JP4498089B2 - Toner evaluation method for electrostatic charge development and toner for electrostatic charge development - Google Patents

Description

  The present invention relates to a toner used in a one-component developing device or a two-component developing device and evaluation means.

As a technique related to electrophotography, a technique for evaluating dispersibility of a toner pigment by examining a change in absorbance of a toner fixed image on an OHP (see Patent Document 1) is disclosed. It is necessary to create a fixed image on the OHP, and this has a problem that it depends on fixing conditions.
Further, an additive that measures an inorganic element using EPMA-WDS and is evaluated by an X-ray intensity ratio from a reference sample (see Patent Document 2) has been disclosed. The internal dispersibility cannot be evaluated.

In particular, the dispersibility of the toner has been highlighted as a problem only after the low temperature fixing of the toner and the oilless fixing have started. Regarding such low-temperature fixing, there is an attempt to add a specific non-olefinic crystalline polymer having sharp melt properties to a binder (see Patent Document 3). There is also an attempt to use a crystalline polyester having sharp melt properties (see Patent Documents 4 and 5).
However, crystalline polyesters with sharp melt properties tend to reduce the kneading shear force and deteriorate the dispersibility of wax and the dispersibility of the crystalline polyester resin itself when the product temperature at the time of kneading is equal to or higher than the glass transition temperature. . In particular, in a full-color toner using a resin having a small elastic component, the deterioration of dispersibility becomes remarkable. Therefore, it becomes easy to produce the problem of the fall of the fluidity by deterioration of a wax dispersibility, and the transparency fall by the deterioration of the dispersibility of crystalline polyester resin. Further, the crystalline polyester resin has a lower pulverization property than the polyester resin having no crystallinity, and the pulverization method has a problem for reducing the particle size.

The image quality of copiers and printers has been improved, and recently, the reproducibility of fine dots has become very important. The dot reproducibility is greatly influenced by the fluidity in addition to the charge amount of the toner and developer, and the uniform toner layer or developer layer can be stably supplied to the fine latent image portion and transported. Is becoming necessary.
Further, as the image quality is improved, the toner used in the toner is becoming smaller in particle size and higher in function. For this reason, the structure of the toner has become complicated, and finer control at the time of production has become necessary. In particular, since the toner fluidity affects various image qualities in addition to dot reproducibility, it is necessary to evaluate the toner dispersibility without deteriorating the toner fluidity.

In addition, when the toner production method changes from the pulverization method to another method such as a polymerization method, the change in the flow characteristics with respect to the manufacturing conditions is large. Evaluation is required.
Further, as the toner is fixed at a low temperature and the oil-less fixing is progressed, the toner base composition and structure become complicated, and the fluidity of the toner is greatly affected. Therefore, structural control with higher accuracy than before is required, and accordingly, a highly sensitive dispersibility evaluation method is required.

JP-A-9-204488 JP 2001-109186 A JP 62-63940 A Japanese Patent No. 2931899 JP 2001-222138 A

By using an evaluation method with high dispersion accuracy and no individual difference, the present invention produces a toner that can be obtained at any time with low temperature fixing, no problem in toner transportability, and high dot reproducibility and high image quality at any time, The purpose is to enable stable production.
In the present invention, the dispersibility of the toner is evaluated from the X-ray diffraction pattern specific to the toner phase of the powder material, so that the evaluation can be performed quantitatively with high accuracy and without individual differences.
Since this method can measure the toner phase as it is in a short time, it can be introduced into a production line, and toner that can realize high image quality with good dot reproducibility can be stably produced.

Above problems, (1) "at least a resin of the present invention, the pigment, Ri Do from the charge control agent, at least one of the resin in the powder is a crystalline polyester represented by the following general formula (1), The powder was irradiated with X-rays with a wavelength of 1.54 mm (CuKα rays) and the X-ray diffraction pattern was measured. A peak in the range of 2θ (θ: Bragg angle) = 21.5 ± 0.5 deg The integrated intensity I including the amorphous part and the integrated intensity Ip of only the peak part are measured, and the dispersibility of the powder is determined depending on whether the integrated intensity ratio Ip / I is 0.05 to 0.20. A toner evaluation method for electrostatic charge development, characterized by being evaluated.

」、（２）「前記第（１）項に記載の粉体の分散性評価法を用いてトナーを評価し、トナーを製造する、静電荷現像用トナー製造方法であって、粉体の分散性評価が、トナー製造における粉砕工程以降の工程において行われるものであることを特徴とする静電荷現像用トナー製造方法」によって解決される。

(2) A method for producing a toner for electrostatic charge development, in which a toner is evaluated by using the powder dispersibility evaluation method described in (1) above, and the toner is produced. The property evaluation is solved by an electrostatic charge developing toner manufacturing method characterized in that the evaluation is performed in a step after the pulverization step in toner manufacturing.

  According to the present invention, the dispersibility of the toner powder is irradiated with X-rays (CuKα rays) having a wavelength of 1.54 mm, and a diffraction peak and an amorphous portion within the range of 2θ = 21.5 ± 0.5 deg. The integrated intensity ratio Ip / I value of the integrated intensity I including the (back part) and the integrated intensity Ip of only the peak part is measured, and the difference between the integrated intensity ratios is fast, accurate, and without individual differences. In this way, it is possible to provide an extremely excellent effect that the conditions of the toner capable of obtaining a high image quality with good dot reproducibility are precisely defined, and the toner capable of obtaining a high image quality by low-temperature fixing can be stably produced.

  The present invention relates to a method of measuring an X-ray diffraction pattern by irradiating a toner powder with X-rays (CuKα rays) having a wavelength of 1.54 mm, 2θ (θ: Bragg angle) = 21.5 ± 0.5 deg. The total integrated intensity I including the peak and the amorphous part within the range and the integrated intensity Ip of only the peak part are measured, and the dispersibility of the powder is evaluated by the integrated intensity ratio Ip / I. The present invention relates to an evaluation method characterized by the above, and an electrostatic charge developing toner which can obtain high image quality by low-temperature fixing evaluated using the evaluation method.

This evaluation method irradiates the toner powder with X-rays (CuKα rays) having a wavelength of 1.54 mm, measures the X-ray diffraction pattern, and 2θ (θ: Bragg angle) = 21.5 ± 0.5 deg. The dispersibility is evaluated by the difference in the integrated intensity ratio Ip / I between the integrated intensity I including the peak and the amorphous part within the range and the integrated intensity Ip of only the peak part.
Since X-rays are used, it has excellent permeability and is suitable for nondestructive analysis. Therefore, the toner powder can be measured without any adjustment. In other words, it is an evaluation method that can be directly applied to a part to be inspected such as a production line.

An outline of the evaluation apparatus of the present invention is shown in FIG.
First, X-rays are generated from an X-ray tube. X-rays are generated by causing electrons to collide with the target cathode at high speed. As the target cathode material, Cr, Fe, Co, Ni, Cu, Mo, or the like is used. In the present invention, a Cu target having a short wavelength is used. When a Cu target is used, various characteristic X-rays are generated. In the present invention, Kα rays are used. The wavelength at that time is 1.54 mm. X-rays are irradiated onto the surface of the sample (toner powder) through a slit (divergence slit). X-rays incident on the sample cause a Bragg diffraction phenomenon corresponding to the internal structure of the toner powder, and enter the counter tube as reflected X-rays through slits (receiving slits, scatter slits). Examples of the counter tube include a Geiger counter tube, a proportional counter tube, a scintillation counter tube, and the like. In the present invention, a scintillation counter tube is used. The pulses generated and amplified in the counter tube are processed by a pulse height analyzer and detected by a counter circuit. As the configuration of the apparatus, this method is an example, and other counters and the like may be adopted. The measurement is performed by using a goniometer to change the incident angle on the sample at a low speed (0.5 to 10 deg / min), and measure and evaluate the reflected X-ray intensity from the sample (toner powder) at that time. .

This sample of the toner powder is measured by fixing the sample directly on the sample table using an adhesive means or the like. At that time, the powder is pressed and fixed with a flat plate so that the powder surface is not uneven. The difference in the dispersion state of the sample is measured as a change in the X-ray diffraction peak intensity characteristic at the Bragg angle θ inherent to the sample (corresponding to the structure). The toner powder sample should be free from unevenness on the surface and have a variation in the thickness of the powder phase depending on the location. The measurement is performed by changing the scan angle 2θ in the range of 10 deg to 50 deg and measuring the X-ray diffraction intensity. In the present invention, the dispersion state of the crystalline polyester in the toner powder is examined. The diffraction peak of the crystalline polyester appears at 2θ = 21.5 ± 0.5 deg. Therefore, the scan angle 2θ may be measured by narrowing it to a range of 10 deg to 30 deg. The X-ray diffraction peak of the crystalline polyester appearing at 2θ = 21.5 ± 0.5 deg changes depending on the state of being dispersed in the resin, particularly the toner powder, and large lumps are observed in some places. The X-ray diffraction peak becomes large when the dispersion state is poor as it exists, and the X-ray diffraction peak becomes small when it is very finely and uniformly dispersed. The evaluation of the size of the X-ray diffraction peak uses the integrated value of the peak. This is because when the peak intensity is used, the variation in data becomes large, causing problems in measurement accuracy and reproducibility. Further, in order to accurately compare the samples, evaluation was performed using an integrated intensity ratio between the total integrated value of the peak (crystalline part) and the back (amorphous part) and the integrated value of only the peak part. When the integrated intensity of the X-ray diffraction peak was used for evaluation, the variation in measurement was small, and stable evaluation could be realized. The measurement may be performed once, but it is more appropriate to repeat the measurement twice or more and evaluate the average. When the toner powder sample is thin, X-rays are transmitted and affected by the base of the sample holder, so care must be taken.
However, the measurement system and measurement conditions are not limited to this.

The toner used in this evaluation method is a crystalline polyester in which at least one of the binder resins has a repeating unit structure represented by the general formula (1), and is irradiated with X-rays (CuKα rays) having a wavelength of 1.54 mm. X-ray diffraction pattern 2θ (θ: Bragg angle) = 21.5 ± 0.5 deg of the whole integrated intensity I including the peak and amorphous part and only the integrated intensity of the peak part It is kneaded and dispersed sufficiently well so that the value of the integrated intensity ratio Ip / I with Ip is 0.05-20. The kneading conditions are determined by the kneading temperature and the kneading rotation speed, but the kneading conditions in the vicinity of the kneading rotation speed of 160 rpm near the general kneading temperature of 160 ° C. for the conventional polyester resin toner are represented by the above general formula (1). It has become apparent in the present invention that the present invention is not suitable for a toner in which a colorant is sufficiently dispersed using a crystalline polyester resin having a repeating unit structure as a binder. Rather than being melted sufficiently to high temperatures and kneading at a high kneading speed in a low viscosity state, an excellent dispersion state appears by applying a high shear stress while maintaining a high viscosity state at a low temperature. can do. A high load is applied to the kneading machine (thus, the kneading speed is low and the torque is large), but the resin material in a hard state (containing the colorant firmly) is repeatedly sufficiently stretched, convolved and sheared. This is because the dispersion of the colorant contained in the resin proceeds.
In order to realize a high-quality image with good dot reproducibility, the average particle size of the toner needs to be 4 to 8 μm. More preferably, it is 5-7 micrometers. If the weight average particle diameter is less than 4 μm, problems such as contamination in the machine due to toner scattering during long-term use, image density reduction in a low-humidity environment, and poor photoconductor cleaning are likely to occur, and there is a concern about the effect on the human body. When the weight average particle size exceeds 8 μm, the resolution of minute spots of 100 μm or less is not sufficient, and the image quality tends to be inferior due to many scattering to non-image areas.

  The developer using this toner needs to have an average particle diameter of the carrier of 20 to 70 μm in order to realize a high quality image. When the average particle diameter of the carrier is in the range of 20 to 70 μm, the charge amount of the toner can be made more uniform when the toner concentration in the developing machine is in the range of 2 to 10% by weight. When the particle size is less than 20 μm, carrier particles are likely to adhere to the photoreceptor, and the stirring efficiency with the toner is deteriorated, so that it is difficult to obtain a uniform charge amount of the toner. On the other hand, when the average particle diameter of the carrier exceeds 70 μm, fine image reproducibility deteriorates and high image quality cannot be obtained.

Details of the toner and developer are shown below.
As resins, polystyrene resin, epoxy resin, polyester resin, polyamide resin, styrene acrylic resin, styrene methacrylate resin, polyurethane resin, vinyl resin, polyolefin resin, styrene butadiene resin, phenol resin, polyethylene resin, silicon resin, butyral resin, terpene There are resins, polyol resins and the like.

  As the vinyl resin, styrene such as polystyrene, poly-p-chlorostyrene, polyvinyltoluene and the like, and a substituted polymer thereof: styrene-p-chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer Polymer, styrene-vinyl naphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methacrylic acid Acid methyl copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ether copolymer Coalescence, styrene-vinyl ethyl acetate Copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, styrene-maleic acid ester Styrene copolymers such as copolymers: polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate and the like.

The polyester resin is composed of a dihydric alcohol as shown in the following group A and a dibasic acid salt as shown in the group B, and further a trihydric or higher alcohol as shown in the group C or Carboxylic acid may be added as a third component.
Group A: ethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4 butanediol, neopentyl glycol, 1,4-butenediol, 1,4-bis (hydroxymethyl) Cyclohexane, bisphenol A, hydrogenated bisphenol A, polyoxyethylenated bisphenol A, polyoxypropylene (2,2) -2,2′-bis (4-hydroxyphenyl) propane, polyoxypropylene (3,3) -2 , 2-bis (4-hydroxyphenyl) propane, polyoxyethylene (2,0) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (2,0) -2,2′-bis ( 4-hydroxyphenyl) propane and the like.
Group B: maleic acid, fumaric acid, mesaconic acid, citraconic acid, itaconic acid, glutaconic acid, phthalic acid, isophthalic acid, terephthalic acid, cyclohexanedicarboxylic acid, succinic acid, adipic acid, sebacic acid, malonic acid, linolenic acid, or These acid anhydrides or esters of lower alcohols.
Group C: Trivalent or higher alcohols such as glycerin, trimethylolpropane and pentaerythritol, and trivalent or higher carboxylic acids such as trimellitic acid and pyromellitic acid.

  As the polyol resin, an alkylene oxide adduct of an epoxy resin and a dihydric phenol, or a compound having one active hydrogen in the molecule that reacts with the glycidyl ether and the epoxy group, and an active hydrogen that reacts with the epoxy resin in the molecule. There are those obtained by reacting two or more compounds.

  As the resin, crystalline polyester may be used. It is an aliphatic polyester having crystallinity, having a sharp molecular weight distribution, and increasing the absolute amount of its low molecular weight as much as possible. This resin undergoes a crystal transition at the glass transition temperature (Tg), and the melt viscosity suddenly decreases from the solid state, thereby exhibiting a fixing function to paper. By using this crystalline polyester resin, low-temperature fixing can be achieved without excessively reducing the Tg and molecular weight of the resin. Therefore, there is no decrease in storage stability associated with a decrease in Tg. Further, there is no excessively high gloss and offset resistance deterioration due to the low molecular weight. Therefore, the introduction of the crystalline polyester resin is very effective for improving the low-temperature fixability of the toner.

  In the toner of the present invention, the content of the crystalline polyester is 1 to 50 with respect to the total amount of the resin and the release agent in the toner in order to exhibit low-temperature fixability and ensure hot offset resistance. The content of the release agent is preferably 2 to 15% by weight. When the content of the crystalline polyester is less than 1% by weight, there is no effect on the low-temperature fixability, and when it exceeds 50% by weight, the hot offset property is deteriorated. When the release agent content is less than 2% by weight, the offset resistance may not be effective, and when it exceeds 15% by weight, the toner fluidity decreases.

  Examples of the resin include a polyester resin and / or a polyol resin conventionally used for color toners. Polyester resins and polyol resins are suitable because they have better low-temperature fixability and relatively better heat-resistant storage stability than the styrene-acrylic resins that have been widely used. However, polyester resins and polyol resins have poor dispersibility of the release agent compared to styrene-acrylic resins. If the dispersibility is poor, the crushing stress tends to concentrate at the interface between the resin and the wax at the time of crushing, so it is easy to crush at the interface between the resin and the release agent. The release agent was exposed to the toner and the fluidity of the toner was deteriorated.

  The molecular structure of the crystalline polyester resin is not limited, but from the viewpoint of the crystallinity and softening point of the polyester resin, a diol compound having 2 to 6 carbon atoms, particularly 1,4-butanediol and 1,6-hexanediol. And an aliphatic polyester represented by the following general formula (1) synthesized using an alcohol component containing these derivatives and maleic acid, fumaric acid, succinic acid, and an acid component containing these derivatives: It is preferable to contain.

（Ｒ_１，Ｒ_２は炭化水素基を表わし、ｎ，ｍは繰り返し単位の数である。）

(R ₁ and R ₂ represent a hydrocarbon group, and n and m are the number of repeating units.)

  From the viewpoint of the crystallinity and softening point of the polyester resin, a trihydric or higher polyhydric alcohol such as glycerin is added to the alcohol component to synthesize a non-linear polyester, and trimellitic anhydride or the like is added to the acid component. Polycondensation may be performed by adding a trivalent or higher polyvalent carboxylic acid.

  The glass transition temperature (Tg) of the crystalline polyester resin is desirably low so long as the heat resistant storage stability does not deteriorate, and is preferably in the range of 80 to 130 ° C. When the glass transition temperature (Tg) is less than 80 ° C., the heat resistant storage stability is deteriorated, and blocking easily occurs at the temperature inside the developing device. Cannot be obtained. The glass transition temperature (Tg) of the crystalline polyester resin is the endothermic peak temperature at the time of 2nd temperature increase by DSC.

The following are used as the pigment used in the present invention.
Examples of black pigments include azine dyes such as carbon black, oil furnace black, channel black, lamp black, acetylene black, and aniline black, metal salt azo dyes, metal oxides, and composite metal oxides.
Examples of yellow pigments include cadmium yellow, mineral fast yellow, nickel titanium yellow, navel yellow, naphthol yellow S, Hansa yellow G, Hansa yellow 10G, benzidine yellow GR, quinoline yellow lake, permanent yellow NCG, and tartrazine lake. .
Examples of the orange pigment include molybdenum orange, permanent orange GTR, pyrazolone orange, Vulcan orange, indanthrene brilliant orange RK, benzidine orange G, and indanthrene brilliant orange GK.
Examples of red pigments include Bengala, Cadmium Red, Permanent Red 4R, Resol Red, Pyrazolone Red, Watching Red Calcium Salt, Lake Red D, Brilliant Carmine 6B, Eosin Lake, Rhodamine Lake B, Alizarin Lake, Brilliant Carmine 3B.
Examples of purple pigments include fast violet B and methyl violet lake.
Examples of blue pigments include cobalt blue, alkali blue, Victoria blue lake, phthalocyanine blue, metal-free phthalocyanine blue, phthalocyanine blue partially chlorinated, first sky blue, and indanthrene blue BC.
Examples of green pigments include chrome green, chromium oxide, pigment green B, and malachite green lake.
These can use 1 type (s) or 2 or more types.

Moreover, in this invention, the metal oxide which consists of Fe oxide and Ti oxide is used as a black pigment. The metal oxide has a spinel structure and basically has the following composition.
(AO) · Fe ₂ O ₃ (A: Ti, Fe)
However, in reality, the reaction is inadequate, and Ti oxides, Fe oxides, etc. often exist in the form of segregation at the grain boundaries.

In the case of a metal oxide composed of Fe oxide and Ti oxide, it is demagnetized by increasing the amount of FeO or TiO ₂ and used as a black pigment.
_{(AO) x · (Fe 2} O 3) 2-x (A: Ti, Fe)
In the above formula, it is necessary to satisfy the condition of 1 ≦ X <2.
The manufacturing method was as follows.

Ti oxide and Fe oxide are weighed and mixed using a ball mill. Next, it was calcined at 600 to 1000 ° C. for 2 to 5 hours with an electric furnace or the like, and the calcined product was put into a ball mill and pulverized. The obtained powder was pressure-molded with a powder press to form a plate, and the molded product was fired at 1100 to 1300 ° C. for 2 to 5 hours in an electric furnace or the like. This fired product was cut with a cutter, ground and pulverized, and classified into a predetermined particle size by a classifier to obtain metal oxide particles composed of Ti oxide and Fe oxide.
The average particle diameter of the metal oxide particles made of Ti oxide and Fe oxide is 0.01 to 0.2 μm. When the average particle diameter of the metal oxide particles composed of Ti oxide and Fe oxide is smaller than 0.01 μm, it is not suitable for aggregation and the like, and when it is larger than 0.2 μm, the coloring power decreases. Not suitable.

  In color toners, uniform dispersion of good pigments is essential, and instead of putting the pigments directly into a large amount of resin, a master batch in which the pigments are once dispersed at a high concentration is prepared and diluted. The method of throwing in the form is used. In this case, a solvent is generally used to assist dispersibility. However, there is a problem of environment and the like, and in the present invention, water is used for dispersion. When water is used, temperature control is important so that residual moisture in the masterbatch does not become a problem.

  In the toner of the present invention, a charge control agent is blended (internally added) inside the toner particles. However, it may be used by mixing (external addition) with toner particles. When adhering or fixing to the surface, it is necessary to use a charge control agent having an average particle size of 20 to 200 nm. The charge control agent enables optimal charge amount control according to the development system.

  For controlling the toner to be positively charged, nigrosine and quaternary ammonium salts, triphenylmethane dyes, imidazole metal complexes and salts can be used alone or in combination of two or more. Further, salicylic acid metal complexes, salts, organic boron salts, calixarene compounds, and the like are used for controlling the toner to be negatively charged.

  Further, a release agent can be internally added to the toner in the present invention to prevent offset at the time of fixing. Release agents include natural waxes such as candelilla wax, carnauba wax, rice wax, montan wax and derivatives thereof, paraffin wax and derivatives thereof, polyolefin wax and derivatives thereof, sazol wax, low molecular weight polyethylene, and low molecular weight polypropylene. And alkyl phosphate esters. The melting point of these release agents is preferably 65 to 90 ° C. When the temperature is lower than this range, blocking during storage of the toner tends to occur, and when the temperature is higher than this range, an offset is likely to occur in a region where the fixing roller temperature is low.

  An additive may be added for the purpose of improving the dispersibility of a release agent or the like. As additives, styrene acrylic resin, polyethylene resin, polystyrene resin, epoxy resin, polyester resin, polyamide resin, styrene methacrylate resin, polyurethane resin, vinyl resin, polyolefin resin, styrene butadiene resin, phenol resin, butyral resin, terpene resin, There are polyol resins and the like, and two or more of these resins may be mixed.

  Further, a grinding aid may be included in the toner in order to improve grindability. Examples of the material include a resin containing a polymer of at least one monomer selected from the group consisting of vinyltoluene, α-methylstyrene, and isopropenyltoluene. This polymer may be a homopolymer of vinyltoluene, α-methylstyrene or isopropenyltoluene, or a copolymer of these monomers. These polymers are preferably not copolymerized with a monomer other than styrene, but may be copolymerized with a monomer other than styrene as long as the object of the present invention is not impaired.

  The content of styrene is 50 mol% or less, preferably 40 to 20 mol%, as a proportion of styrene in all monomers constituting the copolymer. Since these resins are fragile, when used in combination with crystalline polyester, it is possible to improve insufficient pulverization due to the crystallinity of the crystalline polyester.

Examples of the method for producing the toner according to the present invention include a pulverization method and a polymerization method (suspension polymerization, emulsion polymerization dispersion polymerization, emulsion aggregation, emulsion association, etc.), but are not limited to these production methods.
As an example of the pulverization method, first, the above-mentioned resin, pigment or dye as a colorant, charge control agent, release agent, other additives, etc. are sufficiently mixed by a mixer such as a Henschel mixer, and then batch type. The constituent materials are well kneaded using a two-roll, Banbury mixer, continuous twin-screw extruder, continuous single-screw kneader, or the like, and cut after rolling and cooling. After that, the toner kneaded material after cutting is crushed, coarsely pulverized using a hammer mill or the like, and further pulverized by a fine pulverizer or mechanical pulverizer using a jet stream, Classification to a predetermined particle size by a classifier using the Coanda effect. Thereafter, an additive composed of inorganic particles or the like is adhered or fixed to the particle surface by a mixer. The dispersibility of the toner powder after the kneading and rolling cooling step is evaluated using this evaluation method. In this case, the sample is directly attached to the sample holder of the evaluation apparatus shown in FIG. The scan angle 2θ is measured while changing in the range of 10 deg to 40 deg. The number of measurements is two, and the average value is used for evaluation. Further, it is passed through a sieve of 250 mesh or more to remove coarse particles and aggregated particles, and the toner of the present invention is obtained. The dispersibility of the toner powder after the classification step may be evaluated using this evaluation method.

  In the X-ray diffraction pattern, the peak integrated intensity in the range of 2θ (θ: Bragg angle) = 21.5 ± 0.5 deg has a correlation with the dispersion state of the toner powder made of resin, pigment, etc. By evaluating the change in strength, the change in the dispersion state of the toner powder can be examined. In other words, when crystallized PES or the like is finely and uniformly dispersed in the toner powder, the Bragg reflection intensity decreases because the individual fine particles are randomly oriented, and the pigment in the toner powder When crystallized PES (polyester) or the like is coarsely dispersed in a large cluster state, a large Bragg reflection intensity due to regular orientation from the cluster can be obtained.

The characteristics of the evaluation method using X-ray diffraction are as follows, and it is possible to perform non-destructive, quick evaluation and easy measurement, so that measurement without individual differences can be performed.
(1) Non-destructive analysis is possible.
(2) Non-contact analysis is possible.
(3) The sample can be measured as it is.
Therefore, online measurement is also possible, and it can be installed between each process in the manufacturing process to evaluate the quality during the process. For example, after passing through the mixing process as shown in FIG. 3, a sample extraction / measurement zone is provided in the middle of transporting the mixed sample to the next process, and the shutter is opened and closed at a certain timing to allow a certain amount of sample to be measured. Transport to. The sample is mounted on the sample holder inside the sample chamber of the measurement unit, the toner sample is irradiated with X-rays, the reflected light is detected, and the peak integrated intensity is in the range of 2θ = 21.5 ± 0.5 deg. The ratio Ip / I is measured. When the measurement is completed, the sample is returned to the original sample by another route. As a result of the evaluation, if the numerical value is out of the predetermined setting range, the sample is not sent to the pulverization step but is sent to the toner reprocessing step. It is also possible to independently use a toner evaluation apparatus having these functions as an evaluation apparatus in the development stage.

  In the case of toner, as shown in FIG. 4, several diffraction peaks appear in the range of scan angle 2θ = 10 deg to 50 deg. These diffraction peaks are intrinsic to the material constituting the toner (particularly, the material having a crystal structure), and the change in the integrated intensity of the diffraction peak at the diffraction peak position (2θ) is examined. The diffraction angle 2θ of the crystalline polyester composing the toner exists in the vicinity of 21-22 deg and in the vicinity of 23-24 deg. Either diffraction peak may be used, but evaluation was performed using a diffraction peak in the vicinity of 21 to 22 deg that does not overlap with the peaks of other substances. However, any diffraction peak may be used for the evaluation, and the entire diffraction pattern may be used.

  The dispersion state of the toner powder is closely related to the fluidity of the powder. When the dispersion of the toner powder is good, the crystalline PES and the release agent that impede the fluidity are fine. Since it exists in the toner particles, it does not exist greatly on the surface of the toner particles, and each powder particle is easy to move, so that the fluidity is improved. That is, since the toner transportability is improved, the reproducibility in a fine developing portion is improved, and high image quality can be realized. On the other hand, when the dispersibility of the toner powder is poor, crystalline PES and a release agent that impede fluidity often exist as part of a large lump on the toner particle surface, and each powder Since the body particles are difficult to move, the fluidity is deteriorated. As a result, the transportability of the toner in the developing unit is deteriorated, and the image quality is deteriorated. As described above, in the evaluation method of the present invention, dispersibility can be evaluated in the following relationship.

When the dispersibility is good → In the X-ray diffraction pattern of the toner powder, the integrated intensity I including the peak in the range of 2θ = 21.5 ± 0.5 deg and the amorphous part (back part) The integral intensity ratio Ip / I of the integral intensity Ip only at the peak portion becomes small.
When the dispersibility is poor → In the X-ray diffraction pattern of the toner powder, the integrated intensity I including the peak in the range of 2θ = 21.5 ± 0.5 deg and the amorphous part (back part) The integrated intensity ratio Ip / I of the integrated intensity Ip only in the peak portion is increased.

  The dispersibility of the toner powder is almost determined by the kneading process in the toner preparation process. In other words, depending on the state in which the pigment, the charge control agent, etc. are dispersed in the resin, the fluidity and charging characteristics of the toner particles that can be produced in the subsequent steps vary greatly.

  The dispersion state of the toner varies depending on the kneading conditions in the kneading step (preparation amount, rotation speed, temperature, kneading time, etc.). Therefore, kneading conditions play an important role in dispersibility, and evaluation of dispersibility after the kneading step is important. Conventionally, evaluation of dispersibility could not be performed with high accuracy, and thus kneading conditions could not be optimized sufficiently. However, by using the present invention, kneading conditions can be optimized accurately.

As a result of evaluating the dispersibility of the toner by this method using X-ray diffraction and investigating the relationship with dot reproducibility, the toner having good dot reproducibility showed the following X-ray diffraction pattern.
(1) The integrated intensity ratio Ip / I of the integrated intensity Ip including the peak in the range of 2θ = 21.5 ± 0.5 deg and the amorphous part (back part) and the integrated intensity Ip of only the peak part. Is 0.05-0.20.
The evaluation may be performed using a diffraction peak near 2θ = 23 to 24 deg, or the entire diffraction pattern may be used.

  In order to realize high image quality, the average circularity of the toner needs to be 0.9 to 0.99. The shape of the toner particles also greatly affects the fluidity of the toner, and those close to a sphere having an average circularity in the range of 0.9 to 0.99 have excellent toner fluidity and can realize high image quality.

This evaluation method can also be used to evaluate the dispersibility of particles produced by other polymerization methods.
For example, in the toner of the present invention, an oily dispersion liquid in which a polyester-based prepolymer containing at least an isocyanate group is dissolved, a pigment-based colorant is dispersed, and a release agent is dissolved or dispersed in an organic solvent is dissolved in an aqueous medium. A urea-modified polyester resin having a urea group by dispersing in the presence of inorganic fine particles and / or fine polymer particles and reacting the prepolymer with a polyamine and / or a monoamine having an active hydrogen-containing group in the dispersion. And a liquid medium contained in the dispersion containing the urea-modified polyester resin is removed.
In the urea-modified polyester resin, the Tg is 40 to 65 ° C, preferably 45 to 60 ° C. The number average molecular weight Mn is 2500 to 50000, preferably 2500 to 30000. The weight average molecular weight Mw is 10,000 to 500,000, preferably 30,000 to 100,000.

  This toner contains, as a binder resin, a urea-modified polyester resin having a urea bond that has been increased in molecular weight by the reaction between the prepolymer and the amine. The colorant is highly dispersed in the binder resin.

The obtained toner powder after drying is air-classified, and an additive composed of inorganic fine particles or the like is adhered or fixed to the particle surface by a mixer under the optimum mixing conditions. Alternatively, the charge control agent may be applied to the surface of the toner powder after drying and fixedly injected. Further, thereafter, an additive made from inorganic fine particles or the like may be adhered or fixed to the particle surface. By placing the charge control agent on the surface, the charge amount of the toner can be easily controlled.
Specific means for mixing and fixing and injecting are as follows: a method of applying an impact force to the powder mixture with blades rotating at high speed; For example, there is a method of causing the particles to collide with an appropriate collision plate. 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.
Also in the case of these methods, for inspection after granulation, inspection after treatment with charge control agent, inspection after mixing process of additive, inspection after air sieving process after mixing process, inspection before filling, etc. Applicable.

  Further, when used as a two-component developer, a two-component developer is obtained by mixing with a magnetic carrier described later at a predetermined mixing ratio.

  This toner is used as a one-component developer used in a contact or non-contact development system. As the contact or non-contact development method, various known methods are used. For example, there are a contact development method using an aluminum sleeve, a contact development method using a conductive rubber belt, and a non-contact development method using a development sleeve in which a conductive resin layer containing carbon black or the like is formed on the surface of an aluminum base tube. . In addition, when an AC bias voltage component is applied during development using the present toner, development efficiency is improved and image characteristics are improved.

Further, in the one-component development method, the present toner is used in a development method in which a roller-shaped blade for uniformizing the toner layer and a supply roller for supplying toner are provided at the outlet of the toner supply unit. To do. In the case of such a system, not only filming on the photoconductor but also filming on the doctor roller and the supply roller occurs. For this reason, the toner layer cannot be formed uniformly, the toner charge becomes non-uniform, and the toner charge amount becomes small. For this reason, poor development occurs.
However, when the toner of the present invention is used, filming on the doctor roller and the supply roller does not occur, stable development is performed, and the system has excellent durability characteristics (see FIG. 5).

Since the present toner is excellent in fluidity, it can be stored in a cartridge container and is suitable for an apparatus configured to convey toner from the cartridge container to the developing unit.
Examples of the cartridge container include a toner cartridge that fills toner, and a process cartridge that includes at least a photosensitive member and a developing unit, and that fills a toner storage portion of the developing unit. An image is formed by attaching the cartridge to the image forming apparatus.

  Further, when the magnetic toner is used, magnetic particles may be internally added to the toner particles. Examples of the magnetic material include ferromagnetic materials such as ferrite, magnetite, iron, nickel, cobalt, and alloys thereof. The average particle size of the magnetic material is preferably 0.1 to 1 μm. The content of the magnetic material is preferably 10 to 70 parts by weight with respect to 100 parts by weight of the toner.

  As the carrier used in the two-component developer, known ones can be used. For example, magnetic particles such as iron powder, ferrite powder, nickel powder, and magnetite powder, or the surface of these magnetic particles are made of fluorine resin or vinyl resin. And those treated with a silicone-based resin or the like, or magnetic particle-dispersed resin particles in which magnetic particles are dispersed in the resin. The average particle size of these magnetic carriers is preferably 20 to 70 μm.

As described above, the two-component developer of the present invention can be used by adding inorganic fine powder to the toner as a fluidity improver. The average particle size of the inorganic fine powder is preferably 20 to 200 nm. When the average particle size is less than 20 nm, it becomes difficult to control the treatment, and when it exceeds 200 nm, the fluidity is deteriorated.
As the inorganic fine powder of the present invention, Si, Ti, Al, Mg, Ca, Sr, Ba, In, Ga, Ni, Mn, W, Fe, Co, Zn, Cr, Mo, Cu, Ag, V, Zr, etc. And oxides and composite oxides. Of these, fine particles of silicon dioxide (silica), titanium dioxide (titania), and alumina are preferably used. Furthermore, it is effective to perform a surface modification treatment with a hydrophobizing agent or the like. Typical examples of the hydrophobizing agent include the following.

Dimethyldichlorosilane, trimethylchlorosilane, methyltrichlorosilane, allyldimethyldichlorosilane, allylphenyldichlorosilane, benzyldimethylchlorosilane, bromomethyldimethylchlorosilane, α-chloroethyltrichlorosilane, p-chloroethyltrichlorosilane, Chloromethyldimethylchlorosilane, chloromethyltrichlorosilane, hexaphenyldisilazane, hexatolyldisilazane, etc.
The inorganic fine powder is preferably used in an amount of 0.1 to 2% by weight based on the toner. If it is less than 0.1% by weight, the effect of improving toner aggregation is poor, and if it exceeds 2% by weight, problems such as toner scattering between fine wires, contamination in the machine, scratches and abrasion of the photoreceptor tend to occur. is there.

  Further, the developer of the present invention may further contain other additives, for example, a lubricant powder such as Teflon (registered trademark) powder, zinc stearate powder, and polyvinylidene fluoride powder; Abrasives such as cerium powder, silicon carbide powder, and strontium titanate powder; or a conductivity-imparting agent such as carbon black powder, zinc oxide powder, and tin oxide powder can be used in small amounts as a developability improver.

Hereinafter, although an Example is described, this does not limit this invention at all. In this example, toners with different compositions and kneading conditions were prepared and evaluated using this evaluation method for toner dispersibility (evaluation conditions are shown below), and the roughness of the image directly related to dot reproducibility. As evaluated. The running characteristics were evaluated by the toner transportability of the developing unit.
・ X-ray source: CuKα ray ・ Tube voltage: 40 kV
・ Tube current: 40 mA
Scan angle 2θ: 10-50deg
Scan speed: 2 deg / min
In addition, all the parts in the following mixing | blending are a weight part.

Example 1
Resin Polyester resin 85 parts
15 parts of crystalline polyester resin
(Tg = 110 ° C.)
Pigment (Ti-O) .Fe ₂ O ₃ 30 parts Charge control agent Salicylic acid zinc salt 5 parts Mold release agent Low molecular weight polyethylene 5 parts After thoroughly mixing the above raw materials with a mixer, a twin screw extruder under the following conditions Melt kneaded.
Kneading temperature: 110 ° C
Kneading rotation speed: 80rpm
Thereafter, the kneaded product was cooled and rolled, coarsely pulverized with a cutter mill, pulverized with a fine pulverizer using a jet stream, and then classified into a particle size distribution with an average particle size of 6.5 μm using a swirling air classifier. Further, an additive was mixed with 100 parts of the base colored particles under the following mixing conditions to prepare a toner.
Additives Silica fine powder 1.2 parts
Titanium oxide fine powder 0.3 part Mixing rotation speed 800rpm
Mixing time 120sec
Mixer Supermixer X-ray diffraction measurement of the kneaded product after rolling and cooling of this toner is performed, and the entire integration including the peak and amorphous part (back part) in the range of 2θ = 21.5 ± 0.5 deg. As a result of obtaining the values of the intensity I, the integrated intensity Ip of only the peak portion, and the integrated intensity ratio Ip / I, Table 1 was obtained. The obtained toner was set in a copying machine in which the latent image carrier is an OPC drum photoreceptor and the cleaning method is blade cleaning, and image evaluation and running experiments were performed. The results are shown in Table 1.

Example 2
The raw materials similar to those in Example 1 were sufficiently mixed with a mixer, and then melt-kneaded with a twin screw extruder under the following conditions.
Kneading temperature: 110 ° C
Kneading rotation speed: 120rpm
Thereafter, the kneaded product was cooled and rolled, coarsely pulverized with a cutter mill, pulverized with a fine pulverizer using a jet stream, and then classified into a particle size distribution with an average particle size of 6.5 μm using a swirling air classifier. Further, an additive was mixed with 100 parts of the base colored particles under the following mixing conditions to prepare a toner.
Additives Silica fine powder 1.2 parts
Titanium oxide fine powder 0.3 part Mixing rotation speed 800rpm
Mixing time 120sec
Mixer Supermixer X-ray diffraction measurement of the kneaded product after rolling and cooling of this toner is performed, and the entire integration including the peak and amorphous part (back part) in the range of 2θ = 21.5 ± 0.5 deg. As a result of obtaining the values of the intensity I, the integrated intensity Ip of only the peak portion, and the integrated intensity ratio Ip / I, Table 1 was obtained. The obtained toner was set in a copying machine in which the latent image carrier is an OPC drum photoreceptor and the cleaning method is blade cleaning, and image evaluation and running experiments were performed. The results are shown in Table 1.

Example 3
The raw materials similar to those in Example 1 were sufficiently mixed with a mixer, and then melt-kneaded with a twin screw extruder under the following conditions.
Kneading temperature: 110 ° C
Kneading rotation speed: 160rpm
Thereafter, the kneaded product was cooled and rolled, coarsely pulverized with a cutter mill, pulverized with a fine pulverizer using a jet stream, and then classified into a particle size distribution with an average particle size of 6.5 μm using a swirling air classifier. Further, an additive was mixed with 100 parts of the base colored particles under the following mixing conditions to prepare a toner.
Additives Silica fine powder 1.2 parts
Titanium oxide fine powder 0.3 part Mixing rotation speed 800rpm
Mixing time 120sec
Mixer Supermixer X-ray diffraction measurement of the kneaded product after rolling and cooling of this toner is performed, and the entire integration including the peak and amorphous part (back part) in the range of 2θ = 21.5 ± 0.5 deg. As a result of obtaining the values of the intensity I, the integrated intensity Ip of only the peak portion, and the integrated intensity ratio Ip / I, Table 1 was obtained. The obtained toner was set in a copying machine in which the latent image carrier is an OPC drum photoreceptor and the cleaning method is blade cleaning, and image evaluation and running experiments were performed. The results are shown in Table 1.

Example 4
The raw materials similar to those in Example 1 were sufficiently mixed with a mixer, and then melt-kneaded with a twin screw extruder under the following conditions.
Kneading temperature: 70 ° C
Kneading rotation speed: 80rpm
Thereafter, the kneaded product was cooled and rolled, coarsely pulverized with a cutter mill, pulverized with a fine pulverizer using a jet stream, and then classified into a particle size distribution with an average particle size of 6.5 μm using a swirling air classifier. Further, an additive was mixed with 100 parts of the base colored particles under the following mixing conditions to prepare a toner.
Additives Silica fine powder 1.2 parts
Titanium oxide fine powder 0.3 part Mixing rotation speed 800rpm
Mixing time 120sec
Mixer Supermixer X-ray diffraction measurement of the kneaded product after rolling and cooling of this toner is performed, and the entire integration including the peak and amorphous part (back part) in the range of 2θ = 21.5 ± 0.5 deg. As a result of obtaining the values of the intensity I, the integrated intensity Ip of only the peak portion, and the integrated intensity ratio Ip / I, Table 1 was obtained. The obtained toner was set in a copying machine in which the latent image carrier is an OPC drum photoreceptor and the cleaning method is blade cleaning, and image evaluation and running experiments were performed. The results are shown in Table 1.

Example 5
The raw materials similar to those in Example 1 were sufficiently mixed with a mixer, and then melt-kneaded with a twin screw extruder under the following conditions.
Kneading temperature: 150 ° C
Kneading rotation speed: 80rpm
Thereafter, the kneaded product was cooled and rolled, coarsely pulverized with a cutter mill, pulverized with a fine pulverizer using a jet stream, and then classified into a particle size distribution with an average particle size of 6.5 μm using a swirling air classifier. Further, an additive was mixed with 100 parts of the base colored particles under the following mixing conditions to prepare a toner.
Additives Silica fine powder 1.2 parts
Titanium oxide fine powder 0.3 part Mixing rotation speed 800rpm
Mixing time 120sec
Mixer Supermixer X-ray diffraction measurement of the kneaded product after rolling and cooling of this toner is performed, and the entire integration including the peak and amorphous part (back part) in the range of 2θ = 21.5 ± 0.5 deg. As a result of obtaining the values of the intensity I, the integrated intensity Ip of only the peak portion, and the integrated intensity ratio Ip / I, Table 1 was obtained. The obtained toner was set in a copying machine in which the latent image carrier is an OPC drum photoreceptor and the cleaning method is blade cleaning, and image evaluation and running experiments were performed. The results are shown in Table 1.

Example 6
Resin Polyester resin 80 parts
20 parts of crystalline polyester resin
(Tg = 110 ° C.)
Pigment (Ti-O) .Fe ₂ O ₃ 30 parts Charge control agent Salicylic acid zinc salt 5 parts Mold release agent Low molecular weight polyethylene 5 parts After thoroughly mixing the above raw materials with a mixer, a twin screw extruder under the following conditions Melt kneaded.
Kneading temperature: 110 ° C
Kneading rotation speed: 80rpm
Thereafter, the kneaded product was cooled and rolled, coarsely pulverized with a cutter mill, pulverized with a fine pulverizer using a jet stream, and then classified into a particle size distribution with an average particle size of 6.5 μm using a swirling air classifier. Further, an additive was mixed with 100 parts of the base colored particles under the following mixing conditions to prepare a toner.
Additives Silica fine powder 1.2 parts
Titanium oxide fine powder 0.3 part Mixing rotation speed 800rpm
Mixing time 120sec
Mixer Supermixer X-ray diffraction measurement of the kneaded product after rolling and cooling of this toner is performed, and the entire integration including the peak and amorphous part (back part) in the range of 2θ = 21.5 ± 0.5 deg. As a result of obtaining the values of the intensity I, the integrated intensity Ip of only the peak portion, and the integrated intensity ratio Ip / I, Table 1 was obtained.
The toner obtained by the above production method and the carrier were mixed at a ratio of 2.5 parts with respect to 97.5 parts of the carrier to prepare a two-component developer. The obtained developer was set in a copying machine in which the latent image carrier is an OPC drum photoreceptor and the cleaning method is blade cleaning, and image evaluation and running experiments were performed. The results are shown in Table 1.

Example 7
The same raw materials as in Example 6 were sufficiently mixed with a mixer, and then melt kneaded with a twin screw extruder under the following conditions.
Kneading temperature: 110 ° C
Kneading rotation speed: 120rpm
Thereafter, the kneaded product was cooled and rolled, coarsely pulverized with a cutter mill, pulverized with a fine pulverizer using a jet stream, and then classified into a particle size distribution with an average particle size of 6.5 μm using a swirling air classifier. Further, an additive was mixed with 100 parts of the base colored particles under the following mixing conditions to prepare a toner.
Additives Silica fine powder 1.2 parts
Titanium oxide fine powder 0.3 part Mixing rotation speed 800rpm
Mixing time 120sec
Mixer Supermixer X-ray diffraction measurement of the kneaded product after rolling and cooling of this toner is performed, and the entire integration including the peak and amorphous part (back part) in the range of 2θ = 21.5 ± 0.5 deg. As a result of obtaining the values of the intensity I, the integrated intensity Ip of only the peak portion, and the integrated intensity ratio Ip / I, Table 1 was obtained.
The toner obtained by the above production method and the carrier were mixed at a ratio of 2.5 parts with respect to 97.5 parts of the carrier to prepare a two-component developer. The obtained developer was set in a copying machine in which the latent image carrier is an OPC drum photoreceptor and the cleaning method is blade cleaning, and image evaluation and running experiments were performed. The results are shown in Table 1.

Example 8
The same raw materials as in Example 6 were sufficiently mixed with a mixer, and then melt kneaded with a twin screw extruder under the following conditions.
Kneading temperature: 110 ° C
Kneading rotation speed: 160rpm
Thereafter, the kneaded product was cooled and rolled, coarsely pulverized with a cutter mill, pulverized with a fine pulverizer using a jet stream, and then classified into a particle size distribution with an average particle size of 6.5 μm using a swirling air classifier. Further, an additive was mixed with 100 parts of the base colored particles under the following mixing conditions to prepare a toner.
Additives Silica fine powder 1.2 parts
Titanium oxide fine powder 0.3 part Mixing rotation speed 800rpm
Mixing time 120sec
Mixer Supermixer X-ray diffraction measurement of the kneaded product after rolling and cooling of this toner is performed, and the entire integration including the peak and amorphous part (back part) in the range of 2θ = 21.5 ± 0.5 deg. As a result of obtaining the values of the intensity I, the integrated intensity Ip of only the peak portion, and the integrated intensity ratio Ip / I, Table 1 was obtained.
The toner obtained by the above production method and the carrier were mixed at a ratio of 2.5 parts with respect to 97.5 parts of the carrier to prepare a two-component developer. The obtained developer was set in a copying machine in which the latent image carrier is an OPC drum photoreceptor and the cleaning method is blade cleaning, and image evaluation and running experiments were performed. The results are shown in Table 1.

Example 9
The same raw materials as in Example 6 were sufficiently mixed with a mixer, and then melt kneaded with a twin screw extruder under the following conditions.
Kneading temperature: 70 ° C
Kneading rotation speed: 80rpm
Thereafter, the kneaded product was cooled and rolled, coarsely pulverized with a cutter mill, pulverized with a fine pulverizer using a jet stream, and then classified into a particle size distribution with an average particle size of 6.5 μm using a swirling air classifier. Further, an additive was mixed with 100 parts of the base colored particles under the following mixing conditions to prepare a toner.
Additives Silica fine powder 1.2 parts
Titanium oxide fine powder 0.3 part Mixing rotation speed 800rpm
Mixing time 120sec
Mixer Supermixer X-ray diffraction measurement of the kneaded product after rolling and cooling of this toner is performed, and the entire integration including the peak and amorphous part (back part) in the range of 2θ = 21.5 ± 0.5 deg. As a result of obtaining the values of the intensity I, the integrated intensity Ip of only the peak portion, and the integrated intensity ratio Ip / I, Table 1 was obtained.
The toner obtained by the above production method and the carrier were mixed at a ratio of 2.5 parts with respect to 97.5 parts of the carrier to prepare a two-component developer. The obtained developer was set in a copying machine in which the latent image carrier is an OPC drum photoreceptor and the cleaning method is blade cleaning, and image evaluation and running experiments were performed. The results are shown in Table 1.

Example 10
The same raw materials as in Example 6 were sufficiently mixed with a mixer, and then melt kneaded with a twin screw extruder under the following conditions.
Kneading temperature: 150 ° C
Kneading rotation speed: 80rpm
Thereafter, the kneaded product was cooled and rolled, coarsely pulverized with a cutter mill, pulverized with a fine pulverizer using a jet stream, and then classified into a particle size distribution with an average particle size of 6.5 μm using a swirling air classifier. Further, an additive was mixed with 100 parts of the base colored particles under the following mixing conditions to prepare a toner.
Additives Silica fine powder 1.2 parts
Titanium oxide fine powder 0.3 part Mixing rotation speed 800rpm
Mixing time 120sec
Mixer Supermixer X-ray diffraction measurement of the kneaded product after rolling and cooling of this toner is performed, and the entire integration including the peak and amorphous part (back part) in the range of 2θ = 21.5 ± 0.5 deg. As a result of obtaining the values of the intensity I, the integrated intensity Ip of only the peak portion, and the integrated intensity ratio Ip / I, Table 1 was obtained.
The toner obtained by the above production method and the carrier were mixed at a ratio of 2.5 parts with respect to 97.5 parts of the carrier to prepare a two-component developer. The obtained developer was set in a copying machine in which the latent image carrier is an OPC drum photoreceptor and the cleaning method is blade cleaning, and image evaluation and running experiments were performed. The results are shown in Table 1.
The above measurement results are shown in Table 1.

  As can be seen from the results in Table 1, between the peak integrated intensity ratio Ip / I of the X-ray diffraction peak in the range of 2θ = 21.5 ± 0.5 deg of the toner powder and dot reproducibility and running characteristics. When the peak integrated intensity ratio Ip / I is large, it can be said that both dot reproducibility and running characteristics are deteriorated.

In addition, from the results shown in FIG. 2 showing the data in Table 1, the following conditions must be satisfied in order to obtain a toner with good dispersibility necessary for obtaining high image quality with good dot reproducibility. is required.
(1) The integrated intensity ratio Ip / I of the total integrated intensity I including the peak and the amorphous part (back part) in the range of 2θ = 21.5 ± 0.5 deg and the integrated intensity Ip of only the peak part. Is 0.05-0.20.

  When the peak integrated intensity ratio Ip / I of the X-ray diffraction peak in the range of 2θ = 21.5 ± 0.5 deg is less than 0.05, the charging characteristics other than the dispersibility of the toner are deteriorated and the image quality is deteriorated. If it exceeds 0.20, the dispersibility is lowered, the toner fluidity is deteriorated, and the image quality is lowered.

It is the figure which showed the structure outline | summary of the evaluation apparatus of this invention. It is the figure which showed the relationship between the value of the integrated intensity ratio Ip / I of the peak in the range of 2 (theta) = 21.5 +/- 0.5deg of Examples 1-10, and dot reproducibility. It is the figure which showed an example of the toner manufacturing apparatus using an X-ray-diffraction measuring apparatus. FIG. 4 is a diagram illustrating an example of an X-ray diffraction pattern of a toner powder product. It is a figure showing an example of the development process using the toner of the present invention.

Claims (2)

In a powder comprising at least a resin, a pigment, and a charge control agent, and at least one of the resins is a crystalline polyester represented by the following general formula (1), an X-ray (wavelength 1.54 mm) is applied to the powder. The X-ray diffraction pattern is measured by irradiating (CuKα ray), and the total integrated intensity I including the peak and the amorphous portion in the range of 2θ (θ: Bragg angle) = 21.5 ± 0.5 deg. The electrostatic charge is characterized in that the integral intensity Ip of only the peak portion is measured, and the dispersibility of the powder is evaluated based on whether the integral intensity ratio Ip / I is 0.05 to 0.20. Development toner evaluation method.

A method for producing a toner for electrostatic charge development, wherein the toner is produced by using the powder dispersibility evaluation method according to claim 1, wherein the powder dispersibility is evaluated by a pulverization step in toner production. A method for producing a toner for developing electrostatic charge, which is performed in the subsequent steps .

Images