JP2013080096A - Toner and image forming device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide spherical toner having excellent cleaning property and achieving performance to be required for the toner for a high-quality image forming device.SOLUTION: The toner is formed of toner mother particles and inorganic fine particles. The toner mother particle has a sea-island structure including: a base part, as a sea part, of the mother particle comprising at least a resin component (resin and/or its precursor), a mold-releasing agent, and a coloring agent; and a protruding part, as an island part, formed of a resin fine particle on the surface of the base part. The resin component includes at least first resin. The resin fine particle is formed of second resin. The first resin and the second resin are non-crystalline resin. The volume average particle diameter of the mother particle is 4.0-7.0 μm. The average circularity of the mother particle is 0.960-0.985. On a frequency graph of circularity, the toner has a peak between the circularity of 0.87-0.93 in addition to a peak close to circularity 1 (perfect circle).

Description

  The present invention relates to a toner, a production method thereof, a developer, an image forming method using the toner, and an image forming apparatus.

  As so-called chemical toners, many core-shell toners have been proposed so far. Most of them are intended to cover the inside (core) of the toner particles so as to be wrapped with a shell so as to achieve both heat storage stability and low-temperature fixability. Alternatively, it is intended to improve the chargeability by adopting a resin having high functionality for the shell portion or reducing the influence of the colorant by forming a shell in the color toner. On the other hand, MFPs and printers, which are image forming apparatuses using electrophotography, are required to be compact and have a long service life and a high printing speed, and the demand for toner is becoming strict. However, a toner having high durability and satisfying chargeability and low-temperature fixability required for such an image forming apparatus has not been realized. In the toner of the present invention, the shell portion is not a coating layer, but the resin fine particles are adhered so as to be partially embedded in the core portion while maintaining the shape of the fine particles, thereby improving low temperature fixing while improving heat resistant storage stability. Can be compatible. Furthermore, since it is in the form of fine particles rather than a coating layer, the surface area of the shell resin is increased, and the charging property is also improved.

  On the other hand, in order to achieve high image quality and high transfer rate, the effect can be obtained by making the toner particles small and spherical, but the cleaning property on the photoreceptor deteriorates, and so-called defective cleaning is caused. Easy to wake up. In order to improve the cleaning property, attempts have been made to mix amorphous particles such as inorganic fine particles and organic fine particles with a developer, or to mix irregularly pulverized toner produced in another process (Patent Document 1). : JP-A-2003-5434) (Patent Document 2: JP-A-2005-189755). In addition, there is also known a method in which only one color of the color developer is used and toner particles of a slightly smaller size are used and other colors are used by using spherical toner (Patent Document 3: Japanese Patent Application Laid-Open No. 2007-011298). Publication). However, in the above method, toners must be prepared and mixed using at least two types of manufacturing methods. As a result, toners having different methods are mixed, and charging characteristics and other characteristics are mixed. This is a problem that tends to cause problems due to unevenness.

  Therefore, in view of the above-described prior art, the toner of the present invention is formed by adhering the shell part of the toner particle so that the resin fine particle is partially buried in the core while maintaining the shape of the fine particle, not the coating layer. Low temperature fixing can be achieved while improving heat-resistant storage stability. Furthermore, since it is in the form of fine particles rather than a coating layer, the surface area of the shell resin is increased, and the charging property is also improved. Further, according to the method of the present invention, it has been found out that an irregularly shaped toner can be intentionally produced at the same time while maintaining a sharp particle size distribution by controlling when the resin fine particles are adhered. Thus, although the toner of the present invention is a spherical toner, it has excellent cleaning properties and can achieve the performance required for a toner for an image forming apparatus with high image quality.

That is, the said subject is solved by following (1)-(10) of this invention.
(1) A toner comprising toner base particles and inorganic fine particles, wherein the base particles include at least a basic part of base particles containing a resin component (resin and / or precursor thereof), a release agent, and a colorant, The surface of the basic portion is composed of convex portions formed of resin fine particles, and has a sea-island structure in which the basic portion is the sea and the convex portions are islands, and the resin component includes at least the first resin, and the resin fine particles Is made of a second resin, the first resin and the second resin are non-crystalline resins, the base particles have a volume average particle size of 4.0 to 7.0 μm, and the average circularity of the base particles Is a toner having a circularity of 0.87 to 0.93 on the frequency graph of circularity, in addition to a peak close to circularity 1 (perfect circle) on the frequency graph of circularity.
(2) The toner according to item (1), wherein the resin constituting the basic portion contains a polyester resin, and the resin fine particles are made of a vinyl resin.
(3) The toner according to item (1) or (2), wherein the basic part further contains a modified polyester resin having a urethane or / and urea group.
(4) A toner container filled with the toner according to any one of (1) to (3).
(5) A developer containing the toner according to any one of (1) to (3).
(6) A developer carrying member for carrying the developer to be supplied to the latent image carrier on the surface, a developer supplying member for supplying the developer to the surface of the developer carrying member, and a developer container for containing the developer. The developing device is characterized in that the developer described in the item (5) is stored in a developer container.
(7) In a process cartridge in which a latent image carrier and a developing device that develops at least a latent image on the latent image carrier with a developer are integrated and detachable from an image forming apparatus, the developing device includes (6) The process cartridge according to the item (6).
(8) A latent image carrier that carries a latent image, a charging means that uniformly charges the surface of the latent image carrier, and the surface of the charged latent image carrier is exposed based on image data, and electrostatic latent An exposure unit for writing an image, a developing unit for supplying toner to the electrostatic latent image formed on the surface of the latent image carrier to make it visible, and a visible image on the surface of the latent image carrier are transferred to the transfer target An image forming apparatus comprising: a transfer unit; and a fixing unit that fixes a visible image on a transfer target, wherein the developing unit is the developing device described in (6) above. Forming equipment.
(9) A charging step for uniformly charging the surface of the latent image carrier, an exposure step for exposing the surface of the charged latent image carrier based on image data and writing an electrostatic latent image, and a developer carrier Forming a developer layer having a predetermined layer thickness by the developer layer regulating member, developing the electrostatic latent image formed on the surface of the latent image carrier via the developer layer, and developing the visible image; A transfer step of transferring a visible image on the surface of the latent image carrier to a transfer target, and a fixing step of fixing the visible image on the transfer target, as described in (5) above as a developer. An image forming method using the developer.
(10) The method for producing a toner as described in any one of (1) to (3) above, comprising at least the following steps (i) to (iv):
(I) a step of dissolving or dispersing a matrix-forming material containing at least a resin material and / or a precursor thereof comprising a resin component, a release agent and a colorant in an organic solvent,
(Ii) a step of suspending the dissolved product or dispersion in an aqueous medium to produce a core particle dispersion that is a basic part of toner base particles;
(Iii) adding a resin fine particle dispersion to the core particle dispersion to adhere the resin fine particles to the core particle surface;
(Iv) A step of removing the organic solvent.
Further, the present invention includes, as a preferred embodiment thereof, the following toners (1-2) to (11-2) and a method for producing the toner.
(1-2) The frequency (%) of the peak between the circularity of 0.87 and 0.93 is 1.0% or more (FPIA-3000 channel), the item (1) The toner described in 1.
(1-3) The item (1), wherein the sum of the peak frequencies (%) between the circularities of 0.87 to 0.93 (0.873 to 0.933) is 3% or more. Or the toner according to (1-1).
(1-4) Any of (1) to (1-3) above, wherein the toner has a particle size distribution (volume average / number average) Dv / Dn of 1.0 to 1.2. The toner described in 1.
(1-5) The peak between the circularity of 0.87 and 0.93 is formed by a combination of a plurality of substantially spherical particles. The toner according to any one of items 4).
(2-2)
The toner according to any one of (1) to (1-5), wherein the base particles contain a crystalline polyester resin.
(2-3) The above-mentioned (1), wherein the vinyl resin is a vinyl resin obtained by polymerizing a monomer mixture containing 80 to 100% by weight of an aromatic compound having a vinyl polymerizable functional group. Item 2. The toner according to any one of Items (2-2).
(2-4)
Item (1) to (2-3), wherein the vinyl resin is a vinyl resin obtained by polymerizing an aromatic monomer having a vinyl polymerizable functional group, and the monomer is styrene. The toner according to any one of Items.
(2-5)
The toner according to any one of (1) to (2-4) above, wherein the vinyl resin is obtained by polymerizing styrene and butyl acrylate, and styrene is 80% by weight or more. .
(3-2) The modified polyester resin is a modified polyester resin in which the polyester resin is chain-extended or / and cross-linked by a reaction between a modified polyester resin having an isocyanate group at the terminal and amines. The toner according to item (3).
(10-2) The toner production method as described in (10) above, wherein a surfactant is contained in the aqueous medium.
(10-3) The toner according to (10) or (10-2), wherein the resin fine particle dispersion does not contain an organic solvent and the fine particles are dispersed in a solid state. Manufacturing method.
(10-4) The method for producing a toner according to any one of (10) to (10-3), wherein the organic solvent is completely removed after the addition of the resin fine particle dispersion.
(10-5) In the step (iii) of adding the resin fine particle dispersion and attaching the resin fine particles to the core particles, the dispersed core particles contain 10% by mass to 70% by mass of an organic solvent. The method for producing a toner according to any one of (10) to (10-4), wherein:
(10-6) The toner particle that forms a peak close to the circularity of 1 (perfect circle) and the toner particle that forms a peak between circularity of 0.87 and 0.93 are produced simultaneously. ) To (10-5).
(11) An inorganic fine particle is externally added after washing and drying a base of one production lot produced by the toner production method according to any one of (10) to (10-5). A toner obtained through a series of steps and comprising toner base particles and inorganic fine particles, the base particles comprising at least a base portion of base particles containing at least a resin component, a release agent, and a colorant, and a surface of the base portion. And having a sea-island structure composed of convex portions formed of resin fine particles, wherein the basic portion is the sea and the convex portions are the islands, the resin component includes at least a first resin, and the resin fine particles are second The first resin and the second resin are non-crystalline resins, the base particles have a volume average particle size of 4.0 to 7.0 μm, and the base particles have an average circularity of 0.960. ~ 0.985, frequent circularity On the graph, separate from the peak close to the circularity of 1 (true circle), the toner is characterized by having a further peak between circularity from 0.87 to 0.93.
(11-2) characterized in that it contains toner particles that form a peak close to a circularity of 1 (perfect circle) and toner particles that form a peak between circularity of 0.87 and 0.93. The toner according to item (11).

  As will be understood from the following detailed and specific description, the toner of the present invention is excellent in that it is a spherical toner, has excellent cleaning properties, and can achieve the performance required for a toner for an image forming apparatus with high image quality. There is an effect.

In Example 1, it is the figure which showed the average circularity measurement result by the flow type particle image analyzer FPIA-3000S. FIG. 3 is an explanatory diagram illustrating a main part of an embodiment of an image forming apparatus in which the electrostatic image developing toner of the present invention is used. FIG. 3 is an explanatory diagram illustrating a configuration of a fixing device used in an image forming apparatus in which the electrostatic charge image developing toner of the present invention is used. It is explanatory drawing which shows the other example of the image forming apparatus in which the toner for electrostatic image development of this invention is used. It is explanatory drawing which shows the other example of the image forming apparatus in which the toner for electrostatic image development of this invention is used. It is explanatory drawing which shows the process cartridge using the toner for electrostatic image development of this invention.

The present invention will be described in detail.
As described above, the toner of the present invention includes a basic portion (sea portion) containing at least a resin, a release agent, and a colorant, and a convex portion (island portion) made of resin fine particles formed on the surface of the basic portion. It has a sea-island structure.
The resin constituting the sea part is not particularly limited, but includes at least the first resin, while the resin fine particles are composed of the second resin, and the first resin constituting the sea part is polyester-based. A resin is preferably used, and a vinyl resin (radically polymerizable) resin is preferably used as the second resin for the resin fine particles constituting the island portion. By using a polyester-based resin (resin having a polyester skeleton), good storage stability, offset resistance and low-temperature fixability can be obtained. Examples of the resin having a polyester skeleton include a polyester resin and a block polymer of a polyester and a resin having another skeleton, but the uniformity of colored resin particles obtained by using a polyester resin (including a modified polyester) is higher. preferable. In addition to the resin constituting the sea part, there are other resins derived from a colorant masterbatch, a second resin for controlling fineness, for controlling high humidity stability, and for resin fine particles lacking compatibility. On the other hand, it does not interfere with the mixing of other resins that may be added for various reasons, such as not hindering surface adhesion due to excessive repellency, but the amount of these added is the total resin constituting the sea part 50% by weight or less is preferable in the amount

Examples of the polyester resin include ring-opening polymers of lactones, polycondensation products of hydroxycarboxylic acids, polycondensates of polyols and polycarboxylic acids, and the like. Polycondensates are preferred.
The peak molecular weight of the polyester resin is usually 1000 to 30000, preferably 1500 to 10000, and more preferably 2000 to 8000. When it is 1000 or more, heat-resistant storage stability is good, and when it is 30000 or less, low-temperature fixability is good.
The glass transition temperature of the polyester resin is in the range of 35 to 80 ° C, preferably 40 to 70 ° C, more preferably 45 to 65 ° C. When the temperature is 35 ° C. or higher, the toner is not deformed when it is placed in a high temperature environment such as midsummer, and the toner particles do not adhere to each other and cannot behave as original particles. Further, the fixing property is improved when the temperature is 80 ° C. or lower.

The toner of the present invention includes, for example, (i) a step of dissolving or dispersing a matrix-forming material containing a resin component and / or a precursor thereof, a mold release agent, and a colorant in an organic solvent; A step of suspending a solution or dispersion in an aqueous medium to produce a core particle dispersion that is a basic part of toner base particles;
It can be obtained by (iii) adding a resin fine particle dispersion to the core particle dispersion to attach the resin fine particles to the surface of the core particle, and (iv) removing the organic solvent.

<Polyester resin>
Examples of the polyester resin used in the present invention include the following polycondensates of polyol (1) and polycarboxylic acid (2), and any of them can be used. May be used.

(Polyol)
Examples of the polyol (1) 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, Ethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc.); alicyclic diols (1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.); bisphenols (bisphenol A, bisphenol F, 4,4′-dihydroxybiphenyls such as bisphenol S, 3,3′-difluoro-4,4′-dihydroxybiphenyl, etc .; bis (3-fluoro-4-hydroxyphenyl) Nyl) methane, 1-phenyl-1,1-bis (3-fluoro-4-hydroxyphenyl) ethane, 2,2-bis (3-fluoro-4-hydroxyphenyl) propane, 2,2-bis (3 Bis (5-difluoro-4-hydroxyphenyl) propane (also known as: tetrafluorobisphenol A), 2,2-bis (3-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane, etc. Hydroxyphenyl) alkanes; bis (4-hydroxyphenyl) ethers such as bis (3-fluoro-4-hydroxyphenyl) ether); alkylene oxides of the above alicyclic diols (ethylene oxide, propylene oxide, butylene oxide, etc.) Adducts; alkylene oxides of the above bisphenols (ethylene oxide) De, propylene oxide, and the like butylene oxide, 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.

In addition, trihydric or higher polyhydric aliphatic alcohols (glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, etc.); trihydric or higher phenols (trisphenol PA, phenol novolac, cresol novolac, etc.) ); Alkylene oxide adducts of the above trihydric or higher polyphenols.
In addition, the said polyol can be used individually by 1 type or in combination of 2 or more types, It is not limited to the above.

(Polycarboxylic acid)
Examples of the polycarboxylic acid (2) 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, Naphthalenedicarboxylic acid, 3-fluoroisophthalic acid, 2-fluoroisophthalic acid, 2-fluoroterephthalic acid, 2,4,5,6-tetrafluoroisophthalic acid, 2,3,5,6-tetrafluoroterephthalic acid, 5- Trifluoromethylisophthalic acid, 2,2-bis (4-carboxyphenyl) hexafluoropropane, 2,2-bis (4-carboxyphenyl) hexafluoropropane, 2,2-bis (3-carboxyphenyl) hexafluoropropane 2,2′-bis (trifluoromethyl) -4,4′- Phenyldicarboxylic acid, 3,3′-bis (trifluoromethyl) -4,4′-biphenyldicarboxylic acid, 2,2′-bis (trifluoromethyl) -3,3′-biphenyldicarboxylic acid, hexafluoroisopropylidene Dendiphthalic anhydride, etc.).

Of these, preferred are alkenylene dicarboxylic acids having 4 to 20 carbon atoms and aromatic dicarboxylic acids having 8 to 20 carbon atoms. Further, polyvalent polycarboxylic acids having 3 or more valences are aromatic polycarboxylic acids having 9 to 20 carbon atoms (trimellitic acid, pyromellitic acid, etc.), and acid anhydrides or lower alkyl esters (methyl esters, ethyl esters) described above. , Isopropyl ester, etc.) may be used to react with polyol (1).
In addition, the said polycarboxylic acid can be used individually by 1 type or in combination of 2 or more types, It is not limited to the above.

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

(Molecular weight of polyester resin)
The peak molecular weight is usually 1000-30000, preferably 1500-10000, more preferably 2000-8000. If it is less than 1000, the heat-resistant storage stability is deteriorated.

<Modified polyester resin>
The binder resin used in the present invention may contain a modified polyester resin having urethane or / and urea groups for adjusting viscoelasticity. The content of the modified polyester resin having a urethane or / and urea group is preferably 20% or less, more preferably 15% or less, and still more preferably 10% or less in the binder resin. When the content ratio exceeds 20%, the low-temperature fixability is deteriorated. The modified polyester resin having a urethane or / and urea group may be directly mixed with a binder resin, but from the viewpoint of manufacturability, a relatively low molecular weight modified polyester resin having an isocyanate group at the terminal (hereinafter referred to as “polyester resin”). And an amine that reacts with the binder resin is mixed with the binder resin, and during the granulation / after granulation, chain extension or / and cross-linking reaction is carried out to form the urethane or / and urea group. It is preferable to have a modified polyester resin. By doing so, it becomes easy to contain a relatively high molecular weight modified polyester resin for adjusting the viscoelasticity.

(Prepolymer)
Examples of the prepolymer having an isocyanate group include a polycondensate of the polyol (1) and the polycarboxylic acid (2) and a polyester having an active hydrogen group that is further reacted with a polyisocyanate (3). . Examples of the active hydrogen group possessed by the polyester include hydroxyl groups (alcoholic hydroxyl groups and phenolic hydroxyl groups), amino groups, carboxyl groups, mercapto groups, and the like. Among these, alcoholic hydroxyl groups are preferred.

(Polyisocyanate)
Examples of the polyisocyanate (3) include aliphatic polyisocyanates (tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-diisocyanatomethylcaproate, etc.); alicyclic polyisocyanates (isophorone diisocyanate, cyclohexylmethane diisocyanate, etc.); Diisocyanates (tolylene diisocyanate, diphenylmethane diisocyanate, etc.); aromatic aliphatic diisocyanates (α, α, α ′, α′-tetramethylxylylene diisocyanate, etc.); isocyanurates; the polyisocyanates as phenol derivatives, oximes, caprolactam And a combination of two or more of these.

(Ratio of isocyanate group to hydroxyl group)
The ratio of the polyisocyanate (3) is usually 5/1 to 1/1, preferably 4 /, as the equivalent ratio [NCO] / [OH] of the isocyanate group [NCO] and the hydroxyl group [OH] of the polyester having a hydroxyl group. 1 to 1.2 / 1, more preferably 2.5 / 1 to 1.5 / 1. When [NCO] / [OH] exceeds 5, low-temperature fixability deteriorates. If the molar ratio of [NCO] is less than 1, the urea content in the modified polyester will be low, and the offset resistance will deteriorate. The content of the polyisocyanate (3) component in the prepolymer (A) having an isocyanate group at the terminal is usually 0.5 to 40% by mass, preferably 1 to 30% by mass, more preferably 2 to 20% by mass. It is. If it is less than 0.5% by mass, the offset resistance deteriorates. On the other hand, if it exceeds 40% by mass, the low-temperature fixability deteriorates.

(Number of isocyanate groups in the prepolymer)
The number of isocyanate groups contained per molecule in the prepolymer (A) having an isocyanate group is usually 1 or more, preferably 1.5 to 3 on average, more preferably 1.8 to 2.5 on average. It is. When the number is less than 1 per molecule, the molecular weight of the modified polyester after chain extension and / or crosslinking becomes low, and offset resistance deteriorates.

(Chain extension and / or cross-linking agent)
In the present invention, amines can be used as chain extenders and / or crosslinkers. As amines (B), diamine (B1), trivalent or higher polyamine (B2), aminoalcohol (B3), aminomercaptan (B4), amino acid (B5), and amino groups B1 to B5 blocked (B6) etc. are mentioned.

Examples of the diamine (B1) include the following.
Aromatic diamines (phenylenediamine, diethyltoluenediamine, 4,4′diaminodiphenylmethane, tetrafluoro-p-xylylenediamine, tetrafluoro-p-phenylenediamine, etc.);
Alicyclic diamines (4,4′-diamino-3,3′dimethyldicyclohexylmethane, diaminecyclohexane, isophoronediamine, etc.);
And aliphatic diamines (ethylenediamine, tetramethylenediamine, hexamethylenediamine, dodecafluorohexylenediamine, tetracosafluorododecylenediamine, etc.).

Examples of the trivalent or higher polyamine (B2) include diethylenetriamine and triethylenetetramine.
Examples of amino alcohol (B3) include ethanolamine and hydroxyethylaniline.
Examples of amino mercaptan (B4) include aminoethyl mercaptan and aminopropyl mercaptan.

Examples of the amino acid (B5) include aminopropionic acid and aminocaproic acid.
Examples of the B1 to B5 amino group blocked (B6) include ketimine compounds and oxazoline compounds obtained from the B1 to B5 amines and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.).

(Stopper)
Furthermore, if necessary, the molecular extension of the modified polyester after completion of the reaction can be adjusted by using a terminator for the chain extension and / or crosslinking reaction. Examples of the terminator include monoamines (diethylamine, dibutylamine, butylamine, laurylamine, etc.), and those blocked (ketimine compounds).

(Ratio of amino group to isocyanate group)
The ratio of amines (B) is the equivalent ratio [NCO] / [NHx] of isocyanate groups [NCO] in the prepolymer (A) having isocyanate groups and amino groups [NHx] in amines (B). 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 greater than 2 or less than 1/2, the molecular weight of the urea-modified polyester (i) becomes low and the hot offset resistance deteriorates.

<Crystalline polyester resin>
The toner of the present invention contains a crystalline polyester in order to improve low temperature fixability. Crystalline polyester is also obtained as a polycondensate of the above-mentioned polyol and polycarboxylic acid. As the polyol, an aliphatic diol is preferable, specifically ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, neopentyl glycol, 1,4-butenediol, etc. Of these, 1,4-butanediol, 1,6-hexanediol and 1,8-octanediol are preferable, and 1,6-hexanediol is more preferable. The polycarboxylic acid is preferably an aromatic dicarboxylic acid such as phthalic acid, isophthalic acid or terephthalic acid, or an aliphatic carboxylic acid having 2 to 8 carbon atoms, but an aliphatic carboxylic acid is more preferable for increasing the crystallinity. .
A crystalline resin (crystalline polyester) and an amorphous resin are distinguished from each other by thermal characteristics. The crystalline resin refers to a resin having a clear endothermic peak such as wax in DSC measurement. On the other hand, a non-crystalline resin has a gentle curve based on the glass transition.

(Resin fine particles)
As the material for the resin fine particles used in the resin fine particle dispersion for toner production of the present invention, a vinyl resin is preferably used.
Hereinafter, the vinyl resin fine particles will be described.
The resin fine particles made of a vinyl-based resin are preferably obtained by polymerizing a monomer mixture mainly containing an aromatic compound having a vinyl polymerizable functional group as a monomer.
The content of the aromatic compound having a vinyl polymerizable functional group in the monomer mixture is 80 to 100% by mass, preferably 90 to 100% by mass, more preferably 95 to 100% by mass. When the aromatic compound having a vinyl polymerizable functional group is less than 80% by mass, the chargeability of the obtained toner becomes poor.

Examples of the polymerizable functional group in the aromatic compound having a vinyl polymerizable functional group include a vinyl group, an isopropenyl group, an allyl group, an acryloyl group, and a methacryloyl group.
Specific monomers include styrene, α-methylstyrene, 4-methylstyrene, 4-ethylstyrene, 4-tert-butylstyrene, 4-methoxystyrene, 4-ethoxystyrene, 4-carboxystyrene or a metal salt thereof. Examples include 4-styrenesulfonic acid or a metal salt thereof, 1-vinylnaphthalene, 2-vinylnaphthalene, allylbenzene, phenoxyalkylene glycol acrylate, phenoxyalkylene glycol methacrylate, phenoxy polyalkylene glycol acrylate, and phenoxy polyalkylene glycol methacrylate.
Among these, it is preferable to mainly use styrene which is easily available and has excellent reactivity and high chargeability. For example, a butyl acrylate copolymer of styrene can be preferably used.

  Further, the vinyl resin used in the present invention may contain 0 to 7% by mass of a compound having a vinyl polymerizable functional group and an acid group (hereinafter also referred to as “acid monomer”) in the monomer mixture. The content of the acid monomer is preferably 0 to 4% by mass, and more preferably no acid monomer is used. When the acid monomer is used in an amount exceeding 7% by mass, the resulting vinyl resin fine particles have high dispersion stability, and thus such a vinyl resin is contained in a dispersion in which oil droplets are dispersed in an aqueous phase. Even if resin fine particles are added, they are difficult to adhere at room temperature or are easily detached even if they are attached, and they are easily removed in the process of solvent removal, washing, drying, and external addition treatment. Furthermore, when the amount of the acid monomer used is 4% by mass or less, the change in chargeability can be reduced depending on the environment in which the resulting toner is used.

Examples of the acid group in the compound having a vinyl polymerizable functional group and an acid group include carboxylic acid, sulfonyl acid, and phosphonic acid.
Examples of the compound having a vinyl polymerizable functional group and an acid group include a carboxyl group-containing vinyl monomer and a salt thereof ((meth) acrylic acid, (anhydrous) maleic acid, monoalkyl maleate, fumaric acid, monoalkyl fumarate, Crotonic acid, itaconic acid, itaconic acid monoalkyl, itaconic acid glycol monoether, citraconic acid, citraconic acid monoalkyl, cinnamic acid, etc.), sulfonic acid group-containing vinyl monomers, vinyl sulfate monoesters and salts thereof, phosphoric acid Group-containing vinyl monomers and salts thereof. Of these, (meth) acrylic acid, (anhydrous) maleic acid, monoalkyl maleate, fumaric acid, and monoalkyl fumarate are preferred.

If the compatibility of the core part with the resin is high, the desired toner surface state may not be obtained, so if the polarity and structure of the monomer mixture used and the resin of the core part are controlled in the direction of low compatibility, Good.
The solubility in the organic solvent to be used should not be unnecessarily dissolved. In the case where the particles are so dissolved that the fine particle shape cannot be maintained, as a result, a desired toner surface state may not be obtained.

Although it does not specifically limit as a method of obtaining vinyl resin fine particles, The following (a)-(f) is mentioned.
(A) The monomer mixture is reacted by a polymerization reaction such as a suspension polymerization method, an emulsion polymerization method, a seed polymerization method or a dispersion polymerization method to produce a dispersion of vinyl resin fine particles.
(B) The monomer mixture is polymerized in advance, and the resin obtained is pulverized using a mechanical pulverizer or jet pulverizer and then classified to produce resin fine particles.
(C) Resin fine particles are produced by polymerizing the monomer mixture in advance and spraying the resulting resin solution in a solvent in the form of a mist.
(D) polymerizing the monomer mixture in advance, adding a solvent to the resin solution obtained by dissolving the obtained resin in a solvent, or cooling the resin solution previously dissolved in a solvent to precipitate resin fine particles; Resin fine particles are produced by removing the solvent.
(E) A monomer solution is polymerized in advance, and a resin solution obtained by dissolving the obtained resin in a solvent is dispersed in an aqueous medium in the presence of an appropriate dispersant, and the solvent is removed by heating or decompression.
(F) A monomer mixture is polymerized in advance, an appropriate emulsifier is dissolved in a resin solution obtained by dissolving the obtained resin in a solvent, and water is added to perform phase inversion emulsification.
Among them, the method (a) is preferable because it is easy to produce and the resin fine particles can be obtained as a dispersion, and can be smoothly applied to the next step.

  In the method (a), when the polymerization reaction is performed, a dispersion stabilizer is added to the aqueous medium, or the dispersion stability of the resin fine particles obtained by polymerization can be imparted to the monomer that performs the polymerization reaction. It is preferable to add a stable monomer (so-called reactive emulsifier) or use these two means in combination to impart dispersion stability of the resulting vinyl resin fine particles. If a dispersion stabilizer or reactive emulsifier is not used, the dispersion state of the particles cannot be maintained, so the vinyl resin cannot be obtained as fine particles, or the dispersion stability of the obtained resin fine particles is low, so that the storage stability The toner particles are agglomerated during storage, or the dispersion stability of the particles in the resin fine particle adhesion process described later is reduced, so that the core particles easily aggregate and coalesce, resulting in toner particles finally obtained. Since uniformity of a diameter, a shape, a surface, etc. worsens, it is not preferable.

  Examples of the dispersion stabilizer include surfactants and inorganic dispersants. Examples of the surfactant include anionic surfactants such as alkylbenzene sulfonates, α-olefin sulfonates and phosphate esters, and alkylamine salts. Amine salt types such as amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, imidazoline, alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, pyridinium salts, alkylisoquinolinium salts, benzethonium chloride, etc. Nonionic surfactants such as quaternary ammonium salt type cationic surfactants, fatty acid amide derivatives, polyhydric alcohol derivatives, such as alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine and N-alkyl-N Amphoteric surfactants such as N- dimethyl ammonium betaine and the like. As the inorganic dispersant, tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, hydroxyapatite and the like are used.

  In the case of producing the resin fine particles in the present invention, a generally used chain transfer agent can be used for the purpose of adjusting the molecular weight. The chain transfer agent is not particularly limited, but an alkyl mercaptan chain transfer agent having a hydrocarbon group having 3 or more carbon atoms is preferably used. The alkyl mercaptan-based hydrophobic chain transfer agent having a hydrocarbon group having 3 or more carbon atoms is not particularly limited, but butanethiol, octanethiol, decanethiol, dodecanethiol, hexadecanethiol, octadecanethiol, cyclohexyl Mercaptan, thiophenol, octyl thioglycolate, octyl 2-mercaptopropionate, octyl 3-mercaptopropionate, 2-ethylhexyl ester of mercaptopropionate, 2-mercaptoethyl ester of octanoate, 1,8-dimercapto-3,6- Dioxaoctane, decane trithiol, dodecyl mercaptan and the like can be mentioned. In this case, the hydrophobic chain transfer agent may be used alone or in the form of a mixture of two or more.

  At this time, the addition amount of the chain transfer agent is not particularly limited as long as the obtained copolymer can be adjusted so as to have a desired molecular weight, but is preferably 0 with respect to the total moles of the monomer components. 0.01 to 30 parts by mass, more preferably 0.1 to 25 parts by mass. At this time, if the added amount of the chain transfer agent is less than 0.01 parts by mass, the molecular weight of the resulting copolymer becomes too large, so that the fixability is lowered or gelation occurs during the polymerization reaction. there is a possibility. On the contrary, when the addition amount of the chain transfer agent exceeds 30 parts by mass, the chain transfer agent remains in an unreacted state, and the molecular weight of the obtained copolymer is small, causing member contamination.

  The weight average molecular weight of the vinyl resin is 3,000 to 300,000, preferably 4,000 to 100,000, more preferably 5,000 to 50,000. When the weight average molecular weight is less than 3,000, the mechanical strength of the vinyl resin is weak and fragile, and the toner surface easily changes depending on the use situation depending on the application of the finally obtained toner. This is not preferable because it causes a significant change in chargeability, contamination such as adhesion to peripheral agents, and the accompanying quality problems. On the other hand, if it exceeds 300,000, the molecular ends are reduced, so that the entanglement of the molecular chain with the core particle is reduced and the adhesion to the core particle is lowered, which is not preferable.

  The glass transition temperature (Tg) of the vinyl resin is 40 ° C. or higher, preferably 50 ° C. or higher, more preferably 60 ° C. or higher. A temperature lower than 40 ° C. is not preferable because the storage stability may be deteriorated such as blocking when the finally obtained toner is stored at a high temperature.

<Colorant>
As the coloring agent of the present invention, all known dyes and pigments can be used. For example, carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), cadmium yellow, yellow iron oxide , Ocher, yellow lead, titanium yellow, polyazo yellow, oil yellow, Hansa yellow (GR, A, RN, R), pigment yellow L, benzidine yellow (G, GR), permanent yellow (NCG), Vulcan fast yellow ( 5G, R), Tartrazine Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL, Isoindolinone Yellow, Bengala, Red Dan, Lead Zhu, Cadmium Red, Cadmium Mercury Red, Antimon Zhu, Permanent Red 4R, Para Red , Fais red, parachlorol Nitroaniline Red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmine B, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Resol Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Toulouse Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake, Thioindigo red B, thioindigo maroon, oil red, quinacridone red, pyrazolone , Polyazo red, chrome vermillion, benzidine orange, perinone orange, oil orange, cobalt blue, cerulean blue, alkali blue rake, peacock blue rake, Victoria blue rake, metal-free phthalocyanine blue, phthalocyanine blue, fast sky blue, in Dunslen Blue (RS, BC), Indigo, Ultramarine Blue, Bitumen, Anthraquinone Blue, Fast Violet B, Methyl Violet Lake, Cobalt Purple, Manganese Purple, Dioxane Violet, Anthraquinone Violet, Chrome Green, Zinc Green, Chrome Oxide, Pyridian, Emerald Green, Pigment Green B, Naphthol Green B, Green Gold, Acid Green Lake, Malachite Green Lake Phthalocyanine green, anthraquinone green, titanium oxide, zinc white, lithopone and mixtures thereof can be used. The content of the colorant is usually 1 to 15% by mass, preferably 3 to 10% by mass with respect to the toner.

<Release agent>
As the release agent used in the present invention, known ones can be used, for example, polyolefin wax (polyethylene wax, polypropylene wax, etc.); long chain hydrocarbon (paraffin wax, Fischer-Tropsch wax, sazol wax, etc.); carbonyl group Examples thereof include waxes. Carbonyl group-containing waxes include polyalkanoic acid esters (carnauba wax, montan wax, trimethylolpropane tribehenate, pentaerythritol tetrabehenate, pentaerythritol diacetate dibehenate, glycerin tribehenate, 1, 18-octadecanediol distearate etc.); polyalkanol esters (tristearyl trimellitic acid, distearyl maleate etc.); polyalkanoic acid amides (ethylenediamine dibehenyl amide etc.); polyalkylamides (trimellitic acid tristearyl amide etc.) ); And dialkyl ketones (such as distearyl ketone). Of these, polyolefin waxes and long-chain hydrocarbons are preferred because of their low polarity and low melt viscosity, and paraffin wax and Fischer-Tropsch wax are particularly preferred.

<External additive>
(Inorganic fine particles)
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 nm to 2 μm, and particularly preferably 5 nm to 500 nm. 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% by mass of the toner, and particularly preferably 0.01 to 2.0% by mass. Specific examples of the inorganic fine particles include, for example, silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, tin oxide, quartz sand, clay, mica, wollastonite, diatomaceous earth. Examples include soil, chromium oxide, cerium oxide, pengala, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride.

(Polymer fine particles)
Other polymer fine particles such as polystyrene obtained by soap-free emulsion polymerization, suspension polymerization and dispersion polymerization, methacrylic acid ester and acrylic acid ester copolymer, polycondensation system such as silicon, benzoguanamine and nylon, and thermosetting resin Examples include polymer particles.

(Surface treatment of external additives)
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. .

(Cleaning aid)
Examples of the cleaning property improver for removing the developer after transfer remaining on the photoreceptor or the primary transfer medium include, for example, zinc stearate, calcium stearate, fatty acid metal salts such as stearic acid, such as polymethyl methacrylate fine particles, polystyrene fine particles, etc. And polymer fine particles produced by soap-free emulsion polymerization. The polymer fine particles preferably have a relatively narrow particle size distribution and a volume average particle size of 0.01 to 1 μm.

<Toner production method>
The method for producing the toner of the present invention is exemplified below, but is not limited thereto.
<Core particle (basic part) granulation process>
(Organic solvent)
The organic solvent used for granulation is preferably volatile with a boiling point of less than 100 ° C. from the viewpoint of easy removal of the solvent later. Examples of such organic solvents include toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, Ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone and the like can be used alone or in combination of two or more. Particularly preferred are ester solvents such as methyl acetate and ethyl acetate, aromatic solvents such as toluene and xylene, and halogenated hydrocarbons such as methylene chloride, 1,2-dichloroethane, chloroform and carbon tetrachloride. The polyester resin and the colorant may be dissolved or dispersed at the same time, but are usually dissolved or dispersed individually, and the organic solvents used at that time may be different or the same, but considering the subsequent solvent treatment The same is preferable. Moreover, when the solvent (single or mixed) which melt | dissolves a polyester-type resin suitably is selected, the mold release agent used preferably by this invention will hardly melt | dissolve from the difference in the solubility.

(Dissolution or dispersion of polyester resin)
The polyester resin is preferably dissolved or dispersed in a resin concentration of about 40% to 80%. If the concentration is too high, it will be difficult to dissolve or disperse, and the viscosity will be too high to handle. On the other hand, if the concentration is too low, the amount of fine particles produced decreases and the amount of solvent to be removed increases. When mixing a polyester resin with a modified polyester resin having an isocyanate group at the terminal, it may be mixed in the same solution or dispersion, or separately dissolved or dispersed, but the respective solubility In view of the viscosity, it is preferable to prepare separate solutions or dispersions.

(Aqueous medium)
As an aqueous medium to be used, water alone may be used, but a solvent miscible with water may be used in combination. Examples of the miscible solvent include alcohol (methanol, isopropanol, ethylene glycol, etc.), dimethylformamide, tetrahydrofuran, cellosolves (methylcellosolve, etc.), lower ketones (acetone, methyl ethyl ketone, etc.) and the like. The usage-amount of the aqueous medium with respect to 100 mass parts of resin fine particles is 50-2000 mass parts normally, Preferably it is 100-1000 mass parts.

(Inorganic dispersant and organic resin fine particles)
When the dissolved or dispersed solution of the polyester resin and the release agent is dispersed in the aqueous medium, the particle size distribution is sharpened by dispersing the inorganic dispersant or the organic resin fine particles in the aqueous medium in advance. And is preferable in that the dispersion is stable. As the inorganic dispersant, tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, hydroxyapatite and the like are used. As the resin forming the organic 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. Includes vinyl resins, polyurethane resins, epoxy resins, polyester resins, polyamide resins, polyimide resins, silicon resins, phenol resins, melamine resins, urea resins, aniline resins, ionomer resins, polycarbonate resins, and the like. These resins may be used in combination of two or more. Of these, vinyl resins, polyurethane resins, epoxy resins, polyester resins, and combinations thereof are preferable from the viewpoint that an aqueous dispersion of fine spherical resin particles is easily obtained.

(Surfactant)
Moreover, when manufacturing the said resin fine particle, surfactant etc. can also be used as needed. 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. It is.

  Further, by using a surfactant having a fluoroalkyl group, the effect can be obtained in a very small amount. Examples of the anionic surfactant having a fluoroalkyl group preferably used include fluoroalkylcarboxylic 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) ) Carboxylic acid and metal salt, perfluoroalkyl carboxylic acid (C7 to C13) and its metal salt, perfluoroalkyl (C4 to C12) sulfonic acid and its metal salt, perfluorooctane sulfonic acid diethanolamide, N-propyl-N -(2-hydroxyethyl) par Fluorooctanesulfonamide, perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salt, perfluoroalkyl (C6-C10) -N-ethylsulfonylglycine salt, monoperfluoroalkyl (C6-C16) ethyl phosphate, etc. Can be mentioned. In addition, examples of the cationic surfactant include aliphatic quaternary ammonium salts such as aliphatic primary, secondary or secondary amine acids having a fluoroalkyl group, and perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salts. Benzalkonium salt, benzethonium chloride, pyridinium salt, imidazolinium salt and the like.

(Protective colloid)
Further, the dispersed droplets may be stabilized by a polymer protective colloid. For example, acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid or maleic anhydride and other (meth) acrylic monomer Bodies such as β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate, γ-hydroxypropyl acrylate, γ-hydroxypropyl methacrylate, 3-acrylate Chloro-2-hydroxypropyl, 3-chloro-2-hydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerol monoacrylate, glycerol monomethacrylate, N -Of methyl alcohol 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 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 imidazole , Homopolymers or copolymers such as those having a nitrogen atom such as ethyleneimine or its heterocyclic ring, polyoxyethylene, polyoxypropylene, Oxyethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonyl phenyl ether, polyoxyethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ester, polyoxyethylene nonylphenyl Polyoxyethylenes such as esters, celluloses such as methyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose can be used. If an acid such as calcium phosphate salt or an alkali-soluble substance is used as the dispersion stabilizer, the calcium phosphate salt is removed from the fine particles by dissolving the calcium phosphate salt with an acid such as hydrochloric acid and then washing with water. To do. It can also be removed by operations such as enzymatic degradation. When a dispersant is used, the dispersant can remain on the surface of the toner particles, but it is preferable to remove it by washing from the charged surface of the toner.

(Distribution method)
The dispersion method is not particularly limited, and known equipment such as a low-speed shear method, a high-speed shear method, a friction method, a high-pressure jet method, and an ultrasonic wave can be applied. 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 temperature during dispersion is usually 0 to 150 ° C. (under pressure), preferably 20 to 80 ° C.

(Oil phase preparation process)
As a method of preparing an oil phase in which a resin, a colorant, a release agent, etc. are dissolved or dispersed in an organic solvent, the resin, colorant, etc. are gradually added to the organic solvent while stirring and dissolved. Alternatively, it may be dispersed. However, when using a pigment as a colorant or adding a release agent or charge control agent that is difficult to dissolve in an organic solvent, the particles should be made smaller prior to addition to the organic solvent. It is preferable.
As described above, the master batch of the colorant is one of the means, and the same method can be applied to the release agent and the charge control agent.

As another means, it is also possible to add a dispersion aid as necessary in an organic solvent and disperse the colorant, release agent, and charge control agent in a wet manner to obtain a wet master.
As another means, if a material that melts below the boiling point of the organic solvent is dispersed, a dispersion aid is added in the organic solvent as necessary, and the mixture is heated with stirring with the dispersoid. After dissolution, crystallization may be performed by cooling with stirring or shearing to produce dispersoid microcrystals.

  The colorant, release agent, and charge control agent dispersed using the above means may be further dispersed after being dissolved or dispersed together with the resin in the organic solvent. For dispersion, a known disperser such as a bead mill or a disk mill can be used.

(Core particle production process)
The method for producing a dispersion in which the oil phase obtained in the above-described step is dispersed in an aqueous medium and oil droplet particles composed of the oil phase are dispersed in the aqueous dispersion medium is not particularly limited. Known equipment such as a low-speed shear type, a high-speed shear type, a friction type, a high-pressure jet type, and an ultrasonic wave can be applied. In order to make the particle size of the dispersion 2 to 20 μm, a high-speed shearing type is preferable. When a high-speed shearing disperser is used, the rotational speed is not particularly limited, but is usually 1000 to 30000 rpm, preferably 5000 to 20000 rpm. The dispersion time is not particularly limited, but in the case of a batch method, it is usually 0.1 to 5 minutes. If the dispersion is performed for more than 5 minutes, excessively small particles that should grow to the size of the base particle are left behind due to the combination of multiple particles, or the dispersion becomes overdispersed and the system becomes unstable. Aggregates and coarse particles may be generated, which is not preferable. As temperature at the time of dispersion | distribution, it is 0-40 degreeC normally, Preferably it is 10-30 degreeC. If it exceeds 40 ° C., the molecular motion becomes active, so that the dispersion stability is lowered and aggregates and coarse particles are easily generated, which is not preferable. On the other hand, when the temperature is less than 0 ° C., the viscosity of the dispersion increases, and the shear energy required for dispersion increases, so that the production efficiency decreases.

  As the surfactant, the same surfactants as described in the description of the method for producing fine resin particles can be used. However, in order to efficiently disperse oil droplets containing a solvent, a disulfonate having a high HLB is used. preferable. The surfactant has a concentration in the aqueous medium of 1 to 10% by mass, preferably 2 to 8% by mass, more preferably 3 to 7% by mass. If it exceeds 10% by mass, the oil droplets will be too small, or a reverse micelle structure will be formed, and the dispersion stability will be lowered, resulting in the coarsening of the oil droplets. On the other hand, if it is less than 1% by mass, the oil droplets cannot be stably dispersed and the oil droplets become coarse, which is not preferable.

(Resin fine particle adhesion process)
The obtained core particle dispersion can keep the core particle droplets stably while stirring. In this state, the above-mentioned vinyl resin fine particle dispersion is introduced and adhered onto the core particles. The vinyl resin fine particle dispersion is preferably charged over 30 seconds. When the charging is performed in less than 30 seconds, the dispersion system is rapidly changed, so that an excessive amount of composite particles are generated or the adhesion of vinyl resin fine particles becomes uneven. On the other hand, it is not preferable from the viewpoint of production efficiency to add to the dark cloud for a long time, for example, exceeding 60 minutes.

  The resin fine particle dispersion may be diluted or concentrated to adjust the concentration as appropriate before being added to the core particle dispersion. The concentration of the vinyl resin fine particle dispersion is preferably 5 to 30% by mass, and more preferably 8 to 20% by mass. If it is less than 5%, the change in the concentration of the organic solvent accompanying the introduction of the dispersion is large, and the adhesion of the resin fine particles becomes insufficient. Further, if it exceeds 30% by mass, the resin fine particles are likely to be unevenly distributed in the core particle dispersion, and as a result, the adhesion of the resin fine particles becomes non-uniform.

  The reason why the resin fine particles adhere to the core particles with sufficient strength by the method of the present invention is that when the resin fine particles adhere to the droplets of the core particles, the core particles can freely deform and come into contact with the resin fine particle interface. It seems that the surface is sufficiently formed and that the resin fine particles are swollen or dissolved by the organic solvent, and the resin fine particles and the resin in the core particles are likely to adhere to each other. Therefore, in this state, the organic solvent needs to be sufficiently present in the system. Specifically, in the state of the core particle dispersion, 10% by mass to 70% by mass, preferably 30% by mass with respect to the solid content (resin, colorant, and if necessary, release agent, charge control agent, etc.). % To 60% by mass, more preferably 40% to 55% by mass. If it exceeds 70% by mass, the colored resin particles obtained in a single production process are reduced and the production efficiency is low, and if there is a large amount of organic solvent, the dispersion stability is lowered and reagglomeration occurs. It is not preferable because it becomes difficult. Further, if it is less than 10% by mass, the resin fine particles cannot adhere to the core particles with sufficient strength as described above, which is not preferable. However, if the preferred concentration when attaching the resin particles is lower than the preferred organic solvent concentration when producing the core particles, the organic solvent concentration can be adjusted by partially removing the organic solvent after producing the core particles. Then, the resin particles may be adhered, and then the organic solvent may be completely removed. Here, the complete removal of the organic solvent means a level within a range that can be removed by a known method that is usually used in a demelting step described later.

  The temperature at which the vinyl resin fine particles adhere to the core particles is 10 to 60 ° C, preferably 20 to 45 ° C. If the temperature exceeds 60 ° C, the energy required for production increases and the environmental burden on the production increases. In addition, low acid value vinyl resin fine particles may be present on the droplet surface, making dispersion unstable. Since coarse particles may be generated, it is not preferable. On the other hand, when the temperature is lower than 10 ° C., the viscosity of the dispersion is increased, and adhesion of resin fine particles becomes insufficient, which is not preferable.

(Desolation)
In order to remove the organic solvent from the obtained colored resin dispersion, a known method can be used. For example, a method can be employed in which the entire system is gradually heated under normal pressure or reduced pressure to completely evaporate and remove the organic solvent in the droplets.

(Elongation or / and cross-linking reaction)
For the purpose of introducing a modified polyester resin having a urethane or / and urea group, when a modified polyester resin having an isocyanate group at the terminal and an amine capable of reacting with the polyester resin are added, the toner composition is placed in an aqueous medium. Before dispersion, amines may be mixed in the oil phase, or amines may be added to the aqueous medium. The time required for the above reaction is selected depending on the reactivity between the isocyanate group structure of the polyester prepolymer and the added amines, but is usually 1 minute to 40 hours, preferably 1 to 24 hours. The reaction temperature is usually 0 to 150 ° C., preferably 20 to 98 ° C.

<Washing and drying process>
A known technique is used for washing and drying the toner particles dispersed in the aqueous medium.
That is, after solid-liquid separation with a centrifuge, a filter press, etc., the obtained toner cake is redispersed in ion exchange water at about room temperature to about 40 ° C., and after adjusting the pH with acid or alkali as necessary, After removing the impurities and surfactants by repeating the process of solid-liquid separation again and again, the toner powder is obtained by drying with an air dryer, circulating dryer, vacuum dryer, vibration fluid dryer, etc. . At this time, the fine particle component of the toner may be removed by centrifugation or the like, and a desired particle size distribution can be obtained using a known classifier after drying, if necessary.

<External processing>
The obtained dried toner powder is mixed with different kinds of particles such as charge control fine particles and fluidizing agent fine particles, or fixed and fused on the surface by applying a mechanical impact force to the mixed powder. It is possible to prevent the dissociation of the foreign particles from the surface of the resulting composite particle. Specific means include a method of applying an impact force to the mixture by blades rotating at high speed, a method of injecting and accelerating the mixture in a high-speed air stream, and causing particles or composite particles to collide with an appropriate collision plate, etc. is there. As equipment, Ong mill (manufactured by Hosokawa Micron Co., Ltd.), I-type mill (manufactured by Nippon Pneumatic Co., Ltd.) has been modified to lower the pulverization air pressure, hybridization system (manufactured by Nara Machinery Co., Ltd.), kryptron System (manufactured by Kawasaki Heavy Industries, Ltd.), automatic mortar, etc.

[Image Forming Method, Image Forming Apparatus, Process Cartridge]
<Image forming apparatus, process cartridge>
The image forming apparatus of the present invention forms an image using the toner of the present invention. The toner of the present invention can be used as either a one-component developer or a two-component developer, but is preferably used as a one-component developer. The image forming apparatus of the present invention preferably has an endless intermediate transfer unit. Furthermore, the image forming apparatus of the present invention preferably includes a photosensitive member and a cleaning unit that cleans the toner remaining on the photosensitive member and / or the intermediate transfer unit. At this time, the cleaning means may or may not have a cleaning blade. The image forming apparatus of the present invention preferably includes a fixing unit that fixes an image using a roller having a heating device or a belt having a heating device. Further, the image forming apparatus of the present invention preferably has a fixing unit that does not require oil application to the fixing member. Furthermore, it is preferable to include other means appropriately selected as necessary, for example, static elimination means, recycling means, control means, and the like.

  In the image forming apparatus of the present invention, the photosensitive member and the constituent elements such as the developing unit and the cleaning unit may be configured as a process cartridge, and the process cartridge may be configured to be detachable from the image forming apparatus body. Further, at least one of a charging unit, an exposure unit, a developing unit, a transfer unit, a separating unit, and a cleaning unit is supported together with a photosensitive member to form a process cartridge, and a single unit that is detachable from the main body of the image forming apparatus. It is good also as a structure which can be attached or detached using guide means, such as a rail of a forming apparatus main body.

  FIG. 2 shows an example of the image forming apparatus of the present invention. In this image forming apparatus, a latent image carrier (1) that is driven to rotate in the clockwise direction in FIG. 2 is housed in a main body housing (not shown), and around the latent image carrier (1). In addition, a charging device (2), an exposure device (3), a developing device (4) having the toner (T) of the present invention, a cleaning unit (5), an intermediate transfer member (6), a support roller (7), a transfer roller (8) A neutralizing means (not shown) is provided.

  The image forming apparatus includes a paper feed cassette (not shown) that stores a plurality of recording papers (P) as an example of a recording medium, and the recording paper (P) in the paper feed cassette is a paper feed (not shown). After the timing is adjusted by a pair of registration rollers (not shown) one by one by a roller, the sheet is fed between a transfer roller (8) as a transfer means and an intermediate transfer body (6).

  In this image forming apparatus, the latent image carrier (1) is rotated clockwise in FIG. 2 to uniformly charge the latent image carrier (1) with the charging device (2), and then the exposure device ( 3) to irradiate the laser modulated with the image data to form an electrostatic latent image on the latent image carrier (1), and to the developing device (4) on the latent image carrier (1) on which the electrostatic latent image is formed. ) To attach toner and develop. Next, a transfer bias is applied from the latent image carrier (1) on which the toner image is formed by the developing device (4) to the intermediate transfer member (6) to transfer the toner image onto the intermediate transfer member (6). By transferring the recording paper (P) between the intermediate transfer body (6) and the transfer roller (8), the toner image is transferred to the recording paper (P). Further, the recording paper (P) on which the toner image is transferred is conveyed to a fixing means (not shown).

  The fixing unit includes a fixing roller heated to a predetermined fixing temperature by a built-in heater and a pressure roller pressed against the fixing roller with a predetermined pressure, and heats the recording paper conveyed from the transfer roller (8). After pressurizing and fixing the toner image on the recording paper on the recording paper, it is discharged onto a paper discharge tray (not shown).

  On the other hand, the image forming apparatus further rotates the latent image carrier (1) on which the toner image is transferred onto the recording paper by the transfer roller (8), and the cleaning unit (5) applies the surface to the surface of the latent image carrier (1). After the remaining toner is scraped off and removed, the charge is removed by a charge removal device (not shown). The image forming apparatus uniformly charges the latent image carrier (1) neutralized by the static eliminator with the charging device (2), and then performs the next image formation in the same manner as described above.

Hereinafter, each member suitably used for the image forming apparatus of the present invention will be described in detail.
The material, shape, structure, size and the like of the latent image carrier (1) are not particularly limited and may be appropriately selected from known ones. The shape may be a drum shape or a belt shape. Examples of the material include inorganic photoreceptors such as amorphous silicon and selenium, and organic photoreceptors such as polysilane and phthalopolymethine. Among these, amorphous silicon and organic photoreceptors are preferable from the viewpoint of long life.

The electrostatic latent image can be formed on the latent image carrier (1) by, for example, charging the surface of the latent image carrier (1) and then exposing it like an image. It can be performed by latent image forming means. The electrostatic latent image forming means includes, for example, a charging device (2) for charging the surface of the latent image carrier (1) and an exposure device (3) for exposing the surface of the latent image carrier (1) imagewise. At least.
The charging can be performed, for example, by applying a voltage to the surface of the latent image carrier (1) using the charging device (2).

  The charging device (2) is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the charging device (2) includes a conductive or semiconductive roller, brush, film, rubber blade, etc. And non-contact chargers using corona discharge such as corotron and scorotron.

The shape of the charging device (2) may be a magnetic brush, a fur brush or the like in addition to the roller, and can be selected according to the specifications and form of the electrophotographic apparatus. In the case of using a magnetic brush, the magnetic brush is composed of, for example, various ferrite particles such as Zn-Cu ferrite as a charging member, and a non-magnetic conductive sleeve for supporting the same, and a magnet roll included therein. . In addition, when using a brush, for example, as a material of the fur brush, a fur treated with carbon, copper sulfide, metal or metal oxide is used, and this is wound around a metal or other conductive core. It is configured by pasting.
The charging device (2) is not limited to the contact type charger as described above, but an image forming apparatus in which ozone generated from the charger is reduced is obtained. Therefore, a contact type charger is used. It is preferable.

  The exposure can be performed, for example, by exposing the surface of the photoreceptor imagewise using the exposure apparatus (3). The exposure device (3) is not particularly limited as long as the surface of the latent image carrier (1) charged by the charging device (2) can be exposed like an image to be formed. For example, various exposure devices such as a copying optical system, a rod lens array system, a laser optical system, and a liquid crystal shutter optical system may be used.

  The development can be performed, for example, by developing the electrostatic latent image using the toner of the present invention, and can be performed by the developing device (4). The developing device (4) is not particularly limited as long as it can be developed using the toner of the present invention, for example, and can be appropriately selected from known ones. For example, the developing device (4) contains the toner of the present invention, Preferable examples include those having at least a developing unit that can apply toner to the electrostatic latent image in a contact or non-contact manner.

  The developing device (4) carries toner on its peripheral surface, rotates in contact with the latent image carrier (1), and supplies toner to the electrostatic latent image formed on the latent image carrier (1). The developing roller (40) that performs development and a thin layer forming member (41) that contacts the peripheral surface of the developing roller (40) and thins the toner on the developing roller (40) are preferable.

  As the developing roller (40), either a metal roller or an elastic roller is preferably used. There is no restriction | limiting in particular as a metal roller, Although it can select suitably according to the objective, For example, an aluminum roller etc. are mentioned. By performing a blasting process on the metal roller, it is possible to produce the developing roller (40) having an arbitrary surface friction coefficient relatively easily. Specifically, by treating the aluminum roller with glass bead blasting, the roller surface can be roughened, and an appropriate toner adhesion amount can be obtained on the developing roller.

As the elastic roller, a roller coated with an elastic rubber layer is used, and a surface coat layer made of a material that is easily charged to a polarity opposite to that of the toner is provided on the surface. The elastic rubber layer is set to a hardness of 60 degrees or less according to JIS-A in order to prevent toner deterioration due to pressure concentration at the contact portion with the thin layer forming member (41). The surface roughness (Ra) is set to 0.3 to 2.0 μm, and a necessary amount of toner is held on the surface. Further, since the developing roller (40) is applied with a developing bias for forming an electric field with the latent image carrier (1), the elastic rubber layer has a resistance value of 10 ³ to 10 ¹⁰ Ω. Is set. The developing roller (40) rotates in the clockwise direction, and conveys the toner held on the surface to a position facing the thin layer forming member (41) and the latent image carrier (1).

  The thin layer forming member (41) is provided at a position lower than the contact position between the supply roller (42) and the developing roller (40). The thin layer forming member (41) is made of a metal leaf spring material such as stainless steel (SUS) or phosphor bronze, and the free end is brought into contact with the surface of the developing roller (40) with a pressing force of 10 to 40 N / m. Therefore, the toner that has passed under the pressure is thinned and charged by frictional charging. Further, a regulating bias having a value offset in the same direction as the charging polarity of the toner with respect to the developing bias is applied to the thin layer forming member (41) in order to assist frictional charging.

There is no restriction | limiting in particular as a rubber elastic body which comprises the surface of a developing roller (40), Although it can select suitably according to the objective, For example, a styrene-butadiene-type copolymer rubber, an acrylonitrile-butadiene-type copolymer weight Examples include coalesced rubber, acrylic rubber, epichlorohydrin rubber, urethane rubber, silicone rubber, or a blend of two or more thereof. Among these, a blend rubber of epichlorohydrin rubber and acrylonitrile-butadiene copolymer rubber is particularly preferable.
The developing roller (40) is manufactured, for example, by covering the outer periphery of the conductive shaft with a rubber elastic body. The conductive shaft is made of a metal such as stainless steel (SUS), for example.

The transfer can be performed, for example, by charging the latent image carrier (1), and can be performed by a transfer roller. The transfer roller includes a primary transfer unit that transfers a toner image onto an intermediate transfer member (6) to form a transfer image, and a secondary transfer unit (transfer) that transfers the transfer image onto a recording paper (P). An embodiment having a roller (8) is preferred. At this time, two or more colors, preferably full color toners are used as toners, and a primary transfer means for forming a composite transfer image by transferring the toner image onto the intermediate transfer member (6), and recording the composite transfer image An embodiment having secondary transfer means for transferring onto the paper (P) is more preferable.
The intermediate transfer member (6) is not particularly limited, and can be appropriately selected from known transfer members according to the purpose. For example, a transfer belt and the like are preferable.

The transfer means (primary transfer means, secondary transfer means) preferably has at least a transfer device that peels and charges the toner image formed on the latent image carrier (1) to the recording paper (P) side. . There may be one transfer means, or two or more transfer means. Examples of the transfer means include a corona transfer device using corona discharge, a transfer belt, a transfer roller, a pressure transfer roller, and an adhesive transfer device.
The recording paper (P) is typically plain paper, but is not particularly limited as long as it can transfer an unfixed image after development, and can be appropriately selected according to the purpose. A PET base for OHP can also be used.

For example, the fixing can be performed on the toner image transferred to the recording paper (P) by using a fixing unit, and is performed each time the toner image of each color is transferred to the recording paper (P). Alternatively, it may be performed at the same time in a state where toner images of respective colors are laminated.
The fixing unit is not particularly limited and may be appropriately selected depending on the intended purpose. However, a known heating and pressing unit is preferable. Examples of the heating and pressing means include a combination of a heating roller and a pressure roller, a combination of a heating roller, a pressure roller, and an endless belt. In addition, as for the heating temperature by a heating-pressing means, 80-200 degreeC is preferable.

It may be a soft roller type fixing device having a fluorine surface layer composition as shown in FIG.
This is because the heating roller (9) has an elastic body layer (11) made of silicone rubber and a PFA (tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer) surface layer (12) on an aluminum core bar (10). The heater (13) is provided inside the aluminum cored bar. The pressure roller (14) has an elastic layer (16) made of silicone rubber and a PFA surface layer (17) on an aluminum cored bar (15). The recording paper (P) on which the unfixed image (18) is printed is passed as shown.
In the present invention, for example, a known optical fixing device may be used together with or instead of the fixing unit depending on the purpose.

  The neutralization can be performed, for example, by applying a neutralization bias to the latent image carrier, and can be suitably performed by a neutralization unit. The neutralizing means is not particularly limited as long as it can apply a neutralizing bias to the latent image carrier, and can be appropriately selected from known static eliminators. For example, a neutralizing lamp is preferable. It is done.

  Cleaning can be suitably performed, for example, by removing the toner remaining on the photoreceptor by a cleaning means. The cleaning means is not particularly limited and may be any one selected from known cleaners as long as it can remove the toner remaining on the photosensitive member. For example, a magnetic brush cleaner, an electrostatic brush cleaner, or a magnetic roller can be selected. A cleaner, a blade cleaner, a brush cleaner, a web cleaner and the like are preferable.

The recycling can be suitably performed, for example, by transporting the toner removed by the cleaning unit to the developing unit by the recycling unit. There is no restriction | limiting in particular as a recycle means, A well-known conveyance means etc. are mentioned.
Control can be suitably performed by controlling each means by a control means, for example. The control means is not particularly limited as long as each means can be controlled, and can be appropriately selected according to the purpose. Examples thereof include devices such as a sequencer and a computer.

  According to the image forming apparatus, the image forming method, and the process cartridge of the present invention, the electrostatic latent image developing toner is excellent because it has excellent fixability and does not deteriorate due to stress in the developing process, such as aggregation and cracking. Images can be provided.

<Multicolor image forming apparatus>
FIG. 4 is a schematic view showing an example of a multicolor image forming apparatus to which the present invention is applied. FIG. 4 shows a tandem type full-color image forming apparatus.
In FIG. 4, the image forming apparatus stores a latent image carrier (1) that is driven to rotate in the clockwise direction in FIG. 4 in a main body housing (not shown), and around the latent image carrier (1). A charging device (2), an exposure device (3), a developing device (4), an intermediate transfer member (6), a support roller (7), a transfer roller (8) and the like are arranged. Although not shown, the image forming apparatus includes a paper feeding cassette that stores a plurality of recording papers. The recording paper (P) in the paper feeding cassette is fed to a pair of registration rollers (not shown) one by one by a paper feeding roller (not shown). After the timing adjustment, the sheet is fed between the intermediate transfer member (6) and the transfer roller (8) and fixed by the fixing means (19).

  The image forming apparatus rotates the latent image carrier (1) clockwise in FIG. 4 to uniformly charge the latent image carrier (1) with the charging device (2), and then exposes the exposure device (3). The electrostatic image is formed on the latent image carrier (1) by irradiating the laser modulated with the image data, and the developing device (4) forms the latent image carrier (1) on which the electrostatic latent image is formed. Develop with toner attached. The image forming apparatus transfers the toner image formed by attaching the toner to the latent image carrier with the developing device (4) from the latent image carrier (1) to the intermediate transfer member. This is performed for each of the four colors of cyan (C), magenta (M), yellow (Y), and black (K) to form a full-color toner image.

  Next, FIG. 5 is a schematic diagram illustrating an example of a revolver type full-color image forming apparatus. In this image forming apparatus, a plurality of color toners are sequentially developed on one latent image carrier (1) by switching the operation of the developing device. Then, the color toner image on the intermediate transfer body (6) is transferred to the recording paper (P) by the transfer roller (8), the recording paper (P) to which the toner image is transferred is conveyed to the fixing unit, and the fixed image is transferred. obtain.

On the other hand, the image forming apparatus further rotates the latent image carrier (1) on which the toner image is transferred to the recording paper (P) by the intermediate transfer member (6), and the latent image carrier (1) by the cleaning unit (5). ) The toner remaining on the surface is removed by scraping with a blade, and then the charge is removed by the charge removing unit. The image forming apparatus uniformly charges the latent image carrier (1) neutralized by the neutralization unit with the charging device (2), and then performs the next image formation as described above. The cleaning unit (5) is not limited to scraping off the residual toner on the latent image carrier (1) with a blade. For example, the cleaning unit (5) scrapes off the residual toner on the latent image carrier (1) with a fur brush. It may be a thing.
In the image forming method and the image forming apparatus of the present invention, since the toner of the present invention is used as the developer, a good image can be obtained.

<Process cartridge>
The process cartridge of the present invention can develop an electrostatic latent image carrier carrying an electrostatic latent image and the electrostatic latent image carried on the electrostatic latent image carrier using the toner of the present invention. A developing means for forming a visual image, and further comprising other means such as a charging means, a developing means, a transfer means, a cleaning means, and a static elimination means, which are appropriately selected as necessary. The image forming apparatus main body is detachable.

The developing means includes a developer container that contains the toner or developer of the present invention, and a developer carrier that carries and transports the toner or developer contained in the developer container. And a layer thickness regulating member for regulating the thickness of the toner layer to be carried. The process cartridge of the present invention can be detachably provided in various electrophotographic apparatuses, facsimiles, and printers, and is preferably detachably provided in the image forming apparatus of the present invention described later.

  For example, as shown in FIG. 6, the process cartridge includes a latent image carrier (1), and includes a charging device (2), a developing device (4), a transfer roller (8), and a cleaning unit (5). In addition, other means are provided as necessary. In FIG. 6, (L) shows exposure from the exposure apparatus, and (P) shows recording paper. As the latent image carrier (1), the same one as the image forming apparatus can be used. An arbitrary charging member is used for the charging device (2).

  Next, the image forming process using the process cartridge shown in the figure will be described. The latent image carrier (1) is charged by the charging device (2) while being rotated in the direction of the arrow, and exposure by the exposure means (not shown) ( L), an electrostatic latent image corresponding to the exposure image is formed on the surface. The electrostatic latent image is developed with toner by the developing device (4), and the toner development is transferred onto the recording paper (P) by the transfer roller (8) and printed out. Next, the surface of the latent image carrier after the image transfer is cleaned by the cleaning unit (5), further neutralized by a neutralizing unit (not shown), and the above operation is repeated again.

EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further more concretely, this invention is not limited by these Examples.
Hereinafter, “parts” and “%” indicate parts by mass and mass% unless otherwise specified.
Further, in the following examples, the evaluation of the case where the toner of the present invention and the comparative toner are used as a one-component developer is shown, but the toner of the present invention is obtained by using a suitable external treatment and a suitable carrier. It can also be used as a two-component developer.
First, a method for preparing a toner raw material used in Examples and the like will be described.

<Synthesis of non-crystalline polyester>
(Polyester 1)
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen inlet tube, 2765 parts of bisphenol A ethylene oxide 2-mole adduct, 480 parts of bisphenol A propylene oxide 2-mole adduct, 1100 parts of terephthalic acid, 225 parts of adipic acid and dibutyl 10 parts of tin oxide was added and reacted for 8 hours at 230 ° C. under normal pressure. Further, after 5 hours of reaction under reduced pressure of 10 to 15 mmHg, 130 parts of trimellitic anhydride was added to the reaction vessel, and 2 parts at 180 ° C. and normal pressure. Reaction was performed for a time to obtain [Polyester 1]. [Polyester 1] had a number average molecular weight of 2200, a weight average molecular weight of 5600, a Tg of 43 ° C., and an acid value of 24.

(Polyester 3)
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen inlet tube, 264 parts of bisphenol A ethylene oxide 2-mole adduct, 523 parts of bisphenol A propylene oxide 2-mole adduct, 123 parts of terephthalic acid, 173 parts of adipic acid and dibutyl 1 part of tin oxide was added and reacted for 8 hours at 230 ° C. under normal pressure, and further reacted for 8 hours under reduced pressure of 10 to 15 mmHg. Thereafter, 26 parts of trimellitic anhydride was added to the reaction vessel and reacted at 180 ° C. and normal pressure for 2 hours to obtain [Polyester 3]. [Polyester 3] had a number average molecular weight of 4000, a weight average molecular weight of 47000, Tg of 65 ° C., and an acid value of 12.

<Synthesis of crystalline polyester>
(Polyester 4)
500 parts of 1,6-hexanediol, 500 parts of succinic acid, and 2.5 parts of dibutyltin oxide are placed in a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube and reacted at 200 ° C. for 8 hours. Further, the reaction was carried out at a reduced pressure of 10 to 15 mmHg for 1 hour to obtain [Polyester 4]. [Polyester 4] showed an endothermic peak at 65 ° C. by DSC measurement.

<Synthesis of prepolymer>
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction pipe, 366 parts of 1,2-propylene glycol, 566 parts of terephthalic acid, 44 parts of trimellitic anhydride and 6 parts of titanium tetrabutoxide are placed at a normal pressure of 230. The mixture was reacted at 0 ° C. for 8 hours, and further reacted at a reduced pressure of 10 to 15 mmHg for 5 hours to obtain [Intermediate Polyester 1]. [Intermediate polyester 1] had a number average molecular weight of 3200, a weight average molecular weight of 12000, and a Tg of 55 ° C.
Next, 420 parts of [Intermediate polyester 1], 80 parts of isophorone diisocyanate and 500 parts of ethyl acetate are placed in a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, and reacted at 100 ° C. for 5 hours. Polymer] was obtained. [Prepolymer] had a free isocyanate mass% of 1.34%.

<Preparation of resin fine particle dispersion>
(Vinyl copolymer resin fine particles V-1)
Put 1.2 parts of sodium dodecyl sulfate and 500 parts of ion-exchanged water in a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube. What was dissolved in 100 parts of water was added, and 15 minutes later, a mixture of 200 parts of styrene monomer and 1.2 parts of n-octyl mercaptan was added dropwise over 90 minutes, and then kept at 80 ° C. for 60 minutes. Thereafter, the mixture was cooled to obtain a dispersion of [vinyl copolymer resin fine particles V-1]. The solid content concentration of this dispersion was measured and found to be 25%. The volume average particle diameter of the fine particles was 90 nm. When the solid obtained by taking the dispersion liquid in a small petri dish and evaporating the dispersion medium was measured, the number average molecular weight was 18000, the weight average molecular weight was 38000, and Tg was 90 ° C.

(Vinyl copolymer resin fine particles V-2)
Put 1.2 parts of sodium dodecyl sulfate and 500 parts of ion-exchanged water in a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube. A solution dissolved in 100 parts of water is added, and 15 minutes later, a mixed solution of 170 parts of styrene monomer, 30 parts of butyl acrylate and 1.2 parts of n-octyl mercaptan is added dropwise over 90 minutes, and then further heated to 80 ° C. for 60 minutes. Kept. Thereafter, the mixture was cooled to obtain a dispersion of [vinyl copolymer resin fine particles V-2]. The solid content concentration of this dispersion was measured and found to be 25%. The volume average particle diameter of the fine particles was 90 nm. The dispersion was taken in a small petri dish, and the solid obtained by evaporating the dispersion medium was measured. The number average molecular weight was 20000, the weight average molecular weight was 42000, and the Tg was 69 ° C.

(Vinyl copolymer resin fine particles V-3)
Put 1.2 parts of sodium dodecyl sulfate and 500 parts of ion-exchanged water in a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, heat to 80 ° C, and then ion-exchange 2.5 parts of potassium persulfate. What was dissolved in 100 parts of water was added, and 15 minutes later, a mixture of 200 parts of styrene monomer and 3.5 parts of n-octyl mercaptan was added dropwise over 90 minutes, and then kept at 80 ° C. for 60 minutes. Thereafter, the mixture was cooled to obtain a dispersion of [vinyl copolymer resin fine particles V-3]. The solid content concentration of this dispersion was measured and found to be 25%. The volume average particle diameter of the fine particles was 95 nm. When the solid obtained by taking the dispersion in a small petri dish and evaporating the dispersion medium was measured, the number average molecular weight was 8000, the weight average molecular weight was 15000, and Tg was 83 ° C.

<Synthesis of master batch>
Carbon black (Cabot Corp. Regal 400R): 40 parts, Binder resin: Polyester resin (Sanyo Kasei RS-801, acid value 10, Mw 20000, Tg 64 ° C.): 60 parts, water: 30 parts are mixed in a Henschel mixer, A mixture in which water was soaked into the pigment aggregate was obtained. This was kneaded for 45 minutes with two rolls set at a roll surface temperature of 130 ° C. and pulverized to a size of 1 mmφ with a pulverizer to obtain [Masterbatch 1].

[Example 1]
<Production of oil phase>
A container equipped with a stir bar and thermometer is charged with 4 parts of [Polyester 1], 20 parts of [Polyester 4], 8 parts of paraffin wax (melting point 72 ° C.) and 96 parts of ethyl acetate, and the temperature is raised to 80 ° C. with stirring. The sample was kept at 80 ° C. for 5 hours and then cooled to 30 ° C. in 1 hour. Next, after adding 35 parts of [Masterbatch 1] and mixing for 1 hour, the container was transferred, and using a bead mill (Ultra Visco Mill, manufactured by Imex Co., Ltd.), liquid feeding speed 1 kg / hr, disk peripheral speed 6 m / sec. Then, 80% by volume of 0.5 mm zirconia beads were filled and dispersed under the condition of 3 passes to obtain [Material Solution 1]. Next, 74.1 parts of a 70% ethyl acetate solution of [Polyester 1], 21.6 parts of [Polyester 3] and 21.5 parts of ethyl acetate were added to 81.3 parts of [Raw Material Solution 1], and 2 for 3 One Motor. The mixture was stirred for a time to obtain [Oil Phase 1]. Ethyl acetate was added and adjusted so that the solid content concentration of [Oil Phase 1] (measured at 130 ° C. for 30 minutes) was 49%.

<Preparation of aqueous phase>
451 parts of ion exchange water, 94 parts of 50% aqueous solution of dodecyl diphenyl ether disulfonate (Eleminol MON-7: Sanyo Chemical Industries), 67 parts of 1% aqueous solution of carboxymethyl cellulose as a thickener, 4% by weight aqueous solution of sodium hydroxide 12 parts and 50 parts of ethyl acetate were mixed and stirred to obtain a yellow transparent liquid. This is designated as [Aqueous Phase 1].

<Emulsification process>
After adding 28.5 parts of [Prepolymer] to the total amount of [Oil Phase 2], mixing with TK homomixer (made by Tokushu Kika) at 5,000 rpm for 1 minute, then adding [Aqueous Phase 1] total amount, The mixture was mixed with a TK homomixer at a rotational speed of 8,000 to 13,000 rpm for 20 minutes to obtain [core particle slurry 2].
The subsequent steps were performed in the same manner as in Example 1 to obtain [Developer 2]. The analytical measurement and evaluation results of this developer 2 are shown in Tables 1 and 2.

<Protrusion formation process (resin fine particle adhesion process to core particles)>
While stirring [Core Particle Slurry 1] at 200 rpm using a three-one motor, 21.4 parts of [Resin Fine Particle Dispersion V-1] was dropped over 5 minutes, and stirring was continued for 30 minutes. Thereafter, a small amount of the slurry sample was collected, diluted with 10 times water, and centrifuged using a centrifugal separator. As a result, toner base particles settled on the bottom of the test tube, and the supernatant liquid was almost transparent. As described above, [Slurry 1 after forming the protrusions] was obtained.

<Desolvent>
[Slurry 1 after forming convex portions] was put into a container equipped with a stirrer and a thermometer, and the solvent was removed at 30 ° C. for 8 hours to obtain [Dispersed slurry 1].

<Washing->Drying>
[Dispersion Slurry 1] After filtering 100 parts under reduced pressure,
(1): 100 parts of ion-exchanged water was added to the filter cake, mixed with a TK homomixer (10 minutes at 12,000 rpm), and then filtered.
(2): 100 parts of ion-exchanged water was added to the filter cake of (1), ultrasonic vibration was applied, and the mixture was mixed with a TK homomixer (30 minutes at 12,000 rpm) and then filtered under reduced pressure. This operation was repeated so that the electric conductivity of the reslurry liquid was 10 μS / cm or less.
(3): 10% hydrochloric acid was added so that the reslurry liquid of (2) had a pH of 4, and the mixture was filtered as it was with a three-one motor for 30 minutes.
(4): 100 parts of ion-exchanged water was added to the filter cake of (3), mixed with a TK homomixer (10 minutes at 12,000 rpm) and then filtered. This operation was repeated so that the reslurry liquid had an electric conductivity of 10 μS / cm or less to obtain [Filter Cake 1]. The remaining [Dispersion Slurry 1] was washed in the same manner and further mixed as [Filter Cake 1].
[Filtration cake 1] was dried at 45 ° C. for 48 hours in a circulating drier and sieved with a mesh of 75 μm to obtain [Toner base 1]. 50 parts of the base toner is mixed with 1 part of hydrophobic silica having a primary particle diameter of about 30 nm and 0.5 part of hydrophobic silica having a primary particle diameter of about 10 nm using a Henschel mixer, and [Developer 1 of the present invention]. ] Was obtained.
A measurement analysis and evaluation method for the toner of Example 1 obtained in this way will be described below (the measurement and evaluation methods in other examples and comparative examples are also the same).

[Circularity peak]
In order to achieve both high image quality with spherical toner and cleanability with irregular toner, a spherical toner that forms a peak close to circularity 1 (perfect circle) on a circularity frequency graph, and circularity 0.87 to The presence of an irregular shaped toner that forms a peak between 0.93 is necessary, but it is desirable that the particles having these two types of shape are toner particles having substantially the same characteristics. When two different types of toner particles are mixed, non-uniformity of the characteristics inevitably occurs, and for example, different characteristics are exhibited in terms of chargeability and fixability, resulting in problems. Therefore, it is preferable that the toner particles are manufactured simultaneously in a series of toner particle manufacturing steps and are manufactured in a state where two types of toner particles are mixed. According to the production method of the present invention, it has been found that spherical particles having a sharp particle size distribution can be produced at the same time in a state where a mixture of spherical and small-sized particles, which are irregularly shaped and not so large, are mixed. It was. As a result, it is possible to obtain excellent toner particles that satisfy both of the above characteristics and do not cause any problems.
The irregular toner that forms a peak between 0.87 and 0.93 in the circularity of the present invention is mainly formed in the convex portion forming step. In order to achieve the desired circularity peak, it is necessary to control the particle size and weight average molecular weight of the resin fine particles used in the convex forming step to generate appropriate particle coalescence. The particle diameter is a volume average particle diameter, preferably 60 to 140 nm, more preferably 80 to 120 nm, and most preferably 85 to 100 nm. When the particle diameter is smaller than 60 nm, particle coalescence hardly occurs. On the other hand, if it is larger than 140 nm, relatively large particles are coalesced, and coarse particles are likely to be generated, resulting in a broad particle size distribution, which is not desirable. The generation of coarse particles tends to be a factor in the development process. On the other hand, as a weight average molecular weight, Preferably it is 20000-80000, More preferably, it is 30000-60000, Most preferably, it is 38000-42000. When the weight average molecular weight is less than 20000, particle coalescence hardly occurs. On the other hand, if it is larger than 80,000, relatively large particles are coalesced with each other, and coarse particles are likely to be generated, resulting in a broad particle size distribution. Although the mechanism of this phenomenon is not clear, it is speculated that the weight average molecular weight is related to the solubility / swellability of the resin fine particles in the organic solvent present in the convex formation process. The occurrence of coalescence is influenced by the property, and it is considered that the appropriate solubility / swellability is satisfied if the weight average molecular weight is in the above range.

[Average particle size]
Next, a method for measuring the particle size distribution of toner particles will be described.
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 as follows.
First, 0.1 to 5 ml of a surfactant (preferably alkylbenzene sulfonate) is added as a dispersant to 100 to 150 ml of an aqueous electrolytic solution. Here, the electrolytic solution is a solution prepared by preparing a 1% NaCl aqueous solution using primary sodium chloride. For example, ISOTON-II (manufactured by Coulter) can be used. Here, further add 2 to 20 mg of the measurement sample as a solid content. 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 volume average particle diameter (Dv) and the number average particle diameter (Dn) of the toner can be obtained. As a channel, for example, less than 2.00 to 2.52 μm; less than 2.52 to 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; Less than .40 μm; 25.40 to less than 32.00 μm; 13 channels of 32.00 to less than 40.30 μm are used, and particles having a particle size of 2.00 μm to less than 40.30 μm can be targeted. 1A, 1B, and 1C are all of the average circularity described later.

[Average circularity]
As a method for measuring the shape, an optical detection band method is suitable in which a suspension containing particles is passed through an imaging unit detection band on a flat plate, and a particle image is optically detected and analyzed by a CCD camera. The average circularity is a value obtained by dividing the perimeter of an equivalent circle having the same projected area obtained by this method by the perimeter of the actual particle.
This value is a value measured as an average circularity by a flow type particle image analyzer FPIA-3000S. As a specific measuring method, 0.1 to 0.5 ml of a surfactant, preferably alkylbenzene sulfonate is added as a dispersant to 100 to 150 ml of water from which impure solids have been removed in advance, and further measurement is performed. Add about 0.1-0.5g of sample. The suspension in which the sample is dispersed is obtained by performing dispersion treatment for about 1 to 3 minutes with an ultrasonic disperser and measuring the shape and distribution of the toner with the above apparatus at a dispersion concentration of 3000 to 10,000 / μl. . 1A is a number average frequency graph of particle diameters measured with a flow particle image analyzer FPIA-3000S, and FIG. 1B is a horizontal axis particle diameter measured with a flow particle image analyzer FPIA-3000S. Vertical axis circularity distribution graph (Numerical values on the vertical axis are the same as those in (C).) (C) is a frequency graph of circularity measured with a flow particle image analyzer FPIA-3000S. The measurement results are shown in Table 2.

[Volume average particle diameter of resin fine particles]
As a measuring method of the volume average particle diameter of the resin fine particles, it can be measured with a nanotrack particle size distribution measuring apparatus UPA-EX150 (manufactured by Nikkiso, dynamic light scattering method / laser Doppler method). As a specific measuring method, the dispersion in which resin fine particles are dispersed is adjusted to a measurement concentration range for measurement. At that time, the background measurement is performed in advance using only the dispersion solvent of the dispersion. By this measurement method, it is possible to measure several tens of nm to several μm, which is the volume average particle size range of the resin fine particles used in the present invention.

[Molecular weight]
The molecular weights of the polyester resin and vinyl copolymer resin used were measured under the following conditions by ordinary GPC (gel permeation chromatography).
・ Device: HLC-8220GPC (manufactured by Tosoh Corporation)
Column: TSKgel SuperHZM-M x 3
・ Temperature: 40 ℃
・ Solvent: THF (tetrahydrofuran)
・ Flow rate: 0.35 ml / min ・ Sample: 0.01 ml injection of a sample with a concentration of 0.05 to 0.6% Molecular weight calibration curve prepared with a monodisperse polystyrene standard sample from the molecular weight distribution of the toner resin measured under the above conditions Was used to calculate the weight average molecular weight Mw. As monodisperse polystyrene standard samples, 5.8 × 100, 1.085 × 10000, 5.95 × 10000, 3.2 × 100,000, 2.56 × 1000000, 2.93 × 1000, 2.85 × 10000, Ten points of 1.48 × 100,000, 8.417 × 100,000, 7.5 × 1000000 were used.

[Glass transition point and endotherm]
For measuring the glass transition point of the polyester resin or vinyl copolymer resin to be used, for example, using a differential scanning calorimeter (for example, DSC-6220R: Seiko Instruments Inc.) After heating to 150 ° C. for 10 minutes, leave the sample at 150 ° C. for 10 minutes, cool the sample to room temperature, leave it for 10 minutes, heat it again to 150 ° C. at a heating rate of 10 ° C./min, The height of the baseline above the glass transition point can be obtained from a curved portion corresponding to ½.
Moreover, the endothermic quantity and melting | fusing point of a mold release agent, crystalline resin, etc. can be measured similarly. The endothermic amount is obtained by calculating the peak area of the measured endothermic peak. Generally, the release agent used in the toner melts at a temperature lower than the fixing temperature of the toner, and the heat of fusion at that time appears as an endothermic peak. Some releasing agents are accompanied by heat of fusion due to phase transition in the solid phase in addition to the heat of fusion. In the present invention, the total is the endothermic amount of the heat of fusion.

[Stress resistance]
The externally added toner (developer) was continuously printed in a N / N environment (23 ° C., 45%) using a Ricoh ipsio SPC220 with a B / W ratio of 6%. After 2000 continuous printing in N / N environment (after endurance), the toner on the developing roller during blank paper pattern printing is sucked, the charge amount is measured with an electrometer, and the charge amount after 50 sheets and 2000 sheets The difference was evaluated.
A: Absolute value of charge amount difference is 5 μC / g or less ○: Absolute value of charge amount difference is in the range of 5 μC / g to 10 μC / g Δ: Absolute value of charge amount difference is in the range of 10 μC / g to 15 μC / g Inner x: The absolute value of the charge amount difference is 15 μC / g or more

(Environment resistance)
The externally added toner (developer) was continuously printed in a N / N environment (23 ° C., 45%) using a Ricoh ipsio SPC220 with a B / W ratio of 6%. After 2000 sheets of continuous printing in N / N environment (after endurance), change to H / H environment (temperature and humidity, 27 ° C., 80%), suck the toner on the developing roller during blank paper pattern printing, The amount of charge was measured with an electrometer, and the difference in charge amount under the H / H environment after 50 sheets under the N / N environment and after 2000 sheets was evaluated.
○: The absolute value of the charge amount difference is 10 μC / g or less Δ: The absolute value of the charge amount difference is in the range of 10 μC / g to 15 μC / g ×: The absolute value of the charge amount difference is 15 μC / g or more

[Fixability]
Using an externally added toner (developer), Ricoh's ipsio SPC220, an unfixed image with a solid band image (adhesion amount 11 g / m ² ) having a width of 3 mm and a tip of 3 mm on A4 longitudinal paper is produced. did. This unfixed image was fixed at a fixing temperature in increments of 10 ° C. in the range of 115 ° C. to 175 ° C. using the following fixing device, and the separable / non-offset temperature range was determined. The temperature range is a fixing temperature range in which the paper is satisfactorily separated from the heating roller and no offset phenomenon occurs. The paper used and the direction of paper passing were 45 g / m ² paper of Y-th vertical paper that is unfavorable for separability. The peripheral speed of the fixing device was set to 200 mm / sec.
The fixing device is of a soft roller type having a fluorine surface layer composition as shown in FIG. Specifically, the heating roller (9) has an outer diameter of 40 mm, an aluminum core (10) and a 1.5 mm-thick elastic body layer (11) and PFA (ethylene tetrafluoride-perfluoroalkyl). The vinyl ether copolymer) has a surface layer (12), and a heater (13) is provided inside the aluminum cored bar. The pressure roller (14) has an outer diameter of 40 mm, and has an elastic body layer (16) made of silicone rubber and a PFA surface layer (17) made of silicone rubber on an aluminum core bar (15). The paper (P) on which the unfixed image (18) is printed is passed as shown in the figure.
A: Separable / non-offset in the entire range of 110 to 170 ° C., and the fixed image resistance was sufficient.
○: Separable / non-offset in the entire range of 110 to 170 ° C., but the fixed image in the low temperature range was easily peeled or scratched by scratching or rubbing.
Δ: Separable / non-offset temperature range was 30 ° C. or higher and lower than 50 ° C.
X: The separable / non-offset temperature range was less than 30 ° C.

[Heat resistant storage stability]
The toner was stored at 55 ° C. for 8 hours, and then sieved with a 42 mesh screen for 2 minutes. The residual rate on the wire mesh was used as an index for heat resistant storage stability. The heat resistant storage stability was evaluated in the following four stages. The results are shown in Tables 1 and 2.
A: Less than 10% B: 10-20%
Δ: 20-30%
×: 30% or more

[Example 2]
<Preparation of oil phase 2>
A container equipped with a stir bar and thermometer is charged with 4 parts of [Polyester 1], 20 parts of [Polyester 4], 8 parts of paraffin wax (melting point 72 ° C.) and 96 parts of ethyl acetate, and the temperature is raised to 80 ° C. with stirring. The sample was kept at 80 ° C. for 5 hours and then cooled to 30 ° C. in 1 hour. Next, after adding 35 parts of [Masterbatch 1] and mixing for 1 hour, the container was transferred, and using a bead mill (Ultra Visco Mill, manufactured by Imex Co., Ltd.), liquid feeding speed 1 kg / hr, disk peripheral speed 6 m / sec. Then, 80% by volume of 0.5 mm zirconia beads were filled and dispersed under the condition of 3 passes to obtain [Material Solution 1]. Next, 84.4 parts of a 70% ethyl acetate solution of [Polyester 1] was added to 81.3 parts of [Raw Material Solution 1] and stirred with a three-one motor for 2 hours to obtain [Oil Phase 4]. It was adjusted by adding ethyl acetate so that the solid content concentration of [Oil Phase 2] (measured at 130 ° C. for 30 minutes) was 50%.

<Emulsification process>
After adding 0.4 parts of isophorone diamine and 28.5 parts of [prepolymer] to the total amount of [Oil Phase 2] and mixing for 1 minute at 5,000 rpm with a TK homomixer (manufactured by Tokushu Kika), Phase 1] The whole amount was added and mixed for 20 minutes with a TK homomixer while adjusting the rotational speed at 8,000 to 13,000 rpm to obtain [core particle slurry 2].
The subsequent steps were performed in the same manner as in Example 1 to obtain [Developer 2]. The analytical measurement and evaluation results of this developer 2 are shown in Tables 1 and 2.

[Example 3]
[Developer 3] was obtained by changing [resin fine particle dispersion V-1] in Example 1 to [resin fine particle dispersion V-2]. The analytical measurement and evaluation results of this developer are shown in Tables 1 and 2.

[Example 4]
[Developer 4] was obtained by changing [resin fine particle dispersion V-1] in Example 2 to [resin fine particle dispersion V-2]. The analytical measurement and evaluation results of this developer are shown in Tables 1 and 2.

[Comparative Example 1]
After the emulsification step of Example 1, the solvent was removed without passing through the shell step to obtain [Developer 5]. The analytical measurement and evaluation results of this developer are shown in Tables 1 and 2.

[Comparative Example 2]
[Developer 6] was obtained by changing [Resin fine particle dispersion V-1] in Example 1 to [Vinyl copolymer resin fine particle V-3]. Analytical measurements and evaluation results are shown in Tables 1 and 2.

[Comparative Example 3]
[Developer 7] was obtained by changing [Resin fine particle dispersion V-1] of Example 2 to [Vinyl copolymer resin fine particle V-3]. Analytical measurements and evaluation results are shown in Tables 1 and 2.

[Comparative Example 4]
[Developer 8] was obtained by changing the number of revolutions of the three-one motor in the shell process of Example 1 from 200 rpm to 100 rpm. The obtained toner (developer) was subjected to the evaluation test as described above. The results are shown in the following Table 1 and Table 2.

（peakの頻度%：円形度０．８７〜０．９３の間のピークの頻度%）
（合計頻度%：円形度０．８７〜０．９３の間の頻度%の合計）

本実施例では頗る良い評価結果が得られた。一方、比較例１（凸部形成なし）や、比較例２、３のトナー粒子は円形度０．８７〜０．９３の間の個数頻度％は不規則でありピークが存在せず、品質評価に問題があった。また、比較例４のトナー粒子は凝集した粗大粒子が発生し、円形度０．８７〜０．９３の間の個数頻度％は不規則でありピークが存在せず、さらに粒径分布が悪化、現像性が悪化した。

(Peak frequency%: peak frequency% between circularity 0.87 and 0.93)
(Total frequency%: Total frequency% between circularity 0.87 and 0.93)

In this example, good evaluation results were obtained. On the other hand, in the toner particles of Comparative Example 1 (no protrusions) and Comparative Examples 2 and 3, the number frequency% between the circularity of 0.87 and 0.93 is irregular and there is no peak, and the quality evaluation There was a problem. In addition, the toner particles of Comparative Example 4 are aggregated coarse particles, and the number frequency% between 0.87 and 0.93 in the circularity is irregular, no peak is present, and the particle size distribution is further deteriorated. Developability deteriorated.

(About Fig. 2, 3, 4, 5)
1 Latent image carrier
2 Charging device
3 Exposure equipment
4 Development device
5 Cleaning section
6 Intermediate transfer member
7 Support roller
8 Transfer roller
9 Heating roller
10 Aluminum cored bar
11 Silicone rubber elastic layer
12 PFA surface
13 Heater
14 Pressure roller
15 Aluminum core
16 Silicone rubber elastic layer
17 PFA surface layer
18 Unfixed image
19 Fixing means 40 Developing roller
41 Thin layer forming member
42 Supply roller
T Toner
P Recording paper

(About Figure 6)
1 Latent image carrier
2 Charging device
4 Development device
5 Cleaning section
8 Transfer roller
L Exposure from exposure equipment
P Recording paper

JP 2003-5434 A JP 2005-189755 A JP 2007-011298 A

Claims (10)

  A toner comprising toner base particles and inorganic fine particles, wherein the base particles include at least a base part of base particles containing a resin component (resin and / or precursor thereof), a release agent, and a colorant, and a surface of the base part And having a sea-island structure having a convex portion formed of resin fine particles, the basic portion being the sea and the convex portion being the island, wherein the resin component includes at least the first resin, and the resin fine particles are the second The first resin and the second resin are non-crystalline resins, the base particles have a volume average particle size of 4.0 to 7.0 μm, and the base particles have an average circularity of 0.960 to A toner having a circularity of 0.87 to 0.93, which is 0.985, on the frequency graph of circularity, apart from a peak close to circularity 1 (perfect circle).   The toner according to claim 1, wherein the resin constituting the basic part includes a polyester resin, and the resin fine particles are made of a vinyl resin.   The toner according to claim 1, wherein the basic portion further contains a modified polyester resin having a urethane or / and urea group.   A toner container filled with the toner according to claim 1.   A developer comprising the toner according to claim 1.   A developer carrying member for carrying the developer to be supplied to the latent image carrying member on the surface; a developer supplying member for supplying the developer to the surface of the developer carrying member; and a developer container for containing the developer. 6. A developing device according to claim 5, wherein the developer according to claim 5 is stored in a developer container.   In the process cartridge in which the latent image carrier and the developing device that develops at least the latent image on the latent image carrier with the developer are integrated and configured to be detachable from the image forming apparatus, the developing device is described in claim 6. A process cartridge according to claim 1.   A latent image carrier for carrying a latent image, a charging means for uniformly charging the surface of the latent image carrier, and exposing the charged surface of the latent image carrier based on image data to write an electrostatic latent image An exposure unit; a developing unit that supplies toner to the electrostatic latent image formed on the surface of the latent image carrier to make it visible; and a transfer unit that transfers the visible image on the surface of the latent image carrier to the transfer target; An image forming apparatus comprising: a fixing unit that fixes a visible image on a transfer target, wherein the developing unit is the developing device according to claim 6.   A charging step for uniformly charging the surface of the latent image carrier, an exposure step for exposing the surface of the charged latent image carrier based on image data to write an electrostatic latent image, and a developer on the developer carrier A developer layer having a predetermined layer thickness is formed by a layer regulating member, and an electrostatic latent image formed on the surface of the latent image carrier is developed through the developer layer, and a latent image carrying process. The developer according to claim 5, comprising: a transfer step of transferring a visible image on the surface of the body to a transfer target; and a fixing step of fixing the visible image on the transfer target. An image forming method. The method for producing a toner according to claim 1, comprising at least the following steps (1) to (4).
(1) A step of dissolving or dispersing a matrix-forming material containing at least a resin component and / or a precursor thereof comprising a resin component, a release agent and a colorant in an organic solvent,
(2) A step of suspending the dissolved or dispersed material in an aqueous medium to produce a core particle dispersion that is a basic part of toner base particles.
(3) adding a resin fine particle dispersion to the core particle dispersion to attach the resin fine particles to the core particle surface;
(4) Step of removing the organic solvent

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