JP4612887B2 - toner - Google Patents

Description

  The present invention relates to a toner used for developing an electrostatic latent image formed by a method such as electrophotography, electrostatic recording, magnetic recording, or toner jet recording.

  An electrophotographic image forming method generally uses a photoconductive substance, forms an electrostatic latent image on an electrostatic charge image carrier (hereinafter also referred to as “photoreceptor”) by various means, and then forms a toner. The electrostatic latent image is made visible by developing the toner, and the toner image is transferred onto the recording medium by heat or pressure after being transferred to a recording medium such as paper as necessary. To obtain a copy. Examples of such an image forming apparatus include a printer and a copying machine.

  Usually, toners used in these printers and copiers are fine particles mainly composed of a binder resin and a colorant such as a dye, pigment, carbon black, and magnetic substance. About 30 μm is used. In recent years, development methods with particularly high resolution and high definition have been demanded, and as one means for satisfying such demands, a smaller particle size is required for toner. It is becoming.

  In general, a toner is melt-mixed and uniformly dispersed in the thermoplastic resin as a binder resin, and the above-described colorant and, if necessary, a charge control agent, wax, etc., and then finely pulverized and classified. It is manufactured by a so-called pulverization method to obtain a desired particle size. As a requirement to be satisfied by the constituent materials in the production of this toner, for example, a resin composition in which a colorant is dispersed must be sufficiently brittle and capable of being finely pulverized by an economically possible production apparatus. Can be mentioned. However, when the brittleness of the resin composition is increased, there arises a problem that the particle size range of particles obtained by fine pulverization tends to be widened. In addition, even after the toner is formed, it is more likely to be finely pulverized during use in the developing device, and there arises a problem that the colorability is exposed on the fracture surface of the toner particles, resulting in a decrease in developability.

  On the other hand, a toner production method called a suspension polymerization method or a polymer dissolution suspension method has been proposed in order to overcome the problems of the toner due to the pulverization method. The suspension polymerization method is a monomer in which a polymerizable monomer is dissolved or dispersed in a colorant or, if necessary, a polyfunctional monomer, a chain transfer agent, or other substances that must be included in toner particles. The composition is suspended in an aqueous medium containing a dispersion stabilizer together with a polymerization initiator, and polymerized by a method such as heating to obtain toner particles having a desired particle size. The polymer dissolution suspension method is an aqueous system containing a dispersion stabilizer in which a binder resin, a colorant, and other substances that need to be encapsulated in toner particles are dissolved or dispersed in a low-boiling organic solvent. The toner particles are obtained by suspending in a medium and then removing the organic solvent.

  According to these methods, since the pulverization step is not included, the resin material is not required to be brittle and can be used even if it is soft. Further, since the colorant is hardly exposed on the surface of the toner particles, toner particles having uniform triboelectric charging properties and excellent durability can be obtained. Furthermore, since the classification process can be omitted, the cost reduction effect such as energy saving, shortening of the manufacturing time, and improvement of the yield can be increased. However, even in this manufacturing method, when the toner particles are made smaller in size in order to meet the demand for higher definition as described above, the colorant is easily exposed on the surface of the toner particles, and the charging is uniform. May deteriorate the developability.

  Further, for the purpose of improving the fixing property of the toner, a method is generally known in which a low-softening point wax having releasability is included in the toner. However, the wax encapsulated in the toner gradually exudes to the surface of the toner particles as the number of durable sheets increases, and the developability may be lowered, and also causes blocking.

  As a means for preventing the exposure of the colorant to the surface of the toner particles and the exudation of the wax, for example, in the production of the toner by the suspension polymerization method, polyester such as polyester is used in the monomer composition. A method of adding a polar polymer or copolymer has been proposed. Since the polar resin dissolved in the monomer composition tends to be unevenly distributed near the surface of the suspended particles when suspension polymerization is performed in an aqueous medium, this contributes to stabilization of granulation, After the polymerization, an outer shell is formed to cover the surface of the toner particles, so that the above-described exposure of the colorant and exudation of wax can be prevented. In order to make the polar resin unevenly distributed on the toner particle surface more effectively, a polar resin having an acid value of 1 to 50 mgKOH / g is usually used.

  By the way, in order to maintain the charging property of the toner, it is possible to use the frictional charging characteristic of the binder resin itself. However, since this method cannot always obtain a sufficient charging property, in general, charge control is performed. A method of adding an agent is used.

  Conventionally, as a negatively chargeable charge control agent, metal complexes of monoazo dyes, nitrohumic acid and its salts, metal compounds of aromatic carboxylic acids such as salicylic acid, alkylsalicylic acid, dialkylsalicylic acid, naphthoic acid and dicarboxylic acid, boron compounds , Urea compounds, silicon compounds, calixarene, sulfonated copper phthalocyanine pigments, chlorinated paraffins, etc. are known, but these charge control agents are complex in structure, do not have constant properties, and have poor stability. In many cases, there is a problem that the chargeability easily changes depending on the environment such as temperature and humidity.

  In addition, these charge control agents must be present to some extent on the toner particle surface in order to impart the intended triboelectric chargeability. However, the charge control agent falls off the toner surface due to friction between the toners caused by overlapping prints or copies, collision with the carrier, conveyance sleeve or roller, regulation blade, friction with the photosensitive drum, etc. Contamination of the developing member, the photosensitive drum, etc. may occur. As a result, as the number of durable sheets increases, the chargeability decreases and deterioration due to contamination progresses, causing problems such as a change in image density and a decrease in image quality.

  Furthermore, in order to be applied to a full color toner, the charge control agent must be colorless or white, and in order to be used for a polymerized toner, it has no polymerization inhibitory property, and a solubilized product in a dispersion medium is substantially not used. There are restrictions such as not including it.

  In addition to these problems, the uniformity of charging has become more important along with the above-mentioned demand for reducing the particle size of toner particles. This is because when the particle size of the toner is reduced, the fluidity is lowered and the charge amount of each toner particle becomes non-uniform and fog is likely to occur. In addition, in the transfer process, it is compared with the Coulomb force applied to the toner particle. This is because the influence of the adhesion force (such as mirror image force and van der Waals force) of the toner particles to the photosensitive member increases, and the residual toner after transfer tends to increase.

  Against this background, in recent years, studies for making the charging performance of toner more uniform have been actively conducted, and various methods have been proposed.

  For example, suspension polymerization of a polymerizable monomer composition system containing a copolymer of styrene and / or α-methylstyrene and 2-acrylamido-2-methylpropanesulfonic acid as a polar substance in water. Has been proposed (see Patent Document 1).

  Further, the surface of the colored particles mainly composed of a colorant and a thermoplastic resin is coated with a coating layer comprising a charge controllable thermoplastic resin having a sulfonic acid group obtained by reacting a release agent and a fluorine-containing quaternary ammonium salt. A substantially coated toner has been proposed (see Patent Document 2).

  In addition, a toner has been proposed in which a polymer containing a sulfonic acid group-containing vinyl monomer having a specific structure as a monomer component is attached to the surface of capsule particles having at least a surface capable of generating radicals ( (See Patent Document 3).

  Furthermore, there has been proposed a toner comprising a charge control resin comprising a polyester resin formed by polycondensation using a polyvalent carboxylic acid compound containing a sulfonic acid group or a salt thereof and / or a polyhydric alcohol as an essential component ( (See Patent Document 4).

Japanese Patent Laid-Open No. 03-015858 Japanese Patent Laid-Open No. 06-332229 Japanese Patent Laid-Open No. 06-230598 JP 2003-215853 A

  Among the conventional examples described above, according to the method disclosed in Patent Document 1, the granulation property is excellent in the toner manufacturing process, and the polar substance is uniformly oriented in the vicinity of the toner surface, so that even a very small amount of addition is stable. A toner having charging performance can be obtained. However, if the addition amount of the polar substance is small, the conventional problems such as the exposure of the colorant to the toner particle surface and the exudation of the wax cannot be solved. Conversely, the addition amount of the polar substance is excessively large. Then, the granulation stability is lost, and it becomes difficult to obtain a toner having a sharp particle size distribution.

  In addition, among the conventional examples described above, according to the methods disclosed in Patent Document 2 and Patent Document 3, a resin having a charge control function can be present on the surface portion of the toner. However, these methods all form a resin layer having a charge control function as an outer shell after producing core particles, and not only the manufacturing process is complicated, but also the present inventors. However, it has been found that it is difficult to uniformly distribute the resin having the charge control function, and it is not always satisfactory in charge uniformity.

  On the other hand, the method disclosed in Patent Document 4 is advantageous in terms of simplifying the toner manufacturing process and charging uniformity. However, as a result of investigations by the present inventors, it has been found that the chargeability of the obtained toner is not sufficiently satisfactory, and there is room for further improvement in terms of durability.

  As described above, the present situation is that a toner that sufficiently satisfies both charging performance and durability has not yet been obtained.

  Accordingly, an object of the present invention is to provide a toner that solves the above-mentioned conventional problems. That is, an object of the present invention is to provide a toner that has excellent triboelectric chargeability, good developability and transferability, and can obtain a stable image over a long period of time.

To achieve the above object, the toner of the present invention is a toner having toner particles containing at least a binder resin and a colorant, and the toner particles are produced in an aqueous medium, and The toner particles contain at least a polar resin having a polyester resin unit produced by polycondensation of a polyhydric alcohol component and a polycarboxylic acid component and a vinyl resin unit modified with a vinyl monomer ; polar resin is characterized in that it contains is indicated by at least of formula 2 Luz sulfonic acid ester unit.

(In the formula, A represents an aliphatic hydrocarbon group which may have a substituent, and X ₁ Represents a hydrocarbon group selected from a methyl group, an ethyl group and an isopropyl group. )

The toner of the present invention, the vinyl resin unit, and is characterized in that it contains is indicated by at least of formula 2 Luz sulfonic acid ester unit.

The toner of the present invention, the vinyl resin unit, in addition to the scan sulfonic acid ester unit, is characterized in further containing a carboxylic acid unit and / or carboxylic acid ester units.

The toner of the present invention, the total absence sulfonic acid ester units contained in said polar resin is characterized in that a 0.1~0.9mmol / g.

  The toner of the present invention is characterized in that the polar resin has a weight average molecular weight in the range of 2000 to 50000 by gel permeation chromatography.

  In the toner of the present invention, the polar resin has an acid value of 1.0 to 30.0 mgKOH / g.

  Further, in the toner of the present invention, after the toner particles are granulated in a water-based or hydrophilic medium, a polymerizable monomer composition containing at least a polymerizable monomer, a colorant and the polar resin, It is produced by polymerizing the polymerizable monomer.

  In the toner of the present invention, after the toner particles are granulated in an aqueous or hydrophilic medium, a composition in which the binder resin, the colorant, and the polar resin are dissolved or dispersed in at least an organic solvent. It is produced by removing the organic solvent.

  As described below, according to the present invention, it is possible to provide a toner that has excellent triboelectric chargeability, good developability and transferability, and can obtain a stable image over a long period of time.

  Hereinafter, the present invention will be described in more detail with reference to preferred embodiments.

（式中Ｙ ₁ 、Ｙ ₂ は独立に水素原子またはメチル基、エチル基、芳香族基を表し、Ｘ ₁ は水素原子またはメチル基、エチル基、イソプロピル基から選ばれる炭化水素基を表す。） By distributing a polar resin having a specific structure in the vicinity of the surface layer of the toner particles, the inventors have excellent chargeability, good image characteristics such as developability and transferability, and further to the toner particle surface. The present inventors have found that a toner having excellent durability with no exposure of the colorant and no exudation of wax can be obtained, and the present invention has been completed. That is, a polar resin in which at least a polyester resin unit produced by polycondensation of a polyhydric alcohol component and a polycarboxylic acid component and a sulfonic acid unit and / or a sulfonic acid ester unit represented by Formula 1 coexist By using this, this could be achieved.

(Wherein Y ₁ and Y ₂ independently represent a hydrogen atom, a methyl group, an ethyl group or an aromatic group, and X ₁ represents a hydrogen atom or a hydrocarbon group selected from a methyl group, an ethyl group and an isopropyl group.)

  In order to effectively distribute the polar resin as described above near the surface layer of the toner particles, the toner of the present invention is preferably produced in an aqueous medium, and is produced by a suspension polymerization method or a polymer dissolution suspension method. It is particularly preferred.

  Here, the toner production method by the suspension polymerization method and the polymer dissolution suspension method will be described in detail.

  The toner by the suspension polymerization method according to the present invention is manufactured as follows.

  First, at least a colorant and the polar resin are added to a polymerizable monomer, and a monomer composition is prepared by uniformly dissolving or dispersing them using a dispersing machine such as a homogenizer, a ball mill, or a colloid mill. At this time, in the monomer composition, if necessary, a polyfunctional monomer or a chain transfer agent, a wax or a charge control agent as a release agent, a plasticizer, and other additives, For example, a polymer or a dispersant can be added as appropriate.

  Next, the monomer composition is granulated by suspending it in an aqueous medium containing a dispersion stabilizer prepared in advance. At this time, the particle size distribution of the obtained toner particles can be sharpened by using a high-speed disperser such as a high-speed stirrer or an ultrasonic disperser to obtain a desired particle size all at once.

  The polymerization initiator may be added simultaneously with mixing other additives in the polymerizable monomer, or may be mixed immediately before being suspended in the aqueous medium. Moreover, it can also be added in the state melt | dissolved in the polymerizable monomer or another solvent during granulation or after granulation completion, ie, just before starting a polymerization reaction.

  Thereafter, the obtained suspension is subjected to a polymerization reaction while being stirred to such an extent that the particle state is maintained using a normal stirrer and no particle floating or sedimentation occurs. After the polymerization reaction, it is filtered by a known method, washed and then dried. Thus, the suspension polymerization method toner of the present invention is obtained.

  On the other hand, the toner by the polymer solution suspension method according to the present invention is manufactured as follows.

  First, at least a binder resin, a colorant, and the polar resin are added to an organic solvent having a low boiling point, and these are uniformly dissolved or dispersed using a disperser such as a homogenizer, a ball mill, or a colloid mill to obtain a liquid composition. Prepare. At this time, a wax as a mold release agent, a charge control agent, and other additives as necessary can be appropriately added to the composition. Moreover, you may use what was melt-kneaded previously with heat for one part or all part of these materials.

  Next, granulation is performed by suspending the liquid composition in an aqueous medium containing a dispersion stabilizer prepared in advance. At this time, the particle size distribution of the obtained toner particles can be sharpened by using a high-speed disperser such as a high-speed stirrer or an ultrasonic disperser to obtain a desired particle size all at once.

  The obtained suspension is maintained in a particle state and is stirred to such an extent that the particles do not float or settle, and the organic solvent is removed by pressure reduction or heating to precipitate the particles. The obtained toner particles are filtered by a known method, washed, and then dried. Thus, the polymer dissolution suspension method toner of the present invention is obtained.

  In these methods, since the dissolved polar resin has a high polarity of sulfonic acid group, when granulated by suspending in an aqueous medium, compared with a conventional polar resin typified by a polyester resin The orientation toward the surface of the particles is greatly improved. As a result, since a strong dispersant layer is formed at the particle interface by electrically attracting the dispersant dispersed in the aqueous medium, more stable granulation can be performed.

  In addition, the shell layer formed of the polar resin is excellent in covering properties, and can effectively prevent problems such as the exudation of wax on the toner particle surfaces.

  Further, the sulfonic acid groups in the polar resin are more uniformly arranged on the surface layer, and the charging performance of the toner can be greatly improved.

  Part or all of the sulfonic acid groups in the polar resin can be esterified. As a result, the charging performance of the toner is further improved, and in particular, the initial charge rising speed and environmental stability are excellent. Although the mechanism of this action is not clear, it is considered that the sulfonic acid ester group has higher hydrophobicity than the sulfonic acid group and is not easily affected by moisture in the air.

  In addition, if the sulfonic acid group in the polar resin is excessively large, the stability of granulation may be impaired, so its content is limited, but by using a sulfonic acid ester, the granulating property The effect that the influence on is greatly reduced can also be obtained.

  Moreover, when using as a sulfonate ester, it is preferable to use methyl ester, ethyl ester, or isopropyl ester. When an aliphatic group having a carbon number larger than that of the isopropyl group is introduced, the stability of the ester group itself is lowered, and the desired charging performance may not be obtained due to the release of the ester group during toner preparation. Absent.

（式中Ａは置換基があってもよい脂肪族炭化水素基を表し、Ｘ₁ はメチル基、エチル基、イソプロピル基から選ばれる炭化水素基を表す。） Further, the sulfonic acid unit and / or the sulfonic acid ester unit can be further improved by further improving the charging performance by allowing an amide bond to coexist as shown in Formula 2.

(Wherein A represents an aliphatic hydrocarbon group have a substituent, X ₁ is a hydrocarbon group selected ethyl group, an isopropyl group.)

  Furthermore, the polar resin of the present invention may contain a carboxyl group.

  The polar resin having the polyester resin unit may be a polyester resin, but by using a hybrid resin modified with a vinyl monomer, the affinity with the binder resin can be improved. This is preferable because a shell layer having excellent coverage is formed. At this time, the sulfonic acid unit and / or the sulfonic acid ester unit may be present in either the polyester resin unit or the vinyl resin unit, but from the viewpoint of improving the charging performance and manufacturing the toner, It is more preferable to introduce into.

  As a method for introducing the sulfonic acid unit and / or the sulfonic acid ester unit into the polar resin having the polyester resin unit, various known methods can be used.

  As a method for introducing the polyester resin unit, for example, a reaction group of a carboxyl group or a hydroxyl group contained in the polyester structure, or a functional group that can be easily converted into a sulfonic acid (ester) unit introduced in advance, by an organic reaction. The method to introduce is mentioned.

  On the other hand, as a method for introducing into a vinyl resin unit, for example, after making a resin using a monomer having a carboxyl group such as (meth) acrylic acid as one of the vinyl monomers as a raw material, an organic reaction And a method of converting the carboxyl group into a sulfonic acid (ester) unit, a method of converting to a resin using a monomer having a sulfonic acid (ester) unit as one of the vinyl monomers as a raw material, and the like. It is done.

  As a specific method for converting into a sulfonic acid (ester) unit by an organic reaction, for example, a carboxyl group present in a resin is converted into a sulfonic acid group such as aminomethanesulfonic acid or aminoethanesulfonic acid (taurine) and an amino group. The method of amidating using the compound which has can be mentioned.

  Examples of the monomer having a sulfonic acid (ester) unit include 2-acrylamide-2-methylpropanesulfonic acid, 2-acrylamide-n-butanesulfonic acid, 2-acrylamide-n-hexanesulfonic acid, and 2-acrylamide. -N-octanesulfonic acid, 2-acrylamide-n-dodecanesulfonic acid, 2-acrylamide-n-tetradecanesulfonic acid, 2-acrylamido-2-phenylpropanesulfonic acid, 2-acrylamido-2,2,4-trimethylpentane Sulfonic acid, 2-acrylamido-2-methylphenylethanesulfonic acid, 2-acrylamido-2- (4-chlorophenyl) propanesulfonic acid, 2-acrylamido-2-carboxymethylpropanesulfonic acid, 2-acrylamido-2- (2 -Pirigi ) Sulfonic acid groups such as propanesulfonic acid, 2-acrylamido-1-methylpropanesulfonic acid, 3-acrylamido-3-methylbutanesulfonic acid, 2-methacrylamide-n-decanesulfonic acid, 4-methacrylamideamidobenzenesulfonic acid, etc. Examples thereof include (meth) acrylamide, vinyl sulfonic acid, styrene sulfonic acid, and alkali metal salts and ammonium salts thereof. Among these monomers, 2-acrylamido-2-methylpropanesulfonic acid is particularly preferable from the viewpoint of the charging effect of the toner.

  Moreover, as a method of esterifying a sulfonic acid group, a known method can be used. For example, it can be easily performed by using a methyl esterifying agent represented by trimethylsilyldiazomethane. When the vinyl monomer is used, it may be esterified after resinification, or may be resinized after esterification of the vinyl monomer in advance.

  As the polyhydric alcohol component and polyhydric carboxylic acid component constituting the polyester resin unit, the following monomers are used as raw materials.

  Specific examples of the polyhydric alcohol include, for example, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,3-butanediol, 2,3 as divalent alcohol. -Butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanediol, neopentyl glycol, 2,2,4-trimethylpentane-1, 3-diol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, bisphenol A, hydrogenated bisphenol A, bisphenol derivatives represented by the following formula (I), diols represented by the following formula (II), etc. To list It can be.

（式中、Ｒはエチレン又はプロピレン基であり、ｘ及びｙはそれぞれ１以上の整数であり、且つｘ＋ｙの平均値は２〜１０である。）

(In the formula, R is an ethylene or propylene group, x and y are each an integer of 1 or more, and the average value of x + y is 2 to 10.)

（式中、Ｒ’は−ＣＨ₂ＣＨ₂−、−ＣＨ₂ＣＨ（ＣＨ₃）−、または−ＣＨ₂−Ｃ（ＣＨ₃）₂−である。）

(In the formula, R ′ represents —CH ₂ CH ₂ —, —CH ₂ CH (CH ₃ ) —, or —CH ₂ —C (CH ₃ ) ₂ —).

  Further, as trihydric or higher alcohols, sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1 , 2,5-pentanetriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxymethylbenzene, etc. It is done.

  These polyhydric alcohols may be used alone or in a mixed state.

  Specific examples of the polyvalent carboxylic acid include, for example, naphthalenedicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, succinic acid, adipic acid, and sebacin as divalent carboxylic acids. And dicarboxylic acids such as acid and azelaic acid; dicarboxylic anhydrides such as phthalic anhydride and maleic anhydride; and lower alkyl esters of dicarboxylic acids such as dimethyl terephthalate, dimethyl maleate, and dimethyl adipate. In particular, lower alkyl esters of dicarboxylic acids such as dimethyl terephthalate, dimethyl maleate, and dimethyl adipate or derivatives thereof are suitable.

  Moreover, you may make it bridge | crosslink by using trivalent or more carboxylic acid. Examples of the crosslinking component include trimellitic acid, tri n-ethyl 1,2,4-tricarboxylate, tri n-butyl 1,2,4-tricarboxylate, tri n-hexyl 1,2,4-tricarboxylate, Triisobutyl 2,4-benzenetricarboxylate, tri-n-octyl 1,2,4-benzenetricarboxylate, tri-2-ethylhexyl 1,2,4-benzenetricarboxylate and lower alkyl esters of tricarboxylic acid can be used.

  Moreover, you may use a monovalent | monohydric carboxylic acid component and a monovalent alcohol component to such an extent that the characteristic of a polyester resin is not impaired. For example, as a monovalent carboxylic acid component, benzoic acid, naphthalenecarboxylic acid, salicylic acid, 4-methylbenzoic acid, 3-methylbenzoic acid, phenoxyacetic acid, biphenylcarboxylic acid, acetic acid, propionic acid, butyric acid, octanoic acid, decanoic acid, Dodecanoic acid, stearic acid and the like can be added. Further, as monovalent alcohol components, n-butanol, isobutanol, sec-butanol, n-hexanol, n-octanol, lauryl alcohol, 2-ethylhexanol, decanol, cyclohexanol, benzyl alcohol, dodecyl alcohol, etc. Can be added.

  The polyester resin unit can be produced by a method similar to a known polyester synthesis method. For example, a polyvalent carboxylic acid component and a polyhydric alcohol component are heated in an inert gas atmosphere to undergo esterification or transesterification, and then further polycondensed in an inert gas atmosphere or under reduced pressure. Can be obtained by: At this time, an organic solvent azeotropic with water such as toluene and xylene can be used as necessary. A known esterification catalyst can be used for the polycondensation reaction. Specific examples of the esterification catalyst include sulfuric acid, phosphoric acid, p-toluenesulfonic acid, titanium butoxide, dibutyltin oxide, tin acetate, zinc acetate, manganese acetate, magnesium acetate, tin disulfide, antimony trioxide, dioxide Examples include germanium. The polymerization temperature and the amount of catalyst are not particularly limited, and may be arbitrarily selected as necessary.

  The vinyl monomer constituting the vinyl resin unit includes the solubility of the resulting resin in the monomer composition and organic solvent, compatibility with the binder resin constituting the toner, and glass transition. Any point can be selected in consideration of points and the like.

  For example, styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, p-ethylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p- tert-butyl styrene, pn-hexyl styrene, pn-octyl, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p-methoxy styrene, p-phenyl styrene, etc. Styrene monomers, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, n-propyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate , 2-chloroethyl acrylate, phenyl acrylate, acrylic acid-2 Acrylic esters such as hydroxyethyl, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, methacryl Methacrylic acid esters such as stearyl acid, phenyl methacrylate, 2-hydroxyethyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, and others such as acrylic acid, methacrylic acid, acrylonitrile, methacrylonitrile, acrylamide, etc. A mer can be selected.

  The polymerization initiator used for manufacturing the vinyl resin unit is not particularly limited, and a known peroxide polymerization initiator or azo polymerization initiator can be used.

  As the peroxide polymerization initiator, as peroxy ester polymerization initiator, t-butyl peroxylaurate, t-butyl peroxyneodecanoate, t-butyl peroxypivalate, t-butyl peroxy 2-ethylhexanoate, t-butylperoxyisobutyrate, t-butylperoxyacetate, t-butylperoxyisononanoate, t-butylperoxybenzoate, t-amylperoxyneodecanoate, t-amylperoxypivalate, t-amylperoxy-2-ethylhexanoate, t-amylperoxyacetate, t-amylperoxyisononanoate, t-amylperoxybenzoate, t-hexylperoxyneo Decanoate, t-hexyl peroxypivalate, t-hexyl -Oxy-2-ethylhexanoate, t-hexylperoxybenzoate, α-cumylperoxyneodecanoate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 1,1 , 3,3-tetramethylbutylperoxyneodecanoate, 1-cyclohexyl-1-methylethylperoxyneodecanoate, 2,5-dimethyl-2,5-bis (2-ethylhexanoylperoxy) Hexane, 2,5-dimethyl-2,5-bis (benzoylperoxy) hexane, t-butylperoxy-3,5,5-trimethylhexanoate, 2,5-dimethyl-2,5-bis (m -Toluoyl peroxy) hexane etc. are mentioned.

  Further, as peroxydicarbonate-based polymerization initiators, di-n-propyl peroxydicarbonate, di-n-butyl peroxydicarbonate, di-n-pentyl peroxydicarbonate, diisopropyl peroxydicarbonate, di- sec-butyl peroxydicarbonate, di (2-ethylhexyl) peroxydicarbonate, di (2-ethoxyethyl) peroxydicarbonate, di (3-methoxybutyl) peroxydicarbonate, di (4-t-butyl) (Cyclohexyl) peroxydicarbonate and the like.

  Further, as diacyl peroxide polymerization initiators, diisobutyryl peroxide, diisononanoyl peroxide, di-n-octanoyl peroxide, dilauroyl peroxide, distearoyl peroxide, dibenzoyl peroxide, di-m -Toluoyl peroxide, benzoyl-m-toluoyl peroxide, etc. are mentioned.

  Other peroxy monocarbonates such as t-hexyl peroxyisopropyl monocarbonate, t-butyl peroxyisopropyl monocarbonate, t-butyl peroxy 2-ethylhexyl monocarbonate, t-butyl peroxyallyl monocarbonate, 1,1 -Di-t-hexylperoxycyclohexane, 1,1-di-t-butylperoxy-3,3,5-trimethylcyclohexane, 1,1-di-t-butylperoxycyclohexane, 2,2-di- Examples include peroxyketals such as t-butylperoxybutane, dialkyl peroxides such as dicumyl peroxide, di-t-butyl peroxide, and t-butylcumyl peroxide.

  As the azo polymerization initiator, 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile, 1,1′-azobis (cyclohexane-1-carbonitrile) ), 2,2′-azobis-4-methoxy-2,4-dimethylvaleronitrile, azobisisobutyronitrile and the like.

  Among these polymerization initiators, peroxide-based polymerization initiators are preferable because there is little residue of decomposition products. In addition, two or more of these polymerization initiators can be used simultaneously as necessary. At this time, the preferable amount of the polymerization initiator used is 0.1 to 20 parts by mass with respect to 100 parts by mass of the monomer.

A hybrid resin comprising a polyester resin unit and a vinyl resin unit can be produced, for example, by the method shown in the following (1) to (4).
(1) A method of performing addition polymerization by forming a polyester resin unit and then adding a vinyl monomer in the presence thereof.
(2) A method in which after the formation of the vinyl resin unit, a polycondensation reaction is carried out by adding a monomer as a raw material of polyester such as polyhydric alcohol and polycarboxylic acid in the presence thereof.
(3) A method in which a vinyl resin unit and a polyester resin unit are formed and then dissolved or swollen in a small amount of an organic solvent, an esterification catalyst is added, and they are bonded by heating.
(4) A method in which a vinyl monomer and a polyester monomer (polyhydric alcohol, polycarboxylic acid, etc.) are mixed and addition polymerization and polycondensation are continuously performed.

  In these production methods, it is preferable that the polyester resin unit and / or the vinyl resin unit contain a monomer component capable of reacting with both unit components. Examples of monomers capable of reacting with the vinyl resin unit among the monomers constituting the polyester resin unit include unsaturated dicarboxylic acids such as fumaric acid, maleic acid, citraconic acid, and itaconic acid, or anhydrides thereof. Among the monomers constituting the vinyl resin unit, those that can react with the polyester resin unit include those having a carboxyl group or a hydroxy group, acrylic esters, and methacrylic esters.

In addition, in the production method of (1), a block type in which a vinyl resin unit is bonded is obtained by introducing a compound having a vinyl group separately at the end of the polyester resin unit and subjecting the vinyl monomer to addition polymerization. A hybrid resin having the same can also be obtained.
Examples of the compound having a vinyl group include acrylic acid esters having an isocyanate group and methacrylic acid esters having an isocyanate group.

  Among the production methods (1) to (4) described above, the method (1) is preferable because the molecular weight control of the vinyl resin unit is easy, and the block in which the vinyl resin unit is bonded to the terminal of the polyester resin unit described above. A method for producing a hybrid resin of a mold is particularly preferable from the viewpoint of achieving both charging stability and durability.

  When the sulfonic acid unit and / or sulfonic acid ester unit contained in the polar resin is too small, sufficient chargeability cannot be obtained. There is a case. Therefore, the total of the sulfonic acid units and / or sulfonic acid ester units is preferably in the range of 0.1 to 0.9 mmol / g per unit weight of the polar resin.

  Further, when the molecular weight of the polar resin is too small, not only the members such as the sleeve and the carrier may be contaminated but also the charging characteristics may be impaired. On the other hand, if the molecular weight is too large, not only the fixability of the toner may be impaired, but also the resin cannot be stably present in the toner and uniform charging characteristics may not be exhibited. Therefore, the polar resin preferably has a weight average molecular weight calculated by gel permeation chromatography (GPC) in the range of 2000 to 50000. Further, in the molecular weight distribution, it is preferable that the ratio (Mw / Mn) of the weight average molecular weight Mw and the number average molecular weight Mn calculated by GPC is in the range of 1 to 6.

  In addition, the acid value of the polar resin is effective for uniformly localizing the resin in the vicinity of the toner surface, but if it is too high, the stability during granulation may be reduced, and charging characteristics may be reduced. Is not preferable because it may be inhibited. Therefore, the preferable acid value range of the polar resin is 1.0 to 30.0 mgKOH / g.

  Further, when the glass transition point of the polar resin is low, the storage stability of the toner is deteriorated to cause a blocking phenomenon. In particular, in a high temperature environment, the toner is fused in the developing unit or the developing member, or the toners are melted. May cause a decrease in fluidity due to wearing. On the other hand, when the glass transition point is high, there is a possibility that the fixing property of the toner is impaired. Therefore, the polar resin preferably has a glass transition point in the range of 45 ° C. to 90 ° C. as measured by a differential scanning calorimeter (DSC). A more preferable range is 50 ° C to 85 ° C.

  And in order to exhibit the above effect effectively, it is preferable that content of the said polar resin is 0.5-40 mass parts with respect to 100 mass parts of binder resin, More preferably, 1- 20 parts by mass.

  As described above, the present invention seeks to realize both triboelectric chargeability and durability by a new action and effect that is manifested by forming a layer made of a polar resin having a specific structure on the surface of toner particles. Therefore, the object of the present invention cannot be achieved simply by combining conventional polar resins.

  As described above, according to the present invention, the triboelectric chargeability is excellent, the image properties such as developability and transferability are good, and the colorant is exposed to the toner particle surface and the wax exudes. It is possible to realize a toner having excellent durability.

  Here, the molecular weight distribution by gel permeation chromatography (GPC) and the weight average molecular weight can be measured as follows using, for example, a GPC measuring apparatus (HLC-8120GPC) manufactured by Tosoh Corporation.

  First, the sample is immersed in THF, extracted so that the concentration of the resin component is 0.05 to 0.6 parts by mass, and this extract is filtered through a solvent-resistant membrane filter having a pore size of 0.5 μm. Make a solution. Next, the column is stabilized in a heat chamber at 40 ° C., THF is passed through the column at this temperature at a flow rate of 1 ml / min, and 50 to 200 μl of the sample solution is injected and measured.

In calculating the molecular weight of the sample, the molecular weight distribution of the sample is obtained from the relationship between the logarithmic value and the count number using a calibration curve prepared with several types of monodisperse polystyrene standard samples. As a standard polystyrene sample for preparing a calibration curve, for example, Pressure Chemical Co. Manufactured by Tosoh Corporation or having a molecular weight of 6 × 10 ² , 2.1 × 10 ³ , 4 × 10 ³ , 1.75 × 10 ⁴ , 5.1 × 10 ⁴ , 1.1 × 10 ⁵ , 3.9 × It is appropriate to use 10 ⁵ , 8.6 × 10 ⁵ , 2 × 10 ⁶ , 4.48 × 10 ⁶ , and use at least about 10 standard polystyrene samples. An RI (refractive index) detector is used as the detector. In addition, as a column, in order to qualitatively measure the molecular weight region of 10 ³ to 2 × 10 ⁶ , it is preferable to combine a plurality of commercially available polystyrene gel columns. In the present invention, measurement is performed under the following conditions.

GPC measurement condition device: HLC-8120GPC (manufactured by Tosoh Corporation)
Column: KF801, 802, 803, 804, 805, 806, 807 (Shod
ex)
Column temperature: 40 ° C
solv. : THF

  Moreover, an acid value is calculated | required with the following method.

The basic operation is based on JISK-0070.
1) Weigh accurately 0.5-2.0 g of sample into a 300 ml beaker. The weight at this time is Wg.
2) To this, 150 ml of a mixed solution of toluene / ethanol (4/1) is added and dissolved.
3) Titrate with 0.1 mol / l KOH ethanol solution. For titration, for example, automatic titration using a potentiometric titration measuring device AT-400 (winworkstation) manufactured by Kyoto Electronics Co., Ltd. and an ABP-410 electric burette can be used.
4) The consumption of the KOH solution at this time is Sml. At the same time, a blank is measured and the consumption of KOH at this time is defined as Bml.
5) The acid value is calculated by the following formula (1). Note that f is a factor of KOH.
Acid value (mgKOH / g) = {(SB) × 0.1f × 56.1} / W

  Moreover, the above-mentioned glass transition point can be calculated | required as follows using the differential scanning calorimeter (2920MDSC) by TA Instruments, for example.

  For measurement, first weigh approximately 6 mg of sample in an aluminum pan, and prepare an empty aluminum pan as a reference pan. Under a nitrogen atmosphere, the heating rate is 5 ° C / min, the modulation amplitude is ± 0.6 ° C, and the frequency is once. Per minute. A glass transition point is calculated | required by the midpoint method from the reversing heat flow curve at the time of temperature rising.

  When a vinyl polymer is used as the binder resin used in the toner of the present invention, examples of the polymerizable monomer used in the vinyl polymer include the following.

  For example, styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, p-ethylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p- tert-butyl styrene, pn-hexyl styrene, pn-octyl, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p-methoxy styrene, p-phenyl styrene, etc. Styrene monomers, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, n-propyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate , 2-chloroethyl acrylate, phenyl acrylate, acrylic acid-2 Acrylic esters such as hydroxyethyl, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, methacryl Examples include methacrylic acid esters such as stearyl acid, phenyl methacrylate, 2-hydroxyethyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, and other monomers such as acrylonitrile, methacrylonitrile, and acrylamide.

  These monomers can be used alone or in combination. Among these monomers, styrene or a styrene derivative is preferably used alone or mixed with other monomers from the viewpoint of the developing characteristics and durability of the toner.

  In the production of the binder resin used in the toner of the present invention, the polymerization initiator used is not particularly limited, and a known peroxide polymerization initiator or azo polymerization initiator can be used.

  As the peroxide polymerization initiator, as peroxy ester polymerization initiator, t-butyl peroxylaurate, t-butyl peroxyneodecanoate, t-butyl peroxypivalate, t-butyl peroxy 2-ethylhexanoate, t-butylperoxyisobutyrate, t-butylperoxyacetate, t-butylperoxyisononanoate, t-butylperoxybenzoate, t-amylperoxyneodecanoate, t-amylperoxypivalate, t-amylperoxy-2-ethylhexanoate, t-amylperoxyacetate, t-amylperoxyisononanoate, t-amylperoxybenzoate, t-hexylperoxyneo Decanoate, t-hexyl peroxypivalate, t-hexyl -Oxy-2-ethylhexanoate, t-hexylperoxybenzoate, α-cumylperoxyneodecanoate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 1,1 , 3,3-tetramethylbutylperoxyneodecanoate, 1-cyclohexyl-1-methylethylperoxyneodecanoate, 2,5-dimethyl-2,5-bis (2-ethylhexanoylperoxy) Hexane, 2,5-dimethyl-2,5-bis (benzoylperoxy) hexane, t-butylperoxy-3,5,5-trimethylhexanoate, 2,5-dimethyl-2,5-bis (m -Toluoyl peroxy) hexane etc. are mentioned.

  Further, as peroxydicarbonate-based polymerization initiators, di-n-propyl peroxydicarbonate, di-n-butyl peroxydicarbonate, di-n-pentyl peroxydicarbonate, diisopropyl peroxydicarbonate, di- sec-butyl peroxydicarbonate, di (2-ethylhexyl) peroxydicarbonate, di (2-ethoxyethyl) peroxydicarbonate, di (3-methoxybutyl) peroxydicarbonate, di (4-t-butyl) (Cyclohexyl) peroxydicarbonate and the like.

  Further, as diacyl peroxide polymerization initiators, diisobutyryl peroxide, diisononanoyl peroxide, di-n-octanoyl peroxide, dilauroyl peroxide, distearoyl peroxide, dibenzoyl peroxide, di-m -Toluoyl peroxide, benzoyl-m-toluoyl peroxide, etc. are mentioned.

  Other peroxy monocarbonates such as t-hexyl peroxyisopropyl monocarbonate, t-butyl peroxyisopropyl monocarbonate, t-butyl peroxy 2-ethylhexyl monocarbonate, t-butyl peroxyallyl monocarbonate, 1,1 -Di-t-hexylperoxycyclohexane, 1,1-di-t-butylperoxy-3,3,5-trimethylcyclohexane, 1,1-di-t-butylperoxycyclohexane, 2,2-di- Examples include peroxyketals such as t-butylperoxybutane, dialkyl peroxides such as dicumyl peroxide, di-t-butyl peroxide, and t-butylcumyl peroxide.

  As the azo polymerization initiator, 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile, 1,1′-azobis (cyclohexane-1-carbonitrile) ), 2,2′-azobis-4-methoxy-2,4-dimethylvaleronitrile, azobisisobutyronitrile and the like.

  Among these polymerization initiators, peroxide-based polymerization initiators are preferable because there is little residue of decomposition products. In addition, two or more of these polymerization initiators can be used simultaneously as necessary. At this time, the preferable amount of the polymerization initiator used is 0.1 to 20 parts by mass with respect to 100 parts by mass of the monomer.

  Moreover, in this invention, a chain transfer agent can be used as needed. Specific examples include n-pentyl mercaptan, isopentyl mercaptan, 2-methylbutyl mercaptan, n-hexyl mercaptan, n-heptyl mercaptan, n-octyl mercaptan, t-octyl mercaptan, t-nonyl mercaptan, n-dodecyl mercaptan, Alkyl mercaptans such as t-dodecyl mercaptan, n-tetradecyl mercaptan, t-tetradecyl mercaptan, n-pentadecyl mercaptan, n-hexadecyl mercaptan, t-hexadecyl mercaptan, stearyl mercaptan, alkyl esters of thioglycolic acid , Alkyl esters of mercaptopropionic acid, halogenated hydrocarbons such as chloroform, carbon tetrachloride, ethylene bromide, carbon tetrabromide, α-methylstyrene dimer And the like.

  These chain transfer agents are not necessarily used, but a preferable addition amount when used is 0.05 to 3 parts by mass with respect to 100 parts by mass of the polymerizable monomer.

  Moreover, in this invention, a small amount of polyfunctional monomers can be used together. As the polyfunctional monomer, compounds having two or more polymerizable double bonds are mainly used. For example, aromatic divinyl compounds such as divinylbenzene and divinylnaphthalene, such as ethylene glycol diacrylate and ethylene glycol. Carboxylic acid esters having two double bonds such as dimethacrylate and 1,3-butanediol dimethacrylate, or divinyl compounds such as divinylaniline, divinyl ether, divinyl sulfide and divinyl sulfone, and more than two vinyl groups The compound which has is mentioned.

  These polyfunctional monomers are not necessarily used, but a preferable addition amount when used is 0.01 to 1 part by mass with respect to 100 parts by mass of the polymerizable monomer.

  When the toner of the present invention is produced in an aqueous medium, a known surfactant, organic dispersant, or inorganic dispersant can be used as a dispersion stabilizer. Among these, inorganic dispersants can be suitably used because they are less likely to produce harmful ultra fine powders, are less likely to lose stability even when the polymerization temperature is changed, are easy to wash and do not adversely affect the toner. Examples of such inorganic dispersants include polyvalent metal phosphates such as calcium phosphate, magnesium phosphate, aluminum phosphate and zinc phosphate, carbonates such as calcium carbonate and magnesium carbonate, calcium metasuccinate, calcium sulfate and barium sulfate. And inorganic oxides such as calcium hydroxide, magnesium hydroxide, aluminum hydroxide, silica, bentonite, and alumina.

  When these inorganic dispersants are used, they may be used as they are added to the aqueous medium, but in order to obtain finer particles, the inorganic dispersant particles in the aqueous medium using a compound capable of generating the inorganic dispersant. It can also be generated and used. For example, in the case of calcium phosphate, a sodium phosphate aqueous solution and a calcium chloride aqueous solution can be mixed with high-speed stirring to produce water-insoluble calcium phosphate, which enables more uniform and fine dispersion. At the same time, water-soluble sodium chloride is by-produced. However, when a water-soluble salt is present in the aqueous medium, dissolution of the polymerizable monomer in water is suppressed, and an ultrafine particle toner by emulsion polymerization is produced. Since it becomes difficult to generate | occur | produce, it is more convenient. The inorganic dispersant can be almost completely removed by adding an acid or an alkali after the polymerization and dissolving.

  These inorganic dispersants are desirably used alone in an amount of 0.2 to 20 parts by mass with respect to 100 parts by mass of the polymerizable monomer, but if necessary, 0.001 to 0.1 parts by mass. Some surfactants may be used in combination. Examples of the surfactant include sodium dodecylbenzene sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, sodium laurate, sodium stearate, potassium stearate and the like.

  As the colorant used in the present invention, known ones can be used, and examples thereof include carbon black as a black colorant, magnetic powder, and yellow / magenta / cyan colorants shown below.

  As the yellow colorant, compounds represented by condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds are used. Specifically, C.I. I. Pigment Yellow 12, 13, 14, 15, 17, 62, 74, 83, 93, 94, 95, 109, 110, 111, 128, 129, 147, 168, 180, etc. are preferably used.

  As the magenta colorant, condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, and perylene compounds are used. Specifically, C.I. I. Pigment Red 2, 3, 5, 6, 7, 23, 48: 2, 48: 3, 48: 4, 57: 1, 81: 1, 122, 144, 146, 166, 169, 177, 184, 185, 202, 206, 220, 221, 254, etc. are preferably used.

  As the cyan colorant, copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds, basic dye lake compounds, and the like are used. Specifically, C.I. I. Pigment Blue 1, 7, 15, 15: 1, 15: 2, 15: 3, 15: 4, 60, 62, 66 and the like are preferably used.

  These colorants can be used alone or in combination, and further in the form of a solid solution. When magnetic powder is used as the black colorant, the amount added is preferably 40 to 150 parts by mass with respect to 100 parts by mass of the polymerizable monomer. In the case of a color toner, it is selected from the viewpoints of hue angle, saturation, lightness, weather resistance, OHP transparency, and dispersibility in the toner, and the preferred addition amount is 100 parts by weight of the polymerizable monomer. It is 1-20 mass parts with respect to.

  When these colorants are used in suspension polymerization method toners, it is necessary to pay attention to the polymerization inhibitory property and water phase transferability of the colorant, and surface modification, for example, depending on the substance that does not inhibit polymerization. It is preferable to perform a hydrophobic treatment.

  In particular, since dye-based colorants and carbon black often have polymerization inhibiting properties, care must be taken when using them. A preferable method for surface-treating the dye-based colorant includes a method in which a polymerizable monomer is polymerized in the presence of these dyes in advance, and the obtained colored polymer is added to the monomer system. For carbon black, in addition to the same treatment as the above dye, a grafting treatment may be performed with a substance that reacts with the surface functional group of carbon black, for example, polyorganosiloxane.

  In addition, magnetic powder is mainly composed of iron oxide such as triiron tetroxide and γ-iron oxide, and since it is generally hydrophilic, it is magnetic by interaction with water as a dispersion medium. The powder tends to be unevenly distributed on the particle surface, and the resulting toner particles are inferior in fluidity and frictional charging uniformity due to the magnetic powder exposed on the surface. Therefore, the surface of the magnetic powder is preferably subjected to a hydrophobic treatment uniformly with a coupling agent. Examples of the coupling agent that can be used include a silane coupling agent and a titanium coupling agent, and a silane coupling agent is particularly preferably used.

  The toner of the present invention preferably contains a release agent in order to improve fixability. Examples of usable release agents include petroleum waxes and derivatives thereof such as paraffin wax, microcrystalline wax and petrolactam, montan wax and derivatives thereof, hydrocarbon waxes and derivatives thereof by Fischer-Tropsch method, and polyethylene. Polyolefin waxes and derivatives thereof, natural waxes and derivatives thereof, such as carnauba wax and candelilla wax. Derivatives include oxides, block copolymers with vinyl monomers, graft modified products, and the like. Furthermore, fatty acids such as higher aliphatic alcohols, stearic acid and palmitic acid, or compounds thereof, acid amide waxes, ester waxes, ketones, hydrogenated castor oil and derivatives thereof, plant waxes, animal waxes and the like can also be used. These mold release agents may be used independently and may use 2 or more types together.

  Among these release agents, those having a maximum endothermic peak in the region of 40 to 130 ° C. at the time of temperature rise in the DSC curve measured by a differential differential calorimeter are preferable, and further in the region of 45 to 120 ° C. Is more preferable. By using such a release agent, the release property can be effectively expressed while greatly contributing to the low-temperature fixability. When the maximum endothermic peak is less than 40 ° C., the self-aggregating force of the release agent component becomes weak, and as a result, the high temperature offset resistance deteriorates. In addition, exudation of the release agent is likely to occur at times other than fixing, and the charge amount of the toner is reduced, and the durability under high temperature and high humidity is reduced. On the other hand, if the maximum endothermic peak exceeds 130 ° C., the fixing temperature becomes high and low temperature offset tends to occur, which is not preferable. Further, when the toner is produced by the suspension polymerization method, if the maximum endothermic peak temperature is too high, it causes a problem such as precipitation of a release agent component during granulation, and the dispersibility of the release agent is lowered, which is not preferable. .

  The content of the release agent is preferably 1 to 30 parts by mass, and more preferably 3 to 20 parts by mass with respect to the binder resin. When the content of the release agent is less than 1 part by mass, a sufficient addition effect cannot be obtained and the offset suppressing effect is insufficient. On the other hand, when the amount exceeds 30 parts by mass, the long-term storage stability is deteriorated and the dispersibility of other toner materials such as a release agent and a colorant is deteriorated, resulting in a decrease in toner fluidity and image characteristics. . Further, exfoliation of the release agent component occurs other than at the time of fixing, resulting in poor durability under high temperature and high humidity.

  In the toner of the present invention, practically sufficient charging performance can be imparted by the vinyl-modified polyester resin, but a conventional charge control agent may be used in combination for the purpose of fine adjustment. In this case, known charge control agents can be used. Specifically, metal compounds of aromatic carboxylic acids such as salicylic acid, alkylsalicylic acid, dialkylsalicylic acid, naphthoic acid, dicarboxylic acid, azo dyes or Examples thereof include metal salts or metal complexes of azo pigments, boron compounds, urea compounds, silicon compounds, calixarene, and the like.

  The weight average particle diameter of the toner obtained by the present invention is preferably 3 to 10 μm in order to develop finer latent image dots faithfully and obtain a high quality image. When the weight average particle size is less than 3 μm, the transfer residual toner on the photoconductor increases due to a decrease in transfer efficiency, and it becomes difficult to suppress photoconductor shaving and toner fusion in the contact charging step. In addition to an increase in the surface area of the entire toner, fluidity and agitation as a powder decrease, and it becomes difficult to uniformly charge individual toner particles. Since it tends to decrease, it is not preferable. On the other hand, if the weight average particle diameter exceeds 10 μm, the characters and the line image are likely to be scattered and it becomes difficult to obtain high resolution. Also, as the device becomes higher in resolution, the reproducibility of one dot tends to deteriorate.

  Here, the average particle size and particle size distribution of the toner can be measured using a Coulter Counter TA-II type or Coulter Multisizer (both manufactured by Coulter). In the present invention, a Coulter multisizer was used, and an interface (manufactured by Nikka Machine Co., Ltd.) for outputting the number distribution and the volume distribution and a PC9801 personal computer (manufactured by NEC Corporation) were connected thereto. In addition, a 1% NaCl aqueous solution prepared using primary sodium chloride was used as the electrolytic solution.

  As a measuring method, 0.1 to 5 ml of a surfactant, preferably alkylbenzene sulfonate is added as a dispersant to 100 to 150 ml of the electrolytic solution, and 2 to 20 mg of a measurement sample is further added. Next, this electrolytic solution is subjected to a dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes, and the volume and number of toner particles of 2 μm or more are measured using the 100 μm aperture as the aperture by the Coulter Multisizer. The number distribution is calculated. Then, the volume-based weight average particle diameter (D4) obtained from the volume distribution and the number-based length average particle diameter obtained from the number distribution, that is, the number average particle diameter (D1) are obtained.

  The average circularity of the toner obtained by the present invention is preferably 0.970 or more. The average circularity is an index representing the degree of unevenness of toner particles, and is 1.000 when the toner is a perfect sphere, and the value becomes smaller as the surface shape becomes more complicated. That is, that the average circularity is 0.970 or more means that the toner shape is substantially spherical. The toner having such a shape is likely to be uniformly charged, and is effective in suppressing fog and sleeve ghost. Further, since the toner ears formed on the toner carrier are uniform, control in the developing unit is facilitated. Furthermore, since it has a spherical shape, it has good fluidity and is not easily stressed in the developing device, so that the chargeability is not easily lowered even when used for a long time under high humidity. Further, since heat and pressure are easily applied to the entire toner even at the time of fixing, it contributes to improvement of fixing properties.

  The average circularity in the present invention was measured using a flow type particle image analyzer “FPIA-3000 type” (manufactured by Sysmex Corporation).

  As a specific measurement method, a suitable amount of a surfactant, preferably alkylbenzene sulfonate, is added to 20 ml of ion-exchanged water, 0.02 g of a measurement sample is added, and a desktop with an oscillation frequency of 50 kHz and an electrical output of 150 W is added. A dispersion liquid for measurement was obtained by carrying out a dispersion treatment for 2 minutes using a type ultrasonic cleaner disperser (for example, “VS-150” (manufactured by VervoCrea, etc.). It cools suitably so that it may become 40 degreeC or more.

  For the measurement, the flow type particle image measuring apparatus equipped with a standard objective lens (10 times) was used, and a particle sheath “PSE-900A” (manufactured by Sysmex Corporation) was used as the sheath liquid. The dispersion prepared in accordance with the above procedure is introduced into the flow type particle image measuring apparatus, 3000 toner particles are measured in the total count mode, and the analysis particle diameter is set to a circle equivalent diameter of 3.00 μm or more and 200.00 μm or less. The average circularity of the toner particles was determined.

  In the measurement, automatic focus adjustment is performed using standard latex particles (for example, Duke Scientific 5200A diluted with ion-exchanged water) before the measurement is started. Thereafter, it is preferable to perform focus adjustment every two hours from the start of measurement.

    In the embodiment of the present application, a flow type particle image measuring apparatus, which has been calibrated by Sysmex Corporation and has been issued a calibration certificate issued by Sysmex Corporation, has an analysis particle diameter of 3.00 μm. The measurement was performed under the measurement and analysis conditions when the calibration certificate was received, except that it was limited to 200.00 μm or less.

  The toner of the present invention is preferably externally added with a fluidity improver to improve image quality. As the fluidity improver, inorganic fine powders such as silicate fine powder, titanium oxide, and aluminum oxide are preferably used. These inorganic fine powders are preferably hydrophobized with a hydrophobizing agent such as a silane coupling agent, silicone oil or a mixture thereof.

  The toner of the present invention may be used as a one-component developer obtained by mixing toner particles and the external additive, or as a two-component developer obtained by further mixing a magnetic carrier in a mixture of toner particles and the external additive. it can. When the toner of the present invention is used as a two-component developer, examples of the magnetic carrier to be mixed include surface oxidized or unoxidized iron, lithium, calcium, magnesium, nickel, copper, zinc, cobalt, manganese, chromium, and rare earth. Such metal particles, alloy particles thereof, oxide particles, ferrite particles, and the like can be used, but it is more preferable to use a magnetic particle-dispersed resin carrier in which magnetic particles are dispersed in a resin. Charging characteristics can be achieved.

  The coated carrier obtained by coating the surface of the magnetic carrier particles with a resin is particularly preferable in a developing method in which an AC bias is applied to the developing sleeve. Coating methods include a method in which a coating solution prepared by dissolving or suspending a coating material such as a resin in a solvent is adhered to the surface of the magnetic carrier core particles, and a method in which the magnetic carrier core particles and the coating material are mixed with powder. A conventionally known method can be applied.

  Examples of the coating material on the surface of the magnetic carrier core particles include silicone resin, polyester resin, styrene resin, acrylic resin, polyamide, polyvinyl butyral, and aminoacrylate resin. These are used alone or in plural. The treatment amount of the coating material is preferably 0.1 to 30% by mass (preferably 0.5 to 20% by mass) with respect to the carrier core particles.

  The average particle size of these carriers is preferably 10 to 100 μm, more preferably 20 to 70 μm. When the mixing ratio of the toner and the magnetic carrier is 2 to 15% by mass, preferably 4 to 13% by mass as the toner concentration in the developer, usually good results are obtained. If the toner concentration is less than 2% by mass, the image density tends to decrease, and if it exceeds 15% by mass, fogging or in-machine scattering tends to occur.

  Hereinafter, although the manufacturing method of this invention is demonstrated concretely using an Example, this invention is not limited at all by these Examples.

(Synthesis Example 1)
The following monomers were charged into a reaction vessel equipped with a stirrer, condenser, thermometer, and nitrogen introduction tube, and 2.0 parts by mass of potassium titanyl oxalate was added as a condensation catalyst, and the temperature was raised to 230 ° C. in a nitrogen atmosphere. Then, the reaction was carried out for 10 hours while stirring and distilling off the produced methanol.
Bisphenol A-propylene oxide 2-mol adduct: 71.3 parts by mass Terephthalic acid: 28.7 parts by mass

  The reaction was further carried out while reducing the pressure inside the reaction vessel to 5 to 20 mmHg. When the hydroxyl value became 50 or more, the reaction vessel was taken out to obtain a polyester resin (a1).

Next, 100 parts by mass of the obtained polyester resin (a1) was dissolved in 400 parts by mass of methoxybutyl acetate, and 4.0 parts by mass of 2-methacryloyloxyethyl isocyanate, 0.03 parts by mass of dibutyltin laurate. Then, a reaction comprising 20 parts by mass of methoxybutyl acetate was added dropwise to carry out the reaction. The progress of the reaction was monitored by IR (infrared absorption spectrum) until the peak derived from the isocyanate group near 2200 cm ⁻¹ disappeared. Thereafter, the reaction solution was dropped into hexane for reprecipitation purification, filtered and dried to obtain a polyester resin (a2) having an unsaturated bond at the terminal.

  Next, 100 parts by mass of xylene was charged into a reaction vessel equipped with a stirrer, a condenser, a thermometer, and a nitrogen introduction tube, 70 parts by mass of the polyester resin (a2) was added, and the mixture was stirred at 50 ° C. in a nitrogen atmosphere. The temperature rose.

Next, the following monomers were mixed, to which 3.0 parts by mass of t-butylperoxyisopropyl carbonate was added as a polymerization initiator, dropped into the reaction vessel, and further heated to 120 ° C.
Styrene: 22.0 parts by mass Methyl 2-acrylamido-2-methylpropanesulfonate: 7.5 parts by mass Acrylic acid: 0.5 parts by mass

  The polymerization reaction was carried out for 5 hours under the above temperature conditions, and cooled to room temperature. Thereafter, the solution was dropped into hexane for reprecipitation purification, filtered, and further washed / filtered with hexane twice, and dried at 50 ° C. under reduced pressure to obtain a polar resin (a).

(Synthesis Example 2)
The following monomers were charged into a reaction vessel equipped with a stirrer, condenser, thermometer, and nitrogen introduction tube, and 2.0 parts by mass of potassium titanyl oxalate was added as a condensation catalyst, and the temperature was raised to 230 ° C. in a nitrogen atmosphere. Then, the reaction was carried out for 10 hours while stirring and distilling off the produced methanol.
Bisphenol A-propylene oxide 2-mol adduct: 71.0 parts by mass Terephthalic acid: 25.7 parts by mass Trimetic anhydride: 3.3 parts by mass

  The reaction was further carried out while reducing the pressure inside the reaction vessel to 5 to 20 mmHg, and when the acid value reached 10, the polyester resin (b1) was obtained.

Next, 100 parts by mass of the obtained polyester resin (b1) was dissolved in 400 parts by mass of methoxybutyl acetate, and 4.0 parts by mass of 2-methacryloyloxyethyl isocyanate, 0.03 parts by mass of dibutyltin laurate. Then, a reaction comprising 20 parts by mass of methoxybutyl acetate was added dropwise to carry out the reaction. The progress of the reaction was monitored by IR (infrared absorption spectrum) until the peak derived from the isocyanate group near 2200 cm ⁻¹ disappeared. Thereafter, the reaction solution was dropped into hexane for reprecipitation purification, filtered, and dried to obtain a polyester resin (b2) having an unsaturated bond at the terminal.

  A reaction vessel equipped with a stirrer, a condenser, a thermometer, and a nitrogen introduction tube was charged with 100 parts by mass of xylene, 70 parts by mass of the polyester resin (b2) was added, and the temperature was raised to 50 ° C. with stirring in a nitrogen atmosphere. did.

Next, the following monomers were mixed, to which 3.0 parts by mass of t-butylperoxyisopropyl carbonate was added as a polymerization initiator, dropped into the reaction vessel, and further heated to 120 ° C.
Styrene: 18.1 parts by mass 2-acrylamido-2-methylpropane methyl sulfonate: 7.4 parts by mass 2-ethylhexyl acrylate: 4.5 parts by mass

  The polymerization reaction was carried out for 5 hours under the above temperature conditions, and cooled to room temperature. Thereafter, the solution was dropped into hexane for reprecipitation purification, filtered, and further washed / filtered with hexane twice, and dried at 50 ° C. under reduced pressure to obtain a polar resin (b).

(Synthesis Example 3)
A reaction vessel equipped with a stirrer, a condenser, a thermometer, and a nitrogen introduction tube was charged with 100 parts by mass of xylene, 70 parts by mass of the polyester resin (a2) obtained in Synthesis Example 1 was added, and the mixture was stirred in a nitrogen atmosphere. The temperature was raised to 50 ° C.

Next, the following monomers were mixed, to which 3.0 parts by mass of t-butylperoxyisopropyl carbonate was added as a polymerization initiator, dropped into the reaction vessel, and further heated to 120 ° C.
Styrene: 10.3 parts by mass Methyl 2-acrylamido-2-methylpropanesulfonate: 19.2 parts by mass Acrylic acid: 0.5 parts by mass

  The polymerization reaction was carried out for 5 hours under the above temperature conditions, and cooled to room temperature. Thereafter, the solution was dropped into hexane for reprecipitation purification, filtered, and further washed / filtered with hexane twice, and dried at 50 ° C. under reduced pressure to obtain a polar resin (c).

(Synthesis Example 4)
A reaction vessel equipped with a stirrer, a condenser, a thermometer, and a nitrogen introduction tube was charged with 100 parts by mass of xylene, 70 parts by mass of the polyester resin (a2) obtained in Synthesis Example 1 was added, and the mixture was stirred in a nitrogen atmosphere. The temperature was raised to 50 ° C.

Next, the following monomers were mixed, to which 3.0 parts by mass of t-butylperoxyisopropyl carbonate was added as a polymerization initiator, dropped into the reaction vessel, and further heated to 120 ° C.
Styrene: 18.1 parts by mass 2-acrylamido-2-methylpropane methyl sulfonate: 7.4 parts by mass 2-ethylhexyl acrylate: 4.5 parts by mass

  The polymerization reaction was carried out for 5 hours under the above temperature conditions, and cooled to room temperature. Thereafter, the solution was dropped into hexane for reprecipitation purification, filtered, and further washed / filtered with hexane twice, and dried at 50 ° C. under reduced pressure to obtain a polar resin (d).

(Synthesis Example 5)
A reaction vessel equipped with a stirrer, a condenser, a thermometer, and a nitrogen introduction tube was charged with 100 parts by mass of xylene, 70 parts by mass of the polyester resin (a2) obtained in Synthesis Example 1 was added, and the mixture was stirred in a nitrogen atmosphere. The temperature was raised to 50 ° C.

Next, the following monomers were mixed, to which 3.0 parts by mass of t-butylperoxyisopropyl carbonate was added as a polymerization initiator, dropped into the reaction vessel, and further heated to 120 ° C.
Styrene: 22.3 parts by mass 2-acrylamido-2-methylpropanesulfonic acid: 3.2 parts by mass 2-ethylhexyl acrylate: 4.5 parts by mass

  The polymerization reaction was carried out for 5 hours under the above temperature conditions, and cooled to room temperature. Thereafter, the mixture was dropped into hexane for reprecipitation purification, filtered, and further washed / filtered with hexane twice, and dried at 50 ° C. under reduced pressure to obtain a polar resin (e).

(Synthesis Example 6)
A reaction vessel equipped with a stirrer, a condenser, a thermometer, and a nitrogen introduction tube was charged with 100 parts by mass of xylene, 70 parts by mass of the polyester resin (a2) obtained in Synthesis Example 1 was added, and the mixture was stirred in a nitrogen atmosphere. The temperature was raised to 50 ° C.

Next, the following monomers were mixed, to which 3.0 parts by mass of t-butylperoxyisopropyl carbonate was added as a polymerization initiator, dropped into the reaction vessel, and further heated to 120 ° C.
Styrene: 18.2 parts by mass 2-acrylamido-2-methylpropanesulfonic acid: 7.3 parts by mass 2-ethylhexyl acrylate: 4.5 parts by mass

  The polymerization reaction was carried out for 5 hours under the above temperature conditions, and cooled to room temperature. Thereafter, the solution was dropped into hexane for reprecipitation purification, filtered, and further washed / filtered with hexane twice, and dried at 50 ° C. under reduced pressure.

  The obtained polymer was pulverized, 10.0 parts by mass was placed in a reaction vessel, dissolved by adding 350 parts by mass of chloroform and 87.5 parts by mass of methanol, and cooled to 0 ° C. To this was added 7.6 parts by mass of a 2 mol / l trimethylsilyldiazomethane-hexane solution, and after stirring for 4 hours, distillation was performed to distill off the solvent.

  Furthermore, 350 parts by mass of toluene, 80 parts by mass of methanol, and 80 parts by mass of methyl ethyl ketone were added to redissolve the resin, and the solvent was distilled off by distillation. This re-dissolution / distillation operation was repeated three times and dried at 50 ° C. under reduced pressure to obtain a polar resin (f).

(Synthesis Example 7)
The following monomers were mixed, and 3.0 parts by mass of dicumyl peroxide as a polymerization initiator was dissolved in this and placed in a dropping funnel.
Styrene: 16.4 parts by mass Methyl 2-acrylamido-2-methylpropanesulfonate: 6.7 parts by mass 2-ethylhexyl acrylate: 4.1 parts by mass Fumaric acid: 2.8 parts by mass

On the other hand, the following monomers were charged in a reaction vessel equipped with a stirrer, a condenser, a thermometer, and a nitrogen introduction tube, and the temperature was raised to 135 ° C. while stirring in a nitrogen atmosphere.
Bisphenol A-propylene oxide 2-mole adduct: 49.7 parts by mass Terephthalic acid: 18.0 parts by mass Trimetic anhydride: 2.3 parts by mass

  Next, the mixture of the monomer of the dropping funnel and the polymerization initiator was dropped over about 4 hours, held at this temperature condition for 5 hours, heated to 220 ° C., and further reacted for 10 hours. Polar resin (g) was obtained.

(Synthesis Example 8)
The following monomers were charged into a reaction vessel equipped with a stirrer, condenser, thermometer, and nitrogen introduction tube, and 2.0 parts by mass of potassium titanyl oxalate was added as a condensation catalyst, and the temperature was raised to 230 ° C. in a nitrogen atmosphere. Then, the reaction was carried out for 10 hours while stirring and distilling off the produced methanol.
Bisphenol A-propylene oxide 2 mol adduct: 70.4 parts by mass Terephthalic acid: 19.8 parts by mass Trimetic anhydride: 9.8 parts by mass

  The reaction was further carried out while reducing the pressure in the reaction vessel to 5 to 20 mmHg. When the acid value reached 25, the reaction vessel was taken out to obtain a polyester resin (c).

  Next, in a reaction vessel equipped with a stirrer, a condenser, a thermometer, and a nitrogen introduction tube, 100 parts by mass of the obtained polyester resin (c) and 38 parts by mass of taurine were added, and 380 parts by mass of pyridine was added and stirred. 135 parts by mass of triphenyl phosphite was added and heated at 120 ° C. for 6 hours. After completion of the reaction, it was recovered by reprecipitation in 500 parts by mass of ethanol. The obtained polymer was washed twice with 200 parts by mass of 1N hydrochloric acid, then washed twice with 200 parts by mass of water, and dried under reduced pressure.

  Furthermore, 400 parts by mass of trimethyl orthoformate was charged in a reaction vessel equipped with a cooling tube, a stirrer, a thermometer and a nitrogen introduction tube, and heated to 80 ° C. To this, 100 parts by mass of the obtained polymer was added in 5 minutes, and then stirred for 15 hours. Thereafter, the reaction mixture was added dropwise to 9000 parts by mass of hexane with stirring. The resin was deposited and allowed to stand for a while. The supernatant was removed by decantation, and 500 parts by mass of chloroform was added to the residue and dissolved. This was dropped into 7500 parts by mass of hexane with stirring, precipitated and precipitated, the supernatant was removed by decantation, and the residue was dried under reduced pressure. This was washed with 300 parts by mass of methanol and further with 300 parts by mass of water. This was dried under reduced pressure to obtain a polar resin (h).

(Synthesis Example 9)
The following monomers were charged into a reaction vessel equipped with a stirrer, condenser, thermometer, and nitrogen introduction tube, and 2.0 parts by mass of potassium titanyl oxalate was added as a condensation catalyst, and the temperature was raised to 230 ° C. in a nitrogen atmosphere. Then, the reaction was carried out for 10 hours while stirring and distilling off the produced methanol.
Bisphenol A-propylene oxide 2-mol adduct: 70.2 parts by mass Terephthalic acid: 19.6 parts by mass 2-sulfomethylsuccinic acid: 10.2 parts by mass

  The reaction was further carried out while reducing the pressure inside the reaction vessel to 5 to 20 mmHg, and when the acid value reached 25, the reaction vessel was taken out to obtain a polyester resin (d).

  Next, 400 parts by mass of trimethyl orthoformate was charged into a reaction vessel equipped with a stirrer, a condenser, a thermometer, and a nitrogen introduction tube, and heated to 80 ° C. To this, 100 parts by mass of the obtained polyester resin (d) was added in 5 minutes, and then stirred for 15 hours. Thereafter, the reaction mixture was added dropwise to 9000 parts by mass of hexane with stirring. The resin was deposited and allowed to stand for a while. The supernatant was removed by decantation, and 500 parts by mass of chloroform was added to the residue and dissolved. This was dropped into 7500 parts by mass of hexane with stirring, precipitated and precipitated, the supernatant was removed by decantation, and the residue was dried under reduced pressure. This was washed with 300 parts by mass of methanol and further with 300 parts by mass of water. This was dried under reduced pressure to obtain a polar resin (i).

(Synthesis Example 10)
A reaction vessel equipped with a stirrer, a condenser, a thermometer, and a nitrogen introduction tube was charged with 100 parts by mass of xylene, 70 parts by mass of the polyester resin (a2) obtained in Synthesis Example 1 was added, and the mixture was stirred in a nitrogen atmosphere. The temperature was raised to 50 ° C.

Next, the following monomers were mixed, to which 3.0 parts by mass of t-butylperoxyisopropyl carbonate was added as a polymerization initiator, dropped into the reaction vessel, and further heated to 120 ° C.
Styrene: 24.4 parts by mass 2-ethylhexyl acrylate: 5.0 parts by mass Acrylic acid: 0.6 parts by mass

  The polymerization reaction was carried out for 5 hours under the above temperature conditions, and cooled to room temperature. Thereafter, the solution was dropped into hexane for reprecipitation purification, filtered, and further washed / filtered with hexane twice, and dried at 50 ° C. under reduced pressure to obtain a polar resin (j).

(Synthesis Example 11)
A reaction vessel equipped with a stirrer, a condenser, a thermometer, and a nitrogen introduction tube was charged with 67 parts by mass of methanol, 50 parts by mass of toluene, and 83 parts by mass of methyl ethyl ketone, and refluxed in a nitrogen atmosphere.

Subsequently, the following monomers were mixed, and after adding 5.0 parts by mass of dimethyl-2,2′-azobis (2-methylpropionate) as a polymerization initiator to the reaction vessel, The polymerization reaction was carried out for 10 hours.
Styrene: 80.7 parts by mass 2-acrylamido-2-methylpropanesulfonic acid: 6.4 parts by mass 2-ethylhexyl acrylate: 12.9 parts by mass

  Thereafter, distillation was performed to distill off the solvent, followed by drying at 50 ° C. under reduced pressure to obtain a polar resin (k).

Content of sulfonic acid (ester) unit calculated from the results of ¹ H-NMR and ¹³ C-NMR and elemental analysis of the polar resins (a) to (k) obtained in Synthesis Examples 1 to 11, and the weight average The measurement results of molecular weight (Mw) and acid value are shown in Table 1.

  The weight average molecular weight (Mw) and acid value of the polyester resin (a1) used in Synthesis Example 1 and the polyester resin (b1) used in Synthesis Example 2 are also shown.

<Example 1>
Preparation of pigment dispersion paste:
Styrene: 78.0 parts by mass Cu phthalocyanine (Pigment Blue 15: 3): 6.0 parts by mass

  After sufficiently premixing the above materials in a container, the mixture was uniformly dispersed and mixed for about 4 hours using an attritor (manufactured by Mitsui Miike Chemical Co., Ltd.) while maintaining the temperature at 20 ° C. or lower to prepare a pigment dispersion paste.

Preparation of toner particles:
390 parts by mass of 0.1 mol / liter-Na ₃ PO ₄ aqueous solution was added to 1150 parts by mass of ion-exchanged water, and the mixture was heated to 60 ° C. with stirring using CLEARMIX (M Technique Co., Ltd.). An aqueous medium containing a dispersion stabilizer composed of Ca ₃ (PO ₄ ) ₂ was prepared by adding 58 parts by mass of 1.0 mol / liter-CaCl ₂ aqueous solution and further stirring.

On the other hand, the following materials were added to the pigment dispersion paste and dispersed and mixed using an attritor (manufactured by Mitsui Miike Chemical Industries) to prepare a monomer composition.
n-butyl acrylate: 22.0 parts by mass Polar resin (a): 7.0 parts by mass

The monomer composition is heated to 60 ° C., and 13.0 parts by mass of ester wax (main component C ₁₉ H ₂₉ COOC ₂₀ H ₄₁ , mp 68.6 ° C.) is added thereto and mixed and dissolved. did.

  Subsequently, 3.0 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) was further added and dissolved as a polymerization initiator.

  This was put into the aqueous medium, and granulated by stirring for 15 minutes at 10,000 rpm in a nitrogen atmosphere at 60 ° C. using CLEARMIX (M Technique Co., Ltd.).

  Further, polymerization was performed at 70 ° C. for 10 hours while stirring the obtained suspension with a paddle stirring blade. After completion of the reaction, the suspension was cooled and hydrochloric acid was added to dissolve the dispersion stabilizer, followed by filtration, washing with water and drying to obtain toner particles.

Toner preparation:
A hydrophobic silica fine powder treated with hexamethyldisilazane and silicone oil and having a primary particle size of 12 nm and a BET specific surface area of 120 m ² / g is prepared, and the hydrophobic silica fine powder is added to 100 parts by mass of the toner particles. 1 part by mass was added and mixed using a Henschel mixer (manufactured by Mitsui Miike Chemical Industries). Thus, the toner (1) of the present invention was produced.

<Example 2>
A toner (2) of the present invention was produced in the same manner as in Example 1 except that in Example 1, the polar resin (b) was used instead of the polar resin (a).

<Example 3>
A toner (3) of the present invention was produced in the same manner as in Example 1 except that in Example 1, the polar resin (c) was used instead of the polar resin (a).

<Example 4>
A toner (4) of the present invention was produced in the same manner as in Example 1 except that the polar resin (d) was used instead of the polar resin (a) in Example 1.

< Reference Example 5>
A toner (5) of the present invention was produced in the same manner as in Example 1 except that the polar resin (e) was used instead of the polar resin (a) in Example 1.

<Example 6>
A toner (6) of the present invention was produced in the same manner as in Example 1 except that the polar resin (f) was used instead of the polar resin (a) in Example 1.

<Example 7>
A toner (7) of the present invention was produced in the same manner as in Example 1 except that the polar resin (g) was used instead of the polar resin (a) in Example 1.

<Example 8>
A toner (8) of the present invention was produced in the same manner as in Example 1 except that the polar resin (h) was used instead of the polar resin (a) in Example 1.

< Reference Example 9>
A toner (9) of the present invention was produced in the same manner as in Example 1 except that in Example 1, the polar resin (i) was used instead of the polar resin (a).

<Example 10>
Preparation of polyester resin:
Bisphenol A-propylene oxide 2.2 mol adduct: 1206 parts by mass Bisphenol A-ethylene oxide 2.2 mol adduct: 475 parts by mass Terephthalic acid: 249 parts by mass Trimellitic anhydride: 192 parts by mass Fumaric acid: 290 parts by mass Oxidation Dibutyltin: 0.1 part by mass was placed in a 4-liter 4-neck flask made of glass, and a stirrer, condenser, thermometer, and nitrogen inlet tube were attached and placed in a mantle heater. Under a nitrogen atmosphere, reaction was carried out at 220 ° C. for 5 hours to obtain a polyester resin.

Preparation of toner composition mixture:
Polyester resin (Tg: 62 ° C., softening point: 102 ° C., Mw: 16000):
100.0 parts by mass Cu phthalocyanine (Pigment Blue 15: 3): 5.0 parts by mass polymethine wax (Mw: 1850, Mw / Mn: 1.27, melting point: 78.6 ° C.):
8.0 parts by mass Polar resin (a): 1.5 parts by mass Ethyl acetate: 100.0 parts by mass

  After sufficiently premixing the above materials in a container, the mixture was dispersed for about 4 hours using a bead mill while maintaining the temperature at 20 ° C. or lower to prepare a toner composition mixed solution.

Preparation of toner particles:
After adding 78 parts by mass of 0.1 mol / liter-Na ₃ PO ₄ aqueous solution to 240 parts by mass of ion-exchanged water and stirring with Claremix (M Technique), the mixture was heated to 60 ° C., 12 parts by mass of 1.0 mol / liter-CaCl ₂ aqueous solution was added and stirring was continued to obtain an aqueous medium containing a dispersion stabilizer composed of Ca ₃ (PO ₄ ) ₂ . Furthermore, 1.0 part by mass of carboxymethylcellulose (trade name: Cellogen BS-H, manufactured by Daiichi Kogyo Seiyaku) was added and stirred for 10 minutes.

  The aqueous medium was adjusted to 30 ° C., and 180 parts by mass of the toner composition mixed solution adjusted to 30 ° C. was added while stirring at 11,000 rpm using CLEARMIX (manufactured by M Technique). After stirring for a minute, the operation was stopped to obtain a toner composition dispersion suspension.

The obtained toner composition dispersion suspension was kept at 40 ° C. with stirring, the gas phase on the suspension surface was forcibly renewed by a local exhaust device, and the solvent was removed by keeping it for 17 hours. After cooling to room temperature, hydrochloric acid was added to dissolve Ca ₃ (PO ₄ ) ₂ , filtered, washed with water and dried to obtain toner particles.

Toner preparation:
A hydrophobic silica fine powder treated with hexamethyldisilazane and silicone oil and having a primary particle size of 12 nm and a BET specific surface area of 120 m ² / g is prepared, and the hydrophobic silica fine powder is added to 100 parts by mass of the toner particles. 1 part by mass was added and mixed using a Henschel mixer (manufactured by Mitsui Miike Chemical Industries). Thus, a toner (10) of the present invention was produced.

<Example 11>
In Example 10, a toner (11) of the present invention was produced in the same manner as in Example 10 except that the polar resin (h) was used instead of the polar resin (a).

<Comparative Example 1>
In Example 1, 5.0 parts by mass of the polyester resin (a1) used in Synthesis Example 1 was used instead of 7.0 parts by mass of the polar resin (a), and further a commercially available salicylic acid metal salt charge control agent. A comparative toner (12) was prepared in the same manner as in Example 1 except that 2.0 parts by mass of “BONTRON (registered trademark) E-84” (manufactured by Orient Chemical Co., Ltd.) was used.

<Comparative Example 2>
In Example 1, 5.0 parts by mass of the polyester resin (b1) used in Synthesis Example 2 was used instead of 7.0 parts by mass of the polar resin (a), and 2.0 parts by mass of the polar resin (k). Comparative Example Toner (13) was prepared in the same manner as in Example 1 except that the same amount was used.

<Comparative Example 3>
In Comparative Example 1, a toner (14) of Comparative Example was produced in the same manner as Comparative Example 1 except that the polar resin (j) was used instead of the polyester resin (a1).

<Comparative example 4>
In Comparative Example 2, a toner (15) of Comparative Example was produced in the same manner as Comparative Example 2, except that the polar resin (j) was used instead of the polyester resin (b1).

  For each of the toners (1) to (15) obtained in Examples 1 to 11 and Comparative Examples 1 to 4, the weight average molecular weight (Mw), volume average particle diameter, glass transition temperature (Tg), and average circularity are measured. Went. Table 2 summarizes the results.

  As apparent from Table 2, the toners (1) to (11) of Examples 1 to 11 all have good values for both the average particle diameter and the average circularity. However, the toners (4), (8), and (9) having almost no acid value had a slightly larger average particle diameter.

  On the other hand, regarding the toner of the comparative example, in the case of the conventional polyester resin (a1) having no acid value, good granulation property cannot be obtained, and the toner (12) using the polyester resin is not coarse. It was written. Further, in the toners (13) and (15) of the comparative examples, the sulfonic acid group contained in the added polar resin (k) has an adverse effect on the granulation property, and these also have a large average particle diameter. became.

  In the toners (13) and (15) of the comparative examples, the unit content of sulfonic acid groups with respect to the total amount of the two types of polar resins is 0.09 mmol / g. Therefore, in the present invention, the unit content is increased. However, it can be seen that the influence on the granulation property can be avoided. In particular, it has been found that the unit content can be significantly increased by esterifying the sulfonic acid group.

  Further, for each of the toners (1) to (15) obtained in Examples 1 to 11 and Comparative Examples 1 to 4, an image output test and a rise evaluation of image density in a two-component system were performed in accordance with the points described below. went.

(1) Image output test A commercially available full color laser beam printer (LBP-2040, manufactured by Canon Inc.) was used as a test machine. The process cartridge is filled with toner, and replenished with toner as necessary. Under normal temperature and humidity conditions (23 ° C., 60% RH), the printing speed is 16 sheets / minute (A4 size paper) in monochrome mode. 5000 images were printed, and the toner charge amount and image density on the toner carrier were measured before and after image printing.

Further, the toner carrier was removed after 5,000 images were printed, the toner was wiped off, and the surface contamination state was observed with a microscope, and the determination was made according to the following criteria.
A: No particular contamination is observed B: Some deposits are observed C: Toner fusion is observed

(2) Image density rise evaluation The above toner and a magnetic fine particle dispersed resin carrier (average particle size 35 μm) surface-coated with a silicone resin are mixed so that the toner concentration becomes 7.0% by mass and two components are mixed. A developer was used.

  Next, 450 g of the prepared two-component developer was allowed to stand at high temperature and high humidity (30 ° C./80%) for 7 days, and then allowed to stand at room temperature and normal humidity (23 ° C./60%) for another 3 days. Was reset.

These are loaded into the developer unit of a commercially available color copier (CLC-5100, manufactured by Canon), A4 paper image output with an image area ratio of 25% is performed without preliminary rotation, and the number of output sheets until the image density is stabilized Thus, the rise of image density was evaluated. The evaluation criteria are shown below.
A rank: 10 or less, stable density B rank: 11-20, stable density C rank: 21-30, stable density D rank: 31 or more, stable or not stable

  In the above evaluation, the image density was measured using a Macbeth densitometer manufactured by Macbeth. Table 3 summarizes the results.

  As is apparent from Table 3, the toners (1) to (11) of the examples according to the present invention have good charging characteristics from the initial stage in the image output test, and these toners are used even after printing 5000 sheets. You can see that it is maintained. As a result, the image density was stable at a good value throughout the durability. Further, there was almost no contamination on the surface of the toner carrier.

  On the other hand, regarding the toner of the comparative example, the toners (12) and (14) of the comparative example using the conventional charge control agent have high initial chargeability, but the charge amount decreases as the durable number increases. As a result, a decrease in image density was observed. Further, deposits were confirmed on the surface of the toner carrier after printing 5000 sheets.

  In contrast, the toners (13) and (15) of Comparative Examples to which the polar resin (k) was added had insufficient charge rise, had a low charge amount in the initial stage, and a low image density. Although the image density increased with durability, in the toner (13), some deposits were observed on the surface of the toner carrier after printing 5000 sheets.

  On the other hand, also in the evaluation of the rise of the image density by the two-component developer, in particular, in the toners (13) and (15) of the comparative example, fogging occurs in the white background portion in the output image after 10 sheets, and the line image due to toner scattering is generated. Disturbance was observed and a lot of output was required before the image density was stabilized.

  On the other hand, when the toner of the present invention was used, the image density was stabilized with a small number of output sheets, and an image excellent in fine line reproducibility without fogging was obtained.

Claims (8)

A toner having toner particles containing at least a binder resin and a colorant, wherein the toner particles are produced in an aqueous medium, and the toner particles include at least a polyhydric alcohol component and a polyvalent alcohol. contains a polar resin and a vinyl resin unit modified with polyester resin unit and a vinyl monomer which is generated by a carboxylic acid component by polycondensing, Luz polar resin is represented by at least of formula 2 A toner comprising a sulfonic acid ester unit.

(In the formula, A represents an aliphatic hydrocarbon group which may have a substituent, and X ₁ represents a hydrocarbon group selected from a methyl group, an ethyl group or an isopropyl group.) The toner according to claim 1 wherein the vinyl resin unit, characterized in that it contains is indicated by at least of formula 2 Luz sulfonic acid ester unit. The vinyl resin unit, in addition to the scan sulfonic acid ester unit, toner according to claim 1 or 2, characterized by further containing a carboxylic acid unit and / or carboxylic acid ester units. The toner according to the total absence sulfonic acid ester units contained in said polar resin is any one of claims 1 to 3, characterized in that a 0.1~0.9mmol / g. The polar resin, the toner according to any one of claims 1 to 4 weight-average molecular weight by gel permeation chromatography, characterized in that in the range of 2,000 to 50,000. The polar resin, the toner according to any one of claims 1 to 5 acid value characterized in that it is a 1.0~30.0mgKOH / g. The toner particles are produced by granulating a polymerizable monomer composition containing at least a polymerizable monomer, a colorant and the polar resin in an aqueous medium, and then polymerizing the polymerizable monomer. the toner according to any one of claims 1 to 6, characterized in that which is. The toner particles are produced by granulating a composition in which a binder resin, a colorant and the polar resin are dissolved or dispersed in at least an organic solvent in an aqueous medium and then removing the organic solvent. the toner according to any one of claims 1 to 7, characterized in that.