JP4628961B2 - Toner for electrostatic charge development and production method - Google Patents

Description

  The present invention relates to an electrostatic charge image developing toner that visualizes an electrostatic charge image formed on the surface of a photoreceptor in electrophotography, electrostatic recording, and the like, and more particularly to an improved electrostatic production process of toner used for a developer. The present invention relates to a toner for image development and a manufacturing method.

  In recent years, the market demanded smaller particle size for higher image quality and low-temperature fixing for energy saving. In particular, image formation is possible after the image forming apparatus is ready for energy saving. In order to reduce as much as possible the amount of power required for the waiting time (warm-up time of the apparatus) until the time is reached, there is a strong demand for shortening the waiting time. However, the toner obtained by the usual kneading and pulverization method has various problems such as difficulty in reducing the particle size, irregular shape, broad particle size distribution, and high fixing energy. In particular, in the case of fixing, a kneading and pulverizing type toner prepared by a pulverization method has a large amount on the surface because pulverization is broken at the interface of the release agent (wax). Adhesion to the surface easily occurs, and the performance was insufficient.

On the other hand, in order to overcome the above-mentioned problems caused by the kneading and pulverization method, a toner production method by a polymerization method has been actively proposed. This method makes it easy to reduce the particle size of the toner, and the particle size distribution is sharper than the particle size distribution of the toner obtained by the pulverization method. In addition, wax can be included.
So far, a method for producing a polymerized toner by a suspension polymerization method in an aqueous medium has been proposed (see, for example, Patent Documents 1 and 2).

  There have been many reports on the production of polymerized toner by the emulsion aggregation method (see, for example, Patent Document 3), and it is known that a sharp particle size distribution can be obtained as the particle size of the toner is reduced. However, the binder resin component of the polymerized toner by these suspension polymerization method and emulsion aggregation method is a styrene-acrylic resin obtained by radical polymerization, and there remains a problem with respect to a high level of low-temperature fixability.

  In order to achieve low-temperature fixability, it is indispensable to reduce the molecular weight of the binder resin. When the styrene-acrylic resin used as the binder resin in the above polymerized toner is reduced in molecular weight, the toner is reduced in performance. The durability of is insufficient. In addition, since a large amount of catalyst and chain transfer agent are used to reduce the molecular weight, it is necessary not only to affect the toner performance due to residual impurities but also to solve productivity problems such as reaction control and cost. is there.

Further, dry toners excellent in all of heat-resistant storage stability, low-temperature fixability, and hot offset resistance are described (see, for example, Patent Documents 4, 5, 6, and 7), and the toners described in these publications are described. The production method includes a high molecular weight process in which an isocyanate group-containing polyester prepolymer is subjected to a polyaddition reaction with an amine in an organic solvent and an aqueous medium. However, in this production method, the binder resin, the release agent, and the colorant are dissolved or dispersed in an organic solvent, but the molecular weight of the binder resin, the dispersion state of the binder resin, the dispersion state of the release agent, Since the toner particle diameter and particle size distribution vary depending on the dispersion state of the colorant, it becomes difficult to control the toner. As a result, poor dispersion of the colorant and uniform particle size distribution cannot be obtained, which affects the image quality.
JP 2001-296700 A JP 2002-91073 A JP 2001-305797 A JP 2002-287400 A JP 2002-351143 A JP 2003-091100 A JP 2003-098770 A

  The present invention has been made in view of the above-described circumstances. In view of the above-described problems, the present invention is produced in an aqueous medium and includes at least a binder resin and a colorant. In a toner in which -100% by weight is a polyester resin, at least in an organic solvent, a polymer having a site capable of reacting with a compound having an active hydrogen group, an acidic group-containing binder resin, a colorant, and a release agent are dissolved or Disperse, disperse the solution or dispersion in an aqueous solvent, react the polymer having a site capable of reacting with the compound having an active hydrogen group, or remove the organic solvent while reacting, In producing a washed and dried toner, to stably control the target particle size and particle size distribution, to obtain a toner for developing an electrostatic image having excellent image quality in which a colorant is well dispersed, It was, and to obtain a toner that exhibits a low-temperature fixability and hot offset resistance.

  In order to solve the above-described problems, the invention described in claim 1 includes at least a polymer having a site capable of reacting with a compound having an active hydrogen group, an acidic group-containing binder resin, a colorant, and a release agent. A site capable of reacting with a compound having an active hydrogen group by dispersing a solution or dispersion in which a mold agent and a tertiary amine are dissolved or dispersed in an organic solvent or an organic dispersion medium in an aqueous medium containing resin fine particles A toner produced by removing, washing, and drying the organic solvent or the organic dispersion medium after or while reacting the polymer having the acid value, wherein the acid number A of the solution or dispersion is 15 to 30 and the ratio B / A of the acid number A to the base number B of the solution or dispersion is in the range of 1/5 to 1/1, and the toner particle size is 2 μm. The following particle ratio is 5% by number or less Characterized by toner for developing charge image.

  According to a second aspect of the present invention, there is provided the electrostatic image developing toner according to the first aspect, wherein the acidic group-containing binder resin is a polyester resin.

  According to a third aspect of the present invention, there is provided the electrostatic image developing toner according to the second aspect, wherein the content of the acidic group-containing polyester resin in the binder resin is from 50 to 100% by weight.

  According to a fourth aspect of the present invention, there is provided the electrostatic image developing toner according to the second or third aspect, wherein the acidic group-containing polyester resin has a weight average molecular weight of 1,000 to 30,000 in the THF-soluble component. It is characterized by.

  The invention according to claim 5 is the electrostatic charge according to any one of claims 2 to 4, wherein the acid value of the acidic group-containing polyester resin is 1.0 or more and 50.0 or less (KOHmg / g). Features toner for image development.

  The invention according to claim 6 is characterized in that the toner for developing an electrostatic charge image according to any one of claims 2 to 5 has a glass transition point of 35 to 65 ° C. of the acidic group-containing polyester resin. To do.

  In the invention according to claim 7, the polymer having a site capable of reacting with the compound having an active hydrogen group has a weight average molecular weight of 3,000 or more and 20,000 or less. The toner for developing an electrostatic charge image described above is characterized.

  The invention according to claim 8 is characterized in that the toner for developing an electrostatic charge image according to any one of claims 1 to 7 has a volume average particle diameter of the toner in the range of 3 to 9 μm.

  The invention according to claim 9 is the electrostatic charge image according to any one of claims 1 to 8, wherein a ratio Dv / Dn of the volume particle diameter Dv to the number average particle diameter Dn of the toner is 1.25 or less. Features developing toner.

  The invention according to claim 10 is the electrostatic image developing toner according to any one of claims 1 to 9, wherein the toner has an acid value of 0.5 or more and 40.0 or less (KOHmg / g). It is characterized by.

  The invention according to claim 11 is characterized in that the toner for developing an electrostatic charge image according to any one of claims 1 to 10, wherein the toner has a glass transition point of 40 to 70 ° C.

  The invention according to claim 12 is characterized in that the toner for developing an electrostatic charge image according to any one of claims 1 to 11 has an average circularity of 0.94 or more.

The invention according to claim 13 is the electrostatic image developing toner according to any one of claims 1 to 12, wherein the toner has a BET specific surface area of 1.0 to 6.0 m ² / g. It is characterized by.

  The invention according to claim 14 includes at least a polymer having a site capable of reacting with a compound having an active hydrogen group, an acidic group-containing binder resin, a colorant, a release agent, and a tertiary amine. Is dissolved or dispersed in an organic solvent or an organic dispersion medium, and the solution or dispersion is dispersed in an aqueous medium containing resin fine particles to react a polymer having a site capable of reacting with the compound having an active hydrogen group. A method for producing a toner after removing or washing and drying the organic solvent while reacting, wherein the acid number A of the solution or dispersion is 15 or more and 30 or less, and the acid of the solution or dispersion It is characterized by a method for producing a toner for developing an electrostatic charge image, wherein the ratio B / A of the valence A to the base valence B is 1/5 or more and 1/1, and the particle ratio of 2 μm or less is 5% by number or less.

  According to the present invention, at least a polymer having a site capable of reacting with a compound having an active hydrogen group, an acidic group-containing binder resin, a colorant, a release agent, and a tertiary amine are dissolved or dispersed in an organic solvent. The organic solvent is removed after the solution or dispersion is dispersed in an aqueous medium containing resin fine particles and the polymer having a site capable of reacting with the compound having an active hydrogen group is reacted or while reacting. And the acid number A of the solution or dispersion satisfies the formula 15 ≦ A ≦ 30, and the acid number A and base number B of the solution or dispersion are toners manufactured by washing and drying. The ratio B / A of the toner is in the range of 1/5 or more and 1/1 or less, and the particle ratio of 2 μm or less of the produced toner particle diameter is 5% by number or less. Smoothly disperse and stabilize oily components with toner It is possible to obtain a toner for developing an electrostatic image having excellent image quality in which a desired particle size and particle size distribution can be stably controlled, and a colorant is well dispersed.

Hereinafter, embodiments of the present invention will be described in detail.
The inventors have dissolved or dispersed at least a polymer having a site capable of reacting with a compound having an active hydrogen group, an acidic group-containing binder resin, a colorant, and a release agent in an organic solvent or an organic dispersion medium. The organic solvent or dispersion medium is removed and washed after the solution or dispersion is dispersed in an aqueous solvent and the polymer having a site capable of reacting with the compound having an active hydrogen group is reacted. A dried toner, wherein the acid number A of the solution or dispersion is in the range of 15 to 30 and the ratio B / A of the acid number A to the base number B of the solution or dispersion is It has been found that by defining it in the range of 1 or more and 10 or less, the target particle size and particle size distribution can be stably controlled, and a toner for developing an electrostatic charge image having excellent image quality in which a colorant is well dispersed can be obtained. It was.

  According to the present invention, at least a polymer having a site capable of reacting with a compound having an active hydrogen group, an acidic group-containing binder resin, a colorant, and a release agent are dissolved or dispersed in an organic solvent or an organic dispersion medium. The organic solvent or organic dispersion medium is removed and washed after the solution or dispersion is dispersed in an aqueous solvent and the polymer having a site capable of reacting with the compound having an active hydrogen group is reacted. In the dried toner, the acid number A of the solution or dispersion is set to 15 or more and 30 or less, and the ratio B / A of the acid number A to the base number B of the solution or dispersion is 1 or more. In order to obtain the desired particle diameter and particle size distribution stably, it is effective to smoothly disperse and stabilize the oil component by defining it in the range of 10 or less. A stable dispersion state is maintained by generating an acid group and a salt on the surface of the solution or dispersion in which the added tertiary amine is dispersed in an aqueous solvent.

  Acid value of a solution or dispersion in which a polymer having a site capable of reacting with the compound having an active hydrogen group of the present invention, an acidic group-containing binder resin, a colorant, a release agent, or a tertiary amine is dissolved or dispersed. A is obtained by dissolving or dispersing 1.1 g of the solution or dispersion in 100 mL of a mixed solvent in which the ratio of toluene, acetone, and methanol is 75: 12.5: 12.5, and using 0.1N KOH methanol solution. Potentiometric titration was performed, and the acid value per 1 g of the solid content in the solution or dispersion was calculated.

  The base number of a solution or dispersion in which a polymer having a site capable of reacting with the compound having an active hydrogen group of the present invention, an acidic group-containing binder resin, a colorant, a release agent, or a tertiary amine is dissolved or dispersed. Number B is obtained by dissolving or dispersing 5 g of the solution or dispersion in 100 mL of dimethylformamide, performing potentiometric titration with a 0.1N hydrochloric acid ethanol solution, and determining the base number per 1 g of the solid content in the solution or dispersion. Was calculated.

  According to a further study of the present invention, the acidic group-containing polyester resin is used to effectively exhibit low-temperature fixability while maintaining heat-resistant storage stability and to impart offset resistance after modification with a prepolymer. It is preferable that the weight-average molecular weight of the THF-soluble component is 1,000 to 30,000. This is because when the amount is less than 1,000, the oligomer component increases, the heat-resistant storage stability is deteriorated, and when it exceeds 30,000, the modification with the prepolymer is insufficient due to steric hindrance and the offset resistance is deteriorated.

The molecular weight according to the present invention is measured by GPC (gel permeation chromatography) as follows. Stabilize the column in a heat chamber at 40 ° C., flow THF at a flow rate of 1 ml / min through the column at this temperature, and prepare a THF sample solution of resin prepared at a sample concentration of 0.05 to 0.6% by weight. Is measured by injecting 50 to 200 μl. In measuring the molecular weight of the sample, the molecular weight distribution of the sample was calculated from the relationship between the logarithmic value of the prepared calibration curve and the count using several types of monodisperse polystyrene standard samples. As a standard polystyrene sample for preparing a calibration curve, for example, molecular weight of 6 × 10 ² , 2.1 × 10 ³ , 4 × 10 ³ , 1.75 × 10 manufactured by Pressure Chemical Co. or Toyo Soda Industry Co., Ltd. ⁴ , 5.1 × 10 ⁴ , 1.1 × 10 ⁵ , 3.9 × 10 ⁵ , 8.6 × 10 ⁵ , 2 × 10 ⁶ , 4.48 × 10 ⁶ , and at least about 10 points It is appropriate to use standard polystyrene samples. An RI (refractive index) detector is used as the detector.

  Further, by adjusting the acid value of the acidic group-containing polyester resin to 1.0 to 50.0 (KOHmg / g), grain size control by adding a basic compound, low temperature fixability, high temperature offset resistance, heat resistant storage stability, It is possible to improve toner characteristics such as charging stability. 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 a dispersion stabilizing effect due to the base compound during production cannot be obtained, and the elongation or cross-linking reaction of the modified polyester tends to proceed, resulting in a problem in production stability.

  The method for measuring the acid value of the polyester resin of the present invention is based on a method based on JIS K0070. However, when the sample does not dissolve, a solvent such as dioxane or THF is used as the solvent.

  In the present invention, the heat-resistant storage performance of the main component of the polyester resin after modification, that is, the binder resin depends on the glass transition point of the polyester resin before modification, so that the glass transition point of the polyester resin is 35 ° C. to 65 ° C. It is preferable to design. That is, if it is less than 35 ° C., the heat-resistant storage stability is insufficient, and if it exceeds 65 ° C., it adversely affects low-temperature fixing.

  The glass transition point of the present invention is measured by Rigaku THRMOFLEX TG8110 manufactured by Rigaku Corporation under the condition of a temperature rising rate of 10 ° C./min.

  According to a further study of the present invention, the prepolymer for modifying the polyester resin is an important binder resin component for realizing low-temperature fixability and high-temperature offset resistance, and its weight average molecular weight is 3,000 to 20, 000 is preferred. That is, when the weight average molecular weight is less than 3,000, it becomes difficult to control the reaction rate, and problems in production stability begin to occur. On the other hand, when the weight average molecular weight exceeds 20,000, sufficient modified polyester cannot be obtained and the offset resistance starts to be affected.

  Further examination of the present invention revealed that the toner acid value is a more important index than the binder resin acid value for low-temperature fixability and high-temperature offset resistance. The toner acid value of the present invention is derived from the terminal carboxyl group of the unmodified polyester. This unmodified polyester preferably has an acid value of 0.5 to 40.0 (KOHmg / g) in order to control low-temperature fixability (fixing lower limit temperature, hot offset occurrence temperature, etc.) as a toner. In other words, when the toner acid value exceeds 40.0 (KOHmg / g), the modified polyester is insufficiently stretched or cross-linked, affecting high-temperature offset resistance, and less than 0.5 (KOHmg / g). In this case, the dispersion stabilizing effect due to the base compound at the time of production cannot be obtained, and the extension or crosslinking reaction of the modified polyester tends to proceed, resulting in a problem in production stability.

  The glass transition point of the toner of the present invention is preferably 40 to 70 ° C. in order to obtain low temperature fixability, heat resistant storage stability and high durability. That is, when the glass transition point is less than 40 ° C., blocking in the developing machine and filming to the photoreceptor are liable to occur, and when it exceeds 70 ° C., the low-temperature fixability tends to deteriorate.

  The toner of the present invention preferably has a volume average particle diameter (Dv) of 3 to 9 μm, and the ratio (Dv / Dn) to the number average particle diameter (Dn) is Dv / Dn ≦ 1.25. More preferably it is. By defining Dv / Dn in this way, it is possible to obtain a toner with high resolution and high image quality. In order to obtain a higher quality image, the volume average particle diameter (Dv) of the toner is 3 to 7 μm, and the ratio (Dv / Dn) to the number average particle diameter (Dn) is Dv / Dn ≦ 1.20. In addition, the number of particles of 3 μm or less is preferably 1 to 10% by number, and more preferably, the volume average particle diameter is 3 to 6 μm and Dv / Dn is Dv / Dn ≦ 1.15. Is good. Such a toner is excellent in all of heat-resistant storage stability, low-temperature fixability, and hot offset resistance, and particularly excellent in image gloss when used in a full-color copying machine. Even if the toner balance is extended over a long period, the toner particle size fluctuations in the developer are reduced, and good and stable developability can be obtained even with long-term stirring in the developing device.

  For the average particle size and particle size distribution of the toner of the present invention, a Coulter Counter TA-II type is used, and an interface (manufactured by Nikka Giken) that outputs number distribution and volume distribution is connected to a PC 9801 personal computer (manufactured by NEC). And measured.

  The toner of the present invention preferably has a specific shape and shape distribution. When the average circularity is less than 0.94, it is difficult to obtain a high-quality image with satisfactory transferability and no dust. 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 0.94 to 1.00, 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 a high density with a reproducibility of an appropriate density. It is preferable for forming a clear image.

  The particle ratio of 2 μm or less and the circularity of the toner of the present invention can be measured by a flow type particle image analyzer FPIA-2000 (manufactured by Toa Medical Electronics Co., Ltd.). As a specific measuring method, 0.1 to 0.5 ml of a surfactant, preferably alkylbenzene sulfonate is added as a dispersant to 100 to 150 ml of water from which impure solids have been removed in advance, and further measurement is performed. Add about 0.1-0.5g of sample. The suspension in which the sample is dispersed is obtained by performing dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes and measuring the shape and distribution of the toner with the above apparatus at a dispersion concentration of 3000 to 10,000 / μl. It is done.

Of the present invention toner, BET specific surface area is preferably 1.0~6.0m ² / g), BET specific surface area of 1.0 (m ² / g) in the presence or additive coarse particles is less than Due to the inclusion, and when it exceeds 6.0 (m ² / g), the image quality is likely to be affected by the presence of fine particles, the emergence 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.

  Furthermore, the method for producing the toner used in the present invention preferably includes a high molecular weight process in which the isocyanate group-containing polyester prepolymer A dispersed in an aqueous medium containing resin fine particles is reacted with the amine B.

  Next, materials used for the toner of the present invention will be described in detail. In the present invention, the organic solvent is not particularly limited as long as it is a solvent capable of dissolving and / or dispersing the toner composition. 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 or 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 resin fine particles used in the present invention are not particularly limited as long as the resin fine particles can form an aqueous dispersion in an aqueous medium, and can be appropriately selected from known resins according to the purpose. Or a thermosetting resin, for example, vinyl resin, polyurethane resin, epoxy resin, polyester resin, polyamide resin, polyimide resin, silicon resin, phenol resin, melamine resin, urea resin, aniline resin, ionomer Examples thereof include a resin and a polycarbonate resin. These may be used individually by 1 type and may use 2 or more types together. Among these, it is preferable that it is formed of at least one selected from vinyl resins, polyurethane resins, epoxy resins, and polyester resins in that an aqueous dispersion of fine spherical resin particles can be easily obtained. The vinyl resin is a polymer obtained by homopolymerizing or copolymerizing a vinyl monomer. For example, a styrene- (meth) acrylic acid ester resin, a styrene-butadiene copolymer, a (meth) acrylic acid-acrylic acid ester polymer. Styrene-acrylonitrile copolymer, styrene-maleic anhydride copolymer, styrene- (meth) acrylic acid copolymer, and the like.

  The acidic group-containing polyester resin used in the present invention is usually obtained by condensation polymerization of alcohol and carboxylic acid. Examples of the alcohol include glycols such as ethylene glycol, diethylene glycol, triethylene glycol and propylene glycol, etherified bisphenols such as 1.4-bis (hydroxymethyl) cyclohexane and bisphenol A, and other dihydric alcohols. Mention may be made of monomers and trihydric or higher polyhydric alcohol monomers. Examples of carboxylic acids include divalent organic acid monomers such as maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, succinic acid, and malonic acid, 1,2,4-benzenetricarboxylic acid, 1 , 2,5-benzenetricarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methylenecarboxy Mention may be made of trivalent or higher polyvalent carboxylic acid monomers such as propane and 1,2,7,8-octanetetracarboxylic acid.

  Examples of the tertiary amine compound used in the present invention include amines, amino alcohols, amino mercaptans, and amidines. Examples of amines include aromatic amines (such as triphenylamine and triallylamine), alicyclic amines (such as N-methylpiperidine); and aliphatic amines (such as triethylamine and trimethylamine). Examples of amino alcohols include triethanolamine and dihydroxyethylaniline. Examples of amino mercaptans include triethanethiolamine and trimethanethiolamine. Examples of amidine include DBU (1,8-diaza-bicyclo [5.4.0] undecene-7) and DBN (1,5-diaza-bicyclo [4.3.0] nonene-5). It is done. Among these tertiary amine compounds, dimorpholinodiethyl ether is more preferable because of its good solubility in organic solvents and good salt formation with acidic group-containing polyesters.

  The prepolymer used in the present invention is preferably a polyester-based prepolymer A containing an isocyanate group, and is a polycondensate of a polyol (PO) and a polycarboxylic acid (PC) and further having a polyester having an active hydrogen group as a polyisocyanate ( PIC). In this case, examples of the active hydrogen group of 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.

  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. Diol (DIO) includes 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, Ethylene 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 above alicyclic diol; Alkylene oxide phenol compound (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. Trivalent or higher polyols (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 and a mixture of (DIC) and a small amount of (TC) are preferable. Dicarboxylic acids (DIC) 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, naphthalene) Dicarboxylic acid 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 polycarboxylic acid (TC) include aromatic polycarboxylic acids having 9 to 20 carbon atoms (such as trimellitic acid and pyromellitic acid). In addition, as polycarboxylic acid (PC), you may make it react with a polyol (PO) using the above-mentioned acid anhydride or lower alkyl ester (Methyl ester, ethyl ester, isopropyl ester, etc.).

  The ratio of the polyol (PO) and the polycarboxylic acid (PC) is usually 2/1 to 1/1, preferably 1 as the equivalent ratio [OH] / [COOH] of the hydroxyl group [OH] and the carboxyl group [COOH]. 5/1 to 1/1, more preferably 1.3 / 1 to 1.02 / 1.

  Examples of the polyisocyanate (PIC) include aliphatic polyisocyanates (tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-diisocyanatomethylcaproate, etc.); alicyclic polyisocyanates (isophorone diisocyanate, cyclohexylmethane diisocyanate, etc.); Aromatic diisocyanates (tolylene diisocyanate, diphenylmethane diisocyanate, etc.); araliphatic diisocyanates (α, α, α ′, α′-tetramethylxylylene diisocyanate, etc.); isocyanurates; And a combination of two or more of these.

  When obtaining a polyester-based prepolymer having an isocyanate group, the ratio of the polyisocyanate (PIC) to the polyester-based resin (PE) having active hydrogen is such that the isocyanate group [NCO] and the hydroxyl group [OH] of the polyester having a hydroxyl group are The equivalent ratio [NCO] / [OH] is usually 5/1 to 1/1, preferably 4/1 to 1.2 / 1, and more preferably 2.5 / 1 to 1.5 / 1. The content of the polyisocyanate (PIC) component in the 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. .

  As the amine B, polyamines and / or amines having an active hydrogen-containing group are used. In this case, the active hydrogen-containing group includes a hydroxyl group and a mercapto group. Such amines include diamine (B1), tri- or higher polyamine (B2), aminoalcohol (B3), aminomercaptan (B4), amino acid (B5), and amino acids B1-B5 blocked ( B6) and the like. 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, (B1) and a mixture of (B1) and a small amount of (B2) are preferable.

  Furthermore, when the prepolymer A and the amine B are reacted, the molecular weight of the polyester can be adjusted by using an elongation terminator if necessary. Examples of the elongation terminator include monoamines having no active hydrogen-containing groups (diethylamine, dibutylamine, butylamine, laurylamine, and the like), and those blocked (ketimine compounds). The addition amount is appropriately selected in relation to the molecular weight desired for the urea-modified polyester to be produced.

  The ratio of the amine B and the prepolymer A having an isocyanate group is the ratio of the isocyanate group [NCO] in the prepolymer A having an isocyanate group to the amino group [NHx] in the amine B (x is a number from 1 to 2). ) Equivalent ratio [NCO] / [NHx] is usually 1/2 to 2/1, preferably 1.5 / 1 to 1 / 1.5, more preferably 1.2 / 1 to 1 / 1.2. It is.

  As the colorant of the present invention, all known dyes and pigments can be used. For example, 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 , Fais red, parachlorol Nitroaniline 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, Tolujing 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, alkali blue rake, peacock blue rake, Victoria blue rake, metal free phthalocyanine blue, phthalocyanine blue, fast sky blue, in Dunslen 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 Phthalocyanine green, anthraquinone green, titanium oxide, zinc white, litbon 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 polyester resin, styrene such as polystyrene, poly p-chlorostyrene, polyvinyltoluene, and its substituted polymers; 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 Coalesce, styrene-ax Ronitrile copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, styrene-maleic acid ester Styrene copolymers such as copolymers; polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, polyacrylic acid Resins, rosins, modified rosins, terpene resins, aliphatic or alicyclic hydrocarbon resins, aromatic petroleum resins, chlorinated paraffins, paraffin waxes and the like can be used, and these can be used alone or in combination.

  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. Also, a so-called flushing method called watering paste containing water of a colorant is mixed and kneaded together with a resin and an organic solvent, and the colorant is transferred to the resin side to remove moisture and organic solvent components. Since it 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.

  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, 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. Carbonyl group-containing waxes include polyalkanoic acid esters (carnauba wax, montan wax, trimethylolpropane tribehenate, pentaerythritol tetrabehenate, pentaerythritol diacetate dibehenate, glycerin tribehenate, 1,18. -Octadecandiol diol 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 (mPa · S), 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 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 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 (above, Orient Chemical Industry Co., Ltd.), TP-302 of a quaternary ammonium salt molybdenum complex, TP 1415 (above, 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 (above, manufactured by Hoechst), LRA-901, LR-147 which is a boron complex (Nippon Carlit Co., Ltd.), 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 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, or fixed on the toner surface after preparation of toner particles. May be.

As the external additive for assisting the fluidity, developability and chargeability of the colored particles obtained in the present invention, inorganic fine particles can be preferably used. The primary particle diameter of the inorganic fine particles is preferably 5 mμ to 2 μm, and particularly preferably 5 mμ to 500 mμ. 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, pengala, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride.

  Other polymer fine particles such as polystyrene, methacrylic acid ester and acrylic acid ester copolymer obtained by soap-free emulsion polymerization, suspension polymerization, and dispersion polymerization, polycondensation systems such as silicone, benzoguanamine, and nylon, and thermosetting resins Examples include polymer particles.

  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.

  Furthermore, the toner of the present invention can be used as a magnetic toner containing a magnetic substance. Examples of the magnetic material contained in the toner include iron oxides such as magnetite, hematite, and ferrite, metals such as iron, cobalt, and nickel, These metals include alloys of metals such as aluminum, cobalt, copper, lead, magnesium, tin, zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten, vanadium, and mixtures thereof. Magnetite is particularly preferable from the viewpoint of magnetic properties. These ferromagnetic materials preferably have an average particle size of about 0.1 to 2 μm. The amount of the ferromagnetic material to be contained in the toner is about 15 to 200 parts by weight, particularly preferably 100 parts by weight of the resin component, with respect to 100 parts by weight of the resin component. 20 to 100 parts by weight per part.

  The toner of the present invention can be used as a one-component developer or a two-component developer combined with a carrier. As the carrier when the toner of the present invention is used as a two-component developer, all known carriers can be used. For example, magnetic powder such as iron powder, ferrite powder, nickel powder, glass beads, etc. And the like which have been treated with a resin or the like. Examples of the resin powder that can be coated on the carrier in the present invention include a styrene-acrylic copolymer, a silicone resin, a maleic acid resin, a fluorine resin, a polyester resin, and an epoxy resin. In the case of a styrene-acrylic copolymer, those having a styrene content of 30 to 90% by weight are preferred. In this case, when the styrene content is less than 30% by weight, the development characteristics are low, and when it exceeds 90% by weight, the coating film becomes hard and easily peeled, and the life of the carrier is shortened. Moreover, the resin coating of the carrier in the present invention may contain an adhesion-imparting agent, a curing agent, a lubricant, a conductive material, a charge control agent and the like in addition to the resin.

  EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited thereto. Hereinafter, a part shows a weight part.

[Production Example 1]
(Production of resin fine particle dispersion)
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 [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.

(Production of low molecular weight polyester-1)
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction tube, 229 parts of bisphenol A ethylene oxide 2-mole adduct, 529 parts of bisphenol A propylene oxide 3-mole adduct, 208 parts of terephthalic acid, 37.2 parts of succinic acid 2 parts of dibutyltin oxide and 60 parts of trimellitic anhydride in a reaction vessel, reacted at 230 ° C. at normal pressure for 8 hours, and further reacted at reduced pressure of 10 to 15 mmHg for 5 hours. 1] was obtained. [Low molecular polyester-1] had a number average molecular weight of 2,300, a weight average molecular weight of 6,600, a Tg of 43 ° C., and an acid value of 30.

(Prepolymer production)
Into a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introducing tube, 795 parts of bisphenol A ethylene oxide 2-mole adduct, 200 parts of isophthalic acid, 65 parts of terephthalic acid, and 2 parts of dibutyltin oxide were added at normal pressure. Under a nitrogen stream, condensation reaction was performed at 210 ° C. for 8 hours. Next, the reaction was continued for 5 hours while dehydrating under reduced pressure of 10 to 15 mmHg, then cooled to 80 ° C., and reacted with 170 parts of isophorone diisocyanate in ethyl acetate for 2 hours to obtain [Prepolymer-1]. The obtained [Prepolymer-1] had a weight average molecular weight of 5,000.

(Adjustment of toner material oil dispersion 1-1)
In a beaker, 23.4 parts of [Prepolymer-1], 141.6 parts of [Polyester-1] and 80 parts of ethyl acetate were stirred and dissolved. Separately, 15 parts of carnauba wax as a release agent, 20 parts of carbon black pigment, and 120 parts of ethyl acetate were placed in a bead mill and dispersed for 30 minutes. The two liquids were mixed and stirred for 5 minutes at a rotational speed of 12000 rpm using a TK homomixer, and then dispersed in a bead mill for 10 minutes. 2.9 parts of isophorone diamine and 2.2 parts of dimorpholino diethyl ether were added to the dispersion, and the mixture was stirred for 5 minutes at 12000 rpm using a TK homomixer. ] [Toner material oil-based dispersion-1] had an acid value of 27, a base value of 7.9, and an acid value / base value of 3.4.

(Manufacture of toner 1)
In a beaker, 529.5 parts of ion-exchanged water, 70 parts of [resin fine particle dispersion-1] and 0.5 part of sodium dodecylbenzenesulfonate are added to this aqueous dispersion while stirring with a TK homomixer at 12000 rpm. 405.1 parts of [Toner Material Final Oil Dispersion-1] were added and reacted while stirring for 30 minutes. Subsequently, the contents were transferred to a flask equipped with a cooling pipe and aged using a hot water bath. The organic solvent was removed from the ripened dispersion, followed by filtration, washing and drying, followed by air classification to obtain a spherical toner base. 100 parts of the obtained base particles and 0.25 parts of a charge control agent (Bontron E-84 manufactured by Orient Chemical Co., Ltd.) are charged into a Q-type mixer (manufactured by Mitsui Mining Co., Ltd.), and the peripheral speed of the turbine type blade is set to 50 m / sec. And mixed. In this case, the mixing operation was performed for 2 minutes, 5 cycles of 1 minute pause, and the total treatment time was 10 minutes. Further, 0.5 part of hydrophobic silica (H2000, manufactured by Clariant Japan) was added and mixed. In this case, in the mixing operation, the peripheral speed was 15 m / sec, and 30 seconds of mixing and rest for 1 minute were carried out for 5 cycles to obtain the final [Toner 1]. Using the obtained [Toner 1], volume average particle size, particle size distribution, low temperature fixability, high temperature offset resistance, and image quality were evaluated.

[Production Example 2]
(Production of low molecular weight polyester-2)
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 polyester-2]. [Low molecular polyester-2] had a number average molecular weight of 2500, a weight average molecular weight of 6600, a Tg of 44 ° C., and an acid value of 25.

(Adjustment of toner material oil dispersion-2)
In Preparation Example 1 (Preparation of Toner Material Oily Dispersion-1), [Polyester-1] was changed to [Polyester-2], and all the same except that 1.5 parts of dimorpholinodiethyl ether was added, [ Toner material oil-based dispersion-2] was obtained. [Toner material oil dispersion-2] had an acid value of 23, a base value of 6.8, and an acid value / base value of 3.4.

(Manufacture of toner 2)
[Toner 2] [Production of Toner 1] [Production Example 1] [Toner Material Oily Dispersion-1] 405.1 parts [Toner Material Oily Dispersion-2] 404.4 parts Got. Using the obtained [Toner 2], volume average particle size, particle size distribution, low temperature fixability, high temperature offset resistance, and image quality were evaluated.

[Production Example 3]
(Adjustment of toner material oil dispersion-3)
[Toner material oil dispersion-3] was obtained in the same manner as in Preparation Example 2 (Preparation of toner material oil dispersion-2) except that 0.5 part of dimorpholinodiethyl ether was added. [Toner material oil dispersion-3] had an acid value of 23, a base number of 6.1, and an acid value / base number of 3.8.

(Manufacture of toner 3)
In [Production Example 1 (Manufacture of Toner 1)], [Toner 3 Oily Dispersion-1] 405.1 parts [Toner Material Oily Dispersion-3] 403.4 parts [Toner 3 ] Using the obtained [Toner 3], volume average particle size, particle size distribution, low temperature fixability, high temperature offset resistance and image quality were evaluated.

[Production Example 4]
(Production of low molecular weight polyester-3)
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 740 g of polyoxypropylene (2,2) -2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene (2,2) -2 1,2-bis (4-hydroxyphenyl) propane, 466 g of dimethyl terephthalate, 80 g of isododecenyl succinic anhydride, and 114 g of tri-n-butyl 1,2,4-benzenetricarboxylate were added together with the esterification catalyst. Under a nitrogen atmosphere, the temperature was raised to 210 ° C. under the normal pressure, and the reaction was performed while stirring at 210 ° C. under the second half to obtain [Low Molecular Polyester-3]. [Low molecular polyester-3] had a number average molecular weight of 3000, a weight average molecular weight of 13600, a Tg of 62 ° C., and an acid value of 20.

(Adjustment of toner material oil dispersion-4)
In Preparation Example 1 (Preparation of Toner Material Oily Dispersion-1), [Polyester-1] was changed to [Polyester-3], and 0.3 parts of dimorpholinodiethyl ether was added. Toner material oil dispersion-4] was obtained. [Toner material oil dispersion-4] had an acid value of 18, a base value of 5.3, and an acid value / base value of 3.4.

(Manufacture of toner 4)
[Toner 4] was prepared in the same manner as in Production Example 1 (Manufacture of Toner 1) except that 405.1 parts of [Toner Material Oil Dispersion-1] was changed to [Toner Material Oil Dispersion-4] 403.2. Obtained. Using the obtained [Toner 4], volume average particle size, particle size distribution, low temperature fixability, high temperature offset resistance, and image quality were evaluated.

[Production Example 5]
(Adjustment of toner material oil dispersion-5)
[Toner material oil dispersion-5] was obtained in the same manner as in Production Example 4 (Preparation of toner material oil dispersion-4) except that 0.2 part of dimorpholinodiethyl ether was added. [Toner material oil dispersion-5] had an acid value of 18, a base value of 4.7, and an acid value / base value of 3.8.

(Manufacture of toner 5)
In [Production Example 1 (Manufacture of Toner 1)], [Toner Material Oily Dispersion-1] 405.1 parts [Toner Material Oily Dispersion-5] 403.1 parts is the same as [Toner5 ] Using the obtained [Toner 5], volume average particle size, particle size distribution, low temperature fixability, high temperature offset resistance, and image quality were evaluated.

[Production Example 6]
(Adjustment of toner material oil dispersion-6)
[Toner material oil dispersion-6] was obtained in the same manner as in Preparation Example 2 (Preparation of toner material oil dispersion-2) except that dimorpholinodiethyl ether was not added. [Toner material oil dispersion-6] had an acid value of 23, a base value of 4.2, and an acid value / base value of 3.8.

(Production of Toner-6)
In [Production Example 1 (Manufacture of Toner 1)], [Toner 6 Oily Dispersion-1] 405.1 parts was changed to [Toner Material Oily Dispersion-6] 402.9 parts. ] Using the obtained [Toner 6], volume average particle size, particle size distribution, low-temperature fixability, high-temperature offset resistance, and image quality were evaluated.

[Production Example 7]
(Production of low molecular weight polyester-4)
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction tube, 229 parts of bisphenol A ethylene oxide 2-mole adduct, 529 parts of bisphenol A propylene oxide 3-mole adduct, 208 parts of terephthalic acid, 37.2 parts of succinic acid 2 parts of dibutyltin oxide and 18 parts of trimellitic anhydride in a reaction vessel, reacted at 230 ° C. under normal pressure for 8 hours, and further reacted at reduced pressure of 10-15 mmHg for 5 hours. ] Was obtained. [Low molecular polyester-4] had a number average molecular weight of 2,400, a weight average molecular weight of 6,300, Tg of 45 ° C., and an acid value of 10.

(Adjustment of toner material oil dispersion-7)
In Preparation Example 1 (Preparation of Toner Material Oily Dispersion-1), [Polyester-1] was changed to [Polyester-4], and 0.2 parts of dimorpholinodiethyl ether was added. Toner material oil dispersion-7] was obtained. [Toner material oil dispersion-7] had an acid value of 8, a base value of 4.7, and an acid value / base value of 1.7.

(Manufacture of toner 7)
[Toner 7] was prepared in the same manner as in Production Example 1 (Manufacture of Toner 7), except that 405.1 parts of [Toner Material Oil Dispersion-1] was changed to [Toner Material Oil Dispersion-7] 403.1. Obtained. Using the obtained [Toner 7], volume average particle size, particle size distribution, low-temperature fixability, high-temperature offset resistance, and image quality were evaluated.

[Production Example 8]
(Adjustment of Toner Material Oily Dispersion-8) In the same manner as in Preparation Example 7 (Adjustment of Toner Material Oily Dispersion-7), except that dimorpholinodiethyl ether is not added, [Toner Material Oily Dispersion— 8] was obtained. [Toner material oil dispersion-8] had an acid value of 8, a base value of 4.3, and an acid value / base value of 1.3.

(Production of Toner-8)
In [Production Example 1 (Manufacture of Toner 1)], [Toner 8 Oily Dispersion-1] 405.1 parts [Toner Material Oily Dispersion-8] 402.9 parts is the same as [Toner 8 ] Using the obtained [Toner 8], volume average particle size, particle size distribution, low-temperature fixability, high-temperature offset resistance, and image quality were evaluated.

[Production Example 9]
(Production of low molecular weight polyester-5)
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 10-15 mmHg reduced pressure. Then, 10 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 polyester-5]. [Low molecular polyester-5] had a number average molecular weight of 2500, a weight average molecular weight of 6600, a Tg of 44 ° C., and an acid value of 4.

(Adjustment of toner material oil dispersion-9)
In Preparation Example 1 (Preparation of Toner Material Oily Dispersion-1), [Polyester-1] is changed to [Polyester-5], and dimorpholinodiethyl ether is not added. Dispersion-9] was obtained. [Toner material oil dispersion-9] had an acid value of 3.8, a base value of 4.4, and an acid value / base number of 0.86.

(Manufacture of toner 9)
[Toner 9] in the same manner as in Production Example 1 (Production of Toner 1) except that 405.1 parts of [Toner Material Oily Dispersion-1] were changed to 402.9 parts of [Toner Material Oily Dispersion-9]. Got. Using the obtained [Toner 9], volume average particle size, particle size distribution, low temperature fixability, high temperature offset resistance, and image quality were evaluated.

  Table 1 shows the physical properties relating to the polyester from [Toner 1] to [Toner 9] described above.

[Example 1]
Using [Toner 1] obtained in Production Example 1, volume average particle size, particle size distribution, low temperature fixability, high temperature offset resistance, and image quality were evaluated.

[Example 2]
Using [Toner 2] obtained in Production Example 1, volume average particle size, particle size distribution, low-temperature fixability, high-temperature offset resistance, and image quality were evaluated.

[Example 3]
Using [Toner 3] obtained in Production Example 1, volume average particle size, particle size distribution, low-temperature fixability, high-temperature offset resistance, and image quality were evaluated.

[Example 4]
Using [Toner 4] obtained in Production Example 1, volume average particle size, particle size distribution, low temperature fixability, high temperature offset resistance, and image quality were evaluated.

[Example 5]
Using [Toner 5] obtained in Production Example 1, volume average particle size, particle size distribution, low-temperature fixability, high-temperature offset resistance, and image quality were evaluated.

[ Reference Example 6]
Using [Toner 6] obtained in Production Example 1, volume average particle size, particle size distribution, low-temperature fixability, high-temperature offset resistance, and image quality were evaluated.

[ Reference Example 7]
Using [Toner 7] obtained in Production Example 1, volume average particle size, particle size distribution, low temperature fixability, high temperature offset resistance, and image quality were evaluated.

[ Reference Example 8]
Using [Toner 8] obtained in Production Example 1, volume average particle size, particle size distribution, low-temperature fixability, high-temperature offset resistance, and image quality were evaluated.

[ Reference Example 9]
Using [Toner 9] obtained in Production Example 1, volume average particle size, particle size distribution, low-temperature fixability, high-temperature offset resistance, and image quality were evaluated.

  The toner evaluation items and evaluation methods in the examples are shown below, and the evaluation results are shown in Table 2.

(Image density)
Using an evaluation machine, after running 150,000 sheets of an image chart with a 50% image area in monochromatic mode, a solid image was output to 6000 paper manufactured by Ricoh, and the image density was measured using XRite (manufactured by X-Rite). Measurements were made. This was performed for four colors alone, and the average was obtained. When this value is less than 1.2, “x”, when it is 1.2 or more and less than 1.4, “△”, when it is 1.4 or more and less than 1.8, “◯”, 1.8 or more and 2 If less than 2, “◎” was assigned.

(Image graininess, sharpness)
Using an evaluator, a photographic image was output in a single color, and the degree of graininess and sharpness was visually evaluated. In order from the best, “◎” is equivalent to offset printing, “○” is slightly worse than offset printing, “△” is much worse than offset printing, “×” is about the same as conventional electrophotographic images (very much Bad).

(Dirt)
Using an evaluation machine, after running 30,000 sheets of 50% image area image chart in monochrome mode, the blank image is stopped during development, and the developer on the developed photoconductor is transferred to tape and untransferred. The difference from the image density of the tape was measured with a 938 spectrodensitometer (manufactured by X-Rite). The smaller the difference in image density, the better the background stain, and the better ones were ranked in the order of “◎”, “◯”, “Δ”, “×”.

(Toner scattering)
After continuous printing of 50,000 sheets by the evaluation machine, the degree of toner contamination inside the machine was confirmed. A problem-free level was indicated by “◯”, a toner was observed, but a problem-free level was indicated by “Δ”, and a markedly contaminated and problematic problem was indicated by “X”.

(Carrier contamination)
Heat 49g carrier in a 110 ° C constant temperature bath. Here, 0.26 g of the test toner is mixed and vigorously shaken in a 100 mL screw vial while being dissolved by the latent heat of the carrier. After stirring for several minutes with a ball mill, crushing with an aster and air sieving with 400 mesh to adjust the contaminated carrier. 3 g of contaminated carrier and 0.226 g of standard toner were stirred with mag roll for 5 minutes and measured by horizontal blow. The carrier contamination level is confirmed by the decrease rate of the charge amount with respect to the new carrier.
Reduction rate of less than 10%: ◎, reduction rate of 10% or more and less than 20%: ○, reduction rate of 20% or more and less than 50%: Δ, reduction rate of 50% or more: ×

(Fixability evaluation)
Using a device obtained by remodeling the fixing unit MF2200 manufactured by Ricoh Co., Ltd. using a Teflon (registered trademark) roller as a fixing roller, type 6200 paper manufactured by Ricoh was set in this and a copying test was performed. The cold offset temperature (fixing lower limit temperature) and the hot offset temperature (hot offset resistant temperature) were determined by changing the fixing temperature. The minimum fixing temperature of the conventional low-temperature fixing toner is about 140 to 150 ° C. The evaluation conditions for low-temperature fixing are as follows: the paper feed linear speed is 120 to 150 mm / sec, the surface pressure is 1.2 kgf / cm ² , the nip width is 3 mm, and the high temperature offset is the paper feed linear speed of 50 mm / sec. The surface pressure was set to 2.0 kgf / cm @ 2, and the nip width was 4.5 mm. The criteria for each characteristic evaluation are as follows.
Low-temperature fixability (5-level evaluation)
Good: A: Less than 140 ° C., ○: 140-149 ° C., □: 150-159 ° C., Δ: 160-170 ° C., X: 170 ° C. or higher: Evil hot offset property (five-step evaluation)
Good: ◎: 201 ° C or higher, ○: 200-191 ° C, □: 190-181 ° C, Δ: 180-171 ° C, x: 170 ° C or lower: bad

Claims (13)

At least a compound having an active hydrogen group, a polymer having a site capable of reacting with the compound , an acidic group-containing binder resin, a colorant, a release agent, and a tertiary amine are mixed with an organic solvent or organic dispersion. A solution or dispersion dissolved or dispersed in a medium is dispersed in an aqueous medium containing resin fine particles, and a polymer having a site capable of reacting with the compound having an active hydrogen group is subjected to a crosslinking or elongation reaction or reaction. An electrostatic charge image developing toner produced by removing the organic solvent or the organic dispersion medium, washing, and drying,
The acid number A of the solution or dispersion is in the range of 15 to 30, and the ratio B / A of the acid number A to the base number B of the solution or dispersion is from 1/5 to 1/1. of the range, the der 2μm or less of the particles of between 5% by number or less of the toner particle diameter is, the average circularity of the toner for electrostatic image development according to claim der Rukoto 0.97 or more of the toner.   The electrostatic image developing toner according to claim 1, wherein the acidic group-containing binder resin is a polyester resin. The toner according to claim 2, wherein a content of the binder resin of the acid group-containing polyester resin is 50% to 10 0 by weight%.   4. The electrostatic image developing toner according to claim 2, wherein the acidic group-containing polyester resin has a weight average molecular weight of 1,000 to 30,000 in a THF soluble portion.   5. The electrostatic image developing toner according to claim 2, wherein the acid value of the acidic group-containing polyester resin is 1.0 or more and 50.0 or less (KOH mg / g). The toner according to any one of claims 2 to 5, wherein the glass transition point of the acid group-containing polyester resin is 35 ℃ ~ 6 5 ℃.   The electrostatic charge image according to any one of claims 1 to 6, wherein the polymer having a site capable of reacting with the compound having an active hydrogen group has a weight average molecular weight of 3,000 or more and 20,000 or less. Developing toner.   The electrostatic image developing toner according to claim 1, wherein the toner has a volume average particle diameter in the range of 3 to 9 μm. 9. The electrostatic image developing toner according to claim 1, wherein a ratio Dv / Dn of the volume average particle size Dv to the number average particle size Dn of the toner is 1.25 or less.   10. The electrostatic image developing toner according to claim 1, wherein the toner has an acid value of 0.5 or more and 40.0 or less (KOH mg / g). 11. 11. The toner for developing an electrostatic charge image according to claim 1, wherein the toner has a glass transition point of 40 ° C. to 70 ° C. 11. The toner has a BET specific surface area of 1.0 m. ² /G-6.0m ² The electrostatic charge image developing toner according to claim 1, wherein the toner is an electrostatic charge image developing toner. At least a compound having an active hydrogen group, a polymer having a site capable of reacting with the compound, an acidic group-containing binder resin, a colorant, a release agent, and a tertiary amine are mixed with an organic solvent or organic dispersion. After dissolving or dispersing in a medium and dispersing the solution or dispersion in an aqueous medium containing resin fine particles to crosslink or extend a polymer having a site capable of reacting with the compound having an active hydrogen group, or after reaction The organic solvent is removed, washed and dried to produce a toner,
  The acid number A of the solution or dispersion is 15 or more and 30 or less, the ratio B / A of the acid number A to the base number B of the solution or dispersion is 1/5 or more, and 1/1 μm. A method for producing a toner for developing an electrostatic charge image, wherein the following particle ratio is 5% by number or less and the average circularity of the toner is 0.97 or more.