JP4849551B2 - Yellow toner and magenta toner - Google Patents

Description

  The present invention relates to a yellow toner and a magenta toner used for developing a latent image formed in an electrophotographic method, an electrostatic recording method, an electrostatic printing method, and the like, a method for producing the toner, and a color using the toner. The present invention relates to an image forming method.

  Typical properties required for the toner include low-temperature fixability and storage stability. Therefore, as an attempt for low-temperature fixability, many toners containing crystalline polyester and amorphous polyester as binder resins have been studied (see Patent Document 1).

  Further, from the viewpoint of improving the storage stability, a toner added with a crystal nucleating agent is disclosed. For example, in Patent Document 2, amide compounds and quinacridone compounds are used as crystal nucleating agents, and in Patent Document 3, phosphoric acid compounds and montanic acid compounds are used as crystal nucleating agents.

On the other hand, the demand for full-color toner is increasing with the recent improvement in image quality. In an electrophotographic system, printing is performed with toners of four colors, yellow toner, magenta toner, cyan toner, and black toner, so that the toner performance between the colors is required to be the same for good color reproduction. .
JP-A-1-289971 JP 2006-113473 A JP 2006-84953 A

  However, when continuous printing is performed using a full-color toner using crystalline polyester, amorphous polyester and crystal nucleating agent, the charging stability of yellow toner and magenta toner is inferior, and the storage stability at high temperature is insufficient. It turned out to be.

  An object of the present invention is to provide a yellow toner and a magenta toner excellent in all of low-temperature fixability, storage stability, and charging stability, a method for producing the toner, and a color image forming method using the toner. It is in.

The present invention
[1] A yellow toner or a magenta toner containing a crystalline polyester, an amorphous polyester, a yellow colorant or a magenta colorant, and a copper complex compound, wherein the content of the copper complex compound is Yellow toner or magenta toner which is 0.05 to 1.5 parts by weight with respect to 100 parts by weight of the total amount of amorphous polyester,
[2] A method for producing a yellow toner or a magenta toner according to [1], wherein a toner raw material containing a crystalline polyester, an amorphous polyester, a yellow colorant or a magenta colorant, and a copper complex compound is used. A method for producing a yellow toner or a magenta toner comprising a step of melt-kneading at a melting point of crystalline polyester at a temperature of 5 ° C. or higher, and [3] a color image comprising a step of developing the yellow toner or magenta toner according to [1] It relates to a forming method.

  The yellow toner and magenta toner of the present invention exhibit an excellent effect of being excellent in all of low-temperature fixability, storage stability and charge stability.

  Although crystalline polyester is excellent in fixability, it has a drawback in that its preservability is insufficient. On the other hand, a toner containing crystalline polyester, amorphous polyester and a colorant and a conventional crystal nucleating agent results in poor storage stability or charge stability at high temperatures. However, the yellow toner and the magenta toner of the present invention have a great feature in that they contain a copper complex compound, thereby improving storage stability and charge stability without impairing low-temperature fixability. The effect is played. Since copper complex compounds such as copper phthalocyanine exhibit a cyan color, they have been avoided to be used in yellow toners and magenta toners that have a large influence on the hue. It has been found that storage stability and charging stability are improved without impairing the hue, and that the toner of the present invention can be used to continuously obtain images having no hue change even in continuous printing. Further, among copper complex compounds, it has been found that copper phthalocyanine, particularly CI Pigment Green 7, exhibits good storability and charging stability even in a trace amount that does not impair the hue of the toner. It was.

  The content of the copper complex compound in the yellow toner and magenta toner of the present invention is 0.05 to 1.5 parts by weight from the viewpoint of charging stability and hue with respect to 100 parts by weight of the total amount of crystalline polyester and amorphous polyester. The amount is preferably 0.08 to 1.0 part by weight, more preferably 0.08 to 0.2 part by weight, and still more preferably 0.08 to 0.1 part by weight.

  The copper complex compound is more preferably copper phthalocyanine from the viewpoint of dispersibility with respect to the binder resin, particularly polyester, and ease of color adjustment. From the viewpoint of charging stability and the hue of the toner obtained, the formula (I):

C.I. Pigment Green 7 represented by

  Copper phthalocyanine is `` Toner Cyan BG '' (Clariant, CI Pigment Blue 15: 3), `` Cyanine Blue A-293 '' (Daiichi Seika Kogyo), `` Hostapern green gnx D '' (Clariant, CI It is available as a commercial product such as CI Pigment Green 7).

  The yellow toner and magenta toner of the present invention contain at least a crystalline polyester and an amorphous polyester as a binder resin.

  In the present invention, “crystalline polyester” refers to a polyester having a crystallinity index of 0.6 to 1.5, preferably 0.8 to 1.2, and “amorphous polyester” refers to a crystallinity index of greater than 1.5 or 0.6. Polyester less than, preferably greater than 1.5. Here, the crystallinity index is a physical property that is an index of the degree of crystallization of the resin, and is determined by the ratio between the softening point and the maximum endothermic peak temperature by the differential scanning calorimeter (softening point / maximum endothermic peak temperature). Is defined. In general, a resin having a crystallinity index exceeding 1.5 is amorphous, and a resin having a crystallinity index of less than 0.6 has low crystallinity and many amorphous portions. The degree of crystallization can be adjusted by the type and ratio of the raw material monomers, production conditions (for example, reaction temperature, reaction time, cooling rate) and the like. The highest endothermic peak temperature refers to the temperature of the peak on the highest temperature side among the observed endothermic peaks. If the maximum peak temperature is within 20 ° C. from the softening point, the melting point is set, and the peak having a difference from the softening point exceeding 20 ° C. is a peak due to glass transition.

  Both the crystalline polyester and the amorphous polyester are obtained by using an alcohol component and a carboxylic acid component as raw material monomers and subjecting them to condensation polymerization.

  The alcohol component in the crystalline polyester preferably contains a monomer that promotes the crystallinity of the resin, such as an aliphatic diol having 2 to 8 carbon atoms.

  Examples of the aliphatic diol having 2 to 8 carbon atoms include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, Examples include 1,7-heptanediol, 1,8-octanediol, neopentyl glycol, 1,4-butenediol, and α, ω-linear alkanediol is particularly preferable. These may be contained alone or in admixture of two or more.

  From the viewpoint of high crystallinity, the content of the aliphatic diol having 2 to 8 carbon atoms is preferably 80 mol% or more, more preferably 85 mol% or more, and further preferably 90 mol% or more in the alcohol component. Further, when two or more kinds of aliphatic diols having 2 to 8 carbon atoms are used, one kind of the aliphatic diol in them contains 70 mol% or more, preferably 80 to 95 mol% in the alcohol component. It is desirable to occupy. Among these, 1,4-butanediol and 1,6-hexanediol are preferable, and 1,6-hexanediol is more preferable. These are contained in the alcohol component, preferably 70 mol% or more, more preferably 80 mol% or more. It is desirable that

  Examples of the alcohol component in the amorphous polyester include formula (II) such as polyoxypropylene-2,2-bis (4-hydroxyphenyl) propane and polyoxyethylene-2,2-bis (4-hydroxyphenyl) propane:

(In the formula, RO is an alkylene oxide, R is an alkylene group having 2 or 3 carbon atoms, x and y are positive numbers indicating the average number of moles added of alkylene oxide, and the sum of x and y is 1-16. (Preferably 1-8, more preferably 1.5-5)
It is preferable that the monomer which accelerates | stimulates amorphization of resin, such as aromatic diols, such as alkylene oxide adduct of bisphenol A represented by these, is contained.

  The content of the alkylene oxide adduct of bisphenol A represented by the formula (II) is preferably 50 mol% or more, more preferably 70 mol% or more, more preferably 90 mol% or more in the alcohol component from the viewpoint of chargeability. Further preferred.

  The carboxylic acid compound contained in the carboxylic acid component includes fumaric acid, adipic acid, oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, sebacic acid, azelaic acid, n- Aliphatic dicarboxylic acids having 2 to 30 carbon atoms, preferably 2 to 8 carbon atoms such as dodecyl succinic acid and n-dodecenyl succinic acid; Aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid; Dicarboxylic acid: Trivalent or higher polyvalent carboxylic acids such as trimellitic acid and pyromellitic acid, anhydrides of these acids, and alkyl (C1-3) esters of acids. Among these, aliphatic dicarboxylic acid compounds are preferable. In crystalline polyesters, from the viewpoint of crystallinity, aliphatic dicarboxylic acid compounds having 2 to 8 carbon atoms are crystalline polyesters. From the viewpoint of dispersibility, fumaric acid is more preferable.

  The content of the aliphatic dicarboxylic acid compound is preferably 70 mol% or more, more preferably 80 to 100 mol%, still more preferably 90 to 100 mol% in the carboxylic acid component.

  Note that the molar ratio of the carboxylic acid component to the alcohol component (carboxylic acid component / alcohol component) in the crystalline polyester is preferably higher in the alcohol component than the carboxylic acid component when increasing the molecular weight of the crystalline polyester. Further, from the viewpoint of easily adjusting the molecular weight of the polyester by distilling off the alcohol component during the reduced pressure reaction, 0.9 to 1 is preferable, and 0.95 to 1 is more preferable.

  In addition, a monovalent alcohol may be appropriately contained in the alcohol component, and a monovalent carboxylic acid compound may be appropriately contained in the carboxylic acid component from the viewpoint of adjusting the molecular weight.

  The polyester is obtained by polycondensing an alcohol component and a carboxylic acid component, for example, in an inert gas atmosphere, if necessary, in the presence of an esterification catalyst. The reaction temperature is preferably 120 to 230 ° C. in the production of crystalline polyester, and 180 to 250 ° C. in the production of amorphous polyester.

  In the production of crystalline polyester, all monomers are charged together to increase the strength of the resin, or divalent monomers are first reacted in order to reduce low molecular weight components. You may use methods, such as adding a monomer and making it react. Further, the reaction may be accelerated by reducing the pressure of the reaction system in the latter half of the polymerization.

  In order to obtain a higher molecular weight crystalline polyester, the molar ratio of the carboxylic acid component and the alcohol component is adjusted as described above, the reaction temperature is increased, the amount of catalyst is increased, and dehydration is performed for a long time under reduced pressure. What is necessary is just to select reaction conditions, such as performing reaction. In addition, under high power required for stirring, it is possible to produce a high-viscosity crystalline polyester having a high molecular weight. However, when producing without particularly selecting production equipment, the raw material monomer is a non-reactive low-viscosity resin. A method of reacting with a solvent is also an effective means.

  The softening point of the crystalline polyester is preferably from 70 to 140 ° C, more preferably from 80 to 130 ° C, and even more preferably from 105 to 130 ° C, from the viewpoint of low-temperature fixability.

  The melting point of the crystalline polyester is preferably 60 to 140 ° C., more preferably 70 to 130 ° C., and further preferably 80 to 120 ° C. from the viewpoint of fixability.

  The softening point of the amorphous polyester is preferably 80 to 150 ° C, more preferably 85 to 145 ° C, and still more preferably 90 to 145 ° C.

  The acid value of the amorphous polyester is preferably 1 to 50 mgKOH / g, more preferably 10 to 30 mgKOH / g. Further, the glass transition point is preferably 40 to 80 ° C, more preferably 50 to 70 ° C, from the viewpoints of pulverization and storage.

  From the viewpoint of dispersibility of the crystalline polyester, the crystalline polyester and the amorphous polyester are preferably those obtained using at least one common compound as a raw material monomer. Such a common compound is preferably a carboxylic acid component, fumaric acid and phthalic acid are more preferable, and fumaric acid is more preferable from the viewpoint of increasing the crystallinity of the crystalline polyester.

  The amorphous polyester is preferably composed of two types of amorphous polyesters having a softening point of 10 ° C. or higher, more preferably 20 to 60 ° C. from the viewpoint of achieving both low-temperature fixability and offset resistance. . The softening point of the low softening point polyester is preferably 80 to 120 ° C., more preferably 85 to 110 ° C. from the viewpoint of low-temperature fixability, and the softening point of the high softening point polyester is preferably from the viewpoint of offset resistance. Is 120 to 150 ° C, more preferably 130 to 145 ° C. The weight ratio of the high softening point polyester to the low softening point polyester (high softening point polyester / low softening point polyester) is preferably 20/80 to 80/20, and from the viewpoint of suppressing high temperature hot offset, 60/40 to 80 / 20 is preferred.

  The content of the crystalline polyester is preferably 3 to 40% by weight and more preferably 5 to 30% by weight in the yellow toner and the magenta toner from the viewpoint of low-temperature fixability and storage stability.

  The weight ratio of crystalline polyester to amorphous polyester (crystalline polyester / amorphous polyester) is preferably from 3/97 to 40/60, more preferably from 5/95 to 30/70.

  In the present invention, the polyester may be a polyester modified to such an extent that the characteristics are not substantially impaired. Examples of the modified polyester include grafting and blocking with phenol, urethane, epoxy and the like by the methods described in JP-A-11-133668, JP-A-10-239903, JP-A-8-20636, and the like. And a composite resin having two or more kinds of resin units including a polyester unit.

  In the yellow toner and magenta toner of the present invention, in addition to the crystalline polyester and the amorphous polyester, other binder resins may be appropriately contained as long as the effects of the present invention are not impaired. Examples of other binder resins include binder resins other than polyesters such as vinyl resins, epoxy resins, polycarbonates, and polyurethanes. The total content of the crystalline polyester and the amorphous polyester is not particularly limited, but is preferably 80% by weight or more and more preferably 90% by weight or more in the binder resin from the viewpoint of low-temperature fixability.

  The yellow colorant contained in the yellow toner includes CI Pigment Yellow 12, CI Pigment Yellow 13, CI Pigment Yellow 14, CI Pigment Yellow 15, CI Pigment Yellow 17, CI Pigment Yellow 74, CI Pigment Yellow 93, CI Pigment Yellow 94, CI Pigment Yellow 97, CI Pigment Yellow 138, CI Pigment Yellow 180, CI Pigment Yellow 185, and other known pigments / dyes can be used. Among these, CI Pigment Yellow 185 is preferable from the viewpoint of color reproducibility. . The content of the yellow colorant is preferably 1 to 40 parts by weight and more preferably 3 to 10 parts by weight with respect to 100 parts by weight of the binder resin.

  The weight ratio of the yellow colorant to the copper complex compound (yellow colorant / copper complex compound) is preferably 10/2 to 40 / 0.2, more preferably 10/1 to 3 / 0.05.

  The magenta colorants contained in magenta toner include CI Pigment Red 2, CI Pigment Red 3, CI Pigment Red 5, CI Pigment Red 6, CI Pigment Red 7, CI Pigment Red 15, CI Pigment Red 16, and CI Pigment Red. 48: 1, CI Pigment Red 53: 1, CI Pigment Red 57: 1, CI Pigment Red 81: 3, CI Pigment Red 122, CI Pigment Red 123, CI Pigment Red 139, CI Pigment Red 144, CI Pigment Red 149, CI Pigment Red 166, CI Pigment Red 177, CI Pigment Red 178, CI Pigment Red 184, CI Pigment Red 185, CI Pigment Red 222, CI Pigment Red 238, etc. can use known pigments and dyes. From the viewpoint of color reproducibility, CI Pigment Red 122 is preferable. . The content of the magenta colorant is preferably 1 to 40 parts by weight and more preferably 3 to 10 parts by weight with respect to 100 parts by weight of the binder resin.

  The weight ratio of the magenta colorant to the copper complex compound (magenta colorant / copper complex compound) is preferably 10/2 to 40 / 0.2, more preferably 10/1 to 3 / 0.05.

  Further, the yellow toner and the magenta toner of the present invention include a release agent, a charge control agent, a magnetic powder, a conductivity adjusting agent, an extender pigment, a reinforcing filler such as a fibrous substance, an antioxidant, an anti-aging agent, a flow Additives such as a property improving agent and a cleaning property improving agent may be appropriately contained.

  The yellow toner and magenta toner of the present invention may be obtained by any conventionally known method such as a kneading pulverization method, an emulsion phase inversion method, a polymerization method, etc. A pulverized toner obtained by a kneading pulverization method is preferable because the effect is remarkably exhibited. Further, the copper complex compound may be added as a raw material during the production of the polyester or may be added together with an additive such as a colorant during the production of the toner. From the viewpoint of dispersibility, the colorant or the like may be used during the production of the toner. It is preferable to add together with these additives. In the case of obtaining a yellow toner and a magenta toner by a kneading and pulverizing method, for example, a toner material such as a binder resin such as crystalline polyester or amorphous polyester, an additive such as a colorant, or the like is used as a sealed kneader or uniaxial or It can be manufactured by melt-kneading with a twin-screw extruder, etc., cooling, pulverizing, and classifying. In the emulsification phase inversion method, for example, an emulsion is prepared by dissolving or dispersing raw materials in an organic solvent and then adding water. And then separated and classified for production. Furthermore, a fluidity improver such as hydrophobic silica may be externally added to the surface of the yellow toner and the magenta toner as necessary.

  When the yellow toner and magenta toner of the present invention are produced by a kneading and pulverizing method, from the viewpoint of improving the dispersibility of the copper complex compound, in the melt-kneading step, crystalline polyester, amorphous polyester, yellow colorant or magenta A toner raw material containing a colorant and a copper complex compound is preferably melt-kneaded in the temperature range of the melting point (Tm) + 5 ° C., more preferably (Tm + 10) ° C. and (Tm + 30) ° C. of the crystalline polyester. It is preferable.

  In addition, toner materials such as binder resins such as crystalline polyester and amorphous polyester, and additives such as colorants can be premixed uniformly with a mixer such as a Henschel mixer before being subjected to the melt-kneading step. preferable. The addition time when the copper complex compound is added at the time of toner production is not particularly limited, but from the viewpoint of improving dispersibility, the copper complex compound is also preferably added during the preliminary mixing of the raw materials.

The volume median particle size (D ₅₀ ) of the yellow toner and magenta toner of the present invention is preferably 3 to 15 μm. In the present specification, the volume-median particle size (D ₅₀ ) means a particle size at which the cumulative volume frequency calculated by the volume fraction is 50% when calculated from the smaller particle size.

  The yellow toner and magenta toner of the present invention can be used alone as a one-component developer or mixed with a carrier and used as a two-component developer.

  Since the yellow toner and magenta toner of the present invention are excellent in charging stability and color reproducibility, the color image forming method having a step of developing the yellow toner or magenta toner of the present invention is more preferable. In addition to the yellow toner and magenta toner, a cyan toner, preferably, a cyan toner containing copper phthalocyanine as a colorant and a black toner are used for a full color image forming method.

[Softening point of resin]
Using a flow tester (Shimadzu Corporation, CFT-500D), a 1 g sample is heated at a heating rate of 6 ° C / min. While applying a load of 1.96 MPa with a plunger and extruded from a nozzle with a diameter of 1 mm and a length of 1 mm. . The amount of plunger drop of the flow tester is plotted against the temperature, and the temperature at which half of the sample flows out is taken as the softening point.

[Acid value of the resin]
Measured according to the method of JIS K0070. However, only the measurement solvent was changed from the mixed solvent of ethanol and ether specified in JIS K0070 to the mixed solvent of acetone and toluene (acetone: toluene = 1: 1 (volume ratio)).

[Maximum peak temperature and melting point of resin endotherm]
Using a differential scanning calorimeter (Seiko Denshi Kogyo Co., Ltd., DSC210), the temperature is raised to 200 ° C, and the sample cooled to 0 ° C at a temperature drop rate of 10 ° C / min is measured at a temperature rise rate of 10 ° C / min. . Among the observed endothermic peaks, the temperature of the peak on the highest temperature side is defined as the highest endothermic peak temperature. If the maximum peak temperature is within 20 ° C of the softening point, the melting point is assumed.

[Glass transition point of resin]
Using a differential scanning calorimeter (Seiko Denshi Kogyo Co., Ltd., DSC210), the temperature is raised to 200 ° C, and the sample cooled to 0 ° C at a temperature drop rate of 10 ° C / min is measured at a temperature rise rate of 10 ° C / min. . When the difference between the maximum endothermic peak temperature and the softening point is within 20 ° C, the peak extension line below the peak temperature observed at a temperature lower than the maximum endothermic peak temperature and the peak from the rising edge of the peak The temperature at the point of intersection with the tangent indicating the maximum inclination to the top of is read as the glass transition point. When the difference between the maximum endothermic peak temperature and the softening point exceeds 20 ° C, an extension of the baseline below the maximum endothermic peak temperature and a tangent line indicating the maximum slope from the peak of the peak to the peak apex The temperature at the intersection is read as the glass transition point.

[Crystallinity index]
The crystallinity index is calculated as the degree of crystallinity from the following formula using the softening point and the maximum peak temperature of endotherm measured according to the above.
Crystallinity index = softening point / endothermic peak temperature

[Volume-median particle size of toner (D ₅₀ )]
Measuring instrument: Coulter Multisizer II (Beckman Coulter, Inc.)
Aperture diameter: 50μm
Analysis software: Coulter Multisizer AccuComp version 1.19 (Beckman Coulter)
Electrolyte: Isoton II (Beckman Coulter)
Dispersion: Emulgen 109P (manufactured by Kao Corporation, polyoxyethylene lauryl ether, HLB: 13.6) is dissolved in the electrolyte so as to have a concentration of 5% by weight to obtain a dispersion.
Dispersion conditions: 10 mg of a measurement sample is added to 5 mL of the above dispersion, and dispersed for 1 minute with an ultrasonic disperser, then 25 mL of electrolyte is added, and further dispersed for 1 minute with an ultrasonic disperser. Prepare a dispersion.
Measurement conditions: By adding the sample dispersion to 100 mL of the electrolytic solution, the particle size of 30,000 particles is adjusted to a concentration that can be measured in 20 seconds, and then 30,000 particles are measured, Determine the volume median particle size (D ₅₀ ).

Production Example 1 of Crystalline Polyester
The raw material monomers shown in Table 1, 4 g of dibutyltin oxide and 1 g of tert-butylcatechol were placed in a 5-liter four-necked flask equipped with a nitrogen introduction tube, dehydration tube, stirrer and thermocouple, and at 160 ° C. for 5 hours. Then, the temperature was raised to 200 ° C. and the mixture was reacted for 1 hour, and further reacted at 8.3 kPa until a desired crystallinity index was reached to obtain a resin a.

Production Example 1 of Amorphous Polyester
Raw material monomers other than trimellitic anhydride shown in Table 1 and 4 g of dibutyltin oxide are placed in a 5-liter four-necked flask equipped with a nitrogen inlet tube, a dehydrating tube, a stirrer, and a thermocouple. After the reaction, the reaction was carried out at 8.3 kPa for 1 hour, and trimellitic anhydride shown in Table 1 was further added at 210 ° C. until the desired softening point was reached, whereby Resin A was obtained.

Production Example 2 of Amorphous Polyester
The raw material monomers shown in Table 1, 4 g of dibutyltin oxide and 1 g of tert-butylcatechol were placed in a 5-liter four-necked flask equipped with a nitrogen inlet tube, dehydration tube, stirrer and thermocouple, and were heated at 200 ° C for 8 hours. Then, the reaction was carried out at 8.3 kPa for 1 hour, and the reaction was carried out until the desired softening point was reached to obtain Resin B.

Examples 1-4 and Comparative Examples 1-7
Binder resin shown in Table 2, Compound X, yellow pigment “Paliotol Yellow D1155” (manufactured by BASF, CI Pigment Yellow 185) 5.0 parts by weight, charge control agent “LR-147” (manufactured by Nippon Carlit) 1.0 parts by weight, And 2.0 parts by weight of Carnauba Wax No. 1 (manufactured by Kato Yoko Co., Ltd.) were thoroughly mixed with a Henschel mixer, and then melted using a co-rotating twin screw extruder with a kneading part length of 1560mm, screw diameter of 42mm, and barrel inner diameter of 43mm. Kneaded. The barrel set temperature was 90 ° C. (kneading temperature 125 to 140 ° C.), the screw rotation speed was 200 r / min, the mixture supply speed was 10 kg / hour, and the average residence time was about 18 seconds.

The obtained melt-kneaded product was cooled and coarsely pulverized, and then pulverized and classified by a jet mill to obtain a powder having a volume median particle size (D ₅₀ ) of 8.0 μm.

  To the obtained powder, 0.65 parts by weight of hydrophobic silica “TS-530” (manufactured by Cabot) was added as an external additive, and mixed with a Henschel mixer to obtain a yellow toner.

Example 5
A magenta toner was obtained in the same manner as in Example 4 except that 5.0 parts by weight of a magenta pigment “Super Magenta R” (manufactured by Dainippon Ink & Chemicals, Inc., CI Pigment Red 122) was used instead of the yellow pigment.

Comparative Examples 8-9
A yellow toner was obtained in the same manner as in Example 1 except that Compound X was not used.

Comparative Example 10
A magenta toner was obtained in the same manner as in Example 5 except that Compound X was not used.

Test Example 1 [low temperature fixability]
Non-fixed with a solid image area (toner adhesion amount: 0.5mg / cm ² ) of 2cm x 12cm with standard development bias, with toner mounted on the non-magnetic one-component full-color developing device "MICROLINE 5400" (manufactured by Oki Data) I got an image. Using a fixing machine (fixing speed: 100 mm / sec) with an improved fixing machine for the copier “AR-505” (manufactured by Sharp Corporation) that can be fixed outside the machine, the fixing temperature is 90 ° C to 240 ° C. The unfixed image was fixed while gradually increasing to 10 ° C by 10 ° C.

“Unicelohan tape” (Mitsubishi Pencil Co., Ltd., width: 18 mm, JIS Z-1522) was pasted on the fixed image, passed through a fixing roller set at 30 ° C., and then the tape was peeled off. The optical reflection density before and after the tape was peeled off was measured using a reflection densitometer “RD-915” (Macbeth Co., Ltd.). The fixing roller temperature exceeding the minimum fixing temperature was evaluated according to the following evaluation criteria. At the same time, the occurrence of hot offset was visually observed, and the temperature range from the lowest fixing temperature to the temperature at which hot offset occurred was confirmed as the fixing region. The results are shown in Table 2. The paper used for the fixing test is “CopyBond SF-70NA” (manufactured by Sharp Corporation, 75 g / m ² ). The results are shown in Table 2.

[Evaluation criteria for low-temperature fixability]
A: Minimum fixing temperature is less than 140 ° C. ○: Minimum fixing temperature is 140 ° C. or higher and lower than 150 ° C. ×: Minimum fixing temperature is 150 ° C. or higher.

Test Example 2 [Preservation]
4 g of toner was placed in a 20 mL polybin and allowed to stand in an environment of 45 ° C. and 50 ° C. for 48 hours. After standing, the aggregation degree was measured with a powder tester (manufactured by Hosokawa Micron Corporation) by the following method, and the storage stability was evaluated according to the following criteria. The results are shown in Table 2.

(Measurement of cohesion)
Place three different sieves in the order of 250μm on the upper stage, 149μm on the middle stage, and 74μm on the lower stage on the powder tester's shaking table, put 4g of toner on it, give vibration, and measure the weight of toner remaining on each sieve To do. The measured toner weight is applied to the following equation and calculated to obtain the degree of aggregation [%].

Aggregation degree [%] = a + b + c
a = (weight of residual toner on upper stage) / 4 [g] × 100
b = (middle stage residual toner weight) / 4 [g] × 100 × (3/5)
c = (lower stage residual toner weight) / 4 [g] × 100 × (1/5)

(Evaluation criteria for storage stability (aggregation at 45 ° C))
A: The degree of aggregation is less than 10 and the storage stability is very good.
A: The degree of aggregation is 10 or more and less than 20, and the storage stability is good.
X: The degree of aggregation is 20 or more and the storage stability is poor.

(Evaluation criteria for storage stability (aggregation at 50 ° C))
A: The degree of aggregation is less than 10 and the storage stability is good.
A: The degree of aggregation is 10 or more and less than 60, and the storage stability is good.
X: The degree of aggregation is 60 or more and the storage stability is poor.

Test Example 3 [Charging stability]
In an environment with a temperature of 25 ° C and a relative humidity of 50%, put 0.6g of toner and 9.4g of a silicone-coated ferrite carrier (manufactured by Kanto Denka Kogyo Co., Ltd.) with a volume average particle size of 60μm into a 20mL cylindrical plastic bottle. It was fixed in a turbula shaker mixer and rotated at a speed of 90 r / min. Charge over time (mixing time 1 min, 3 min, 5 min, 10 min) was measured with a q / m meter (Epping) and each mixing time (1 min, 3 min, 5 min) The charge stability was evaluated according to the following criteria from the average value of charge amount (min. Charge amount average value) at 10 minutes). The results are shown in Table 2.

[Q / m meter setting]
Mesh size: 400 mesh (made of stainless steel)
Soft blow suction time (Blow pressure 1050V): 90 seconds charge amount (μC / g) = Total amount of electricity (μC) after 90 seconds of toner suction time / Amount of toner sucked (g)

[Evaluation criteria for charging stability]
A: Charge amount difference between the charge amount average value and each mixing time is less than 2 μC / ○: Charge amount difference between the charge amount average value and each mixing time is 2 μC / g or more and less than 5 μC / g ×: Charge amount average value and each Charge amount difference during mixing time is 5μC / g or more

Test Example 4 [Color]
As for the color of the toner as a powder, the yellow toner of Comparative Example 9 containing no compound X is used for the yellow toner, and the magenta toner of Comparative Example 10 containing no compound X is used for the magenta toner. The color was evaluated as a standard. The results are shown in Table 2.

[Color]
A: The same level as the standard toner.
○: Slight dullness is observed with respect to the reference toner.
Δ: Although slightly inferior in color to the standard, there is no problem in actual use. Although greenish with respect to the reference toner, there is no problem in actual use.
×: Color is very inferior

  From the above results, it can be seen that, compared with the toner of the comparative example, the toner of the example has improved storage stability and charging stability without impairing the low-temperature fixability and color.

  The yellow toner and magenta toner of the present invention are suitably used for developing a latent image formed in electrophotography, electrostatic recording method, electrostatic printing method and the like.

Claims (8)

Crystalline polyester, amorphous polyester, a yellow colorant, and a yellow toner over comprising a copper complex compound, said a copper complex compound CI Pigment Green 7, the content of the copper complex compound, yellow toner over a 0.05 to 1.5 parts by weight per 100 parts by weight of the crystalline polyester to the amorphous polyester. The weight ratio of the crystalline polyester to the amorphous polyester (crystalline polyester / amorphous polyester) is 3 / 97-40 / 60 in which claim 1 Symbol placement of yellow toner over. A method according to claim 1 or 2, wherein the yellow toner chromatography, crystalline polyester, amorphous polyester, a yellow colorant, and the toner material containing the CI Pigment Green 7, the melting point of the crystalline polyester + 5 ° C. method for producing a yellow toner over including the step of melt-kneading at a temperature above. Having Claim 1 or process for developing the yellow toner over the 2 wherein a color image forming method. A magenta toner comprising a crystalline polyester, an amorphous polyester, a magenta colorant, and a copper complex compound, wherein the copper complex compound is CI Pigment Green 7, and the content of the copper complex compound is a crystal Magenta toner which is 0.05 to 1.5 parts by weight based on 100 parts by weight of the total amount of the conductive polyester and amorphous polyester. The magenta toner according to claim 5, wherein a weight ratio of the crystalline polyester to the amorphous polyester (crystalline polyester / amorphous polyester) is 3/97 to 40/60. The method for producing a magenta toner according to claim 5 or 6, wherein a toner raw material containing crystalline polyester, amorphous polyester, magenta colorant, and CI Pigment Green 7 is added to a melting point of the crystalline polyester + 5 ° C or higher. A method for producing a magenta toner, comprising a step of melt-kneading at a temperature of 1. A color image forming method comprising a step of developing the magenta toner according to claim 5.