JP2015040912A - Toner for electrostatic charge image development - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner for electrostatic charge image development that exhibits environmental stability and durable stability.SOLUTION: There is provided a toner for electrostatic charge image development that contains a crystalline polyester resin, an amorphous polyester resin including a constitutional unit derived from a polyvalent carboxylic acid having an adamantane skeleton or a derivative thereof, and a mold release agent.

Description

  The present invention relates to a toner used in an electrophotographic image forming method.

  In recent years, electrophotographic image forming apparatuses have been used as ordinary copying machines and printers for printing office documents or as simple copies, to the field of creating printed materials for office use, specifically electronic data. Since variable information can be printed easily, the application has expanded to the on-demand printing (POD) market, which is a light printing area, and several copiers and printers have been installed in the office. As a whole, the amount of power consumption has increased.

  In the POD market, since a value is required for the printed matter, not for copying, it is required to form a high-quality image as the printed matter.

  In order to obtain printed matter with high image quality, it is known that reducing the particle size of toner is effective, and various so-called chemical toners have been proposed for realizing this. Since this chemical toner is a method of granulating in an aqueous medium or the like, unlike the pulverization method, it has an advantage that toner particles having a small particle diameter can be obtained with high uniformity.

  On the other hand, it is effective to use a polyester resin as the binder resin that constitutes the toner particles in order to give high gloss and give a high image quality print without causing an offset phenomenon during fixing. Is known (see Patent Document 1).

  Further, it is known that crystalline polyester is used as a polyester resin for fixing at a low temperature by utilizing its low melt viscosity performance. In order to further improve the offset property, a method of dispersing a crystalline polyester resin in a matrix of an amorphous polyester resin is a known method (see Patent Documents 2 to 4).

  By the way, recently, in order to cope with various user use environments and use image modes, there is a demand for stable image formation even in severe temperature and humidity repetitive environments. Therefore, it has become an even more important issue to improve the charging stability (environmental stability, durability stability) in order to ensure a stable state. In order to solve such a problem, a technique for improving charging stability with an external additive or the like is also known (see Patent Documents 5 to 6).

JP 2008-139647 A JP 2008-40319 A JP 2006-276305 A JP 2005-91525 A JP 9-258474 A JP 2005-292592 A

  However, at present, a toner having sufficient environmental stability and durability stability in which the change in charging characteristics with the toner in the initial use of the same lot is suppressed cannot be provided. Accordingly, the present invention has been made in view of the above problems, and the object of the present invention is to provide a toner for developing an electrostatic image that exhibits environmental stability and durability stability.

  An electrostatic charge image developing comprising: a crystalline polyester resin; a non-crystalline polyester resin containing a structural unit derived from a polyvalent carboxylic acid having an adamantane skeleton or a derivative thereof; and a release agent. The above problem is solved by providing toner.

  According to the present invention, it is possible to provide an electrostatic charge image developing toner exhibiting environmental stability and durability stability, in which a change in charging characteristics with the initial toner is suppressed.

  Embodiments of the present invention will be described below. In addition, this invention is not limited only to the following embodiment. In the present specification, “X to Y” indicating a range means “X or more and Y or less”, and “weight” and “mass”, “wt%” and “mass%”, “part by weight” and “ “Part by mass” is treated as a synonym. Unless otherwise specified, measurement of operation and physical properties is performed under conditions of room temperature (20 to 25 ° C.) / Relative humidity 40 to 50%.

  The present invention includes a crystalline polyester resin; and an amorphous polyester resin containing a structural unit derived from a polyvalent carboxylic acid having an adamantane skeleton or a derivative thereof; and a release agent. This is a charge image developing toner.

  In the present specification, a non-crystalline polyester resin includes: a structural unit (A) derived from a polyvalent carboxylic acid having an adamantane skeleton or a derivative thereof (hereinafter, also simply referred to as “structural unit”), The crystalline polyester resin may also be referred to as a binder resin. In the present specification, the “electrostatic image developing toner” may be simply referred to as “toner”.

  As in the present invention, when a constitutional unit derived from a polyvalent carboxylic acid having an adamantane skeleton or a derivative thereof is included as a constituent of the toner, an electrostatic charge image developing toner exhibiting environmental stability and durability stability is provided. be able to. The reason why such a toner can be provided is estimated as follows. However, the technical scope of the present invention is not hindered by the following mechanism.

  That is, generally, the amount of water adsorbed on the toner differs between a low humidity environment and a high humidity environment, and the charging characteristics can be different. On the other hand, the adamantane skeleton has a hydrophobic and bulky structure and suppresses water adsorption to the toner. That is, water is prevented from approaching the hydrophilic portion (for example, ester portion) in the binder resin, and moisture adsorption is suppressed. Therefore, in the toner of the present invention containing a structural unit derived from a polyvalent carboxylic acid having an adamantane skeleton or a derivative thereof, the difference in moisture adsorption due to temperature and humidity changes is reduced. For this reason, the chargeability is stabilized even when the environment changes, such as in a low-humidity environment or a high-humidity environment, even if the amount of moisture attached to the toner differs.

  Further, when printing is performed over a long period of time in the image forming apparatus, the toner continues to be stirred in the developing device and is subjected to strong stress. This is particularly noticeable in the low printing rate mode where the toner consumption is small. When the toner base particles that have been exposed to strong stress for a long time include an external additive, which will be described later, the external additive is buried in the resin constituting the toner base particles, and the charging characteristics change from that of the initial toner. . In contrast, in the present invention, the resin constituting the toner includes a structural unit derived from a polyvalent carboxylic acid having an adamantane skeleton or a derivative thereof. Since the structure of adamantane is highly symmetric and extremely stable, even if the toner is stressed, the burying of the external additive is suppressed, and the charging property is stable even when printing is repeated. Here, the “toner base particles” in the present specification are particles constituting the toner, and preferably include an internal additive described later and no external additive. Only toner base particles can be used as a toner, and the toner may be further included by including an external additive.

  As described above, by using a resin having an adamantane skeleton that is highly stable due to high symmetry and hydrophobic, even when the toner is stressed, the toner base particles of the external additive can be obtained. By suppressing the burying in the constituent resin and reducing the amount of water adsorbed to the toner, the chargeability is stabilized even when printing is repeated. As a result, it is possible to provide an electrostatic image developing toner and an image forming apparatus that do not cause image gloss and image density fluctuation.

  Furthermore, the use of a resin having an adamantane skeleton also has the effect of improving the dispersibility of the release agent. When the dispersibility of the release agent is improved, the chargeability is improved.

  Hereinafter, the present invention will be described in detail.

<Crystalline polyester resin>
In the present invention, the crystalline polyester resin means a polyester resin having a clear endothermic peak without having a step-like endothermic change in the differential scanning calorimetry (DSC) described in the examples. In other words, in the differential scanning calorimetry (DSC) described in the examples, the crystalline polyester resin indicates a resin having a clear endothermic peak, and the resin having no endothermic peak is classified as an amorphous polyester resin. To do.

  If it is such a crystalline polyester resin, it is not particularly limited. For example, for a resin having a structure in which other components are copolymerized on the main chain of the crystalline polyester resin, the resin has a clear endothermic peak as described above. If it shows, it corresponds to the crystalline polyester resin said by this invention.

  The weight average molecular weight (Mw) of this crystalline polyester resin is preferably 10,000 to 30,000, more preferably 15,000 to 25,000. The molecular weight distribution (Mw / Mn) of this crystalline polyester resin is preferably 3.0 to 6.0, more preferably 3.5 to 5.5. In such a range, it prevents and suppresses compatibility with the amorphous polyester resin in the aggregation / fusion process described later, and the resulting toner does not have a low melting point as a whole and has excellent blocking resistance. Moreover, it is excellent in low-temperature fixability. There is also an effect of suppressing contamination of the member. Moreover, the endothermic peak temperature of this crystalline polyester resin becomes like this. Preferably it is 50-80 degreeC, More preferably, it is 55-75 degreeC. In addition, endothermic peak temperature is measured by the method as described in an Example.

  The crystalline polyester resin can be produced from a polyvalent carboxylic acid component and a polyhydric alcohol component (a process for synthesizing a crystalline polyester resin). In this case, the valence is preferably 2 to 3, and particularly preferably 2 respectively. Therefore, the case where the valence is 2 (that is, a dicarboxylic acid component and a diol component) is described as a particularly preferable form. To do.

  As the dicarboxylic acid component, an aliphatic dicarboxylic acid is preferably used, and an aromatic dicarboxylic acid may be used in combination. As the aliphatic dicarboxylic acid, it is preferable to use a linear one. By using a linear type, there is an advantage that crystallinity is improved. The dicarboxylic acid component is not limited to one type, and two or more types may be mixed and used. If too many kinds of monomer components are used, it may be difficult to obtain a crystal structure.

  Examples of the aliphatic dicarboxylic acid include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelic acid, sebacic acid, 1,8-octanedicarboxylic acid, and 1,9-nonanedicarboxylic acid. Acid, 1,10-decanedicarboxylic acid, 1,10-dodecanedicarboxylic acid (1,10-dodecanedioic acid), 1,11-undecanedicarboxylic acid, 1,12-dodecanedicarboxylic acid, 1,13-tridecanedicarboxylic acid Examples include acids, 1,14-tetradecanedicarboxylic acid, 1,16-hexadecanedicarboxylic acid, 1,18-octadecanedicarboxylic acid, and the like, and lower alkyl esters and acid anhydrides thereof can also be used.

  Among the above aliphatic dicarboxylic acids, succinic acid, sebacic acid, 1,8-octanedicarboxylic acid, 1,9-nonanedicarboxylic acid, and 1,10-decanedicarboxylic acid are used from the viewpoints of availability and low-temperature fixability. It is preferable to use an acid, 1,10-dodecanedicarboxylic acid (1,10-dodecanedioic acid).

  Examples of the aromatic dicarboxylic acid that can be used together with the aliphatic dicarboxylic acid include terephthalic acid, isophthalic acid, orthophthalic acid, t-butylisophthalic acid, 2,6-naphthalenedicarboxylic acid, and 4,4′-biphenyldicarboxylic acid. Is mentioned. Among these, terephthalic acid, isophthalic acid, and t-butylisophthalic acid are preferably used from the viewpoints of availability and emulsification ease.

  The amount of aromatic dicarboxylic acid used is preferably 20 component mol% or less, more preferably 10 component mol%, based on 100 mol% of the entire dicarboxylic acid component for forming the crystalline polyester resin. Hereinafter, it is particularly preferably 5 constituent mol% or less. When the amount of aromatic dicarboxylic acid used is 20 constituent mol% or less, the crystallinity of the crystalline polyester resin can be ensured, and excellent low-temperature fixability can be obtained in the produced toner. Glossiness is obtained in the formed image, and deterioration of image storage stability due to melting point depression is suppressed. Furthermore, when oil droplets are formed using an oil phase liquid containing the crystalline polyester resin, it is surely emulsified. Can be obtained. The dicarboxylic acid component is not limited to one type, and two or more types may be mixed and used.

  Moreover, it is preferable to use aliphatic diol as a diol component, and you may contain diols other than aliphatic diol as needed.

  As the diol component, it is more preferable to use a linear aliphatic diol having 2 to 22 carbon atoms constituting the main chain among the aliphatic diols, and further, availability and reliable low-temperature fixing. It is particularly preferable to use a straight-chain aliphatic diol having 2 to 14 carbon atoms constituting the main chain from the viewpoint of exhibiting properties and obtaining an image having high gloss.

  The level at which low-temperature fixability is inhibited even when an aromatic dicarboxylic acid is used in combination as the dicarboxylic acid component because the number of carbon atoms constituting the main chain of the linear aliphatic diol used is 2 to 22 A polyester resin having a melting point of 5 is not formed, sufficient low-temperature fixability is obtained for the produced toner, and high glossiness is obtained for the finally formed image.

  As the diol component, a branched aliphatic diol can also be used. In this case, from the viewpoint of ensuring crystallinity, it is used together with a linear aliphatic diol and the linear aliphatic diol. It is preferable to use at a higher ratio. By using the linear aliphatic diol in such a high proportion, it is possible to reliably obtain excellent low-temperature fixability in a toner manufactured with ensured crystallinity, and finally form an image. In this case, a decrease in image storability due to a decrease in melting point is suppressed, and further, blocking resistance can be reliably obtained. The diol component is not limited to one type, and two or more types may be mixed and used.

  As the diol component for forming the crystalline polyester resin, the content of the aliphatic diol is preferably 80 constituent mol% or more, more preferably 90 constituent mol% or more. When the content of the aliphatic diol in the diol component is 80 constituent mol% or more, the crystallinity of the crystalline polyester resin can be ensured, and excellent low-temperature fixability can be obtained in the manufactured toner. Glossiness can be obtained in an image formed automatically.

  Examples of the aliphatic diol include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8- Octanediol, 1,9-nonanediol, 1,10-dodecanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1,18- Octadecane diol, 1,20-eicosane diol and the like can be mentioned. Among these, from the viewpoint of availability and low temperature fixability, 1,3-propanediol, 1,5-pentanediol, ethylene glycol, 1 , 4-butanediol, 1,6-hexanediol, 1,9-nonanediol, 1,10- It is preferable to use a Kanji-ol.

  Examples of the diol other than the aliphatic diol include a diol having a double bond and a diol having a sulfonic acid group. Specifically, examples of the diol having a double bond include 2-butene-1,4. -Diol, 3-butene-1,6-diol, 4-butene-1,8-diol and the like. The content of the diol having a double bond in the diol component is preferably 20 constituent mol% or less. When the content of the diol having a double bond is 20 constituent mol% or less, the resulting polyester resin does not have a greatly reduced melting point, and therefore there is little risk of filming.

  The use ratio of the diol component to the dicarboxylic acid component is such that the equivalent ratio [OH] / [COOH] of the hydroxyl group [OH] of the diol component to the carboxyl group [COOH] of the dicarboxylic acid component is 1.5 / 1. It is preferable to be set to ˜1 / 1.5, and more preferably 1.2 / 1 to 1 / 1.2. When the use ratio of the diol component and the dicarboxylic acid component is in the above range, a crystalline polyester resin having a desired molecular weight can be obtained reliably, and the acid value and hydroxyl value of the resin can be easily adjusted. be able to.

<Amorphous polyester resin containing a structural unit derived from a polyvalent carboxylic acid having an adamantane skeleton or a derivative thereof>
The amorphous polyester resin of the present invention includes a structural unit derived from a polyvalent carboxylic acid having an adamantane skeleton or a derivative thereof. In the present specification, the “amorphous polyester resin including a structural unit derived from a polyvalent carboxylic acid having an adamantane skeleton or a derivative thereof” is also simply referred to as “amorphous polyester resin”.

  In the present invention, the amorphous polyester resin is a polyester resin other than the above-described crystalline polyester resin. That is, it usually has no melting point and has a relatively high glass transition temperature (Tg). More specifically, the glass transition temperature (Tg) is preferably 80 to 220 ° C, and particularly preferably 80 to 150 ° C. The glass transition temperature (Tg) is measured by the method described in the examples.

  The amorphous polyester resin has a weight average molecular weight (Mw) of preferably 3,000 to 100,000, more preferably 4,000 to 70,000. The molecular weight distribution (Mw / Mn) of this amorphous polyester resin is preferably 3.0 to 6.0, more preferably 3.5 to 5.5. When the weight average molecular weight (Mw) of the amorphous polyester resin is within such a range, the obtained toner has excellent blocking resistance and low temperature fixability.

  The amorphous polyester resin of the present invention can be synthesized using a polyhydric alcohol component and a polyvalent carboxylic acid having an adamantane skeleton or a derivative thereof in the same manner as the above-described crystalline polyester resin synthesis step. In this case, the valence is preferably 2 to 3, and particularly preferably 2 respectively.

  Examples of the polyhydric alcohol component that can form the amorphous polyester resin of the present invention include, in addition to the above-mentioned aliphatic diols, bisphenols such as bisphenol A and bisphenol F, and these ethylene oxide adducts and propylene oxide additions. Examples include alkylene oxide adducts of bisphenols such as products, and examples of trihydric or higher polyhydric alcohol components include glycerin, trimethylolpropane, pentaerythritol, and sorbitol. Furthermore, cyclohexane dimethanol, cyclohexane diol, neopentyl alcohol, or the like may be used from the viewpoint of production cost and environmental properties. These can be used individually by 1 type or in combination of 2 or more types. Examples of the polyhydric alcohol component capable of forming an amorphous polyester resin include unsaturated polyvalent compounds such as 2-butyne-1,4 diol, 3-butyne-1,4 diol, and 9-octadezene-7,12 diol. Alcohol and the like can also be used.

  Among these, from the viewpoint of ensuring the strength of the resin, it is preferable to use bisphenol A ethylene oxide adduct and propylene oxide adduct, cyclohexanedimethanol, cyclohexanediol, and neopentyl alcohol as the polyhydric alcohol component.

  In the present invention, the amorphous polyester resin contains a polyvalent carboxylic acid having an adamantane skeleton or a derivative thereof as an essential component.

  Examples of the polyvalent carboxylic acid having an adamantane skeleton include 1,3-adamantane dicarboxylic acid, 5-tert-butyl-1,3-adamantane dicarboxylic acid, dimethyl 4-oxo-1,3-adamantane dicarboxylate, 1,3- Examples include dimethyl adamantanedicarboxylate, adamantanetricarboxylic acid, 5,7-dimethyl-1,3-adamantanediol, and 5,7-diethyl-1,3-adamantanediol. Among these, 1,3-adamantane dicarboxylic acid, 5-tert-butyl-1,3-adamantane dicarboxylic acid, and dimethyl 1,3-adamantane dicarboxylate are preferable from the viewpoint of availability and imparting hydrophobicity.

  The derivative is an adamantane dicarboxylic acid having a substituent, and the substituent is an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 18 carbon atoms. Is preferred. Of these, those having hydrophobic characteristics are preferred from the viewpoint of suppressing the change in the amount of water, and in this respect, an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 18 carbon atoms is preferable. As the group, those that are tougher than styrene-acrylic resins are preferred.

  The number of carbon atoms in the alkyl group is more preferably 1 to 4, and still more preferably 3 to 5 carbon atoms. Specifically, linear, branched, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl It is preferably a group or a hexyl group. Moreover, as a C1-C6 alkoxy group, it has the structure which the C1-C6 alkyl group quoted above couple | bonded with the oxygen atom. Moreover, as a C6-C18 aryl group, it is preferable that they are a phenyl group, a naphthyl group, or an anthracenyl group.

  In particular, since the ester group contained in the binder resin has hydrophilicity, a substituent that inhibits the hydrophilic effect is preferable (that is, a substituent that inhibits water molecules from coming close to the ester group is preferable). . In that sense, hydrophobic and bulky substituents such as tert-butyl group, isobutyl group and phenyl group are preferred. Of course, as described above, if it has an adamantane skeleton having a hydrophobic and bulky structure, water adsorption to the toner can be suppressed, and that alone has the desired effect of the present invention.

  In addition to the essential components, the amorphous polyester resin may have an aromatic dicarboxylic acid such as phthalic acid, isophthalic acid, terephthalic acid, and naphthalenedicarboxylic acid in addition to the aliphatic dicarboxylic acid described above. Further, for the purpose of making the melt viscosity of the obtained amorphous polyester resin appropriate, a trivalent or higher polyvalent carboxylic acid such as trimellitic acid or pyromellitic acid may be used. These acid anhydrides or acid chlorides may also be used.

  In addition, unsaturated aliphatic dicarboxylic acids such as maleic acid, fumaric acid, itaconic acid, citraconic acid, glutaconic acid, isododecenyl succinic acid, dodecenyl succinic acid, octenyl succinic acid; and their acid anhydrides or acid chlorides Unsaturated polyvalent carboxylic acids can also be used. A small amount of monocarboxylic acid having a polymerizable unsaturated bond such as caffeic acid may be used in combination with the polyvalent carboxylic acid component to form the amorphous polyester resin. These can be used individually by 1 type or in combination of 2 or more types. In addition, according to this invention, since it has essential polyhydric carboxylic acid which has an adamantane skeleton, it is suitable at the point which can be used also as a substitute of the dodecenyl succinic acid used conventionally well.

  Among these, as the polyvalent carboxylic acid component, terephthalic acid, isophthalic acid, trimellitic anhydride, maleic acid, fumaric acid, isodode are used from the viewpoint of obtaining availability, resin strength, and low-temperature fixability. Cenyl succinic acid and dodecenyl succinic anhydride are preferably used.

  In preferable embodiment of this invention, it is preferable that content of a structural unit is 3-30 mol% with respect to all the structural units in an amorphous polyester resin, More preferably, it is 4-29 mol%. More preferably, it is 5 mol% or more. Within such a range, when an external additive is used, it is preferable in that it can be efficiently attached without being liberated. In terms of the initial environmental difference, the larger the amount of structural units introduced, the better. However, from the viewpoint of durability stability, it is preferably 13 to 18 mol%.

<Release agent (wax)>
The release agent constituting the toner of the present invention is not particularly limited, and known ones can be used. Specifically, for example, low molecular weight polyolefins such as polyethylene, polypropylene and polybutene; plant waxes such as synthetic ester wax, carnauba wax, rice wax, candelilla wax, wood wax, jojoba oil; montan wax, paraffin wax , Minerals such as microcrystalline wax and Fischer-Tropsch wax, petroleum-based wax; and modified products thereof. Among these, synthetic ester waxes are preferable, and pentaerythritol tetrabehenate and the like can be suitably used as the synthetic ester wax.

  The amount of the release agent added is usually 0.5 to 25% by mass, preferably 3 to 15% by mass with respect to the toner base particles. Such a range is sufficient for fixing.

  Moreover, as a magnitude | size of a mold release agent, 10-1000 nm and 50-500 nm are preferable at a volume average particle diameter, Furthermore, 80-300 nm is especially preferable.

  According to the present invention, since it includes a structural unit derived from a polyvalent carboxylic acid having an adamantane skeleton or a derivative thereof, the dispersibility of the release agent is improved by appropriately disposing the hydrophobic portion in the toner. In addition, the charging stability is improved.

  Incidentally, the toner of the present invention may contain a colorant as an internal additive, if necessary. Here, the internal additive is a component present in a form contained in the toner base particles. This will be described below.

<Colorant>
As the colorant that can constitute the toner of the present invention, carbon black, a magnetic material, a dye, a pigment, and the like can be arbitrarily used. As the carbon black, channel black, furnace black, acetylene black, thermal black, lamp black, and the like can be used. Etc. are used. Magnetic materials include ferromagnetic metals such as iron, nickel and cobalt, alloys containing these metals, compounds of ferromagnetic metals such as ferrite and magnetite, alloys that do not contain ferromagnetic metals but exhibit ferromagnetism by heat treatment, For example, a kind of alloy called Heusler alloy such as manganese-copper-aluminum and manganese-copper-tin, chromium dioxide, and the like can be used.

  Examples of the black colorant include carbon black such as furnace black, channel black, acetylene black, thermal black, and lamp black, and magnetic powder such as magnetite and ferrite.

  Examples of the colorant for magenta or red include C.I. I. Pigment red 2, C.I. I. Pigment red 3, C.I. I. Pigment red 5, C.I. I. Pigment red 6, C.I. I. Pigment red 7, C.I. I. Pigment red 15, C.I. I. Pigment red 16, C.I. I. Pigment red 48: 1, C.I. I. Pigment red 53: 1, C.I. I. Pigment red 57: 1, C.I. I. Pigment red 122, C.I. I. Pigment red 123, C.I. I. Pigment red 139, C.I. I. Pigment red 144, C.I. I. Pigment red 149, C.I. I. Pigment red 150, C.I. I. Pigment red 166, C.I. I. Pigment red 177, C.I. I. Pigment red 178, pigment red 184, C.I. I. And CI Pigment Red 222.

  Examples of the colorant for orange or yellow include C.I. I. Pigment orange 31, C.I. I. Pigment orange 43, C.I. I. Pigment yellow 12, C.I. I. Pigment yellow 13, C.I. I. Pigment yellow 14, C.I. I. Pigment yellow 15, C.I. I. Pigment yellow 17, C.I. I. Pigment yellow 74, C.I. I. Pigment yellow 93, C.I. I. Pigment yellow 94, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 155, C.I. I. Pigment yellow 180, C.I. I. And CI Pigment Yellow 185.

  Further, as a colorant for green or cyan, C.I. I. Pigment blue 15, C.I. I. Pigment blue 15: 2, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 16, C.I. I. Pigment blue 60, C.I. I. Pigment blue 62, C.I. I. Pigment blue 66, C.I. I. And CI Pigment Green 7.

  These colorants can be used alone or in combination of two or more as required.

  The addition amount of the colorant is in the range of 1 to 30% by mass, preferably 2 to 20% by mass, based on the toner base particles. In such a range, a sufficient image density can be obtained and the charging stability is excellent.

  Moreover, as a magnitude | size of a coloring agent, 10-1000 nm and 50-500 nm are preferable at a volume average particle diameter, Furthermore, 80-300 nm is especially preferable.

  Moreover, you may contain a charge control agent and various inorganic fine particles as an external additive as needed. Here, the external additive is a component that exists in a form of being attached to the outside of the toner base particles. This will be described below.

<Charge control agent>
Various known compounds can be used as the charge control agent.

  The addition amount of the charge control agent is usually 0.1 to 10 parts by mass, preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the binder resin in the toner base particles.

  As a magnitude | size of the charge control agent particle | grains of this invention, 10-1000 nm and 50-500 nm are preferable at a number average primary particle diameter, Furthermore, 80-300 nm is especially preferable.

<Inorganic fine particles>
As the inorganic fine particles, silica, silica sand, magnesium oxide, zirconium oxide, clay, titania, barium titanate, magnesium titanate, potassium titanate, strontium titanate, alumina, zinc oxide and the like are preferable. Hydrophobic treatment with a silane coupling agent or a titanium coupling agent is preferred.

  The amount of the inorganic fine particles added is 0.1 to 5.0% by mass, preferably 0.5 to 4.0% by mass, based on the toner base particles. Various inorganic fine particles may be used in combination.

  Further, the toner base particles of the present invention may contain not only the above components but also additives (external additives) used in the art such as organic fine particles or lubricants as necessary. That is, the external additive is preferably at least one selected from the group consisting of inorganic fine particles, organic fine particles, charge control agents, and lubricants.

  The average particle size of the toner of the present invention is 3.0 to 8.0 μm, preferably 4.0 to 7.5 μm in terms of volume average particle size. By being in the above range, the amount of toner having a large adhesion force that flies at the time of fixing and adheres to the heating member to generate a fixing offset is reduced, and the transfer efficiency is increased to improve the halftone image quality. The image quality of dots and dots is improved. In addition, the toner on the photoreceptor and the intermediate transfer belt can be cleaned well.

  As will be described later, the average particle size of the toner of the present invention is controlled by the concentration of the aggregating agent, the amount of the solvent added in the agglomeration and fusing step during the production of the toner, the fusing time, and the composition of the polyester resin. be able to.

  The volume-based particle size dispersion (CVvol value) in the toner of the present invention is 15 to 25, preferably 15 to 22.

<Method for Producing Toner of the Present Invention>
Subsequently, a preferred embodiment of the toner production method of the present invention will be specifically described. A method for producing a toner according to a preferred embodiment of the present invention includes:
(1-1) A crystalline polyester resin is synthesized, and an oil phase liquid in which the crystalline polyester resin is dissolved or dispersed in an organic solvent (solvent) is prepared (solution preparation step or dispersion preparation step). A liquid dispersion of fine particles of the crystalline polyester resin (hereinafter also referred to as “crystalline polyester resin fine particles”) is prepared by removing the organic solvent after forming oil droplets of the oil phase liquid in the medium. A step of preparing a crystalline polyester resin fine particle dispersion;
(1-2) An amorphous polyester resin is synthesized, an oil phase liquid is prepared by dissolving or dispersing the amorphous polyester resin in an organic solvent (solvent), and oil droplets are formed in the aqueous medium by the oil phase liquid. Amorphous polyester resin fine particles for preparing a dispersion of fine particles (hereinafter also referred to as “amorphous polyester resin fine particles”) of the amorphous polyester resin by removing the organic solvent after forming Dispersion preparation step;
(1-3) A release agent in which a release agent (wax) is finely dispersed in an aqueous medium to prepare a dispersion of release agent fine particles (hereinafter also referred to as “release agent fine particles”). Fine particle dispersion preparation step;
(1-4) Colorant fine particle dispersion for preparing a dispersion of colorant fine particles (hereinafter also referred to as “colorant fine particles”) by dispersing the colorant in fine particles in an aqueous medium as necessary. Liquid preparation step;
(2) Toner base by agglomerating and fusing toner constituent components such as crystalline polyester resin fine particles, amorphous polyester resin fine particles, release agent fine particles, and if necessary, colorant fine particles in an aqueous medium. Aggregation / fusion process to form particles;
(3) A filtration / washing step in which the obtained toner base particles are filtered from an aqueous medium, pH is adjusted, and pulverized to remove the surfactant and the like from the toner base particles.
(4) A drying step in which the washed toner base particles are further pulverized and dried as necessary;
And if necessary,
(5) an external additive addition step of adding an external additive to the dried toner base particles;
Have In this way, a toner according to a preferred embodiment of the present invention can be produced.

  The toner base particles constituting the toner of the present invention include a core particle containing a crystalline polyester resin, an amorphous polyester resin and a release agent, and a shell layer made of a shell resin covering the outer peripheral surface of the core particle. A core-shell structure may be used. As the shell resin constituting the shell layer, it is preferable to use only an amorphous polyester resin. According to the toner composed of toner base particles having a shell layer made only of an amorphous polyester resin, contamination of the photoreceptor is suppressed, and excellent low-temperature fixability and high mechanical strength can be obtained. Further, from the viewpoint of suppressing the high temperature offset phenomenon, an amorphous polyester resin and a crosslinked acrylic resin can be used in combination as the shell resin constituting the shell layer.

  When the toner base particles have a core-shell structure, in the (2) agglomeration / fusion step of an example of the above production method, first, amorphous polyester resin fine particles and crystalline polyester forming core particles Fine particles of toner constituents such as resin fine particles, release agent fine particles and, if necessary, fine particles by colorant fine particles are aggregated and fused in an aqueous medium to form core particles, and then in a dispersion of core particles A shell layer that covers the surface of the core particles is formed by adding amorphous polyester resin fine particles to form a shell layer to the surface and aggregating and fusing the amorphous polyester resin fine particles on the surface of the core particles. By doing so, it can be manufactured.

  This embodiment is described in more detail below.

(1-1) Crystalline polyester resin fine particle dispersion preparation step This crystalline polyester resin fine particle dispersion preparation step synthesizes a crystalline polyester resin as a binder resin material constituting the toner base particles, In this step, the polyester resin is dispersed in the form of fine particles in an aqueous medium to prepare a dispersion of crystalline polyester resin fine particles.

  As a method of dispersing the crystalline polyester resin in the aqueous medium, an oil phase liquid is prepared by dissolving or dispersing the crystalline polyester resin in an organic solvent (solvent), and the oil phase liquid is obtained by phase inversion emulsification or the like. There is a method in which an organic solvent is removed after forming oil droplets in a state of being controlled to have a desired particle size by dispersing in an aqueous medium.

  The organic solvent (solvent) used for the preparation of the oil phase liquid is preferably one having a low boiling point and low solubility in water from the viewpoint of easy removal after the formation of oil droplets. Specific examples include methyl acetate, ethyl acetate, methyl ethyl ketone, isopropyl alcohol, methyl isobutyl ketone, toluene, xylene and the like. These can be used alone or in combination of two or more.

  The amount of the organic solvent (solvent) used (when two or more types are used, the total amount used) is usually 1 to 300 parts by weight, preferably 10 to 200 parts by weight, based on 100 parts by weight of the crystalline polyester resin. Preferably it is 25-100 mass parts.

  In the present invention, the “aqueous medium” refers to a medium containing at least 50% by mass of water, and examples of components other than water include organic solvents that dissolve in water, such as methanol, ethanol, isopropanol. , Butanol, acetone, methyl ethyl ketone, dimethylformamide, methyl cellosolve, tetrahydrofuran and the like. Among these, it is preferable to use an organic organic solvent such as methanol, ethanol, isopropanol, and butanol, which is an organic solvent that does not dissolve the resin. Preferably, only water is used as the aqueous medium.

  The amount of the aqueous medium used is preferably 50 to 2,000 parts by mass and more preferably 100 to 1,000 parts by mass with respect to 100 parts by mass of the oil phase liquid. By making the usage-amount of an aqueous medium into said range, an oil phase liquid can be emulsified and dispersed to a desired particle size in an aqueous medium.

  A dispersion stabilizer may be dissolved in the aqueous medium, and a surfactant or resin fine particles may be added for the purpose of improving the dispersion stability of the oil droplets.

  Examples of the dispersion stabilizer include inorganic compounds such as tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, and hydroxyapatite, but it is necessary to remove the dispersion stabilizer from the obtained toner base particles. Therefore, it is preferable to use an acid or alkali-soluble material such as tricalcium phosphate, or from the environmental viewpoint, it is preferable to use a material that can be decomposed by an enzyme.

  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 salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, pyridinium salts, alkylisoquinolinium salts, benzethonium chloride, fatty acid amide derivatives, polyhydric alcohols Nonionic surfactants such as derivatives, amphoteric surfactants such as alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine and N-alkyl-N, N-dimethylammonium betaine Gerare also anionic surfactants and cationic surfactants having a fluoroalkyl group can be used.

  The fine resin particles for improving the dispersion stability are preferably those having a particle size of 0.5 to 3 μm. Specifically, polymethyl methacrylate resin fine particles having a particle size of 1 μm and 3 μm, Examples thereof include polystyrene resin fine particles of 0.5 μm and 2 μm, polystyrene-acrylonitrile resin fine particles having a particle diameter of 1 μm, and the like.

  Such emulsification and dispersion of the oil phase liquid can be performed using mechanical energy, and the disperser for performing the emulsification and dispersion is not particularly limited. Dispersers, friction dispersers, high-pressure jet dispersers, ultrasonic dispersers, high-pressure impact dispersers, optimizers, and the like. Specifically, for example, TK homomixer (manufactured by Koki Kogyo Co., Ltd.) Can be mentioned.

  The removal of the organic solvent after the formation of oil droplets is performed by gradually heating the entire dispersion liquid in which the crystalline polyester resin fine particles are dispersed in the aqueous medium in a stirring state, and giving strong stirring in a certain temperature range. Then, it can be performed by an operation such as desolvation. Alternatively, it can be removed while reducing the pressure using an apparatus such as an evaporator.

  The particle size of the crystalline polyester resin fine particles (oil droplets) in the prepared crystalline polyester resin fine particle dispersion is preferably a volume average particle size of 60 to 1000 nm, more preferably 80 to 500 nm. It is. In addition, this volume average particle diameter is measured by the method as described in an Example. The volume average particle diameter of the oil droplets can be controlled by the magnitude of mechanical energy during emulsification dispersion.

  In addition, the content of the crystalline polyester resin fine particles in the crystalline polyester resin fine particle dispersion is preferably in the range of 10 to 50% by mass, and more preferably in the range of 15 to 40% by mass. Within such a range, the spread of the particle size distribution can be suppressed and the toner characteristics can be improved.

(1-2) Amorphous polyester resin fine particle dispersion preparation step This amorphous polyester resin fine particle dispersion preparation step synthesizes an amorphous polyester resin as a binder resin material constituting the toner base particles, In this step, the amorphous polyester resin is dispersed in the form of fine particles in an aqueous medium to prepare a dispersion of amorphous polyester resin fine particles.

  As a method for dispersing the amorphous polyester resin in the aqueous medium, the amorphous polyester resin is dissolved or dispersed in an organic solvent (solvent) in the same manner as when the crystalline polyester resin is dispersed in the aqueous medium. An oil phase liquid is prepared, and the oil phase liquid is dispersed in an aqueous medium by phase inversion emulsification or the like to form oil droplets in a state of being controlled to a desired particle size, and then an organic solvent (solvent) is added. The method of removing is mentioned.

  As the organic solvent (solvent) used for the preparation of the oil phase liquid, the boiling point is low and the solubility in water is low from the viewpoint of easy removal after the formation of oil droplets, as described above. Specific examples thereof include methyl acetate, ethyl acetate, methyl ethyl ketone, isopropyl alcohol, methyl isobutyl ketone, toluene, xylene and the like. These can be used alone or in combination of two or more.

  The amount of the organic solvent (solvent) used (when two or more types are used, the total amount used) is usually 1 to 300 parts by weight, preferably 10 to 200 parts by weight, based on 100 parts by weight of the amorphous polyester resin. More preferably, it is 25-100 mass parts.

  The amount of the aqueous medium used is preferably 50 to 2,000 parts by mass and more preferably 100 to 1,000 parts by mass with respect to 100 parts by mass of the oil phase liquid. By making the usage-amount of an aqueous medium into said range, an oil phase liquid can be emulsified and dispersed to a desired particle size in an aqueous medium.

  Similarly to the above, a dispersion stabilizer may be dissolved in the aqueous medium, and a surfactant or resin fine particles may be added for the purpose of improving the dispersion stability of the oil droplets. Good.

  Such an emulsified dispersion of the oil phase liquid can be performed using mechanical energy as described above, and the disperser for performing the emulsified dispersion is not particularly limited, and is a low-speed shearing type. Dispersers, high-speed shear dispersers, friction dispersers, high-pressure jet dispersers, ultrasonic dispersers, high-pressure impact dispersers, optimizers, etc. (Manufactured by Kogyo Co., Ltd.).

  The removal of the organic solvent after the formation of the oil droplets is performed by gradually heating the entire dispersion liquid in which the amorphous polyester resin fine particles are dispersed in the aqueous medium in a stirring state and performing strong stirring in a certain temperature range. After giving, it can be performed by an operation such as desolvation. Alternatively, it can be removed while reducing the pressure using an apparatus such as an evaporator.

  The particle size of the amorphous polyester resin fine particles (oil droplets) in the prepared amorphous polyester resin fine particle dispersion is preferably a volume average particle size of 60 to 1000 nm, more preferably 80. ~ 500 nm. In addition, this volume average particle diameter is measured by the method as described in an Example. The volume average particle diameter of the oil droplets can be controlled by the magnitude of mechanical energy during emulsification dispersion.

  In addition, the content of the amorphous polyester resin fine particles in the amorphous polyester resin fine particle dispersion is preferably in the range of 10 to 50% by mass, and more preferably in the range of 15 to 40% by mass. Within such a range, the spread of the particle size distribution can be suppressed and the toner characteristics can be improved.

(1-3) Release Agent Fine Particle Dispersion Preparation Step This release agent fine particle dispersion preparation step is a step of preparing a release agent fine particle dispersion by dispersing a release agent in the form of fine particles in an aqueous medium. is there.

  The aqueous medium is as described above, and a surfactant or resin fine particles may be added to the aqueous medium for the purpose of improving dispersion stability.

  The release agent can be dispersed using mechanical energy. Such a disperser is not particularly limited, and as mentioned above, a low-speed shear disperser, a high-speed shear Dispersers, friction dispersers, high-pressure jet dispersers, ultrasonic dispersers, high-pressure impact dispersers, optimizers, or high-pressure homogenizers. Specific examples include Manton Gorin high-pressure homogenizers (Gorin) And so on.

  In dispersing the release agent, heating may be performed as necessary.

  The volume average particle size of the release agent fine particles is preferably 10 to 300 nm, more preferably 100 to 200 nm, and particularly preferably 100 to 150 nm.

  Further, the content of the release agent fine particles in the release agent fine particle dispersion is preferably in the range of 10 to 50% by mass, and more preferably in the range of 15 to 40% by mass. Within such a range, aggregation of the release agent particles hardly occurs and the stability of the dispersion is excellent.

(1-4) Colorant Fine Particle Dispersion Preparation Step This colorant fine particle dispersion preparation step is a step that is performed as necessary when a toner containing a colorant is desired as toner base particles. This is a step of preparing a dispersion of fine colorant particles by dispersing in fine particles in an aqueous medium.

  The aqueous medium is as described above, and a surfactant or resin fine particles may be added to the aqueous medium for the purpose of improving dispersion stability.

  Dispersion of the colorant can be performed using mechanical energy, and such a disperser is not particularly limited, and as mentioned above, a low-speed shear disperser, a high-speed shear disperser Dispersers, friction dispersers, high-pressure jet dispersers, ultrasonic dispersers, or high-pressure impact dispersers, such as an optimizer, specifically, for example, HJP30006 manufactured by Sugino Machine Co., Ltd. Can do.

  The volume average particle diameter of the colorant fine particles is preferably 10 to 300 nm, more preferably 100 to 200 nm, and particularly preferably 100 to 150 nm.

  In addition, the content of the colorant fine particles in the colorant fine particle dispersion is preferably in the range of 10 to 50% by mass, and more preferably in the range of 15 to 40% by mass. Within such a range, aggregation of the colorant particles hardly occurs and the stability of the dispersion is excellent.

(2) Aggregation / fusion process This aggregation / fusion process is carried out by dispersing a dispersion of crystalline polyester resin fine particles, a dispersion of amorphous polyester resin fine particles, a dispersion of release agent fine particles, or coloring if necessary. Add and mix other components such as fine particle dispersion, slowly agglomerate the average particle size while balancing the repulsive force of the fine particle surface by pH adjustment and the agglomeration force by adding the flocculant made of electrolyte. This is a step of forming toner base particles by performing association while controlling the diameter and particle size distribution, and at the same time, fusing the fine particles by heating and stirring to control the shape. This agglomeration / fusion process can also be performed using mechanical energy or heating means as required. In the fusing step, under the stirring conditions in accordance with the agglomeration step, the agglomeration suspension is stopped by raising the pH of the suspension of the agglomerated particles and heated at a temperature equal to or higher than the melting point of the crystalline polyester resin. Fusing the agglomerated particles. Moreover, when it coat | covers with an amorphous polyester resin, this amorphous polyester resin is also united and a core aggregated particle is coat | covered. The heating time may be as long as fusion is performed, and may be performed for about 0.5 to 10 hours. Cool after fusion to obtain fused particles. Further, in the cooling step, crystallization may be promoted by so-called gradual cooling in which the cooling rate is decreased in the range of the melting point of the crystalline polyester resin ± 15 ° C. The fused particles obtained by fusing can be made into toner base particles through a solid-liquid separation process such as filtration and, if necessary, a washing process and a drying process.

  In the agglomeration step, first, the obtained dispersion liquid of the crystalline polyester resin particles, the dispersion liquid of the amorphous polyester resin particles, the dispersion liquid of the release agent fine particles, the colorant dispersion liquid, and the like are mixed to obtain a mixed liquid. Aggregates by heating at a temperature not higher than the glass transition temperature of the crystalline polyester resin to form aggregated particles. Aggregated particles are formed by acidifying the pH of the mixed solution with stirring. As pH, the range of 2-7 is desirable, The range of 2.2-6 is more desirable, The range of 2.4-5 is still more desirable. At this time, it is also effective to use a flocculant.

  As the flocculant to be used, a surfactant having a reverse polarity to the surfactant used for the dispersant, an inorganic metal salt, and a metal complex having a valence of 2 or more can be preferably used.

  Examples of inorganic metal salts include metal salts such as calcium chloride, calcium nitrate, barium chloride, magnesium chloride, zinc chloride, aluminum chloride, and aluminum sulfate, and inorganic substances such as polyaluminum chloride, polyaluminum hydroxide, and calcium polysulfide. Examples thereof include metal salt polymers. Of these, aluminum salts and polymers thereof are particularly preferred. In order to obtain a sharper particle size distribution, it is more suitable that the valence of the inorganic metal salt is bivalent than monovalent, trivalent than bivalent, and tetravalent than trivalent.

  When the agglomerated particles have reached a desired particle size, a toner having a structure in which the surface of the core agglomerated particles is coated with the amorphous polyester resin can be produced by adding amorphous polyester resin fine particles. In the case of additional addition, a flocculant may be added or pH adjustment may be performed before additional addition.

  In this aggregation / fusion process, a surfactant may be added to the aqueous medium in order to stably disperse each fine particle in the aggregation system.

  The surfactant is not particularly limited, and various known ones can be used, but sulfonates such as sodium dodecylbenzenesulfonate and sodium arylalkylpolyethersulfonate; sodium dodecylsulfate, sodium tetradecylsulfate, Sulfate esters such as sodium pentadecyl sulfate, sodium octyl sulfate; anionic, such as fatty acid salts such as sodium oleate, sodium laurate, sodium caprate, sodium caprylate, sodium caproate, potassium stearate, calcium oleate, An ionic surfactant containing a cationic property can be exemplified as a suitable one.

  Also, polyethylene oxide, polypropylene oxide, combination of polypropylene oxide and polyethylene oxide, ester of polyethylene glycol and higher fatty acid, alkylphenol polyethylene oxide, ester of higher fatty acid and polyethylene glycol, ester of higher fatty acid and propylenoxide, sorbitan ester Nonionic surfactants such as can also be used. The above surfactants can be used singly or in combination of two or more as desired.

  Moreover, the addition ratio (mass ratio) of the amorphous polyester resin fine particles / crystalline polyester resin fine particles in the aggregation / fusion step is preferably 1 to 100, more preferably 5 to 50, and still more preferably. 8-20. Within such a range, the obtained toner has excellent heat-resistant storage properties and excellent low-temperature fixability.

  When other internal additives are introduced into the toner base particles, a dispersion liquid of internal additive fine particles consisting only of the internal additives is prepared before the aggregation / fusion step (2), and the aggregation / fusion is performed. In the fusing step (2), a method of mixing the dispersion of the internal additive fine particles together with the dispersion of the crystalline polyester resin fine particles and the dispersion of the amorphous polyester resin fine particles is preferable.

(3) Filtration / Washing Step In this filtration / washing step, the obtained dispersion of toner base particles is cooled to form a cooled slurry, and a solvent such as water is removed from the cooled dispersion of toner base particles. Filter process for solid-liquid separation of toner base particles and filtering the toner base particles, and cleaning process for removing deposits such as surfactant from the filtered toner base particles (cake-like aggregate) And is given. Specific examples of the solid-liquid separation and washing method include a centrifugal separation method, a vacuum filtration method using an aspirator, Nutsche and the like, a filtration method using a filter press, etc., and these are not particularly limited. . In this filtration / washing step, pH adjustment or pulverization may be performed as appropriate. Such an operation may be repeated.

(4) Drying Step In this drying step, the toner base particles that have been washed are subjected to a drying treatment. Dryers used in this drying process include ovens, spray dryers, vacuum freeze dryers, vacuum dryers, stationary shelf dryers, mobile shelf dryers, fluidized bed dryers, rotary dryers, and stirrers A dryer etc. are mentioned, These are not specifically limited. The water content in the dried toner base particles is preferably 5% by mass or less.

  In addition, when the dried toner base particles are aggregated by weak interparticle attraction to form an aggregate, the aggregate may be crushed. Here, as the crushing treatment apparatus, a mechanical crushing apparatus such as a jet mill, a comb mill, a Henschel mixer, a coffee mill, or a food processor can be used.

(5) External additive addition step This external additive addition step is a step of adding a charge control agent and various inorganic fine particles to the dried toner base particles for the purpose of improving fluidity, chargeability and cleaning properties. , A step of adding an organic fine particle or an external additive such as a lubricant, which is performed as necessary. Examples of the apparatus used for adding the external additive include various known mixing apparatuses such as a Turbuler mixer, a Henschel mixer, a Nauter mixer, a V-type mixer, and a sample mill. Further, sieving classification may be performed as necessary in order to make the particle size distribution of the toner within an appropriate range.

  According to the manufacturing method as described above, a high-quality image can be basically formed. Further, while having excellent low-temperature fixability, it has excellent high-temperature offset resistance, and an excellent machine. Toner having high strength can be easily manufactured with a small manufacturing load.

<Developer>
For example, the above toner may be used as a one-component magnetic toner containing a magnetic material, mixed with a so-called carrier to be used as a two-component developer, or a non-magnetic toner may be used alone. Any of these can be suitably used.

  As the carrier constituting the two-component developer, magnetic particles made of conventionally known materials such as metals such as iron, ferrite, and magnetite, and alloys of these metals with metals such as aluminum and lead can be used. It is particularly preferable to use ferrite particles.

  The carrier preferably has a volume average particle diameter of 15 to 100 μm, more preferably 25 to 60 μm. The volume average particle diameter (volume-based median diameter) of the carrier can be measured by the method described in the examples.

  As the carrier, it is preferable to use a carrier coated with a resin, or a so-called resin dispersion type carrier in which magnetic particles are dispersed in a resin. The resin composition for coating is not particularly limited. For example, olefin resin, cyclohexyl methacrylate / methyl methacrylate copolymer, styrene resin, styrene-acrylic resin, silicone resin, ester resin, or fluorine-containing resin. Polymer based resins and the like are used. In addition, the resin for constituting the resin-dispersed carrier is not particularly limited, and known resins can be used. For example, acrylic resins, styrene-acrylic resins, polyester resins, fluorine resins, phenolic resins Resin etc. can be used.

<Image forming method>
The above toner can be suitably used in an image forming method including a fixing step by a contact heating method. Specifically, as an image forming method, an electrostatic latent image formed electrostatically on, for example, an image carrier using the toner as described above, and a developer in a developing device by a friction charging member. By revealing the toner image by charging to obtain a toner image, transferring the toner image to the recording material, and then fixing the toner image transferred on the recording material to the recording material by a contact heating type fixing process, A visible image is obtained. That is, the toner of the present invention is used for developing an electrostatic image.

<Fixing method>
As a suitable fixing method using the toner of the present invention, a so-called contact heating method can be mentioned. Examples of the contact heating method include a heat pressure fixing method, a heat roll fixing method, and a pressure contact heat fixing method in which fixing is performed by a rotating pressure member including a fixedly arranged heating body.

  In the fixing method of the hot roll fixing method, usually, an upper roller provided with a heat source inside a metal cylinder made of iron or aluminum whose surface is coated with fluororesin, etc., and a lower roller formed of silicone rubber or the like Is used.

  As the heat source, a linear heater is used, and the surface temperature of the upper roller is heated to about 120 to 200 ° C. by this heater. A pressure is applied between the upper roller and the lower roller, and the lower roller is deformed by this pressure, so that a so-called nip is formed in the deformed portion. The width of the nip is 1 to 10 mm, preferably 1.5 to 7 mm. The fixing linear velocity is preferably 40 mm / sec to 600 mm / sec. If the nip width is too small, heat cannot be uniformly applied to the toner, which may cause uneven fixing. On the other hand, if the nip width is too large, the toner is contained in the toner. The melting of the polyester resin is accelerated, and there is a possibility that fixing offset occurs.

  According to the toner as described above, when a constitutional unit derived from a polyvalent carboxylic acid having an adamantane skeleton or a derivative thereof is included as a component of the toner, the adamantane skeleton has a hydrophobic and bulky structure. Therefore, the moisture adsorption to the toner is suppressed, and the charging property is stabilized even when the environment is changed or the amount of water adhering to the toner is different as in the low humidity environment and the high humidity environment. That is, it is possible to stabilize the chargeability in a high temperature and high humidity environment. In addition, the structure of adamantane is highly symmetric and extremely stable, so that even when the toner is stressed, the embedding of the external additive into the resin constituting the toner base particles is suppressed, and the charging property is maintained even when printing is repeated. Stabilize. As a result, it is possible to provide an electrostatic image developing toner and an image forming apparatus that do not cause image gloss and image density fluctuation. Furthermore, the use of a resin having an adamantane skeleton also has the effect of improving the dispersibility of the release agent. When the dispersibility of the release agent is improved, the chargeability is improved.

As mentioned above, although embodiment of this invention was described, this invention is not limited to said aspect, A various change can be added.

  Hereinafter, representative embodiments of the present invention will be shown and the present invention will be further described, but the present invention is of course not limited to these embodiments. In the examples, unless otherwise specified, “part” represents “part by mass” and “%” represents “% by mass”.

<Measuring method of various characteristics>
First, methods for measuring physical properties of toners and the like used in Examples and Comparative Examples will be described.

(Measurement method of toner particle size and particle size distribution and volume average particle size)
In the present invention, the toner particle size and particle size distribution were measured using Multisizer II type (manufactured by Beckman-Coulter) as the measuring device, and ISOTON-II (manufactured by Beckman-Coulter) as the electrolyte.

  As a measurement method, 10 mg of a measurement sample was added to 2 ml of a 5% aqueous solution of a surfactant (sodium dodecylbenzenesulfonate) as a dispersant, and this was added to 100 ml of the electrolytic solution.

  The electrolytic solution in which the sample is suspended is subjected to a dispersion treatment with an ultrasonic disperser for about 1 minute, and the particle size distribution of particles of 2 to 60 μm is measured using the Multisizer II type with an aperture diameter of 100 μm, and the volume is measured. The average particle size was determined. The number of particles to be measured was 50,000.

(Measurement method of weight average molecular weight and molecular weight distribution of resin)
In the present invention, the molecular weight of the resin or the like is measured under the following conditions. GPC uses “HLC-8120GPC, SC-8020 (manufactured by Tosoh Corporation)”, and the column uses two “TSKgel, SuperHM-H (6.0 mm ID × 15 cm, manufactured by Tosoh Corporation)” THF (tetrahydrofuran) was used as an eluent. As experimental conditions, the experiment was performed using a sample concentration of 0.5%, a flow rate of 0.6 ml / min, a sample injection amount of 10 μl, a measurement temperature of 40 ° C., and an IR detector. The calibration curve is “polystylen standard sample TSK standard” manufactured by Tosoh Corporation: “A-500”, “F-1”, “F-10”, “F-80”, “F-380”, “A-2500”. ”,“ F-4 ”,“ F-40 ”,“ F-128 ”, and“ F-700 ”.

(Volume average particle diameter of resin particles, colorant particles, etc.)
Volume average particle diameters of resin particles, colorant particles, and the like were measured with a laser diffraction particle size distribution measuring apparatus (LA-700, manufactured by Horiba, Ltd.).

(Measuring method of glass transition temperature and endothermic peak temperature of resin)
The endothermic peak temperature of the crystalline polyester resin and the glass transition temperature (Tg) of the amorphous polyester resin were obtained using a differential scanning calorimeter (manufactured by Shimadzu Corporation: DSC-60A) in accordance with ASTM D3418. The temperature correction of the detection part of this apparatus (DSC-60A) was performed using the melting point of indium and zinc, and the heat of fusion of indium was used to correct the amount of heat. For the sample, an aluminum pan was used, an empty pan was set for control, the temperature was raised at a rate of temperature increase of 10 ° C / min, held at 200 ° C for 5 minutes, and liquid nitrogen was used from 200 ° C to 0 ° C. The temperature was lowered at 10 ° C./min, held at 0 ° C. for 5 minutes, and again heated from 0 ° C. to 200 ° C. at 10 ° C./min. The analysis was performed from the endothermic curve during the second temperature increase, and the onset temperature was set to Tg for the amorphous polyester resin, and the endothermic peak temperature from the maximum peak for the crystalline polyester resin.

<Preparation of resin particle dispersion, release agent dispersion, and colorant dispersion>
<Synthesis of Crystalline Polyester Resin (C1)>
1,10-dodecanedioic acid: 50 mol%
・ 1,9-nonanediol: 50 mol%
The monomer component is placed in a reaction vessel equipped with a stirrer, a thermometer, a condenser and a nitrogen gas introduction tube. After the inside of the reaction vessel is replaced with dry nitrogen gas, titanium tetrabutoxide (reagent) is added in 100 parts by mass of the monomer component. 0.25 parts by mass with respect to the amount was added. After stirring and reacting at 170 ° C. for 3 hours under a nitrogen gas stream, the temperature was further raised to 210 ° C. over 1 hour, the pressure inside the reaction vessel was reduced to 3 kPa, and the stirring reaction was performed for 13 hours under reduced pressure to produce crystals. -Soluble polyester resin (C1) was obtained. The weight average molecular weight of this resin was 24,000. The molecular weight distribution (Mw / Mn) was 5.0. The endothermic peak temperature was 65 ° C.

<Synthesis of crystalline polyester resin (C2)>
・ 1,8-octanedicarboxylic acid: 50 mol%
・ 1,9-nonanediol: 50 mol%
Crystalline polyester resin (C2) was obtained by the same operation as that for crystalline polyester resin (C1). The weight average molecular weight of this resin was 23000. The molecular weight distribution (Mw / Mn) was 4.9. The endothermic peak temperature was 64 ° C.

<Synthesis of crystalline polyester resin (C3)>
・ 1,10-decanedicarboxylic acid: 50 mol%
・ 1,6-hexanediol: 50 mol%
Crystalline polyester resin (C3) was obtained by the same operation as that for crystalline polyester resin (C1). The weight average molecular weight of this resin was 24,000. The molecular weight distribution (Mw / Mn) was 5.1. The endothermic peak temperature was 64 ° C.

<Preparation of crystalline polyester resin dispersion (EC1)>
In a jacketed 3 liter reactor (Tokyo Rika Kikai Co., Ltd .: BJ-30N) equipped with a condenser, thermometer, water dropping device, anchor blade, 300 parts by mass of the crystalline polyester resin (C1) and methyl ethyl ketone ( Solvent (160 parts by mass) and isopropyl alcohol (solvent) (100 parts by mass) were added, and the resin was dissolved while being stirred and mixed at 100 rpm while being maintained at 70 ° C. in a water circulating thermostatic bath (solution preparation step).

  Thereafter, the stirring speed was set to 150 rpm, the water circulating thermostat was set to 66 ° C., 17 parts by mass of 10% by mass ammonia water (reagent) was added over 10 minutes, and then ion-exchanged water kept at 66 ° C. was added to 7 parts. A total of 900 parts by mass was dropped at a rate of parts by mass / min to cause phase inversion to obtain an emulsion.

  Immediately, 800 parts by mass of the obtained emulsion and 700 parts by mass of ion-exchanged water were placed in a 2-liter eggplant flask and set in an evaporator (Tokyo Rika Kikai Co., Ltd.) equipped with a vacuum control unit via a trap ball. did. While rotating the eggplant flask, the mixture was heated in a hot water bath at 60 ° C., and the solvent was removed by reducing the pressure to 7 kPa while paying attention to bumping. When the amount of recovered solvent reached 1,100 parts by mass, the pressure was returned to normal pressure, and the eggplant flask was cooled with water to obtain a dispersion. There was no solvent odor in the obtained dispersion. The volume average particle diameter D50v of the resin particles in this dispersion was 130 nm. Thereafter, ion exchange water was added to prepare a solid content concentration of 20% by mass, and this was used as a crystalline polyester resin dispersion (EC1).

<Preparation of crystalline polyester resin dispersion (EC2)>
A crystalline polyester resin dispersion (EC2) was obtained in the same manner except that the crystalline polyester resin (C2) was used instead of the crystalline polyester resin (C1).

<Preparation of crystalline polyester resin dispersion (EC3)>
A crystalline polyester resin dispersion (EC3) was obtained in the same manner except that the crystalline polyester resin (C3) was used instead of the crystalline polyester resin (C1).

<Synthesis of Amorphous Polyester Resin (A1)>
-Bisphenol A ethylene oxide 2.2 mol adduct: 40 mol%
-Bisphenol A propylene oxide 2.2 mol adduct: 60 mol%
・ Terephthalic acid: 47 mol%
・ Fumaric acid: 40 mol%
-1,3-adamantane dicarboxylic acid: 15 mol%
-Trimellitic anhydride: 3 mol%
In addition, content (mol%) of the monomer which comprises an amorphous polyester resin is 100 mol% of alcohol components (bisphenol A ethylene oxide 2.2 mol addition product and bisphenol A propylene oxide 2.2 mol addition product). The standard. The same applies hereinafter.

  In a reaction vessel equipped with a stirrer, a thermometer, a condenser and a nitrogen gas introduction tube, fumaric acid and trimellitic anhydride other than fumaric acid and trimellitic anhydride among the above monomer components, and 100 parts by mass of the above monomer components in total 0.25 part by mass was added. In this way, the crosslinking is adjusted. After reacting at 235 ° C. for 6 hours under a nitrogen gas stream, the temperature was lowered to 200 ° C., and the fumaric acid and trimellitic anhydride were added and reacted for 1 hour. The temperature was further raised to 220 ° C. over 4 hours, and polymerization was performed under a pressure of 10 kPa until the weight average molecular weight reached 40,000 to obtain a light yellow transparent amorphous polyester resin (A1).

  The amorphous polyester resin had a glass transition temperature (Tg) of 55 ° C.

<Synthesis of Amorphous Polyester Resin (A2)>
-Bisphenol A ethylene oxide 2.2 mol adduct: 40 mol%
-Bisphenol A propylene oxide 2.2 mol adduct: 60 mol%
・ Terephthalic acid: 47 mol%
・ Fumaric acid: 40 mol%
-5-tertbutyl-1,3-adamantane dicarboxylic acid: 15 mol%
-Trimellitic anhydride: 3 mol%
In addition to fumaric acid and trimellitic anhydride as in the synthesis of amorphous polyester resin (A1), 0.25 parts by mass of tin dioctanoate was added to 100 parts by mass of the monomer components. The temperature was lowered to 200 ° C., and the fumaric acid and trimellitic anhydride were added and reacted for 1 hour. The temperature was further raised to 220 ° C. over 4 hours, and polymerization was carried out under a pressure of 10 kPa until the weight average molecular weight reached 40,000 to obtain a light yellow transparent amorphous polyester (A2). The amorphous polyester resin had a glass transition temperature (Tg) of 55 ° C.

<Synthesis of Amorphous Polyester Resin (A3)>
-Bisphenol A ethylene oxide 2.2 mol adduct: 40 mol%
-Bisphenol A propylene oxide 2.2 mol adduct: 60 mol%
・ Terephthalic acid: 39 mol%
・ Fumaric acid: 33 mol%
-1,3-adamantane dicarboxylic acid: 30 mol%
-Trimellitic anhydride: 3 mol%
In addition to fumaric acid and trimellitic anhydride as in the synthesis of amorphous polyester resin (A1), 0.25 parts by mass of tin dioctanoate was added to 100 parts by mass of the monomer components. The temperature was lowered to 200 ° C., and the fumaric acid and trimellitic anhydride were added and reacted for 1 hour. The temperature was further raised to 220 ° C. over 4 hours, and polymerization was carried out under a pressure of 10 kPa until the weight average molecular weight reached 40,000 to obtain a light yellow transparent amorphous polyester (A3). The amorphous polyester resin had a glass transition temperature (Tg) of 56 ° C.

<Synthesis of Amorphous Polyester Resin (A4)>
-Bisphenol A ethylene oxide 2.2 mol adduct: 40 mol%
-Bisphenol A propylene oxide 2.2 mol adduct: 60 mol%
・ Terephthalic acid: 50 mol%
・ Fumaric acid: 42 mol%
・ 1,3-adamantane dicarboxylic acid: 5 mol%
-Dodecenyl succinic anhydride: 5 mol%
-Trimellitic anhydride: 3 mol%
In addition to fumaric acid and trimellitic anhydride as in the synthesis of amorphous polyester resin (A1), 0.25 parts by mass of tin dioctanoate was added to 100 parts by mass of the monomer components. The temperature was lowered to 200 ° C., and the fumaric acid and trimellitic anhydride were added and reacted for 1 hour. The temperature was further raised to 220 ° C. over 4 hours, and polymerization was carried out under a pressure of 10 kPa until the weight average molecular weight reached 40,000 to obtain a light yellow transparent amorphous polyester (A4). The amorphous polyester resin had a glass transition temperature (Tg) of 55 ° C.

<Synthesis of Amorphous Polyester Resin (B1)>
-Bisphenol A ethylene oxide 2.2 mol adduct: 40 mol%
-Bisphenol A propylene oxide 2.2 mol adduct: 60 mol%
・ Terephthalic acid: 55 mol%
・ Fumaric acid: 47 mol%
-Trimellitic anhydride: 3 mol%
In addition to fumaric acid and trimellitic anhydride as in the synthesis of amorphous polyester resin (A1), 0.25 parts by mass of tin dioctanoate was added to 100 parts by mass of the monomer components. The temperature was lowered to 200 ° C., and the fumaric acid and trimellitic anhydride were added and reacted for 1 hour. The temperature was further raised to 220 ° C. over 4 hours, and polymerization was carried out under a pressure of 10 kPa until the weight average molecular weight reached 40,000 to obtain a light yellow transparent amorphous polyester (B1). The amorphous polyester resin had a glass transition temperature (Tg) of 54 ° C.

<Synthesis of Amorphous Resin Dispersion (EA1)>
While maintaining a jacketed 3 liter reaction tank (manufactured by Tokyo Rika Kikai Co., Ltd .: BJ-30N) equipped with a condenser, a thermometer, a water dropping device, and an anchor wing at 40 ° C. in a water circulation thermostat, the reaction tank Into this, a mixed solvent of 160 parts by mass of ethyl acetate and 100 parts by mass of isopropyl alcohol was added, and 300 parts by mass of the amorphous polyester resin (A1) was added thereto, and the mixture was dissolved by stirring at 150 rpm using a three-one motor. Oil phase was obtained. To the stirred oil phase, 14 parts by mass of a 10% by mass aqueous ammonia solution was added dropwise for 5 minutes, and after mixing for 10 minutes, 900 parts by mass of ion-exchanged water was further added dropwise at a rate of 7 parts by mass per minute. The phase was inverted to obtain an emulsion.

  Immediately, 800 parts by mass of the obtained emulsion and 700 parts by mass of ion-exchanged water were placed in a 2-liter eggplant flask and set in an evaporator (Tokyo Rika Kikai Co., Ltd.) equipped with a vacuum control unit via a trap ball. did. While rotating the eggplant flask, the mixture was heated in a hot water bath at 60 ° C., and the solvent was removed by reducing the pressure to 7 kPa while paying attention to bumping. When the amount of recovered solvent reached 1,100 parts by mass, the pressure was returned to normal pressure, and the eggplant flask was cooled with water to obtain a dispersion. There was no solvent odor in the obtained dispersion. The volume average particle diameter D50v of the resin particles in this dispersion was 130 nm. Then, ion-exchange water was added and it prepared so that solid content concentration might be 20 mass%, and this was made into the amorphous polyester resin dispersion liquid (EA1).

<Synthesis of Amorphous Resin Dispersion (EA2)>
An amorphous polyester resin dispersion (EA2) was obtained in the same manner except that the amorphous polyester resin (A2) was used instead of the amorphous polyester resin (A1).

<Synthesis of Amorphous Resin Dispersion (EA3)>
An amorphous polyester resin dispersion (EA3) was obtained in the same manner except that the amorphous polyester resin (A3) was used instead of the amorphous polyester resin (A1).

<Synthesis of Amorphous Resin Dispersion (EA4)>
An amorphous polyester resin dispersion (EA4) was obtained in the same manner except that the amorphous polyester resin (A4) was used instead of the amorphous polyester resin (A1).

<Synthesis of Amorphous Resin Dispersion (EB1)>
An amorphous polyester resin dispersion (EB1) was obtained in the same manner except that the amorphous polyester resin (B1) was used instead of the amorphous polyester resin (A1).

-Preparation of release agent dispersion (W1)-
Pentaerythritol tetrabehenate (ester wax WEP5) (manufactured by NOF Corporation): 50 parts Sodium alkylbenzenesulfonate (anionic surfactant) (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen RK): 5 parts Ion exchange Water: 200 parts or more was heated to 110 ° C. and dispersed using a homogenizer (manufactured by IKA: Ultra Tarrax T50), then dispersed with a Menton Gorin high-pressure homogenizer (Gorin), and the average particle size was reduced to 0.00. A release agent dispersion liquid (W1) (release agent concentration: 26% by mass) obtained by dispersing a release agent of 21 μm was prepared.

-Preparation of colorant dispersion (PC1)-
Cyan pigment (Daiichi Seika Co., Ltd., Pigment Blue 15: 3 (copper phthalocyanine)): 100 parts Polyoxyethylene nonylphenol ether (anionic surfactant) (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen R): 15 parts Ion Exchange water: 900 parts or more are mixed, dissolved, and dispersed for about 1 hour using a high-pressure impact disperser Ultimateizer (manufactured by Sugino Machine, HJP30006) to disperse the colorant (cyan pigment). A colorant dispersion (PC1) was prepared. The average particle diameter of the colorant (cyan pigment) in the colorant dispersion was 0.13 μm, and the colorant particle concentration was 25% by mass.

-Preparation of colorant dispersion (PM1)-
Magenta pigment (CI Pigment Red 122): 70 parts Nonionic surfactant (Nonipol 400: manufactured by Sanyo Chemical Co., Ltd.): 5 parts Ion-exchanged water: 200 parts Mixing the above components to disperse the colorant The same treatment as in the liquid (PC1) was performed to prepare a colorant dispersant (PM1).

-Preparation of colorant dispersion (PY1)-
Yellow pigment (CI Pigment Yellow 180): 100 parts Nonionic surfactant (Nonipol 400: manufactured by Sanyo Chemical Co., Ltd.): 5 parts Ion-exchanged water: 200 parts Mixing the above components to disperse the colorant The same treatment as in the liquid (PC1) was performed to prepare a colorant dispersant (PY1).

-Preparation of colorant dispersion (PK1)-
Carbon black (Mogal L: manufactured by Cabot): 50 parts Nonionic surfactant (Nonipol 400: manufactured by Sanyo Chemical Co., Ltd.): 5 parts Ion-exchanged water: 200 parts The same treatment as in PC1) was performed to prepare a colorant dispersant (PK1).

<Preparation of aqueous aluminum sulfate solution (SA)>
-Aluminum sulfate powder (Asada Chemical Industry Co., Ltd .: 17% aluminum sulfate): 35 parts by mass-Ion exchange water: 1,965 parts by mass The mixture was stirred and mixed until it disappeared to prepare an aqueous aluminum sulfate solution.

<Example 1>
<Preparation of toner base particles (TC1)>
Crystalline polyester resin dispersion (EC1): 63 parts by mass Amorphous polyester resin dispersion (EA1): 637 parts by weight Colorant dispersion (PC1): 128 parts by weight Release agent dispersion (W1) : 128 parts by mass ・ Ion-exchanged water: 320 parts by mass ・ Alkyldiphenyl oxide disulfonate (anionic surfactant) (Dowfax 2A1, manufactured by Dow Chemical Co., Ltd.): 2.7 parts by mass In a 3 liter reaction vessel equipped with a vessel, and at a temperature of 25 ° C., 1.0% by mass nitric acid was added to adjust the pH to 3.0, and then a homogenizer (manufactured by IKA Japan Co., Ltd .: Ultra Tarax T50) While being dispersed at 5,000 rpm, 125 parts by mass of the prepared aluminum sulfate aqueous solution (SA) was added and dispersed for 6 minutes.

  Thereafter, a stirrer and a mantle heater are installed in the reaction vessel, and the temperature increase rate is 0.2 ° C./min up to a temperature of 40 ° C. while adjusting the rotation speed of the stirrer so that the slurry is sufficiently stirred. After exceeding ° C., the temperature was raised at a temperature raising rate of 0.05 ° C./min, and the particle size was measured every 10 minutes with Multisizer II (aperture diameter: 50 μm, manufactured by Beckman-Coulter). The temperature was maintained when the volume average particle size reached 5.0 μm. At this point, the components constituting the core are fused together. An amorphous surfactant (Dowfax 2A1, manufactured by Dow Chemical Co., Ltd.) was stirred in a 500-ml beaker containing 350 parts by mass of an amorphous polyester resin dispersion (EA1) and stirred with a magnetic stirrer at a speed that does not entrap bubbles. 1.5 parts by mass), and after stirring for 10 minutes, an additional amorphous polyester resin particle dispersion (EA1 ′) adjusted to have a pH of 3.2 using 1.0% by mass nitric acid was added. Charged over 5 minutes.

  After the additional amorphous polyester resin dispersion (EA1 ') was added and maintained for 30 minutes, the pH was adjusted to 9.0 using a 1 mass% aqueous sodium hydroxide solution. Thereafter, the temperature was raised to 90 ° C. at a rate of temperature rise of 1 ° C./min while maintaining the temperature at 90 ° C. while adjusting the pH to 9.0 at every 5 ° C. in the same manner. When the particle shape and surface property were observed with an optical microscope and a scanning electron microscope (FE-SEM) every 15 minutes, the coalescence of the particles was confirmed at 2.0 hours. Cooled to 5 ° C. over 5 minutes.

  The slurry after cooling was passed through a nylon mesh having a mesh size of 15 μm to remove coarse powder, and the toner base particle slurry that passed through the mesh was adjusted to pH 6.0 by adding nitric acid, and then filtered under reduced pressure with an aspirator. The toner base particles remaining on the filter paper are crushed as finely as possible by hand, poured into ion-exchanged water 10 times the amount of the toner base particles at a temperature of 30 ° C., stirred and mixed for 30 minutes, and filtered again under reduced pressure with an aspirator. The electrical conductivity of the liquid was measured. This operation was repeated until the electric conductivity of the filtrate reached 10 μS / cm or less, and the toner base particles were washed.

  The washed toner base particles were finely pulverized with a wet dry granulator (Comil) and then vacuum-dried in an oven at 35 ° C. for 36 hours to obtain washed toner base particles. The toner base particles contain 12% by mass of a colorant and 12% by mass of a release agent. To 100 parts by mass of the toner base particles, 1.0 part by mass of hydrophobic silica (manufactured by Nippon Aerosil Co., Ltd., RY50) was added and mixed and blended at 13,000 rpm for 30 seconds using a sample mill. Thereafter, the mixture was sieved with a vibration sieve having an opening of 45 μm to obtain cyan toner (TC1) (volume average particle diameter: 5.8 μm).

  Similarly, using the colorant dispersions (PM1), (PY1), and (PK1) instead of the colorant dispersion (PC1), the volume average particle diameter is 5.8 μm according to the production conditions described above. Toner TM1 (magenta toner), toner TY1 (yellow toner) having a volume average particle size of 5.8 μm, and toner TK1 (black toner) having a volume average particle size of 5.8 μm were obtained.

<Preparation of developer (DC1)>
100 parts by mass of ferrite core and 5 parts by mass of copolymer resin particles of cyclohexyl methacrylate / methyl methacrylate (copolymerization ratio 5/5) are put into a high-speed mixer equipped with stirring blades and stirred and mixed at 120 ° C. for 30 minutes. Then, a resin coat layer was formed on the surface of the ferrite core by the action of mechanical impact force to obtain a carrier having a volume-based median diameter of 50 μm.

  The volume-based median diameter of the carrier was measured by a laser diffraction particle size distribution measuring apparatus “HELOS” (manufactured by Sympathic) equipped with a wet disperser.

  Toner TC1 is added to the carrier so that the toner concentration is 6% by mass, and the mixture is put into a micro-type V-type mixer (Tsutsui Rikenki Co., Ltd.) and mixed at a rotational speed of 45 rpm for 30 minutes to produce developer DC1. did.

  Similarly, instead of the toner (TC1), toners (TM1), (TY1), (TK1) are used, and developers DM1 (magenta developer), DY1 (yellow developer), DK1 (black developer) Got.

<Example 2>
<Preparation of Toner (TC2)>
Developer DC2 (cyan developer), DM2 (magenta developer), DY2 (dye) are used in the same manner except that the amorphous resin particle dispersion (EA2) is used instead of the amorphous resin particle dispersion (EA1). Yellow developer) and DK2 (black developer) were obtained.

<Examples 3 to 9, Comparative Example 1, Comparative Example 2>
Amorphous resin particle dispersions (EA1) to (EA4), (EB1), and combinations of crystalline resin particle dispersions (EC1) to (EC3) were changed, and Examples 3 to 9 similarly shown in Table 1 were used. Developers of Comparative Examples 1 and 2 were obtained.

-Evaluation method-
(Charge stability)
A commercially available copier “bizhub PRO C6501” (manufactured by Konica Minolta Business Technologies) was prepared as a two-component developer evaluation device, and the above-described two-component developer prepared above was sequentially loaded into the above-mentioned copier. In an environment of low temperature and low humidity (10 ° C., 20% RH) and high temperature and high humidity (30 ° C., 80% RH), 500,000 character images with a printing rate of 5% were printed on A4 size transfer paper.

  The charge amount of the two-component developer is set such that 50 mg of the two-component developer is slid between the parallel plate (aluminum) electrodes, the gap between the electrodes is 0.5 mm, the DC bias is 1.0 kV, and the AC bias is 4 When the toner is developed under the conditions of 0.0 kV and 2.0 kHz, the charge amount Q and the mass m of the toner supplied to the development area are measured, and the charge amount Q / m (μC / g) per unit mass is obtained. The value was defined as the charge amount.

  Measure the amount of charge in low temperature and low humidity environment (10 ° C, 20% RH) (LL) and high temperature and high humidity environment (30 ° C, 80% RH) (HH). And asked.

  The environmental difference in the charge amount of the two-component developer (LL-HH) is the initial charge in the low temperature and low humidity environment (10 ° C., 20% RH) (LL) and the high temperature and high humidity environment (30 ° C., 80% RH) (HH). The difference in quantity was evaluated as follows.

Less than 25 μC: Good 25 μC / g or more and less than 30 μC / g: Practical use 30 μC / g or more: Impractical use The durability stability of the charge amount of the two-component developer (after printing 500,000 sheets-initial) is low temperature and low humidity environment (10 ° C. , 20% RH) (LL) and initial charge amount after 500,000 prints, initial charge amount in high temperature and high humidity environment (30 ° C, 80% RH) (HH) and 500,000 prints The subsequent charge amount difference was used, and rank evaluation was performed as follows.

In both HH environment and LL environment, less than 10 μC / g: good In both HH environment and LL environment, less than 15 μC / g: practical use In either HH environment or LL environment, 15 μC / g or more: impractical use Table 1 shows the evaluation results.

  As shown in Table 1, in Examples 1 to 9, the charge amount is stable even after printing 500,000 sheets, and the change in the charge amount is small even when the printing environment changes, and the effects of the present invention are exhibited. Was confirmed. On the other hand, in Comparative Examples 1 and 2, it was confirmed that there was a problem with any of the above evaluation items and the effects of the present invention were not achieved.

Claims (5)

With crystalline polyester resin;
An amorphous polyester resin comprising a structural unit derived from a polyvalent carboxylic acid having an adamantane skeleton or a derivative thereof;
A mold release agent;
An electrostatic charge image developing toner comprising: The derivative is an adamantanedicarboxylic acid which may have a substituent,
2. The electrostatic image development according to claim 1, wherein the substituent is an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 18 carbon atoms. toner.   3. The electrostatic image developing toner according to claim 1, wherein the content of the structural unit is 3 to 30 mol% with respect to all the structural units in the non-crystalline polyester resin.   The electrostatic image developing toner according to claim 1, further comprising an external additive.   The electrostatic charge image developing toner according to claim 4, wherein the external additive is at least one selected from the group consisting of inorganic fine particles, organic fine particles, a charge control agent, and a lubricant.