JP2007058125A - Electrostatic charge image developing toner and method for manufacturing same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electrostatic charge image developing toner with which excellent low-temperature fixability and thermal stress resistance can be made compatible with each other and a method for manufacturing the same. <P>SOLUTION: The electrostatic charge image developing toner contains at least a binder resin, a colorant and a crystalline compound, in which the crystalline compound contains maleic acid anhydride adduct of olefin or paraffine. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an electrostatic image developing toner used in electrophotography and a method for producing the same.

  An image forming method for visualizing image information through electrostatic charge image formation by an electrophotographic method or the like is currently used in various fields. In addition, advances in digitization and advanced image processing techniques have advanced, and techniques for obtaining higher image quality are required. In particular, the spread of color machines is remarkable, and higher image quality including color development is more demanded. In response to such a demand for higher image quality, the electrostatic charge image developing toner (hereinafter sometimes simply referred to as “toner”) is reduced in diameter and the particle size distribution is made uniform.

On the other hand, demands on the environment, such as low energy, low cost, and long life, are also strongly demanded for toner. In particular, CO ₂ reduction is important in terms of the environment. Means for achieving the toner include reducing the energy required for the production of the toner. In the kneading and pulverizing method described above, a kneading step by heat melting, a pulverizing step, and a classification step are required to make the particle size uniform, and a lot of production energy is required. As a method for producing toner with low energy, a method is conceivable in which resin fine particles, colorant fine particles and the like dispersed in an aqueous dispersion medium are aggregated using metal ions and thermally fused at a low temperature to obtain a toner. In this method, it is possible to produce toner with low energy without the need for kneading with high heat or a classification step.

In addition, low temperature fixing in which a fixing process is performed at a low temperature is considered in a copying machine or a printer when considering low energy.
As a method for achieving low-temperature fixing with a toner, a method using a resin having a low glass transition point as a binder resin of the toner is generally performed. However, a toner using a binder resin having a low glass transition point can achieve low-temperature fixability, but significantly deteriorates the stability of the toner such as storage stability of toner, cohesion in a developing machine, and fixing property.

  Further, as a means for achieving low-temperature fixing, a method using a crystalline resin has been proposed (see, for example, Patent Documents 1 and 2). Although these methods can lower the fixing temperature, there is a problem that the toner melted at the time of fixing penetrates too much into the paper and a uniform and high-density image cannot be obtained.

Furthermore, many techniques have been proposed in which a crystalline resin is not used alone as a binder resin but is used in combination with an amorphous resin. For example, a technique that uses a crystalline resin and an amorphous resin in combination (for example, see Patent Document 3), and a technique that uses a polymer obtained by chemically bonding a crystalline resin and an amorphous resin are disclosed. (For example, refer to Patent Documents 4 to 7). However, when the amorphous resin is more than the crystalline resin, the amorphous resin becomes a continuous phase and the crystalline resin becomes a dispersed phase, but in this case, the melting of the entire toner is caused by the softening temperature of the amorphous resin. Dominated and low temperature fixing is difficult. In addition, when low-temperature fixing is enabled by using a crystalline resin having higher plasticity than an amorphous resin, the stability of the toner is the same as when a resin having a low glass transition point is used as the binder resin of the toner. At the same time, due to the low volume resistance of the crystalline resin, the chargeability is poor particularly in a high-temperature and high-humidity environment, resulting in poor transferability.
On the contrary, when the amount of the crystalline resin is larger than that of the amorphous resin, the effect of using the amorphous resin together cannot be sufficiently obtained.

  Further, proposals have been made to achieve low-temperature fixing by using a low melting point wax (see, for example, Patent Documents 8 and 9). These methods use wax as a mold release agent, and the wax melted at the time of fixing exudes to the surface of the image to make it peelable. However, in these methods, the melt viscosity of the wax is lowered and the offset is reduced. It tends to occur and is effective only at temperatures sufficiently higher than the melting point. Furthermore, the current situation is that the exudation of the wax depends on the compatibility between the binder resin and the wax and the melt viscosity of the binder resin, making it difficult to achieve low temperature fixing.

  Further, when a crystalline resin or a low melting point wax is used in combination, there is a problem that the resistance of the toner to a strong stress accompanying heat (heat stress resistance) is deteriorated. More specifically, the resistance to strong pressure and friction due to abnormal temperature rise in the image forming apparatus and defects in the developing device and the cleaning device.

To solve the above problem, for example, a binder resin is a polyester resin, and a wax and an α-olefin-maleic anhydride copolymer-maleic anhydride monoester copolymer are combined to form an α-olefin-maleic anhydride copolymer- A proposal has been made to improve the compatibility between the binder resin and the wax by using a maleic anhydride monoester copolymer (see, for example, Patent Document 10). However, although this means shows an effect on hot offset resistance, it does not show an effect on low-temperature fixing, and the problem of coexistence of heat stress resistance and low-temperature fixing has not yet been solved. Currently.
Japanese Patent Publication No. 4-24702 Japanese Patent Laid-Open No. 9-329917 Japanese Patent Laid-Open No. 2-79860 JP-A-1-163756 JP-A-4-81770 JP-A-4-155351 JP-A-5-44032 JP-A-4-107567 JP-A-8-114942 JP 2004-133095 A

The object of the present invention is to solve the above-mentioned problems of the prior art.
That is, an object of the present invention is to provide a toner for developing an electrostatic image capable of achieving both excellent low-temperature fixability and strong heat stress resistance, and a method for producing the same.

As a result of intensive studies to overcome the problems in the prior art, the present inventors have found that the above problems can be achieved by the following means, and have completed the present invention.
That is, the present invention

<1> An electrostatic charge image developing toner containing a binder resin, a colorant and a crystalline compound, wherein the crystalline compound contains an olefin or paraffin maleic anhydride adduct. .

<2> The electrostatic image developing toner according to <1>, wherein the crystalline compound is a mixture of an α-olefin maleic anhydride adduct and a copolymer of an α-olefin and maleic anhydride. .

<3> The crystalline compound according to <1>, wherein the mixture of a maleic anhydride adduct of α-olefin and a copolymer of α-olefin and maleic anhydride is partially monoesterified. This is a toner for developing an electrostatic image.

<4> The electrostatic image developing toner according to any one of <1> to <3>, wherein the binder resin is a polyester resin.

<5> A method for producing an electrostatic charge image developing toner according to any one of <1> to <4>,
A dispersion step of dispersing at least resin fine particles, colorant particles and crystalline compound particles in an aqueous dispersion medium; an agglomeration step of aggregating the dispersed particles to form aggregated particles; and heat fusion for thermally fusing the aggregated particles. A process for producing an electrostatic charge image developing toner.

  According to the present invention, it is possible to provide a toner for developing an electrostatic image capable of achieving both excellent low-temperature fixability and strong heat stress resistance, and a method for producing the same.

Hereinafter, the present invention will be described in detail.
<Toner for electrostatic image development>
The toner for developing an electrostatic charge image of the present invention is a toner for developing an electrostatic charge image containing at least a binder resin, a colorant and a crystalline compound, wherein the crystalline compound is a maleic anhydride adduct of olefin or paraffin. It is characterized by including.

  Examples of the maleic anhydride adduct in the present invention include those in which a part of the linear portion of olefin or paraffin is substituted with hydrogen and a maleic anhydride molecule is added, and the like. Is the number of 5 molecules or less.

  Such maleic anhydride adducts of olefins or paraffins are crystalline compounds (compounds that exhibit a melting point in thermal analysis), but they are excellent in binding resins due to the action of maleic anhydride added in the molten state during heating. Compatible. However, since it is a compound with strong crystallinity, in the solidified state that is not heated, the crystallinity of the alkyl part of the olefin or paraffin is strong, so the state of complete compatibility with the binder resin is not maintained and phase separation is performed as microcrystals. To do.

Therefore, at the time of fixing, the viscosity of the toner decreases due to the compatibility of both, and good low-temperature fixability is exhibited. On the other hand, when the resin is not melted, the two are not in a compatible state, and the glass transition point of the binder resin is close to the original value, so that the thermal stress resistance of the toner is good.
As described above, the toner of the present invention can achieve both excellent low-temperature fixability and strong heat stress resistance.

Hereinafter, each component used in the toner for developing an electrostatic charge image of the present invention, characteristics of the toner, and the like will be described in detail.
(Crystalline compound)
The crystalline compound used in the present invention contains an olefin or paraffin maleic anhydride adduct (hereinafter sometimes referred to as “maleic anhydride adduct”). The olefin or paraffin moiety is preferably a linear saturated hydrocarbon, and the average carbon number is preferably in the range of 22 to 55. More preferably, it is the range of 36-46. It is preferable that the olefin or paraffin moiety is a straight-chain saturated hydrocarbon because it has high crystallinity and is stable to heat.

When the average carbon number is in the range of 22 to 55, it is preferable because the crystallinity can be maintained against the crystallinity inhibition by maleic anhydride. Furthermore, it is more preferable that the average carbon number is in the range of 30 to 46 because sharp melting characteristics are obtained from the beginning of melting to the end of melting due to heating.
In addition, the said average carbon number measures carbon number distribution of an olefin or a paraffin part by using isooctane as a solvent by gas chromatogram (GC), and averages them. The same applies hereinafter.

Addition of maleic anhydride to an olefin or paraffin can be performed by a conventional method. In this case, the amount of maleic anhydride added is preferably in the range of 14 to 65 parts by mass and more preferably in the range of 20 to 50 parts by mass with respect to 100 parts by mass of the olefin or paraffin.
If the added amount is less than 14 parts by mass, the compatibility with the binder resin may not be sufficiently good at the time of melting. When it exceeds 65 parts by mass, the crystallinity is impaired, and the thermal characteristics of the toner may be deteriorated.

In the present invention, the saponification value of the maleic anhydride adduct of olefin or paraffin is preferably in the range of 80 to 200 mg KOH / g. It is preferable that the saponification value of the crystalline compound is 80 to 200 mg / KOH because the compatibility with the binder resin is suitable.
Here, the saponification value of the maleic anhydride adduct is a method defined in JIS standard K0070 “Testing method for acid value, saponification value, ester value, iodine value, hydroxyl value and unsaponified product of chemical products”, Specifically, it can be determined by dissolving the maleic anhydride adduct in a solvent and then neutralizing and titrating with a KOH alcohol solution using phenolphthalein as an indicator.

The melting point of the maleic anhydride adduct of olefin or paraffin is preferably in the range of 40 to 100 ° C, more preferably in the range of 60 to 90 ° C.
This melting point can be measured by differential scanning calorimetry described later.

  The melting point can be measured as follows. A differential thermal scanning calorimeter DSC-7 manufactured by Perkin Elmer is used, the melting points of indium and zinc are used for temperature correction of the detection part of the apparatus, and the heat of fusion of indium is used for correction of the heat quantity. An aluminum pan was used for the sample, an empty pan was set for the control, the temperature was raised from room temperature to 150 ° C. at a rate of 10 ° C./min, and from 150 ° C. to −30 ° C. at a rate of 10 ° C./min. The temperature was lowered, the temperature was further increased from −30 ° C. to 150 ° C. at a rate of 10 ° C./min, and the maximum endothermic peak temperature at the second temperature increase was taken as the melting point.

As the crystalline compound used in the present invention, a maleic anhydride adduct of α-olefin, which is the maleic anhydride adduct, and a copolymer of α-olefin and maleic anhydride (hereinafter referred to as “copolymer”). In some cases, it is preferable to use a mixture.
The maleic anhydride adduct of α-olefin is highly compatible with the binder resin, and the copolymer of α-olefin and maleic anhydride has higher crystallinity of the α-olefin moiety. However, although the copolymer of α-olefin and maleic anhydride is highly compatible with the binder resin, it is difficult to sufficiently reduce the toner viscosity when melted with the copolymer alone. Therefore, the presence of an α-olefin maleic anhydride adduct and a copolymer thereof can increase crystallinity while maintaining compatibility with the binder resin, and can exhibit a sharp melt.

  The α-olefin is preferably a straight-chain saturated hydrocarbon except for the double bond at the α-position, and preferably has an average carbon number in the range of 22 to 55. More preferably, it is the range of 30-46. The α-olefin moiety is preferably a straight-chain saturated hydrocarbon because it has high crystallinity and is stable to heat. When the average carbon number is in the range of 22 to 55, the crystallinity can be maintained against the crystallinity inhibition by maleic anhydride, which is preferable. Furthermore, it is more preferable that the average carbon number is 30 to 46 because the melting from the beginning to the end of the melting becomes sharp.

  Examples of the α-olefin include 1-docosene, 1-tetracocene, 1-hexacocene, 1-octacocene, 1-triacontene, 1-dotriacontene, 1-tetratriacontene, 1-hexatriacontene, 1-octatria. Examples thereof include content, 1-tetracontene and the like, and mixtures thereof.

  The copolymerization method of the α-olefin and maleic anhydride may be carried out without using a solvent or in combination with a solvent. In addition, maleic anhydride may be charged together with the α-olefin at once, or may be gradually added to the polymerization system. These polymerization methods are not particularly limited. Polymerization initiators used here include azobis compounds such as azobisisobutyronitrile and azobis 2,4-dimethylvaleronitrile, cumene hydroperoxide, t-butyl hydroperoxide, benzoyl peroxide, diisopropyl peroxycarbonate, diisopropyl Examples thereof include peroxides such as t-butyl peroxide, lauroyl peroxide, t-butyl peroxybenzoate, potassium persulfate, and ammonium persulfate. Although not particularly limited to these, it is preferable to use an organic peroxide or an organic azo compound.

When the molecular weight is W, the calculated molecular weight of 1 mole of α-olefin is Wa, and the calculated molecular weight of 1 mole of maleic anhydride is Wm, 1.6 ≦ W / (Wa + Wm) ≦ 3. 2 is preferable. Within this range, the compatibility with the binder resin is good.
Specifically, the weight average molecular weight of the copolymer is preferably in the range of 1000 to 10,000, and more preferably in the range of 1200 to 8000.

The above weight average molecular weight is obtained by measuring a THF (tetrahydrofuran) soluble material using a molecular weight calibration curve prepared with a monodisperse polystyrene standard sample by measuring HLC-8020 manufactured by Tosoh Corporation. It is.
Specifically, TSK gei, SuperHM-H (6.0 mmID × 15 cm × 2) is used as a column, THF is used as a solution, and measurement conditions are a sample concentration of 0.5% and a flow rate of 0.6 ml / min. Sample injection volume 10 μl, measurement temperature 40 ° C., calibration curve is A-500, F-1, F-10, F-80, F-380, A-2500, F-4, F-40, F-128, Made from 10 samples of F-700. The data collection interval in sample analysis was 300 ms.

The mixture of the maleic anhydride adduct and the copolymer may be mixed after preparing each, or the maleic anhydride adduct is also formed simultaneously with the formation of the copolymer during the polymerization of the copolymer. It can also be.
The copolymer ratio with respect to the maleic anhydride adduct is preferably in the range of 40 to 60% by mass, more preferably in the range of 45 to 55% by mass.

Furthermore, as the crystalline compound used in the present invention, a mixture of an α-olefin maleic anhydride adduct and a copolymer of α-olefin and maleic anhydride is partially monoesterified. preferable.
In the maleic anhydride adduct and copolymer of the mixture in which the maleic anhydride portion is monoesterified, one carboxylic acid of maleic acid becomes an ester and the other exists as a carboxylic acid. . In this way, the anhydride is monoesterified, so that the chargeability of the toner at high temperature and high humidity becomes better.

  The alcohol used for monoesterification is preferably a primary alcohol having 4 to 12 carbon atoms. This range is preferable because the compatibility with the binder resin is not deteriorated and the crystallinity is not affected. Further, two or more kinds of the above alcohols may be used in combination.

Esterification can be performed by a conventional method. In this case, it is preferable that a part of the mixture is monoesterified. Specifically, it is preferable that 20 to 60 mol% of the maleic anhydride part in the mixture is monoesterified.
The esterification rate of maleic anhydride can be determined by IR spectrum analysis of the compound before and after the reaction.

When the crystalline compound in the present invention is a mixture of the maleic anhydride adduct and a copolymer or a monoester product thereof, the melting point thereof is preferably in the range of 40 to 100 ° C, and preferably 60 to 90 More preferably, it is in the range of ° C.
Here, the melting point refers to the maximum endothermic peak in the DSC endothermic curve.

  These crystalline compounds are preferably contained in a binder resin described later in a range of 5 to 40% by mass, and more preferably in a range of 10 to 20% by mass. When the content is within this range, it is possible to lower the viscosity of the toner even in a low temperature region at the time of fixing.

(Binder resin)
The binder resin in the present invention is not particularly limited, and for example, a homopolymer or a copolymer of an ethylenically unsaturated monomer including a vinyl monomer can be used. Examples of monomers constituting these homopolymers or copolymers include styrenes such as styrene, parachlorostyrene, and α-methylstyrene; methyl acrylate, ethyl acrylate, n-propyl acrylate, acrylic (Meth) acrylic acid esters such as n-butyl acid, lauryl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, lauryl methacrylate, 2-ethylhexyl methacrylate; acrylonitrile, Ethylenically unsaturated nitriles such as methacrylonitrile; Ethylenically unsaturated carboxylic acids such as acrylic acid, methacrylic acid and crotonic acid; Vinyl ethers such as vinyl methyl ether and vinyl isobutyl ether; Vinyl methyl ketone, vinyl ethyl ketone and vinyl Vinyl ketones such as Puropeniruketon, ethylene, propylene, and the like olefins such as butadiene, beta-carboxyethyl acrylate can be exemplified. A homopolymer composed of these monomers, a copolymer obtained by copolymerizing two or more of these, and a mixture thereof can be used.

  As a polymerization initiator for the monomer, any suitable polymerization initiator such as 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 other azo or diazo polymerization initiators, Examples include benzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl peroxycarbonate, cumene hydroperoxide, peroxide-based polymerization initiators such as 2,4-dichlorobenzoyl peroxide, lauroyl peroxide, thiols such as dodecanethiol, and ammonium peroxodisulfate.

  In addition, the binder resin in the present invention includes an epoxy resin, a polyester resin, a polyurethane resin, a polyamide resin, a cellulose resin, a polyether resin, and the like, a non-vinyl condensation resin, or these and the ethylenically unsaturated addition polymer resin. And a graft polymer obtained by polymerizing an ethylenically unsaturated monomer in the presence of these.

  Among these, it is preferable to use a polyester resin as the binder resin in the present invention. The polyester resin can be preferably used from the viewpoint of flexibility of the fixing film and low viscosity at low temperature. In the case of using a polyester resin, it is advantageous in that a resin fine particle dispersion described later can be easily prepared by adjusting the acid value of the resin or emulsifying and dispersing it using an ionic surfactant.

The polyester resin is synthesized from a polyvalent carboxylic acid and a polyhydric alcohol.
Examples of polyvalent carboxylic acids include aromatic carboxylic acids such as terephthalic acid, isophthalic acid, phthalic anhydride, trimellitic anhydride, pyromellitic acid, naphthalenedicarboxylic acid, maleic anhydride, fumaric acid, succinic acid, alkenyl. Examples thereof include aliphatic carboxylic acids such as succinic anhydride and adipic acid, and alicyclic carboxylic acids such as cyclohexanedicarboxylic acid. These polyvalent carboxylic acids can be used alone or in combination of two or more. Among these polyvalent carboxylic acids, it is preferable to use aromatic carboxylic acids, and in order to secure a good fixing property, trivalent or higher carboxylic acids (trimerits) together with dicarboxylic acids to form a crosslinked structure or a branched structure. It is preferable to use an acid or an acid anhydride thereof in combination.

  Examples of polyhydric alcohols include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, butanediol, hexanediol, neopentyl glycol, glycerin and other aliphatic diols, cyclohexanediol, cyclohexanedimethanol, hydrogenated bisphenol A, etc. And aromatic diols such as bisphenol A ethylene oxide adduct and bisphenol A propylene oxide adduct. One or more of these polyhydric alcohols can be used. Among these polyhydric alcohols, aromatic diols and alicyclic diols are preferable, and among these, aromatic diols are more preferable. In order to secure good fixing properties, a trihydric or higher polyhydric alcohol (glycerin, trimethylolpropane, pentaerythritol, etc.) may be used in combination with the diol in order to obtain a crosslinked structure or a branched structure.

  A polyester resin obtained by polycondensation of a polyvalent carboxylic acid and a polyhydric alcohol is further added with a monocarboxylic acid and / or monoalcohol to esterify the hydroxyl group and / or carboxyl group at the polymerization terminal, thereby producing a polyester. The acid value of the resin may be adjusted. Examples of the monocarboxylic acid include acetic acid, acetic anhydride, benzoic acid, trichloroacetic acid, trifluoroacetic acid, propionic anhydride and the like, and examples of the monoalcohol include methanol, ethanol, propanol, octanol, 2-ethylhexanol, and trifluoroethanol. , Trichloroethanol, hexafluoroisopropanol, phenol and the like.

  The polyester resin can be produced by subjecting the polyhydric alcohol and polyhydric carboxylic acid to a condensation reaction according to a conventional method. For example, the above polyhydric alcohol and polyvalent carboxylic acid, if necessary, a catalyst, and blended in a reaction vessel equipped with a thermometer, a stirrer, a flow-down condenser, and in the presence of an inert gas (such as nitrogen gas), Heat at 150 to 250 ° C. to continuously remove by-product low-molecular compounds out of the reaction system, stop the reaction when a predetermined acid value is reached, cool, and obtain the desired reactant Can be manufactured.

  Examples of the catalyst used for the synthesis of this polyester resin include esterification catalysts such as organic metals such as dibutyltin dilaurate and dibutyltin oxide, and metal alkoxides such as tetrabutyl titanate. The amount of such a catalyst added is preferably in the range of 0.01 to 1% by mass relative to the total amount of raw materials.

The glass transition point of the binder resin used in the present invention is preferably in the range of 52 to 68 ° C, and more preferably in the range of 55 to 64 ° C. It is preferable for the glass transition temperature to be in the above-mentioned range since the thermal characteristics and powder characteristics of the toner are suitable.
The weight average molecular weight Mw of the binder resin used in the present invention is preferably 5000 to 50000, and more preferably 8000 to 30000.

  The mode of using these binder resins in the toner is not particularly limited. For example, when used in a wet production method described later, a resin fine particle dispersion containing an ionic surfactant is prepared and used. To do.

  For example, when the ethylenically unsaturated monomer is polymerized, a resin fine particle dispersion can be prepared by carrying out emulsion polymerization using an ionic surfactant or the like. In addition, in the case of other resins, if the resin is soluble in an oily solvent with relatively low solubility in water, the resin is dissolved in those solvents and a homogenizer together with an ionic surfactant or polymer electrolyte in water. The resin fine particle dispersion can be prepared by dispersing as fine particles in water using a disperser and then evaporating the solvent by heating or decompressing.

The particle size of the resin fine particles in the dispersion is preferably 120 to 340 nm, and more preferably 160 to 260 nm. When the particle size is in the above range, the particle size distribution of the obtained toner is narrow, free particles are not generated, and the performance and reliability of the toner are improved. The particle size of the resin fine particles in these dispersions is preferably , And can be measured with a laser diffraction particle size distribution measuring apparatus LA-700 (manufactured by Horiba, Ltd.).

(Coloring agent)
As the colorant used in the present invention, known ones can be used. Examples of the black pigment include carbon black, copper oxide, manganese dioxide, aniline black, activated carbon, nonmagnetic ferrite, and magnetite. Examples of yellow pigments include yellow lead, zinc yellow, yellow iron oxide, cadmium yellow, chrome yellow, Hansa yellow, Hansa yellow 10G, benzidine yellow G, benzidine yellow GR, selenium yellow, quinoline yellow, and permanent yellow. NCG etc. are mentioned.

Examples of the orange pigment include red yellow lead, molybdenum orange, permanent orange GTR, pyrazolone orange, Vulcan orange, benzidine orange G, indanthrene brilliant orange RK, indanthrene brilliant orange GK and the like.
Red pigments include Bengala, cadmium red, red lead, mercury sulfide, watch young red, permanent red 4R, risor red, brilliantamine 3B, brilliantamine 6B, dapon oil red, pyrazolone red, rhodamine B rake, lake red C , Rose bengal, oxin red, alizarin lake and the like.

Blue pigments include bitumen, cobalt blue, alkali blue rake, Victoria blue rake, fast sky blue, induslen blue BC, aniline blue, ultramarine blue, calco oil blue, methylene blue chloride, phthalocyanine blue, phthalocyanine green, malachite green oxare. Rate and so on. Examples of purple pigments include manganese purple, fast violet B, and methyl violet lake.
Examples of the green pigment include chromium oxide, chromium green, pigment green, malachite green lake, final yellow green G, and the like.
Examples of white pigments include zinc white, titanium oxide, antimony white, and zinc sulfide.

Examples of extender pigments include barite powder, barium carbonate, clay, silica, white carbon, talc, and alumina white.
Furthermore, examples of the dye include various dyes such as basic, acidic, dispersion, and direct dyes, such as nigrosine, methylene blue, rose bengal, quinoline yellow, and ultramarine blue.

  The colorant used in the present invention is selected from the viewpoints of hue angle, saturation, brightness, weather resistance, OHP permeability, and dispersibility in the toner. The addition amount of the colorant is in the range of 1 to 20 parts by mass with respect to 100 parts by mass of the binder resin of the toner. When using a magnetic material as the black colorant, it is added in the range of 30 to 100 parts by mass, unlike other colorants.

  When the toner of the present invention is used as a magnetic toner, magnetic powder may be contained in the binder resin. As such magnetic powder, a substance magnetized in a magnetic field is used. Specifically, ferromagnetic powders such as iron, cobalt and nickel, or compounds such as ferrite and magnetite can be used. In particular, in the present invention, in order to obtain the toner in the aqueous phase, the aqueous phase migration of the magnetic material is important. It is preferable to perform surface modification, for example, hydrophobization treatment.

These colorants can be used singly or in combination, and even in a solid solution state. These colorants are dispersed by a known method. For example, a media type dispersing machine such as a rotary shear type homogenizer, a ball mill, a sand mill, or an attritor, a high-pressure opposed collision type dispersing machine, or the like is preferably used.
Furthermore, when these colorants are used for toner production by a wet method, which will be described later, a polar surfactant is used and dispersed in the aqueous system as colorant particles by the homogenizer.

  The volume average particle diameter of the colorant particles is preferably in the range of 120 to 360 nm, more preferably in the range of 160 to 260 nm. It is preferable that the volume average particle diameter is in the above range since the color development property, color reproducibility, OHP permeability, etc. of the toner can be improved.

In addition to the binder resin, colorant and crystalline compound, the toner for developing an electrostatic image of the present invention includes a release agent, an internal additive, a charge control agent, inorganic fine particles, organic fine particles, and a lubricant as necessary. It is possible to contain additives such as abrasives.
It is preferable to include a release agent in the toner of the present invention in order to improve releasability during fixing. Examples of specific substances used as the release agent are as follows. Low molecular weight polyolefin waxes such as polyethylene, polypropylene, polybutene, plant waxes such as carnauba wax, rice wax, candelilla wax, tree wax, jojoba oil, animal waxes such as beeswax, montan wax, ozokerite, Examples thereof include minerals such as ceresin, paraffin wax, microcrystalline wax, and Fischer-Tropsch wax, petroleum wax, and modified products thereof.

  Of the above, paraffin wax, microcrystalline wax, and polyolefin wax are preferable, and paraffin wax and polyethylene wax are particularly preferable. A release agent having a small polarization, such as paraffin wax and polyethylene wax, is preferable because it has a low affinity with the binder resin and crystalline compound of the toner and the release agent can be easily oozed out during fixing.

  The melting point of the release agent used in the toner of the present invention is preferably in the range of 60 to 120 ° C., and more preferably in the range of 85 to 105 ° C. Further, the addition amount of the release agent is preferably in the range of 2 to 20 parts by mass with respect to 100 parts by mass of the binder resin, and more preferably in the range of 5 to 10 parts by mass.

  Similarly to the above, when used for wet toner production, it can be used as a dispersion of release agent particles, and the volume average particle diameter of the release agent particles is preferably in the range of 120 to 360 nm. A range of 300 nm is more preferable. A volume average particle size within the above range is preferable because uneven distribution of the composition among the toner particles can be suppressed, and the performance and reliability of the toner are improved. The average volume particle size can be measured using a laser diffraction type particle size distribution analyzer as in the case of the resin fine particles.

  In the present invention, a charge control agent can be blended in order to further improve and stabilize the chargeability of the toner. As the charge control agent, quaternary ammonium salt compounds, nigrosine compounds, dyes composed of complexes of aluminum, iron, chromium, and triphenylmethane pigments can be used. In order to control the ionic strength that affects the properties and reduce the contamination of wastewater, materials that are difficult to dissolve in water are better.

  In the present invention, inorganic fine particles can be added in a wet manner in order to stabilize the chargeability of the toner. Examples of inorganic fine particles include silica, alumina, titania, calcium carbonate, magnesium carbonate, and tricalcium phosphate, all of which are usually used as external additives on the toner surface, such as ionic surfactants and polymer acids. It can be used by dispersing in a polymer base.

  Also, for the purpose of imparting fluidity and improving cleaning properties, the toner is dried and then fine particles such as silica, alumina, titania and calcium carbonate, vinyl resin, polyester, silicone, etc. The organic fine particles can be added to the toner surface by applying a shearing force in a dry state and used as a fluidity aid or a cleaning aid.

A method for producing the toner for developing an electrostatic charge image of the present invention by a wet method will be described later.
On the other hand, when the toner particles in the present invention are obtained by the kneading and pulverization method, first, the resin (binder resin), the colorant, the release agent, and the like are mixed with a mixer such as a Nauter mixer or a Henschel mixer, Kneading with a single-screw or twin-screw extruder such as an extruder. After rolling and cooling this, it is finely pulverized with a mechanical or air-flow pulverizer represented by I-type mill, KTM, jet mill, etc., and then a classifier using the Coanda effect such as an elbow jet or turbo crash Classify using an airflow classifier such as Fire or Accucut. Furthermore, a treatment such as driving resin fine particles or the like into the surface of the produced toner particles by a dry method may be performed.

  The volume average particle size of the toner of the present invention is preferably in the range of 3 to 9 μm. When the volume average particle diameter of the toner particles exceeds 9 μm, the ratio of coarse particles increases, and the reproducibility and gradation of fine lines and fine dots of the image obtained through the fixing process are lowered. On the other hand, when the volume average particle size of the toner particles is less than 3 μm, the powder fluidity, developability, or transferability of the toner deteriorates, and the cleaning property of the toner remaining on the surface of the image carrier decreases. Various problems occur in other processes due to the deterioration of characteristics.

  Further, as the particle size distribution index of the toner particles used in the present invention, the volume average particle size distribution index GSDv is preferably 1.30 or less, and the ratio GSDv / GSDp to the number average particle size distribution index GSDp is 0.95 or more. It is more preferable that When the volume distribution index GSDv exceeds 1.30, the unevenness of the fixed image described above becomes large, and uneven glossiness may easily occur. Further, when the ratio between the volume average particle size distribution index GSDv and the number average particle size distribution index GSDp is less than 0.95, the amount of small particle size toner increases, and the amount of release agent contained per toner is uneven. May occur, and as a result, peeling failure may occur and a desired glossiness may not be obtained.

  Regarding the above, further preferable ranges are D50v in the range of 4.0 to 8.0 μm, GSDv in the range of 1.0 to 1.28, and GSDv / GSDp in the range of 0.95 to 1.2. When the volume average particle diameter D50v of the toner is within the above range, the amount of toner necessary for obtaining the desired color can be reduced, fixing with low energy is possible, and this is advantageous for low-temperature fixability. Similarly, it is preferable because there is little transfer residue from the photoreceptor, which is advantageous for transferability. When the volume average particle size distribution index GSDv is within the above range, high resolving power is obtained. It is preferable that the ratio (GSDv / GSDp) of the volume average particle size distribution index and the number average particle size distribution index is in the above range because good chargeability can be obtained and image defects such as toner scattering and fogging do not occur.

The volume average particle size and the particle size distribution index were measured and calculated as follows. First, the volume and number of individual toner particles are accumulated from the smaller diameter side with respect to the divided particle size range (channel) of the toner particle size distribution measured using a Coulter Counter TAII (manufactured by Beckman-Coulter) as a measuring device. Draw a distribution and define the particle size to be 16% cumulative as the volume average particle size D16v and the number average particle size D16p. The particle size to be 50% cumulative is the volume average particle size D50v (this value is the volume average particle size And D50p. Similarly, the particle diameters with an accumulation of 84% are defined as volume average particle diameters D84v and D84p. Using these, the volume average particle size distribution index GSDv is defined as (D84v / D16v) ^1/2 , and the number average particle size distribution index GSDp is defined as (D84p / D16p) ^1/2 .

Further, the toner shape factor SF1 in the present invention is preferably in the range of 110 to 140.
If the shape factor SF1 is less than 110, the blade cleaning property of the transfer residual toner on the photoconductor is impaired. If the shape factor SF1 exceeds 140, the fluidity of the toner is lowered, and the transferability may be adversely affected from the beginning. A more preferable range of the shape factor SF1 is a range of 125 to 138.

Here, the shape factor SF1 is obtained by the following equation 1.
SF1 = (ML ² / A) × (π / 4) × 100 Expression 1
In the above formula 1, ML represents the absolute maximum length of the toner particles, and A represents the projected area of the toner particles.

  The SF1 is quantified mainly by analyzing a microscope image or a scanning electron microscope (SEM) image using an image analyzer, and can be calculated as follows, for example. That is, an optical microscope image of the toner spread on the surface of the slide glass is taken into a Luzex image analyzer through a video camera, and the maximum length and projected area of 100 or more toner particles are obtained. It is obtained by seeking.

  The acid value of the toner in the present invention not only improves and stabilizes the inclusion of crystalline compound particles, colorant particles and the like in the toner, but is also important for charging properties, and ranges from 5 to 50 mg KOH / g. Is preferred. When the acid value is in the above range, the inclusion property and stability of the crystalline compound particles, the colorant particles and the like are improved, and appropriate charging can be obtained. Moreover, since the component which gives an acid value is a suitable quantity and it does not produce bridge | crosslinking, favorable fixability is obtained.

The glass transition point (Tg) of the toner of the present invention is preferably in the range of 49 to 65 ° C. More preferably, it is the range of 51-58 degreeC. When the Tg is in the range of 49 to 65 ° C., the toner can be preferably used because it has good image durability such as toner storage stability and document offset.
Note that the glass transition point is the intersection of the extension line of the maximum slope and the baseline when the endothermic amount during the second temperature increase is greatly changed in the differential scanning calorimetry (DSC) performed under the melting point measurement conditions. Determined by

  Further, the glass transition point of the toner in the present invention is such that the Tg difference (Tg1−Tg2) between the first temperature increase and the second temperature increase in the DSC measurement is in the range of 0.1 to 8.0 ° C. Preferably there is. If the Tg difference is larger than this range, the toner may not have sufficient heat stress resistance.

  The charge amount of the toner for developing an electrostatic charge image of the present invention is preferably in the range of 20 to 80 μC / g in absolute value, and more preferably in the range of 25 to 35 μC / g. If the charge amount is less than 20 μC / g, background stains (fogging) are likely to occur, and if it exceeds 80 μC / g, the image density tends to decrease. The ratio of the charge amount in the summer (high temperature and high humidity) and the charge amount in the winter (low temperature and low humidity) of the toner for developing an electrostatic charge image is preferably in the range of 0.5 to 1.5. A range of 3 is more preferred. When the ratio is outside these ranges, the charging property is highly dependent on the environment, and the charging stability is poor, which is not preferable for practical use.

<Method for producing toner for developing electrostatic image>
The method for producing the toner for developing an electrostatic charge image of the present invention is not particularly limited, but the structure of the toner of the present invention can be efficiently controlled as described above. It is preferable to use a manufacturing method.
Hereinafter, the production method of the electrostatic image developing toner of the present invention will be described in more detail.

  The method for producing an electrostatic image developing toner of the present invention comprises a dispersion step of dispersing at least resin fine particles, colorant particles and crystalline compound particles in an aqueous dispersion medium, and aggregating the dispersed particles into aggregated particles. It includes an aggregating step and a heat fusing step for thermally fusing the agglomerated particles.

In the dispersion step, it is preferable to disperse resin fine particles, colorant particles and crystalline compound particles in an aqueous dispersion medium. That is, it is preferable to prepare a resin fine particle dispersion, a colorant particle dispersion, and a crystalline compound particle dispersion and mix them. As a method for producing each dispersion, for example, a resin fine particle dispersion is obtained by applying shear force to a solution obtained by mixing an aqueous medium and a mixed liquid (polymer liquid) containing a binder resin and, if necessary, a colorant. Formed by giving.
At this time, the viscosity of the polymer liquid can be lowered to form emulsified particles by heating or dissolving the resin in the organic solvent. However, it is better not to use the organic solvent as much as possible from the viewpoint of environmental pollution. Moreover, a dispersing agent can also be used for stabilization of emulsified particles and thickening of the aqueous medium.

  The dispersion medium used in the dispersion step is an aqueous dispersion medium. For example, it contains water such as distilled water and ion-exchanged water as a main component, and contains a small amount (30% by volume or less) of a water-miscible solvent such as alcohol. good. The water-miscible dispersion medium may be included alone or in combination of two or more.

  Examples of the dispersant include water-soluble polymers such as polyvinyl alcohol, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, sodium polyacrylate, and sodium polymethacrylate, sodium dodecylbenzenesulfonate, sodium octadecylsulfate, and oleic acid. Anionic surfactants such as sodium, sodium laurate, potassium stearate, cationic surfactants such as laurylamine acetate, stearylamine acetate, lauryltrimethylammonium chloride, zwitterionic surfactants such as lauryldimethylamine oxide, Such as polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene alkylamine, etc. Anion surfactants such as surfactants, tricalcium phosphate, aluminum hydroxide, calcium sulfate, calcium carbonate, and inorganic compounds such as barium carbonate.

When an inorganic compound is used as the dispersant, a commercially available product may be used as it is. However, for the purpose of obtaining fine particles, a method of producing fine particles of an inorganic compound in the dispersant may be employed.
As the usage-amount of the said dispersing agent, the range of 0.01-20 mass parts is preferable with respect to 100 mass parts of said binder resins. Further, as a dispersing means, a general means such as a rotary shear type homogenizer or a ball mill having a medium, a sand mill, or a dyno mill can be used.

  In the toner production method of the present invention, it is preferable to further add a release agent, and the release agent particles are preferably added in the dispersion step. That is, resin fine particles, colorant particles, crystalline compound particles, and release agent particles are each dispersed in an aqueous dispersion medium (dispersion step), and a mixed solution of these dispersions is aggregated by, for example, metal ions (aggregation step). Further, it is preferable to produce the aggregated particles by heat-sealing (heat-sealing step).

  The other additive may be dispersed in any one of the resin fine particle dispersion, the colorant particle dispersion, the crystalline compound particle dispersion, or the release agent particle dispersion, or a dispersion obtained by dispersing the additive. You may add and mix a liquid.

  As the aggregating agent used in the aggregating step, a surfactant having a polarity opposite to that of the surfactant used for the dispersing agent, an inorganic metal salt, or a divalent or higher-valent metal complex can be preferably used. In particular, the use of a metal complex is particularly preferable because the amount of the surfactant used can be reduced and the charging characteristics are improved.

As the inorganic metal salt, an inorganic metal salt having a divalent or higher charge can be used. The metal element constituting the inorganic metal salt is a group 2A, 3A, 4A, 5A, 6A, 7A, 8, 1B, 2B, 3B in the periodic table (LUPAC's 1989 inorganic chemical nomenclature) The revised group number has a charge of two or more valences belonging to Group 2 to Group 8 and Group 11 to Group 13).
Specifically, for example, metal salts such as calcium chloride, calcium nitrate, barium chloride, magnesium chloride, zinc chloride, aluminum chloride, and aluminum sulfate, and inorganic metal salts such as polyaluminum chloride, polyaluminum hydroxide, and calcium polysulfide A polymer etc. are mentioned. Among these, an aluminum salt and a polymer thereof are particularly preferable. In order to obtain a sharper particle size distribution, the valence of the inorganic metal salt is bivalent than monovalent, trivalent than bivalent, trivalent than trivalent, and tetravalent than trivalent. The inorganic metal salt polymer is more suitable.

  The amount of the flocculant to be added is not particularly limited as long as it does not inhibit the present invention, but specifically, it is in the range of 0.01 to 10% by mass, preferably 0. It is the range of 05-5 mass%, More preferably, it is the range of 0.1-2 mass%. When the amount added is less than 0.01% by mass, dispersions such as resin fine particle dispersion and colorant particle dispersion become unstable, resulting in aggregation and stability between particles during aggregation. Therefore, there are problems such as the release of specific particles. On the other hand, if it exceeds 10% by mass, the particle size distribution of the agglomerated particles becomes wide and it becomes difficult to control the particle size.

  As the agglomeration step and the heat fusion step, for example, a resin fine particle dispersion containing an ionic surfactant is mixed with a colorant particle dispersion and an ionic interface having a polarity opposite to that of the ionic surfactant is used. Aggregated particles having a toner diameter are formed by causing hetero-aggregation with an activator, and then the glass transition temperature of the binder resin (the glass of the resin having the lowest glass point transition temperature when there are two or more types of resin) It is possible to obtain a toner by heating above the lowest transition temperature) to heat-fuse the aggregated particles, washing and drying.

  The thermal fusion process is preferably performed at a melting point or lower of the low melting point compound measured from a DSC (differential scanning calorimetry) curve at the first temperature increase of the electrostatic charge image developing toner. Moreover, it is preferable that the heat sealing | fusion process is performed at the temperature more than the glass transition point of binder resin.

  It is also preferable to obtain toner by the following method. That is, in the initial stage of mixing the resin fine particle dispersion, the colorant particle dispersion, and the crystalline compound particle dispersion, the balance of the amount of the ionic dispersant of each polarity is shifted in advance, and inorganic such as polyaluminum chloride is used. A metal salt polymer is added for ionic neutralization, and then the first-stage base aggregated particles are formed and stabilized at a temperature below the glass transition point of the binder resin. As a second step, a resin fine particle dispersion treated with an ionic dispersant of a polarity and quantity that compensates for the ionic balance deviation is added, and if necessary, the resin fine particles in the aggregated particles and additional resin fine particles are added. Slightly heat below the glass transition point of the resin contained, stabilize at a higher temperature, and then heat above the glass transition point to add the particles added in the second stage of agglomeration to the surface of the base aggregate particles It may be heat-sealed while being attached to. Further, this stepwise operation of aggregation may be repeated a plurality of times. This two-stage method is effective for improving the inclusion of the crystalline compound, the release agent and the colorant.

  The two-stage method will be described in detail. Between the agglomeration step and the heat fusion step, a fine particle dispersion in which fine particles are dispersed is added and mixed in the agglomerated particle dispersion to adhere the fine particles to the aggregated particles. And a step (attachment step) of forming attached particles.

  In the adhering step, the fine particle dispersion is added to and mixed with the aggregated particle dispersion prepared in the aggregating step to form the adhered particles by adhering the fine particles to the aggregated particles. Since this corresponds to newly added particles as seen from the aggregated particles, it may be referred to as “additional fine particles” in this specification. As the additional fine particles, in addition to the fine resin particles, crystalline compound particles, release agent particles, colorant particles and the like may be used singly or in combination. The method of additionally mixing the fine particle dispersion is not particularly limited, and may be performed gradually, for example, or may be performed stepwise by dividing into a plurality of times. In this way, by adding and mixing fine particles (additional fine particles), the generation of fine particles can be suppressed, and the particle size distribution of the resulting electrostatic image developing toner can be sharpened, contributing to higher image quality. To do.

  In addition, by providing the adhesion step, a pseudo shell structure can be formed, and the toner surface exposure of an internal additive such as a colorant or a low melting point compound can be reduced. As a result, the chargeability and the life are improved. be able to. Furthermore, at the time of fusing in the heat fusing process, the particle size distribution can be maintained and fluctuations thereof can be suppressed, and a surfactant or a stabilizer such as a base or an acid can be used to enhance the stability at the time of fusing. It is advantageous in that the addition can be made unnecessary or the amount of addition can be suppressed to the minimum, and the cost can be reduced and the quality can be improved. Further, if this method is used, the toner shape can be easily controlled by adjusting the temperature, the number of stirrings, the pH, and the like in the heat sealing step.

  In the aggregation step of the aggregated particles and / or the adhesion step of various fine particles, the type and amount of the ionic surfactant that adjusts the polarity of the dispersion liquid are selected to control the degree of aggregation and / or adhesion. Can do. For example, by dispersing resin fine particles in a solution containing an anionic surfactant, dispersing a colorant in a solution containing a cationic surfactant, and mixing both, resin fine particles and colorant particles, etc. Can be agglomerated.

  Also, the balance of the polarity and blending amount of the ionic surfactant contained in the dispersion to be mixed is shifted in advance, and the polarity and amount of the ionic surfactant is added to compensate for the balance shift. It is also possible to carry out agglomeration and / or adhesion.

  After completion of the thermal fusion process, a desired toner can be obtained through any washing process, solid-liquid separation process, and drying process. However, the washing process is sufficiently ion-exchanged water to develop and maintain the chargeability. It is preferable to perform replacement washing with. The solid-liquid separation step is not particularly limited, but suction filtration, pressure filtration, and the like are preferably used from the viewpoint of productivity. Further, the drying process is not particularly limited, but freeze drying, flash jet drying, fluidized drying, vibration fluidized drying and the like are preferably used from the viewpoint of productivity.

  The toner of the present invention is used in a method called a two-component developer comprising a toner and a carrier, in addition to being used in a method of using a one-component developer having a charge imparting structure in a developing device. The carrier is preferably a carrier coated with a resin using ferrite, iron powder or the like as a core material. The core material (carrier core material) used is not particularly limited, and examples thereof include magnetic metals such as iron, steel, nickel, and cobalt, magnetic oxides such as ferrite and magnetite, and glass beads. From the viewpoint of use, a magnetic carrier is desirable. The volume average particle diameter of the carrier core material is preferably 3 to 10 times the average toner particle diameter.

  Examples of carrier coating resins include acrylic resins, styrene resins, urea, urethane, melamine, guanamine, aniline and other amino resins, amide resins, and urethane resins. These copolymer resins may also be used. Two or more of the above resins may be used in combination as the coating resin for the carrier. Further, for the purpose of controlling charging, resin fine particles, inorganic fine particles or the like may be dispersed in the coating resin.

  Examples of the method for forming the resin coating layer on the surface of the carrier core material include an immersion method in which a powder of the carrier core material is immersed in the solution for forming the coating layer, and a solution for forming the coating layer on the surface of the carrier core material. Spraying method for spraying, fluidized bed method for spraying the solution for forming the coating layer in a state where the carrier core material is floated by flowing air, and a kneader for mixing the carrier core material and the coating layer forming solution in a kneader coater to remove the solvent. Examples of the coater method include a powder coat method in which a coating resin is finely divided and mixed in a carrier core material and a kneader coater at a temperature equal to or higher than the melting point of the coating resin, and then cooled to form a coating.

  The amount of the resin film formed by the above method is used by coating the carrier core material in an amount of 0.5 to 10% by weight. The mixing ratio (mass ratio) of the toner as the two-component developer and the carrier is in the range of toner: carrier = 1: 100 to 30: 100, and more preferably in the range of 3: 100 to 20: 100. preferable.

Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited thereto.
<Production of toner>
The toners used in the following examples and comparative examples were produced by the following method. That is, a resin fine particle dispersion, a colorant particle dispersion, and a release agent particle dispersion were prepared, respectively, and a polymer of an inorganic metal salt was added and ionically neutralized while mixing and stirring a predetermined amount thereof. The aggregate of each particle was formed. After adjusting the pH of the system from a weakly acidic to a weakly alkaline range with an inorganic hydroxide, it was heated to a temperature equal to or higher than the glass transition point of the resin fine particles and heat-sealed. Thereafter, a desired toner was obtained through sufficient washing, solid-liquid separation, and drying processes. Specific examples of the method for preparing each material and the method for producing aggregated particles are shown below.

  In addition, the resin molecular weight, melting | fusing point, fine particle dispersion diameter, etc. in the following were measured by the above-mentioned method. In addition, the acid value is measured by weighing 2 g of the resin and dissolving it in 160 ml of tetrahydrofuran, or dissolving it if it is insufficiently soluble, and then using this sample by the potentiometric titration method of JIS K0070-1992. It was.

(Preparation of crystalline compound 1 (paraffin maleic anhydride adduct))
-Oil phase 1-
-Refined paraffin having an average carbon number of 36 (carbon number distribution: 30 to 46) 50 parts by mass-t-butyl hydroperoxide (manufactured by Wako Pure Chemical Industries, Ltd.) 2 parts by mass-Toluene (manufactured by Wako Pure Chemical Industries, Ltd.) 100 Part by mass-oil phase 2-
-Maleic anhydride (Wako Pure Chemical Industries, Ltd.) 40 parts by mass-Toluene (Wako Pure Chemicals Co., Ltd.) 80 parts by mass

  One component of the oil phase was placed in a flask, the inside of the container was sufficiently replaced with nitrogen, and the mixture was heated to 140 ° C. To this, the component of oil phase 2 was gradually added dropwise over 2 hours, and after completion of the addition, the mixture was heated to 160 ° C. to continue the addition reaction, and the reaction was terminated after 2 hours. After cooling the reaction solution, solid-liquid separation was performed by filtration. Next, the obtained solid was put into a flask, 200 parts by mass of ion-exchanged water was added, and the mixture was heated to 90 ° C. A 1N sodium hydroxide aqueous solution was gradually added with sufficient stirring, and the liquid in the flask was adjusted to pH 8.5. The mixture was stirred for 30 minutes as it was, and the resulting maleic anhydride adduct of paraffin was dissolved. The reaction mixture was cooled to 50 ° C. and filtered to obtain a crystalline compound 1.

  The melting point of the obtained crystalline compound 1 was 74 ° C. as a result of measurement using a differential thermal scanning calorimeter DSC-7 manufactured by PerkinElmer. Further, the saponification value of the crystalline compound 1 was 140 mgKOH / g.

(Preparation of crystalline compound 2 (mixture of maleic anhydride adduct and copolymer))
Dialene 30, which is an α-olefin manufactured by Mitsubishi Chemical Corporation, is dissolved in toluene at 50 ° C. and solid-liquid separated, and the obtained solid is further dissolved in toluene at 90 ° C. to obtain a solid-liquid separation. The dissolved solution was cooled to obtain a purified α-olefin. The average carbon number of this purified α-olefin was 30 as measured by gas chromatography.

-Oil phase 1-
-Purified α-olefin 50 parts by mass-Toluene (manufactured by Wako Pure Chemical Industries, Ltd.) 100 parts by mass-Oil phase 2-
-Maleic anhydride (manufactured by Wako Pure Chemical Industries, Ltd.) 40 parts by mass-Toluene (manufactured by Wako Pure Chemical Industries, Ltd.) 80 parts by mass-initiator-
・ T-butyl hydroperoxide (Wako Pure Chemical Industries, Ltd.) 2 parts by mass

  One component of the oil phase was placed in a flask, and the inside of the container was sufficiently replaced with nitrogen, and heated to 140 ° C. To this, the components of the oil phase 2 and the initiator were gradually added dropwise over 2 hours, and the addition reaction was continued by heating to 160 ° C. after completion of the addition, and the reaction was terminated after 2 hours. After cooling the reaction solution, solid-liquid separation was performed by filtration. Next, the obtained solid was put into a flask, 200 parts by mass of ion-exchanged water was added, and the mixture was heated to 90 ° C. A 1N sodium hydroxide aqueous solution was gradually added with sufficient stirring, and the liquid in the flask was adjusted to pH 8.5. Stirring was continued for 30 minutes to dissolve the resulting maleic anhydride adduct and copolymer. The reaction mixture was cooled to 50 ° C. and filtered to obtain a crystalline compound 2.

  The melting point of the obtained crystalline compound 2 was 69 ° C. as a result of measurement using a differential thermal scanning calorimeter DSC-7 manufactured by PerkinElmer. In addition, in the molecular weight measurement by GPC, peaks were detected at 600 and 1300, and it was confirmed that the mixture was an α-olefin maleic anhydride adduct having a molecular weight of 600 and a copolymer of an α-olefin having a molecular weight of 1300 and maleic anhydride. It was done. The peak molecular weight ratio of the copolymer of α-olefin and maleic anhydride to the molecular weight calculated from the average carbon number of 30 of the original purified α-olefin was 2.8. Furthermore, the ratio of the copolymer with respect to the maleic anhydride adduct was 55 mass% from the peak ratio by GPC.

(Preparation of crystalline compound 3 (monoesterified product of mixture))
-Crystalline compound 2 100 parts by mass-Stearyl alcohol (manufactured by Wako Pure Chemical Industries, Ltd.) 2 parts by mass The crystalline compound 2 and stearyl alcohol are charged into a flask and the temperature is raised to 160 ° C over 1 hour. After confirming that the inside was uniformly stirred, 1.0 part by mass of dibutyltin oxide was added. Further, while distilling off the water produced, the temperature was raised from the same temperature to 200 ° C. over 6 hours, and the dehydration condensation reaction was continued at 200 ° C. for another 4 hours to complete the reaction. After cooling the reaction solution, solid-liquid separation was performed, and the obtained solid was dried under vacuum at 40 ° C. to obtain a crystalline compound 3.

  The melting point of the obtained crystalline compound 3 was 64 ° C. as a result of measurement using a differential thermal scanning calorimeter DSC-7 manufactured by PerkinElmer. From the analysis of acid anhydride, carboxylic acid and ester group by IR spectrum analysis of crystalline compounds 2 and 3, the esterification rate of maleic anhydride was 40 mol%.

(Preparation of crystalline compound 4 (maleic anhydride adduct of paraffin))
-Oil phase 1-
-50 parts by mass of polyethylene (polywax 850, manufactured by Toyo Petrolite Co., Ltd.)-2 parts by mass of t-butyl hydroperoxide (produced by Wako Pure Chemical Industries, Ltd.)-100 masses of toluene (produced by Wako Pure Chemical Industries, Ltd.) Part-oil phase 2-
-Maleic anhydride (Wako Pure Chemical Industries, Ltd.) 40 parts by mass-Toluene (Wako Pure Chemicals Co., Ltd.) 80 parts by mass

  One component of the oil phase was placed in a flask, the inside of the container was sufficiently replaced with nitrogen, and the mixture was heated to 160 ° C. To this, the component of oil phase 2 was gradually added dropwise over 2 hours, and after completion of the addition, the mixture was heated to 180 ° C. to continue the addition reaction, and the reaction was terminated after 2 hours. After cooling the reaction solution, solid-liquid separation was performed by filtration. Next, the obtained solid was put into a flask, 200 parts by mass of ion-exchanged water was added, and the mixture was heated to 90 ° C. A 1N sodium hydroxide aqueous solution was gradually added with sufficient stirring, and the liquid in the flask was adjusted to pH 8.5. Stirring was continued for 30 minutes to dissolve the maleic anhydride adduct. The reaction mixture was cooled to 50 ° C. and then filtered to obtain a crystalline compound 4.

  The melting point of the obtained crystalline compound 4 was 97 ° C. as a result of measurement using a differential thermal scanning calorimeter DSC-7 manufactured by PerkinElmer. Further, the saponification value of the crystalline compound 4 was 80 mgKOH / g.

(Preparation of each dispersion)
-Resin fine particle dispersion 1-
・ Ethylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.) 50 parts by mass ・ Neopentyl glycol (manufactured by Wako Pure Chemical Industries, Ltd.) 65 parts by mass ・ Terephthalic acid (manufactured by Wako Pure Chemical Industries, Ltd.) 96 parts by mass The monomer was charged into the flask, and the temperature was raised to 190 ° C. over 1 hour. After confirming that the reaction system was uniformly stirred, 1.2 parts by mass of dibutyltin oxide was added. Further, while distilling off the generated water, the temperature was raised from the same temperature to 240 ° C. over 6 hours, and the dehydration condensation reaction was continued at 240 ° C. for further 4 hours. The acid value was 10.0 mgKOH / g, and the weight average molecular weight. A polyester resin having 12,000 and a glass transition point of 60 ° C. was obtained.

Next, this was transferred in a molten state to Cavitron CD1010 (manufactured by Eurotech Co., Ltd.) at a rate of 100 g / min. A 0.37% by mass diluted ammonia water obtained by diluting reagent ammonia water with ion-exchanged water is placed in a separately prepared aqueous medium tank, and heated at 120 ° C. with a heat exchanger at a rate of 0.1 liter per minute. Simultaneously with the polyester resin melt, it was transferred to the Cavitron. A Cavitron is operated under conditions of a rotor rotation speed of 60 Hz and a pressure of 5 kg / cm ² , a resin having a volume average particle size of 160 nm, a solid content of 30% by mass, a glass transition point of 62 ° C., and a weight average molecular weight Mw of 12,000. A fine particle dispersion 1 was obtained.

-Resin fine particle dispersion 2-
(Oil phase)
・ Styrene (manufactured by Wako Pure Chemical Industries, Ltd.) 30 parts by mass ・ n-butyl acrylate (manufactured by Wako Pure Chemical Industries, Ltd.) 10 parts by mass ・ β-carboxyethyl acrylate (manufactured by Rhodia Nikka Co., Ltd.) 1 .3 parts by mass / dodecanethiol (Wako Pure Chemical Industries, Ltd.) 0.4 parts by mass (aqueous phase 1)
・ Ion-exchanged water 17 parts by mass ・ Anionic surfactant (Dowfax, manufactured by Dow Chemical) 0.4 parts by mass (aqueous phase 2)
・ Ion-exchanged water 40 parts by mass ・ Anionic surfactant (Dowfax, manufactured by Dow Chemical) 0.05 part by mass ・ Ammonium peroxodisulfate (Wako Pure Chemical Industries, Ltd.) 0.4 part by mass

  The oil phase component and the water phase 1 component were placed in a flask and mixed with stirring to obtain a monomer emulsion dispersion. The component of the aqueous phase 2 was charged into the reaction vessel, the inside of the vessel was sufficiently replaced with nitrogen, and the reaction system was heated to 75 ° C. with an oil bath while stirring. The monomer emulsified dispersion was gradually dropped into the reaction vessel over 3 hours to carry out emulsion polymerization. After completion of the dropwise addition, the polymerization was further continued at 75 ° C., and the polymerization was terminated after 4 hours.

About the obtained resin fine particles, the volume average particle diameter D50v was measured to be 200 nm, the glass transition point was measured to be 60 ° C., and the weight was measured using a molecular weight measuring device (HLC-8020, manufactured by Tosoh Corporation). It was 28,000 when the average molecular weight (polystyrene conversion) was measured.
As a result, a resin fine particle dispersion 2 having a volume average particle size of 200 nm, a solid content of 42% by mass, a glass transition point of 60 ° C., and a weight average molecular weight Mw of 28,000 was obtained.

-Colorant particle dispersion-
Cyan pigment (CI Pigment Blue 15: 3, manufactured by Dainichi Seika Kogyo Co., Ltd.) 10 parts by mass Anionic surfactant (Neogen SC, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 2 parts by mass 80 parts by mass The above components are mixed and dispersed for 1 hour by a high-pressure impact disperser ultimateizer (HJP30006, manufactured by Sugino Machine Co., Ltd.), and a colorant particle dispersion having a volume average particle size of 180 nm and a solid content of 20% by mass. Got.

-Crystalline compound particle dispersion 1-
-Crystalline compound 1 50 parts by mass-Anionic surfactant (Neogen SC, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 2 parts by mass-200 parts by mass of ion-exchanged water The above components are heated to 120 ° C and manufactured by IKA After sufficiently dispersing with Ultra Turrax T50, the dispersion was treated with a pressure discharge type homogenizer to obtain a crystalline compound particle dispersion 1 having a volume average particle size of 225 nm and a solid content of 20% by mass.

-Crystalline compound particle dispersions 2-4-
Crystalline compound particle dispersions 2 to 4 were obtained in the same manner except that crystalline compounds 2 to 4 were used in place of crystalline compound 1 in the preparation of crystalline compound particle dispersion 1. The volume average particle size of the crystalline compound particles in each dispersion was as follows. In addition, all solid content was 20 mass%.
-Crystalline compound particle dispersion 2 ... 200 nm
・ Crystalline compound particle dispersion 3 ... 210 nm
・ Crystalline compound particle dispersion 4 ・ ・ ・ 250 nm

-Crystalline compound particle dispersion 5-7-
In the preparation of the crystalline compound particle dispersion 1, the crystalline compound particle dispersions 5 to 7 were obtained in the same manner except that the crystalline compounds 5 to 7 shown in Table 1 were used instead of the crystalline compound 1, respectively. It was. The volume average particle size of the crystalline compound particles in each dispersion was as follows. In addition, all solid content was 20 mass%.
-Crystalline compound particle dispersion 5 ... 220 nm
-Crystalline compound particle dispersion 6 ... 220 nm
・ Crystalline compound particle dispersion 7 ・ ・ ・ 240nm

-Release agent particle dispersion-
-Ester wax (WEP-5, manufactured by NOF Corporation) 50 parts by mass-Anionic surfactant (Neogen SC, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 2 parts-Ion-exchanged water 200 parts by weight After heating to 120 ° C. and sufficiently dispersing with IKA's Ultra Turrax T50, it is dispersed with a pressure discharge homogenizer to obtain a release agent particle dispersion having a volume average particle size of 240 nm and a solid content of 20% by mass. It was.

<Example 1>
(Manufacture of toner)
-Resin fine particle dispersion 1 150 parts by weight-Colorant particle dispersion 25 parts by weight-Crystalline compound particle dispersion 1 50 parts by weight-Release agent particle dispersion 30 parts by weight-Polyaluminum chloride 0.4 part by weight-Ion 100 parts by mass of exchanged water The above components were sufficiently mixed and dispersed in a round stainless steel flask using IKA Ultra Turrax T50, and then heated to 48 ° C. while stirring the flask in a heating oil bath. After maintaining at 48 ° C. for 60 minutes, 70 parts by mass of the resin fine particle dispersion 1 was gently added thereto.

  Then, after adjusting the pH in the system to 8.0 using an aqueous sodium hydroxide solution having a concentration of 0.5 mol / L, the stainless steel flask is sealed, and the stirring shaft seal is magnetically sealed while stirring is continued. Heat to 90 ° C. and hold for 3 hours. After the completion of the reaction, the temperature lowering rate was cooled at 2 ° C./min, filtered, sufficiently washed with ion exchange water, and then subjected to solid-liquid separation by Nutsche suction filtration. This was further redispersed with 3 L of ion exchange water at 30 ° C., and stirred and washed at 300 rpm for 15 minutes. This washing operation was further repeated 6 times, and when the pH of the filtrate was 7.54 and the electric conductivity was 6.5 μS / cm, No. was obtained by Nutsche suction filtration. Solid-liquid separation was performed using 5A filter paper. Next, vacuum drying was continued for 12 hours to obtain toner 1.

The volume average particle diameter D50v of the toner 1 was measured with a Coulter counter and found to be 6.0 μm and the volume average particle size distribution index GSDv was 1.20. When the shape was observed with a Luzex image analyzer manufactured by Luzex, the shape factor SF1 of the particles was 128, and it was observed that the particles were spherical.
Further, the glass transition point (Tg) of the toner was such that Tg1 at the first temperature increase was 60 ° C. and Tg2 at the second temperature increase was 56 ° C.

Further, this toner 1 is further mixed with silica (SiO ₂ ) fine particles having a primary particle average particle size of 40 nm, which has been subjected to a surface hydrophobization treatment with hexamethyldisilazane (hereinafter sometimes abbreviated as “HMDS”), metatitanic acid and isobutyltrimethoxy Metatitanic acid compound fine particles having a primary particle average particle diameter of 20 nm, which is a reaction product of silane, are added so that the coverage of the surface of each colored particle is 40%, mixed with a Henschel mixer, and electrostatic image development Toner 1 was prepared.

(Preparation of developer)
Using the produced electrostatic charge image developing toner 1, a ferrite carrier having a volume average particle diameter of 50 μm coated with 1% by weight of polymethacrylate (manufactured by Soken Chemical Co., Ltd.) is weighed so that the toner concentration becomes 5% by weight. A developer (1) was prepared by stirring and mixing for 5 minutes in a ball mill.

(Evaluation of toner)
-Heat stress resistance-
The heat stress resistance of the manufactured toner 1 was confirmed by the following cohesion test.
Specifically, a certain amount of toner is stored for 24 hours in an atmosphere of 60 ° C., the stored toner is put on a net having an opening of 105 μm, and a constant vibration (frequency 3600 VPM, 60 Hz for 3 minutes) is applied. The amount of toner remaining on the net was measured. The aggregation degree was calculated according to the following formula 2, and the target aggregation degree of 20% or less was regarded as acceptable, and the storage characteristics were judged.
Aggregation degree (%) = (residual toner mass / input toner mass) × 100 Formula 2

-Fixability-
The fixability of the manufactured toner was confirmed by confirming image defects at fixing temperatures of 100 ° C. and 180 ° C.
In the test, using DocuColor 1250, the applied toner amount was adjusted to 0.6 g / m ² , and a solid image of 25 mm × 25 mm was output as an unfixed image, and this was output to an external fixing device without an oil supply device. Used, fixing was performed at a Nip width of 6.5 mm and a fixing speed of 90 mm / sec. The fixing temperature was controlled by the surface temperature of the fixing roll, and was set to 100 ° C. and 180 ° C.

In the evaluation, the low-temperature fixability was evaluated by a fixed image at 100 ° C. Specifically, the image was bent using a weight with a constant load, and an image having no image defect at that portion was marked with ◯, an image with a slight defect on the streak was marked with Δ, and an image with a greatly broken bent portion was marked with x. Further, the fixing latitude was confirmed by a fixed image at 180 ° C. Specifically, a case where there was no offset was indicated as “◯”, a case where even a slight offset occurred was indicated as “Δ”, and a case where offset occurred was indicated as “X”.
The above evaluation results are summarized in Table 2.

<Example 2>
Toner particles 2 were obtained in exactly the same manner as in Example 1 except that the crystalline compound particle dispersion 2 was used instead of the crystalline compound particle dispersion 1.
The volume average particle diameter D50v of the toner particles 2 was measured with a Coulter counter to be 6.1 μm, the volume average particle size distribution index GSDv was 1.21, and the shape factor SF1 was 128. Further, the glass transition point (Tg) of this toner was 60 ° C. at the first temperature rise, and Tg 2 at the second temperature rise was 58 ° C.

Using this toner particle 2, a toner and developer for developing an electrostatic charge image were prepared in the same manner as in Example 1, and the same evaluation was performed.
The results are summarized in Table 2.

<Example 3>
Toner particles 3 were obtained in exactly the same manner as in Example 1 except that the crystalline compound particle dispersion 3 was used instead of the crystalline compound particle dispersion 1.
When the volume average particle diameter D50v of the toner particles 3 was measured with a Coulter counter, it was 6.2 μm, the volume average particle size distribution index GSDv was 1.20, and the shape factor SF1 was 130 round potato shape. Further, the glass transition point (Tg) of this toner was 60 ° C. at the first temperature rise, and Tg 2 at the second temperature rise was 58 ° C.

Using this toner particle 3, a toner and developer for developing an electrostatic charge image were prepared in the same manner as in Example 1, and the same evaluation was performed.
The results are summarized in Table 2.

<Example 4>
Toner particles 4 were obtained in exactly the same manner as in Example 1 except that the crystalline compound particle dispersion 4 was used instead of the crystalline compound particle dispersion 1.
When the volume average particle diameter D50v of the toner particles 4 was measured with a Coulter counter, it was 6.1 μm, the volume average particle size distribution index GSDv was 1.21, and the shape factor SF1 was 132. Further, the glass transition point (Tg) of this toner was 60 ° C. at the first temperature rise, and Tg 2 at the second temperature rise was 58 ° C.

Using this toner particle 4, a toner and developer for developing an electrostatic image were prepared in the same manner as in Example 1, and the same evaluation was performed.
The results are summarized in Table 2.

<Example 5>
In the production of the toner of Example 1, toner particles 5 were obtained in exactly the same manner except that resin fine particle dispersion 2: 100 parts by mass was used instead of resin fine particle dispersion 1: 150 parts by mass.
When the volume average particle diameter D50v of the toner particles 5 was measured with a Coulter counter, it was 6.1 μm, the volume average particle size distribution index GSDv was 1.21, and the shape factor SF1 was 132. Further, the glass transition point (Tg) of this toner was 58 ° C. at Tg 1 at the first temperature rise and 54 ° C. at Tg 2 at the second temperature rise.

Using this toner particle 5, an electrostatic charge image developing toner and developer were prepared in the same manner as in Example 1, and the same evaluation was performed.
The results are summarized in Table 2.

<Comparative Example 1>
Toner particles 6 were obtained in exactly the same manner as in Example 1 except that the crystalline compound particle dispersion 5 was used instead of the crystalline compound particle dispersion 1.
When the volume average particle diameter D50v of the toner particles 6 was measured with a Coulter counter, it was 6.2 μm, the volume average particle size distribution index GSDv was 1.22, and the shape factor SF1 was 131 rounded potato shape. Further, the glass transition point (Tg) of the toner was such that Tg1 at the first temperature increase was 60 ° C. and Tg2 at the second temperature increase was 60 ° C.

Using this toner particle 6, an electrostatic charge image developing toner and developer were prepared in the same manner as in Example 1, and the same evaluation was performed.
The results are summarized in Table 2.

<Comparative example 2>
Toner particles 7 were obtained in exactly the same manner as in Example 1 except that the crystalline compound particle dispersion 6 was used instead of the crystalline compound particle dispersion 1.
When the volume average particle diameter D50v of the toner particles 7 is measured with a Coulter counter, it is 6.0 μm, the volume average particle size distribution index GSDv is 1.23, and the shape factor SF1 is 129. Further, the glass transition point (Tg) of this toner overlapped with the endothermic peak of the crystalline compound and could not be discriminated.

Using this toner particle 7, an electrostatic charge image developing toner and developer were prepared in the same manner as in Example 1, and the same evaluation was performed.
The results are summarized in Table 2.

<Comparative Example 3>
In the production of the toner of Example 1, toner particles 8 were obtained in exactly the same manner except that the crystalline compound particle dispersion 7 was used instead of the crystalline compound particle dispersion 1.
When the volume average particle diameter D50v of the toner particles 8 was measured with a Coulter counter, it was 6.1 μm, the volume average particle size distribution index GSDv was 1.22, the shape factor SF1 was 130, and it was a round potato shape. Further, the glass transition point (Tg) of this toner was 60 ° C. at the first temperature rise, and Tg 2 at the second temperature rise was 58 ° C.

Using this toner particle 8, a toner and developer for developing an electrostatic image were prepared in the same manner as in Example 1, and the same evaluation was performed.
The results are summarized in Table 2.

  As shown in Table 2, the toner using the crystalline compound of the present invention used in the examples had good heat stress resistance while maintaining low-temperature fixability. On the other hand, in the comparative example, some problems occurred in the low temperature fixability and heat stress resistance.

Claims (5)

  An electrostatic charge image developing toner containing a binder resin, a colorant and a crystalline compound, wherein the crystalline compound contains an olefin or paraffin maleic anhydride adduct .   2. The electrostatic image developing toner according to claim 1, wherein the crystalline compound is a mixture of an α-olefin maleic anhydride adduct and a copolymer of α-olefin and maleic anhydride. .   2. The crystalline compound is obtained by partially monoesterifying a mixture of an α-olefin maleic anhydride adduct and a copolymer of an α-olefin and maleic anhydride. The toner for developing an electrostatic image according to the description.   The electrostatic image developing toner according to claim 1, wherein the binder resin is a polyester resin. A method for producing an electrostatic charge image developing toner according to any one of claims 1 to 4,
A dispersion step of dispersing at least resin fine particles, colorant particles and crystalline compound particles in an aqueous dispersion medium; an agglomeration step of aggregating the dispersed particles to form aggregated particles; and heat fusion for thermally fusing the aggregated particles. A method for producing a toner for developing an electrostatic image, comprising: an attaching step.