JP4360982B2 - Toner for developing electrostatic image and method for producing the same, colorant, developer for developing electrostatic image, and image forming method - Google Patents

Description

The present invention relates to a toner for developing an electrostatic image , a colorant, a method for producing a toner for developing an electrostatic image, a developer for developing an electrostatic image, and an image forming method.

  In electrophotographic apparatuses, electrostatic recording apparatuses, and the like, electrical and magnetic latent images are visualized with toner. For example, in electrophotography, an image is formed by developing an electrostatic charge image formed on a photoreceptor using toner. Usually, such an image is transferred onto a transfer material such as paper and fixed by a method such as heating. In general, toner used for developing an electrostatic image is colored particles in which a binder resin contains a colorant, a charge control agent, and other additives.

  In recent years, in a fixing process by a contact heating method performed using a heating member such as a heat roller, it is desired to fix at a low temperature from the viewpoint of energy saving. In such a case, when a low molecular weight binder resin is used, since the softening temperature and the glass transition temperature are low, it can be melted and fixed at a low temperature, but the toner adheres to the heating member. For this reason, it is difficult to achieve both low-temperature fixability and offset resistance. In order to solve this problem, a crystalline polyester resin is used as a binder resin for toner. For example, by using a crystalline polyester having a crosslinked structure with an unsaturated site, a toner having excellent low-temperature fixability and good offset resistance is obtained (see Patent Document 1). Further, it is known that a high-quality image can be obtained by using a metal compound of a salicylic acid derivative together with a crystalline polyester resin as a charge control agent (see Patent Document 2).

  On the other hand, color image formation by full-color electrophotography generally reproduces all colors using three primary colors, magenta, cyan and yellow, and preferably four colors of black toner for inking. It is. For example, first, light from an original is color-separated in an analog or digital manner and guided to the photoconductive layer of the photoconductor to form an electrostatic charge image of the first color. Subsequently, the toner is held on a transfer material such as paper through development and transfer processes. Further, for the second and subsequent colors, the above-described steps are sequentially performed a plurality of times, and after a plurality of color toners are superimposed on the same transfer material, a final full-color image is obtained by a single fixing. For this reason, if the light transmittance of each toner is insufficient, the color reproducibility deteriorates and it becomes difficult to obtain a clear image. This phenomenon is particularly noticeable when a full-color image is formed on a transparent substrate such as an OHP sheet. When a crystalline polyester resin having low transparency as described above is used, it is difficult to obtain a good transparent image, and the quality is high. Toners that form images are desired.

  As a countermeasure, it has been proposed to improve pigment dispersion, that is, to reduce the pigment particle diameter in the toner. In general, since pigments have the property of aggregating when dried, a resin or resin solution is added to an aqueous slurry or aqueous cake, which is an aqueous dispersion of a pigment containing a high concentration of pigment, and the mixture is stirred and mixed. A flushing method in which moisture and a solvent are removed after replacing moisture with a resin or a resin solution has attracted attention. In this method, since aggregation of the pigment hardly occurs, the pigment particles can be dispersed in the resin in a fine state. Therefore, when a pigment dispersed by this method is used as a colorant, a toner suitable for a color image can be obtained (see Patent Documents 3 and 4).

However, as the formation of full-color images with color toners has become common, the quality demanded by users has improved, and in electrophotography, the same quality as ordinary silver salt photography has come to be demanded. For this reason, it is necessary to further improve the dispersion of the pigment in the toner, sufficiently develop the color of the pigment, and obtain a good image having a high density, and form a full-color image on a transparent substrate such as an OHP sheet. In such a case, it has been required to improve the clarity and transparency of the image.
JP 2001-117268 A JP 2002-351137 A JP-A-7-128911 JP 2003-173043 A

In view of the above-described problems of the prior art, the present invention is used for an electrostatic charge image developing toner having excellent low-temperature fixability, good offset resistance, and ensuring a color reproduction range , and the electrostatic charge image developing toner. It is colorant, and an object thereof is to provide an electrostatic charge image developer containing preparation and toner for electrostatic charge image developing toner for electrostatic charge image developing. Another object of the present invention is to provide an image forming method having excellent low-temperature fixability, good offset resistance, and a color reproduction range.

According to the first aspect of the present invention, in the toner for developing an electrostatic image having a binder resin containing 50% by weight or more of a polyester resin containing a crystalline polyester resin and a colorant, the colorant is a pigment by a flushing method. Is a colorant obtained by dispersing in a non-crystalline polyester resin and then adding and dispersing the crystalline polyester resin.

According to the invention described in claim 1, the colorant is a colorant obtained by dispersing a pigment in an amorphous polyester resin by a flushing method, and then adding and dispersing the crystalline polyester resin. Therefore, it is possible to provide a toner for developing an electrostatic image having excellent low-temperature fixability, good offset resistance, and a color reproduction range.

  The invention described in claim 2 is the electrostatic charge image developing toner according to claim 1, characterized in that the crystalline polyester resin has a softening temperature and a glass transition temperature of 65 ° C. or more and 140 ° C. or less, respectively. To do.

  According to the second aspect of the present invention, since the softening temperature and glass transition temperature of the crystalline polyester resin are 65 ° C. or more and 140 ° C. or less, respectively, the low-temperature fixing property and the offset resistance of the toner are more reliably maintained. can do.

  According to a third aspect of the present invention, in the electrostatic image developing toner according to the first or second aspect, the number average molecular weight by GPC of the crystalline polyester resin soluble in o-dichlorobenzene is 500 or more and 6000 or less. It is characterized by being.

  According to invention of Claim 3, since the number average molecular weight by GPC of the o-dichlorobenzene soluble part of the said crystalline polyester resin is 500-6000, Softening temperature and glass transition temperature of crystalline polyester resin Can be made relatively cold.

  According to a fourth aspect of the present invention, in the electrostatic charge image developing toner according to any one of the first to third aspects, the crystalline polyester resin has a number average molecular weight determined by GPC of an o-dichlorobenzene soluble part. The ratio of the weight average molecular weight is 2 or more and 8 or less.

  According to invention of Claim 4, since ratio of the weight average molecular weight with respect to the number average molecular weight by GPC of the o-dichlorobenzene soluble part of the said crystalline polyester resin is 2-8, glass transition temperature of The crystalline polyester resin can be melted in a relatively narrow temperature range around the periphery.

  According to a fifth aspect of the present invention, in the electrostatic image developing toner according to any one of the first to fourth aspects, the acid value of the crystalline polyester resin is 5 mgKOH / g or more and 45 mgKOH / g or less. It is characterized by that.

  According to the invention described in claim 5, since the crystalline polyester resin has an acid value of 5 mgKOH / g or more and 45 mgKOH / g or less, it is possible to achieve both low temperature fixability and hot offset property of the toner.

  According to a sixth aspect of the present invention, in the electrostatic image developing toner according to any one of the first to fifth aspects, the crystalline polyester resin has a hydroxyl value of 5 mgKOH / g or more and 50 mgKOH / g or less. It is characterized by that.

  According to the invention described in claim 6, since the hydroxyl value of the crystalline polyester resin is 5 mgKOH / g or more and 50 mgKOH / g or less, it is possible to achieve both low-temperature fixability and charging characteristics of the toner.

  The invention according to claim 7 is the electrostatic charge image developing toner according to any one of claims 1 to 6, characterized in that the crystalline polyester resin contains a crystalline unsaturated polyester resin. To do.

  According to the invention described in claim 7, since the crystalline polyester resin contains a crystalline unsaturated polyester resin, the softening temperature and the glass transition temperature are within a temperature range in which the low-temperature fixability and offset resistance of the toner are good. Can be.

The invention according to claim 8 is the electrostatic image developing toner according to claim 7, wherein the infrared absorption spectrum of the crystalline unsaturated polyester resin has a wave number of 965 ± 10 cm ⁻¹ and 990 ± 10 cm ⁻¹ . It has an absorption peak in at least one.

According to the invention described in claim 8, since the infrared absorption spectrum of the crystalline unsaturated polyester resin has an absorption peak in at least one of 965 ± 10 cm ⁻¹ and 990 ± 10 cm ⁻¹ , Existence can be easily confirmed.

The invention according to claim 8 is the electrostatic image developing toner according to claim 6 or 7 , wherein the crystalline unsaturated polyester resin is represented by the general formula:

で示される樹脂であり、ｌは、１以上３以下の整数であり、ｍ及びｎは、それぞれ整数であり、Ｒ_１、Ｒ_２、Ｒ_３及びＲ_４は、それぞれ水素原子又は炭素数４以下の炭化水素基であることを特徴とする。

Wherein l is an integer of 1 or more and 3 or less, m and n are each an integer, and R ₁ , R ₂ , R ₃ and R ₄ are each a hydrogen atom or a carbon number of 4 or less. It is characterized by being a hydrocarbon group.

According to the invention of claim 8 , the crystalline unsaturated polyester resin has the general formula

で示される樹脂であり、ｌは、１以上３以下の整数であり、ｍ及びｎは、それぞれ整数であり、Ｒ_１、Ｒ_２、Ｒ_３及びＲ_４は、それぞれ水素原子又は炭素数４以下の炭化水素基であるので、トナーの低温定着性と耐オフセット性を両立させることができる。

Wherein l is an integer of 1 or more and 3 or less, m and n are each an integer, and R ₁ , R ₂ , R ₃ and R ₄ are each a hydrogen atom or a carbon number of 4 or less. Therefore, it is possible to achieve both low-temperature fixability and offset resistance of the toner.

According to a ninth aspect of the present invention, in the electrostatic image developing toner according to the eighth aspect , m is an integer of 2-6.

According to the ninth aspect of the invention, since m is an integer of 2 or more and 6 or less, both the low-temperature fixability and the offset resistance of the toner can be achieved.

According to a tenth aspect of the present invention, in the electrostatic image developing toner according to any one of the first to ninth aspects, the binder resin further contains a urea- modified polyester resin.

According to the invention described in claim 10 , since the binder resin further contains a urea- modified polyester resin, the offset resistance of the toner can be improved.

According to an eleventh aspect of the present invention, in the electrostatic image developing toner according to the tenth aspect , the binder resin further contains an amorphous polyester resin having a glass transition temperature of 30 ° C. or higher and 70 ° C. or lower. It is characterized by that.

According to the eleventh aspect of the invention, since the binder resin further contains an amorphous polyester resin having a glass transition temperature of 30 ° C. or higher and 70 ° C. or lower, the low-temperature fixability can be improved.

According to a twelfth aspect of the invention, in the electrostatic image developing toner according to the eleventh aspect, the acid value of the non-crystalline polyester resin having a glass transition temperature of 30 ° C. or higher and 70 ° C. or lower is 30 mg KOH / g or lower. It is characterized by being.

According to the invention of claim 12, since the acid value of the non-crystalline polyester resin having a glass transition temperature of 30 ° C. or higher and 70 ° C. or lower is 30 mgKOH / g or lower, it is possible to suppress image deterioration. it can.

According to a thirteenth aspect of the present invention, in the electrostatic image developing toner according to the eleventh or twelfth aspect , the binder resin further contains a urea- modified polyester resin, and the weight of the urea- modified polyester resin is The ratio of the total weight of the amorphous polyester resin and the crystalline polyester resin is 3 or more and 19 or less.

According to the invention of claim 13 , the binder resin further contains a urea- modified polyester resin, and the total weight of the non-crystalline polyester resin and the crystalline polyester resin with respect to the weight of the urea- modified polyester resin. Since the ratio is 3 or more and 19 or less, both hot offset resistance and low-temperature fixability can be achieved.

According to a fourteenth aspect of the present invention, in the electrostatic image developing toner according to any one of the first to thirteenth aspects, the toner further includes a release agent.

According to the fourteenth aspect of the present invention, since the release agent is further included , the offset resistance of the toner can be improved.

According to a fifteenth aspect of the present invention, in the electrostatic image developing toner according to the fourteenth aspect , the content of the release agent is 1 wt% or more and 40 wt% or less.

According to the invention described in claim 15 , since the content of the release agent is 1% by weight or more and 40% by weight or less, the effect of the release agent can be expressed more effectively.

A sixteenth aspect of the present invention is the electrostatic image developing toner according to the fourteenth or fifteenth aspect , wherein the releasing agent has a melting point of 40 ° C. or higher and 160 ° C. or lower.

According to the sixteenth aspect of the present invention, since the melting point of the release agent is 40 ° C. or higher and 160 ° C. or lower, it is possible to achieve both heat resistant storage stability and cold offset resistance of the toner.
The invention according to claim 17 is characterized in that the colorant is obtained by dispersing a pigment in an amorphous polyester resin by a flushing method and then adding and dispersing the crystalline polyester resin.

The invention according to claim 18 is a method for producing a toner for developing an electrostatic image having a binder resin containing 50% by weight or more of a polyester resin containing a crystalline polyester resin and a colorant, After dispersing in the non-crystalline polyester resin, the step of adding and dispersing the crystalline polyester resin to obtain the colorant, the polyester resin containing the crystalline polyester resin, the colorant and the organic solvent are contained And a step of dispersing the mixture in an aqueous solvent.

According to the invention described in claim 18, after the pigment is dispersed in the amorphous polyester resin by a flushing method , the crystalline polyester resin is added and dispersed to obtain the colorant, and the crystal A step of obtaining a polyester resin-containing polyester resin, a mixture containing the colorant and an organic solvent, and a step of dispersing the mixture in an aqueous solvent, so that it has excellent low-temperature fixability and good offset resistance. Furthermore, it is possible to provide a method for producing a toner for developing an electrostatic charge image that further secures a color reproduction range .

The invention of claim 19 is a method of manufacturing a toner according to claim 1 8, to obtain the mixture to obtain a dispersion by dispersing the colorant in the organic solvent It has the process and the process of obtaining the mixture containing the polyester resin containing the said crystalline polyester resin, the said dispersion liquid, and the said organic solvent, It is characterized by the above-mentioned.

According to the invention described in claim 19 , the step of obtaining the mixture includes the step of obtaining a dispersion by dispersing the colorant in the organic solvent, the polyester resin containing the crystalline polyester resin, and the dispersion. Since it has the process of obtaining the mixture containing a liquid and the said organic solvent, the uniformity of the distribution of the coloring agent in binder resin can be improved.

According to a twentieth aspect of the invention, in the method for producing a toner for developing an electrostatic charge image according to the nineteenth aspect, the ratio of the weight of the organic solvent to the weight of the colorant in the step of obtaining the dispersion is 1 or more. 19 or less.

According to the invention of claim 20 , since the ratio of the weight of the organic solvent to the weight of the colorant in the step of obtaining the dispersion is 1 or more and 19 or less, the colorant is uniformly distributed in the organic solvent. Can be dispersed.

The invention according to claim 21 is the method for producing a toner for developing an electrostatic charge image according to any one of claims 18 to 20 , wherein the crystalline polyester resin contains a crystalline unsaturated polyester resin. It is characterized by.

According to the invention of claim 21 , since the crystalline polyester resin contains a crystalline unsaturated polyester resin, the softening temperature and the glass transition temperature are within a temperature range in which the low-temperature fixability and offset resistance of the toner are good. In addition, the dispersibility of the colorant in the resin can be improved.

The invention according to claim 22 is the method for producing a toner for developing an electrostatic charge image according to any one of claims 18 to 21 , wherein the functional group capable of reacting with the active hydrogen-containing group is obtained in the step of obtaining the mixture. A polyester resin having a functional group capable of reacting the compound having an active hydrogen-containing group with the active hydrogen-containing group after the step of further mixing the polyester resin having a compound having the active hydrogen-containing group and dispersing in the aqueous solvent It has the process made to react with.

According to the invention described in claim 22 , in the step of obtaining the mixture, a polyester resin having a functional group capable of reacting with an active hydrogen-containing group and a compound having an active hydrogen-containing group are further mixed and dispersed in the aqueous solvent. Since there is a step of reacting the compound having an active hydrogen-containing group with a polyester resin having a functional group capable of reacting with the active hydrogen-containing group after the step of forming, the uniformity of the toner composition can be improved.

According to a twenty- third aspect of the present invention, an electrostatic charge image developing toner is manufactured by the method for manufacturing an electrostatic charge image developing toner according to any one of the eighteenth to twenty-second aspects.

According to the twenty- third aspect of the present invention, the toner is manufactured by the method for manufacturing a toner for developing an electrostatic charge image according to any one of the eighteenth to twenty-second aspects. It is possible to provide a toner for developing an electrostatic image that is good and further secures a color reproduction range.

According to a twenty-fourth aspect of the present invention, in the developer for developing an electrostatic charge image, the electrostatic image developing toner according to any one of the first to sixteenth and twenty- third aspects is contained.

According to the invention of claim 24 , since it contains the electrostatic image developing toner according to any one of claims 1 to 16 and 23 , it has excellent low-temperature fixability and good offset resistance, Furthermore, it is possible to provide a developer for developing an electrostatic charge image that secures a color reproduction range.

According to a twenty-fifth aspect of the invention, in the developer for developing an electrostatic charge image according to the twenty-fourth aspect , a carrier for carrying the toner for developing the electrostatic charge image is contained.

According to the 25th aspect of the invention, since the carrier for carrying the toner for developing an electrostatic image is contained, a two-component developer for developing an electrostatic image can be provided.

According to a twenty-sixth aspect of the present invention, in the image forming method, the electrostatic charge image developing developer according to the twenty- fourth or twenty-fifth aspect is used to form an image.

According to the twenty-sixth aspect of the present invention, since the image is formed using the developer for developing an electrostatic charge image according to the twenty-fourth or twenty-fifth aspect , the low-temperature fixability is excellent, the offset resistance is good, and the color It is possible to provide an image forming method that also secures a reproduction area.

According to the present invention, the toner for developing an electrostatic image having excellent low-temperature fixability, good offset resistance, and ensuring a color reproduction range , the colorant used for the toner for developing the electrostatic image , and the electrostatic image it is possible to provide an electrostatic charge image developer containing preparation and toner for electrostatic charge image developing toner for developing. In addition, according to the present invention, it is possible to provide an image forming method that is excellent in low-temperature fixability, excellent in offset resistance, and further ensures a color reproduction range.

  Next, the best mode for carrying out the present invention will be described with reference to the drawings.

In the toner of the present invention, since 50% by weight or more of the binder resin is a polyester resin containing a crystalline polyester resin, the toner is brought into contact with a heat fixing roller and heated and melted to a temperature higher than the glass transition temperature of the crystalline polyester resin. In addition, the crystalline polyester resin rapidly changes from a solid state to a molten state and penetrates into paper. Further, immediately after leaving the fixing roller, the crystalline polyester resin crystallizes and solidifies rapidly. At this time, in order to have excellent low-temperature fixability, the glass transition temperature and softening temperature of the crystalline polyester resin are required to be low within the range that maintains the heat-resistant storage stability and offset resistance of the toner. In any case, the temperature is preferably from 65 ° C to 140 ° C, and more preferably from 80 ° C to 135 ° C. When the glass transition temperature and the softening temperature are higher than these ranges, the lower limit fixing temperature of the toner is increased, so that the low temperature fixing property of the toner is deteriorated. The softening temperature was measured using an elevated flow tester CFT-500 (manufactured by Shimadzu Corporation) under conditions of a die diameter of 1 mm, a pressure of 10 kg / cm ² , and a heating rate of 3 ° C./min. The softening temperature is a temperature at which 1/2 of the total outflow amount flows out when a 1 cm ³ sample is melted out. The glass transition temperature was measured using a TG-DSC system TAS-100 manufactured by Rigaku Corporation. First, about 10 mg of a sample is put in an aluminum sample container, placed on a holder unit, and set in an electric furnace. Next, the sample was heated from room temperature to 150 ° C. at a rate of temperature increase of 10 ° C./min, allowed to stand at 150 ° C. for 10 minutes, then cooled to room temperature and left for 10 minutes. This was heated again to 150 ° C. at a temperature rising rate of 10 ° C./min in a nitrogen atmosphere, DSC measurement was performed, and a glass transition temperature was calculated.

  The crystalline polyester resin is characterized by having a crystal structure. In the powder X-ray diffraction pattern by Cu-Kα rays, the crystal structure can be confirmed by the appearance of a diffraction peak. Specifically, in the X-ray diffraction pattern, at least one diffraction peak is present at a position where an angle 2θ formed by incident X-rays and diffraction X-rays is 20 ° or more and 25 ° or less. At this time, it is preferable that diffraction peaks exist at positions where 2θ is 19 ° to 20 °, 21 ° to 22 °, 23 ° to 25 °, and 29 ° to 31 °. The powder X-ray diffraction was measured by using a Rigaku Denki RINT1100, using a wide-angle goniometer under the conditions that the tube was Cu and the tube voltage-current was 50 kV-30 mA.

  The crystalline polyester resin preferably contains a crystalline unsaturated polyester resin from the viewpoint of bringing the glass transition temperature and the softening temperature into a preferable temperature range. Such crystalline unsaturated polyester resins have the general formula

で表される。ｌは１以上３以下の整数が好ましい。ｌが４以上の整数になると、共役二重結合の広がりにより反応性が高くなり、経時安定性が低くなる。また、ｍは２以上６以下の整数であることが好ましい。ｍが７以上の整数になると、結晶性が高く溶融させにくい傾向にあり、分散しにくくなる。さらに、Ｒ_１、Ｒ_２、Ｒ_３及びＲ_４は、それぞれ水素原子又は炭素数４以下の炭化水素基が好ましい。このような観点から、１，４−ブタンジオール、１，６−ヘキサンジオール及びこれらの誘導体を８０モル％以上、好ましくは８５モル％以上含有したジオールとフマル酸又は不飽和二重結合を有するカルボン酸及びこれらの誘導体を縮合したポリエステル樹脂が好ましい。

It is represented by l is preferably an integer of 1 to 3. When l is an integer of 4 or more, the reactivity increases due to the spread of the conjugated double bond, and the stability over time decreases. Further, m is preferably an integer of 2 or more and 6 or less. When m is an integer of 7 or more, the crystallinity tends to be high and the melt tends to be difficult, and the dispersion is difficult. Furthermore, R ₁ , R ₂ , R ₃ and R ₄ are each preferably a hydrogen atom or a hydrocarbon group having 4 or less carbon atoms. From such a viewpoint, a diol containing 1,4-butanediol, 1,6-hexanediol and derivatives thereof at 80 mol% or more, preferably 85 mol% or more, and a carboxyl having fumaric acid or an unsaturated double bond. Polyester resins obtained by condensing acids and their derivatives are preferred.

  In addition, as a method for controlling the glass transition temperature and softening temperature of the crystalline polyester resin, a trihydric or higher polyhydric alcohol such as glycerin is used as the alcohol, and a trivalent or higher polyvalent carboxylic acid such as trimellitic anhydride is used as the acid. And a method using a branched polyester resin condensed.

The presence of the molecular structure of the above general formula can be confirmed by NMR, X-ray diffraction, GC / MS, LC / MS, IR, etc., but for convenience, in the infrared absorption spectrum, 965 ± 10 cm ⁻¹ and 990 ± It can be confirmed by having an absorption peak based on δCH (out-of-plane variable vibration) of olefin in at least one of the wave numbers of 10 cm ⁻¹ . The infrared absorption spectrum was measured by a Fourier transform infrared spectrophotometric transmission method using Nicolet Magna 850.

The molecular weight of the crystalline polyester resin is preferably a low molecular weight as long as offset resistance can be maintained from the viewpoint of low-temperature fixability, and the molecular weight distribution is preferably narrow from the viewpoint of sharp melt. Specifically, the number average molecular weight of the crystalline polyester resin soluble in o-dichlorobenzene by GPC is preferably 500 or more and 6000 or less, and the ratio of the weight average molecular weight to the number average molecular weight is preferably 2 or more and 8 or less. . GPC was measured as follows. After stabilizing the column in a heat chamber at 145 ° C., the sample was adjusted to 0.3% by weight by flowing o-dichlorobenzene containing 0.3% by weight BHT as an eluent at a flow rate of 1 ml / min. The solution of o-dichlorobenzene was measured by injecting 50 μl or more and 200 μl or less. As a measuring instrument, Waters 150CV type was used, and ShodexAT-G + AT-806MS (two pieces) was used as a column. In measuring the molecular weight of the sample, the molecular weight distribution of the sample was calculated from the relationship between the logarithmic value of the calibration curve prepared from several monodisperse polystyrene standard samples and the number of counts. The slice width is 0.05 seconds. As standard polystyrene samples for preparing calibration curves, molecular weights of 6 × 10 ² , 2.1 × 10 ³ , 4 × 10 ³ , 1.75 × 10 ⁴ , 1.75 × 10 ⁴ , manufactured by Pressure Chemical or Toyo Soda Kogyo Co., Ltd. 1 × 10 ⁴ , 1.1 × 10 ⁵ , 3.9 × 10 ⁵ , 8.6 × 10 ⁵ , 2 × 10 ⁶ , 4.48 × 10 ⁶ , and at least about 10 standard polystyrene samples And a calibration curve was created. A refractive index detector was used as the detector.

  The acid value of the crystalline polyester resin used in the present invention is 5 KOH / g or more and 45 mg KOH in order to achieve the desired low-temperature fixability and further improve the hot offset property from the viewpoint of the affinity between paper and resin. / K or less is preferable, and 10 KOH / g or more and 40 mg KOH / g or less is more preferable. In addition, the hydroxyl value of the crystalline polyester resin is preferably 5 KOH / g or more and 50 mg KOH / g or less, more preferably 10 to 45 mg KOH / g, in order to achieve low temperature fixability and obtain good charging characteristics. . In addition, an acid value and a hydroxyl value are obtained by the method prescribed | regulated to JISK0070. However, when the sample does not dissolve, a solvent such as dioxane, THF, or o-dichlorobenzene may be used as the solvent.

  The binder resin used in the present invention preferably contains a modified polyester resin in addition to the crystalline polyester resin. The modified polyester resin is obtained by reacting a polyester resin having a functional group capable of reacting with an active hydrogen-containing group (hereinafter referred to as a polyester prepolymer) and a compound having an active hydrogen-containing group, and is a dry toner, particularly a fixing heating medium. It is convenient to ensure offset resistance and fixing property (oilless low-temperature fixing property) in a wide range of applications without a release oil application mechanism. Any functional group capable of reacting with the active hydrogen-containing group can be used as long as it is known, and examples thereof include an isocyanate group, an epoxy group, and a carboxyl group. Examples of the active hydrogen-containing group include hydroxyl groups (alcoholic hydroxyl groups and phenolic hydroxyl groups), amino groups, carboxyl groups, mercapto groups, and the like. The modified polyester resin is preferably a urea-modified polyester resin, which can suppress adhesion to the heating medium for fixing while maintaining high fluidity and transparency in the fixing temperature range of the polyester resin. The urea-modified polyester resin can be obtained by addition reaction of a polyester prepolymer having an isocyanate group and amines described later. The polyester prepolymer having an isocyanate group can be obtained by addition reaction of a polyester resin having an active hydrogen-containing group, which is a polycondensate of a polyol and a polycarboxylic acid, with a polyisocyanate.

  Examples of the polyol include a diol and a tri- or higher valent polyol, and a diol alone or a mixture of a diol and a small amount of a polyol is preferable. Examples of the diol include alkylene glycol (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, etc.); alkylene ether glycol (diethylene glycol, triethylene glycol, Dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc.); alicyclic diols (1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.); bisphenols (bisphenol A, bisphenol F, bisphenol S, etc.) ); Alkylene oxides (ethylene oxide, propylene oxide, butylene oxide, etc.) adducts of the above alicyclic diols and the above bisphenols. . Among these, alkylene glycols having 2 to 12 carbon atoms and alkylene oxide adducts of bisphenols are preferable, and the combination of alkylene oxide adducts of bisphenols and alkylene glycols having 2 to 12 carbon atoms is particularly preferable. The trihydric or higher polyols include trihydric or higher polyhydric aliphatic alcohols (glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, etc.); trihydric or higher phenols (trisphenol) PA, phenol novolak, cresol novolak, etc.); alkylene oxide adducts of the above trihydric or higher polyphenols.

  Examples of the polycarboxylic acid include dicarboxylic acids and trivalent or higher polycarboxylic acids, and preferred are carboxylic acids alone or a mixture of a dicarboxylic acid and a small amount of a polycarboxylic acid. Dicarboxylic acids include alkylene dicarboxylic acids (succinic acid, adipic acid, sebacic acid, etc.); alkenylene dicarboxylic acids (maleic acid, fumaric acid, etc.); aromatic dicarboxylic acids (phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, etc.) ) And the like. Among these, alkenylene dicarboxylic acids having 4 to 20 carbon atoms and aromatic dicarboxylic acids having 8 to 20 carbon atoms are preferable. Examples of the trivalent or higher polycarboxylic acid include aromatic polycarboxylic acids having 9 to 20 carbon atoms (trimellitic acid, pyromellitic acid, etc.). In addition, as polycarboxylic acid, you may make it react with a polyol using the acid anhydride and lower alkyl ester (methyl ester, ethyl ester, isopropyl ester, etc.) of the above-mentioned thing.

  Polyisocyanates include aliphatic polyisocyanates (tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-diisocyanatomethylcaproate, etc.); alicyclic polyisocyanates (isophorone diisocyanate, cyclohexylmethane diisocyanate, etc.); aromatic diisocyanates ( Tolylene diisocyanate, diphenylmethane diisocyanate, etc.); araliphatic diisocyanates (α, α, α ′, α′-tetramethylxylylene diisocyanate, etc.); isocyanurates; blocked with phenol derivatives of the above polyisocyanates, oximes, caprolactam, etc. And combinations of two or more of these.

  The equivalent ratio of the isocyanate group of the polyisocyanate to the hydroxyl group of the polyester resin is usually 1 or more and 5 or less, preferably 1.2 or more and 4 or less, and more preferably 1.5 or more and 2.5 or less. When this equivalent ratio exceeds 5, the low-temperature fixability deteriorates. When it is less than 1, the urea content decreases in the case of a urea-modified polyester, and the hot offset resistance deteriorates. The content of the polyisocyanate component in the polyester prepolymer having an isocyanate group at the terminal is usually 0.5% by weight to 40% by weight, preferably 1% by weight to 30% by weight, and preferably 2% by weight to 20%. More preferably, it is not more than% by weight. When the content is less than 0.5% by weight, the hot offset resistance is deteriorated, and it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability. On the other hand, if it exceeds 40% by weight, the low-temperature fixability deteriorates.

  The average number of isocyanate groups contained in one molecule of the polyester prepolymer is usually 1 or more, preferably 1.5 or more and 3 or less, and more preferably 1.8 or more and 2.5 or less. When the average number is less than 1, the molecular weight of the modified polyester is lowered, and the hot offset resistance is deteriorated.

  Examples of the amines include diamines, trivalent or higher polyamines, amino alcohols, amino mercaptans, amino acids, and those obtained by blocking these amino groups. Examples of the diamine include aromatic diamines (phenylenediamine, diethyltoluenediamine, 4,4′-diaminodiphenylmethane, etc.); alicyclic diamines (4,4′-diamino-3,3′-dimethyldicyclohexylmethane, diaminecyclohexane, isophorone) Diamines; and aliphatic diamines (ethylenediamine, tetramethylenediamine, hexamethylenediamine, etc.) and the like. Examples of trivalent or higher polyamines include diethylenetriamine and triethylenetetramine. Examples of amino alcohols include ethanolamine and hydroxyethylaniline. Examples of amino mercaptans include aminoethyl mercaptan and aminopropyl mercaptan. Examples of amino acids include aminopropionic acid and aminocaproic acid. Examples of the blocked amino group include ketimine compounds and oxazolyson compounds obtained by reacting amines with ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.). Of these amines, diamines and mixtures of diamines and small amounts of polyamines are preferred.

  Further, the molecular weight of a modified polyester resin such as a urea-modified polyester resin can be adjusted using an elongation terminator. Examples of the elongation terminator include monoamines (diethylamine, dibutylamine, butylamine, laurylamine, etc.) and ketimine compounds blocking these. The equivalent ratio of amino groups of amines to isocyanate groups in the modified polyester resin is usually 0.5 or more and 2 or less, preferably 2/3 or more and 1.5 or less, and more preferably 5/6 or more and 1.2 or less. . When the equivalent ratio exceeds 2 and less than 0.5, the molecular weight of the modified polyester such as urea-modified polyester is lowered, and the hot offset resistance is deteriorated. In the present invention, the urea-modified polyester may contain a urethane bond as well as a urea bond. The ratio of the number of urethane bonds to the sum of the number of urea bonds and the number of urethane bonds is usually 0.9 or less, preferably 0.2 or more and 0.8 or less, and more preferably 0.4 or more and 0.7 or less. When this ratio exceeds 0.9, hot offset resistance deteriorates.

  Modified polyester resins such as urea-modified polyester resins used in the present invention are produced by a one-shot method and a prepolymer method. The weight average molecular weight of the modified polyester resin is usually 10,000 or more, preferably 20,000 to 1,000,000, more preferably 30,000 to 1,000,000. When the weight average molecular weight is less than 10,000, the hot offset resistance deteriorates. The number average molecular weight of the urea-modified polyester resin is not particularly limited when a low molecular weight polyester resin described later is used, and may be a number average molecular weight that can be easily obtained to obtain the above weight average molecular weight. In the case of the modified polyester resin alone, the number average molecular weight is usually 20000 or less, preferably 1000 or more and 10,000 or less, and more preferably 2000 or more and 8000 or less. When the number average molecular weight exceeds 20000, the low-temperature fixability and the gloss when used in a full-color device are deteriorated.

  The acid value of the modified polyester resin is usually 30 mgKOH / g or less, preferably 5 mgKOH / g or more and 30 mgKOH / g or less. In addition, it tends to be negatively charged by giving an acid value. In addition, those having an acid value exceeding this range are easily affected by the environment in a high-temperature, high-humidity and low-temperature, low-humidity environment, and are liable to cause image deterioration.

  In the present invention, from the viewpoint of low-temperature fixability, the modified polyester resin is preferably mixed with an amorphous polyester resin having a glass transition temperature of 30 ° C. or higher and 70 ° C. or lower in addition to the crystalline polyester resin. When the glass transition temperature of the amorphous polyester resin is less than 30 ° C., the heat resistant storage stability is deteriorated, and when it exceeds 70 ° C., the low temperature fixability is deteriorated. Examples of the amorphous polyester resin include polycondensates of polyols and polycarboxylic acids similar to the modified polyester resin. The non-crystalline polyester resin is not limited to an unmodified polyester resin, but may be modified with a chemical bond other than a urea bond, for example, a urethane bond.

  The weight average molecular weight of the main peak of the amorphous polyester resin is usually 1000 or more and 30000 or less, preferably 1500 or more and 10,000 or less, and more preferably 2000 or more and 8000 or less. When the component having a weight average molecular weight of less than 1000 is increased, the heat resistant storage stability is deteriorated and carrier contamination occurs. Therefore, this component is preferably 5% by weight or less. When the component having a weight average molecular weight of 30000 or more increases, the low-temperature fixability tends to decrease. For this reason, the content of components having a weight average molecular weight of 30000 or more is usually 1% or more and preferably 3% or more and 6% or less, although it varies depending on the toner material. If it is less than 1%, sufficient hot offset resistance cannot be obtained.

  The number average molecular weight of the amorphous polyester resin is 2000 or more and 15000 or less, and the ratio of the weight average molecular weight to the number average molecular weight is preferably 5 or less. When this ratio exceeds 5, the sharp melt property is lost and the glossiness is impaired.

  The acid value of the amorphous polyester resin is usually 30 mgKOH / g or less, preferably 5 mgKOH / g or more and 30 mgKOH / g or less. By giving an acid value, it tends to be negatively charged. In addition, those having an acid value exceeding this range are easily affected by the environment in a high-temperature, high-humidity and low-temperature, low-humidity environment, and are liable to cause image deterioration. The hydroxyl value is usually 5 mgKOH / g or more, preferably 10 mgKOH / g or more and 120 mgKOH / g or less, more preferably 20 mgKOH / g or more and 80 mgKOH / g or less. A hydroxyl value of less than 5 is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability.

  The crystalline polyester resin, modified polyester resin and non-crystalline polyester resin in the present invention are preferably at least partially compatible with each other in terms of low-temperature fixability and hot offset resistance. For this reason, it is preferable that these polyester resins have a similar structure. The ratio of the weight of the amorphous polyester resin and the total weight of the crystalline polyester resin to the weight of the modified polyester resin is usually 3 or more and 19 or less, preferably 3 or more and 9 or less, and 11/39 or more and 22/3. More preferred are: Furthermore, the ratio of the weight of the crystalline polyester to the weight of the amorphous polyester resin is 1 or more and 99 or less, preferably 1.2 or more and 19 or less, and particularly preferably 12/7 or more and 9 or less. Outside this range, hot offset resistance deteriorates, and it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability.

  The colorant of the present invention only needs to contain a hydrophobic pigment, and various organic pigments, inorganic pigments and mixtures thereof used in toners can be used. For example, phthalocyanine pigments such as phthalocyanine blue and phthalocyanine green, insoluble azo pigments such as toluidine red, toluidine maroon, Hansa Yellow, benzidine yellow and pyrazolone red, azo lake pigments, anthraquinone pigments, quinacridone red pigments such as quinacridone magenta, dioxazine Examples include pigments, diketopyrrolopyrrole pigments, anthrapyrimidine pigments, ansanthrone pigments, indanthrone pigments, flavanthrone pigments, perinone pigments, perylene red, perylene scarlet and other perylene pigments, isoindolinone pigments, thioindigo pigments, etc. Can do. The content of the colorant is usually 1% by weight to 15% by weight, and preferably 3% by weight to 10% by weight with respect to the toner.

  Although details will be described later, the colorant of the present invention is obtained by dispersing a pigment in a resin by a flushing method. When the flushing method is used, the aggregation of the pigment can be prevented, so that the particle diameter of the pigment is reduced and the color reproduction range of the toner can be secured.

  The toner of the present invention preferably contains a release agent together with a binder resin and a colorant. Known release agents can be used, and include polyolefin waxes such as polyethylene wax and polypropylene wax, long-chain hydrocarbons such as paraffin wax and sazol wax, and carbonyl group-containing waxes. Among these, a carbonyl group-containing wax is preferable. Examples of the carbonyl group-containing wax include carnauba wax, montan wax, trimethylolpropane tribehenate, pentaerythritol tetrabehenate, pentaerythritol diacetate dibehenate, glycerin tribehenate, 1,18-octadecanediol distea. Polyalkanoic acid esters such as rate, polyalkanol esters such as tristearyl trimellitic acid and distearyl maleate, polyalkanoic acid amides such as ethylenediamine dibehenyl amide, polyalkylamides such as trimellitic acid tristearyl amide, distearyl ketone And dialkyl ketones. Among these carbonyl group-containing waxes, polyalkanoic acid esters are preferred. The melting point of the release agent is usually 40 ° C. or higher and 160 ° C. or lower, preferably 50 ° C. or higher and 120 ° C. or lower, more preferably 60 ° C. or higher and 90 ° C. or lower. A mold release agent having a melting point of less than 40 ° C. adversely affects the heat resistant storage stability. A release agent having a melting point exceeding 160 ° C. is liable to cause a cold offset when fixing at a low temperature. The content of the release agent in the toner is usually 40% by weight or less, preferably 3% by weight or more and 30% by weight or less, considering the balance with the performance of other toner materials.

  In addition to these, the toner of the present invention may contain a charge control agent, resin fine particles for controlling the toner shape, inorganic fine particles for assisting heat storage stability and chargeability, and the like.

  The method for producing an electrostatic image developing toner of the present invention includes a step of obtaining a colorant by dispersing a pigment in a resin by a flushing method. First, a resin is added to an aqueous dispersion of a hydrophobic pigment and mixed and stirred with a kneader such as a kneader. During the mixing and stirring process, the pigment present in the water is transferred into the resin. In parallel with this, impurities contained in the water and in the pigment are separated from the mixture. The flushing method refers to an operation of transferring a pigment into a resin and simultaneously separating moisture and the like. Here, when removing the separated water, a resin may be appropriately added in order to keep the load of the kneader constant and maintain the efficiency of the kneading. The dehydration process is performed in two stages: primary dehydration that mainly removes water under normal pressure after mixing and stirring, and then vacuum dehydration that is performed under reduced pressure while keeping the viscosity of the mixture constant by adding a resin. Can do.

  As the pigment aqueous dispersion, a pigment wet cake having a pigment concentration of about 25% by weight to 40% by weight or a pigment slurry having a pigment concentration of about 2% by weight to 10% by weight in the production process of various pigments can be used.

  In the case of using a pigment wet cake, the initial blending of the flushing method takes into consideration the load of the kneader and the dewatering efficiency, and the resin wet resin of 40 parts by weight to 60 parts by weight of 30 parts by weight to 60 parts by weight Is preferably added. At this time, an organic solvent of 10 parts by weight or less can be added. As the kneader, a kneader or the like that can apply a shearing force to the mixture is preferable. Moreover, primary dehydration can be performed at 40 ° C. or higher and 80 ° C. or lower for about 5 minutes or more and 20 minutes or less, thereby removing moisture of about 60% or more and 70% or less. Although the water removal rate in the primary dehydration can be increased by increasing the temperature and extending the time, the dehydration efficiency can be further improved by performing vacuum dehydration when the water removal rate is 60% to 70%. it can. In order to maintain the kneading efficiency when starting the vacuum dehydration, a resin, an organic solvent, or the like can be added so as to keep the load of the kneader within a certain range. The organic solvent is not particularly limited as long as it dissolves or disperses the resin, and a volatile organic solvent having a boiling point of less than 150 ° C. is preferable from the viewpoint of easy removal. Specifically, toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, methyl acetate, ethyl acetate, methyl ethyl ketone, acetone, tetrahydrofuran Etc., and can be used alone or in combination of two or more. The vacuum dehydration is performed at a degree of vacuum of 400 hPa to 900 hPa and a temperature of about 80 ° C. to 120 ° C. for about 30 minutes to 120 minutes. The water content at the end of vacuum dehydration is preferably 1% by weight or less.

  When the above pigment slurry is used as an aqueous pigment dispersion, the pigment slurry and the resin are 90 parts by weight or more and 95 parts by weight or less and 5 parts by weight or more and 10 parts by weight or less, respectively, as the initial blending of the flushing method Is preferred. Furthermore, you may add 5 weight part or less of organic solvents. As the kneader, a tank mixer or the like that can apply a shearing force to the mixture is preferable. Similarly to the kneading by the kneader described above, in order to maintain the kneading efficiency, a resin, an organic solvent, or the like can be added so as to keep the load of the kneader within a certain range.

  After dispersing the pigment in the resin by the flushing method, a colorant can be obtained by adding a resin, an organic solvent, and various additives as necessary.

  In general, as a resin used for the flushing method, polystyrene, poly-p-chlorostyrene, polyvinyltoluene, and other styrene and substituted polymers thereof; styrene-p-chlorostyrene copolymer, styrene-propylene copolymer, Styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer Polymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene- Vinyl methyl ketone copolymer, styrene Styrene copolymer such as butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, styrene-maleic acid ester copolymer; polymethyl methacrylate, Polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester resin, epoxy resin, epoxy polyol resin, polyurethane resin, polyamide resin, polyvinyl butyral, polyacrylic acid resin, rosin, modified rosin, terpene resin, fat Examples thereof include alicyclic hydrocarbon resins, aromatic petroleum resins, chlorinated paraffins and paraffin waxes, and these can be used alone or in combination.

  In the present invention, a polyester resin is preferable from the viewpoint of compatibility with the binder resin, and an unsaturated polyester resin is more preferable. Since the unsaturated polyester resin has a relatively high affinity with water, the pigment is easily transferred from the aqueous phase to the resin phase, which leads to an improvement in the dispersibility of the colorant in the binder resin. When the resin is added to the pigment aqueous dispersion, it may be dissolved or dispersed in an organic solvent, and the weight ratio of the resin to the organic solvent is about 0.25 to 1.5.

  Further, as the pigment dispersant, a basic polymer copolymer dispersant, a modified polyurethane dispersant, a polyester dispersant, a polymer of acrylic acid, methacrylic acid or an ester thereof, a derivative of a colorant, or the like may be used. it can. The pigment dispersant may be added when dispersed by the flushing method, or may be added after the treatment by the flushing method.

  The particle diameter of the colorant when dissolved or dispersed in an organic solvent is desirably 1 μm or less. If the particle diameter is larger than 1 μm, the particle diameter of the colorant becomes large when the toner is formed, and the image quality tends to deteriorate. This phenomenon is remarkable because the optical transparency decreases in the case of OHP. The particle diameter can be determined with a laser diffraction / scattering particle size distribution measuring device “LA-920” (manufactured by Horiba, Ltd.).

  In order to enhance the interaction between the colorant and the pigment dispersant and stabilize the dispersion of the pigment, it is preferable to perform a surface treatment of the colorant. Examples of surface treatment agents for colorants include natural rosins such as gum rosin, wood rosin and tall rosin, and abietic acid derivatives such as abietic acid, levopimaric acid and dextropimalic acid, and metal salts such as calcium salts, sodium salts, potassium salts and magnesium salts thereof. Rosin modified maleic acid resin, rosin modified phenolic resin and the like. In particular, an acidic surface treatment agent is preferably used in order to increase the affinity with the pigment dispersant. The addition amount of the colorant derivative and the surface treatment agent of the colorant is preferably 0.1% by weight or more, more preferably 0.1% by weight or more and 10% by weight or less based on the colorant derivative and the colorant. .

  The method for producing a toner of the present invention includes a step of obtaining a mixture containing a polyester resin containing a crystalline polyester resin, a colorant and an organic solvent.

  The organic solvent used here is not particularly limited as long as it can dissolve or disperse the toner raw material composition (hereinafter referred to as toner raw material), and the same organic solvent used in the flushing method is used. be able to.

  The amount of the organic solvent used is usually 40 to 300 parts by weight, preferably 60 to 140 parts by weight, more preferably 80 to 120 parts by weight, based on 100 parts by weight of the toner raw material.

  At this time, by preparing a dispersion in which a colorant is dispersed in an organic solvent in advance, and obtaining a mixture containing the dispersion, a polyester resin containing a crystalline polyester resin, and an organic solvent, the colorant is a polyester resin. Since it disperses | distributes more uniformly in inside, it is preferable. Further, the ratio of the weight of the organic solvent to the weight of the colorant in the dispersion is preferably 1 or more and 19 or less. If this ratio is less than 1, the amount of organic solvent is large, so that the loss in dispersion in an aqueous solvent, which will be described later, increases.

  In the present invention, a polyester resin (polyester prepolymer) having a functional group capable of reacting with an active hydrogen-containing group and a compound having an active hydrogen-containing group are further added to the above mixture, and in an aqueous solvent as described later. It is preferable to form a toner by dispersing the polyester prepolymer and an active hydrogen-containing group. As described above, the modified polyester resin formed here is preferably a urea-modified polyester resin obtained by addition reaction of a polyester prepolymer having an isocyanate group and amines, and the reaction time is set to the reactivity of the functional group. Although it depends, it is usually 10 minutes or longer and 40 hours or shorter, and preferably 2 hours or longer and 24 hours or shorter. The reaction temperature is usually 0 ° C. or higher and 150 ° C. or lower, and preferably 40 ° C. or higher and 98 ° C. or lower. Moreover, a well-known catalyst can be used as needed. Specific examples include dibutyltin laurate and dioctyltin laurate.

  The method for producing a toner of the present invention includes a step of dispersing the mixture in an aqueous solvent.

  The aqueous solvent used in the present invention may be water alone, or an organic solvent miscible with water may be used in combination. Examples of miscible organic solvents include alcohol (methanol, isopropanol, ethylene glycol, etc.), dimethylformamide, tetrahydrofuran, cellosolves (methyl cellosolve, etc.), lower ketones (acetone, methyl ethyl ketone, etc.) and the like.

  The dispersion method is not particularly limited, and known equipment such as a low-speed shear type, a high-speed shear type, a friction type, a high-pressure jet type, and an ultrasonic wave can be applied. In order to make the particle size of the dispersion 2 μm or more and 20 μm or less, the high speed shearing method is preferable. When a high-speed shearing disperser is used, the number of rotations is not particularly limited, but is usually 1000 rpm to 30000 rpm, preferably 5000 rpm to 20000 rpm. The dispersion time is not particularly limited, but in the case of a batch method, it is usually from 0.1 minutes to 5 minutes. The temperature during dispersion is usually 0 ° C. or higher and 150 ° C. or lower (under pressure), preferably 40 ° C. or higher and 98 ° C. or lower. Higher temperatures are preferred because the viscosity of the dispersion decreases and dispersion is easier. Moreover, a dispersing agent can also be used as needed. The use of a dispersant is preferable in that the particle size distribution becomes sharp and the dispersion is stable.

  Anionic surfactants such as alkylbenzene sulfonates, α-olefin sulfonates, phosphate esters, alkylamines, etc. as dispersants for dispersing components in which toner raw materials are dissolved or dispersed in organic solvents Quaternary compounds such as amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, amine salts such as imidazoline, alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, pyridinium salts, alkylisoquinolinium salts, benzethonium chloride, etc. Nonionic surfactants such as ammonium salt type cationic surfactants, fatty acid amide derivatives, polyhydric alcohol derivatives, such as alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine and N-alkyl-N, - amphoteric surfactants, such as dimethyl ammonium betaine.

  Further, by using a surfactant having a fluoroalkyl group, the same effect as the above-described dispersant can be obtained with a small amount of addition. Examples of the anionic surfactant having a fluoroalkyl group include fluoroalkylcarboxylic acids having 2 to 10 carbon atoms and metal salts thereof, disodium perfluorooctanesulfonylglutamate, 3- [ω-fluoroalkyl (C6 to C11) oxy. ] Sodium 1-alkyl (C3-C4) sulfonate, sodium 3- [ω-fluoroalkanoyl (C6-C8) -N-ethylamino] -1-propanesulfonate, fluoroalkyl (C11-C20) carboxylic acid and Metal salts, perfluoroalkyl carboxylic acids (C7 to C13) and their metal salts, perfluoroalkyl (C4 to C12) sulfonic acids and their metal salts, perfluorooctane sulfonic acid diethanolamide, N-propyl-N- (2- Hydroxyethyl) perfluorooctane Sulfonamide, perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salt, perfluoroalkyl (C6-C10) -N-ethylsulfonylglycine salt, monoperfluoroalkyl (C6-C16) ethyl phosphate, etc. . Product names include Surflon S-111, S-112, S-113 (Asahi Glass Co., Ltd.), Florard FC-93, FC-95, FC-98, FC-129 (Sumitomo 3M Co., Ltd.), Unidyne DS-101. DS-102 (Daikin Kogyo Co., Ltd.), MegaFuck F-110, F-120, F-113, F-191, F-812, F-833 (Dainippon Ink Co., Ltd.), Xtop EF-102 , 103, 104, 105, 112, 123A, 123B, 306A, 501, 201, 204 (manufactured by Tochem Products Co., Ltd.), and Fgentent F-100, F-150 (manufactured by Neos).

  Further, as the cationic surfactant, aliphatic primary, secondary or tertiary amine acids having a fluoroalkyl group, aliphatic quaternary ammonium salts such as perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salt, Benzalkonium salt, benzethonium chloride, pyridinium salt, imidazolinium salt, trade names include Surflon S-121 (manufactured by Asahi Glass), Florard FC-135 (manufactured by Sumitomo 3M), Unidyne DS-202 (manufactured by Daikin Industries) ), Megafuck F-150, F-824 (Dainippon Ink Co., Ltd.), Xtop EF-132 (Tochem Products Co., Ltd.), Footgent F-300 (Neos Co., Ltd.), and the like.

  In addition, as the inorganic compound dispersant that is hardly soluble in water, calcium phosphate, calcium carbonate, titanium oxide, colloidal silica, hydroxyapatite, and the like can also be used. In the case where a dispersant that can be dissolved in an acid such as calcium phosphate and an alkali is used, the calcium phosphate is removed from the fine particles by a method such as washing with water after dissolving the calcium phosphate with an acid such as hydrochloric acid. It can also be removed by operations such as enzymatic degradation.

  Further, the dispersed droplets may be stabilized by a polymer protective colloid. For example, a monomer having a carboxyl group such as acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid, maleic anhydride; acrylic acid β- Hydroxyethyl, β-hydroxyethyl methacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate, γ-hydroxypropyl acrylate, γ-hydroxypropyl methacrylate, 3-chloro-2-hydroxypropyl acrylate , 3-chloro-2-hydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerol monoacrylate, glycerol monomethacrylate, N-methylol acrylate Acrylic monomers having a hydroxyl group such as luamide and N-methylol methacrylamide; vinyl ethers having an ether group such as vinyl methyl ether, vinyl ethyl ether and vinyl propyl ether; vinyl esters such as vinyl acetate, vinyl propionate and vinyl butyrate; Acrylamides such as acrylamide, methacrylamide, diacetone acrylamide and the like, and methylol compounds thereof; acid chlorides such as acrylic acid chloride and methacrylic acid chloride; nitrogen-containing compounds such as pinylviridine, vinylpyrrolidone, vinylimidazole, ethyleneimine, etc. Homopolymer or copolymer using polyoxyethylene, polyoxypropylene, polyoxyethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkyl Polyoxyethylenes such as amide, polyoxypropylene alkylamide, polyoxyethylene nonylphenyl ether, polyoxyethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ether; celluloses such as methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, etc. it can.

  When a dispersant is used, the dispersant can remain on the surface of the toner particles, but it is preferable to remove it by washing from the charged surface of the toner.

  The amount of the aqueous solvent used relative to 100 parts by weight of the toner raw material containing the polyester resin is usually 50 parts by weight or more and 20000 parts by weight or less, and preferably 100 parts by weight or more and 10,000 parts by weight or less. When the amount of the aqueous solvent used is less than 50 parts by weight, the toner raw material is not well dispersed and a toner having a desired particle diameter cannot be obtained. Moreover, when the usage-amount of an aqueous solvent exceeds 20000 weight part, it is not economical.

  In the present invention, toner raw materials such as a colorant and a release agent are not necessarily mixed when forming particles in an aqueous solvent, and may be added after the particles are formed. For example, after forming particles not containing a colorant, the colorant can be added by a known dyeing method.

  In order to remove the organic solvent from the obtained dispersion liquid, a method of gradually elevating the temperature of the entire system and completely evaporating and removing the organic solvent in the droplets can be employed. It is also possible to spray the dispersion into a dry atmosphere to completely remove the water-insoluble organic solvent in the droplets to form toner fine particles, and to evaporate and remove the dispersant. As the drying atmosphere in which the dispersion is sprayed, a gas obtained by heating air, nitrogen, carbon dioxide gas, combustion gas, or the like, in particular, various air streams heated to a temperature equal to or higher than the boiling point of the highest boiling solvent used are generally used. The desired quality can be obtained by short-time treatment such as spray dryer, belt dryer, rotary kiln.

  Moreover, when the particle size distribution at the time of emulsification dispersion is wide, and washing and drying processes are performed while maintaining the particle size distribution, the particle size distribution can be adjusted by classification into a desired particle size distribution. Examples of the classification operation include an operation of removing fine particles in a liquid by a cyclone, a decanter, centrifugation, or the like. The dried powder may be classified, but classification in the state of a dispersion is preferable in terms of efficiency. The obtained unnecessary fine particles and coarse particles can be returned to the kneading step and used for forming particles. At that time, the fine particles and coarse particles may be wet.

  The obtained toner powder after drying is mixed with different kinds of particles such as release agent fine particles, charge control fine particles, fluidizing agent fine particles, and colorant fine particles, or mechanical impact force is applied to the mixed powder. By fixing and fusing on the surface, it is possible to prevent the dissociation of the foreign particles from the surface of the resulting composite particle.

  Specific means include a method of applying an impact force to the mixture by blades rotating at high speed, a method of injecting and accelerating the mixture into a high-speed air stream, and causing particles or composite particles to collide with an appropriate collision plate, etc. is there. As equipment, Ong mill (manufactured by Hosokawa Micron Co., Ltd.), I-type mill (manufactured by Nippon Pneumatic Co., Ltd.) has been modified to reduce the pulverization air pressure, hybridization system (manufactured by Nara Machinery Co., Ltd.), kryptron Examples include a system (manufactured by Kawasaki Heavy Industries, Ltd.) and an automatic mortar.

  When the toner of the present invention is used as a developer, it may be used by mixing with a magnetic carrier. The carrier to toner content ratio in the developer is 1 part by weight or more and 10 parts by weight of toner with respect to 100 parts by weight of carrier. The following is preferred. As the magnetic carrier, conventionally known ones such as iron powder, ferrite powder, magnetite powder, magnetic resin carrier having a particle diameter of about 20 μm to 200 μm can be used. Examples of the coating material include amino resins such as urea-formaldehyde resin, melamine resin, benzoguanamine resin, urea resin, polyamide resin, and epoxy resin. Polyvinyl and polyvinylidene resins such as acrylic resins, polymethyl methacrylate resins, polyacrylonitrile resins, polyvinyl acetate resins, polyvinyl alcohol resins, polyvinyl butyral resins, polystyrene resins, and copolymers of styrene and acrylic monomers Polystyrene resin, halogenated olefin resin such as polyvinyl chloride, polyester resin such as polyethylene terephthalate resin and polybutylene terephthalate resin, polycarbonate resin, polyethylene resin, polyvinyl fluoride resin, polyvinylidene fluoride resin, polytrifluoroethylene Resin, polyhexafluoropropylene resin, copolymer of vinylidene fluoride and acrylic monomer, copolymer of vinylidene fluoride and vinyl fluoride, tetrafluoroethylene and vinyl fluoride Fluoro such as terpolymers of den and non-fluoride monomers including, silicone resins. Moreover, you may contain electrically conductive powder etc. in coating resin as needed. As the conductive powder, metal powder, carbon black, titanium oxide, tin oxide, zinc oxide or the like can be used. These conductive powders preferably have an average particle diameter of 1 μm or less. When the average particle diameter is larger than 1 μm, it becomes difficult to control electric resistance. The toner of the present invention can also be used as a developer that does not use a carrier.

  As a method for forming an image using the developer of the present invention, a known method can be used. For example, there is a method in which an electrostatic charge image formed on a photoconductor is transferred onto a transfer material such as paper using toner and fixed by a method such as heating. When forming a color image, all three colors are generally reproduced using three primary colors, magenta, cyan, and yellow, and preferably four black toners for inking. That is, a full color image can be obtained by sequentially performing the above-described transfer process for each color, fixing a plurality of color toners on the same transfer material, and fixing them.

All parts in this example are parts by weight, and this example is merely illustrative of the present invention, and the present invention is not limited by these examples.
(Synthesis of resin fine particles)
In a reaction vessel equipped with a stirrer and a thermometer, water 683 parts, ethylene salt methacrylate adduct sulfate sodium salt Eleminol RS-30 (manufactured by Sanyo Chemical Industries), 83 parts styrene, 83 parts methacrylic acid, acrylic When 110 parts of butyl acid and 1 part of ammonium persulfate were charged and stirred at 400 rpm for 15 minutes, a white emulsion was obtained. This was heated up until the system temperature reached 75 ° C. and reacted for 5 hours. Further, 30 parts of 1% ammonium persulfate aqueous solution was added and aged at 75 ° C. for 5 hours to vinyl resin (styrene, methacrylic acid and butyl acrylate-methacrylic acid ethylene oxide adduct sulfate sodium salt copolymer) An aqueous dispersion (hereinafter referred to as resin fine particle dispersion) was obtained. The volume average particle diameter of the resin fine particle dispersion measured by LA-920 was 105 nm. The glass transition temperature of the dried resin content of the resin fine particle dispersion was 59 ° C., and the weight average molecular weight was 150,000.
(Preparation of aqueous solvent)
990 parts of water, 83 parts of resin fine particle dispersion, 37 parts of a 48.5% aqueous solution of sodium dodecyl diphenyl ether disulfonate, Eleminol MON-7 (manufactured by Sanyo Chemical Industries) and 90 parts of ethyl acetate were mixed and stirred to give a milky white liquid (hereinafter referred to as “white milk”) , Referred to as an aqueous solvent).
(Synthesis of non-crystalline polyester resin)
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction tube, 229 parts of bisphenol A ethylene oxide 2-mole adduct, 529 parts of bisphenol A propylene oxide 3-mole adduct, 208 parts terephthalic acid, 46 parts adipic acid and oxidation After charging 2 parts of dibutyltin (IV) and reacting at 230 ° C. for 8 hours under normal pressure and further reacting under reduced pressure of 10 mmHg to 15 mmHg for 5 hours, 44 parts of trimellitic anhydride was added, The mixture was reacted at 180 ° C. for 2 hours to obtain an amorphous polyester resin. The number average molecular weight was 2500, the weight average molecular weight was 6700, the glass transition temperature was 43 ° C., and the acid value was 25 mgKOH / g.
(Synthesis of polyester prepolymer)
In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, 682 parts of bisphenol A ethylene oxide 2-mole adduct, 81 parts of bisphenol A propylene oxide 2-mole adduct, 283 parts of terephthalic acid, trimellitic anhydride 22 Part and 2 parts of dibutyltin oxide (IV) were charged, reacted at 230 ° C. under normal pressure for 8 hours, and further reacted under reduced pressure of 10 mmHg to 15 mmHg for 5 hours to obtain an intermediate polyester resin. The number average molecular weight was 2,100, the weight average molecular weight was 9,500, the glass transition temperature was 55 ° C., the acid value was 0.5 mgKOH / g, and the hydroxyl value was 51 mgKOH / g.

Next, 410 parts of an intermediate polyester resin, 89 parts of isophorone diisocyanate and 500 parts of ethyl acetate are added to a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, and reacted at 100 ° C. for 5 hours. A polymer was obtained. The free isocyanate weight percent was 1.53%.
(Synthesis of ketimine compounds)
In a reaction vessel equipped with a stir bar and a thermometer, 170 parts of isophoronediamine and 75 parts of methyl ethyl ketone were charged and reacted at 50 ° C. for 5 hours to obtain a ketimine compound. The amine value was 418 mgKOH / g.
(Synthesis of crystalline polyester resin)
In a 5-liter four-necked flask equipped with a nitrogen inlet tube, dehydration tube, stirrer and thermocouple, 2,253 parts of 1,4-butanediol, 2757 parts of fumaric acid, 317 parts of trimellitic anhydride, 5.3 parts of hydroquinone Was reacted at 160 ° C. for 5 hours, heated to 200 ° C. and reacted for 1 hour, and further reacted at 83 hPa for 1 hour to obtain a crystalline polyester resin. The melting point was 119 ° C., the number average molecular weight was 710, the weight average molecular weight was 2100, the acid value was 24 mgKOH / g, and the hydroxyl value was 28 mgKOH / g.
(Preparation of pigment dispersion by flushing method)
As an aqueous dispersion of magenta pigment, 1130 parts of an intermediate of 25.6% by weight of pigment wet cake PR269 (manufactured by Dainippon Ink & Chemicals, Inc.) and 214 parts of an amorphous polyester resin were mixed with a kneader 2L kneader (manufactured by Inoue Seisakusho). ). After kneading for 25 minutes at 45 ° C., about 500 g of the separated water was removed. Next, 214 parts of a crystalline polyester resin and 214 parts of an amorphous polyester resin were added and kneaded at 120 ° C. for 3 hours under a reduced pressure of 400 hPa or more and 800 hPa or less to obtain a magenta pigment dispersion 1.

  In the same manner as above, 1130 parts of PR269 intermediate and 214 parts of non-crystalline polyester resin were kneaded with a 2 L kneader. After kneading for 25 minutes at 45 ° C., about 500 g of the separated water was removed. Next, 428 parts of amorphous polyester was added and kneaded at 120 ° C. for 3 hours under a reduced pressure of 400 hPa to 800 hPa to obtain a magenta pigment dispersion 2.

  1200 parts of water, 540 parts of powder pigment PR269, 400 parts of crystalline polyester resin and 800 parts of amorphous polyester resin were mixed with a Henschel mixer (Mitsui Mining Co., Ltd.). Next, after kneading at 150 ° C. for 30 minutes using two rolls, rolling and cooling and pulverizing with a pulverizer, a magenta pigment dispersion 3 was obtained.

  As an aqueous dispersion of a yellow pigment, 1200 parts of an intermediate of 24.3% by weight of a pigment wet cake PY74 (manufactured by Sanyo Dye) and 216 parts of an amorphous polyester resin were kneaded with a 2 L kneader. After kneading at 45 ° C. for 10 minutes, about 600 g of the separated water was removed. Next, 216 parts of a crystalline polyester resin and 216 parts of an amorphous polyester resin were added and kneaded at 80 ° C. for 3 hours under a reduced pressure of 400 hPa or more and 530 hPa or less to obtain a yellow pigment dispersion 1.

  In the same manner as above, 1200 parts of PY74 intermediate and 216 parts of non-crystalline polyester resin were kneaded with a 2 L kneader. After kneading at 45 ° C. for 10 minutes, about 600 g of the separated water was removed. Next, 432 parts of an amorphous polyester resin was added and kneaded at 80 ° C. for 3 hours under a reduced pressure of 400 hPa or more and 530 hPa or less to obtain a yellow pigment dispersion 2.

  1200 parts of water, 540 parts of powder pigment PY74, 400 parts of crystalline polyester resin and 800 parts of amorphous polyester resin were mixed with the Henschel mixer. Next, after kneading at 150 ° C. for 30 minutes using two rolls, rolling and cooling and pulverizing with a pulverizer, yellow pigment dispersion 3 was obtained.

  As an aqueous dispersion of a cyan pigment, 900 parts of an intermediate of 35.7% by weight of pigment wet cake PB15: 3 (manufactured by Toyo Ink Co., Ltd.) and 238 parts of an amorphous polyester resin were kneaded with a 2 L kneader. After kneading at 60 ° C. for 10 minutes, about 350 g of the separated water was removed. Next, 238 parts of a crystalline polyester resin and 238 parts of an amorphous polyester resin were added and kneaded at 120 ° C. for 3 hours under a reduced pressure of 400 hPa or more and 800 hPa or less to obtain a cyan pigment dispersion 1.

  In the same manner as described above, 900 parts of PB15: 3 intermediate and 238 parts of non-crystalline polyester resin were kneaded with a 2 L kneader. After kneading at 60 ° C. for 10 minutes, about 350 g of the separated water was removed. Next, 476 parts of an amorphous polyester resin was added and kneaded at 120 ° C. for 3 hours under a reduced pressure of 400 hPa or more and 800 hPa or less to obtain a cyan pigment dispersion 2.

1200 parts of water, 540 parts of powder pigment PB15: 3, 400 parts of crystalline polyester resin and 800 parts of amorphous polyester resin were mixed with the Henschel mixer. Next, after kneading at 150 ° C. for 30 minutes using two rolls, rolling and cooling and pulverizing with a pulverizer, a cyan pigment dispersion 3 was obtained.
(Preparation of toner raw material dispersion)
In a container in which a stir bar and a thermometer are set, 378 parts of an amorphous polyester resin, 110 parts of carnauba wax, 22 parts of a salicylic acid metal complex E-84 (manufactured by Orient Chemical Co., Ltd.), and 947 parts of ethyl acetate are charged. The temperature was raised to 0 ° C., kept at 80 ° C. for 5 hours, and then cooled to 30 ° C. over 1 hour. Next, 500 parts of magenta pigment dispersion 1 and 500 parts of ethyl acetate were added and mixed for 1 hour to obtain magenta raw material mixture 1.

  Transfer 1324 parts of the magenta raw material mixture to a container, and fill it with 80% by volume of 0.5 mm zirconia beads at a feeding speed of 1 kg / h and a disk peripheral speed of 6 m / sec using an ultra visco mill (manufactured by IMEX) as a bead mill. Then, dispersion was performed under the condition of 3 passes. Next, 1324 parts of a 65% ethyl acetate solution of an amorphous polyester resin was added, and one pass was performed with a bead mill under the above conditions to obtain a magenta raw material dispersion 1. The solid concentration when dried at 130 ° C. for 30 minutes was 50%.

  Similarly to the above, the magenta raw material dispersion 2 was prepared from the magenta pigment dispersion 2 through the magenta raw material mixture 2.

  In the same manner as described above, the magenta raw material dispersion 3 was prepared from the magenta pigment dispersion 3 through the magenta raw material mixture 3.

  Similarly to the above, the yellow raw material dispersion 1 was prepared from the yellow pigment dispersion 1 through the yellow raw material mixture 1.

  In the same manner as above, the yellow raw material dispersion 2 was prepared from the yellow pigment dispersion 2 through the yellow raw material mixture 2.

  Similarly to the above, the yellow raw material dispersion 3 was prepared from the yellow pigment dispersion 3 through the yellow raw material mixture 3.

  Similarly to the above, the cyan raw material dispersion 1 was prepared from the cyan pigment dispersion 1 through the cyan raw material mixture 1.

  Similarly to the above, the cyan raw material dispersion 2 was prepared from the cyan pigment dispersion 2 through the cyan raw material mixture 2.

Similarly to the above, the cyan raw material dispersion 3 was prepared from the cyan pigment dispersion 3 through the cyan raw material mixture 3.
(Example 1)
664 parts of magenta raw material dispersion 1, 109.4 parts of polyester prepolymer, 73.9 parts of crystalline polyester resin, and 4.6 parts of ketimine compound are charged into a container, and a TK homomixer (manufactured by Koki Co., Ltd.) is used. After mixing at 5000 rpm for 1 minute, 1200 parts of an aqueous solvent was added and mixed at 13000 rpm for 20 minutes using a TK homomixer to obtain an emulsified slurry. This was put into a container equipped with a stirrer and a thermometer, desolvated at 30 ° C. for 8 hours, and then aged at 45 ° C. for 4 hours to obtain a dispersed slurry.

100 parts of ion-exchanged water was added to a filter cake obtained by filtering 100 parts of the dispersion slurry under reduced pressure, and the mixture was mixed for 10 minutes at 12000 rpm using a TK homomixer, followed by filtration. To this filter cake, 100 parts of a 10% aqueous sodium hydroxide solution was added, mixed at 12000 rpm for 30 minutes using a TK homomixer, and then filtered under reduced pressure. To this filter cake, 100 parts of 10% hydrochloric acid was added, mixed at 12000 rpm for 10 minutes using a TK homomixer, and then filtered. After adding 300 parts of ion-exchanged water to this filter cake and mixing for 10 minutes at 12000 rpm using a TK homomixer, the operation of filtering was performed twice. This filter cake was dried at 45 ° C. for 48 hours using a circulating drier, and sieved with a mesh having an opening of 75 μm to obtain magenta toner 1.
(Example 2)
A yellow toner 1 was obtained in the same manner as in Example 1 except that the magenta raw material dispersion 1 in Example 1 was changed to the yellow raw material dispersion 1.
(Example 3)
A cyan toner 1 was obtained in the same manner as in Example 1 except that the magenta raw material dispersion 1 in Example 1 was changed to the cyan raw material dispersion 1.
(Comparative Example 1)
A magenta toner 2 was obtained in the same manner as in Example 1 except that the magenta raw material dispersion 1 in Example 1 was changed to the magenta raw material dispersion 2.
(Comparative Example 2)
A magenta toner 3 was obtained in the same manner as in Example 1 except that the magenta raw material dispersion 1 in Example 1 was changed to the magenta raw material dispersion 3.
(Comparative Example 3)
A yellow toner 2 was obtained in the same manner as in Example 1 except that the magenta raw material dispersion 1 in Example 1 was changed to the yellow raw material dispersion 2.
(Example 4)
A yellow toner 3 was obtained in the same manner as in Example 1 except that the magenta raw material dispersion 1 in Example 1 was changed to the yellow raw material dispersion 3.
(Comparative Example 5)
A cyan toner 2 was obtained in the same manner as in Example 1 except that the magenta raw material dispersion 1 in Example 1 was changed to the cyan raw material dispersion 2.
(Comparative Example 6)
A cyan toner 3 was obtained in the same manner as in Example 1 except that the magenta raw material dispersion 1 in Example 1 was changed to the cyan raw material dispersion 3.
(Evaluation method and evaluation results)
After 100 parts of the toner thus obtained, 0.7 part of hydrophobic silica and 0.3 part of hydrophobic acid value titanium were mixed with a Henschel mixer, the toner was evaluated, and the results are shown in Table 1. .

トナーの熱特性を測定するフローテスターとしては、高架式フローテスターＣＦＴ５００型（島津製作所社製）を用いた。なお、口径０．５０ｍｍ、長さ１０．０ｍｍのダイを用い、１０ｋｇｆ／ｃｍ^２の圧力で３℃／分の昇温をすることにより測定を実施した。その結果、結晶性ポリエステル樹脂を用いない比較例１、３及び５では、軟化温度及び流出開始温度のいずれも、結晶性ポリエステル樹脂を用いた実施例及び比較例２、４及び６より高温になる傾向が見られた。

As a flow tester for measuring the thermal characteristics of the toner, an elevated flow tester CFT500 type (manufactured by Shimadzu Corporation) was used. The measurement was carried out by using a die having a diameter of 0.50 mm and a length of 10.0 mm and raising the temperature by 3 ° C./min at a pressure of 10 kgf / cm ² . As a result, in Comparative Examples 1, 3 and 5 in which no crystalline polyester resin is used, both the softening temperature and the outflow start temperature are higher than those in Examples and Comparative Examples 2, 4 and 6 using the crystalline polyester resin. There was a trend.

  The toner was transferred onto a transparent plastic film (OHP sheet), and its turbidity was measured using a haze meter TC-H3DP (manufactured by Tokyo Denshoku) to evaluate the film transparency. In addition, (circle), (triangle | delta), and x show that turbidity is less than 10, 10 or more and less than 20, and 20 or more, respectively. As a result, in Comparative Examples 2, 4 and 6 using the powder pigment, the transparency tends to be lower than in Examples and Comparative Examples 1, 3 and 5 using the colorant obtained by the flushing method. It was.

  Next, a developer composed of 5% by weight of toner subjected to external additive treatment and 95% by weight of a copper-zinc ferrite carrier having an average particle diameter of 40 μm coated with a silicone resin was prepared. This developer was evaluated by continuously printing A4 size paper at 45 sheets / minute using imagio Neo 450 (manufactured by Ricoh Co., Ltd.). The results are shown in Table 1.

After adjusting the temperature of the fixing belt to be variable, 1.0 ± 0.1 mg / cm ² of toner was developed as a solid image, and the fixing characteristics were evaluated. The hot offset occurrence temperature was measured using a plain paper transfer paper type 6200 (manufactured by Ricoh), and the fixing lower limit temperature was measured using a thick copy printing paper <135> (manufactured by NBS Ricoh). . Further, the fixing roll temperature at which the residual ratio of the image density after rubbing the obtained fixed image with a pad becomes 70% or more was defined as the minimum fixing temperature. As a result, in Comparative Examples 1, 3 and 5 in which no crystalline polyester resin was used, a relatively high temperature with a minimum fixing temperature of around 140 ° C. was required, whereas examples using crystalline polyester resin and In Comparative Examples 2, 4 and 6, fixing was performed at around 120 ° C. Further, in Comparative Examples 2, 4 and 6 using powder pigments instead of the colorant obtained by the flushing method, an offset occurred near 200 ° C., whereas the colorant obtained by the flushing method was used. In Examples and Comparative Examples 1, 3 and 5, no offset occurred at 220 ° C. or lower.

  The contamination of the cleaning roller was evaluated by measuring the amount of deposits on the cleaning roller after printing 100,000 sheets, and evaluating it in four levels between almost none, a small amount, many, and good and bad. As a result, in both the examples and the comparative examples, good results (◯) in which the amount of deposits was very small were obtained, and no significant difference was observed.

  Further, the state of occurrence of toner filming on the developing roller or the photoreceptor after printing 100,000 sheets was observed. In addition, (circle), (triangle | delta), and x show the state without filming, the state where the filming on a streak is seen, and the state with filming as a whole, respectively. As a result, filming was not observed in any of the examples and comparative examples.

Claims (26)

In a toner for developing an electrostatic image having a binder resin containing 50% by weight or more of a polyester resin containing a crystalline polyester resin and a colorant,
The colorant is a colorant obtained by dispersing a pigment in an amorphous polyester resin by a flushing method , and then dispersing the pigment by adding a crystalline polyester resin. toner.   The electrostatic image developing toner according to claim 1, wherein the crystalline polyester resin has a softening temperature and a glass transition temperature of 65 ° C. or more and 140 ° C. or less, respectively.   3. The toner for developing an electrostatic charge image according to claim 1, wherein the crystalline polyester resin has a number average molecular weight by GPC of o-dichlorobenzene soluble part of 500 to 6000. 4.   The ratio of the weight average molecular weight with respect to the number average molecular weight by GPC of the o-dichlorobenzene soluble part of the crystalline polyester resin is 2 or more and 8 or less. Toner for developing electrostatic images.   5. The electrostatic charge image developing toner according to claim 1, wherein an acid value of the crystalline polyester resin is 5 mgKOH / g or more and 45 mgKOH / g or less.   6. The electrostatic charge image developing toner according to claim 1, wherein the crystalline polyester resin has a hydroxyl value of 5 mgKOH / g or more and 50 mgKOH / g or less.   The electrostatic image developing toner according to claim 1, wherein the crystalline polyester resin contains a crystalline unsaturated polyester resin. The crystalline unsaturated polyester resin has a general formula

It is a resin indicated by
l is an integer of 1 to 3,
m and n are each an integer;
The electrostatic image developing toner according to claim 6, wherein R ₁ , R ₂ , R _3, and R ₄ are each a hydrogen atom or a hydrocarbon group having 4 or less carbon atoms.   The toner for developing an electrostatic charge image according to claim 8, wherein m is an integer of 2 or more and 6 or less.   The electrostatic charge image developing toner according to claim 1, wherein the binder resin further contains a urea-modified polyester resin.   The toner for developing an electrostatic charge image according to claim 10, wherein the binder resin further contains an amorphous polyester resin having a glass transition temperature of 30 ° C. or higher and 70 ° C. or lower. 12. The toner for developing an electrostatic charge image according to claim 11, wherein the acid value of the amorphous polyester resin having a glass transition temperature of 30 ° C. or more and 70 ° C. or less is 30 mgKOH / g or less. The binder resin further contains a urea-modified polyester resin,
13. The electrostatic charge image according to claim 11, wherein a ratio of a total weight of the amorphous polyester resin and the crystalline polyester resin to a weight of the urea-modified polyester resin is 3 or more and 19 or less. Development toner.   The electrostatic image developing toner according to claim 1, further comprising a release agent.   The electrostatic charge image developing toner according to claim 14, wherein the content of the releasing agent is 1 wt% or more and 40 wt% or less.   The toner for developing an electrostatic charge image according to claim 14, wherein the releasing agent has a melting point of 40 ° C. or higher and 160 ° C. or lower. A colorant obtained by dispersing a pigment in an amorphous polyester resin by a flushing method and then dispersing the pigment by adding a crystalline polyester resin. In a method for producing a toner for developing an electrostatic charge image, comprising a binder resin containing 50% by weight or more of a polyester resin containing a crystalline polyester resin and a colorant,
A step of dispersing the pigment in the non-crystalline polyester resin by a flushing method, and then adding and dispersing the crystalline polyester resin to obtain the colorant;
Obtaining a polyester resin containing the crystalline polyester resin, a mixture containing the colorant and an organic solvent;
A method for producing a toner for developing an electrostatic charge image, comprising the step of dispersing the mixture in an aqueous solvent. The step of obtaining the mixture includes the step of dispersing the colorant in the organic solvent to obtain a dispersion,
The method for producing a toner for developing an electrostatic charge image according to claim 18, further comprising a step of obtaining a mixture containing the polyester resin containing the crystalline polyester resin, the dispersion, and the organic solvent. 20. The method for producing a toner for developing an electrostatic charge image according to claim 19 , wherein the ratio of the weight of the organic solvent to the weight of the colorant in the step of obtaining the dispersion is 1 or more and 19 or less. The method for producing a toner for developing an electrostatic charge image according to any one of claims 18 to 20 , wherein the crystalline polyester resin contains a crystalline unsaturated polyester resin. In the step of obtaining the mixture, a polyester resin having a functional group capable of reacting with an active hydrogen-containing group and a compound having an active hydrogen-containing group are further mixed,
22. A step of reacting a compound having an active hydrogen-containing group with a polyester resin having a functional group capable of reacting with the active hydrogen-containing group after the step of dispersing in the aqueous solvent. The method for producing a toner for developing an electrostatic charge image according to any one of the above. An electrostatic image developing toner produced by the method of producing an electrostatic image developing toner according to any one of claims 18 to 22 . An electrostatic charge image developing developer comprising the electrostatic charge image developing toner according to any one of claims 1 to 16 and 23 . 25. The developer for developing an electrostatic charge image according to claim 24 , further comprising a carrier carrying the toner for developing the electrostatic charge image. An image forming method comprising forming an image using the developer for developing an electrostatic charge image according to claim 24 or 25 .