JP4101165B2 - Toner for developing electrostatic image and method for producing the same - Google Patents

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 and electrostatic recording, a developer using the toner, and a method for manufacturing the same.

  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.

  Production of polymerized toner by suspension polymerization in an aqueous medium such as Patent Document 1 (JP 2001-296700) and Patent Document 2 (JP 2002-91073), Patent Document 3 (JP 2001-305797), etc. Many reports on the production of polymerized toner by the emulsion aggregation method have been made, 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 in Patent Document 4 (Japanese Patent Laid-Open No. 2002-287400), Patent Document 5 (Japanese Patent Laid-Open No. 2002-351143), and the like. The toner production methods described in these publications include 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, JP 2002-91073, JP 2001-305797 A JP 2002-287400 A JP 2002-351143 A

  In view of the current problems as described above, the present invention is excellent in low-temperature fixability and high-temperature offset resistance, stably controls the target particle size and particle size distribution, and uniformly disperses the colorant. An object of the present invention is to provide a toner for developing an electrostatic image that can maintain an excellent particle size distribution and exhibits excellent image quality.

  As a result of intensive studies by the present inventors, a toner produced in an aqueous medium and comprising at least a binder resin and a colorant, and preferably 50 to 100% by weight of the binder resin 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, a colorant, and a release agent are dissolved or dispersed, and the solution or dispersion is dispersed in an aqueous solvent. Among these, after reacting or reacting a polymer having a site capable of reacting with a compound having an active hydrogen group and an active hydrogen-containing compound, the organic solvent is removed, and the toner is stable and washed. In order to obtain the desired particle size and particle size distribution, the oily component is smoothly applied against the shearing force when the binder resin, colorant, release agent solution or dispersion is dispersed in an aqueous solvent. Is distributed Are, also it has been found to be important to maintain the dispersion state. Therefore, the present inventors have determined that the viscosity and viscosity ratio of the solution or dispersion greatly affect the dispersion state in the aqueous solvent and its maintenance, and only within a certain range of viscosity and viscosity ratio. As a result, it was concluded that good colorant dispersibility and a stable particle size distribution can be obtained, and further studies have been made to achieve the present invention.

That is, according to the present invention,
(1) A polymer having a site capable of reacting with a compound having an active hydrogen group serving as a binder resin, a colorant, and a release agent are dissolved or dispersed in at least an organic solvent, and the solution or dispersion is dissolved in an aqueous solvent. In the solvent, the organic solvent is removed and washed after or while reacting the polymer having a site capable of reacting with the compound having an active hydrogen group with the active hydrogen-containing compound. In the dried toner, the polymer having a site capable of reacting with the compound having an active hydrogen group as the binder resin is an isocyanate group-containing polyester prepolymer, and the compound having the active hydrogen group is an amine, The viscosity of the solution or dispersion at 25 ° C. at 6 rpm with a rotational viscometer is 300 to 50000 mPa · s, and the viscosity with a rotational viscometer represented by the following formula: A toner for developing electrostatic images, wherein the ratio is 1.5 to 25.0;
Viscosity ratio = (viscosity at 6 rpm) / (viscosity at 60 rpm)
(2) The electrostatic charge image developing toner according to (1) above, further comprising a polyester resin as an binder resin in an organic solvent,
( 3) The toner for developing an electrostatic charge image according to ( 2) above, wherein the polyester resin has a THF-soluble component having a weight average molecular weight of 1,000 to 30,000,
( 4) The electrostatic value image development according to any one of (2) to ( 3) , wherein the polyester resin has an acid value of 1.0 to 50.0 (KOHmg / g). toner,
( 5) The electrostatic charge image developing toner according to any one of (2) to ( 4) , wherein the polyester resin has a glass transition point of 35 to 65 ° C.
( 6) Any one of the above (1) to ( 5) , 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 to 20,000. The toner for developing an electrostatic image according to the item,
( 7) The toner for developing an electrostatic charge image according to any one of (1) to ( 6) , wherein the toner has an acid value of 0.5 to 40.0 (KOHmg / g). ,
( 8) The toner for developing an electrostatic charge image according to any one of (1) to ( 7) , wherein the toner has a glass transition point of 40 to 70 ° C.
( 9) The electrostatic charge image developing toner according to any one of (1) to ( 8) , wherein the toner has a volume average particle diameter of 3 to 8 μm,
( 10) The toner for developing an electrostatic charge image according to any one of (1) to ( 9) , wherein Dv / Dn of the toner is 1.25 or less,
( 11) The toner for developing an electrostatic charge image according to any one of (1) to ( 10) , wherein the toner has an average circularity of 0.94 to 1.00.
( 12) The toner for developing an electrostatic charge image according to any one of (1) to ( 11) , wherein the toner has a BET specific surface area of 1.0 to 6.0 m ² / g.
( 13) A polymer having a site capable of reacting with a compound having an active hydrogen group as a binder resin, a colorant, and a release agent are dissolved or dispersed in at least an organic solvent, and the solution or dispersion is dispersed in an aqueous medium. In the solvent, the organic solvent is removed and washed after or while reacting the polymer having a site capable of reacting with the compound having an active hydrogen group with the active hydrogen-containing compound. In the dried toner, the polymer having a site capable of reacting with the compound having an active hydrogen group as the binder resin is an isocyanate group-containing polyester prepolymer, and the compound having the active hydrogen group is an amine, The viscosity of the solution or dispersion at 25 ° C. at 6 rpm with a rotational viscometer is 300 to 50000 mPa · s, and according to the rotational viscometer represented by the following formula: A method for producing a toner for developing an electrostatic image, wherein the viscosity ratio is 1.5 to 25.0;
Viscosity ratio = (viscosity at 6 rpm) / (viscosity at 60 rpm)

  According to the present invention, it is possible to obtain a toner for developing an electrostatic image that has excellent low-temperature fixability and high-temperature offset resistance, excellently disperses a colorant, maintains a uniform particle size distribution, and exhibits excellent image quality. is there.

  The present invention is described in detail below. In order to stably obtain the desired particle size and particle size distribution, the present inventors have carried out shearing when the binder resin, colorant, release agent solution or dispersion is dispersed in an aqueous solvent. It is necessary to control the viscosity and viscosity ratio of the oily solution or dispersion in order to disperse the oily component smoothly against the force and to maintain the dispersion state, thereby favorably coloring the colorant. It was found that a toner exhibiting excellent image quality in which a uniform particle size distribution is maintained can be obtained.

  According to the study of the present inventors, in a toner produced in an aqueous medium and comprising at least a binder resin and a colorant, and preferably 50 to 100% by weight of the binder resin is a polyester resin, the toner is at least in an organic solvent. In addition, a polymer having a site capable of reacting with a compound having an active hydrogen group, a colorant, and a release agent are dissolved or dispersed, and the solution or dispersion is dispersed in an aqueous solvent. After the polymer having a site capable of reacting with the compound having a hydrogen group is reacted with the active hydrogen-containing compound or while reacting, the organic solvent is removed, washed and dried in the toner in the solution or dispersion. It is necessary to control the viscosity at 25 ° C. to 300 to 50000 mPa · s in order to stably obtain the target particle size and particle size distribution. When the viscosity at 25 ° C. of the solution or dispersion is less than 300 mPa · s, fine powder increases because the oily raw material is finely dispersed more than necessary due to the shearing force when dispersed in an aqueous solvent. Further, the coalescence of the finely dispersed oily raw material easily occurs, resulting in a non-uniform particle size and a sharp particle size distribution cannot be obtained. Moreover, when the viscosity at 25 ° C. of the solution or dispersion exceeds 50000 mPa · s, there arises a problem that the shearing force is insufficient and the particle size reduction necessary for obtaining high resolution cannot be achieved.

  Furthermore, it is necessary to control the viscosity ratio of the solution or dispersion of the present invention to 1.5 to 25.0 in order to stably obtain the target particle size and particle size distribution. When the viscosity ratio is less than 1.5, the dispersed particle size of the binder resin, the release agent, and the colorant becomes large, and the dispersed state of each component in the toner particles and between the toner particles becomes non-uniform. The image quality cannot be obtained. Further, when the viscosity ratio exceeds 25.0, thixotropy is large, and therefore, when the oily raw material is dispersed by shearing force in an aqueous solvent, the dispersion state changes with time. As a result, there arises a problem that a stable particle size and particle size distribution cannot be obtained.

The viscosity of the present invention can be measured with a DV-E rotational viscometer manufactured by Brookfield, and indicates the viscosity measured at a rotational speed of 6 rpm for a sample adjusted to 25 ° C. in a thermostatic bath. Further, the viscosity ratio is obtained by the following equation by measuring the viscosity at the rotation speed of 60 rpm using the same sample.
Viscosity ratio = viscosity (6 rpm) / viscosity (60 rpm)

  According to a further study of the present invention, in the case of using a prepolymer and a polyester resin which are polymers having a site capable of reacting with the compound having an active hydrogen group as a binder resin, while maintaining heat resistant storage stability, In order to effectively exhibit low-temperature fixability and to provide offset resistance after modification with a prepolymer, the polyester resin has a THF-soluble weight average molecular weight of 1,000 to 30,000. preferable. This is because when less than 1,000, the oligomer component increases, the heat-resistant storage stability deteriorates, and when it exceeds 30,000, the dispersibility of the prepolymer becomes insufficient due to steric hindrance or viscosity increase, and offset resistance deteriorates. is there.

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, Pressure Chemical Co. Or molecular weight made by Toyo Soda Industry Co., Ltd. is 6 × 10 ² , 2.1 × 10 ³ , 4 × 10 ³ , 1.75 × 10 ⁴ , 5.1 × 10 ⁴ , 1.1 × 10 ⁵ , 3.9. It is appropriate to use x10 ⁵ , 8.6 × 10 ⁵ , 2 × 10 ⁶ , 4.48 × 10 ⁶ , and use at least about 10 standard polystyrene samples. An RI (refractive index) detector is used as the detector.

  In addition, by setting the acid value of the polyester resin to 1.0 to 50.0 (KOHmg / g), toner properties such as low-temperature fixability, high-temperature offset resistance, heat-resistant storage stability, and charge stability are improved. Is possible. That is, when the acid value exceeds 50.0 (KOHmg / g), the prepolymer elongation or crosslinking reaction becomes insufficient, and the high-temperature offset resistance is affected. When the acid value is less than 1.0 (KOHmg / g) This is because the prepolymer is likely to elongate or undergo a cross-linking reaction, causing a problem in production stability.

  The acid value measuring method 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, since the heat resistant storage performance of the main component of the polyester resin, that is, the binder resin depends on the glass transition point of the polyester resin, it is preferable to design the glass transition point of the polyester resin at 35 ° C. to 65 ° C. 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 with a Rigaku THRMOFLEX TG8110 manufactured by Rigaku Corporation at a temperature increase rate of 10 ° C./min.

  According to a further study of the present invention, a prepolymer that forms a high molecular weight body by elongation or crosslinking reaction is an important binder resin component for realizing low-temperature fixability and high-temperature offset resistance, and its weight average molecular weight. Is preferably 3,000 to 20,000. 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, the dispersibility of the prepolymer itself becomes insufficient and starts to affect the offset resistance.

  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, if the toner acid value exceeds 40.0 (KOHmg / g), the prepolymer elongation or crosslinking reaction becomes insufficient, and the high temperature offset resistance is affected, and less than 0.5 (KOHmg / g). In this case, the elongation or crosslinking reaction of the prepolymer is likely to proceed, causing 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 8 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 average 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. .

The toner of the present invention preferably has a BET specific surface area of 1.0 to 6.0 (m ² / g), and if the BET specific surface area is less than 1.0 (m ² / g), the presence or addition of coarse particles When the amount exceeds 6.0 (m ² / g), the image quality is likely to be affected by the presence of fine particles, the presence of additives, and surface irregularities.

  The BET specific surface area of the toner of the present invention can be obtained by measuring using a device capable of complying with JIS standards (Z8830 and R1626) such as NOVA series manufactured by Yuasa Ionics.

  Furthermore, the method for producing the toner used in the present invention comprises a step of increasing the molecular weight of reacting an isocyanate group-containing polyester prepolymer A dispersed in an aqueous medium containing inorganic fine particles and / or polymer fine particles with an amine B. It is preferable to include.

  Next, materials used for the toner of the present invention will be described in detail. The 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.

  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; phenols, oximes, caprolactam 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 B1 to B5 blocked amino groups (B6) include ketimine compounds and oxazoline compounds obtained from the amines of B1 to B5 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.

  In the present invention, the prepolymer and the polyester resin described above are contained as a binder resin, the dispersion of the organic solvent solution or dispersion in the aqueous solvent does not become unstable, and the compound reacts with a compound having an active hydrogen group. A resin other than a polyester resin can be used as a binder resin in blend use as long as it does not inhibit the reaction between the polymer having a possible site and the active hydrogen-containing compound.

  Examples of usable resins other than the polyester resin include the following. Polystyrene, chloropolystyrene, poly α-methylstyrene, styrene / chlorostyrene copolymer, styrene / propylene copolymer, styrene / butadiene copolymer, styrene / vinyl chloride copolymer, styrene / vinyl acetate copolymer, styrene / Maleic acid copolymer, styrene / acrylic acid ester copolymer (styrene / methyl acrylate copolymer, styrene / ethyl acrylate copolymer, styrene / butyl acrylate copolymer, styrene / octyl acrylate copolymer) Styrene / phenyl acrylate copolymer), styrene / methacrylic acid ester copolymer (styrene / methyl methacrylate copolymer, styrene / ethyl methacrylate copolymer, styrene / butyl methacrylate copolymer, styrene) / Phenyl methacrylate copolymer, etc.) Styrene resins (homopolymers or copolymers containing styrene or styrene-substituted products) such as styrene / α-chloromethyl acrylate copolymer, styrene / acrylonitrile / acrylate ester copolymer, vinyl chloride resin, styrene / Vinyl acetate copolymer, rosin-modified maleic acid resin, phenol resin, epoxy resin, polyethylene resin, polypropylene resin, ionomer resin, polyurethane resin, silicone resin, ketone resin, ethylene / ethyl acrylate copolymer, xylene resin, polyvinyl butyral resin Petroleum resin, hydrogenated petroleum resin, etc.

  The method for producing these resins is not particularly limited, and any of bulk polymerization, solution polymerization, emulsion polymerization, and suspension polymerization can be used.

  As the coloring agent 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 kneaded together with the production of the masterbatch or the masterbatch, in addition to the above-described 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, 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. -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, 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. Any known charge control agent can be used. For example, nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts (fluorine-modified) Quaternary ammonium salts), alkylamides, phosphorus simple substances or compounds, tungsten simple substances or compounds, fluorine-based activators, salicylic acid metal salts, and metal salts of salicylic acid derivatives. Specifically, Nitronine-based dye Bontron 03, quaternary ammonium salt Bontron P-51, metal-containing azo dye Bontron S-34, oxynaphthoic acid metal complex E-82, salicylic acid metal complex E- 84, E-89 of a phenol-based condensate (manufactured by Orient Chemical Industry Co., Ltd.), TP-302 of a quaternary ammonium salt molybdenum complex, TP-415 (manufactured by Hodogaya Chemical Industry Co., Ltd.), quaternary ammonium Copy charge PSY VP2038 of salt, copy blue PR of triphenylmethane derivative, copy charge of quaternary ammonium salt NEG VP2036, copy charge NX VP434 (manufactured by Hoechst), LRA-901, LR-147 which is a boron complex (Nippon Carlit), copper phthalocyanine, perylene, quinaclide And azo pigments, and other high molecular compounds having a functional group such as a sulfonic acid group, a carboxyl group, and a quaternary ammonium salt.

  In the present invention, the amount of charge control agent used is determined by the toner production method including the type of binder resin, the presence or absence of additives used as necessary, and the dispersion method, and is uniquely limited. However, it is preferably used in the range of 0.1 to 10 parts by weight with respect to 100 parts by weight of the binder resin. The range of 0.2 to 5 parts by weight is preferable. When the amount exceeds 10 parts by weight, the chargeability of the toner is too high, the effect of the main charge control agent is reduced, the electrostatic 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 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, and thermosetting resin 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 ones can be used. For example, magnetic powder such as iron powder, ferrite powder, nickel powder, glass beads, and the like, and these 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
(Example of polyester production)
690 parts of bisphenol A ethylene oxide 2-mole adduct and 335 parts of terephthalic acid are charged into a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, and condensed at 210 ° C. for 10 hours under a normal pressure nitrogen stream. Reacted. Next, the reaction was continued for 5 hours while dehydrating under reduced pressure of 10 to 15 mmHg, followed by cooling to obtain polyester (A). The obtained polyester resin had a weight average molecular weight of 6,000, an acid value of 10 KOH mg / g, and a glass transition point of 48 ° C.

(Prepolymer production example)
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 a prepolymer (a). The obtained prepolymer had a weight average molecular weight of 5,000.

(Production example of ketimine compound)
With a stir bar and thermometer, 30 parts of isophoronediamine and 70 parts of methyl ethyl ketone were charged into the reaction vessel and reacted at 50 ° C. for 5 hours to obtain a ketimine compound (1).

(Dispersion adjustment)
In a beaker, 14.3 parts of prepolymer (a), 55 parts of polyester (A) and 78.6 parts of ethyl acetate were stirred and dissolved. Separately, 10 parts of rice wax as a release agent, 4 parts of copper phthalocyanine blue pigment and 100 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 for 10 minutes with a bead mill to obtain a toner material oil dispersion (1). The obtained dispersion had a viscosity at 25 ° C. of 1500 mPa · s and a viscosity ratio of 3.0.

(Example of toner production)
In a beaker, 306 parts of ion exchange water, 265 parts of tricalcium phosphate 10% suspension, and 0.2 part of sodium dodecylbenzenesulfonate were added, and the above-mentioned aqueous dispersion was added to this aqueous dispersion while stirring at 12000 rpm with a TK homomixer. Toner material oil dispersion (1) and 2.7 parts of ketimine compound (1) were added and allowed to react for 30 minutes while stirring. 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 part of a charge control agent (Bontron E-84 manufactured by Orient Chemical Co., Ltd.) were charged into a Q-type mixer (Mitsui Mining Co., Ltd.), and the peripheral speed of the turbine blades was 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 (I).

Production Example 2
(Example of polyester production)
690 parts of bisphenol A propylene oxide 2-mole adduct, 275 parts of terephthalic acid, and 8 parts of trimellitic anhydride are put into a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe, The condensation reaction was carried out at 210 ° C. for 10 hours. Next, the reaction was continued for 4 hours while dehydrating under reduced pressure of 10 to 15 mmHg, followed by cooling to obtain polyester (B). The obtained polyester resin had a weight average molecular weight of 26,000, an acid value of 2 KOH mg / g, and a glass transition point of 63 ° C.

(Dispersion adjustment)
In a beaker, 14.3 parts of prepolymer (a), 55 parts of polyester (B), and 78.6 parts of ethyl acetate were stirred and dissolved. Separately, 10 parts of rice wax as a release agent, 4 parts of copper phthalocyanine blue pigment and 100 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. This is designated as toner material oil dispersion (2). The obtained dispersion had a viscosity at 25 ° C. of 12000 mPa · s and a viscosity ratio of 6.5.

(Example of toner production)
In a beaker, 306 parts of ion exchange water, 265 parts of tricalcium phosphate 10% suspension, and 0.2 part of sodium dodecylbenzenesulfonate were added, and the above-mentioned aqueous dispersion was added to this aqueous dispersion while stirring at 12000 rpm with a TK homomixer. Toner material oily dispersion (2) and 2.7 parts of ketimine compound (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 part of a charge control agent (Bontron E-84 manufactured by Orient Chemical Co., Ltd.) were charged into a Q-type mixer (Mitsui Mining Co., Ltd.), and the peripheral speed of the turbine blades was 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 performed for 5 cycles to obtain the final toner (II).

Production Example 3
(Dispersion adjustment)
In a beaker, 14.3 parts of prepolymer (a), 55 parts of polyester (B), and 38 parts of ethyl acetate were stirred and dissolved. Separately, 5 parts of release agent carnauba wax as a release agent, 10 parts of carbon black (# 44: manufactured by Mitsubishi Chemical), 1 part of a metal-containing azo compound and 65 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. This is designated as toner material oil dispersion (3). The resulting dispersion had a viscosity at 25 ° C. of 32000 mPa · s and a viscosity ratio of 14.6.

(Example of toner production)
Toner (III) was obtained in the same manner as in Production Example 2, except that oil dispersion (3) was used instead of oil dispersion (2).

Production Example 4
(Example of polyester production)
670 parts of bisphenol A ethylene oxide 2-mole adduct and 335 parts of terephthalic acid are charged into a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, and condensed at 210 ° C. for 10 hours under a normal pressure nitrogen stream. Reacted. Next, the reaction was continued for 3 hours while dehydrating under reduced pressure of 10 to 15 mmHg, followed by cooling to obtain polyester (C). The obtained polyester resin had a weight average molecular weight of 6,000, an acid value of 35 KOHmg / g, and a glass transition point of 52 ° C.

(Dispersion adjustment)
In a beaker, 14.3 parts of prepolymer (a), 55 parts of polyester (C), and 110 parts of ethyl acetate were stirred and dissolved. Separately, 5 parts of dereleased fatty acid type carnauba wax as a release agent, 8 parts of carbon black (# 44: manufactured by Mitsubishi Chemical) and 130 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. This is designated as toner material oil dispersion (4). The obtained dispersion had a viscosity of 980 mPa · s at 25 ° C. and a viscosity ratio of 1.9.

(Example of toner production)
Toner (IV) was obtained in the same manner as in Production Example 2, except that oil dispersion (4) was used instead of oil dispersion (2).

Production Example 5
(Prepolymer production example)
Into a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction 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, and atmospheric pressure nitrogen was added. Under an air stream, the 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 175 parts of isophorone diisocyanate in ethyl acetate for 3 hours to obtain a prepolymer (b). The obtained prepolymer had a weight average molecular weight of 11,000.

(Dispersion adjustment)
In a beaker, 14.3 parts of prepolymer (b), 55 parts of polyester (B), and 78.6 parts of ethyl acetate were stirred and dissolved. Separately, 10 parts of rice wax as a release agent, 4 parts of copper phthalocyanine blue pigment and 100 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. This is designated as toner material oil dispersion (5). The obtained dispersion had a viscosity of 14000 mPa · s at 25 ° C. and a viscosity ratio of 7.0.

(Example of toner production)
Toner (V) was obtained in the same manner as in Production Example 2, except that oil dispersion (5) was used instead of oil dispersion (2).

  Table 1 shows the physical properties of the polyester and prepolymer up to the toner (V) described above.

Example 1
Using the toner (I) obtained in Production Example 1, the low temperature fixability, the high temperature offset resistance, the heat resistant storage stability, and the image quality were evaluated.

Example 2
Using the toner (II) obtained in Production Example 2, the low temperature fixability, the high temperature offset resistance, the heat resistant storage stability, and the image quality were evaluated.

Example 3
Using the toner (III) obtained in Production Example 3, the low temperature fixability, the high temperature offset resistance, the heat resistant storage stability, and the image quality were evaluated.

Example 4
Using the toner (IV) obtained in Production Example 4, the low temperature fixability, the high temperature offset resistance, the heat resistant storage stability, and the image quality were evaluated.

Example 5
Using the toner (V) obtained in Production Example 5, the low temperature fixability, the high temperature offset resistance, the heat resistant storage stability, and the 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.

(Fixability evaluation)
A Ricoh Copier Co., Ltd. using a Teflon (registered trademark) roller as a fixing roller MF2200 A machine with a modified fixing part was used to set a Ricoh type 6200 paper for a copying test. 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 velocity 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 evaluation condition for the paper feed linear velocity is 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 ◎: less than 140 ° C,
○: 140-149 ° C.
□: 150-159 ° C.
Δ: 160-169 ° C.
×: 170 ° C. or higher Evil Hot offset property (5-level evaluation)
Good ◎: 201 ° C or higher,
○: 200-191 ° C.
□: 190-181 ° C.
Δ: 180-171 ° C.
×: 170 ° C or lower

(Heat resistant storage stability evaluation)
20 g of toner sample is put in a 20 ml glass bottle, and the glass bottle is tapped about 50 times to harden the sample tightly, then left in a high temperature bath at 50 ° C. for 24 hours, and then the needle is loaded with a weight of 50 g according to JIS K2207. The penetration was determined as follows using an penetration tester.
(Good) ◎: Through,
○: ~ 26mm
□ 25-21mm,
Δ: 20 to 16 mm,
×: 15 mm or less (bad)

(image quality)
Fog, toner scattering, and background contamination were evaluated, and when satisfactory results were obtained for each evaluation item, it was determined that the image quality was good.
The evaluation method for each item is as follows.
(Image density)
After outputting a solid image, the image density was measured with X-Rite (manufactured by X-Rite). This was measured at five points for each color alone, and the average was obtained for each color.
(Fog)
The degree of toner contamination on the transfer paper upper surface was visually evaluated.
(Toner scattering)
The state of toner contamination in the copying machine was visually evaluated.
In addition, fog and toner scattering were evaluated using a IPSIO color 8000 remodeling machine manufactured by Ricoh, after each image was subjected to an output durability test with a 5% image area ratio 5% chart.

Production Example 6
(Dispersion adjustment)
In a beaker, 14.3 parts of prepolymer (a), 55 parts of polyester (C), and 110 parts of ethyl acetate were stirred and dissolved. Separately, 5 parts of dereleased fatty acid type carnauba wax as a release agent, 6 parts of carbon black (# 44: manufactured by Mitsubishi Chemical) and 130 parts of ethyl acetate were placed in a bead mill and dispersed for 15 minutes. The two liquids were mixed, stirred for 3 minutes at a rotation speed of 8000 rpm using a TK homomixer, and then dispersed in a bead mill for 5 minutes. This is designated as toner material oil dispersion (6). The obtained dispersion had a viscosity at 25 ° C. of 250 mPa · s and a viscosity ratio of 1.2.

(Example of toner production)
Toner (1) was obtained in the same manner as in Production Example 2, except that oil dispersion (6) was used instead of oil dispersion (2).

Production Example 7
(Dispersion adjustment)
In a beaker, 14.3 parts of prepolymer (a), 55 parts of polyester (B) and 30 parts of ethyl acetate were stirred and dissolved. Separately, 7 parts of a release agent carnauba wax as a release agent, 12 parts of carbon black (# 44: manufactured by Mitsubishi Chemical), and 60 parts of ethyl acetate were placed in a bead mill and dispersed for 60 minutes. The two liquids were mixed and stirred for 15 minutes at a rotational speed of 12000 rpm using a TK homomixer, and then dispersed in a bead mill for 15 minutes. This is designated as toner material oil dispersion (7). The obtained dispersion had a viscosity at 25 ° C. of 55000 mPa · s and a viscosity ratio of 26.0.

(Example of toner production)
Toner (2) was obtained in the same manner as in Production Example 2, except that oil dispersion (7) was used instead of oil dispersion (2).

Production Example 8
(Example of polyester production)
Into a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, 600 parts of bisphenol A propylene oxide 2-mole adduct, 30 parts of diethylene glycol and 180 parts of terephthalic acid were charged, and 210 ° C. under a normal pressure nitrogen stream. For 10 hours. Next, the reaction was continued for 1 hour while dehydrating under reduced pressure of 10 to 15 mmHg, followed by cooling to obtain polyester (D). The obtained polyester resin had a weight average molecular weight of 800, an acid value of 2 KOH mg / g, and a glass transition point of 30 ° C.

(Dispersion adjustment)
In a beaker, 14.3 parts of prepolymer (a), 55 parts of polyester (D), and 78.6 parts of ethyl acetate were stirred and dissolved. Separately, 10 parts of rice wax as a release agent, 4 parts of copper phthalocyanine blue pigment and 100 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 for 10 minutes with a bead mill to obtain an oily dispersion (8) of the toner material. The dispersion obtained had a viscosity at 25 ° C. of 450 mPa · s and a viscosity ratio of 1.4.

(Example of toner production)
Toner (3) was obtained in the same manner as in Production Example 2, except that oil dispersion (8) was used instead of oil dispersion (2).

Production Example 9
(Example of polyester production)
690 parts of bisphenol A propylene oxide 2-mole adduct, 310 parts of terephthalic acid, and 10.5 parts of trimellitic anhydride were introduced into a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe. Originally, the condensation reaction was carried out at 210 ° C. for 10 hours. Next, the reaction was continued for 5 hours while dehydrating under reduced pressure of 10 to 15 mmHg, followed by cooling to obtain polyester (E). The obtained polyester resin had a weight average molecular weight of 38,000, an acid value of 10 KOHmg / g, and a glass transition point of 70 ° C.

(Dispersion adjustment)
In a beaker, 14.3 parts of prepolymer (a), 55 parts of polyester (E), and 78.6 parts of ethyl acetate were stirred and dissolved. Separately, 5 parts of rice wax as a release agent, 3 parts of copper phthalocyanine blue pigment, and 100 parts of ethyl acetate were placed in a bead mill and dispersed for 15 minutes. The two liquids were mixed and stirred for 5 minutes at a rotational speed of 6000 rpm using a TK homomixer, and then dispersed for 10 minutes using a bead mill to obtain an oily dispersion (9) of the toner material. The dispersion obtained had a viscosity at 25 ° C. of 25000 mPa · s and a viscosity ratio of 1.4.

(Example of toner production)
Toner (4) was obtained in the same manner as in Production Example 2, except that oil dispersion (9) was used instead of oil dispersion (2).

  As a comparative example, Table 3 shows physical properties relating to the polyester and prepolymer up to the toner (4) described above.

Comparative Example 1
Using the toner (1) obtained in Production Example 6, the low temperature fixability, the high temperature offset resistance, the heat resistant storage stability, and the image quality were evaluated.

Comparative Example 2
Using the toner (2) obtained in Production Example 7, the low temperature fixability, the high temperature offset resistance, the heat resistant storage stability, and the image quality were evaluated.

Comparative Example 3
Using the toner (3) obtained in Production Example 8, the low temperature fixability, the high temperature offset resistance, the heat resistant storage stability and the image quality were evaluated.

Comparative Example 4
Using the toner (4) obtained in Production Example 9, the low temperature fixability, the high temperature offset resistance, the heat resistant storage stability, and the image quality were evaluated.
According to the same procedure.

Claims (13)

Dissolve or disperse a polymer having a site capable of reacting with a compound having an active hydrogen group serving as a binder resin, a colorant, and a release agent in at least an organic solvent, and disperse the solution or dispersion in an aqueous solvent. In the solvent, the organic solvent is removed, washed and dried after reacting or reacting the polymer having a site capable of reacting with the active hydrogen group-containing compound with the active hydrogen-containing compound. In the toner, the polymer having a site capable of reacting with the compound having an active hydrogen group serving as the binder resin is an isocyanate group-containing polyester prepolymer, the compound having the active hydrogen group is an amine, the solution or The viscosity of the dispersion at 25 ° C. at 6 rpm by a rotational viscometer is 300 to 50000 mPa · s, and the viscosity ratio by a rotational viscometer represented by the following formula is 1 The toner for developing electrostatic images, which is a 5 to 25.0.
Viscosity ratio = (viscosity at 6 rpm) / (viscosity at 60 rpm)   The toner for developing an electrostatic charge image according to claim 1, wherein a polyester resin is further contained in an organic solvent as a binder resin. The electrostatic charge image developing toner according to claim 2, wherein the polyester resin has a THF-soluble component having a weight average molecular weight of 1,000 to 30,000. The toner according to any one of claims 2-3, wherein the acid value of the polyester resin is 1.0~50.0 (KOHmg / g). The electrostatic charge image developing toner according to any one of claims 2 to 4 , wherein the polyester resin has a glass transition point of 35 to 65 ° C. The electrostatic charge according to any one of claims 1 to 5 , 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 to 20,000. Toner for image development. The toner according to any one of claims 1 to 6, wherein the acid value of the toner is 0.5~40.0 (KOHmg / g). The toner for electrostatic image development according to any one of claims 1 to 7 , wherein the toner has a glass transition point of 40 to 70 ° C. The toner for developing an electrostatic charge image according to claim 1, wherein the toner has a volume average particle diameter of 3 to 8 μm. The toner according to any one of claims 1 to 9, wherein the toner Dv / Dn is 1.25 or less. The toner according to any one of claims 1 to 10, wherein the average circularity of the toner is 0.94 to 1.00. Claim 1-11 toner according to any one of, wherein the BET specific surface area of the toner is 1.0~6.0m ² / g. Dissolve or disperse a polymer having a site capable of reacting with a compound having an active hydrogen group as a binder resin, a colorant, and a release agent in at least an organic solvent, and disperse the solution or dispersion in an aqueous medium. In the solvent, the organic solvent is removed, washed and dried after reacting or reacting the polymer having a site capable of reacting with the active hydrogen group-containing compound with the active hydrogen-containing compound. In the toner, the polymer having a site capable of reacting with the compound having an active hydrogen group serving as the binder resin is an isocyanate group-containing polyester prepolymer, the compound having the active hydrogen group is an amine, the solution or The viscosity of the dispersion at 25 ° C. at 6 rpm with a rotational viscometer is 300 to 50000 mPa · s, and the viscosity ratio by the rotational viscometer represented by the following formula is Method for producing a toner for electrostatic image development, which is a .5～25.0.
Viscosity ratio = (viscosity at 6 rpm) / (viscosity at 60 rpm)