate groups [NCO] in the prepolymer (A) having isocyanate groups and amino groups [NHx] in amines (B). The ratio is usually 1/2 to 2/1, preferably 1.5 / 1 to 1 / 1.5, more preferably 1.2 / 1 to 1 / 1.2. When [NCO] / [NHx] exceeds 2 or less than 1/2, the molecular weight of a modified polyester such as urea-modified polyester (UMPE) becomes low, and the hot offset resistance deteriorates. In the present invention, the polyester modified with urea bonds (UMPE) may contain urethane bonds as well as urea bonds. The molar ratio of the urea bond content to the urethane bond content is usually 100/0 to 10/90, preferably 80/20 to 20/80, and more preferably 60/40 to 30/70. When the molar ratio of the urea bond is less than 10%, the hot offset resistance is deteriorated.

As a crosslinking agent or an extender for the modified polyester used in the present invention, an active hydrogen compound capable of reacting with a reactive group such as an isocyanate group, preferably the amines (B) can be used.
The modified polyester such as urea-modified polyester (UMPE) used as the binder resin in the present invention is produced by a one-shot method or a prepolymer method. The weight average molecular weight of the modified polyester such as urea-modified polyester is usually 10,000 or more, preferably 20,000 to 1,000,000, and more preferably 30,000 to 1,000,000. If it is less than 10,000, the hot offset resistance deteriorates. The number average molecular weight of the modified polyester such as urea-modified polyester is not particularly limited when the unmodified polyester (PE) described later is used, and may be a number average molecular weight that can be easily obtained to obtain the weight average molecular weight. . In the case of the modified polyester alone, the number average molecular weight is usually 20000 or less, preferably 1000 to 10000, and more preferably 2000 to 8000. When it exceeds 20000, the low-temperature fixability and the glossiness when used in a full-color apparatus are deteriorated.

(Crosslinking agent and extender)
In the present invention, amines can be used as a crosslinking agent and / or an extender. As amines (B), diamine (B1), trivalent or higher polyamine (B2), aminoalcohol (B3), aminomercaptan (B4), amino acid (B5), and amino acids B1-B5 blocked (B6) etc. are mentioned. Examples of the diamine (B1) include aromatic diamines (phenylenediamine, diethyltoluenediamine, 4,4′diaminodiphenylmethane, etc.); alicyclic diamines (4,4′-diamino-3,3′dimethyldicyclohexylmethane, diaminecyclohexane, Isophorone diamine etc.); and aliphatic diamines (ethylene diamine, tetramethylene diamine, hexamethylene diamine etc.) and the like. Examples of the trivalent or higher polyamine (B2) include diethylenetriamine and triethylenetetramine. Examples of amino alcohol (B3) include ethanolamine and hydroxyethylaniline. Examples of amino mercaptan (B4) include aminoethyl mercaptan and aminopropyl mercaptan. Examples of the amino acid (B5) include aminopropionic acid and aminocaproic acid. Examples of the B1 to B5 amino group blocked (B6) include ketimine compounds and oxazoline compounds obtained from the B1 to B5 amines and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.). Among these amines (B), preferred are B1 and a mixture of B1 and a small amount of B2.

  Furthermore, if necessary, the molecular weight of the modified polyester after completion of the reaction can be adjusted by using a terminator for crosslinking and / or elongation. Examples of the terminator include monoamines (diethylamine, dibutylamine, butylamine, laurylamine, etc.), and those blocked (ketimine compounds).

(Non-modified polyester)
In the present invention, not only the modified polyester (A) is used alone, but also the unmodified polyester (C) having an acid value of 0.5 to 40 mgKOH / g is used together with the modified polyester (A). It can also be contained as (binder resin component). By using (C) in combination, the low-temperature fixability and the glossiness when used in a full-color apparatus are improved. Examples of (C) include the same polycondensates of polyol (1) and polycarboxylic acid (2) as in the polyester component (A), and preferred ones are also the same as (C). (C) is not limited to unmodified polyester, but may be modified with a chemical bond other than a urea bond, and may be modified with, for example, a urethane bond.

  It is preferable that (A) and (C) are at least partially compatible with each other in terms of low-temperature fixability and hot offset resistance. Accordingly, the polyester component (A) and (C) preferably have similar compositions. When (A) is contained, the weight ratio of (A) to (C) is usually 5/95 to 75/25, preferably 10/90 to 25/75, more preferably 12/88 to 25/75, Especially preferably, it is 12 / 88-22 / 78. If the weight ratio of (A) is less than 5%, the hot offset resistance deteriorates, and it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability.

  The molecular weight distribution of the unmodified polyester (C) is measured by the following method. After about 1 g of unmodified polyester (C) is precisely weighed in an Erlenmeyer flask, 10 to 20 g of THF (tetrahydrofuran) is added to obtain a THF solution having a binder concentration of 5 to 10%. The column is stabilized in a heat chamber at 40 ° C., and THF as a solvent is allowed to flow through the column at this temperature at a flow rate of 1 ml / min, and 20 μl of the THF sample solution is injected.

The molecular weight of the sample is calculated from the relationship between the retention value and the logarithmic value of a calibration curve prepared from a monodisperse polystyrene standard sample. A calibration curve is created using a polystyrene standard sample. As a monodisperse polystyrene standard sample, the thing of the range of molecular weight 2.7 * 10 < ² > -6.2 * 10 < ⁶ > by Tosoh Corporation is used, for example. A refractive index (RI) detector is used as the detector. As the column, for example, TSKgel, G1000H, G2000H, G2500H, G3000H, G4000H, G5000H, G6000H, G7000H, GMH manufactured by Tosoh Corporation are used in combination.

  The main peak molecular weight is usually 1000 to 30000, preferably 1500 to 10000, more preferably 2000 to 8000. When the amount of the component having a molecular weight of less than 1000 is increased, the heat resistant storage stability tends to deteriorate and carrier contamination occurs. Therefore, the content is preferably 5.0% by weight or less. If the component exceeding the molecular weight of 30000 increases, the low-temperature fixability tends to decrease, but the decrease can be suppressed as much as possible by balance control. The content of the component having a molecular weight exceeding 30000 is 1% or more, and varies depending on the toner material, but is preferably 3 to 6%. If it is less than 1%, sufficient hot offset resistance cannot be obtained, and if it is 10% or more, the glossiness and transparency may be deteriorated.

  Mn is 2000 to 15000 and the value of Mw / Mn is preferably 5 or less. When it exceeds 5, sharp melt property is lacking and glossiness is impaired. Moreover, it leads to an improvement in hot offset by using a polyester resin containing 1 to 15% of THF insoluble matter. Insoluble in THF is effective for hot offset in color toners, but it is definitely negative in terms of gloss and transparency of OHP, but it is effective within 1 to 15% to widen the mold release width. There is also.

The hydroxyl value of (C) is preferably 5 or more, more preferably 10 to 120, and particularly preferably 20 to 80. If it is less than 5, it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability.
The acid value of (C) is usually 0 to 30 mgKOH / g, preferably 5 to 25 mgKOH / g. By having an acid value, it tends to be negatively charged. In addition, those having an acid value and a hydroxyl value exceeding these ranges are easily affected by the environment under high temperature and high humidity and low temperature and low humidity, and are liable to cause image deterioration.

The THF-insoluble matter in the toner can be adjusted by controlling the elongation and / or crosslinking of the modified polyester by the acid value of the unmodified polyester. The measurement method is shown below.
<Method for measuring THF-insoluble matter>
About 1.0 g (A) of resin or toner is weighed. To this, about 50 g of THF is added and left at 20 ° C. for 24 hours. This is first separated by centrifugation and filtered using JIS standard (P3801) type 5 C filter paper for quantification. The solvent content of this filtrate is vacuum-dried, and the residual amount (B) is measured only for the resin content. This residual amount is the amount dissolved in THF.
The THF insoluble content (%) is obtained from the following formula.
THF insoluble matter (%) = (A−B) / A
In the case of toner, the THF-insoluble component amount (W1) and the THF-soluble component amount (W2) other than the resin are separately obtained by a known method, for example, a thermal loss method by the TG method, and obtained from the following formula.
THF insoluble matter (%) = (A−B−W2) / (A−W1−W2) × 100

Here, the acid value (AV) and the hydroxyl value (OHV) in the present invention are specifically determined by the following procedure.
Measuring device: potentiometric automatic titrator DL-53 Titrator (manufactured by METTLER TOLEDO)
Electrode used: DG113-SC (Metler Toledo)
Analysis software: LabX Light Version 1.00.000
Calibration of the apparatus: Use a mixed solvent of 120 ml of toluene and 30 ml of ethanol.
Measurement temperature: 23 ° C
The measurement conditions are as follows.
Stir
Speed [%] 25
Time [s] 15
EQP titration
Titrant / Sensor
Titrant CH3ONa
Concentration [mol / L] 0.1
Sensor DG115
Unit of measurement mV
Predispensing to volume
Volume [mL] 1.0
Wait time [s] 0
Titrant addition Dynamic
dE (set) [mV] 8.0
dV (min) [mL] 0.03
dV (max) [mL] 0.5
Measure mode Equilibrium controlled
dE [mV] 0.5
dt [s] 1.0
t (min) [s] 2.0
t (max) [s] 20.0
Recognition
Threshold 100.0
Steepest jump only No
Range No
Tendency None
Termination
at maximum volume [mL] 10.0
at potential No
at slope No
after number EQPs Yes
n = 1
comb. termination conditions No
Evaluation
Procedure Standard
Potential 1 No
Potential 2 No
Stop for reevaluation No

(Measurement method of acid value)
Measurement is performed under the following conditions in accordance with the measurement method described in JIS K0070-1992.
Sample preparation: 0.5 g of toner (0.3 g for ethyl acetate soluble component) is added to 120 ml of toluene and dissolved by stirring for about 10 hours at room temperature (23 ° C.). Further, 30 ml of ethanol is added to prepare a sample solution.
The measurement can be calculated by the apparatus described above, but specifically, the calculation is performed as follows.
Titrate with a pre-standardized N / 10 caustic potash to alcohol solution, and determine the acid value from the consumption of the alcohol potash solution by the following calculation.
Acid value = KOH (ml) x N x 56.1 / sample weight (where N is a factor of N / 10 KOH)
(Measurement method of hydroxyl value)
Weigh accurately 0.5 g of sample into a 100 ml volumetric flask and add 5 ml of acetylating reagent correctly. Then, it is immersed in a bath at 100 ° C. ± 5 ° C. and heated. After 1-2 hours, the flask is removed from the bath, allowed to cool, water is added and shaken to decompose acetic anhydride. Furthermore, in order to complete the decomposition, the flask is again heated in a bath for 10 minutes or more and allowed to cool, and then the wall of the flask is thoroughly washed with an organic solvent. This solution is subjected to potentiometric titration with an N / 2 potassium hydroxide ethyl alcohol solution using the electrode to determine the OH value (according to JISK0070-1966).

(Toner and glass transition point of unmodified polyester)
In the present invention, a modified polyester and an unmodified polyester are included as a resin component of the toner. However, since a polymer obtained by extending and / or crosslinking the modified polyester has a high molecular weight, no clear glass transition behavior is observed. Therefore, there is no difference between the glass transition point (Tg) of the toner and the glass transition point (Tg) of the unmodified polyester, and the glass transition point (Tg) of the toner is adjusted by the glass transition point (Tg) of the unmodified polyester. The glass transition point of the toner is usually 40 to 70 ° C., preferably 45 to 55 ° C. If it is less than 40 ° C., the heat-resistant storage stability of the toner deteriorates, and if it exceeds 70 ° C., the low-temperature fixability becomes insufficient. Due to the coexistence of the crosslinked and / or elongated polyester resin, the dry toner of the present invention tends to have good heat-resistant storage stability even when the glass transition point is low, as compared with known polyester-based toners.

<Measuring method of glass transition point (Tg)>
Here, the glass transition point (Tg) in the present invention is specifically determined by the following procedure. Using Shimadzu TA-60WS and DSC-60 as measuring devices, the measurement was performed under the following measurement conditions.
Measurement conditions Sample container: Aluminum sample pan (with lid)
Sample amount: 5mg
Reference: Aluminum sample pan (alumina 10mg)
Atmosphere: Nitrogen (flow rate 50 ml / min)
Temperature conditions Starting temperature: 20 ° C
Temperature increase rate: 10 ° C / min
End temperature: 150 ° C
Holding time: None Temperature drop: 10 ° C / min
End temperature: 20 ° C
Holding time: None Temperature increase rate: 10 ° C / min
End temperature: 150 ° C

The measurement results were analyzed using the data analysis software (TA-60, version 1.52) manufactured by Shimadzu Corporation. The analysis method is to specify a range of ± 5 ° C centering on the point showing the maximum peak on the lowest temperature side of the DrDSC curve, which is the DSC differential curve of the second temperature rise, and use the peak analysis function of the analysis software to determine the peak temperature. Ask. Next, the maximum endothermic temperature of the DSC curve is determined using the peak analysis function of the analysis software in the range of the peak temperature + 5 ° C. and −5 ° C. in the DSC curve. The temperature shown here corresponds to the Tg of the toner.

(Coloring agent)
As the colorant of the present invention, the formula (I):
And chromoftal yellow 3G (manufactured by CIBA), C.I. I. Commercial products such as CI Pigment Yellow PY93 3G (manufactured by Ciba Specialty Chemicals) can be used.
The content of the compound represented by the formula (I) is preferably 1 to 25 parts by weight, and more preferably 2.5 to 15.0 parts by weight with respect to 100 parts by weight of the binder resin.

  In the present invention, a pigment derivative having a high affinity for the colorant is added in order to enhance the interaction between the colorant and the dispersant and to stabilize the colorant in dispersion. Specific examples of the colorant (pigment) derivative include dimethylaminoethylquinacridone, dihydroquinacridone, a carboxylic acid derivative of anthraquinone, a sulfonic acid derivative of anthraquinone, Solsperse 2000 (manufactured by Avicia), and EKKA-6750 (manufactured by EFKA Chemicals). ) And the like. The amount of the pigment derivative added is preferably from 0.1 to 100% by weight, more preferably from 0.1 to 10% by weight, based on the colorant.

In the toner of the present invention, the following dispersant is used together with the colorant.
(Dispersant)
An example of an acrylic copolymer having an N, N-disubstituted amino group and an acidic group in the main chain or side chain used as a dispersant in the present invention is a (meth) acrylic monomer, one It is obtained by copolymerizing a monomer having an N, N-disubstituted amino group and an ethylenic double bond in the molecule and a monomer having an acidic group and an ethylenic double bond in one molecule.
Examples of the (meth) acrylic monomer include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, β-hydroxyethyl (meth) acrylate, benzyl ( Well-known (meth) acrylic acid esters, such as (meth) acrylate, are mentioned. Examples of the monomer having an N, N-disubstituted amino group and an ethylenic double bond in one molecule include dimethylaminoethyl (meth) acrylate, diethylaminopropyl (meth) acrylate, dimethylaminoethyl vinyl ether, and the like. It is done. Examples of the monomer having an acidic group and an ethylenic double bond in one molecule include (meth) acrylic acid, p-styrenesulfonic acid, p-styrenecarboxylic acid, p-hydroxystyrene, mono (2- ( And (meth) acryloyloxyethyl) phosphate, di (2- (meth) acryloyloxyethyl) phosphate, tri (2- (meth) acryloyloxyethyl) phosphate, and the like. Among them, it is preferable to use a monomer having a carboxyl group or a phenolic hydroxyl group.

  The acid value of the acrylic copolymer having an N, N-disubstituted amino group and an acidic group used as a dispersant in the present invention is preferably 1 to 30 mgKOH / g, and the amine value is in the range of 1 to 100. Are preferred. When the acid value exceeds 30 mgKOH / g, the chargeability under high humidity is lowered and the pigment dispersibility is also insufficient. Also, when the amine value is less than 1 and when the amine value exceeds 100, the pigment dispersibility is insufficient. The acid value can be measured by the method described in JIS K0070, and the amine value can be measured by the method described in JIS K7237. The dispersant is preferably highly compatible with the binder resin in terms of pigment dispersibility.

  Examples of commercially available dispersants that can be used in the present invention include BYK-2001, Disperbyk-2001, EFKA-4406, manufactured by EFKA, and the like. The dispersant is preferably blended in the toner at a ratio of 0.1 wt% to 10 wt% with respect to the colorant. If the amount is less than 0.1% by weight, the pigment dispersibility is insufficient. If the amount is more than 10% by weight, the chargeability under high humidity may be lowered. The weight average molecular weight of the dispersant is the maximum molecular weight of the main peak in terms of styrene in gel permeation chromatography, preferably 2000 or more, and more preferably 3000 or more in pigment dispersibility. In particular, about 5000 to 50000 is preferable, and 5000 to 30000 is more preferable. When the molecular weight is less than 2000, the polarity increases and the dispersibility of the colorant tends to decrease. When the molecular weight exceeds 100,000, the affinity with the solvent increases and the dispersibility of the colorant tends to decrease.

  Moreover, it is preferable that the addition amount of a dispersing agent is 1 to 50 weight part with respect to 100 weight part of coloring agents, and it is more preferable that it is 5 to 30 weight part. This is because if the amount is less than 1 part by weight, the dispersibility is lowered, and if it exceeds 50 parts by weight, the chargeability tends to decrease. These dispersants may be used alone or in combination with other dispersants. Examples of other dispersants that can be used include polyester dispersants, acrylic acid, methacrylic acid and / or ester polymers thereof, and colorant derivatives.

  In the present invention, an acrylic copolymer having an N, N-disubstituted amino group and an acidic group in the main chain or side chain is used as a dispersant for the colorant, and an acidic type colorant (pigment) derivative is used in combination. Thus, the amine sites of the dispersant are adsorbed on the surface of the colorant derivative via the colorant derivative, and the dispersion used for granulation in the aqueous phase by the acid groups of the dispersant facing the outside of the toner particles. The arrangement of the colorant in the toner can be controlled by the amount of the agent, and the adverse effect of the dispersant having an amine value that tends to be positively charged is eliminated. In other words, the amount of colorant present in the vicinity of the toner surface layer can be controlled, so that not only the shape of the toner can be modified, but also the amount of acid sites in the dispersant increases on the toner surface side. Will not be disturbed.

  Moreover, it is preferable that the mixture ratio of the coloring agent and the organic solvent in the dispersion liquid of the coloring component is in the range of 5:95 to 50:50. If the blending ratio of the colorant is less than this, the amount of the dispersion is increased at the time of toner preparation, and the efficiency of toner preparation tends to be reduced. If the blending ratio of the colorant is larger than this, the dispersion of the pigment tends to be insufficient.

  The colorant may be used as a dispersion of a colorant obtained by dispersing only the colorant in an organic solvent in advance, or may be directly dispersed in an organic solvent together with a binder resin, a dispersant, and a dispersion resin. . Even when the colorant is dispersed in advance, in order to apply an appropriate shearing force when dispersing the pigment, a part of the binder resin may be added to adjust the viscosity.

  The particle size of the colorant in the dispersion after dispersing the colorant is desirably 1 μm or less. When the particle size is larger than 1 μm, the particle size of the colorant is increased when the toner is formed, and the image quality is liable to be deteriorated. In particular, the light transmittance of OHP is liable to be lowered. The particle size of the colorant can be determined with a laser Doppler type distribution measuring apparatus UPA-150 (manufactured by Nikkiso Co., Ltd.).

(Toner shape)
For the purpose of improving the cleaning property, various proposals have been made to control the shape of a spherical or small particle toner. For example, the shape of the toner is represented by using a shape factor SF-1 which is an index representing the degree of roundness of the toner particles and a shape factor SF-2 which is an index representing the degree of unevenness of the toner particles, and SF-1, SF -2 is defined to control the toner shape to improve the cleaning property. The present invention is characterized in that SF-1 is 135 to 138 and SF-2 is 125 to 130 .

The shape factor SF-2 indicates the ratio of the unevenness of the toner shape and is represented by the formula (2). FIG. 1 is a diagram schematically showing the shape of the toner for explaining the shape factor SF-2. L is the major axis length of the projected measured particle, C is the perimeter, and A is the projected area. Therefore, when the value of SF-2 is 100, it represents a true sphere, and the toner surface has no irregularities. The larger the SF-2 value, the more the irregularities of the toner surface become more prominent.
SF-2 = {C ² / A} × (100 / 4π) (2)

When SF-2 is increased, the unevenness of the toner surface is increased, the toner surface is non-uniformly charged, the background is stained, and the image quality is lowered. For this reason, SF-2 should not exceed 130 . Furthermore, it is preferable that SF-2 exists in the range of 125-140. When SF-2 is less than 125, the toner surface is smooth, so that the external additive is easy to roll and the contact with the carrier is weak and the desired charge amount is not easily obtained, and the cleaning property of the toner is also deteriorated. If SF-2 exceeds 130 , the external additive is gathered in the concave portion, the toner fluidity is lowered, the charging rise is delayed, and an abnormal image such as background fogging at the time of toner replenishment may occur. .
Since the external additive has a higher hardness than the binder resin of the toner, it is easily embedded in the toner. In particular, in a toner having a low SF-2 and low unevenness, the external additive is buried from the toner surface to the inside, and the effect of contributing to the charge amount of the external additive tends to be lost.

The toner of the present invention has a shape factor SF-1 of 135 to 138 . FIG. 1 is a diagram schematically showing the shape of the toner in order to explain the shape factor SF-1. The shape factor SF-1 indicates the ratio of the roundness of the toner shape and is represented by the following formula (1).
SF-1 = {L ² / A} × (100π / 4) (1)
L is the major axis length of the projected particle to be measured, C is the peripheral length, A is a true sphere when the value of the projected area SF-1 is 100, and becomes irregular as the value of SF-1 increases. .

Here, when the shape factor SF-1 exceeds 138 , the surface area increases with respect to a constant weight, but the proper charge amount (μC / g) of toner per unit weight depends on conditions such as each process. When the weight of the charge control agent is increased as the surface area is increased, the charge amount is increased, so that the charge amount may be larger than the appropriate charge amount, and the charge amount distribution is broadened. Further, if SF-1 exceeds 138 , it becomes difficult to faithfully move along the electric field in development and transfer, and a high-definition image cannot be obtained. Further, the cleaning performance is substantially deteriorated with toner particles having a substantially spherical shape with SF-1 smaller than 135, and the cleaning performance is improved because the toner particles have a shape distribution even with toner particles having a shape with SF-1 of 125 to 135. Tend to get worse. Therefore, the shape factor SF-1 is more preferably in the range of 135 to 138 .

  The toner shape factor SF-1 was obtained by randomly sampling 100 toner images enlarged by a magnification of 500 times using FE-SEM (S-800) manufactured by Hitachi, Ltd. It can be obtained by analyzing with an image analysis device (Luzex III).

  The colorant used in the present invention may be subjected to a surface treatment, and any conventional treatment method can be adopted as a method for treating the colorant with a rosin resin. For example, rosin is dissolved in a solvent, After the colorant is dispersed and the rosin is adsorbed to the colorant, the colorant and the rosin liquid are filtered and the colorant is dried, or the method described in JP-A-7-188575 or the like. Examples include a method in which rosin is adsorbed or precipitated.

  Moreover, the kind of rosin used in this case can be any general rosin and known ones. There are rosins mainly composed of abietic acid and dextropimaric acid, for example, natural rosins such as wood rosin and gum rosin. Further, modified rosins obtained by polymerizing, hydrogenating or oxidizing them, or rosin derivatives such as rosin alkyd adduct, rosin alkylene oxide adduct, rosin modified phenol, and the like can be mentioned.

  In performing the rosin-based resin treatment, the amount of rosin to be adsorbed on the colorant is preferably 0.1 to 10% by mass with respect to 100% by mass of the colorant. Although the action of rosin itself is not well understood, the color of the present colorant becomes clear when the rosin resin treatment is performed. Further, the dispersibility with the resin is improved, and there is a dispersant effect. Moreover, even a small amount is effective. However, if the amount of rosin is too large, the binding property with the binder resin may be weakened, and unevenness may occur in the finally obtained toner chargeability.

  An example of the pigment surface treatment method is sulfonation. If a solvent that is insoluble or sparingly soluble in the pigment is selected without causing the dispersion solvent in the reaction system to react with the sulfonation reagent, a sulfonation reaction that can be performed by a normal organic reaction can be used. As the sulfonating agent, sulfuric acid, fuming sulfuric acid, sulfur trioxide, chlorosulfuric acid, fluorosulfuric acid, amidosulfuric acid and the like are used. In addition, if the trioxide itself is too reactive and inappropriate, or if the presence of a strong acid is not preferred, sulfonation can be performed using a complex of sulfur trioxide and a tertiary amine. . In some cases, Lewis acids such as aluminum chloride and tin chloride can be used as a catalyst. However, the type of solvent in the reaction, reaction temperature, reaction time, type of sulfonating agent and the like differ depending on the type of pigment and the reaction system.

  The colorant used in the present invention can also be used as a master batch combined with a resin. As the binder resin to be kneaded together with the production of the masterbatch or the masterbatch, in addition to the modified and unmodified polyester resins mentioned above, styrene such as polystyrene, poly p-chlorostyrene, polyvinyltoluene, and polymers of substituted products thereof; Styrene-p-chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer Styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α- Chloromethyl methacrylate copolymer, Tylene-acrylonitrile copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, styrene-malein Styrene copolymers such as acid ester copolymers; polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, poly Acrylic resin, rosin, modified rosin, terpene resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, paraffin wax, etc. The

  This master batch can be obtained by mixing and kneading a resin for a master batch and a colorant under a high shear force to obtain a master batch. At this time, an organic solvent can be used to enhance the interaction between the colorant and the resin. In addition, a so-called flushing method, which is a wet cake of a coloring agent, is a method of mixing and kneading an aqueous paste containing water of a coloring agent together with a resin and an organic solvent, transferring the coloring agent to the resin side, and removing moisture and organic solvent components. Since it can be used as it is, it is not necessary to dry and is preferably used. For mixing and kneading, a high shear dispersion device such as a three-roll mill is preferably used.

(Release agent)
Further, a wax may be contained as a release agent together with the binder resin and the colorant. Known waxes can be used as the wax of the present invention, and examples thereof include polyolefin waxes (polyethylene wax, polypropylene wax, etc.); long-chain hydrocarbons (paraffin wax, sazol wax, etc.); carbonyl group-containing waxes. Of these, carbonyl group-containing waxes are preferred. Examples of the carbonyl group-containing wax include polyalkanoic acid esters (carnauba wax, montan wax, trimethylolpropane tribehenate, pentaerythritol tetrabehenate, pentaerythritol diacetate dibehenate, glycerin tribehenate, 1,18. -Octadecanediol distearate, etc.); polyalkanol esters (tristearyl trimellitic acid, distearyl maleate, etc.); polyalkanoic acid amides (ethylene diamine dibehenyl amide, etc.); polyalkylamides (trimellitic acid tristearyl amide, etc.) And dialkyl ketones (such as distearyl ketone). Among these carbonyl group-containing waxes, polyalkanoic acid esters are preferred. The melting point of the wax of the present invention is usually 40 to 160 ° C, preferably 50 to 120 ° C, more preferably 60 to 90 ° C. A wax having a melting point of less than 40 ° C. has an adverse effect on heat resistant storage stability, and a wax having a melting point of more than 160 ° C. tends to cause a cold offset when fixing at a low temperature. Further, the melt viscosity of the wax is preferably 5 to 1000 cps, more preferably 10 to 100 cps as a measured value at a temperature 20 ° C. higher than the melting point. Waxes exceeding 1000 cps have poor effects for improving hot offset resistance and low-temperature fixability. The content of the wax in the toner is usually 0 to 40% by weight, preferably 3 to 30% by weight.

The softening point Tm of the release agent in the present invention is determined by the peak top indicating the maximum endotherm of the DSC curve in differential scanning calorimetry (DSC). The measurement was performed under the following measurement conditions using TA-60WS and DSC-60 manufactured by Shimadzu Corporation.
Measurement conditions Sample container: Aluminum sample pan (with lid)
Sample amount: 5mg
Reference: Aluminum sample pan (alumina 10mg)
Atmosphere: Nitrogen (flow rate 50 ml / min)
Temperature conditions The measurement results were analyzed using the data analysis software (TA-60, version 1.52) manufactured by Shimadzu Corporation. Starting temperature: 20 ° C
Temperature increase rate: 10 ° C / min
End temperature: 150 ° C
Holding time: None Temperature drop: 10 ° C / min
End temperature: 20 ° C
Holding time: None Temperature increase rate: 10 ° C / min
End temperature: 150 ° C
The analysis method specifies a range of ± 5 ° C. around the point showing the maximum peak of the DrDSC curve which is the DSC differential curve of the second temperature rise, and obtains the peak temperature using the peak analysis function of the analysis software. Next, the maximum endothermic temperature of the DSC curve is determined using the peak analysis function of the analysis software in the range of the peak temperature + 5 ° C. and −5 ° C. in the DSC curve. The temperature indicated here corresponds to the Tm of the wax.

(Charge control agent)
The toner of the present invention may contain a charge control agent as necessary. All known charge control agents can be used, such as nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts (fluorine-modified). Quaternary ammonium salts), alkylamides, phosphorus simple substances or compounds, tungsten simple substances or compounds, fluorine-based activators, salicylic acid metal salts, and metal salts of salicylic acid derivatives.

  Specifically, Nitronine-based dye Bontron 03, quaternary ammonium salt Bontron P-51, metal-containing azo dye Bontron S-34, oxynaphthoic acid metal complex E-82, salicylic acid metal complex E- 84, E-89 of a phenol-based condensate (manufactured by Orient Chemical Industry Co., Ltd.), TP-302 of a quaternary ammonium salt molybdenum complex, TP-415 (manufactured by Hodogaya Chemical Industry Co., Ltd.), quaternary ammonium Copy charge PSY VP2038 of salt, copy blue PR of triphenylmethane derivative, copy charge of quaternary ammonium salt NEG VP2036, copy charge NX VP434 (manufactured by Hoechst), LRA-901, LR-147 which is a boron complex (Nippon Carlit), copper phthalocyanine, perylene, quinaclide And azo pigments, and other high molecular compounds having a functional group such as a sulfonic acid group, a carboxyl group, and a quaternary ammonium salt.

  In the present invention, the amount of charge control agent used is determined by the toner production method including the type of binder resin, the presence or absence of additives used as necessary, and the dispersion method, and is uniquely limited. However, it is preferably used in the range of 0.1 to 10 parts by weight with respect to 100 parts by weight of the binder resin. The range of 0.2 to 5 parts by weight is preferable. When the amount exceeds 10 parts by weight, the chargeability of the toner is too high, the effect of the main charge control agent is reduced, the electrostatic attraction force with the developing roller is increased, the developer fluidity is lowered, and the image density is lowered. Invite. These charge control agents can be dissolved and dispersed after being melt-kneaded with a masterbatch and resin, and of course, they can be added directly when dissolved and dispersed in an organic solvent, or fixed on the toner surface after preparation of toner particles. May be.

(Resin fine particles)
The resin fine particles used in the present invention are added in the production process in order to control the toner shape (circularity, particle size distribution, etc.), and have a glass transition point (Tg) of 30 to 70 ° C. and a weight average. If the molecular weight is 8000 to 400,000, Tg is less than 30 ° C. and / or the weight average molecular weight is less than 8000, the storage stability of the toner deteriorates, and blocking occurs during storage and in the developing machine. Resulting in. When Tg exceeds 70 ° C. and / or the weight average molecular weight exceeds 400,000, the resin fine particles inhibit the adhesion to the fixing paper, and the minimum fixing temperature is increased.

Therefore, it is important that the resin fine particles have a residual ratio of 0.5 to 5.0 wt% with respect to the toner particles. When the residual ratio is less than 0.5 wt%, the storage stability of the toner is deteriorated, and blocking occurs during storage and in the developing machine. When the residual amount is 5.0 wt% or more, the resin fine particles are not present. The exudation of the wax is obstructed, the effect of releasing the wax is not obtained, and the occurrence of offset is observed.
The residual rate of the resin fine particles can be measured by analyzing a substance caused by the resin fine particles, not by the toner particles, using a pyrolysis gas chromatograph mass spectrometer, and calculating from the peak area. The detector is preferably a mass spectrometer, but is not particularly limited.

The resin fine particles may be any resin as long as it can form an aqueous dispersion, and may be a thermoplastic resin or a thermosetting resin. For example, vinyl resins, polyurethane resins, epoxy resins, polyester resins, polyamide resins, polyimides Examples thereof include resins, silicon-based resins, phenol resins, melamine resins, urea resins, aniline resins, ionomer resins, and polycarbonate resins. As the resin fine particles, two or more of the above resins may be used in combination. Of these, vinyl resins, polyurethane resins, epoxy resins, polyester resins, and combinations thereof are preferred because an aqueous dispersion of fine spherical resin particles is easily obtained.
The particle size of the resin fine particles is preferably 5 to 500 nm. When the average particle size of the resin fine particles is less than 5 nm, the resin fine particles remaining on the toner surface become a film or cover the entire toner surface, and the release agent fine particles are formed between the binder resin component in the toner and the fixing paper. Adhesion is hindered, the minimum fixing temperature is increased, and the particle size and shape are also difficult to control. Also, if the particle size of the resin fine particles is larger than 500 nm, the resin fine particles remaining on the toner surface largely protrude as convex portions, or the resin fine particles remain as a multilayered layer in a rough state. Desorption of mold fine particles is observed.

The particle size of the resin fine particles can be measured using a laser Doppler particle size distribution measuring instrument (Nikkiso Co., Ltd.).
Method:
(1) The sample is diluted with ion-exchanged water, and the solid content of the resin fine particles is adjusted to 0.6% (set in the range of 0.5% to 1.0%).
(2) Measuring conditions of measuring instrument
Distribution display: Volume
Number of channels: 52
Measurement time: 30 sec
Particle refractive index: 1.81
Temperature: 25 ° C
Particle shape: non-spherical
Viscosity (CP): 0.8750
Solvent refractive index: 1.333
Solvent name: Water
(3) The sample diluent to be measured is added using a dropper or a syringe so that it falls within (1 to 100) while watching the sample loading of the measuring instrument.

  The vinyl resin constituting the fine resin particles is a polymer obtained by homopolymerization or copolymerization of a vinyl monomer, such as styrene- (meth) acrylic acid ester resin, styrene-butadiene copolymer, (meth) acrylic acid-acrylic. Examples include acid ester polymers, styrene-acrylonitrile copolymers, styrene-maleic anhydride copolymers, styrene- (meth) acrylic acid copolymers, and the like.

(Inorganic fine particles)
In order to assist the heat resistant storage stability and chargeability of the colored particles obtained in the present invention, inorganic fine particles can be used. The primary particle diameter of the inorganic fine particles is preferably 0.5 nm to 200 nm, and particularly preferably 0.5 nm to 50 nm. Moreover, it is preferable that the specific surface area by BET method is 20-500 m < ² > / g. The use ratio of the inorganic fine particles is preferably 0.01 to 5 wt% of the toner, and particularly preferably 0.01 to 2.0 wt%. Specific examples of inorganic fine particles include, for example, tricalcium phosphate, colloidal silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, tin oxide, silica sand, clay, mica. , Wollastonite, diatomaceous earth, chromium oxide, cerium oxide, bengara, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, silicon nitride, hydroxyapatite, etc. .

(BET specific surface area)
The toner of the present invention preferably has a BET specific surface area of 0.5 to 6.0 (m ² / g), and if the BET specific surface area is less than 0.5 (m ² / g), the presence or addition of coarse particles When the amount exceeds 6.0 (m ² / g), the image quality is likely to be affected by the presence of fine particles, the presence of additives, and surface irregularities. The BET specific surface area of the toner of the present invention can be obtained by measuring using a device capable of complying with JIS standards (Z8830 and R1626) such as NOVA series manufactured by Yuasa Ionics.

(External additive)
In order to assist the fluidity and developability of the colored particles obtained in the present invention, polymer fine particles such as soap-free emulsion polymerization, suspension polymerization, dispersion polymerization, polystyrene, methacrylate ester and acrylate ester copolymer Examples thereof include polymer particles such as coalescence, polycondensation systems such as silicone, benzoguanamine, and nylon, and thermosetting resins.
Such a fluidizing agent can be surface-treated to increase hydrophobicity and prevent deterioration of flow characteristics and charging characteristics even under high humidity. For example, silane coupling agents, silylating agents, silane coupling agents having an alkyl fluoride group, organic titanate coupling agents, aluminum coupling agents, silicone oils, modified silicone oils and the like are preferable surface treatment agents. .

  Examples of the cleaning property improver for removing the developer after transfer remaining on the photoreceptor or the primary transfer medium include, for example, zinc stearate, calcium stearate, fatty acid metal salts such as stearic acid, such as polymethyl methacrylate fine particles, polystyrene fine particles, etc. And polymer fine particles produced by soap-free emulsion polymerization. The polymer fine particles preferably have a relatively narrow particle size distribution and a volume average particle size of 0.01 to 1 μm.

(Volume average particle diameter, number average particle diameter of toner)
Further, the toner of the present invention has a volume average particle diameter (Dv) of 3.0 to 8.0 μm, and a ratio (Dv / Dn) of the volume average particle diameter (Dv) to the number average particle diameter (Dn). It is preferable that it is 1.00-1.30. By using a toner having such a particle size and particle size distribution, it is excellent in heat-resistant storage stability, low-temperature fixability, and hot offset resistance, and particularly when used in a full-color copying machine, etc. Sex is obtained. In general, it is said that the smaller the particle size of the toner, the more advantageous it is to obtain a high-resolution and high-quality image, but it is disadvantageous for transferability and cleaning properties. is there. In addition, when the volume average particle size is smaller than the range of the present invention, in the case of a two-component developer, the toner is fused to the surface of the magnetic carrier during a long period of stirring in the developing device, and the charging ability of the magnetic carrier is reduced. When used as a developer, toner filming on the developing roller and toner fusion to a member such as a blade for thinning the toner are likely to occur. On the contrary, when the volume average particle diameter of the toner is larger than the range of the present invention, it becomes difficult to obtain a high-resolution and high-quality image, and when the balance of the toner in the developer is performed. In many cases, the variation in toner particle size becomes large. On the other hand, if Dv / Dn exceeds 1.30, the charge amount distribution becomes wide and the resolving power decreases, which is not preferable.

  The volume average particle diameter (Dv) and the number average particle diameter (Dn) of the toner of the present invention are measured using a particle size measuring device (Multisizer III, manufactured by Beckman Coulter, Inc.) with an aperture diameter of 100 μm, and analyzed software (Beckman Coulter). Analysis was performed using Multisizer 3 Version 3.51). Specifically, 0.5 ml of 10 wt% surfactant (alkylbenzene sulfonate Neogen SC-A; manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was added to a glass 100 ml beaker, 0.5 g of each toner was added, and the mixture was stirred with a micropartel. Subsequently, 80 ml of ion-exchanged water was added. The obtained dispersion was subjected to a dispersion treatment for 10 minutes with an ultrasonic disperser (W-113MK-II, manufactured by Honda Electronics Co., Ltd.). The dispersion was measured using the Multisizer III and Isoton III (manufactured by Beckman Coulter) as the measurement solution. In the measurement, the toner sample dispersion was dropped so that the concentration indicated by the apparatus was 8 ± 2%. In this measurement method, it is important that the concentration is 8 ± 2% from the viewpoint of the reproducibility of the particle size. Within this concentration range, no error occurs in the particle size.

(Average circularity of toner particles) Refer to Japanese Patent Application Laid-Open No. 2005-3751 The average circularity of toner particles is 0.95 to 0.995 because dot reproducibility is excellent and transferability is also good. From the viewpoint of obtaining Such a toner having a high average circularity is liable to slip on the surface of a frictional charging member such as a magnetic carrier, which is disadvantageous in terms of charging speed and charging level. However, by having the surface properties of the toner particles according to claim 1, a sufficient triboelectric chargeability can be obtained, and a toner excellent in developability and transferability can be obtained. When the average circularity is less than 0.95 and the toner is separated from the spherical shape, it is difficult to obtain a high-quality image with sufficient transferability or dust. Such irregularly shaped particles have many points of contact with the smooth medium on the photoreceptor and the charge concentrates on the tip of the protrusion, so van der Waals force and mirror force are more than those with relatively spherical particles. Wearing power is high. For this reason, in the electrostatic transfer process, the spherical particles are selectively moved in the toner in which the amorphous particles and the spherical particles are mixed, and the character portion and the line portion image are lost. Further, the remaining toner has to be removed for the next development step, and there arises a problem that a cleaning device is necessary and the toner yield (the ratio of toner used for image formation) is low.

  The average circularity in the present invention is measured using a flow particle image analyzer (FPIA-2100; manufactured by Sysmex Corporation), and analyzed using analysis software (FPIA-2100 Data Processing Program for FPIA version 00-10). It was. Specifically, 0.1 to 0.5 ml of 10 wt% surfactant (alkylbenzene sulfonate Neogen SC-A; manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) is added to a glass 100 ml beaker, and each toner 0.1 to. 5 g was added and stirred with a microspatel, and then 80 ml of ion-exchanged water was added. The obtained dispersion was subjected to a dispersion treatment for 3 minutes with an ultrasonic disperser (manufactured by Honda Electronics Co., Ltd.). The shape and distribution of the toner were measured using the FPIA-2100 until the density of the dispersion was 5000 to 15000 / μl. In this measurement method, it is important that the concentration of the dispersion liquid is 5000 to 15000 / μl from the viewpoint of measurement reproducibility of the average circularity. In order to obtain the dispersion concentration, it is necessary to change the conditions of the dispersion, that is, the amount of surfactant to be added and the amount of toner. The amount of the surfactant varies depending on the hydrophobicity of the toner as in the measurement of the toner particle diameter described above. If it is added in a large amount, noise due to bubbles is generated. If the amount is too small, the toner cannot be sufficiently wetted. It becomes insufficient. Further, the toner addition amount differs from the particle size, and it is necessary to decrease the small particle size and increase the large particle size. When the toner particle size is 3 to 7 μm, the toner amount is 0.1 to 0. By adding 0.5 g, the dispersion concentration can be adjusted to 5000 to 15000 / μl.

  The sample dispersion liquid is passed through a flow path (expanded along the flow direction) of a flat and flat transparent flow cell (thickness: about 200 μm). In order to form an optical path that passes across the thickness of the flow cell, the strobe and the CCD camera are mounted on the flow cell so as to be opposite to each other. While the sample dispersion is flowing, strobe light is irradiated at 1/30 second intervals to obtain an image of the particles flowing through the flow cell, so that each particle has a certain range parallel to the flow cell. Photographed as a two-dimensional image. From the area of the two-dimensional image of each particle, the diameter of a circle having the same area is calculated as the equivalent circle diameter. In about 1 minute, the equivalent circle diameter of 1200 or more particles can be measured, and the number based on the equivalent circle diameter distribution and the ratio (number%) of particles having a prescribed equivalent circle diameter can be measured. As shown in Table 1, the results (frequency% and cumulative%) can be obtained by dividing the range of 0.06-400 μm into 226 channels (divided into 30 channels for one octave). In actual measurement, particles are measured in the range where the equivalent circle diameter is 0.60 μm or more and less than 159.21 μm.

(Inorganic filler) See JP-A-2005-49853. The inorganic filler is present in the vicinity of the surface of the toner base particles, and serves to control the shape of the toner base particles during the manufacturing process. Examples of inorganic fillers include silica, diatomaceous earth, alumina, zinc oxide, titania, zirconia, calcium oxide, magnesium oxide, iron oxide, copper oxide, tin oxide, chromium oxide, antimony oxide, yttrium oxide, cerium oxide, and samarium oxide. , Metal oxides such as lanthanum oxide, tantalum oxide, terbium oxide, europium oxide, neodymium oxide, ferrites, metal hydroxides such as calcium hydroxide, magnesium hydroxide, aluminum hydroxide, basic magnesium carbonate, heavy Metal carbonates such as calcium carbonate, light calcium carbonate, zinc carbonate, barium carbonate, dawsonite, hydrotalcite, metal sulfates such as calcium sulfate, barium sulfate, gypsum fiber, calcium silicate (wollastonite, zonotlite), kaolin, clei , Talc, mica, montmorillonite, bentonite, activated clay, sepiolite, imogolite, sericite, glass fiber, glass, glass flake and other metal silicates, aluminum nitride, boron nitride, silicon nitride and other metal nitrides, potassium titanate Metal titanates such as calcium titanate, magnesium titanate, barium titanate, lead zirconate titanate aluminum borate, metal borates such as zinc borate and aluminum borate, metal phosphoric acids such as tricalcium phosphate Examples thereof include salts, metal sulfides such as molybdenum sulfide, metal carbides such as silicon carbide, carbons such as carbon black, graphite, and carbon fiber, and other fillers. Of these, silica, alumina, and titania are preferable.

  In order to disperse the inorganic filler in the organic solvent, it is preferable to use it in the form of the following organosol. In order to obtain an organosol of an inorganic filler, for example, a dispersion of a hydrogel of an inorganic filler synthesized by a wet method (hydrothermal synthesis method, sol-gel method, etc.) is hydrophobized with a surface treatment agent, and water is added. Examples of the method include substitution with an organic solvent such as methyl ethyl ketone and ethyl acetate. Examples of the surface treatment agent include silicone oil, coupling agents (for example, silane coupling agents, titanate coupling agents and aluminate coupling agents), amine compounds, and various commercially available pigment dispersants. Silicon oil, silane coupling agents, and amine compounds are preferably used. Examples of silicone oil include straight silicone oil such as dimethyl silicone oil, methylphenyl silicone oil, and methylhydrogen silicone oil, methacrylic acid modified silicone oil, epoxy modified silicone oil, fluorine modified silicone oil, polyether modified silicone oil, amino Examples include modified silicone oil such as modified silicone oil. Examples of the silane coupling agent include organoalkoxysilane, organochlorosilane, organosilazane, organodisilazane, organosiloxane, organodisiloxane, and organosilane. As the amine compound, a compound that is compatible with an organic solvent and has at least one of a primary amine group, a secondary amine group, and a tertiary amine group can be used. The amine compound is a polyester prepolymer. In particular, it is preferable to use a compound having a tertiary amine group that does not contain active hydrogen. Examples of such tertiary amine compounds include triethylamine, N, N′-dimethylaminodiethyl ether, tetramethylhexamethylenediamine, tetramethylethylenediamine, dimethylethanolamine, N-methyl-N ′-(2-dimethylamino). ) Ethylpiperazine, 1,2-dimethylimidazole, triethylenediamine, N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine, N, N, N ′, N ″, N ″ -pentamethyldipropylenetriamine, Examples include tetramethylguanidine, 1,8-diazabicyclo [5,4,0] undecene-7, bis (2-morpholinoethyl) ether, and the like. Of these, triethylamine, 1,8-diazabicyclo [5,4,0] undecene-7, and bis (2-morpholinoethyl) ether are particularly preferable.

  As a method for producing an inorganic sol organosol, for example, the method described in JP-A No. 11-43319 can be suitably used. Examples of commercially available organosols include organosilica sols MEK-ST and MEK-ST-UP (both Nissan Chemical Industries, Ltd.). The particle size of the inorganic filler is preferably 5 to 100 nm, more preferably 10 to 30 nm. The addition amount is 1 to 10 parts by weight, preferably 2 to 7 parts by weight, based on 100 parts by weight of the toner resin component (including the binder and the wax component as a release agent). When added as an organosol, the addition amount is adjusted so that the solid content is in the above range. The toner of the present invention, that is, the toner having a surface shape in which the A / S value is in a specified range and the contact with the member is a line contact, is adjusted by adjusting the kind of inorganic filler and the addition amount thereof. To obtain the toner.

(Binder resin production method)
The toner binder can be produced by the following method. The polyol (1) and the polycarboxylic acid (2) are heated to 150 to 280 ° C. in the presence of a known esterification catalyst such as tetrabutoxytitanate or dibutyltin oxide, and the generated water is distilled off as necessary. Thus, a polyester having a hydroxyl group is obtained. Next, this is reacted with polyisocyanate (3) at 40 to 140 ° C. to obtain a prepolymer (A) having an isocyanate group.

The dry toner of the present invention can be produced by the following method, but is not limited thereto.
(Toner Production Method in Aqueous Medium) See Japanese Patent No. 3631468. The toner of the present invention is a matrix composed of at least a binder resin produced in an aqueous medium, a colorant, a dispersant, and a pigment derivative. The following particles can also be produced as follows. That is, a method in which a resin in which a colorant is dispersed in a resin is heated or dispersed in a toner particle size in an air stream or an aqueous medium by using a solvent (dissolution suspension method), polymerizability Resin particles can be produced by a so-called suspension polymerization method in which a colorant or the like dispersed in a monomer is dispersed and polymerized in an aqueous medium.

  The aqueous phase used in the present invention is used by adding organic fine particles in advance. The water used for the aqueous phase may be water alone, or a solvent miscible with water may be used in combination. Examples of the miscible solvent include alcohol (methanol, isopropanol, ethylene glycol, etc.), dimethylformamide, tetrahydrofuran, cellosolves (methylcellosolve, etc.), lower ketones (acetone, methyl ethyl ketone, etc.) and the like.

  In the case of the dissolution suspension method, in order to add a polymer having a urea bond to toner particles, a dispersion composed of a polyester prepolymer (A) having an isocyanate group is reacted with amines (B) in an aqueous medium. The urea-modified polyester (i) produced in advance may be used. As a method for stably forming a dispersion comprising a urea-modified polyester (i) or a polyester prepolymer (A) in an aqueous medium, the urea-modified polyester (i) or the polyester prepolymer (A) is formed in an aqueous medium. Examples thereof include a method of adding a toner raw material composition and dispersing it by shearing force. The polyester prepolymer (A) and other toner compositions (hereinafter referred to as toner raw materials), a colorant, a release agent, an unmodified polyester resin, etc. may be mixed when forming a dispersion in an aqueous medium. However, it is more preferable to mix the toner raw materials in advance and then add and disperse the mixture in the aqueous medium. In the present invention, other toner raw materials such as a colorant and a release agent are not necessarily mixed when forming particles in an aqueous medium, and are added after the particles are formed. May be. For example, after forming particles containing no colorant, the colorant can be added by a known dyeing method.

  The dispersion method is not particularly limited, and known equipment such as a low-speed shear method, a high-speed shear method, a friction method, a high-pressure jet method, and an ultrasonic wave can be applied. In order to make the particle size of the dispersion 2 to 8 μm, a high-speed shearing type is preferable. When a high-speed shearing disperser is used, the rotational speed is not particularly limited, but is usually 1000 to 30000 rpm, preferably 5000 to 20000 rpm. The dispersion time is not particularly limited, but in the case of a batch method, it is usually 0.1 to 5 minutes. The temperature during dispersion is usually 0 to 150 ° C. (under pressure), preferably 40 to 98 ° C. Higher temperatures are preferable in that the dispersion of the urea-modified polyester (i) or the polyester prepolymer (A) has a low viscosity and is easily dispersed.

  The amount of the aqueous medium used is usually 50 to 2000 parts by weight, preferably 100 to 1000 parts by weight, based on 100 parts of the toner composition containing the vinyl polymerizable monomer, urea-modified polyester (i) and polyester prepolymer (A). If the amount is less than 50 parts by weight, the dispersion state of the toner composition is poor, and toner particles having a predetermined particle diameter cannot be obtained. If it exceeds 20000 parts by weight, the production cost increases. Further, it is preferable to use a dispersant because the particle size distribution becomes sharp and the dispersion is stable.

  The amount of the aqueous phase used relative to 100 parts of the toner composition containing the polyester prepolymer (A) is usually 50 to 20000 parts by weight, preferably 100 to 10,000 parts by weight. If the amount is less than 50 parts by weight, the dispersion state of the toner composition is poor, and toner particles having a predetermined particle diameter cannot be obtained. If it exceeds 20000 parts by weight, it is not economical. Further, it is preferable to use a dispersant because the particle size distribution becomes sharp and the dispersion is stable.

  Anionic surfactants such as alkylbenzene sulfonates, α-olefin sulfonates, phosphate esters, alkylamine salts, amino acids as dispersants for emulsifying and dispersing the oily phase in which the toner composition is dispersed in the aqueous phase Amine salt types such as alcohol fatty acid derivatives, polyamine fatty acid derivatives, imidazoline, and quaternary ammonium such as alkyltrimethylammonium salt, dialkyldimethylammonium salt, alkyldimethylbenzylammonium salt, pyridinium salt, alkylisoquinolinium salt, benzethonium chloride Nonionic surfactants such as salt-type cationic surfactants, fatty acid amide derivatives, polyhydric alcohol derivatives, such as alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine and N-alkyl-N, N − Amphoteric surfactants such as ammonium betaine.

Further, by using a surfactant having a fluoroalkyl group, the effect can be obtained in a very small amount. Examples of the anionic surfactant having a fluoroalkyl group preferably used include fluoroalkylcarboxylic acids having 2 to 10 carbon atoms and metal salts thereof, disodium perfluorooctanesulfonyl glutamate, 3- [omega-fluoroalkyl (C6- C11) sodium oxy] -1-alkyl (C3-C4) sulfonate, sodium 3- [omega-fluoroalkanoyl (C6-C8) -N-ethylamino] -1-propanesulfonate, fluoroalkyl (C11-C20) Carboxylic acid and metal salt, perfluoroalkyl carboxylic acid (C7 to C13) and metal salt thereof, perfluoroalkyl (C4 to C12) sulfonic acid and metal salt thereof, perfluorooctane sulfonic acid diethanolamide, N-propyl-N- (2-hydroxyethyl) -Fluorooctanesulfonamide, perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salt, perfluoroalkyl (C6-C10) -N-ethylsulfonylglycine salt, monoperfluoroalkyl (C6-C16) ethyl phosphate, etc. Is mentioned.
Product names include Surflon S-111, S-112, S-113 (Asahi Glass Co., Ltd.), Florard FC-93, FC-95, FC-98, FC-129 (Sumitomo 3M Co., Ltd.), Unidyne DS-101. , DS-102, (Daikin Kogyo Co., Ltd.), MegaFuck F-l10, F-l20, F-113, F-191, F-812, F-833 (Dainippon Ink Co., Ltd.), Xtop EF-102 , 103, 104, 105, 112, 123A, 123B, 306A, 501, 201, 204 (manufactured by Tochem Products), and Fagento F-100, F150 (manufactured by Neos).

  Examples of cationic surfactants include aliphatic primary, secondary or secondary amine acids having a fluoroalkyl group, aliphatic quaternary ammonium salts such as perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salt, benza Luconium salt, benzethonium chloride, pyridinium salt, imidazolinium salt, trade names include Surflon S-121 (Asahi Glass), Florard FC-135 (Sumitomo 3M), Unidyne DS-202 (Daikin Industries) , Megafac F-150, F-824 (Dainippon Ink Co., Ltd.), Xtop EF-132 (Tochem Products Co., Ltd.), Footgent F-1300 (Neos Co., Ltd.), and the like.

Further, tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, hydroxyapatite and the like can be used as an inorganic compound dispersant which is hardly soluble in water.
Further, the dispersed droplets may be stabilized by a polymer protective colloid. For example, acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid or maleic anhydride and other (meth) acrylic monomers containing hydroxyl groups Such as β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate, γ-hydroxypropyl acrylate, γ-hydroxypropyl methacrylate, 3-chloroacrylate 2-hydroxypropyl, 3-chloro-2-hydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerol monoacrylate, glycerol monomethacrylate, N -Methylol acrylamide, N-methylol methacrylamide, etc., vinyl alcohol or ethers with vinyl alcohol, such as vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, etc., or esters of compounds containing vinyl alcohol and carboxyl groups, such as Vinyl acetate, vinyl propionate, vinyl butyrate, etc., acrylamide, methacrylamide, diacetone acrylamide or their methylol compounds, acid chlorides such as acrylic acid chloride, methacrylic acid chloride, vinyl pyridine, vinyl pyrrolidone, vinyl imidazole, ethyleneimine, etc. Homopolymers or copolymers such as those having a nitrogen atom or a heterocyclic ring thereof, polyoxyethylene, polyoxypropylene, Oxyethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonyl phenyl ether, polyoxyethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ester, polyoxyethylene nonyl phenyl ester Polyoxyethylenes such as, celluloses such as methyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose can be used.

In addition, when an acid such as calcium phosphate salt or an alkali-soluble substance is used as the dispersion stabilizer, the calcium phosphate salt is removed from the fine particles by a method such as dissolving the calcium phosphate salt with an acid such as hydrochloric acid and washing with water. To do. It can also be removed by operations such as enzymatic degradation.
When a dispersant is used, the dispersant may remain on the surface of the toner particles, but it is preferable from the charged surface of the toner that the dispersant is washed and removed after the elongation and / or crosslinking reaction.

  The elongation and / or cross-linking reaction time is selected depending on the reactivity of the isocyanate group structure of the prepolymer (A) and the amines (B), but is usually 10 minutes to 40 hours, preferably 2 to 24 hours. is there. The reaction temperature is generally 0 to 150 ° C, preferably 40 to 98 ° C. Moreover, a well-known catalyst can be used as needed. Specific examples include dibutyltin laurate and dioctyltin laurate.

  In order to remove the organic solvent from the obtained emulsified dispersion, a method in which the temperature of the entire system is gradually raised to completely evaporate and remove the organic solvent in the droplets can be employed. Alternatively, the emulsified dispersion can be sprayed into a dry atmosphere to completely remove the water-insoluble organic solvent in the droplets to form toner fine particles, and the aqueous dispersant can be removed by evaporation together. . As a dry atmosphere in which the emulsified dispersion is sprayed, a gas obtained by heating air, nitrogen, carbon dioxide gas, combustion gas, or the like, in particular, various air currents heated to a temperature equal to or higher than the boiling point of the highest boiling solvent used is generally used. Sufficient quality can be obtained with a short treatment such as spray dryer, belt dryer or rotary kiln.

  When the particle size distribution at the time of emulsification dispersion is wide and washing and drying processes are performed while maintaining the particle size distribution, the particle size distribution can be adjusted by classifying into a desired particle size distribution. In the classification operation, the fine particle portion can be removed in the liquid by a cyclone, a decanter, centrifugation, or the like. Of course, the classification operation may be performed after obtaining the powder as a powder after drying. The unnecessary fine particles or coarse particles obtained can be returned to the kneading step and used for the formation of particles. At that time, fine particles or coarse particles may be wet. The dispersant used is preferably removed from the obtained dispersion as much as possible, but it is preferable to carry out it simultaneously with the classification operation described above.

Mixing or giving mechanical impact force to the powder mixture after drying with different types of particles such as release agent fine particles, charge control fine particles, fluidizing agent fine particles, and colorant fine particles By immobilizing and fusing on the surface, it is possible to prevent detachment of foreign particles from the surface of the resulting composite particle.
Specific means include a method of applying an impact force to the mixture by blades rotating at high speed, a method of injecting and accelerating the mixture in a high-speed air stream, and causing particles or composite particles to collide with an appropriate collision plate, etc. is there. As equipment, Ong mill (manufactured by Hosokawa Micron Co., Ltd.), I-type mill (manufactured by Nippon Pneumatic Co., Ltd.) has been modified to reduce the pulverization air pressure, hybridization system (manufactured by Nara Machinery Co., Ltd.), kryptron System (manufactured by Kawasaki Heavy Industries, Ltd.), automatic mortar, etc.

(Carrier for two components)
When the toner of the present invention is used for a two-component developer, it may be used by mixing with a magnetic carrier. Part is preferred. As the magnetic carrier, conventionally known ones such as iron powder, ferrite powder, magnetite powder, magnetic resin carrier having a particle diameter of about 20 to 200 μm can be used. Examples of the coating material include amino resins such as urea-formaldehyde resin, melamine resin, benzoguanamine resin, urea resin, polyamide resin, and epoxy resin. Polyvinyl and polyvinylidene resins such as acrylic resins, polymethyl methacrylate resins, polyacrylonitrile resins, polyvinyl acetate resins, polyvinyl alcohol resins, polyvinyl butyral resins, polystyrene resins and styrene acrylic copolymer resins, Halogenated olefin resins such as vinyl, polyester resins such as polyethylene terephthalate resin and polybutylene terephthalate resin, polycarbonate resins, polyethylene resins, polyvinyl fluoride resins, polyvinylidene fluoride resins, polytrifluoroethylene resins, polyhexafluoro Propylene resin, copolymer of vinylidene fluoride and acrylic monomer, copolymer of vinylidene fluoride and vinyl fluoride, tetrafluoroethylene and vinylidene fluoride And fluoro such as terpolymers of non-fluoride monomers including, and silicone resins. Moreover, you may contain electrically conductive powder etc. in coating resin as needed. As the conductive powder, metal powder, carbon black, titanium oxide, tin oxide, zinc oxide or the like can be used. These conductive powders preferably have an average particle diameter of 1 μm or less. When the average particle diameter is larger than 1 μm, it becomes difficult to control electric resistance. The toner of the present invention can also be used as a one-component magnetic toner that does not use a carrier or a non-magnetic toner.

~ Synthesis of resin fine particle emulsion ~
Production Example 1
In a reaction vessel equipped with a stirrer and a thermometer, 683 parts of water, 11 parts of sodium salt of ethylene oxide methacrylate adduct sulfate (Eleminol RS-30, manufactured by Sanyo Chemical Industries), 83 parts of styrene, 83 parts of methacrylic acid, When 110 parts of butyl acrylate and 1 part of ammonium persulfate were added and stirred at 400 rpm for 15 minutes, a white emulsion was obtained. The system was heated to raise the system temperature to 75 ° C. and reacted for 5 hours. Further, 30 parts of a 1% ammonium persulfate aqueous solution was added, and the mixture was aged at 75 ° C. for 5 hours to give a vinyl resin (a copolymer of styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate sodium salt). An aqueous dispersion [resin fine particle dispersion 1] was obtained. The volume average particle diameter of [resin fine particle dispersion 1] measured with LA-920 was 105 nm. A portion of [resin fine particle dispersion 1] was dried to isolate the resin component. The resin content had a Tg of 59 ° C. and a weight average molecular weight of 150,000.

-Adjustment of aqueous phase-
Production Example 2
990 parts of water, 83 parts of [resin fine particle dispersion 1], 37 parts of 48.5% aqueous solution of sodium dodecyl diphenyl ether disulfonate (Eleminol MON-7: manufactured by Sanyo Chemical Industries) and 90 parts of ethyl acetate were mixed and stirred. A liquid was obtained. This is designated as [Aqueous Phase 1].

~ Synthesis of low molecular weight polyester ~
Production Example 3
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen inlet tube, 229 parts of bisphenol A ethylene oxide 2-mole adduct, 529 parts of bisphenol A propylene oxide 3-mole adduct, 208 parts terephthalic acid, 46 parts adipic acid and dibutyl 2 parts of tin oxide was added, reacted at 230 ° C. for 8 hours at normal pressure, and further reacted for 5 hours at a reduced pressure of 10 to 15 mmHg. Then, 44 parts of trimellitic anhydride was added to the reaction vessel, and 2 parts at 180 ° C. and normal pressure. The reaction was performed for a while to obtain [Low molecular weight polyester 1]. [Low molecular polyester 1] had a number average molecular weight of 2500, a weight average molecular weight of 6700, a Tg of 43 ° C., and an acid value of 25.

~ Synthesis of intermediate polyester ~
Production Example 4
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction tube, 682 parts of bisphenol A ethylene oxide 2-mole adduct, 81 parts of bisphenol A propylene oxide 2-mole adduct, 283 parts of terephthalic acid, 22 parts of trimellitic anhydride Then, 2 parts of dibutyltin oxide was added, reacted at 230 ° C. for 8 hours at normal pressure, and further [intermediate polyester 1] reacted for 5 hours at a reduced pressure of 10 to 15 mmHg. [Intermediate Polyester 1] had a number average molecular weight of 2,100, a weight average molecular weight of 9,500, Tg of 55 ° C., an acid value of 0.5, and a hydroxyl value of 51.
Next, 410 parts of [Intermediate polyester 1], 89 parts of isophorone diisocyanate, and 500 parts of ethyl acetate are placed in a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, and reacted at 100 ° C. for 5 hours. Polymer 1] was obtained. [Prepolymer 1] had a free isocyanate weight% of 1.53%.

~ Synthesis of ketimine ~
Production Example 5
In a reaction vessel equipped with a stirrer and a thermometer, 170 parts of isophoronediamine and 75 parts of methyl ethyl ketone were charged and reacted at 50 ° C. for 5 hours to obtain [ketimine compound 1]. The amine value of [ketimine compound 1] was 418.

~ Synthesis of MB ~
Production Example 6
1200 parts water C.I. I. Pigment Yellow PY93 3G (manufactured by Ciba Specialty Chemicals) 540 parts, Dispersant Disperbyk-2001 (amine number: 29, acid value: 19 mg KOH / g manufactured by BYK Chemie) 108 parts, pigment derivative Solsperse 22000 (manufactured by Abyssia) 16 Part, 1200 parts of a polyester resin, and mixing with a Henschel mixer (Mitsui Mining Co., Ltd.), kneading the mixture for 30 minutes at 150 ° C. using two rolls, rolling and cooling, pulverizing with a pulverizer, [Masterbatch 1] Obtained.

~ Creation of oil phase ~
Production Example 7
In a container equipped with a stir bar and a thermometer, 378 parts of [Low molecular weight polyester 1], 110 parts of Carnauba WAX, and 947 parts of ethyl acetate were charged, heated to 80 ° C. with stirring, and kept at 80 ° C. for 5 hours. It was cooled to 30 ° C at 1 hour. Next, 500 parts of [Masterbatch 1] and 500 parts of ethyl acetate were charged in a container and mixed for 1 hour to obtain [Raw material solution 1].
[Raw material solution 1] 1324 parts are transferred to a container, and using a bead mill (Ultra Visco Mill, manufactured by Imex Co., Ltd.), a liquid feeding speed of 1 kg / hr, a disk peripheral speed of 6 m / sec, and 0.5 mm zirconia beads are 80% by volume. Pigment yellow and WAX were dispersed under conditions of filling and 3 passes. Next, 1324 parts of a 65% ethyl acetate solution of [low molecular weight polyester 1] was added, followed by one pass with a bead mill under the above conditions to obtain [Pigment / WAX dispersion 1]. The solid content concentration of [Pigment / WAX Dispersion 1] (130 ° C., 30 minutes) was 50%.

~ Emulsification Desolvent ~
[Example 1]
[Pigment / WAX Dispersion 1] 749 parts, [Prepolymer 1] 115 parts, [Ketimine Compound 1] 2.9 parts in a container, and TK homomixer (manufactured by Tokushu Kika) at 5,000 rpm for 1 minute After mixing, 1200 parts of [Aqueous phase 1] was added to the container, and mixed with a TK homomixer at 13,000 rpm for 20 minutes to obtain [Emulsion slurry 1].
[Emulsion slurry 1] was put into a container equipped with a stirrer and a thermometer, and after removing the solvent at 30 ° C. for 8 hours, aging was carried out at 45 ° C. for 4 hours to obtain [Dispersion slurry 1]. [Dispersion Slurry 1] had a volume average particle size of 4.78 μm and a number average particle size of 5.16 μm (measured with Multisizer III).

~ Washing drying ~
[Dispersion Slurry 1] After filtering 100 parts under reduced pressure,
(1): 100 parts of ion-exchanged water was added to the filter cake, mixed with a TK homomixer (10 minutes at 12,000 rpm), and then filtered.
(2) 10% hydrochloric acid was added to the filter cake of (1) above to adjust to pH 2.8, mixed with a TK homomixer (rotation speed: 12,000 rpm for 10 minutes), and then filtered.
(3) Add 300 parts of ion-exchanged water to the filter cake of (2) above, mix with a TK homomixer (10 minutes at 12,000 rpm) and then filter twice to obtain [Filter cake 1]. It was.
[Filtration cake 1] was dried at 45 ° C. for 48 hours in a circulating drier, and sieved with a mesh of 75 μm to obtain [Toner 1].

~ Synthesis of MB ~
Production Example 8
1200 parts of water, C.I. I. 540 parts of Pigment Yellow PY93 3G (manufactured by Ciba Specialty Chemicals), 162 parts of dispersant Disperbyk-2001 (amine value: 29, acid value: 19 mg KOH / g manufactured by BYK Chemie), pigment derivative Solsperse 22000 (manufactured by Abyssia) 16 Part, 1200 parts of polyester resin, and mixed with a Henschel mixer (Mitsui Mining Co., Ltd.), kneaded the mixture at 150 ° C. for 30 minutes using two rolls, rolled and cooled, and pulverized with a pulverizer. Obtained.

[Example 2]
[Toner 2] was obtained in the same manner as in Example 1 except that [Masterbatch 2] was used instead of [Masterbatch 1] in Example 1.

~ Suspension polymerization ~
Example 3
A mixture of 165 parts of styrene, 35 parts of n-butyl acrylate, 20 parts of [Masterbatch 1], 8 parts of styrene-methacrylic acid copolymer and 20 parts of paraffin wax is heated to 60 ° C. and uniformly at 12000 rpm with a TK homomixer. A polymerizable monomer composition was prepared by adding 10 parts of 2,2'-azobis (2,4-valeronitrile) as a polymerization initiator and dissolving. Next, 450 parts of a 0.1 M sodium phosphate aqueous solution was added to 710 parts of ion-exchanged water, and 68 parts of 1.0 M calcium chloride was gradually added while stirring at 13,000 rpm with a TK homomixer to suspend the tricalcium phosphate. A liquid was prepared. The polymerizable monomer composition was added to this suspension, and stirred at 10,000 rpm for 20 minutes with a TK homomixer to granulate the polymerizable monomer composition. Then, it was made to react at 75-95 degreeC for 5 to 15 hours using the reaction apparatus equipped with the stirring blade. Tricalcium phosphate was dissolved and removed with hydrochloric acid, and then classified in the liquid by centrifugal sedimentation using a centrifugal separator, and then filtered, washed and dried to obtain [Toner 3].

~ Synthesis of MB ~
Production Example 9
1200 parts of water, C.I. I. Pigment Yellow PY93 3G (manufactured by Ciba Specialty Chemicals) 540 parts, pigment derivative Solsperse 22000 (manufactured by Abyssia) 16 parts, polyester resin 1200 parts are added and mixed with a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.). This roll was kneaded at 150 ° C. for 30 minutes, then cooled by rolling and pulverized with a pulverizer to obtain [Masterbatch 3].

[Comparative Example 1]
[Toner 4] was obtained in the same manner as in Example 1 except that [Masterbatch 3] was used instead of [Masterbatch 1] in Example 1.

~ Synthesis of MB ~
Production Example 10
1200 parts of water, C.I. I. 540 parts of Pigment Yellow PY93 3G (Ciba Specialty Chemicals) and 1200 parts of polyester resin were added and mixed with a Henschel mixer (Mitsui Mining Co., Ltd.), and the mixture was kneaded at 150 ° C. for 30 minutes using two rolls. Then, it was cooled by rolling and pulverized with a pulverizer to obtain [Masterbatch 4].

[Comparative Example 2]
[Toner 5] was obtained in the same manner as in Example 1 except that [Masterbatch 4] was used instead of [Masterbatch 1] in Example 1.

[Comparative Example 3]
Similar to Example 1 except that [Masterbatch 4] was used instead of [Masterbatch 1] in Example 1 and MEK-ST-UP (solid content 20%; manufactured by Nissan Chemical Industries) was added during emulsification. [Toner 6] was obtained.

[Comparative Example 4]
[Toner 7] was obtained in the same manner as in Example 1 except that the dispersant was changed to Azisper PB821 (amine value: 10, acid value: 18 mg KOH / g, manufactured by Ajinomoto Fine Techno Co., Ltd.).

[Comparative Example 5]
[Toner 8] was obtained in the same manner as in Example 1 except that the dispersant was changed to EFKA-4060 (amine value: 6-10, manufactured by EFKA).

[Comparative Example 6]
[Toner 9] was obtained in the same manner as in Example 3 except that [Masterbatch 4] was used instead of [Masterbatch 1] in Example 3.

(Evaluation of toner)
(Chargeability)
10 g of each toner thus obtained and 100 g of ferrite carrier were mixed in an environment having a temperature of 28 ° C. and a humidity of 80%, and the charge amount of the toner was measured by a blow-off method. In addition, the charge distribution at this time was sharp.
(Particle size)
The particle size of the toner was measured using a particle size measuring device Coulter Counter TAII manufactured by Coulter Electronics Co., Ltd., with an aperture diameter of 100 μm. The volume average particle diameter and the number average particle diameter were determined by the particle size measuring instrument. The surface shape of the toner was observed with a scanning electron microscope.
(Fixability)
Remodeled Ricoh's imgio Neo 450 as a belt-fixing system, with a solid image and 1.0 ± 0.1mg / cm2 toner on plain paper and cardboard transfer paper (Ricoh type 6200 and NBS Ricoh copy printing paper) Fixation was evaluated by the amount of adhesion. The fixing test was conducted by changing the temperature of the fixing belt, and the upper limit temperature at which hot offset did not occur on plain paper was defined as the upper limit temperature for fixing. Further, the minimum fixing temperature was measured with a thick paper.
The lower limit fixing temperature was determined as the fixing lower limit temperature at the fixing roll temperature at which the residual ratio of the image density after rubbing the obtained fixed image with a pad was 70% or more. The case where the upper limit fixing temperature was 190 ° C. or higher and the lower limit fixing temperature was 140 ° C. or lower was evaluated as “◯”, and the case where it was not satisfied was evaluated as “X”.

(Image density)
The image density is 1.0 ± 0.1 mg / cm using a solid image on a plain paper and a thick paper transfer paper (Ricoh type 6200 and NBS Ricoh copy printing paper <135>) using Ricoh's imgio Neo 450. ² is developed so that the temperature of the fixing belt is variable, and after the solid image is output, the image density is measured by X-Rite 938 (manufactured by X-Rite). This was measured at five points for each color alone, and the average was obtained for each color.

(Light resistance)
The solid image A1 obtained with the above Ricoh imagio Neo 450 was measured with a reflection densitometer X-Rite 938 (trade name: manufactured by X-rite), and a sun tester XF-180CPS (manufactured by Shimadzu Corporation) was obtained. The used image was irradiated with xenon light (illuminance 765 w / m 2, temperature 50 ° C.) for 25 hours. The solid image density A2f after the irradiation was measured, and the density residual ratio ({A2 / A1} × 100 [%]) was calculated from the ratio of the reflection density before and after the xenon light irradiation.

(Turbidity)
Next, 1 part by weight of silica R972 (manufactured by Nippon Aerosil Co., Ltd.) as an external additive is added to 100 parts by weight of the toner, and the silica externally added toner mixed by a sample mill for 1 minute is electrophotographic full-color copying machine imagio Neo 450 ( Using a modified machine manufactured by Ricoh Co., Ltd., fixing was performed without the fuser oil for fixing, and an OHP fixed image was created. The turbidity was measured by fixing a solid color image on a transparent sheet for OHP and using a direct reading haze degree computer HGM-2DP manufactured by Suga Test Instruments Co., Ltd. This haze degree is also referred to as haze, and is measured as a measure of the transparency of the toner. The lower the value, the higher the transparency and the better the color developability when an OHP sheet is used.

(Toner shape)
The shape of the toner was confirmed by using an FE-SEM (S-800) manufactured by Hitachi, Ltd. and an acceleration voltage of 2.5 kV. 2 is an SEM photograph of toner particles of Example 1, FIG. 3 is an SEM photograph of toner particles of Example 2, FIG. 4 is Comparative Example 1, FIG. 5 is Comparative Example 2, FIG. 6 is Comparative Example 3, and FIG. 7 is an SEM photograph of the toner particles of Comparative Example 4. Comparing FIG. 2 with FIG. 3, it can be seen that in FIG. 3, the uneven distribution of the colorant in the toner decreases when the surface has less unevenness and the addition amount of the dispersant is small. Comparative Example 1 in FIG. 4, Comparative Example 2 in FIG. 5, Comparative Example 3 in FIG. 6, and FIG. 7 show that the toner in Comparative Example 4 is spherical, a system from which a dispersant is removed, a system from which a pigment derivative is removed, and an inorganic filler It is considered that the colorant in the toner is disposed in the toner in the system in which the additive is added and the system in which the dispersant type is changed. As for the toner obtained by suspension polymerization, the dispersant-added system (toner 3) has many irregularities on the surface as in FIG. 2, and the system without the dispersant (toner 9) as in FIGS. It was spherical.

(Pigment dispersion in toner by confocal laser scanning microscope)
The cross section of the toner was observed with a confocal laser scanning microscope FV1000 (Olympus) equipped with a 100 × oil immersion objective lens and 405 nm laser light. For cross-sectional observation, a cross-sectional image was taken at a pitch of 0.35 μm from the top of the toner, and an image of a 3 μm portion was extracted from the top of the toner, which was the central portion of the toner, and observed. FIG. 8 is a confocal laser scanning micrograph showing the particle structure of the toner of Comparative Example 2, and FIG. 9 is Example 1. In these photographs, the fluorescent material is the colorant. Comparing FIG. 8 and FIG. 9, FIG. 8 shows that the pigment is present inside the toner, but FIG. 9 shows that the amount of pigment unevenly distributed in the vicinity of the toner surface is large.

(Cleanability)
For cleaning performance, after outputting 1,000 sheets of a 95% image area ratio chart, the transfer residual toner on the photosensitive member that has passed the cleaning process is transferred to white paper with a scotch tape (manufactured by Sumitomo 3M), and this is transferred to a Macbeth reflection densitometer RD514. Measured with a mold, “◎” indicates that the difference from the blank is less than 0.005, “◯” indicates 0.005-0.010, “Δ” indicates 0.011-0.02, “0” Those exceeding .02 were evaluated as “x”.

These evaluation results are shown in Table 1.

FIG. 4 is a diagram schematically illustrating a toner shape for explaining a shape factor SF-2. 2 is a SEM photograph of toner particles of Example 1. 4 is a SEM photograph of toner particles of Example 2. 3 is a SEM photograph of toner particles of Comparative Example 1. 4 is a SEM photograph of toner particles of Comparative Example 2. 6 is a SEM photograph of toner particles of Comparative Example 3. 6 is an SEM photograph of toner particles of Comparative Example 4. 6 is a confocal laser scanning micrograph showing the toner particle structure of Comparative Example 2. 2 is a confocal laser scanning micrograph showing the toner particle structure of Example 1. FIG.

Claims (21)

In a toner produced in an aqueous medium and comprising at least a binder resin, a colorant, a dispersant for dispersing the colorant, and a pigment derivative for dispersing the colorant, the colorant is represented by the formula ( I):

And the dispersant is an acrylic copolymer having an N, N-disubstituted amino group and an acidic group in the main chain or side chain, and the toner is represented by the following formula (1): And a shape factor SF-1 represented by (2) is 135 or more and 138 or less, and SF-2 is 125 or more and 130 or less.
SF-1 = {L ² / A} × (100π / 4) (1)
SF-2 = {C ² / A} × (100 / 4π) (2)
(L is the major axis length of the projected particles to be measured, C is the perimeter, and A is the projected area)
The colorant is C.I. I. The yellow toner for image formation according to claim 1, which is CI Pigment Yellow 93. 3. The yellow toner for image formation according to claim 1, wherein the dispersant has an acid value of 1 to 30 mg KOH / g or less and an amine value of 1 to 100. 4. The yellow toner for image formation according to any one of claims 1 to 3, wherein 50 to 100% by weight of the binder resin is a polyester resin. The yellow toner for image formation according to claim 1, wherein the method of producing in an aqueous medium is a suspension polymerization method. 5. The yellow toner for image formation according to claim 1, wherein the method of producing in the aqueous medium is a dissolution suspension method. The method of producing in the aqueous medium is to dissolve or disperse a polymer and a colorant that form a binder resin having at least a site capable of reacting with a compound having an active hydrogen group in an organic solvent, and The organic solvent is removed, washed and dried after the binder resin having a site capable of reacting with the compound having an active hydrogen group is reacted in or dispersed in an aqueous medium. The yellow toner for image formation according to any one of claims 1 to 4. The polymer to be a binder resin having a site capable of reacting with the compound having an active hydrogen group is a modified polyester resin and a non-modified polyester resin, and the weight of the modified polyester resin and the non-modified polyester resin The yellow toner for image formation according to claim 7, wherein the ratio is 5/95 to 75/25. 9. The yellow toner for image formation according to claim 8, wherein the acid value of the modified polyester resin and the non-modified polyester resin is 0 to 30 mg KOH / g. 10. The yellow toner for image formation according to claim 5, wherein the method of producing in the aqueous medium includes a step of containing resin fine particles and adhering them to the toner surface. 11. The yellow toner for image formation according to claim 10, wherein the resin fine particles have an average particle diameter of 5 to 500 nm. The yellow toner for image formation according to claim 1, wherein the dispersant is compatible with a binder resin. The image forming yellow toner according to claim 1, wherein the dispersant has a weight average molecular weight of 2,000 to 100,000. The yellow toner for image formation according to any one of claims 1 to 10, wherein the addition amount of the dispersant is 1 to 50 parts by weight with respect to 100 parts by weight of the colorant. 12. The yellow toner for image formation according to claim 1, wherein the dispersant is contained in the toner at a ratio of 0.1 to 10% by weight. The yellow toner for image formation according to any one of claims 1 to 12, wherein a release agent is contained in the image formation toner. The yellow toner for image formation according to any one of claims 1 to 13, wherein the releasing agent has a melting point of 40 to 160 ° C. The image forming toner according to claim 1, wherein a blending ratio of the colorant and the organic solvent is in a range of 5:95 to 50:50. The volume average particle diameter Dv of the yellow toner is 3.0 to 8.0 μm, and the ratio Dv / Dn of the volume average particle diameter Dv to the number average particle diameter Dn is 1.00 to 1.30. The yellow toner for image formation according to any one of -18. A one-component developer for developing an electrostatic latent image, wherein the yellow toner for image formation according to any one of claims 1 to 19 is used. 20. A two-component developer for developing an electrostatic latent image, comprising the yellow toner for image formation according to claim 1 and a carrier.