JP4213067B2 - Image forming toner and developer, method for producing the same, image forming method using the same, and image forming apparatus - Google Patents

Description

  The present invention relates to an image forming toner, a developer, a toner container, and an image forming method for developing an electrostatic latent image on an image carrier in an electrophotographic apparatus or an electrostatic recording apparatus.

  In the developing process, the developer used in electrophotography, electrostatic recording, electrostatic printing, etc. is once attached to an image carrier such as a photoreceptor on which an electrostatic charge image is formed, and then After being transferred from the photoreceptor to a transfer medium such as transfer paper in the transfer process, it is fixed on the paper surface in the fixing process. At that time, as a developer for developing the electrostatic image formed on the latent image holding surface, a two-component developer composed of a carrier and a toner, and a one-component developer that does not require a carrier (magnetic toner, Non-magnetic toners are known.

  Conventionally, as dry toners used for electrophotography, electrostatic recording, electrostatic printing, and the like, toner binders such as styrene resins and polyesters are melt-kneaded together with colorants and finely pulverized. In order to obtain high-quality and high-quality images, improvements have been made by reducing the particle diameter of the toner, but the particle shape is indefinite in the production method using the usual kneading and pulverization methods. Internally, the toner is further pulverized by agitation with the carrier in the developing unit, and when it is used as a one-component developer, contact stress between the developing roller and the toner supply roller, the layer thickness regulating blade, the friction charging blade, etc. Or the phenomenon that the image quality deteriorates because the fluidizing agent is embedded in the toner surface. Further, because of its shape, the fluidity as a powder is poor, a large amount of fluidization is required, and the filling rate into the toner bottle is low, which is an obstacle to downsizing. Therefore, the current situation is that the merit of reducing the particle size is not utilized. In the pulverization method, there is a limit of the particle size, and it cannot cope with further reduction in the particle size. Further, due to the poor transferability due to the irregular shape such as the pulverized toner, there are problems such as the transfer of the transferred image and the consumption of toner to compensate for it.

  Therefore, there is an increasing demand for further improving transfer efficiency to reduce toner consumption to obtain a high-quality image without missing images and to reduce running costs. If the transfer efficiency is very good, there is no need for a cleaning unit for removing untransferred toner from the photoreceptor or transfer medium, which has the advantages of reducing the size and cost of the equipment and eliminating waste toner. Because. Various spherical toner manufacturing methods have been devised to compensate for the disadvantages of such irregular shape effects.

  However, the spherical toner cannot be removed by a device (for example, a cleaning blade or a cleaning brush) for removing the toner remaining on the photosensitive member or the transfer medium, resulting in poor cleaning. In addition, because the toner surface is spherical, the toner surface is exposed to the outside in all directions, and is easily exposed to contact with a charging member such as a carrier or a charging blade, and is an external additive on the toner surface or a charge control agent present on the outermost surface. However, there is a problem in durability such that the toner is easily embedded in the toner surface and the fluidity of the toner is immediately lowered. These dry toners are developed and transferred onto paper or the like, and then fixed by heating and melting using a hot roll. At that time, if the temperature of the hot roll is too high, a problem that the toner is excessively melted and fused to the hot roll (hot offset) occurs. On the other hand, if the heat roll temperature is too low, there is a problem that the toner is not sufficiently melted and fixing becomes insufficient. From the viewpoint of energy saving and downsizing of the apparatus, a toner having a higher hot offset generation temperature (hot offset resistance) and a lower fixing temperature (low temperature fixing property) is required. In addition, heat storage stability is required so that the toner is not blocked during storage and at ambient temperature in the apparatus.

  As a method for solving these problems, Japanese Patent Application Laid-Open No. 7-152202 (Patent Document 1) discusses a method involving volume shrinkage called a polymer dissolution suspension method. In this method, a toner material is dispersed and dissolved in a volatile solvent such as a low-boiling organic solvent, and this is emulsified and formed into droplets in an aqueous medium containing a dispersant, and then the volatile solvent is removed. At that time, the volumetric shrinkage of the droplets occurred, but when a solid fine particle dispersant that does not dissolve in an aqueous medium was selected as the dispersant, only amorphous particles were obtained. When the solid content in the solvent was increased in order to increase productivity, the viscosity of the dispersed phase increased, and the resulting particles had a large particle size and a broad distribution. Conversely, when the molecular weight of the resin used is lowered and the viscosity of the dispersed phase is lowered, the fixability (particularly hot offset resistance) must be sacrificed.

  On the other hand, in Japanese Patent Application Laid-Open No. 11-149179 (Patent Document 2), the resin used in the polymer dissolution suspension method has a low molecular weight to reduce the viscosity of the dispersed phase, facilitate emulsification, and cause the polymerization reaction in the particles. To improve fixability. However, the transferability and cleaning properties were not improved by adjusting the shape of the particles.

JP-A-7-152202 JP-A-11-149179

  An object of the present invention is to provide an image forming toner, a developer, a toner container, and an image forming method that are excellent in low-temperature fixability and hot offset resistance.

  As a result of extensive studies by the present inventors, a toner composition containing a modified polyester resin capable of reacting with a compound having an active hydrogen group in an organic solvent is dissolved or / and dispersed, and the solution or dispersion is In the method of obtaining toner particles by reacting with a crosslinking agent and / or an extender in an aqueous medium containing resin fine particles, it is preferable that the toner binder contains a crystalline polyester resin together with the modified polyester. It was found to be closely related to the expression. Further, in order to obtain a toner satisfying low-temperature fixing and having good hot offset resistance, the crosslinking or elongation reaction of the modified polyester is controlled, and the outflow start temperature (Tfb) as the toner after the reaction is 70 to 150 ° C. I found out that it is important. In addition, it has been found that controlling the dispersion diameter of the crystalline polyester in the toner to an optimum size and having a great effect on the low-temperature fixability have led to the completion of the present invention.

That is, according to the present invention, the following toner, developer, toner container, and image forming method are provided.
(1) A toner composition containing a modified polyester resin capable of reacting with a compound having an active hydrogen group in an organic solvent is dissolved or / and dispersed, and the solution or dispersion is dissolved in an aqueous medium containing resin fine particles. A toner for image formation, characterized in that, in a toner obtained by reacting with a compound having an active hydrogen group, a toner binder contains a crystalline polyester resin together with the modified polyester resin.
(2) The toner binder contains, together with the modified polyester resin (i), an unmodified polyester resin (ii) and a crystalline polyester resin (iii), and (i) and (ii) + (iii) The image forming toner according to (1), wherein the weight ratio is 5/95 to 25/75, and the weight ratio of (ii) and (iii) is 99/1 to 50/50. .
( 3 ) The toner for image formation as described in any one of (1) to ( 2 ) above, wherein the outflow start temperature (Tfb) of the toner is 70 to 150 ° C.
( 4 ) The toner for image formation as described in any one of (1) to ( 3 ) above, wherein the toner particles have a volume average particle diameter of 4 to 8 μm.
( 5 ) A ratio Dv / Dn between the volume average particle diameter (Dv) and the number average particle diameter (Dn) of the toner particles is 1.00 to 1.25, 4 ) The image forming toner according to any one of the above.
( 6 ) The toner for image formation as described in any one of (1) to ( 5 ) above, wherein the toner particles have an average circularity of 0.99 to 0.95.
( 7 ) The image forming toner according to any one of (1) to ( 6 ), wherein the step of removing the solvent of the emulsified dispersion is performed at least under reduced pressure and / or heating conditions. .
( 8 ) The toner for image formation as described in any one of (1) to ( 7 ) above, wherein the resin fine particles have a volume average particle diameter of 5 to 500 nm.
( 9 ) The toner for image formation as described in any one of (1) to ( 8 ) above, wherein the toner contains a wax as a release material.
( 10 ) The image forming toner according to any one of (1) to ( 9 ), wherein the toner contains a charge control agent.
( 11 ) The image formation as described in any one of (1) to ( 10 ) above, wherein in the toner, the dispersed particle diameter of the crystalline polyester resin is 0.2 to 3.0 μm in major axis diameter. Toner.
( 12 ) The image forming toner according to any one of (1) to ( 11 ), wherein the crystalline polyester resin has a DSC endothermic peak temperature of 50 to 150 ° C.
( 13 ) The molecular weight distribution by GPC of the soluble portion of orthodichlorobenzene of the crystalline polyester resin described in (1) is 1000 to 6500 in terms of weight average molecular weight (Mw), 500 to 2000 in terms of number average molecular weight (Mn), Mw / Mn is 2-5, The toner for image formation in any one of said (1)-( 12 ) characterized by the above-mentioned.
( 14 ) The alcohol component of the crystalline polyester resin contains a diol compound having 2 to 6 carbon atoms, and the acid component contains at least one of maleic acid, fumaric acid, succinic acid, and derivatives thereof. The toner for image formation as described in any one of (1) to ( 13 ) above.
( 15 ) Any of the above (1) to ( 14 ), wherein the alcohol component of the crystalline polyester resin contains at least one of 1,4-butanediol, 1,6-hexanediol and derivatives thereof The image forming toner according to claim 1.
( 16 ) The toner for image formation as described in any one of (1) to ( 15 ) above, wherein the glass transition point (Tg) of the unmodified polyester resin is 40 to 80 ° C.
( 17 ) The image-forming toner as described in any one of (1) to ( 16 ) above, wherein the unmodified polyester resin has a weight average molecular weight of 2000 to 90000.
( 18 ) The toner for image formation as described in any one of (1) to ( 17 ) above, wherein the wax has a melting point of 40 to 160 ° C.
( 19 ) The image forming toner according to any one of (1) to ( 18 ), wherein at least inorganic fine particles and / or resin fine particles are externally added.
( 20 ) The toner for image formation as described in any one of (1) to ( 19 ) above, which is produced using a crystalline polyester resin dispersion having a volume average particle size of 0.2 μm to 3 μm. Manufacturing method.
( 21 ) A one-component developer comprising the image forming toner according to any one of (1) to ( 20 ).
( 22 ) A two-component developer comprising the image forming toner according to any one of (1) to ( 19 ) and a carrier powder.
( 23 ) A toner container filled with the developer according to any one of ( 21 ) to ( 22 ).
( 24 ) The electrostatic latent image formed on the image carrier is developed using the developer according to any one of ( 21 ) to ( 22 ), and the toner image formed on the image carrier is converted into an image. An image forming method comprising a step of transferring a toner image to a support and fixing the transferred toner image by heating and pressing with a roller-like or belt-like fixing member to obtain a fixed image.

  According to the present invention, a conventional problem can be solved, and an image forming toner, a developer, a toner container, and an image forming method excellent in low-temperature fixability and hot offset resistance can be provided.

The present invention is described in detail below.
(Effect of crystalline polyester)
Since the crystalline polyester resin in the toner of the present invention has crystallinity, it exhibits a heat-melting characteristic that shows a sudden decrease in viscosity near the fixing start temperature.
In other words, the toner has good heat-resistant storage stability due to crystallinity until just before the melting start temperature, and suddenly drops in viscosity (sharp melt) at the melting start temperature and fixes, so it has both good heat storage stability and low-temperature fixability. Can be designed.
It was also found that good results were obtained with respect to the release width (difference between the fixing lower limit temperature and the hot offset occurrence temperature).

(Circularity and circularity distribution)
It is important that the toner in the present invention has a specific shape and shape distribution. An toner having an average circularity of less than 0.95 and an irregular shape that is too far from a spherical shape exhibits satisfactory transferability and dust. A high-quality image with no image cannot be obtained. As a method for measuring the shape, an optical detection band method is suitable in which a suspension containing particles is passed through an imaging unit detection band on a flat plate, and a particle image is optically detected and analyzed by a CCD camera. A toner with an average circularity of 0.99 to 0.95, 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 was found to be effective in forming a clear image. More preferably, particles having an average circularity of 0.99 to 0.96 and a circularity of less than 0.96 are 10% or less. Further, when the average circularity is 0.991 or more, in a system that employs blade cleaning or the like, a cleaning failure occurs on the photosensitive member and the transfer belt, causing stain on the image. For example, development / transfer with a low image area ratio results in a small amount of residual toner and poor cleaning does not pose a problem, but images with a high image area ratio such as photographic images, and untransferred images due to poor paper feed, etc. The formed toner may be generated as a transfer residual toner on the photoconductor, and if accumulated, the image may be soiled. In addition, the charging roller that contacts and charges the photosensitive member is contaminated, and the original charging ability cannot be exhibited. This value can be measured as an average circularity 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. .

(Dv / Dn (ratio of volume average particle diameter / number average particle diameter))
The toner has a volume average particle diameter (Dv) of 4 to 8 μm and a ratio (Dv / Dn) to the number average particle diameter (Dn) of 1.25 or less, preferably 1.05 to 1.20. The toner has excellent heat resistance, low-temperature fixability, and hot offset resistance, particularly excellent image gloss when used in full-color copiers, etc. Even if the balance is performed, the fluctuation of the toner particle diameter in the developer is reduced, and good and stable developability can be obtained even with long-term stirring in the developing device. Even when used as a one-component developer, even if the balance of the toner is performed, the fluctuation of the toner particle diameter is reduced, and the toner filming on the developing roller and the toner layer are made thin. The toner was not fused to a member such as a blade, and good and stable developability and images were obtained even when the developing device was used (stirred) for a long time.

In general, it is said that the smaller the particle size of the toner, the more advantageous it is to obtain a high-resolution and high-quality image, but it is disadvantageous for transferability and cleaning properties. is there. Further, when the volume average particle diameter is smaller than the range of the present invention, in the case of the two-component developer, the toner is fused to the surface of the carrier during a long period of stirring in the developing device, and the charging ability of the carrier is reduced, or the one-component development is performed. When used as an agent, toner filming on the developing roller and toner fusion to a member such as a blade for thinning the toner are likely to occur.
Further, these phenomena are the same for the toner having a fine powder content larger than the range of the present invention.
On the contrary, when the particle diameter of the toner is larger than the range of the present invention, it becomes difficult to obtain a high resolution and high quality image, and when the balance of the toner in the developer is performed, In many cases, the variation of the particle size becomes large. It was also clarified that the same applies when the volume average particle diameter / number average particle diameter is larger than 1.25.
Further, when the volume average particle size / number average particle size is smaller than 1.05, there are preferable aspects from the viewpoint of stabilizing the behavior of the toner and uniformizing the charge amount, but the toner can be sufficiently charged. It became clear that there was a case where it was not able to be performed or the cleaning property was deteriorated.

(Modified polyester resin)
Examples of the modified polyester resin (i) include polyester prepolymers modified with isocyanate or epoxy. This undergoes an extension reaction with a compound having an active hydrogen group (such as amines), and has an effect of improving the release width (difference between the minimum fixing temperature and the hot offset generation temperature). As a method for synthesizing the modified polyester resin (i), it can be easily synthesized by reacting a conventionally known isocyanate agent or epoxidizing agent with a base polyester resin. Isocyanating agents 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; block the polyisocyanates with phenol derivatives, oximes, caprolactam, etc. And combinations of two or more of these. Moreover, epichlorohydrin etc. can be mentioned as the representative example as an epoxidizing agent.

  The ratio of the isocyanate agent is usually 5/1 to 1/1, preferably 4/1 to 1 as an equivalent ratio [NCO] / [OH] of the isocyanate group [NCO] and the hydroxyl group [OH] of the base polyester. 1.2 / 1, more preferably 2.5 / 1 to 1.5 / 1. When [NCO] / [OH] exceeds 5, low-temperature fixability deteriorates. If the molar ratio of [NCO] is less than 1, the urea content in the modified polyester will be low, and the hot offset resistance will deteriorate. The content of the isocyanate agent in the modified polyester resin is usually 0.5 to 40% by weight, preferably 1 to 30% by weight, and more preferably 2 to 20% by weight. If it is less than 0.5% by weight, the hot offset resistance deteriorates, and it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability. On the other hand, if it exceeds 40% by weight, the low-temperature fixability deteriorates.

  The number of isocyanate groups contained per molecule in the modified polyester resin is usually 1 or more, preferably 1.5 to 3 on average, and more preferably 1.8 to 2.5 on average. When the number is less than 1 per molecule, the molecular weight of the urea-modified polyester after the elongation reaction becomes low, and the hot offset resistance deteriorates. Examples of amines include diamine compounds, trivalent or higher polyamine compounds, amino alcohol compounds, amino mercaptan compounds, amino acid compounds, and compounds in which these amino groups are blocked. Examples of diamine compounds include aromatic diamines (phenylenediamine, diethyltoluenediamine, 4,4′diaminodiphenylmethane, etc.); alicyclic diamines (4,4′-diamino-3,3′dimethyldicyclohexylmethane, diaminecyclohexane, isophoronediamine). Etc.); and aliphatic diamines (ethylenediamine, tetramethylenediamine, hexamethylenediamine, etc.) and the like. Examples of the trivalent or higher polyamine compound include diethylenetriamine and triethylenetetramine. Examples of amino alcohol compounds include ethanolamine and hydroxyethylaniline. Examples of the amino mercaptan compound include aminoethyl mercaptan and aminopropyl mercaptan. Examples of amino acid compounds include aminopropionic acid and aminocaproic acid. Examples of the compounds in which these amino groups are blocked include ketimine compounds and oxazoline compounds obtained from the amines and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.). Among these amines, preferred are a diamine compound and a mixture of a diamine compound and a small amount of a polyamine compound. Moreover, amines can be used as a crosslinking agent and an extender.

  Furthermore, if necessary, the molecular weight of the urea-modified polyester can be adjusted using an elongation terminator. Examples of the elongation terminator include monoamines (diethylamine, dibutylamine, butylamine, laurylamine, etc.), and those obtained by blocking them (ketimine compounds).

  The ratio of amines is usually 1/2 to 2/1 as equivalent ratio [NCO] / [NHx] of isocyanate group [NCO] in modified polyester resin and amino group [NHx] in amines, preferably The ratio is 1.5 / 1 to 1 / 1.5, more preferably 1.2 / 1 to 1 / 1.2. When [NCO] / [NHx] exceeds 2 or less than 1/2, the molecular weight of the urea-modified polyester after the elongation reaction is lowered, and the hot offset resistance is deteriorated. In the present invention, the urea-modified polyester may contain a urethane bond together with a urea bond. The molar ratio of the urea bond content to the urethane bond content is usually 100/0 to 10/90, preferably 80/20 to 20/80, and more preferably 60/40 to 30/70. When the molar ratio of the urea bond is less than 10%, the hot offset resistance is deteriorated.

  The urea-modified polyester after the elongation reaction in the present invention is produced by a one-shot method or a prepolymer method. The weight average molecular weight of the urea-modified polyester is usually 10,000 or more, preferably 20,000 to 10,000,000, and more preferably 30,000 to 1,000,000. If it is less than 10,000, the hot offset resistance deteriorates. The number average molecular weight of the urea-modified polyester is not particularly limited when using an unmodified polyester described later, and may be a number average molecular weight that can be easily obtained to obtain the weight average molecular weight. When used alone, the number average molecular weight is usually 20000 or less, preferably 1000 to 10000, and more preferably 2000 to 8000. When it exceeds 20000, the low-temperature fixability and the glossiness when used in a full-color apparatus are deteriorated.

(Unmodified polyester)
In the present invention, not only the urea-modified polyester but also a polyester resin (ii) not modified with the urea-modified polyester can be contained as a toner binder component. By using (ii) in combination, the low-temperature fixability and glossiness when used in a full-color apparatus are improved, which is preferable to single use. The above (i) and (ii) are preferably at least partially compatible in terms of low temperature fixability and hot offset resistance. Accordingly, the polyester component (i) and (ii) preferably have similar compositions.
The peak molecular weight of (ii) is usually 1000-30000, preferably 1500-10000, more preferably 2000-8000. If it is less than 1000, heat-resistant storage stability will deteriorate, and if it exceeds 10,000, low-temperature fixability will deteriorate. The weight average molecular weight of the unmodified polyester resin (ii) is preferably 2000 to 90000, and the glass transition point (Tg) is preferably 40 to 80 ° C.
The hydroxyl value of (ii) is preferably 5 or more, more preferably 10 to 120, and particularly preferably 20 to 80. If it is less than 5, it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability. The acid value of (ii) is usually 1-30, preferably 5-20. By having an acid value, it tends to be negatively charged. Further, those having an acid value and a hydroxyl value exceeding these ranges are easily affected by the environment under high temperature and high humidity and low temperature and low humidity, and are liable to cause image deterioration.

（式中、Ｒ_１、Ｒ_２は炭化水素基であり、その炭素数は１〜２０である。また、ｎは自然数である。）
また、結晶性ポリエステル樹脂の結晶性および軟化点を制御する方法として、ポリエステル合成時にアルコール成分にグリセリン等の３価以上の多価アルコールや、酸成分に無水トリメリット酸などの３価以上の多価カルボン酸を追加して縮重合を行った非線状ポリエステルなどを設計、使用するなどの方法が挙げられる。 (Crystalline polyester)
The crystalline polyester (iii) is a polyester having at least a melting point.
Examples of the crystalline polyester (iii) include diol compounds having 2 to 6 carbon atoms, particularly alcohol components containing 1,4-butanediol, 1,6-hexanediol and derivatives thereof, maleic acid, and fumaric acid. A crystalline polyester resin having a repeating unit represented by the following general formula (1) synthesized using an acid component containing succinic acid and succinic acid is preferable.

_(Wherein, R 1, _{R 2} is a hydrocarbon group, the number of carbon atoms from 1 to 20.. The, n is a natural number.)
In addition, as a method for controlling the crystallinity and softening point of the crystalline polyester resin, a trivalent or higher polyhydric alcohol such as glycerin as an alcohol component and a trivalent or higher polyvalent such as trimellitic anhydride as an acid component can be used during polyester synthesis. Examples thereof include a method of designing and using a non-linear polyester that has been subjected to condensation polymerization by adding a polyvalent carboxylic acid.

The molecular structure of the crystalline polyester can be confirmed by solid NMR. As for the molecular weight, as a result of intensive studies from the viewpoint that the above-mentioned molecular weight distribution is sharp and the low molecular weight is excellent in low-temperature fixability, the molecular weight distribution by GPC of the soluble part of o-dichlorobenzene is expressed by log (M ), The peak position of the molecular weight distribution diagram in which the vertical axis is expressed in weight% is in the range of 3.5 to 4.0, the half width of the peak is 1.5 or less, and the weight average molecular weight (Mw) is 1000 to 1000. It was found that 6500, the number average molecular weight (Mn) is 500 to 2000, and Mw / Mn is preferably 2 to 5. It has been found that the melting temperature and F1 _{/ 2} temperature are desirably low so long as the heat resistant storage stability does not deteriorate, and are preferably in the range of 50 to 130 ° C.
When the melting temperature and F _1/2 temperature are 50 ° C. or lower, the heat-resistant storage stability is deteriorated, and blocking tends to occur at the temperature inside the developing device. Fixability cannot be obtained.
The dispersed particle diameter of the crystalline polyester resin in the toner is preferably 0.2 to 3.0 μm in major axis diameter.

  The acid value of the crystalline polyester is 8 mgKOH / g or more, more preferably 20 mgKOH / g or more in order to achieve the desired low-temperature fixability from the viewpoint of the affinity between paper and resin. On the other hand, in order to improve the hot offset property, it is preferably 45 mgKOH / g or less. Further, the hydroxyl value of the crystalline polymer is preferably 0 to 50 mgKOH / g, more preferably 5 to 50 mgKOH / g in order to achieve a predetermined low-temperature fixability and to achieve good charging characteristics. .

  In the toner according to the present invention, the weight ratio of the above (i), (ii), and (iii) in the toner is usually 5 for (i) / (ii) + (iii) in order to develop low temperature fixability. / 95 to 25/75, preferably 10/90 to 25/75, more preferably 12/88 to 25/75, particularly preferably 12/88 to 22/78, and (ii) and (iii) The weight ratio is 99/1 to 50/50, preferably 95/5 to 60/40, and more preferably 90/10 to 65/35. Outside the above range, hot offset resistance deteriorates, and it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability.

In the present invention, the glass transition point (Tg) of the toner binder is usually 40 to 70 ° C., preferably 40 to 65 ° C. If it is less than 40 ° C., the heat-resistant storage stability of the toner is deteriorated, and if it exceeds 70 ° C., the low-temperature fixability becomes insufficient. Due to the coexistence of the urea-modified polyester resin, the image-forming toner of the present invention tends to have good heat-resistant storage stability even when the glass transition point is low, as compared with known polyester-based toners. As the storage elastic modulus of the toner binder, the temperature (TG ′) at which 10000 dyne / cm ² is obtained at a measurement frequency of 20 Hz is usually 100 ° C. or higher, preferably 110 to 200 ° C. If it is less than 100 ° C., the resistance to hot offset deteriorates. As the viscosity of the toner binder, the temperature (Tη) at 1000 poise at a measurement frequency of 20 Hz is usually 180 ° C. or lower, preferably 90 to 160 ° C. If it exceeds 180 ° C., the low-temperature fixability deteriorates. That is, from the viewpoint of achieving both low temperature fixability and hot offset resistance, TG ′ is preferably higher than Tη. In other words, the difference between TG ′ and Tη (TG′−Tη) is preferably 0 ° C. or higher. More preferably, it is 10 degreeC or more, Most preferably, it is 20 degreeC or more. The upper limit of the difference is not particularly limited. Further, from the viewpoint of achieving both heat-resistant storage stability and low-temperature fixability, the difference between Tη and Tg is preferably 0 to 100 ° C. More preferably, it is 10-90 degreeC, Most preferably, it is 20-80 degreeC.
In the molecular weight distribution of the THF-soluble component of the polyester resin contained in the toner, the molecular weight peak is 1000 to 30000, the molecular weight is 30,000 or more, the component is 1 to 80% by weight, and the number average molecular weight is 2000 to 15000. It is preferable that Further, in the molecular weight distribution of the THF-soluble component of the polyester resin contained in the toner, the component having a molecular weight of 1000 or less is preferably 0.1 to 5.0% by weight. The polyester resin contained in the toner preferably has a THF insoluble content of 1 to 15% by weight.

(Coloring agent)
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, lithobon 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 masterbatch or the masterbatch, in addition to the above-mentioned modified and unmodified polyester resins, styrene such as polystyrene, poly p-chlorostyrene, polyvinyltoluene, and substituted polymers thereof; Styrene-p-chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer Styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α- Chloromethyl methacrylate copolymer, Tylene-acrylonitrile copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, styrene-maleic acid Styrene copolymers such as acid ester copolymers; polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, poly Acrylic resin, rosin, modified rosin, terpene resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, paraffin wax, etc. can be used alone or in combination. The

  This master batch can be obtained by mixing and kneading a resin for a master batch and a colorant under a high shear force to obtain a master batch. At this time, an organic solvent can be used to enhance the interaction between the colorant and the resin. 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.

(Release agent)
Further, a wax can be contained together with the toner binder and the colorant. Known waxes can be used as the wax of the present invention, such as polyolefin wax (polyethylene wax, polypropylene wax, etc.); long chain hydrocarbon (paraffin wax, sasol wax, etc.); carbonyl group-containing wax, etc. It is done. Of these, carbonyl group-containing waxes are preferred. Carbonyl group-containing waxes include polyalkanoic acid esters (carnauba wax, montan wax, trimethylolpropane tribehenate, pentaerythritol tetrabehenate, pentaerythritol diacetate dibehenate, glycerin tribehenate, 1,18 -Octadecanediol distearate, etc.); polyalkanol esters (trimellitic acid tristearyl, distearyl maleate, etc.); polyalkanoic acid amides (ethylenediamine 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.

(Charge control agent)
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, quinacridone Azo pigments, sulfonate group, carboxyl group, and polymer compounds having a functional group such as a quaternary ammonium salt.

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

(Resin fine particles)
The resin fine particles used in the present invention can be any resin as long as it can form an aqueous dispersion, and may be a thermoplastic resin or a thermosetting resin. For example, vinyl resins, polyurethane resins, epoxy resins, Examples thereof include polyester resin, polyamide resin, polyimide resin, silicon resin, phenol resin, melamine resin, urea resin, aniline resin, ionomer resin, and polycarbonate resin. As the resin fine particles, two or more of the above resins may be used in combination. Of these, vinyl resins, polyurethane resins, epoxy resins, polyester resins, and combinations thereof are preferred because an aqueous dispersion of fine spherical resin particles is easily obtained.
The vinyl resin is a polymer obtained by homopolymerization or copolymerization of a vinyl monomer, such as a styrene- (meth) acrylate resin, a styrene-butadiene copolymer, a (meth) acrylic acid-acrylate polymer, Examples include styrene-acrylonitrile copolymers, styrene-maleic anhydride copolymers, styrene- (meth) acrylic acid copolymers, and the like.
It is preferable that the resin fine particles have a volume average particle diameter of 5 to 500 nm.

(External additive)
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, bengara, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride.

In addition, polymer fine particles such as polystyrene obtained by soap-free emulsion polymerization, suspension polymerization and dispersion polymerization, methacrylic acid ester and acrylic acid ester copolymer, polycondensation system such as silicone, benzoguanamine and nylon, thermosetting resin And polymer particles.
Such a fluidizing agent 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.

(Production method)
The toner binder can be produced by the following method. The polyol (1) and the polycarboxylic acid (2) are heated to 150 to 280 ° C. in the presence of a known esterification catalyst such as tetrabutoxytitanate or dibutyltin oxide, and the generated water is distilled off as necessary. Thus, a polyester having a hydroxyl group is obtained. Next, this is reacted with polyisocyanate (3) at 40 to 140 ° C. to obtain a prepolymer (A) having an isocyanate group. Further, (A) is reacted with amines (B) at 0 to 140 ° C. to obtain a polyester modified with a urea bond. When (3) is reacted and (A) and (B) are reacted, a solvent can be used as necessary. Usable solvents include aromatic solvents (toluene, xylene, etc.); ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.); esters (ethyl acetate, etc.); amides (dimethylformamide, dimethylacetamide, etc.) and ethers And those inert to the isocyanate (3), such as tetrahydrofuran (such as tetrahydrofuran). When the unmodified polyester (ii) is used in combination, (ii) is produced in the same manner as the polyester having a hydroxyl group, and this is dissolved and mixed in the solution after completion of the reaction of (i).
The dry toner of the present invention can be produced by the following method, but is not limited thereto.

(Toner production method in aqueous medium)
As an aqueous medium used in the present invention, water alone may be used, but a solvent miscible with water may be used in combination. Examples of the miscible solvent include alcohol (methanol, isopropanol, ethylene glycol, etc.), dimethylformamide, tetrahydrofuran, cellosolves (methyl cellosolve, etc.), lower ketones (acetone, methyl ethyl ketone, etc.), and the like.

  The toner particles may be formed by reacting a dispersion composed of a prepolymer (A) having an isocyanate group in an aqueous medium with (B), or using a urea-modified polyester (i) produced in advance. good. As a method for stably forming a dispersion comprising urea-modified polyester (i) or prepolymer (A) in an aqueous medium, a toner raw material comprising urea-modified polyester (i) or prepolymer (A) in an aqueous medium is used. And a method of dispersing by shearing force. The prepolymer (A) and other toner compositions (hereinafter referred to as toner raw materials), a colorant masterbatch, a release agent, a charge control agent, an unmodified polyester resin, etc. are dispersed in an aqueous medium. It may be mixed at the time of formation, but it is more preferable to mix the toner raw materials in advance and then add and disperse the mixture in the aqueous medium. In the present invention, other toner materials such as a colorant, a release agent, and a charge control agent do not necessarily have to be mixed when forming particles in an aqueous medium, but after the particles are formed. , May be added. For example, after forming particles containing no colorant, the colorant can be added by a known dyeing method.

  The dispersion method is not particularly limited, and known equipment such as a low-speed shear method, a high-speed shear method, a friction method, a high-pressure jet method, and an ultrasonic wave can be applied. In order to make the particle size of the dispersion 2 to 20 μm, a high-speed shearing type is preferable. When a high-speed shearing disperser is used, the rotational speed is not particularly limited, but is usually 1000 to 30000 rpm, preferably 5000 to 20000 rpm. The dispersion time is not particularly limited, but in the case of a batch method, it is usually 0.1 to 5 minutes. The temperature during dispersion is usually 0 to 150 ° C. (under pressure), preferably 40 to 98 ° C. Higher temperatures are preferable in that the dispersion of the urea-modified polyester (i) or prepolymer (A) has a low viscosity and is easily dispersed.

  The amount of the aqueous medium used relative to 100 parts of the toner composition containing the urea-modified polyester (i) and the prepolymer (A) is usually 50 to 2000 parts by weight, preferably 100 to 1000 parts by weight. If the amount is less than 50 parts by weight, the dispersion state of the toner composition is poor, and toner particles having a predetermined particle diameter cannot be obtained. If it exceeds 20000 parts by weight, it is not economical. Moreover, a dispersing agent can also be used as needed. It is preferable to use a dispersant because the particle size distribution becomes sharp and the dispersion is stable.

  In the step of synthesizing the urea-modified polyester (i) from the prepolymer (A), the amine (B) may be added and reacted before the toner composition is dispersed in the aqueous medium, or may be dispersed in the aqueous medium. An amine (B) may be added later to cause a reaction from the particle interface. In this case, urea-modified polyester is preferentially produced on the surface of the manufactured toner, and a concentration gradient can be provided inside the particles.

  Anionic surfactants such as alkylbenzene sulfonates, α-olefin sulfonates and phosphates, alkylamines as dispersants for emulsifying and dispersing the oily phase in which the toner composition is dispersed in a liquid containing water Amine salts such as salts, aminoalcohol fatty acid derivatives, polyamine fatty acid derivatives, imidazolines, alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, pyridinium salts, alkylisoquinolinium salts, benzethonium chloride, etc. Nonionic surfactants such as quaternary ammonium salt type cationic surfactants, fatty acid amide derivatives, polyhydric alcohol derivatives, such as alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine and N-alkyl N, amphoteric surfactants such as N- dimethyl ammonium betaine.

  Further, by using a surfactant having a fluoroalkyl group, the effect can be obtained in a very small amount. Preferred anionic surfactants having a fluoroalkyl group include fluoroalkyl carboxylic acids having 2 to 10 carbon atoms and metal salts thereof, disodium perfluorooctanesulfonyl glutamate, 3- [omega-fluoroalkyl (C6-C11 ) Oxy] -1-alkyl (C3-C4) sodium sulfonate, 3- [omega-fluoroalkanoyl (C6-C8) -N-ethylamino] -1-propanesulfonic acid sodium, fluoroalkyl (C11-C20) carvone Acids and metal salts, perfluoroalkylcarboxylic acids (C7 to C13) and metal salts thereof, perfluoroalkyl (C4 to C12) sulfonic acids and metal salts thereof, perfluorooctanesulfonic acid diethanolamide, N-propyl-N- ( 2-hydroxyethyl) -Fluorooctanesulfonamide, perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salt, perfluoroalkyl (C6-C10) -N-ethylsulfonylglycine salt, monoperfluoroalkyl (C6-C16) ethyl phosphate, etc. Is mentioned.

  Product names include Surflon S-111, S-112, S-113 (Asahi Glass Co., Ltd.), Florard FC-93, FC-95, FC-98, FC-129 (Sumitomo 3M Co., Ltd.), Unidyne DS-101. DS-102 (Daikin Kogyo Co., Ltd.), Mega-Fac F-l0, F-l20, F-113, F-191, F-812, F-833 (Dainippon Ink Co., Ltd.), Xtop EF-102 , 103, 104, 105, 112, 123A, 123B, 306A, 501, 201, 204 (manufactured by Tochem Products), and Fagento F-100, F150 (manufactured by Neos).

  Examples of cationic surfactants include aliphatic primary, secondary or secondary amine acids having a fluoroalkyl group, aliphatic quaternary ammonium salts such as perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salt, benza Luconium salt, benzethonium chloride, pyridinium salt, imidazolinium salt, trade names include Surflon S-121 (manufactured by Asahi Glass), Florard FC-135 (manufactured by Sumitomo 3M), Unidyne DS-202 (manufactured by Daikin Industries) , Megafac F-150, F-824 (Dainippon Ink Co., Ltd.), Xtop EF-132 (Tochem Products Co., Ltd.), Footgent F-300 (Neos Co., Ltd.), and the like.

  Further, tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, hydroxyapatite and the like can be used as an inorganic compound dispersant which is hardly soluble in water.

  Further, the dispersed droplets may be stabilized by a polymer protective colloid. For example, acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid or maleic anhydride and other (meth) acrylic monomers containing hydroxyl groups Bodies such as β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate, γ-hydroxypropyl acrylate, γ-hydroxypropyl methacrylate, 3-acrylate Chloro-2-hydroxypropyl, 3-chloro-2-hydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerol monoacrylate, glycerol monomethacrylate, N- Methylol acrylamide, N-methylol methacrylamide, etc., vinyl alcohol or ethers with vinyl alcohol, such as vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, etc., or esters of compounds containing vinyl alcohol and carboxyl groups, eg acetic acid Vinyl, vinyl propionate, vinyl butyrate, acrylamide, methacrylamide, diacetone acrylamide or their methylol compounds, acid chlorides such as acrylic acid chloride, methacrylic acid chloride, vinyl pyridine, vinyl pyrrolidone, vinyl imidazole, ethylene imine, etc. Homopolymers or copolymers such as those having a nitrogen atom or its heterocyclic ring, polyoxyethylene, polyoxypropylene, poly Xylethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonyl phenyl ether, polyoxyethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ester, polyoxyethylene nonyl phenyl ester Polyoxyethylenes such as, celluloses such as methyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose can be used.

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

  Furthermore, in order to lower the viscosity of the toner composition, a solvent in which the urea-modified polyester (i) or the prepolymer (A) is soluble can be used. The use of a solvent is preferable in that the particle size distribution becomes sharp. The solvent is preferably volatile with a boiling point of less than 100 ° C. from the viewpoint of easy removal. Examples of the solvent include toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, ethyl acetate, Methyl ethyl ketone, methyl isobutyl ketone and the like can be used alone or in combination of two or more. In particular, aromatic solvents such as toluene and xylene and halogenated hydrocarbons such as methylene chloride, 1,2-dichloroethane, chloroform, and carbon tetrachloride are preferable. The usage-amount of the solvent with respect to 100 parts of prepolymers (A) is 0-300 parts normally, Preferably it is 0-100 parts, More preferably, it is 25-70 parts. When a solvent is used, it is removed by heating under normal pressure or reduced pressure after the elongation and / or crosslinking reaction.

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

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

In the classification operation, the fine particle portion can be removed in the liquid by a cyclone, a decanter, centrifugation, or the like. Of course, the classification operation may be performed after obtaining the powder as a powder after drying. The unnecessary fine particles or coarse particles obtained can be returned to the kneading step and used for the formation of particles. At that time, fine particles or coarse particles may be wet.
The dispersant used is preferably removed from the obtained dispersion as much as possible, but it is preferable to carry out it simultaneously with the classification operation described above.
By mixing the resulting dried toner powder with dissimilar particles such as release agent fine particles, charge control fine particles, fluidizing agent fine particles, and colorant fine particles, or by giving mechanical impact force to the mixed powder By immobilizing and fusing on the surface, it is possible to prevent detachment of the foreign particles from the surface of the resulting composite particle.

  Specific means include a method of applying an impact force to the mixture by blades rotating at high speed, a method of injecting and accelerating the mixture in a high-speed air stream, and causing particles or composite particles to collide with an appropriate collision plate, etc. is there. As equipment, Ong mill (manufactured by Hosokawa Micron Co., Ltd.), I-type mill (manufactured by Nippon Pneumatic Co., Ltd.) has been modified to reduce pulverization air pressure, hybridization system (manufactured by Nara Machinery Co., Ltd.), kryptron system (Made by Kawasaki Heavy Industries, Ltd.), automatic mortar and the like.

(Carrier for two components)
When the toner of the present invention is used for a two-component developer, it may be used by mixing with a magnetic carrier, and the content ratio of the carrier and the toner in the developer is 1 to 10 wt. Part is preferred. As the magnetic carrier, conventionally known ones such as iron powder, ferrite powder, magnetite powder, magnetic resin carrier having a particle diameter of about 20 to 200 μm can be used. Examples of the coating material include amino resins such as urea-formaldehyde resin, melamine resin, benzoguanamine resin, urea resin, polyamide resin, and epoxy resin. Polyvinyl and polyvinylidene resins such as acrylic resins, polymethyl methacrylate resins, polyacrylonitrile resins, polyvinyl acetate resins, polyvinyl alcohol resins, polyvinyl butyral resins, polystyrene resins and styrene acrylic copolymer resins, Halogenated olefin resin such as vinyl, polyester resin such as polyethylene terephthalate resin and polybutylene terephthalate resin, polycarbonate resin, polyethylene resin, polyvinyl fluoride resin, polyvinylidene fluoride resin, polytrifluoroethylene resin, polyhexafluoro Propylene resin, copolymer of vinylidene fluoride and acrylic monomer, copolymer of vinylidene fluoride and vinyl fluoride, tetrafluoroethylene and vinylidene fluoride And fluoro such as terpolymers of non-fluoride monomers including, and silicone resins. Moreover, you may make conductive powder etc. contain in coating resin as needed. As the conductive powder, metal powder, carbon black, titanium oxide, tin oxide, zinc oxide or the like can be used. These conductive powders preferably have an average particle diameter of 1 μm or less. When the average particle diameter is larger than 1 μm, it becomes difficult to control electric resistance.
The toner of the present invention can also be used as a one-component magnetic toner that does not use a carrier or a non-magnetic toner.

FIG. 1 shows an example of an image forming apparatus of the present invention. First, a schematic configuration of the image forming apparatus will be described. The surface of the photoreceptor (image carrier) 1 is uniformly charged by the charger 2 while being driven to rotate in the direction of the arrow. Next, the photosensitive member 1 is irradiated with image light γ by an exposure unit (not shown) at an exposure portion at a downstream portion of the charger 2 in the rotation direction. As a result, the charge on the surface of the photoconductor at the portion irradiated with the image light γ disappears, and an electrostatic latent image corresponding to the image light is formed on the surface of the photoconductor 1.

  A developing device 3 as a developing unit is disposed at a downstream portion of the exposure unit, and a toner 4 as a developer is accommodated in the developing device 3. The toner 4 is stirred and mixed by a paddle (stirring mechanism) 14 provided with a conveying screw 13 and is frictionally charged to a predetermined polarity. Then, the developing sleeve 5 is used to nip the developing sleeve 5 and the photoconductor 1 ( (Development area). The toner conveyed to the developing area is moved from the surface of the developing sleeve 5 to the surface side of the photosensitive member 1 by the developing electric field formed in the developing area by a developing bias applying means (not shown), and is moved to the surface of the photosensitive member. The electrostatic latent image deposited and formed on the surface of the photoreceptor is converted into a toner image (visualized image).

  The toner image formed on the photosensitive member 1 in this way is transferred to the transfer conveying belt 6 as a transfer unit disposed in the vicinity of the photosensitive member 1 on the downstream side of the developing unit 3 and the photosensitive member. The image is transferred onto a transfer sheet S as a transfer body fed to the transfer portion by the registration roller 18 by a nip portion (transfer portion) with the body 1. The transfer paper on which the toner image has been transferred is fixed on the toner image by a fixing roller (not shown) disposed on the downstream side in the rotation direction of the transfer conveyance belt 6 and then discharged (not shown). The paper is discharged onto a paper discharge tray outside the apparatus main body. The transfer conveyance belt 6 is suspended from a bias roller 6a.

  On the other hand, the toner (residual toner) not transferred onto the transfer paper in the transfer portion but remaining on the photoreceptor 1 is cleaned as a cleaning unit disposed on the downstream side of the transfer portion in the photoreceptor rotation direction. The photosensitive member 1 is removed by the cleaning blade 7, the recovery spring 8 and the recovery coil 9 of the apparatus. Further, the residual charge remaining on the photoreceptor 1 after the cleaning of the residual toner is removed by a static eliminator 20 including a static elimination lamp. In the figure, 16 is a reflection density detection sensor (P sensor), and 17 is a toner density sensor. Reference numeral 10 denotes a photoreceptor and a cleaning unit (PCU).

  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
(Synthesis of organic fine particle emulsion)
In a reaction vessel equipped with a stir bar 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), 138 parts of styrene, 138 parts of methacrylic acid, When 1 part of ammonium persulfate was charged 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 dispersion of a vinyl resin (a copolymer of styrene-methacrylic acid-methacrylic acid ethylene oxide adduct sulfate sodium salt) [fine particles Dispersion 1] was obtained. The volume average particle diameter of the [fine particle dispersion 1] measured by LA-920 was 0.14 μm. A portion of [Fine Particle Dispersion 1] was dried to isolate the resin component. The resin content Tg was 152 ° C.

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

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

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

Production Example 4-2
(Synthesis of crystalline polyester)
A 5-liter four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer and a thermocouple was added to 25 mol of 1,4-butanediol, 23.75 mol of fumaric acid, 1.65 mol of trimellitic anhydride, hydroquinone 5.3 g was added, reacted at 160 ° C. for 5 hours, heated to 200 ° C., reacted for 1 hour, and further reacted at 8.3 KPa for 1 hour to obtain [Crystalline Polyester Resin 1]. Melting point was 119 ° C., Mn710, Mw2100, acid value 24, hydroxyl value 28.

Production Examples 4-3 to 4-6
[Crystalline polyester resins 2 to 6] were obtained in the same manner as in Production Example 4-2 except that the raw materials were changed to the following.
Crystalline polyester 2
1,4-butanediol 25 mol fumaric acid 21.25 mol trimellitic anhydride 5 mol hydroquinone 5.7 g
Melting point was 96 ° C, Mn620, Mw1750, acid value 37, hydroxyl value 8.

Crystalline polyester 3
1,4-butanediol 23.75 mol ethylene glycol 1.25 mol fumaric acid 22.75 mol trimellitic anhydride 1.65 mol hydroquinone 4.8 g
Melting point was 128 ° C., Mn 1650, Mw 6400, acid value 24, hydroxyl value 44.

Crystalline polyester 4
1,4-butanediol 22.5 mol ethylene glycol 5 mol fumaric acid 23.75 mol trimellitic anhydride 5 mol hydroquinone 5.8 g
Melting point was 82 ° C., Mn 1100, Mw 4700, acid value 25, hydroxyl value 33.

Crystalline polyester 5
1,4-butanediol 25 mol fumaric acid 22.5 mol succinic acid 1.25 mol trimellitic anhydride 1.65 mol hydroquinone 5.3 g
Melting point was 113 ° C., Mn780, Mw2400, acid value 22 and hydroxyl value 28.

Crystalline polyester 6
1,4-butanediol 23.75 mol 1,6-hexanediol 1.25 mol fumaric acid 23 mol maleic acid 0.75 mol trimellitic anhydride 1.65 mol hydroquinone 5.2 g
Melting point was 128 ° C., Mn850, Mw3450, acid value 28, hydroxyl value 22.

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

Production Example 6
(Synthesis of master batch (MB))
1200 parts of water, 540 parts of carbon black (made by Printex 35 Dexa) [DBP oil absorption = 42 ml / 100 mg, pH = 9.5] and 1200 parts of polyester resin are added and mixed with a Henschel mixer (made by Mitsui Mining Co., Ltd.). After kneading at 150 ° C. for 30 minutes using two rolls, rolling and cooling and pulverizing with a pulverizer, [Masterbatch 1] was obtained.

Production Example 7
(Create oil phase)
In a container equipped with a stir bar and a thermometer, 378 parts of [Low molecular weight polyester 1], Carnaba WAX11O part, 22 parts of CCA (salicylic acid metal complex E-84: Orient Chemical Industry), and 947 parts of ethyl acetate were charged with stirring. The temperature was raised to 0 ° C., kept at 80 ° C. for 5 hours, and then cooled to 30 ° C. over 1 hour. Next, 500 parts of [Masterbatch 1] and 500 parts of ethyl acetate were placed in a container and mixed for 1 hour to obtain [Raw material solution 1].
[Raw material solution 1] 1324 parts are transferred to a container, and using a bead mill (Ultra Visco Mill, manufactured by Imex Co., Ltd.), a liquid feeding speed of 1 kg / hr, a disk peripheral speed of 6 m / sec, and 0.5 mm zirconia beads are 80 vol% Carbon black and WAX were dispersed under conditions of filling and 3 passes. Next, 1042.3 parts of a 65% ethyl acetate solution of [low molecular weight polyester 1] was added, and one pass was performed with a bead mill under the above conditions to obtain [Pigment / WAX Dispersion 1]. The solid content concentration of [Pigment / WAX Dispersion 1] (130 ° C., 30 minutes) was 50%.

Production Example 8
(Preparation of crystalline polyester dispersion)
100 g of [Crystalline Polyester Resin 1] and 400 g of ethyl acetate were taken in a metal 2 L container, heated and dissolved or dispersed at 79 ° C., and then rapidly cooled in an ice-water bath. To this, 500 ml of glass beads (3 mmφ) was added, and stirred for 10 hours with a batch type sand mill apparatus (manufactured by Campehapio) to obtain [Crystalline Polyester Dispersion 1] having a volume average particle size of 0.4 μm.

Production Examples 9-13
In Production Example 8, [Crystalline Polyester Resin Dispersions 2 to 6] were obtained in the same manner as in Production Example 8 except that [Crystalline Polyester 1] was changed to the following crystalline polyester resin.

[Example 1]
(Emulsification ⇒ Solvent removal)
[Pigment / WAX Dispersion 1] 664 parts, [Prepolymer 1] 109.4 parts, [Crystalline Polyester Dispersion 1] 73.9 parts, [Ketimine Compound 1] 4.6 parts, After mixing for 1 minute at 5,000 rpm with a TK homomixer (made by Tokushu Kika), add 1200 parts of [Aqueous Phase 1] to the container and mix with a TK homomixer at 13,000 rpm for 20 minutes [emulsified slurry 1] was obtained.
[Emulsion slurry 1] was put into a container equipped with a stirrer and a thermometer, and after removing the solvent at 30 ° C. for 8 hours, aging was carried out at 45 ° C. for 4 hours to obtain [Dispersion slurry 1].

(Washing ⇒ drying)
[Emulsified slurry 1] After 100 parts were filtered under reduced pressure, (1): 100 parts of ion-exchanged water was added to the filter cake, and the mixture was mixed with a TK homomixer (rotation speed: 12,000 rpm for 10 minutes) and then filtered.
(2): 1O parts of 10% sodium hydroxide aqueous solution was added to the filter cake of (1), mixed with a TK homomixer (30 minutes at 12,000 rpm), and then filtered under reduced pressure.
(3): 100 parts of 10% hydrochloric acid was added to the filter cake of (2), mixed with a TK homomixer (rotation speed: 12,000 rpm for 10 minutes), and then filtered.
(4): Add 300 parts of ion-exchanged water to the filter cake of (3), mix with a TK homomixer (10 minutes at 12,000 rpm) and then filter twice to obtain [Filter cake 1]. It was.
[Filtration cake 1] was dried at 45 ° C. for 48 hours in a circulating drier, and sieved with an opening of 75 μm mesh to obtain [Toner 1].

[Examples 2 to 6]
In Example 1, the weight ratio of prepolymer / low molecular weight polyester / crystalline polyester in the toner was unchanged without using 109.4 parts of [Prepolymer 1] and 4.6 parts of [ketimine compound 1]. [Toners 2 to 6] were obtained in the same manner as in Example 1 except that the raw materials were charged so as to satisfy the following table.

〔実施例７〜１１〕
実施例１において、結晶性ポリエステル分散液１の代わりに、製造例２〜６で得られた結晶性ポリエステル分散液を使用するほかは、実施例１と同様に操作して［トナー７〜１１］を得た。

[Examples 7 to 11]
In Example 1, instead of the crystalline polyester dispersion 1, the same operation as in Example 1 was performed except that the crystalline polyester dispersion obtained in Production Examples 2 to 6 was used [Toners 7 to 11]. Got.

[Comparative Example 1]
[Toner 12] was obtained in the same manner as in Example 1 except that the crystalline polyester dispersion was not used.

[Comparative Example 2]
Crystalline polyester resin 1 10 parts Low molecular weight polyester resin B1 70 parts Styrene-methyl acrylate resin C1 15 parts Polyethylene wax (melting point 99 ° C., penetration 1.5, SP value 8.1) 5 parts Charge control agent (salicylic acid derivative) 2 parts Colorant (copper phthalocyanine blue pigment) 2.5 parts (however,
B1: THF insoluble matter 0, weight average molecular weight 17000, Tg 59 ° C
C1: THF insoluble content 0, weight average molecular weight 15000, Tg 62 ° C.
Resin C1 had higher grindability than Resin B1 and polyethylene wax. )
The above materials were sufficiently mixed with a blender and then kneaded with a twin screw extruder, cooled, pulverized and classified to obtain toner 13 having a volume average particle diameter of about 7.5 μm.

To 100 parts of the toner thus obtained, 0.7 part of hydrophobic silica and 0.3 part of hydrophobic titanium oxide were mixed with a Henschel mixer. The obtained toner physical property values are shown in Table 1.
A developer composed of 5% by weight of toner subjected to external additive treatment and 95% by weight of a copper-zinc ferrite carrier coated with a silicone resin and having an average particle diameter of 40 μm can be prepared, and 45 sheets of A4 size paper can be printed per minute. Using Ricoh's imgio Neo 450, continuous printing was performed and evaluated according to the following criteria.

(Evaluation item)
(A) Particle Size The particle size of the toner was measured using a particle size measuring device “Coulter Counter TAII” manufactured by Coulter Electronics Co., Ltd., with an aperture diameter of 100 μm. The volume average particle diameter and the number average particle diameter were determined by the particle size measuring instrument.

(B) Circularity The average circularity can be measured with a flow particle image analyzer FPIA-1000 (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 a 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. .

(C) Charge amount 6 g of developer is weighed, charged into a metal cylinder that can be sealed, and blown to obtain the charge amount. The toner concentration is adjusted to 4.5 to 5.5 wt%.

(D) Toner thermal characteristics (flow tester characteristics)
An example of a flow tester for measuring the thermal characteristics of toner is an elevated flow tester CFT500 manufactured by Shimadzu Corporation. The flow curve of this flow tester becomes the data shown in FIGS. 2A and 2B, from which each temperature can be read. In the figure, Ts is the softening temperature, Tfb is the outflow start temperature, and the melting temperature in the 1/2 method is the T1 / 2 temperature.

"Measurement condition"
Load: 10 kg / cm ₂
Temperature increase rate: 3.0 ° C./min,
Die diameter: 0.50mm
Die length: 10.0mm

(E) Fixability 1.0 ± 0.1 mg of solid image on solid paper and cardboard transfer paper (Ricoh Type 6200 and NBS Ricoh Copy Printing Paper <135>) using Ricoh's imgio Neo 450 Adjustment was made so that toner of / cm ² was developed, and adjustment was made so that the temperature of the fixing belt was variable, and the temperature at which no offset occurred on plain paper and the minimum fixing temperature on thick paper were measured.
The lower limit fixing temperature was determined as the fixing lower limit temperature at the fixing roll temperature at which the residual ratio of the image density after rubbing the obtained fixed image with a pad was 70% or more.

(F) Image density After outputting a solid image, the image density was measured by X-Rite (manufactured by X-Rite). This was measured at five points for each color alone, and the average was obtained for each color.

(G) Background stain A blank image is stopped during development, the developer on the developed photoreceptor is tape transferred, and the difference from the image density of the untransferred tape is determined by 938 Spectrodensitometer (manufactured by X-Rite) )

(H) Cleaning property The transfer residual toner on the photosensitive member that has passed the cleaning process is transferred to white paper with a scotch tape (manufactured by Sumitomo 3M Co., Ltd.), and measured with a Macbeth reflection densitometer RD514. Those with 0.01 or less were evaluated as ◯ (good), and those exceeding it were evaluated as x (bad).

(I) Filming The presence or absence of toner filming on the developing roller or the photoreceptor was observed. ○ indicates no filming, Δ indicates filming on streaks, and × indicates filming as a whole.

  From these results, according to the present invention, the initial printing quality is good, the image quality in continuous printing is excellent, the cleaning property is stable, and filming contamination to the photoconductor, the developing roller, etc. is prevented. A low-temperature fixing toner can be obtained.

The present invention can be used as an image forming toner, a developer, a toner container, and an image forming method for developing an electrostatic latent image on an image carrier in an electrophotographic apparatus or an electrostatic recording apparatus. it can.

1 is a schematic configuration diagram illustrating an example of an image forming method and apparatus according to the present invention. The flow curve of a flow tester is shown. (A) The relationship between temperature Tfb melting temperature and piston stroke is shown. (B) The relationship between the melting temperature and the piston stroke in the 1/2 method is shown.

Explanation of symbols

1 Photoconductor (image carrier)
2 Charging roller 3 Developing device 4 Developer 5 Developing sleeve (Developer carrier)
6 Transfer belt (transfer means)
6a Bias roller 7 Cleaning blade 8 Recovery spring 9 Recovery coil 10 Photoreceptor and cleaning unit (PCU)
13 Conveying screw 14 Paddle (stirring mechanism)
16 Reflection density detection sensor (P sensor)
17 Toner concentration sensor 18 Registration roller 20 Static elimination lamp S Transfer paper

Claims (24)

The toner set component comprising a compound having an active hydrogen group in an organic solvent modified polyester resin reactive with dissolution and / or dispersing, the lysis solution or dispersion in an aqueous medium containing resin fine particles, the active hydrogen group It is reacted with a compound having, in the resulting toner, the toner binder, with the modified polyester resin, the image forming toner characterized by containing the crystalline polyester resin. The toner binder contains, together with the modified polyester resin (i), an unmodified polyester resin (ii) and a crystalline polyester resin (iii), and the weight ratio of (i) and (ii) + (iii) is 2. The toner for image formation according to claim 1, wherein the weight ratio of (ii) to (iii) is 99/1 to 50/50. The toner for image formation according to any one of claims 1 to 2, wherein an outflow start temperature (Tfb) of the toner is 70 to 150 ° C. The image forming toner according to claim 1, wherein the toner particles have a volume average particle diameter of 4 to 8 μm. The ratio Dv / Dn between the volume average particle diameter (Dv) and the number average particle diameter (Dn) of the toner particles is 1.00 to 1.25. The toner for image formation as described. 6. The image forming toner according to claim 1, wherein the toner particles have an average circularity of 0.99 to 0.95. The image forming toner according to claim 1, wherein the step of removing the solvent of the emulsified dispersion is performed at least under reduced pressure and / or heating conditions. The toner for image formation according to claim 1, wherein the resin fine particles have a volume average particle diameter of 5 to 500 nm. The image forming toner according to claim 1, wherein the toner contains a wax as a release material. The image forming toner according to claim 1, wherein the toner contains a charge control agent. 11. The image forming toner according to claim 1, wherein the dispersed particle diameter of the crystalline polyester resin is 0.2 to 3.0 μm in major axis. The toner for image formation according to claim 1, wherein the DSC endothermic peak temperature of the crystalline polyester resin is 50 to 150 ° C. The molecular weight distribution by GPC of the soluble part of orthodichlorobenzene of the crystalline polyester resin according to claim 1 is 1000 to 6500 in weight average molecular weight (Mw), 500 to 2000 in number average molecular weight (Mn), and Mw / Mn is The toner for image formation according to any one of claims 1 to 12, wherein the toner is 2 to 5. The alcohol component of the crystalline polyester resin contains a diol compound having 2 to 6 carbon atoms, and the acid component contains at least one of maleic acid, fumaric acid, succinic acid, and derivatives thereof. The image forming toner according to claim 1. 15. The image formation according to claim 1, wherein the alcohol component of the crystalline polyester resin contains at least one of 1,4-butanediol, 1,6-hexanediol, and derivatives thereof. Toner. The toner for image formation according to any one of claims 1 to 15, wherein a glass transition point (Tg) of the unmodified polyester resin is 40 to 80 ° C. The image forming toner according to claim 1, wherein the unmodified polyester resin has a weight average molecular weight of 2000 to 90000. The melting point of the wax is 40 to 160 ° C.
The image forming toner according to claim 1. The toner for image formation according to claim 1, wherein at least inorganic fine particles and / or resin fine particles are externally added. The method for producing an image forming toner according to claim 1, wherein the toner is produced using a crystalline polyester resin dispersion having a volume average particle size of 0.2 μm to 3 μm. A one-component developer comprising the image forming toner according to claim 1. A two-component developer comprising the image forming toner according to claim 1 and a carrier powder. A toner container filled with the developer according to claim 21. The electrostatic latent image formed on the image carrier is developed using the developer according to any one of claims 21 to 22, and the toner image formed on the image carrier is transferred to the image support. And an image forming method including a step of heating and pressure-fixing the transferred toner image with a roller-like or belt-like fixing member to obtain a fixed image.

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