JP2007264619A - Toner for electrostatic charge image development - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide toner for electrostatic charge image development having superior low-temperature fixability, establishing a wide fixation temperature range, having superior offset resistance and providing an excellent high-definition image. <P>SOLUTION: The toner for electrostatic charge image development is obtained by removing an organic solvent after or while organic solvent liquid obtained by dissolving or dispersing a composition for toner containing at least a compound (A) having an active hydrogen group, a polymer (B) having a moiety capable of reacting with the active hydrogen group, a coloring agent, and a releasing agent in the organic solvent is dispersed in droplets in a water-based medium to make the compound (A) having the active hydrogen group and the polymer (B) having the moiety capable of reacting with the active hydrogen group react with each other, and then washing and drying the composition. The toner for electrostatic charge image development is characterized in that the weight average molecular weight of the polymer (B) having the moiety capable of reacting with the active hydrogen group by GPC is 50,000 to 200,000 and the molecular weight showing a maximum peak is 20,000 to 40,000. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an electrostatic charge image developing toner for developing an electrostatic charge image formed on the surface of a photoreceptor in electrophotography, electrostatic recording, and the like, a toner base for developing an electrostatic charge image, and a developer using the toner. About.

  Image formation by electrophotography is disclosed in Patent Document 1 (US Pat. No. 2,297,691), Patent Document 2 (Japanese Patent Publication No. 49-23910) and Patent Document 3 (Japanese Patent Publication No. 43-24748). In general, an electrical latent image is formed on a photoconductor produced using a photoconductive substance by various means, and then the latent image is developed using a developer. After development, an image formed by the developer is transferred to paper or the like as necessary, and further fixed by heating, pressurization, solvent vapor, or the like.

  Methods for developing electrical latent images can be broadly divided into liquid development methods that use a liquid developer in which various pigments and dyes are finely dispersed in an insulating organic liquid, a cascade method, a magnetic brush method, and a powder cloud. There is a dry development method using a dry developer (hereinafter referred to as toner) prepared by dispersing a colorant such as carbon black in a natural or synthetic resin as in the method, etc., and in recent years, the dry development method has been widely used. .

As a fixing method used in the dry development method, a heating heat roller method is widely used because of its energy efficiency. In recent years, in order to save energy by fixing the toner at a low temperature, the thermal energy given to the toner at the time of fixing tends to be small. The 1999 DEM (Demand-side Management) program of the International Energy Agency (IEA) has a technology procurement project for next-generation copiers, and the required specifications have been published. For copiers of 30 cpm and above, It is required to achieve dramatic energy saving compared to conventional copying machines so that the standby time is within 10 seconds and the standby power consumption is 10 to 30 watts or less (differs depending on the copying speed). One method for achieving this requirement is to reduce the heat capacity of a fixing member such as a heated heat roller to improve the temperature responsiveness of the toner, but it is not fully satisfactory.
In order to achieve the above-mentioned requirement and minimize the waiting time, it is considered that it is an essential technical achievement matter to lower the fixing temperature of the toner itself and to lower the toner fixing temperature when it can be used.

In order to cope with such low-temperature fixing, an attempt has been made to use a polyester resin having excellent low-temperature fixability and relatively good heat-resistant storage stability in place of the styrene-acrylic resin that has been widely used in the past (Patent Document 4; JP-A-60-90344, Patent Document 5; JP-A-64-15755, Patent Document 6; JP-A-2-82267, Patent Document 7; JP-A-3-229264, Patent Document 8; JP-A-3-41470, Patent Document 9; JP-A-11-305486, etc.).
In addition, an attempt to add a specific non-olefinic crystalline polymer into a binder for the purpose of improving low-temperature fixability (Patent Document 10; JP-A-62-63940), an attempt to use a crystalline polyester (Patent Document) 11; Japanese Patent No. 2931899), but it cannot be said that the molecular structure and molecular weight are optimized.
Further, even if these conventionally known techniques are applied, it is impossible to achieve the specifications of a DSM (Demand-side Management) program, and it is necessary to establish a low-temperature fixing technique that is further advanced than the conventional technical field.

  For further low-temperature fixing, it is necessary to control the thermal characteristics of the resin itself. However, if the glass transition temperature (Tg) is lowered too much, the heat-resistant storage stability is deteriorated, and the resin is reduced by reducing the molecular weight. If the F1 / 2 temperature is lowered too much, there are problems such as lowering the hot offset occurrence temperature. Therefore, by controlling the thermal characteristics of the resin itself, it has not been possible to obtain a toner that has excellent low-temperature fixability and a high hot offset occurrence temperature.

On the other hand, toner production methods used for electrostatic image development are roughly classified into a pulverization method and a polymerization method.
In the pulverization method, a colorant, a charge control agent, an offset preventive agent, and the like are melt-mixed and uniformly dispersed in the thermoplastic resin described above, and the resulting composition is pulverized and classified to produce a toner. ing. 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. Therefore, when the above composition is actually pulverized into particles, a high-range particle size distribution is likely to be formed, and when attempting to obtain a copy image with good resolution and gradation, for example, toner volume The average particle size must be reduced, and fine powder with a particle size of 4 μm or less and coarse powder with a particle size of 15 μm or more must be removed by classification, which has the disadvantage that the toner 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. Such dispersion adversely affects toner fluidity, developability, durability, image quality, and the like.

  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 or an emulsion polymerization aggregation method (Patent Document 12; Japanese Patent No. 2537503). It is.

  However, in these production methods, a polyester resin superior in low-temperature fixability cannot be used as a toner. In order to solve these problems, a toner obtained by sphering a toner composed of a polyester-based resin with a solvent in water (Patent Document 13; Japanese Patent Laid-Open No. 9-34167), or a toner using an isocyanate reaction (Patent) Document 14; Japanese Patent Application Laid-Open No. 11-149180) and the like have been proposed, but the low-temperature fixability and toner productivity were not satisfactory.

US Pat. No. 2,297,691 Japanese Patent Publication No.49-23910 Japanese Patent Publication No.43-24748 JP 60-90344 A JP-A 64-15755 Japanese Patent Laid-Open No. 2-82267 JP-A-3-229264 JP-A-3-41470 JP-A-11-305486 JP 62-63940 A Japanese Patent No. 2931899 Japanese Patent No. 2537503 JP-A-9-34167 JP-A-11-149180

  An object of the present invention is to provide a toner for developing an electrostatic charge image for the purpose of obtaining excellent low-temperature fixability, establishment of a wide range of fixing temperature, excellent offset resistance, and good high-definition images. is there.

The said subject is achieved by (1)-(9) of this invention.
(1) "Toner composition containing at least a compound having an active hydrogen group (A), a polymer having a site capable of reacting with an active hydrogen group (B), a colorant and a release agent is dissolved in an organic solvent. Alternatively, the organic solvent liquid obtained by dispersion is dispersed in the form of droplets in an aqueous medium, and the compound (A) having the active hydrogen group and the polymer (B) having a site capable of reacting with the active hydrogen group are obtained. After or after the reaction, the toner having the organic solvent removed, washed and dried, and having a site capable of reacting with the active hydrogen group (B) has a weight average molecular weight of 5 by GPC. A toner for developing electrostatic images characterized by having a molecular weight of 20,000 to 200,000 and a maximum peak molecular weight of 20,000 to 40,000 ",
(2) The electrostatic image developing toner according to (1) above, wherein a molecular weight of 100,000 or more exists in a molecular weight distribution by GPC of the polymer (B) of 15% to 40%. "
(3) The electrostatic image developing toner according to (1) or (2), wherein the site capable of reacting with active hydrogen in the polymer (B) is an isocyanate group "
(4) "The toner for developing an electrostatic charge image according to any one of (1) to (3) above, wherein the toner particles have a glass transition point of 40 to 70 degrees",
(5) The electrostatic image developing toner according to any one of (1) to (4) above, wherein the toner particles have a volume average particle diameter (Dv) of 3 to 8 μm. "
(6) Any one of the above items (1) to (5), wherein the volume average particle diameter (Dv) / number average particle diameter (Dn) of the toner particles is 1.25 or less. Toner for developing electrostatic image as described in "
(7) The electrostatic image developing toner according to any one of (1) to (6), wherein the toner particles have an average circularity of 1.00 to 0.90. "
(8) "The toner for developing an electrostatic charge image according to any one of (1) to (7) above, wherein the toner particles have an acid value of 1 to 30 mgKOH",
(9) “Toner composition containing at least a compound having an active hydrogen group (A), a polymer having a site capable of reacting with an active hydrogen group (B), a colorant, and a release agent is dissolved in an organic solvent. Alternatively, the organic solvent liquid obtained by dispersion is dispersed in the form of droplets in an aqueous medium, and the compound (A) having the active hydrogen group and the polymer (B) having a site capable of reacting with the active hydrogen group are obtained. After or after the reaction, the toner having the organic solvent removed, washed and dried, and having a site capable of reacting with the active hydrogen group (B) has a weight average molecular weight of 5 by GPC. A toner base for developing an electrostatic charge image having a molecular weight of 10,000 to 200,000 and a maximum molecular weight of 20,000 to 40,000 ”.

  According to the present invention, compared to the prior art, the toner for developing an electrostatic charge image, which has excellent low-temperature fixability, establishment of a wide range of fixing temperature, excellent offset resistance, and good high-definition images can be obtained. Is now available.

Hereinafter, the present invention will be described in more detail.
The present inventors have intensively studied to solve the problems of the present invention, and at least a compound having an active hydrogen group (A), a polymer having a site capable of reacting with an active hydrogen group (B), a colorant, An organic solvent liquid obtained by dissolving or dispersing a toner composition containing a release agent in an organic solvent is dispersed in the form of droplets in an aqueous medium, the active hydrogen group-containing compound (A), and the active After reacting or reacting the polymer (B) having a site capable of reacting with a hydrogen group, the toner is removed, washed and dried, and the site capable of reacting with the active hydrogen group The polymer (B) having a weight average molecular weight by GPC of 50,000 to 200,000 and the molecular weight exhibiting the maximum peak of 20,000 to 40,000 satisfy low temperature fixing and have good offset resistance. I found it.

(Dv / Dn (ratio of volume average particle diameter / number average particle diameter))
The toner (including the toner base) of the present invention has a volume average particle diameter (Dv) of 3 to 8 μm and a ratio (Dv / Dn) to the number average particle diameter (Dn) of 1.25 or less, preferably 1. The dry toner of 10 to 1.25 is excellent in heat-resistant storage stability, low-temperature fixability, and hot offset resistance, particularly excellent in image glossiness when used in a full-color copying machine, and two-component development. In the developer, even if the balance of the toner for a long time is performed, the fluctuation of the toner particle diameter in the developer is reduced, and good and stable developability can be obtained even in the long-term stirring in the developing device. Even when used as a one-component developer, even if the balance of the toner is performed, the fluctuation of the toner particle diameter is reduced, and the toner is filmed on the developing roller and the toner is thinned. The toner was not fused to a member such as a blade, and good and stable developability and images were obtained even when the developing device was used (stirred) for a long time.

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. Further, when the volume average particle diameter is smaller than the range of the present invention, in the case of the two-component developer, the toner is fused to the surface of the carrier during long-term stirring in the developing device, leading to a decrease in the charging ability of the carrier, 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.
Further, these phenomena are the same for the toner having a fine powder content larger than the range of the present invention.
On the contrary, when the 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 of the particle size becomes large. It was also clarified that the same applies when the volume average particle diameter / number average particle diameter is larger than 1.25.
Further, when the volume average particle size / number average particle size is smaller than 1.05, there are preferable aspects from the viewpoint of stabilizing the behavior of the toner and equalizing the charge amount, but the toner becomes insufficiently charged. In some cases, it was also found that the cleaning property may be deteriorated.

(Glass transition temperature of toner)
Since the heat resistant storage performance depends on the glass transition point of the toner particles (including toner base particles), it is preferable to design the glass transition point of the toner particles to 40 ° C. to 70 ° C. That is, if it is less than 40 ° C., the heat-resistant storage stability is insufficient, and if it exceeds 70 ° C., it adversely affects low-temperature fixing.

(Binder resin)
By fixing the acid value of the toner binder resin (the acid value in the present invention is actually the acid value measured from the toner particles or the toner base particles) to 1.0 to 50.0 (KOHmg / g), the low temperature fixing Toner properties such as heat resistance, high-temperature offset resistance, heat-resistant storage stability, and charging stability can be improved. That is, when the acid value exceeds 50.0 (KOHmg / g), the extension or crosslinking reaction of the modified polyester becomes insufficient, and the high-temperature offset resistance is affected, and when it is less than 1.0 (KOHmg / g) This is because the extension or crosslinking reaction of the modified polyester is likely to proceed, causing problems in production stability. The acid value of the toner binder resin in the present invention is more preferably 1.0 to 30.0 (KOH mg / g).

  Further, by setting the hydroxyl value to 1.0 to 100.0 (KOHmg / g), it is possible to suppress toner dissolution from the cleaning roller. That is, when the hydroxyl value is less than 1.0 (KOHmg / g), the reaction with the blocked isocyanate in the toner becomes insufficient, and there is a concern about toner dissolution from the cleaning roller. On the other hand, if the hydroxyl value exceeds 100.0 (KOHmg / g), the hydrophilicity of the toner is increased and there is a risk of causing problems in charging characteristics under high temperature and high humidity conditions.

  Since the heat-resistant storage performance depends on the glass transition point of the binder resin, it is preferable to design the glass transition point of the binder resin at 30 ° C. to 50 ° C. That is, if it is less than 30 ° C., the heat-resistant storage stability is insufficient, and if it exceeds 50 ° C., the low-temperature fixing is adversely affected.

(Modified polyester)
When the weight average molecular weight of the modified polyester (the reaction product of the compound (A) having an active hydrogen group and the polymer (B) having a site capable of reacting with the active hydrogen group) is 50,000 or less, hot offset property Gets worse. On the other hand, if it exceeds 200,000, the viscosity of the modified polyester is so high that there is a concern that the toner productivity may deteriorate.
Moreover, even if it exists in the range of the said weight average molecular weight, when the ratio of molecular weight 100,000 or more is less than 15%, hot offset property will deteriorate. On the other hand, if it exceeds 40%, there is a concern that the modified polyester has a high viscosity and the toner productivity is deteriorated.
Thus, it can be said that the present invention has one meaning in using the polymer (B) having a site capable of reacting with an active hydrogen group having a molecular weight defined (50,000 to 200,000). In order to satisfy this rule, it is necessary or preferable that the molecular weight of the intermediate polyester is high to some extent.
As will be understood from the examples described in detail later, when the molecular weight of the intermediate polyester is small, the molecular weight of the polymer (B) does not satisfy the specified molecular weight of the present invention, and therefore the molecular weight of the polymer (B). In order to reliably achieve 50,000 or more, the polymer (B) can be advantageously synthesized with an intermediate polyester having a molecular weight of about 30,000.
The present invention relates to a toner composition obtained by dispersing or dissolving an active hydrogen group-containing compound, a polymer capable of reacting with an active hydrogen group, a colorant, and a release agent in an organic solvent. A toner particle matrix obtained by extending and / or cross-linking the active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group in an aqueous medium in which the liquid is dispersed in the form of droplets. A number of developers to be used have already been proposed, but in these known or preceding developers, the molecular weight of the intermediate polyester used is approximately 10,000, so that the molecular weight of the polymer (B) exceeds 50,000. Can not.

(Organic solvent)
In the present invention, a toner composition (including at least a compound (A) having an active hydrogen group, a polymer (B) having a site capable of reacting with an active hydrogen group, a colorant, and a release agent) is dissolved as an organic solvent. And / or a dispersible solvent is not particularly limited. As a preferable thing, it is preferable from the point that removal is easy that the boiling point of this solvent is less than 150 degreeC. 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.

(Coloring agent)
As the coloring agent of the present invention, known dyes and pigments can be used, such as carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), cadmium yellow, yellow iron oxide, Ocher, yellow lead, titanium yellow, polyazo yellow, oil yellow, Hansa yellow (GR, A, RN, R), pigment yellow L, benzidine yellow (G, GR), permanent yellow (NCG), Vulcan fast yellow (5G) , R), Tartrazine Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL, Isoindolinone Yellow, Bengala, Red Dan, Lead Zhu, Cadmium Red, Cadmium Mercury Red, Antimon Zhu, Permanent Red 4R, Para Red, Fayce Red, Parachlor Ortoni Roaniline Red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmine B, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Resol Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Toluidine Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake, Thioindigo red B, thioindigo maroon, oil red, quinacridone red, pyrazolone , Polyazo Red, Chrome Vermillion, Benzidine Orange, Perinone Orange, Oil Orange, Cobalt Blue, Cerulean Blue, Alkaline Blue Lake, Peacock Blue Lake, Victoria Blue Lake, Metal Free Phthalocyanine Blue, Phthalocyanine Blue, Fast Sky Blue, Indanthrene Blue (RS, BC), Indigo, Ultramarine Blue, Bitumen, Anthraquinone Blue, Fast Violet B, Methyl Violet Lake, Cobalt Purple, Manganese Purple, Dioxane Violet, Anthraquinone Violet, Chrome Green, Zinc Green, Chrome Oxide, Pyridian, Emerald Green, Pigment Green B, Naphthol Green B, Green Gold, Acid Green Lake, Malachite Green Lake, Fu Talocyanine green, anthraquinone green, titanium oxide, zinc white, lithopone and mixtures thereof can be used. The content of the colorant is usually 1 to 15% by weight, preferably 3 to 10% by weight, based on the toner.

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 master batch or the master batch, in addition to the above-mentioned modified and unmodified polyester resins, styrene such as polystyrene, poly p-chlorostyrene, and polyvinyl toluene, 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-maleic acid 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

  The 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 in order to enhance the interaction between the colorant and the resin. In addition, a so-called flushing method, which is a wet method of 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 the cake can be used as it is, it does not need to be dried 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 together with the toner binder and the colorant. Known waxes can be used as the wax of the present invention, such as polyolefin wax (polyethylene wax, polypropylene wax, etc.); long chain hydrocarbon (paraffin wax, sasol wax, etc.); carbonyl group-containing wax, etc. It is done.
Of these, carbonyl group-containing waxes are preferred. Carbonyl group-containing waxes 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 1000 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.

(Charge control agent)
The toner (including the toner base) of the present invention may contain a charge control agent as necessary. 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 4 Secondary ammonium salts or compounds, tungsten simple substances or compounds, fluorine 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 phenol-based condensate (above, manufactured by Orient Chemical Industries), TP-302, TP-415 of quaternary ammonium salt molybdenum complex (above, manufactured by Hodogaya Chemical 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, quinacridone Azo pigments, sulfonate group, carboxyl group, and polymer compounds having a functional group such as 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 attractive force with the developing roller is increased, the flowability of the developer is reduced, and the image density is reduced. Incurs a decline. 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. May be.

(External additive)
As the external additive for assisting the fluidity, developability and chargeability of the colored resin particles (toner base material) obtained in the present invention, inorganic fine particles can be preferably used. The primary particle diameter of the inorganic fine particles is preferably 5 μm to 2 μm, and particularly preferably 5 μm to 500 μm. Moreover, it is preferable that the specific surface area by BET method is 20-500 m < ² > / g. The proportion of the inorganic fine particles used is preferably 0.01 to 5% by weight of the toner, and particularly preferably 0.01 to 2.0% by weight. Specific examples of the inorganic fine particles include, for example, silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, tin oxide, quartz sand, clay, mica, wollastonite, diatomaceous earth. Examples include soil, chromium oxide, cerium oxide, bengara, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride.
In addition, polymer fine particles such as polystyrene obtained by soap-free emulsion polymerization, suspension polymerization and dispersion polymerization, methacrylic acid ester and acrylic acid ester copolymer, polycondensation system such as silicone, benzoguanamine and nylon, thermosetting resin And polymer particles.

  Such a fluidizing agent performs surface treatment to increase hydrophobicity, and can 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. Examples thereof include 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.

The dry toner and toner base of the present invention can be produced by the following method, but are not limited thereto.
(Toner production method in aqueous medium)
The aqueous phase used in the present invention is used by adding resin 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 miscible solvents include alcohol (methanol, isopropanol, ethylene glycol, etc.), dimethylformamide, tetrahydrofuran, cellosolves (methyl cellosolve, etc.), lower ketones (acetone, methyl ethyl ketone, etc.), and the like.
The toner particles and the toner base particles are a dispersion comprising an active hydrogen group-containing compound (A) and a polymer (B) having a site capable of reacting with active hydrogen groups dissolved or dispersed in an organic solvent in an aqueous phase. It is obtained by reacting and forming. As a method for stably forming a dispersion comprising a polymer (B) in an aqueous phase, a composition of a toner raw material comprising a polymer (B) dissolved or dispersed in an organic solvent in an aqueous phase is added. And a method of dispersing by shearing force. Polymer (B) dissolved or dispersed in an organic solvent and other toner composition components (hereinafter referred to as toner raw materials), colorant masterbatch, release agent, charge control agent, binder resin May be mixed when the dispersion is formed in the aqueous phase, but after the toner raw material is mixed in advance and dissolved or dispersed in an organic solvent, the mixture liquid is added to the aqueous phase and dispersed. Is more preferable. In the present invention, other toner raw materials such as a colorant, a release agent, and a charge control agent do not necessarily have to be mixed when forming particles in the aqueous phase, but after the particles are formed. , May be added. For example, after forming particles not containing a 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 20 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 preferred in that the dispersion made of the polymer (B) has a low viscosity and is easy to disperse.

  The amount of the aqueous phase used relative to 100 parts of the toner composition containing the polymer (B) is usually 50 to 2000 parts by weight, preferably 100 to 1000 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 2000 parts by weight, it is not economical. Moreover, a dispersing agent can also be used as needed. 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 Alcohol fatty acid derivatives, polyamine fatty acid derivatives, amine salt types such as imidazoline, 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. Preferred anionic surfactants having a fluoroalkyl group include fluoroalkyl carboxylic acids having 2 to 10 carbon atoms and metal salts thereof, disodium perfluorooctanesulfonyl glutamate, 3- [omega-fluoroalkyl (C6-C11 ) Oxy] -1-alkyl (C3-C4) sodium sulfonate, 3- [omega-fluoroalkanoyl (C6-C8) -N-ethylamino] -1-propanesulfonic acid sodium, fluoroalkyl (C11-C20) carvone Acids and metal salts, perfluoroalkylcarboxylic acids (C7 to C13) and metal salts thereof, perfluoroalkyl (C4 to C12) sulfonic acids and metal salts thereof, perfluorooctanesulfonic 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-110, F-120, 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 Fgentent 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 (manufactured by Dainippon Ink, Inc.), Xtop EF-132 (manufactured by Tochem Products), and Footgent F-300 (manufactured by Neos).
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, acrylamide, methacrylamide, diacetone acrylamide or their methylol compounds, acid chlorides such as acrylic acid chloride, methacrylic acid chloride, vinyl pyridine, vinyl pyrrolidone, vinyl imidazole, ethylene imine, 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 nonylphenyl Polyoxyethylenes such as esters, 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 one is used as the dispersion stabilizer, the calcium phosphate salt is removed from the fine particles by a method such as washing with water after dissolving the calcium phosphate salt with an acid such as hydrochloric acid. 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 structure of the site capable of reacting with the active hydrogen group of the polymer (B) and the reactivity depending on the combination of the compound having active hydrogen group (A). Min to 40 hours, preferably 2 to 24 hours. The reaction temperature is generally 0 to 150 ° C, preferably 40 to 98 ° C. Moreover, a well-known catalyst can be used as needed.

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 time treatment such as spray dryer, belt dryer, 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 classification 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, but it is preferable in the liquid to perform the classification operation. 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.

The obtained toner base powder after drying is mixed with different kinds of particles such as release agent fine particles, charge control fine particles, fluidizing agent fine particles, and colorant fine particles, or mechanical impact force is applied to the mixed powder. As a result, it is possible to prevent the dissociation of the foreign particles from the surface of the composite particle obtained by immobilizing and fusing on the surface.
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 Examples include a system (manufactured by Kawasaki Heavy Industries, Ltd.) and an automatic mortar.

(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. The carrier to toner content ratio in the developer is 1 to 10 weights of toner with respect to 100 parts by weight of 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.

EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not limited to this.
<Examples and Comparative Examples>
~ Synthesis of organic fine particle emulsion ~
(Production Example 1; Production of [Fine Particle Dispersion 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, and an aqueous vinyl resin (a copolymer of styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate sodium salt). A dispersion [fine particle dispersion 1] was obtained. The volume average particle diameter of [fine particle dispersion 1] measured by LA-920 was 105 nm. A portion of [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.

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

(Production Example 3; Synthesis of low molecular weight polyester)
In a reaction vessel equipped with a condenser, stirrer and 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 Add 2 parts of tin oxide, react for 8 hours at 230 ° C. under normal pressure, and further react for 5 hours under reduced pressure of 10 to 15 mmHg. The mixture was reacted for 2 hours to obtain [Low molecular 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 mgKOH.

(Production Example 4: Synthesis of MB)
1200 parts of water, 540 parts of carbon black (made by Printex 35 Dexa) [DBP oil absorption = 42 ml / 100 mg, pH = 9.5] and 1200 parts of polyester resin are added and mixed with a Henschel mixer (made by Mitsui Mining Co., Ltd.). After kneading at 150 ° C. for 30 minutes using two rolls, rolling and cooling and pulverizing with a pulverizer, [Masterbatch 1] was obtained.

~ Synthesis of Intermediate Polyester 1 ~
428 parts of ethylene glycol, 745 parts of terephthalic acid, 109 parts of trimellitic anhydride and 2 parts of titanium tetrabutoxide are placed in a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction pipe, and 8 parts at 230 ° C. under normal pressure. The reaction was continued for a further 5 hours at a reduced pressure of 10 to 15 mmHg to obtain [Intermediate Polyester 1]. [Intermediate Polyester 1] had a weight average molecular weight of 31,000, Tg of 38 ° C., an acid value of 0.5, and a hydroxyl value of 15.8.

(Production Example 5; Production of [Prepolymer 1] as an example of polymer (B))
Next, 250 parts of [Intermediate polyester 1], 17.2 parts of isophorone diisocyanate, and 250 parts of ethyl acetate were placed in a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe, and the mixture was heated at 100 ° C. for 5 hours. 1] was obtained. The isocyanate weight percent of [Prepolymer 1] was 0.58%.

-Manufacture of [raw material solution 1]-
In a container equipped with a stirrer and a thermometer, 378 parts of [Low molecular weight polyester 1], 110 parts of Carnauba WAX, 22 parts of CCA (salicylic acid metal complex E-84: Orient Chemical Industry), and 947 parts of ethyl acetate were charged with stirring. The temperature was raised to 0 ° C., kept at 80 ° C. for 5 hours, and then cooled to 30 ° C. over 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].

(Production Example 6; Production of [Pigment / WAX Dispersion 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. Carbon black 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 and possessed 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⇒Desolvation ~
[Example 1]
[Pigment / WAX Dispersion 1] 749 parts, [Prepolymer 1] 115 parts, and isophoronediamine 1.2 parts in a container and mixed with a TK homomixer (manufactured by Tokushu Kika) at 5,000 rpm for 1 minute Then, 1200 parts of [Aqueous phase 1] was added to the container, and mixed with a TK homomixer at a rotational speed of 13,000 rpm for 20 minutes to obtain [Emulsified 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 5.11 μm and a number average particle size of 4.49 μm (measured with Multisizer II).
[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): 100 parts of distilled water was added to the filter cake of (1), mixed with a TK homomixer (30 minutes at 12,000 rpm), and then filtered under reduced pressure.
(3): 100 parts of 10% hydrochloric acid was added to the filter cake of (2), mixed with a TK homomixer (rotation speed: 12,000 rpm for 10 minutes), and then filtered.
(4): Add 300 parts of ion-exchanged water to the filter cake of (3), 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 with a circulating drier, and sieved with an opening of 75 μm mesh to obtain [Toner (toner base) 1].
In this example, the toner characteristics were evaluated using the toner base. There is no significant difference between the toner and the toner base in the characteristic values other than the charging characteristics. In the following description of Examples and Comparative Examples, “toner” means “toner base”.

(Production Example 7; Synthesis of [Prepolymer 2])
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 250 parts of [Intermediate polyester 1], 17.2 parts of isophorone diisocyanate and 250 parts of ethyl acetate were added and reacted at 100 ° C. for 4 hours. ] Was obtained. The isocyanate weight% of [Prepolymer 2] was 0.64%.

(Production Example 8; Synthesis of [Prepolymer 3])
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introducing tube, 250 parts of [Intermediate polyester 1], 17.2 parts of isophorone diisocyanate, 0.5 part of bismuth catalyst (Neostan U-600), 250 parts of ethyl acetate A prepolymer 3 was obtained by reacting at 100 ° C. for 5 hours. The isocyanate weight% of [Prepolymer 3] was 0.51%.

(Production Example 9; Synthesis of [Prepolymer 4])
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introducing tube, 250 parts of [Intermediate polyester 1], 17.2 parts of isophorone diisocyanate, 0.5 part of bismuth catalyst (Neostan U-600), 250 parts of ethyl acetate A prepolymer 4 was obtained by reacting at 100 ° C. for 3 hours. The isocyanate weight percent of [Prepolymer 4] was 0.64%.

(Production Example 10; Synthesis of [Prepolymer 5])
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 250 parts of [Intermediate polyester 1], 19.5 parts of isophorone diisocyanate, 0.5 parts of bismuth catalyst (Neostan U-600), 250 parts of ethyl acetate A part was added and reacted at 100 ° C. for 5 hours to obtain [Prepolymer 5]. The isocyanate weight percent of [Prepolymer 5] was 0.69%.

[Synthesis of Intermediate Polyester 2]
463 parts of propylene glycol, 657 parts of terephthalic acid, 96 parts of trimellitic anhydride and 2 parts of titanium tetrabutoxide are placed in a reaction vessel equipped with a condenser, a stirrer, and a nitrogen introduction pipe. The reaction was continued for 4 hours, and further reacted for 4 hours at a reduced pressure of 10 to 15 mmHg to obtain [Intermediate Polyester 2]. [Intermediate Polyester 2] had a weight average molecular weight of 19000, Tg of 34 ° C., an acid value of 0.5, and a hydroxyl value of 19.2.

(Production Example 11; Synthesis of [Prepolymer 6])
Next, 250 parts of [Intermediate polyester 2], 25 parts of isophorone diisocyanate, 0.5 part of bismuth-based catalyst (Neostan U-600), 250 parts of ethyl acetate are placed in a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe. Part was added and reacted at 100 ° C. for 5 hours to obtain [Prepolymer 6]. The isocyanate weight% of [Prepolymer 6] was 1.02%.

[Example 2]
[Toner 2] was obtained in the same manner as in Example 1 except that [Prepolymer 2] was replaced with [Prepolymer 2] in Example 1 and 1.2 parts of isophoronediamine was changed to 1.3 parts.

Example 3
[Toner 3] was obtained in the same manner as in Example 1 except that [Prepolymer 3] in Example 1 was replaced with 1.1 parts of 1.2 parts of isophoronediamine.

Example 4
[Toner 4] was obtained in the same manner as in Example 1 except that [Prepolymer 4] was replaced with [Prepolymer 4] in Example 1 and 1.2 parts of isophoronediamine was changed to 1.3 parts.

Example 5
[Toner 5] was obtained in the same manner as in Example 1 except that [Prepolymer 5] was replaced with [Prepolymer 5] in Example 1 and 1.4 parts of isophoronediamine was changed to 1.4 parts.

Example 6
[Toner 6] was obtained in the same manner as in Example 1 except that [Prepolymer 6] was replaced with [Prepolymer 6] in Example 1 and 1.5 parts of isophoronediamine was changed to 1.5 parts.

[Synthesis of Intermediate Polyester 3]
463 parts of propylene glycol, 657 parts of terephthalic acid, 96 parts of trimellitic anhydride and 2 parts of titanium tetrabutoxide are placed in a reaction vessel equipped with a condenser, a stirrer, and a nitrogen introduction pipe. The reaction was continued for 3 hours, and further [intermediate polyester 3] was reacted for 3 hours at a reduced pressure of 10 to 15 mmHg. [Intermediate Polyester 3] had a weight average molecular weight of 11,000, Tg of 33 ° C., an acid value of 0.5, and a hydroxyl value of 22.1.

(Production Example 12; Synthesis of [Prepolymer 7] (for comparison))
Next, 250 parts of [Intermediate polyester 3], 25 parts of isophorone diisocyanate, 0.5 part of bismuth-based catalyst (Neostan U-600), 250 parts of ethyl acetate are placed in a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe. A [Prepolymer 7] was obtained at 100 ° C. for 5 hours. The isocyanate weight percent of [Prepolymer 7] was 0.84%.

(Production Example 13; Synthesis of [Prepolymer 8] (for comparison))
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introducing tube, 250 parts of [Intermediate polyester 1], 17.2 parts of isophorone diisocyanate and 250 parts of ethyl acetate were placed at 100 ° C. for 3 hours [Prepolymer 8]. Got. The isocyanate weight percent of [Prepolymer 8] was 0.71%.

[Comparative Example 1]
[Toner 7] was obtained in the same manner as in Example 1 except that [Prepolymer 7] was replaced with [Prepolymer 7] in Example 1 and 1.8 parts of isophoronediamine was changed to 1.8 parts.

[Comparative Example 2]
[Toner 8] was obtained in the same manner as in Example 1 except that [Prepolymer 8] was replaced with [Prepolymer 8] in Example 1 and 1.5 parts of isophoronediamine was changed to 1.5 parts.

(Evaluation item)
-Measurement of NCO% The method of measuring NCO% is according to the method specified in JIS K1603.
-Method for measuring acid value The method for measuring acid value is as defined in JIS K0070. However, if the sample does not dissolve, a solvent such as dioxane or THF is used as the solvent.
-Measuring method of hydroxyl value The measuring method of a hydroxyl value is based on the method prescribed | regulated to JISK0070. However, if the sample does not dissolve, a solvent such as dioxane or THF is used as the solvent.
·Particle size

Toner particle size and circularity The particle size of the toner was measured with 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 toner in the present invention preferably has a specific shape and shape distribution. With an irregularly shaped toner having an average circularity of less than 0.90 and too far away from a sphere, a high-quality image without satisfactory transferability and dust may not be obtained. As a method for measuring the shape, an optical detection band method is suitable in which a suspension containing particles is passed through an imaging unit detection band on a flat plate, and a particle image is optically detected and analyzed by a CCD camera. Toner having an average circularity of 1.00 to 0.90, which is a value obtained by dividing the perimeter of an equivalent circle having the same projected area obtained by this method by the perimeter of the actual particle, has high reproducibility with an appropriate density reproducibility. It has been found to be particularly effective in forming a clear image. This value was measured as an average circularity by a flow type particle image analyzer FPIA-2100 (manufactured by Toa Medical Electronics Co., Ltd.).
That is, as a specific measurement method, a surfactant, preferably an alkylbenzene sulfonate, is added in an amount of 0.1 to 0.5 ml as a dispersant in 100 to 150 ml of water from which impure solids have been removed in advance. Further, about 0.1 to 0.5 g of a measurement sample is added. The suspension in which the sample is dispersed is obtained by performing dispersion treatment for about 1 to 3 minutes with an ultrasonic disperser and measuring the shape and distribution of the toner with the above apparatus at a dispersion concentration of 3000 to 10,000 / μl. .

-Average molecular weight The weight average molecular weight (Mw) of the resin was measured by GPC (gel permeation chromatography) under the following conditions.
Apparatus: GPC-150C (manufactured by Waters)
Column: KF801-807 (manufactured by Shodex)
Temperature: 40 ° C
Solvent: THF (tetrahydrofuran)
Flow rate: 1.0 ml / min Sample: 0.1 ml injection of 0.05-0.6% concentration sample Use molecular weight calibration curve prepared from monodisperse polystyrene standard sample from molecular weight distribution of toner resin measured under the above conditions The weight average molecular weight (Mw) of the toner was calculated.
Moreover, when measuring GPC of NCO terminal modified polyester, 3 times mole amount dibutylamine is added with respect to NCO, the sample which sealed NCO terminal was prepared, and it uses for GPC measurement.

-Tg measuring method An outline of the Tg measuring method will be described. As an apparatus for measuring Tg, a TG-DSC system TAS-100 manufactured by Rigaku Corporation was used.
First, about 10 mg of a sample is placed in an aluminum sample container, which is placed on a holder unit and set in an electric furnace. First, after heating from room temperature to 150 ° C. at a temperature rising rate of 10 ° C./min, the sample was allowed to stand at 150 ° C. for 10 minutes, the sample was cooled to room temperature and allowed to stand for 10 minutes, and the temperature rising rate was again increased to 150 ° C. under a nitrogen atmosphere. DSC measurement was carried out by heating at / min. Tg was calculated from the contact point between the tangent line of the endothermic curve near the Tg and the base line using the analysis system in the TAS-100 system.

-Heat-resistant storage stability After storing the toner at 50 ° C for 8 hours, the toner was screened with a 42 mesh screen for 2 minutes, and the residual rate on the wire mesh was defined as heat-resistant storage stability. A toner having better heat-resistant storage stability has a lower residual ratio. The following four levels were evaluated.
×: 30% or more △: 20-30%
○: 10 to 20%
A: Less than 10%

・ Fixability Using a RICOH Imagio Neo 450, a solid image and a thick paper transfer paper (Ricoh Type 6200 and NBS Ricoh Copied Printing Paper <135>), 1.0 ± 0.1 mg / cm as a solid image Adjustment was performed so that toner No. ² was developed, and the temperature of the fixing belt was adjusted to be variable, and the temperature at which no offset occurred on plain paper and the lower limit fixing temperature on thick paper were measured. 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.

・ Charging characteristics (1) 15 seconds stirring Q / M
Silicon resin-coated ferrite carrier (average particle size 50 μm) 100 parts 4 parts of the test toner was placed in a stainless steel pot up to 30% of the internal volume, stirred for 15 seconds at a stirring speed of 100 rpm, and determined by a blow-off method.
(2) 10 minutes stirring Q / M
Charge amount when stirring for 10 minutes as in (1)

Claims (9)

A toner composition containing at least a compound (A) having an active hydrogen group, a polymer (B) having a site capable of reacting with the active hydrogen group, a colorant, and a release agent is dissolved or dispersed in an organic solvent. After the obtained organic solvent liquid is dispersed in the form of droplets in an aqueous medium, the compound (A) having the active hydrogen group and the polymer (B) having a site capable of reacting with the active hydrogen group are reacted. Or a toner obtained by removing the organic solvent while washing, washing, and drying, wherein the polymer (B) having a site capable of reacting with the active hydrogen group has a weight average molecular weight by GPC of 50,000 to 200,000. A toner for developing an electrostatic charge image, wherein the toner has a maximum molecular weight of 2 to 40,000. 2. The electrostatic image developing toner according to claim 1, wherein the polymer (B) has a molecular weight distribution by GPC of 15% to 40% of a molecular weight of 100,000 or more. The electrostatic image developing toner according to claim 1, wherein the site capable of reacting with active hydrogen in the polymer (B) is an isocyanate group. 4. The electrostatic image developing toner according to claim 1, wherein the toner particles have a glass transition point of 40 to 70 degrees. 5. The electrostatic image developing toner according to claim 1, wherein the toner particles have a volume average particle diameter (Dv) of 3 to 8 μm. 6. The electrostatic image developing toner according to claim 1, wherein the toner particles have a volume average particle diameter (Dv) / number average particle diameter (Dn) of 1.25 or less. 7. The electrostatic image developing toner according to claim 1, wherein the toner particles have an average circularity of 1.00 to 0.90. The electrostatic image developing toner according to claim 1, wherein the toner particles have an acid value of 1 to 30 mg KOH. A toner composition containing at least a compound (A) having an active hydrogen group, a polymer (B) having a site capable of reacting with the active hydrogen group, a colorant, and a release agent is dissolved or dispersed in an organic solvent. After the obtained organic solvent liquid is dispersed in the form of droplets in an aqueous medium, the compound (A) having the active hydrogen group and the polymer (B) having a site capable of reacting with the active hydrogen group are reacted. Or a toner obtained by removing the organic solvent while washing, washing, and drying, wherein the polymer (B) having a site capable of reacting with the active hydrogen group has a weight average molecular weight by GPC of 50,000 to 200,000. A toner base for developing an electrostatic charge image, wherein the molecular weight exhibiting the maximum peak is 2 to 40,000.