JP4589209B2 - Toner, image forming apparatus, and toner manufacturing method - Google Patents

Description

  The present invention relates to a toner for visualizing an electrostatic charge image formed on the surface of an image carrier such as a photoreceptor in electrophotography or electrostatic recording, and an image forming apparatus and an image forming method using the toner. .

In image formation by electrophotography, as described in various methods in Patent Documents 1 to 3, generally, an electric latent image is formed on a photoreceptor prepared using a photoconductive substance by various means. And then developing the latent image with a developer, and then transferring the image with the developer to paper or the like as necessary, followed by fixing by heating, pressurization, or solvent vapor. It is.
The methods for developing electrical latent images can be broadly divided into a liquid development method using a liquid developer in which various pigments and dyes are finely dispersed in an insulating organic liquid, a cascade method, a magnetic brush method, and a powder cloud. There is a dry development method using a dry developer (hereinafter referred to as toner) prepared by dispersing a colorant such as carbon black in a natural or synthetic resin as in the method, etc., and in recent years, the dry development method has been widely used. .

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

In order to achieve the above requirement and minimize the waiting time, it is considered to be an essential technical achievement matter to lower the fixing temperature of the toner itself and lower the toner fixing temperature when it can be used. In order to cope with such low-temperature fixing, an attempt has been made to use a polyester resin having excellent low-temperature fixability and relatively good heat-preservability in place of the conventionally used styrene-acrylic resins (for example, Patent Document 4). ~ 9). Further, for the purpose of improving low-temperature fixability, an attempt to add a specific non-olefinic crystalline polymer into the binder (for example, see Patent Document 10) and an attempt to use a crystalline polyester (for example, see Patent Document 11). However, it cannot be said that the molecular structure and molecular weight are optimized.
Further, even if these conventionally known techniques are applied, it is impossible to achieve the specifications of a DSM (Demand-side Management) program, and it is necessary to establish a low-temperature fixing technique that is further advanced than the conventional technical field.

For further low-temperature fixing, it is necessary to control the thermal characteristics of the resin itself. However, if the glass transition temperature (Tg) is lowered too much, the heat-resistant storage stability is deteriorated or the molecular weight is decreased to reduce the resin. If the F1 _{/ 2} temperature is lowered too much, there are problems such as lowering the hot offset occurrence temperature. Therefore, it has yet to achieve a high toner over the superior and hot offset occurrence temperature in the low temperature fixing property by controlling the thermal characteristics of the resin itself.

On the other hand, toner production methods are roughly classified into a pulverization method and a polymerization method.
In the pulverization method, a colorant, a charge control agent, an offset preventive agent, and the like are melt-mixed and dispersed uniformly in the above thermoplastic resin, and the resulting composition is pulverized and classified to produce a toner. Yes. According to the pulverization method, a toner having some excellent characteristics can be produced, but there is a limitation in the selection of the toner material. For example, the composition obtained by melt mixing must be capable of being pulverized and classified by economically usable equipment. From this requirement, the melt-mixed composition must be made sufficiently brittle. For this reason, when the above composition is actually pulverized into particles, a wide range of particle size distribution is likely to be formed, and when trying to obtain a copy image with good resolution and gradation, for example, toner weight average The particle size must be reduced, and fine powder with a particle size of 4 μm or less and coarse powder with a particle size of 15 μm or more must be removed by classification, which has the disadvantage that the toner yield becomes very low. Further, in the pulverization method, it is difficult to uniformly disperse the colorant, the charge control agent, and the like in the thermoplastic resin. Such dispersion adversely affects toner fluidity, developability, durability, image quality, and the like.

In recent years, in order to overcome these problems in the pulverization method, a toner production method by a suspension polymerization method has been proposed and implemented. Techniques for producing a toner for developing an electrostatic image by a polymerization method are known, and for example, toner particles are obtained by a suspension polymerization method or an emulsion polymerization aggregation method (see, for example, Patent Document 12).
However, in these production methods, a polyester resin superior in low-temperature fixability cannot be used as a toner. Further in order to solve these problems, using a polyester resin in the binder resin, and a technique for particles of the toner in water with isocyanate reactions it has been proposed (e.g., see Patent Document 13.)

In the invention described in Patent Document 13, a low molecular weight polyester resin and a high molecular weight polyester resin are contained in a binder resin, and the low molecular weight polyester resin is imparted with a low temperature fixability (cold offset property). The polyester resin has heat-resistant storage stability (hot offset property), so that a wide range of fixing temperatures can be obtained.
However, in the invention described in Patent Document 13, if the characteristics of the respective resins are to be increased, the difference in viscosity between these two types of polyester resin solutions becomes large, so that the diffusibility when the solutions are mixed is poor. As a result, a locally non-uniform state occurs, and a stable granulated state cannot be obtained.

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

  Therefore, the present invention has been made in view of the above circumstances, and can obtain a wide fixing temperature and form a high-quality image with good developability by stabilizing the emulsification behavior in the production process. It is an object of the present invention to provide a toner capable of printing, an image forming apparatus using the toner, and an image forming method.

The features of the present invention, which is a means for solving the above problems, are listed below.
1. The present invention is a toner including at least a colorant and a binder resin, and the toner includes at least an unmodified polyester resin solution α containing an unmodified polyester (A), and a polyester as a precursor (B And at least a secondary modified prepolymer (D) obtained by a first extension reaction of a prepolymer (C) obtained by primary modification of the precursor (B), and the primary modified prepolymer (C). In the toner obtained by granulating an oil phase obtained by mixing the modified polyester resin solution β containing in an aqueous medium, the viscosity ηα of the unmodified polyester resin solution α and the modified polyester resin solution β The toner has a viscosity ηβ satisfying the following formula. ηα ≦ ηβ ≦ 2 × ηα (Formula 1)
2. The toner of the present invention is 1. The primary modified prepolymer (C) has a site capable of reacting with an active hydrogen group, and the secondary modified prepolymer (C) is subjected to a first extension reaction with the compound (E1) having an active hydrogen group. A modified prepolymer (D) is produced.
3. The toner of the present invention is 1. Or 2. In the organic solvent, the primary modified prepolymer (C) and the secondary modified prepolymer (D) having a site capable of reacting with an active hydrogen group, and the compound (E2) having an active hydrogen group. An oil phase obtained by dissolving or dispersing a toner composition containing a binder component is dispersed in an aqueous medium to obtain a dispersion, and the dispersion has a portion capable of reacting with the active hydrogen group. Toner particles are formed and dispersed by a second extension reaction in which the secondary modified prepolymer (C) and the secondary modified prepolymer (D) are extended and / or cross-linked with the compound (E2) having the active hydrogen group. It is manufactured through a step of removing the organic solvent in the liquid.
4). The toner of the present invention is 1. Or 3. In any one of the inventions, the functional group contained in the primary modified prepolymer (C) is an isocyanate group.
5). The toner of the present invention is 1. Or 4. In any one of the inventions, the secondary modified prepolymer (D) is obtained by a first extension reaction in which the primary modified polyester and water are reacted.
6). The toner of the present invention is 1. Or 5. In the invention according to any one of the above, the primary modified prepolymer (C) and / or the secondary modified prepolymer (D) are crosslinked with the compound (E2) having an active hydrogen group by a urea reaction. or it characterized to be extended.
7). The toner of the present invention is 1. Or 6. In the invention according to any one of the above, the precursor (B) has a glass transition point Tg in the range of 30 to 60 ° C.
8). The toner of the present invention is 1. Or 7. In the invention of any one of a glass transition point Tg, characterized in that in the range of 40 to 55 ° C..
9. The toner of the present invention is 1. Or 8. In the invention according to any one of the above, the acid value of the unmodified polyester (A) is 0.5 to 40 KOH mg / g.
10. The toner of the present invention is 1. Or 9. In the invention according to any one of the above, the hydroxyl value of the unmodified polyester (A) is 0.5 to 80 KOHmg / g.
11. The toner of the present invention is 1. Or 10. In the toner according to any one of
The toner has an average circularity of 0.90 to 0.98.
12 The toner of the present invention is 1. To 11. In the invention according to any one of the above, the volume average particle diameter is 3.0 to 8.0 μm, and the ratio (Dv / Dn) of the volume average particle diameter (Dv) to the number average particle diameter (Dn) is 1.00. it is in the range of ～1.40.
13. The toner of the present invention is 1. Or 12. In the invention described in any one of the above, it is used by being mixed with a magnetic carrier coated with a resin.
14 The toner of the present invention is 1. Thru 13. In any one of the inventions, the colorant is composed of at least yellow, magenta, cyan, and black.

15. Further, the image forming apparatus of the present invention includes a latent image carrier that carries a latent image, a charging unit that uniformly charges the surface of the latent image carrier, and image data on the surface of the charged latent image carrier. An exposure means for exposing and writing an electrostatic latent image, a developing means for supplying toner to the electrostatic latent image formed on the surface of the latent image carrier to visualize it, and the surface of the latent image carrier The image forming apparatus includes a transfer unit that transfers the visible image to the recording member, and a fixing unit that fixes the visible image on the recording member. The fixing unit heats the visible image on the recording member. And / or a fixing roller for fixing by applying pressure, and a fixing cleaning roller for removing residual toner on the fixing roller, and the toner used in the developing means includes at least a colorant and a binder resin And at least an unmodified polyester ( ) Containing an unmodified polyester resin solution α, and a secondary obtained by a first extension reaction of a prepolymer (C) obtained by using polyester as a precursor (B) and at least pre-modifying the precursor (B). A toner obtained by granulating an oil phase obtained by mixing a modified prepolymer (D) and a modified polyester resin solution β containing the primary modified prepolymer (C) in an aqueous medium. The viscosity ηα of the unmodified polyester resin solution α and the viscosity ηβ of the modified polyester resin solution β satisfy the following formula. ηα ≦ ηβ ≦ 2 × ηα (Formula 1)
16. The image forming apparatus further includes: Or 14. The toner according to any one of the above is used.

17. Further, the image forming apparatus of the present invention is described in 15. Or 16. The image forming apparatus main body integrally supports the image carrier that carries the electrostatic latent image and at least the developing device that is disposed to face the image carrier that carries the electrostatic latent image. And a removable process cartridge.

18. The image forming method of the present invention also includes a charging step for uniformly charging the surface of the image carrier, an exposure step for forming an electrostatic latent image by irradiating the charged image carrier surface with exposure light, and an image carrier. an electrostatic latent image on the body, a developing step of forming a toner image by developing with a developer containing a toner, and a transfer step of transferring the transfer sheet to toner over image on the image bearing member, transfer paper a toner image A fixing step of fixing the visible image on the recording member by applying heat and / or pressure to the recording member, and a fixing step on the fixing roller. And a step of removing residual toner with a fixing cleaning roller. The toner used in the development step comprises at least a colorant and a binder resin, and at least unmodified polyester (A). Contains unmodified polyester A secondary modified prepolymer (D) obtained by a first extension reaction of a resin solution α, a polyester (B), and at least a prepolymer (C) obtained by primary modification of the precursor (B), And a modified polyester resin solution β containing the primary modified prepolymer (C), and a toner obtained by granulating an oil phase in an aqueous medium, the unmodified polyester resin The viscosity ηα of the solution α and the viscosity ηβ of the modified polyester resin solution β satisfy the following formula. ηα ≦ ηβ ≦ 2 × ηα (Formula 1)
19. The image forming method further includes Or 14. Characterized by using a toner according to any one of.

20. The toner production method of the present invention is a toner production method including at least a colorant and a binder resin, and includes at least an unmodified polyester resin solution α containing an unmodified polyester (A), A secondary modified prepolymer (D) obtained by a first extension reaction of a prepolymer (C) obtained by using polyester as a precursor (B) and at least a primary modification of the precursor (B), and the primary modification A toner obtained by granulating an oil phase obtained by mixing a modified polyester resin solution β containing a prepolymer (C) in an aqueous medium, the viscosity ηα of the unmodified polyester resin solution α And the viscosity ηβ of the modified polyester resin solution β satisfies the following formula. ηα ≦ ηβ ≦ 2 × ηα (Formula 1)
21. Further, the method for producing the toner further comprises 2. Or 14. The toner according to any one of the above is produced.

  According to the present invention, it is possible to provide a toner having a target particle size characteristic while having a wide fixing temperature of an unprecedented level. In addition, an image forming apparatus and an image forming method using the toner as a developer can form a high-quality image with good developability over the long term.

Hereinafter, embodiments of the present invention will be described.
The toner in the present invention includes at least an unmodified polyester resin solution α containing unmodified polyester (A), a prepolymer (C) obtained by primary modification of at least a polyester as a precursor (B), and a prepolymer (C The toner obtained by granulating an oil phase obtained by mixing the modified polyester resin solution β containing the secondary modified prepolymer (D) obtained by the first extension reaction in an aqueous medium. In other words, the viscosity ηα of the unmodified polyester resin solution α and the viscosity ηβ of the modified polyester resin solution β satisfy the following formula (1).
ηα ≦ ηβ ≦ 2 × ηα (Formula 1)
Thus, by producing toner using two types of polyester resin solutions, the binder resin can contain a high molecular weight polyester resin and a low molecular weight polyester resin, and the toner has a wide range of fixing temperatures. On the other hand, if the viscosity difference between these two types of solutions is large, the diffusibility when these solutions are mixed deteriorates and a locally non-uniform state appears.
If the non-modified polyester and the secondary modified prepolymer are present non-uniformly in the toner particles, the thermal characteristics of the toner are lowered, both the hot offset property and the cold offset property are disadvantageous, and the fixing property is deteriorated.
By having the above relationship between the viscosity ηα of the unmodified polyester resin solution α and the viscosity ηβ of the modified polyester resin solution β, the diffusibility when mixing two types of polyester resin solutions can be improved. In addition, it is possible to obtain a toner excellent in both hot offset property and cold offset property.

The toner according to the present invention includes an oil phase obtained by mixing an unmodified polyester resin solution α containing an unmodified polyester (A) and a modified polyester resin solution β containing a modified polyester in an aqueous medium. Obtained by dispersing.
The modified polyester refers to a state in which a bonding group other than an ester bond is present in the polyester resin, or resin components having different configurations are bonded to the polyester resin by a covalent bond, an ionic bond, or the like. In the present invention, as the modified polyester contained in the modified polyester resin solution β, the prepolymer (C) in which a functional group is introduced into the polyester (B) as a precursor and the prepolymer (C) are subjected to a first extension reaction. Secondary modified prepolymer (D).

(Modified polyester resin)
The polyester (B) as a precursor of the modified polyester contained in the modified polyester resin solution β is a polycondensate of a polyhydric alcohol (PO) and a polyvalent carboxylic acid (PC) and has an active hydrogen group. Is mentioned.
In addition, as an active hydrogen group which polyester (A) has, a hydroxyl group (alcoholic hydroxyl group and phenolic hydroxyl group), an amino group, a carboxyl group, a mercapto group, etc. are mentioned, Among these, an alcoholic hydroxyl group is preferable.

  Examples of the polyhydric alcohol compound (PO) include dihydric alcohol (DIO) and trihydric or higher polyhydric alcohol (TO). (DIO) alone or a mixture of (DIO) and a small amount of (TO) preferable. Examples of the dihydric alcohol (DIO) include alkylene glycol (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, etc.); alkylene ether glycol (diethylene glycol) , Triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc.); alicyclic diols (1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.); bisphenols (bisphenol A, bisphenol) F, bisphenol S, etc.); alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adduct of the above alicyclic diol; Alkylene oxide bisphenol (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. As trihydric or higher polyhydric alcohol (TO), 3 to 8 or higher polyhydric aliphatic alcohol (glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, etc.); trihydric or higher phenols (Trisphenol PA, phenol novolak, cresol novolak, etc.); and alkylene oxide adducts of the above trivalent or higher polyphenols.

Examples of the polyvalent carboxylic acid (PC) include divalent carboxylic acid (DIC) and trivalent or higher polyvalent carboxylic acid (TC). (DIC) alone and (DIC) with a small amount of (TC) Mixtures are preferred. Divalent carboxylic 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) And naphthalenedicarboxylic acid). 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 polyvalent carboxylic acid (TC) include aromatic polycarboxylic acids having 9 to 20 carbon atoms (such as trimellitic acid and pyromellitic acid). In addition, as polyhydric carboxylic acid (PC), you may make it react with polyhydric alcohol (PO) using the above-mentioned acid anhydride or lower alkyl ester (Methyl ester, ethyl ester, isopropyl ester, etc.).
The ratio of the polyhydric alcohol (PO) to the polycarboxylic acid (PC) is usually 2/1 to 1/1, preferably as the equivalent ratio [OH] / [COOH] of the hydroxyl group [OH] and the carboxyl group [COOH]. Is 1.5 / 1 to 1/1, more preferably 1.3 / 1 to 1.02 / 1.

In addition, it is preferable that the polyester (B) as a precursor is a range whose glass transition point Tg is 30-60 degreeC.
In addition, it outlines about the measuring method of glass transition point Tg. Hereinafter, Tg was measured in the same manner.
As an apparatus for measuring Tg, a TG-DSC system TAS-100 manufactured by Rigaku Corporation was used.
First, about 10 mg of a sample is placed in an aluminum sample container, which is placed on a holder unit and set in an electric furnace. First, after heating from room temperature to 150 ° C. at a temperature rising rate of 10 ° C./min, the sample was allowed to stand at 150 ° C. for 10 minutes, the sample was cooled to room temperature and left for 10 minutes, and the temperature rising rate was again increased to 150 ° C. under a nitrogen atmosphere. DSC measurement was performed by heating at min. Tg was calculated from the tangent of the endothermic curve near the Tg and the base line using the analysis system in the TAS-100 system.

Moreover, as prepolymer (C), the polyester which introduce | transduced the site | part which can react with an active hydrogen group is mentioned to polyester (B) as a precursor.
Examples of functional groups capable of reacting with active hydrogen groups include isocyanate groups, blocked isocyanate groups, and epoxy groups. Of these, an isocyanate group and a blocked isocyanate group are preferable, and an isocyanate group is more preferable.

Examples of the polyvalent isocyanate compound (PIC) introduced into the polyester (B) include aliphatic polyisocyanates (tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-diisocyanatomethyl caproate, etc.); alicyclic polyisocyanates (Isophorone diisocyanate, cyclohexylmethane diisocyanate, etc.); aromatic diisocyanates (tolylene diisocyanate, diphenylmethane diisocyanate, etc.); araliphatic diisocyanates (α, α, α ′, α′-tetramethylxylylene diisocyanate, etc.); Polyisocyanates blocked with phenol derivatives, oximes, caprolactams, etc .; and combinations of two or more of these.
The ratio of the polyvalent isocyanate compound (PIC) is usually 5/1 to 1/1, preferably as an equivalent ratio [NCO] / [OH] of the isocyanate group [NCO] and the hydroxyl group [OH] of the polyester having a hydroxyl group. 4/1 to 1.2 / 1, more preferably 2.5 / 1 to 1.5 / 1. When [NCO] / [OH] exceeds 5, low-temperature fixability deteriorates. When the molar ratio of [NCO] is less than 1, when a urea-modified polyester is used, the urea content in the ester is lowered and hot offset resistance is deteriorated.

The content of the polyvalent isocyanate compound (PIC) component in the polyester prepolymer (C) having an isocyanate group is usually 0.5 to 40 wt%, preferably 1 to 30 wt%, more preferably 2 to 20 wt%. . If it is less than 0.5 wt%, 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 wt%, the low-temperature fixability deteriorates.
The number of isocyanate groups contained per molecule in the polyester prepolymer (C) having an isocyanate group is usually 1 or more, preferably 1.5 to 3 on average, more preferably 1.8 to 2 on average. Five. If it is less than 1 per molecule, the molecular weight of the urea-modified polyester will be low, and the hot offset resistance will deteriorate.
The molecular weight MwC of the primary modified prepolymer (C) is preferably 10,000 to 90,000.

In addition, as the secondary modified prepolymer (D), a functional group capable of reacting with an active hydrogen group and a compound (E1) having an active hydrogen group introduced into the primary modified prepolymer (C) are the first. The polyester resin obtained by extending | stretching reaction of this is mentioned.
In the present invention, specifically, water can be used as the compound (E1) having an active hydrogen group. A secondary modified prepolymer (D) having an amino group at the terminal can be obtained by decarboxylation with water as the compound (E1) in which the isocyanate group has an active hydrogen group.
The molecular weight MwD of the secondary modified prepolymer (D) is preferably 20,000 to 1,000,000.

These primary modified prepolymer (C) and secondary modified prepolymer (D) have an isocyanate group and an amino group at their terminals, and these functional groups have compound (E2) and urea having an active hydrogen group. A modified polyester resin is produced by a second extension reaction that is crosslinked and / or extended by the reaction.
Compared to the case where only the primary modified prepolymer (C) is contained by crosslinking and / or extension reaction in the solution containing the secondary modified prepolymer (D) in addition to the primary modified prepolymer (C). Since a modified polyester having a large molecular weight can be obtained, the function of hot offset resistance can be further increased.

Examples of the compound (E2) having an active hydrogen group to be reacted with the primary modified prepolymer (C) and / or the secondary modified prepolymer (D) include amines. As the amines (E2), a divalent amine compound (E2-1), a trivalent or higher polyvalent amine compound (E2-2), an amino alcohol (E2-3), an amino mercaptan (E2-4), an amino acid ( E2-5), and those in which the amino groups of E2-1 to E2-5 are blocked (E2-6).
Examples of the divalent amine compound (E2-1) include aromatic diamines (phenylenediamine, diethyltoluenediamine, 4,4′-diaminodiphenylmethane, etc.); alicyclic diamines (4,4′-diamino-3,3′-). Dimethyl dicyclohexyl methane, diamine cyclohexane, isophorone diamine, etc.); and aliphatic diamines (ethylene diamine, tetramethylene diamine, hexamethylene diamine, etc.) and the like. Examples of the trivalent or higher polyvalent amine compound (E2-2) include diethylenetriamine and triethylenetetramine. Examples of amino alcohol (E2-3) include ethanolamine and hydroxyethylaniline. Examples of amino mercaptan (E2-4) include aminoethyl mercaptan and aminopropyl mercaptan. Examples of amino acids (E2-5) include aminopropionic acid and aminocaproic acid. C1-C5 amino groups blocked (E2-6) include ketimine compounds and oxazolidine compounds obtained from the amines of E2-1 to E2-5 and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.) Etc. Among these amines (E2), preferred are E2-1 and a mixture of E2-1 and a small amount of E2-2.

The ratio of amines (E2) is the equivalent ratio [NCO] / [NHx] of isocyanate groups [NCO] in the prepolymer (C) having isocyanate groups and amino groups [NHx] in amines (E2). The ratio is usually 1/2 to 2/1, preferably 1.5 / 1 to 1 / 1.5, more preferably 1.2 / 1 to 1 / 1.2. When [NCO] / [NHx] is more than 2 or less than 1/2, the molecular weight of the urea-modified polyester is lowered, and the hot offset resistance is deteriorated.
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 modified polyester contained in the modified polyester resin β used in the present invention is produced by a one-shot method or a prepolymer method. The weight average molecular weight of the modified polyester is usually 10,000 or more, preferably 20,000 to 10,000,000, more preferably 30,000 to 1,000,000. The peak molecular weight at this time is preferably 1000 to 10,000, and if it is less than 1,000, the elongation reaction hardly occurs and the elasticity of the toner is small, and as a result, the resistance to hot offset deteriorates. On the other hand, if it exceeds 10,000, the problem in production becomes high in the case of a decrease in fixability, particle formation or pulverization.
The number average molecular weight of the modified polyester is not particularly limited when a non-modified polyester described later is used, and may be a number average molecular weight that can be easily obtained to obtain the weight average molecular weight. In the case of the modified polyester alone, the number average molecular weight is usually 20000 or less, preferably 1000 to 10000, and more preferably 2000 to 8000. When it exceeds 20000, the low-temperature fixability and the glossiness when used in a full-color device are deteriorated.
In the crosslinking and / or extension reaction of the prepolymer (C) and the secondary modified prepolymer (D) and the amines (E2) in order to obtain a modified polyester, a urea obtained by using a reaction terminator if necessary. The molecular weight of the modified polyester can be adjusted. Examples of the reaction terminator include monoamines (diethylamine, dibutylamine, butylamine, laurylamine, etc.), and those obtained by blocking them (ketimine compounds).
The average number molecular weight Mn of the toner was measured by GPC (gel permeation chromatography) under the following conditions. The following average number molecular weight Mn was measured in the same manner.
Apparatus: GPC-150C (manufactured by Waters)
Column: KF801-807 (manufactured by Shodex)
Temperature: 40 ° C
Solvent: THF (tetrahydrofuran)
Flow rate: 1.0 ml / min Sample: 0.1 ml injection of 0.05-0.6% concentration sample Use molecular weight calibration curve prepared from monodisperse polystyrene standard sample from molecular weight distribution of toner resin measured under the above conditions The average number molecular weight Mn of the toner was calculated.

(Unmodified polyester)
Further, in the present invention, not only the modified polyester alone but also the modified polyester resin α containing the unmodified polyester (A) is used together with the modified polyester, and the unmodified polyester (A) is used as a binder resin. It can also be contained as a component. By using the unmodified polyester (A) in combination, the low-temperature fixability and the gloss when used in a full-color apparatus are improved, which is preferable to the single use. Examples of the unmodified polyester (A) include polycondensates of polyvalent alcohol (PO) and polyvalent carboxylic acid (PC) similar to the polyester component (B) of the modified polyester (C) or (D). Preferred examples are also the same as (B). The unmodified polyester (A) is not limited to unmodified polyester, but may be modified with a chemical bond other than a urea bond, for example, may be modified with a urethane bond. The modified polyester (C) or (D) and the unmodified polyester (A) are preferably at least partially compatible with each other in terms of low-temperature fixability and hot offset resistance. Therefore, the polyester component of the modified polyester (C) or (D) and the unmodified polyester (A) preferably have similar compositions. When the unmodified polyester (A) is contained, the weight ratio of the unmodified polyester (A) to the modified polyesters (C) and (D) is usually 5/95 to 80/20, preferably 5/95 to 30 /. 70, more preferably 5/95 to 25/75, particularly preferably 7/93 to 20/80. If the weight ratio of (i) is less than 5%, the hot offset resistance deteriorates, and it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability.

  The ratio of the polyhydric alcohol (PO) and the polycarboxylic acid (PC) in the polyester resin is usually 2/1 to 1 as an equivalent ratio [OH] / [COOH] of the hydroxyl group [OH] and the carboxyl group [COOH]. The ratio is 1/1, preferably 1.5 / 1 to 1/1, and more preferably 1.3 / 1 to 1.02 / 1.

  The unmodified polyester (A) has a (peak) molecular weight of usually 1000 to 10,000, preferably 3,000 to 10,000. If it is less than 3000, the heat-resistant storage stability is deteriorated, and if it exceeds 10,000, the low-temperature fixability is deteriorated.

The unmodified polyester (A) preferably has an acid value of 0.5 to 40 KOHmg / g, and the hydroxyl value of the unmodified polyester (A) is preferably 0.5 to 80 KOHmg / g. preferable.
When the pigment is used in the toner constituent material, the solubility when these pigments are dissolved or dispersed in the resin solution is the function that the wettability of the pigment surface to the resin solution is localized on the pigment surface. It varies depending on the type of group.
For this reason, it is preferable to define the acid value and hydroxyl value of the unmodified polyester depending on the type of pigment used. When the following pigment is used in the toner of the present invention, the acid value and the base value have the above relationship. By using the polyester resin which has, the solubility of a pigment becomes favorable and the stable emulsification behavior can be obtained.

  The glass transition point (Tg) of the binder resin is usually 35 to 70 ° C, preferably 55 to 65 ° C. If the temperature is lower than 35 ° C., the heat-resistant storage stability of the toner deteriorates, and if it exceeds 70 ° C., the low-temperature fixability becomes insufficient. Since the urea-modified polyester is likely to be present on the surface of the obtained toner base particles, the toner of the present invention tends to have good heat storage stability even when the glass transition point is low, as compared with known polyester-based toners. Show.

(Solid content concentration)
In addition, by adjusting the solid content concentration of the two types of polyester resin solutions, the unmodified polyester resin solution α and the modified polyester resin solution β, the viscosity difference between the two types of polyester resin solution has the above relationship. can do.
In particular, when the unmodified polyester resin has a cold offset function and the modified polyester resin has a hot offset function, the viscosity of the unmodified polyester resin solution α becomes relatively small, and the modified polyester resin Since the viscosity of the solution β becomes relatively large, the difference in viscosity between these two types of polyester resin solutions becomes large, but the difference in viscosity between these solutions can be eliminated.
In the present embodiment, the solid content concentration Dα (hereinafter referred to as Dα) of the unmodified polyester resin solution and the solid content concentration Dβ (hereinafter referred to as Dβ) of the modified polyester resin solution are used.
By adjusting the solid content concentration Dα of the unmodified polyester resin solution and the solid content concentration Dβ of the modified polyester resin solution to be within the above ranges, the above two types of polyester resin solutions are expressed by the formula (1). The viscosity relationship shown can be obtained, and a stable emulsification behavior can be obtained.
From the viewpoint of production efficiency, Dα and Dβ are preferably 50% or more. However, as described above, in order to increase the temperature range between the cold offset and the hot offset, the viscosity of the unmodified polyester resin solution α becomes relatively small, and the viscosity of the modified polyester resin solution β becomes relatively large. If the values of Dα and Dβ are based on 50%, it is preferable to make Dα higher than 50% and Dβ smaller than 50% in order to eliminate the viscosity difference. The solid content concentration is preferably adjusted such that the polyester resin in the solution does not precipitate.
In order to maintain the production efficiency, it is preferable that the weighted average of Dα and Dβ in consideration of the prescription amounts of the unmodified polyester resin solution and the modified polyester resin solution is 50% or more.

  The viscosity ηα of the unmodified polyester resin solution α and the viscosity ηβ of the modified polyester resin solution β preferably satisfy the relational expression ηα ≦ ηβ ≦ 2 × ηα.

(Coloring agent)
As the colorant, 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, Phi Sayred, Parachlor Ortonito Aniline 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, Thio Indigo Red B, Thioindigo Maroon, Oil Red, Quinacridone Red, Pyrazolone Red Polyazo Red, Chrome Vermillion, Benzidine Orange, Perinone Orange, Oil Orange, Cobalt Blue, Cerulean Blue, Alkaline Blue Lake, Peacock Blue Lake, Victoria Blue Lake, Metal Free Phthalocyanine Blue, Phthalocyanine Blue, Fast Sky Blue, Indanthrene Blue (RS, BC), indigo, ultramarine blue, bitumen, anthraquinone blue, fast violet B, methyl violet lake, cobalt purple, manganese purple, dioxane violet, anthraquinone violet, chrome green, zinc green, chromium oxide, pyridian, emerald green, pigment Green B, Naphthol Green B, Green Gold, Acid Green Lake, Malachite Green Lake, Lid Russian nin 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 can also be used as a master batch combined with a resin. As a binder resin to be kneaded with the production of the master batch or the master batch, a polymer of styrene such as polystyrene, poly-p-chlorostyrene, polyvinyl toluene or the like, or a copolymer of these and a vinyl compound, Polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, polyacrylic acid resin, rosin, modified rosin, terpene resin, fat Aromatic or alicyclic hydrocarbon resins, aromatic petroleum resins, chlorinated paraffins, paraffin waxes and the like can be mentioned, and these can be used alone or in combination.

(Charge control agent)
Known charge control agents can be used, such as nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts (fluorine-modified 4 Secondary ammonium salts or compounds, tungsten simple substances or compounds, fluorine activators, salicylic acid metal salts, and metal salts of salicylic acid derivatives. Specifically, Bontron 03 of a nigrosine dye, Bontron P-51 of a quaternary ammonium salt, Bontron S-34 of a metal-containing azo dye, E-82 of an oxynaphthoic acid metal complex, E-84 of a salicylic acid metal complex , Phenol-condensate E-89 (above, manufactured by Orient Chemical Co., Ltd.), quaternary ammonium salt molybdenum complex TP-302, TP-415 (above, manufactured by Hodogaya Chemical Co., Ltd.), quaternary ammonium salt copy Charge PSY VP2038, 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) Manufactured), copper phthalocyanine, perylene, quinacridone, azo series Fee, a sulfonic acid group, a carboxyl group, and polymer compounds having a functional group such as quaternary ammonium salts. Of these, substances that control the negative polarity of the toner are particularly preferably used.
The amount of the charge control agent used is determined by the type of binder resin, the presence or absence of additives used as necessary, and the toner production method including the dispersion method, and is not uniquely limited. The amount is preferably 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 charge control agent is reduced, the electrostatic attraction with the developing roller is increased, the flowability of the developer is lowered, and the image density is lowered. Invite.

(Release agent)
As a release agent, a low melting point wax having a melting point of 50 to 120 ° C. works more effectively as a release agent in the dispersion with the binder resin between the fixing roller and the toner interface. The effect on high temperature offset is exhibited without applying a release agent such as oil. Examples of such a wax component include the following. Examples of waxes and waxes include plant waxes such as carnauba wax, cotton wax, wood wax, rice wax, animal waxes such as beeswax and lanolin, mineral waxes such as ozokerite and cercin, and paraffin, microcrystalline, And petroleum waxes such as petrolatum. In addition to these natural waxes, synthetic hydrocarbon waxes such as Fischer-Tropsch wax and polyethylene wax, and synthetic waxes such as esters, ketones, and ethers can be used. Furthermore, fatty acid amides such as 12-hydroxystearic acid amide, stearic acid amide, phthalic anhydride imide, chlorinated hydrocarbon, and low molecular weight crystalline polymer resin, poly-n-stearyl methacrylate, poly-n- A crystalline polymer having a long alkyl group in the side chain such as a homopolymer or copolymer of polyacrylate such as lauryl methacrylate (for example, a copolymer of n-stearyl acrylate-ethyl methacrylate, etc.) can also be used. .
The charge control agent and the release agent can be melt-kneaded together with the master batch and the binder resin, and of course, they may be added when dissolved and dispersed in the organic solvent.

(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 × ¹⁰ -3 ~2μm, it is particularly preferably 5 × ¹⁰ -3 ~0.5μm. Moreover, it is preferable that the specific surface area by BET method is 20-500 m < ² > / g. The use ratio of the inorganic fine particles is preferably 0.01 to 5 wt% of the toner, and particularly preferably 0.01 to 2.0 wt%.
Specific examples of the inorganic fine particles include, for example, silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, tin oxide, silica 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.

  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 systems such as silicone, benzoguanamine, and nylon, thermosetting resins 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. . In particular, it is preferable to use hydrophobic silica and hydrophobic titanium oxide obtained by subjecting silica and titanium oxide to the above surface treatment.

Next, a toner manufacturing method will be described. Here, although a preferable manufacturing method is shown, it is not limited to this.
(Toner production method)
1) A toner material liquid is prepared by dispersing a colorant, unmodified polyester, polyester prepolymer (C) having an isocyanate group, secondary modified prepolymer (D), and a release agent in an organic solvent.
The organic solvent is preferably volatile with a boiling point of less than 100 ° C. from the viewpoint of easy removal after toner base particle formation. Specifically, 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 an organic solvent is 0-300 weight part normally with respect to 100 weight part of polyester prepolymers, Preferably it is 0-100 weight part, More preferably, it is 25-70 weight part.

2) The toner material liquid is emulsified in an aqueous medium in the presence of a surfactant and resin fine particles.
The aqueous medium may be water alone or an organic solvent such as alcohol (methanol, isopropyl alcohol, ethylene glycol, etc.), dimethylformamide, tetrahydrofuran, cellosolves (methyl cellosolve, etc.), lower ketones (acetone, methyl ethyl ketone, etc.). It may be included.
The amount of the aqueous medium used relative to 100 parts by weight of the toner material liquid 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 material liquid is poor, and toner particles having a predetermined particle diameter cannot be obtained. If it exceeds 20000 parts by weight, it is not economical.

Further, in order to improve the dispersion in the aqueous medium, a dispersant such as a surfactant and resin fine particles is appropriately added.
As surfactants, anionic surfactants such as alkylbenzene sulfonates, α-olefin sulfonates, phosphate esters, alkylamine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, amine salt types such as imidazoline, Quaternary ammonium salt type cationic surfactants such as alkyltrimethylammonium salt, dialkyldimethylammonium salt, alkyldimethylbenzylammonium salt, pyridinium salt, alkylisoquinolinium salt, benzethonium chloride, fatty acid amide derivative, polyhydric alcohol Nonionic surfactants such as derivatives, for example, amphoteric surfactants such as alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine and N-alkyl-N, N-dimethylammonium betaine And the like.

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- [ω-fluoroalkyl (C6-C11 ) Oxy] -1-alkyl (C3-C4) sodium sulfonate, 3- [ω-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) Perful Olooctanesulfonamide, perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salt, perfluoroalkyl (C6-C10) -N-ethylsulfonylglycine salt, monoperfluoroalkyl (C6-C16) ethyl phosphate, etc. Can be 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 (manufactured by Daikin Industries, Ltd.), Megafac F-110, F-120, F-113, F-191, F-812, F-833 (manufactured by Dainippon Ink, Inc.), Xtop EF-102, 103, 104, 105, 112, 123A, 123B, 306A, 501, 201, 204 (manufactured by Tochem Products), and Fgentent F-100, F150 (manufactured by Neos).

As the cationic surfactants, aliphatic primary to have a fluoroalkyl group, 2 primary or secondary amine acids, aliphatic quaternary ammonium, such as perfluoroalkyl (C6 ~ C10) sulfonamide propyl trimethyl ammonium salt Salt, benzalkonium salt, benzethonium chloride, pyridinium salt, imidazolinium salt, trade names include Surflon S-121 (Asahi Glass Co., Ltd.), Florard FC-135 (Sumitomo 3M Co., Ltd.), Unidyne DS-202 (Daikin Industries) Smoke), Megafac F-150, F-824 (Dainippon Ink Co., Ltd.), Xtop EF-132 (Tochem Products), Footage F-300 (Neos), and the like.

As the resin fine particles, any resin can be used as long as it can form an aqueous dispersion, and it may be a thermoplastic resin or a thermosetting resin. Examples thereof include vinyl resins, polyurethane resins, epoxy resins, polyester resins, polyamide resins, polyimide resins, silicon resins, phenol resins, melamine resins, urea resins, aniline resins, ionomer resins, and polycarbonate resins. As the resin, 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. For example, vinyl resins are polymers obtained by homopolymerization or copolymerization of vinyl monomers, such as styrene- (meth) acrylic acid ester copolymers, styrene-butadiene copolymers, (meth) acrylic acid-acrylic acid esters. Examples thereof include resins such as a polymer, a styrene-acrylonitrile copolymer, a styrene-maleic anhydride copolymer, and a styrene- (meth) acrylic acid copolymer. The average particle size of the resin fine particles is 5 to 200 nm, preferably 20 to 300 nm. In addition, inorganic compound dispersants such as tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, and hydroxyapatite can also be used.

  As a dispersant that can be used in combination with the above resin fine particles and inorganic compound dispersant, 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 acrylic acid-β-hydroxyethyl, methacrylic acid-β-hydroxyethyl, acrylic acid-β-hydroxypropyl, methacrylic acid-β-hydroxypropyl, acrylic acid-γ-hydroxypropyl, methacrylic acid-γ-hydroxy Propyl, acrylic acid-3-chloro-2-hydroxypropyl, methacrylic acid-3-chloro-2-hydroxypropyl, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerol monoacrylate, glycerol monomethacrylate Luric acid esters, 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, or compounds containing vinyl alcohol and a carboxyl group Esters such as vinyl acetate, vinyl propionate, vinyl butyrate, acrylamide, methacrylamide, diacetone acrylamide or their methylol compounds, acid chlorides such as acrylic acid chloride, methacrylic acid chloride, vinyl pyridine, vinyl pyrrolidone, vinyl Nitrogen compounds such as imidazole and ethyleneimine, or homopolymers or copolymers such as those having a heterocyclic ring thereof, polyoxyethylene, poly Xoxypropylene, polyoxyethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonylphenyl ether, polyoxyethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ester, polyoxy Polyoxyethylenes such as ethylene nonylphenyl ester, celluloses such as methyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose can be used.

  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. Among these, the high-speed shearing method is preferable in order to make the particle size of the dispersion 2 to 20 μm. 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.

3) At the same time as the preparation of the emulsion, the amines (E2) are added to cause the reaction with the prepolymer (C) having an isocyanate group and the secondary modified prepolymer (D).
This reaction involves molecular chain crosslinking and / or elongation. The reaction time is selected depending on the reactivity of the isocyanate group structure of the prepolymer (C) and the amino group structure of the secondary modified prepolymer (D) with the amines (E2). 40 hours, preferably 2 to 24 hours. The reaction temperature is generally 0 to 150 ° C, preferably 40 to 98 ° C. Moreover, a well-known catalyst can be used as needed. Specific examples include dibutyltin laurate and dioctyltin laurate.

4) After completion of the reaction, the organic solvent is removed from the emulsified dispersion (reactant), washed and dried to obtain toner base particles.
In order to remove the organic solvent, the temperature of the entire system is gradually raised in a laminar stirring state, and after giving strong stirring in a certain temperature range, the solvent base is removed to produce spindle-shaped toner base particles. . Further, when an acid such as calcium phosphate salt or an alkali-soluble material is used as the dispersion stabilizer, the calcium phosphate salt is dissolved from the toner base particles by a method such as dissolving the calcium phosphate salt with an acid such as hydrochloric acid and washing with water. Remove. It can also be removed by operations such as enzymatic degradation.

5) A charge control agent is injected into the toner base particles obtained above, and then inorganic fine particles such as silica fine particles and titanium oxide fine particles are externally added to obtain a toner.
The injection of the charge control agent and the external addition of the inorganic fine particles are performed by a known method using a mixer or the like.
Thereby, a toner having a small particle size and a sharp particle size distribution can be easily obtained. Furthermore, by giving strong agitation in the process of removing the organic solvent, the shape between the true spherical shape and the rugby ball shape can be controlled, and the surface morphology is also controlled between the smooth shape and the umeboshi shape. be able to.

The glass transition point of the toner is preferably in the range of 40 to 55 ° C.
If it is less than 40 ° C., toner blocking and filming on the photosensitive member are likely to occur in the developing device, and if it exceeds 55 ° C., the low-temperature fixability tends to deteriorate.
The toner of the present invention uses the above-mentioned polyester (A) as a precursor substance and contains a resin containing this as a crosslinking unit, so that it has a glass transition point within the above range, and has low temperature fixability and heat resistance storage. And a toner having both high durability and high durability.

Measurement of glass transition temperature (Tg), by Rigak u T HRMOFLE X T G8110 of Rigaku Corporation, is measured under conditions of Atsushi Nobori rate 10 ° C. / min.
The molecular weight 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 the standard polystyrene samples for preparing the calibration curve, for example, Pressur e C hemica l C o . 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. ^{× 10 5, 8.6 × 10 5} , 2 × 10 6, used as a 4.48 × 10 ^6, it is appropriate to use at least about 10 standard polystyrene samples. An RI (refractive index) detector is used as the detector.

(Average circularity)
The toner of the present invention preferably has an average circularity of 0.90 to 0.98. Average circularity SR = (peripheral length of circle having the same area as the projected particle area / perimeter length of projected particle image) × 100%. The closer the toner is to a true sphere, the closer to 100%. Toner having a high degree of circularity is easily affected by the developing electric field, and is developed faithfully along the electric field of the electrostatic latent image.
Thereby, a high-definition image with an appropriate image density can be formed with good reproducibility. When the average circularity is less than 0.90, it is difficult to obtain a satisfactory transferability and a high-quality image free from dust.

  The average circularity of the toner can be measured by a flow type particle image analyzer FPIA-2000 (manufactured by Toa Medical Electronics Co., Ltd.). As a specific measurement method, 0.1 to 0.5 ml of a surfactant, preferably an alkylbenzene sulfonate, is added as a dispersant to 100 to 150 ml of water from which impure solids have been removed in advance. About 0.1 to 0.5 g. 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. .

(Average particle diameter, Dv / Dn)
The volume average particle diameter (Dv) of the toner of the present invention is preferably 3.0 to 8.0 μm, and the ratio (Dv / Dn) to the number average particle diameter (Dn) is 1.00 to 1. More preferably, it is in the range of .40. 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, it is preferable to set Dv to 3 to 7 μm, Dv / Dn to 1.00 to 1.40, and particles 3 μm or less to 1% to 10% by number. More preferably, it is preferable to set Dv to 3 to 6 μm and Dv / Dn to 1.00 to 1.15. 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, a Coulter Counter TA-II type is used, and an interface (manufactured by Nikka Giken) that outputs the number distribution and volume distribution is connected to a PC 9801 personal computer (manufactured by NEC). It was measured.
As an apparatus for measuring the particle size distribution of toner particles by the Coulter counter method, there are Coulter Counter TA-II and Coulter Multisizer II (both manufactured by Coulter). The measurement method is described below.
First, a surfactant (preferably alkylbenzene phon salt) is added 0.1~5ml as dispersing agent in the electrolytic solution 100 to 150 ml. Here, the electrolytic solution is a solution prepared by preparing a 1% NaCl aqueous solution using first grade sodium chloride. For example, ISOTON-II (manufactured by Coulter) can be used. Here, 2 to 20 mg of a measurement sample is further added. The electrolytic solution in which the sample is suspended is subjected to a dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes, and the measurement device is used to measure the volume and number of toner particles or toner using a 100 μm aperture as an aperture. Volume distribution and number distribution are calculated. From the obtained distribution, the weight average particle diameter (D4) and the number average particle diameter of the toner can be obtained.
As channels, 2.00 to less than 2.52 μm; 2.52 to less than 3.17 μm; 3.17 to less than 4.00 μm; 4.00 to less than 5.04 μm; 5.04 to less than 6.35 μm; 6 .35 to less than 8.00 μm; 8.00 to less than 10.08 μm; 10.08 to less than 12.70 μm; 12.70 to less than 16.00 μm; 16.00 to less than 20.20 μm; Uses 13 channels of less than 40 μm; 25.40 to less than 32.00 μm; 32.00 to less than 40.30 μm, and targets particles having a particle size of 2.00 μm to less than 40.30 μm.

The toner of the present invention is preferably a toner having a shape factor SF-1 in the range of 100 to 180 and SF-2 in the range of 100 to 180. SF-1 is more preferably 110 to 170, more preferably 120 to 160, and particularly preferably 130 to 150. SF-2 is more preferably 110 to 170, more preferably 120 to 160, and particularly preferably 130 to 150.
The shape factors SF-1 and SF-2 are expressed by the following formulas (1) and (2) as described above.
SF-1 = {(MXLNG) ² / AREA} × (100π / 4) (1)
SF-2 = {(PERI) ² / AREA} × ( 100 / 4π ) (2)
When the value of SF-1 is 100, the shape of the toner becomes a true sphere, and becomes larger as the value of SF-1 increases. Further, when the value of SF-2 is 100, the unevenness does not exist on the toner surface, and as the SF-2 value increases, the unevenness of the toner surface becomes more prominent.
The shape factor SF-1 is 100 images of toner particles magnified by a magnification of 500 using an electron microscope (for example, FE-SEM (S-800) manufactured by Hitachi, Ltd., and the same applies hereinafter). Randomly sampled and the image information is sent via an interface to an image analysis device [eg, Nexus NEW CUBE ver. 2.5 (manufactured by NEXUS), Luzex III (manufactured by Nicole) and the like, and so on. It is a value obtained by introducing into and analyzing and calculating from equation (1).
The shape factor SF-2 is obtained by randomly sampling 50 toner particle images magnified to a magnification of 3500 times using an electron microscope, introducing the image information into an image analysis apparatus via an interface, and performing analysis. It is a value obtained from 2).

  When the shape factors SF-1 and SF-2 are both close to 100 and the shape of the toner is close to a true sphere, the contact between the toner and the toner or the toner and the image carrier becomes a point contact. Accordingly, the fluidity is increased and the adhesion between the toner and the image carrier is also weakened, and the transfer rate is increased. The dot reproducibility is also improved. On the other hand, when the toner shape factors SF-1 and SF-2 are large to some extent, the margin for cleaning increases, and there is no problem such as defective cleaning. Therefore, it is preferable that the shape factors SF-1 and SF-2 are in the range of 100 to 180 as a range in which the image quality is not deteriorated from the balance between the two.

  The toner of the present invention can be mixed with a magnetic carrier and used as a two-component developer. In this case, the carrier to toner content ratio in the developer is preferably 1 to 10 parts by weight of toner with respect to 100 parts by weight of carrier. As the magnetic carrier, conventionally known ones such as iron powder, ferrite powder, magnetite powder, magnetic resin carrier having a particle diameter of about 20 to 200 μm can be used. Examples of the coating material include amino resins such as urea-formaldehyde resin, melamine resin, benzoguanamine resin, urea resin, polyamide resin, and epoxy resin. Polyvinyl and polyvinylidene resins such as acrylic resins, polymethyl methacrylate resins, polyacrylonitrile resins, polyvinyl acetate resins, polyvinyl alcohol resins, polyvinyl butyral resins, polystyrene resins and styrene acrylic copolymer resins, Halogenated olefin resins such as vinyl, polyester resins such as polyethylene terephthalate resin and polybutylene terephthalate resin, polycarbonate resins, polyethylene resins, polyvinyl fluoride resins, polyvinylidene fluoride resins, polytrifluoroethylene resins, polyhexafluoro Propylene resin, copolymer of vinylidene fluoride and acrylic monomer, copolymer of vinylidene fluoride and vinyl fluoride, tetrafluoroethylene and vinylidene fluoride and non- Monomers including a fluoro terpolymers such, and silicone resins. Moreover, you may contain electrically conductive powder etc. in coating resin as needed. As the conductive powder, metal powder, carbon black, titanium oxide, tin oxide, zinc oxide or the like can be used. These conductive powders preferably have an average particle diameter of 1 μm or less. When the average particle diameter is larger than 1 μm, it becomes difficult to control electric resistance.

  The toner of the present invention can also be used as a one-component magnetic toner that does not use a carrier or a non-magnetic toner.

(Image forming device)
An example of an embodiment of the present invention will be described with reference to the drawings.
FIG. 1 is a schematic sectional view showing an example of an image forming apparatus according to the present invention. A digital copying machine 40 shown in FIG. 1 is an image forming apparatus using a well-known electrophotographic system, and includes a drum-shaped photoreceptor 1 inside. A charging device 2, an exposure device 3, a developing device 4, a transfer device 5, a cleaning device 6, and a fixing device 10 that perform an electrophotographic copying process are arranged around the photosensitive member 1 along a rotation direction indicated by an arrow A. ing. The exposure device 3 forms an electrostatic latent image on the photoreceptor 1 on the basis of an image signal obtained by reading a document placed on the document placing table 7 on the upper surface of the copying machine by a reading device (not shown). The electrostatic latent image formed on the photosensitive member 1 is converted into a toner image by the developing device 4, and the toner image is electrostatically transferred by the transfer device 5 to the transfer paper fed from the paper supply device 9. The transfer paper on which the toner image is placed is conveyed and fixed to the fixing device 10 and then discharged outside the apparatus. On the other hand, the untransferred portion and the photosensitive member 1 with dirt are cleaned by the cleaning device 6, and the next image forming step is started.

Next, the fixing device 10 will be described in detail. Figure 2 shows an example of a thermal low la scheme of the fixing device, a fixing roller 21 having a heating device 24 (hereinafter referred to as "heaters".) Such as a halogen lamp as a basic structure, on a core metal 26 an elastic layer 27 such as foamed silicone rubber, and a pressure roller 25 which is pressed against the fixing low La 2 1. A release layer 28 made of a PFA tube or the like is provided on the elastic layer 27 of the pressure roller 25. In the fixing roller 21, an elastic layer 22 such as silicone rubber is provided on a core metal 30, and a resin surface layer 23 having a good releasability such as a fluororesin is formed for the purpose of preventing adhesion due to the viscosity of the toner. . The thickness of the elastic layer 22 is usually preferably about 100 to 500 μm in consideration of image quality and heat transfer efficiency during fixing. The resin surface layer 23 is composed of a PFA tube or the like similarly to the pressure roller 25, and its thickness is preferably about 10 to 50 μm in consideration of mechanical deterioration. A temperature detector 29 is provided on the outer peripheral surface of the fixing roller 21, and the heater 24 is controlled so as to keep the temperature substantially constant by detecting the surface temperature of the fixing roller 21.

In the fixing device having such a configuration, the fixing roller 21 and the pressure roller 25 are pressed against each other with a predetermined pressure to form a fixing nip portion N, which is driven by a driving unit (not shown) and receives arrows. By rotating in the R21 direction and the arrow R25 direction, the transfer material P is nipped and conveyed at the fixing nip portion N described above. At this time, the fixing roller 21 is controlled to a predetermined temperature by the heater 24, and when the toner image T on the transfer paper P passes between the two rollers, it is melted by heat while receiving pressure, and the roller pair is ejected. By being cooled, it is fixed on the transfer paper P as a permanent image.
The pressure roller 25 has an outer diameter of 30 mm, a wall thickness of 6 mm, a surface covered with a conductive PFA tube, and an on-axis rubber hardness of 42 HS (Asuka C). The fixing roller is made of an aluminum core and has a thickness of 0.4 mm. In this configuration, in order to obtain the nip N, pressure is applied to both ends of the roller, and the contact pressure at that time is 8.3 N / cm ² .

In the heat roller type fixing device as described above, the toner on the fixing roller 21 is transferred onto the pressure roller 25 as a result of use over time, and the toner is transferred to cause stain on the back surface of the recording paper. To do.
The fixing device 10 of the present invention includes a fixing cleaning roller 31 so as to contact the surface of the pressure roller 25 in order to remove such residual toner on the pressure roller 25.
Thereby, a small amount of toner adhering to the pressure roller 25 is removed, and contamination on the back surface of the transfer paper can be prevented.

The surface temperature of the fixing roller 21 is preferably controlled within a suitable fixing temperature range by the temperature detecting means 29.
As described above, when the fixing device 10 including the fixing cleaning roller 31 is used at a high temperature, the toner accumulated on the fixing cleaning roller 31 is melted by heat and is reversely transferred to the pressure roller 25. Occurs.
Since the toner of the present invention has improved low-temperature fixability, even if the surface temperature of the fixing roller 21 is used within the above range, a good image can be stably provided without causing fixing failure. Can do.

  EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited thereto. In the following description, “parts” and “%” are based on weight unless otherwise specified.

Production Example 1
[Synthesis Example of Unmodified Polyester (A)]
Add 378 parts of bisphenol A ethylene oxide 2-mole adduct, 402 parts of bisphenol A propylene oxide 2-mole adduct, 100 parts of isophthalic acid, 205 parts of terephthalic acid and 2 parts of dibutyltin oxide, and polycondensate at 230 ° C for 6 hours under normal pressure. And then reacted for 5 hours while dehydrating at a reduced pressure of 10 to 15 mmHg to obtain a low molecular weight polyester having Mn2800, Mw5100, OHV = 53, AV = 1.2.

Production Example 2
[Synthesis example of masterbatch resin]
1200 parts of water, carbon black (Printex3 made 5 de grasses) 54 parts [DBP oil absorption amount = 42ml / 100mg, pH = 9.5], 120 parts of low molecular weight polyester resin obtained by the manufacturing Zorei 1 addition, a pressure kneader The mixture was kneaded at 150 ° C. for 30 minutes using two rolls, rolled and cooled, and pulverized with a pulverizer to obtain a carbon black masterbatch resin.

Production Example 3
[Synthesis example of blocked amine products]
30 parts of isophoronediamine and 70 parts of methyl ethyl ketone were charged into a reaction vessel equipped with a stir bar and a thermometer, and reacted at 50 ° C. for 5 hours to obtain an amine blocked product (BR).

Production Example 4
[Preparation of unmodified polyester (A) solution]
In a beaker, add 32 parts of carbon black masterbatch resin, 50 parts of ethyl acetate solution of carnauba wax (wax concentration 10%) and 54 parts of ethyl acetate wet-dispersed with a bead mill until the average particle size becomes 0.5 μm and uniformly disperse. Stir until Furthermore, 62 parts of unmodified polyester (A) and 11.2 parts of blocked amine product (BR) were mixed to obtain a resin / colorant adjusting solution (1) having a solid content concentration of 50%. The viscosity of the adjustment liquid (1) was 500 mPa · s / 25 ° C.

Production Example 5
[Synthesis of Precursor Polyester (B1)]
809 parts of bisphenol A propylene oxide 3 mol adduct, 196 parts of terephthalic acid, 44 parts of adipic acid, 5.8 parts of trimellitic anhydride and dibutyltin oxide in a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introducing pipe 2 parts were added, reacted at 230 ° C. at normal pressure for 8 hours, and further reacted for 5 hours while dehydrating at a reduced pressure of 10 to 15 mmHg to obtain a precursor polyester (B1) of OHV52 and AV0.8. The weight average molecular weight Mw of (B1) was 10200, and the glass transition point Tg was 30.2 ° C.

Production Example 6
[Synthesis of Secondary Modified Prepolymer (D1)]
409 parts of the precursor polyester (B1) described in Production Example 5 and 495 parts of ethyl acetate were placed in a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, dissolved with stirring at room temperature, and then 95. 5 parts were added and reacted at 80 ° C. for 18 hours to obtain an ethyl acetate solution (solid content concentration 50.5%) of the primary modified prepolymer (C1). Furthermore, 0.4 parts of water and 50 parts of ethyl acetate were added and reacted at 80 ° C. for 18 hours to obtain an ethyl acetate solution (solid content concentration 48%) of the secondary modified prepolymer (D1).
The secondary modified prepolymer (D1) solution contains a part of the unreacted primary modified prepolymer (C1). The viscosity of (C1) was 1,100 mPa · s / 25 ° C., the viscosity of the solution (D1) was 800 mPa · s / 25 ° C., and the isocyanate content was 1.52%.

<Example 1>
[Synthesis of base particles (1)]
In a beaker, 100 parts of the unmodified polyester (A) solution described in Production Example 4 and 10 parts of the secondary modified prepolymer (D1) solution described in Production Example 6 were charged, and mixed with a disper at 4,000 rpm for 1 minute.
After adding 165 parts of water and 3 parts of sodium dodecylnaphthalene sulfonate to this beaker, using a TK homomixer (manufactured by Tokushu Kika), mixing at 25 ° C. for 1 minute at a rotational speed of 12000 rpm, the emulsion dispersion (X )
100 parts of this emulsified dispersion (X) was transferred to a stainless steel Kolben equipped with a stirring blade, and the ethyl acetate was removed under reduced pressure (10 kPa) while stirring until the ethyl acetate concentration in the emulsion became 1%.
Centrifugation of 100 parts of this emulsified liquid, and then adding 60 parts of water to the recovered cake and centrifuging and solid-liquid separation was repeated 5 times, followed by drying at 35 ° C. for 48 hours to form base particles (1) Got. Table 1 shows the physical property values of the base particles (1).

<Example 2>
Except for changing [Precursor polyester (B1)] to [Precursor polyester (B2)] and [Secondary modified prepolymer (D1)] to [Secondary modified prepolymer (D2)], Examples In the same manner as in No. 1, mother particles (2) were obtained. The physical property values of (2) are shown in Table 1.

Production Example 7
[Synthesis of Precursor Polyester (B2)]
Other than using 730 parts of bisphenol A propylene oxide 3 mol adduct, 65 parts bisphenol A ethylene oxide 2 mol adduct, 234 parts terephthalic acid, 23 parts adipic acid, 6.1 parts trimellitic anhydride and 2 parts dibutyltin oxide Obtained the precursor polyester (B2) of OHV43 and AV0.7 in the same manner as in Production Example 5.
The weight average molecular weight Mw of this precursor polyester (B2) was 13300, and the glass transition point Tg was 35.0 degreeC.

Production Example 8
[Synthesis of secondary modified prepolymer (D2)]
An ethyl acetate solution of the primary modified prepolymer (C2) in the same manner as in Production Example 6 except that 422 parts of polyester (B2), 495 parts of ethyl acetate and 83.4 parts of isophorone diisocyanate described in Production Example 6 were used. Solid content concentration 50.5%) was obtained. Furthermore, an ethyl acetate solution (solid content concentration 47%) of the secondary modified prepolymer (D2) was obtained in the same manner as in Production Example 6 except that 0.6 parts of water and 75 parts of ethyl acetate were used.
The secondary modified prepolymer (D2) solution contains a part of the unreacted primary modified prepolymer (C2). The viscosity of (C2) was 1,600 mPa · s / 25 ° C., the viscosity of the solution (D2) was 720 mPa · s / 25 ° C., and the isocyanate content was 1.28%.

<Example 3>
Except for changing [Precursor Polyester (B1)] to [Precursor Polyester (B3)] and [Secondary Modified Prepolymer (D1)] to [Secondary Modified Prepolymer (D3)], Examples In the same manner as in No. 1, mother particles (3) were obtained. The physical property values of (3) are shown in Table 1.

Production Example 9
[Synthesis of Precursor Polyester (B3)]
649 parts of bisphenol A propylene oxide 3 mol adduct, 70 parts of bisphenol A propylene oxide 2 mol adduct, 65 parts of bisphenol A ethylene oxide 2 mol adduct, 234 parts of terephthalic acid, 37 parts adipic acid, trimellitic anhydride 6.5 A polyester (B3) of OHV32 and AV1.4 was obtained in the same manner as in Production Example 5, except that 2 parts and 2 parts of dibutyltin oxide were used.
The weight average molecular weight Mw of (B3) was 19200, and the glass transition point Tg was 40.0 ° C.

Production Example 10
[Synthesis of secondary modified prepolymer (D3)]
The ethyl acetate solution of the primary modified prepolymer (C3) was prepared in the same manner as in Production Example 6 except that 438 parts of polyester (B3) described in Production Example 9 and 495 parts of ethyl acetate and 67.3 parts of isophorone diisocyanate were used. Solid content concentration 50.5%) was obtained. Furthermore, an ethyl acetate solution (solid content concentration 45%) of the secondary modified prepolymer (D3) was obtained in the same manner as in Production Example 6, except that 0.4 part of water and 125 parts of ethyl acetate were used.
The secondary modified prepolymer (D3) solution contains a part of the unreacted primary modified prepolymer (C3). The viscosity of the (C3) was 2,800 mPa · s / 25 ° C., the viscosity of the solution (D3) was 660 mPa · s / 25 ° C., and the isocyanate content was 1.15%.

<Comparative Example 1>
Except for changing [precursor polyester (B1)] to [precursor polyester (B4)] and [secondary modified prepolymer (D1)] to [secondary modified prepolymer (D4)], Examples In the same manner as in No. 1, mother particles (4) were obtained. The physical property values of (4) are shown in Table 1.

Comparative production example 1
[Synthesis of Precursor Polyester (B4)]
Except for using 81 parts of bisphenol A propylene oxide 2 mol adduct, 681 parts of bisphenol A ethylene oxide 2 mol adduct, 275 parts of terephthalic acid, 7 parts of adipic acid, 22 parts of trimellitic anhydride and 2 parts of dibutyltin oxide, A precursor polyester (B4) of OHV54 and AV0.9 was obtained in the same manner as in Production Example 5.
The (B4) had a weight average molecular weight Mw of 9,200 and a glass transition point Tg of 54.3 ° C.

Comparative production example 2
[Synthesis of secondary modified prepolymer (D4)]
An ethyl acetate solution of the primary modified prepolymer (C4) in the same manner as in Production Example 6 except that 404 parts of the precursor polyester (B4) described in Comparative Production Example 1, 495 parts of ethyl acetate and 101 parts of isophorone diisocyanate were used. (Solid concentration 50.5%) was obtained. Furthermore, an ethyl acetate solution (solid content concentration 45%) of the secondary modified prepolymer (D4) was obtained in the same manner as in Production Example 6 except that 0.1 part of water and 125 parts of ethyl acetate were used.
The secondary modified prepolymer (D4) solution contains a part of the unreacted primary modified prepolymer (C4). The viscosity of the solution (C4) was 830 mPa · s / 25 ° C., the viscosity of the solution (D4) was 350 mPa · s / 25 ° C., and the isocyanate content was 1.38%.

<Comparative example 2>
Except for changing [Precursor polyester (B1)] to [Precursor polyester (B5)] and [Secondary modified prepolymer (D1)] to [Secondary modified prepolymer (D5)], Examples In the same manner as in No. 1, mother particles (5) were obtained. The physical property values of (5) are shown in Table 1.

Comparative production example 3
[Synthesis of Precursor Polyester (B5)]
Bisphenol A propylene oxide 3 mol adduct 415 parts, bisphenol A propylene oxide 2 mol adduct 214 parts, bisphenol A ethylene oxide 2 mol adduct 134 parts, terephthalic acid 260 parts, adipic acid 20 parts, trimellitic anhydride 3.6 The precursor polyester (B5) of OHV20 and AV1.8 was obtained in the same manner as in Production Example 5, except that 2 parts and 2 parts of dibutyltin oxide were used.
The (B5) had a weight average molecular weight Mw of 76000 and a glass transition point Tg of 59.6 ° C.

Comparative production example 4
[Synthesis of secondary modified prepolymer (D5)]
An ethyl acetate solution of the primary modified prepolymer (C5) in the same manner as in Production Example 6 except that 457 parts of the precursor polyester (B5) described in Comparative Production Example 3, 495 parts of ethyl acetate and 48 parts of isophorone diisocyanate were used. (Solid concentration 50.5%) was obtained. Furthermore, an ethyl acetate solution (solid concentration 45%) of the secondary modified prepolymer (D5) was obtained in the same manner as in Production Example 6 except that 0.1 part of water and 10 parts of ethyl acetate were used.
The secondary modified prepolymer (D5) solution contains a part of the unreacted primary modified prepolymer (C5). The viscosity of the (C5) was 3,800 mPa · s / 25 ° C., the viscosity of the solution (D5) was 3,600 mPa · s / 25 ° C., and the isocyanate content was 1.05%.

Next, with respect to 100 parts of the base particles (1) to (5) of the obtained colored powder, 0.25 part of a charge control agent (Bontron E-84 manufactured by Orient Chemical Co., Ltd.) was added to a Q-type mixer (Mitsui Mining Co., Ltd.). The peripheral speed of the turbine type blades was set to 50 m / sec, the 2-minute operation and the 1-minute pause were performed for 5 cycles, and the total treatment time was 10 minutes.
Further, 0.5 part of hydrophobic silica (H2000, manufactured by Clariant Japan) was added, mixed for 30 seconds at a peripheral speed of 15 m / sec, and suspended for 1 minute for 5 cycles to obtain black toners a to e.

[Example of carrier production]
Silicone resin (organostraight silicone) 100 parts Toluene 100 parts γ- (2-Aminoethyl) aminopropyltrimethoxysilane 5 parts Carbon black 10 parts The above mixture was dispersed with a homomixer for 20 minutes to prepare a coating layer forming solution. This coat layer forming liquid was coated on the surface of 1,000 parts of spherical magnetite having a particle diameter of 50 μm using a fluid bed type coating apparatus to obtain a magnetic carrier A.

The toner a to e4 parts and the magnetic carrier A 96 parts were mixed with a turbula mixer to prepare two-component developers 1 to 5 and evaluated as follows.
The evaluation results are also shown in Table 2.

The evaluation relating to Table 2 was performed as follows.
As an image forming apparatus, a Ricoh Co., Ltd. imageio NEO 451 was used, and Ricoh's My Recycle 100W paper was set on this, and a copying test was performed.
(Cold offset evaluation)
With this image forming apparatus, the fixing temperature was set to 160 ° C., A4 of the dedicated chart (6% area ratio) was printed on both sides and continuously running, and the presence or absence of cold offset was visually evaluated. The case where no cold offset was observed was evaluated as “◯”, and the case where the cold offset was confirmed was evaluated as “×”.
(Hot offset evaluation)
In this image forming apparatus, the fixing temperature was set to 180 ° C., A4 of a dedicated chart (6% area ratio) was printed on both sides and continuously running, and the presence or absence of hot offset was visually evaluated. The case where no hot offset was observed was evaluated as “◯”, and the case where it was confirmed was evaluated as “×”.
(Cleanability evaluation)
With this image forming apparatus, the fixing temperature was set to 170 ° C., A4 of the dedicated chart (6% area ratio) was printed on both sides and continuously running, and the toner with poor cleaning on the photoreceptor was visually evaluated. The case where no cleaning failure was observed was evaluated as “◯”, and the case where it was confirmed was evaluated as “×”.

  As is clear from the results in Table 2, all of Examples 1 to 3 were good results with “C” along with cold offset, hot offset, and cleaning property. On the contrary, Comparative Examples 1 and 2 did not satisfy these three simultaneously.

1 is a schematic cross-sectional view illustrating an example of an image forming apparatus according to the present invention. It is a schematic sectional view showing an example of a thermal low la scheme of fixing devices.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Photoconductor 2 Charging device 3 Exposure device 4 Developing device 5 Transfer device 6 Cleaning device 7 Document placing table 9 Paper feeding device 10 Fixing device 21 Fixing rollers 22, 27 Elastic layer 23 Resin surface layer 24 Heating device (heater)
25 Pressure roller 26, 30 Core metal 28 Release layer 29 Temperature detection means 31 Fixing cleaning roller 40 Image forming apparatus N Fixing nip P Transfer paper

Claims (21)

A toner comprising at least a colorant and a binder resin,
The toner includes at least an unmodified polyester resin solution α containing an unmodified polyester (A),
A secondary modified prepolymer (D) obtained by a first extension reaction of a prepolymer (C) obtained by using polyester as a precursor (B) and at least a primary modification of the precursor (B), and the primary modification Modified polyester resin solution β containing prepolymer (C),
In a toner obtained by granulating an oil phase obtained by mixing in an aqueous medium,
A toner in which the viscosity ηα of the unmodified polyester resin solution α and the viscosity ηβ of the modified polyester resin solution β satisfy the following formula:
ηα ≦ ηβ ≦ 2 × ηα (Formula 1) The toner according to claim 1.
The primary modified prepolymer (C) has a site capable of reacting with an active hydrogen group,
A toner characterized by producing the secondary modified prepolymer (D) by a first extension reaction with a compound (E1) having an active hydrogen group. The toner according to claim 1 or 2,
The toner includes a binder composed of a primary modified prepolymer (C) and a secondary modified prepolymer (D) having a site capable of reacting with an active hydrogen group and a compound (E2) having an active hydrogen group in an organic solvent. An oil phase obtained by dissolving or dispersing a toner composition containing components is dispersed in an aqueous medium to obtain a dispersion, and the primary modification having a site capable of reacting with the active hydrogen group in the dispersion In the dispersion liquid, toner particles are formed by a second extension reaction in which the prepolymer (C) and the secondary modified prepolymer (D) are extended and / or cross-linked with the compound (E2) having the active hydrogen group. A toner produced through a step of removing the organic solvent. The toner according to any one of claims 1 to 3,
The functional group contained in the primary modified prepolymer (C) is an isocyanate group. In the toner according to any one of claims 1 to 4,
The toner, wherein the secondary modified prepolymer (D) is obtained by a first extension reaction in which the primary modified polyester and water are reacted. The toner according to any one of claims 1 to 5,
The primary modified prepolymer (C) and / or the secondary modified prepolymer (D) is crosslinked and / or extended by a urea reaction with the compound (E2) having an active hydrogen group. toner. The toner according to any one of claims 1 to 6,
The toner according to claim 1, wherein the precursor (B) has a glass transition point Tg of 30 to 60 ° C. The toner according to any one of claims 1 to 7,
The toner has a glass transition point Tg in the range of 40 to 55 ° C. The toner according to any one of claims 1 to 8,
The toner according to claim 1, wherein the unmodified polyester (A) has an acid value of 0.5 to 40 KOHmg / g . The toner according to claim 1,
The toner according to claim 1, wherein the unmodified polyester (A) has a hydroxyl value of 0.5 to 80 KOHmg / g . The toner according to any one of claims 1 to 10,
The toner has an average circularity of 0.90 to 0.98 . The toner according to any one of claims 1 to 11,
The toner has a volume average particle diameter of 3.0 to 8.0 μm and a ratio (Dv / Dn) of the volume average particle diameter (Dv) to the number average particle diameter (Dn) of 1.00 to 1.40. Toner characterized by being in range . The toner according to any one of claims 1 to 12,
The toner is used by mixing with a magnetic carrier coated with a resin. The toner according to any one of claims 1 to 13,
The toner, wherein the colorant is composed of at least yellow, magenta, cyan, and black . A latent image carrier for carrying a latent image;
Charging means for uniformly charging the surface of the latent image carrier;
Exposure means for exposing the surface of the charged latent image carrier on the basis of image data and writing an electrostatic latent image;
Developing means for supplying toner to the electrostatic latent image formed on the surface of the latent image carrier to visualize it;
Transfer means for transferring a visible image on the surface of the latent image carrier to a recording member;
In an image forming apparatus including a fixing unit that fixes a visible image on a recording member,
The fixing unit includes a fixing roller for fixing a visible image on a recording member by applying heat and / or pressure, and a fixing cleaning roller for removing residual toner on the fixing roller,
The toner used in the developing unit includes at least a colorant and a binder resin, and includes at least an unmodified polyester resin solution α containing an unmodified polyester (A) and a polyester as a precursor (B And at least a secondary modified prepolymer (D) obtained by a first extension reaction of a prepolymer (C) obtained by primary modification of the precursor (B), and the primary modified prepolymer (C). A toner obtained by granulating an oil phase obtained by mixing a modified polyester resin solution β in an aqueous medium, the viscosity ηα of the unmodified polyester resin solution α, and the modified polyester resin The viscosity ηβ of the solution β satisfies the following formula
An image forming apparatus.
ηα ≦ ηβ ≦ 2 × ηα (Formula 1) The image forming apparatus further uses the toner according to claim 2.
An image forming apparatus. The image forming apparatus according to claim 15 or 16,
The image forming apparatus integrally supports an image carrier that carries an electrostatic latent image and at least a developing device that is disposed to face the image carrier that carries an electrostatic latent image. With removable process cartridge
An image forming apparatus. A charging process for uniformly charging the surface of the image carrier, an exposure process for forming an electrostatic latent image by irradiating the charged surface of the image carrier with exposure light, and an electrostatic latent image on the image carrier. The image forming process includes: a developing step of developing with a developer containing a toner to form a toner image; a transferring step of transferring the toner image on the image carrier onto the transfer paper; In the method
The fixing step includes a step of fixing a visible image on a recording member by applying heat and / or pressure with a fixing roller, and a step of removing residual toner on the fixing roller with a fixing cleaning roller. ,
The toner used in the development step includes at least a colorant and a binder resin, and includes at least an unmodified polyester resin solution α containing an unmodified polyester (A) and a polyester as a precursor (B And at least a secondary modified prepolymer (D) obtained by a first extension reaction of a prepolymer (C) obtained by primary modification of the precursor (B), and the primary modified prepolymer (C). A toner obtained by granulating an oil phase obtained by mixing a modified polyester resin solution β in an aqueous medium, the viscosity ηα of the unmodified polyester resin solution α, and the modified polyester resin The viscosity ηβ of the solution β satisfies the following formula
An image forming apparatus.
ηα ≦ ηβ ≦ 2 × ηα (Formula 1) The image forming method further uses the toner according to claim 2.
An image forming method. A method for producing a toner comprising at least a colorant and a binder resin,
The toner production method includes at least a non-modified polyester resin solution α containing an unmodified polyester (A) and a polyester as a precursor (B), and at least the precursor (B) is a primary modified prepolymer. An oil phase obtained by mixing the secondary modified prepolymer (D) obtained by the first extension reaction of (C) and the modified polyester resin solution β containing the primary modified prepolymer (C). The toner obtained by granulation in an aqueous medium, wherein the viscosity ηα of the unmodified polyester resin solution α and the viscosity ηβ of the modified polyester resin solution β satisfy the following formula:
And a method for producing the toner.
ηα ≦ ηβ ≦ 2 × ηα (Formula 1) The method for producing the toner further comprises producing the toner according to claim 2.
And a method for producing the toner.

Images