JP4295034B2 - Toner and method for producing the same, developer, toner container, process cartridge, image forming apparatus, and image forming method - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a toner suitably used in an electrophotographic method, an electrostatic recording method, an electrostatic printing method, and the like, a manufacturing method thereof, a developer using the toner, a container containing a toner, a process cartridge, an image forming apparatus, and The present invention relates to an image forming method.
[0002]
[Prior art]
Image formation by electrophotography generally forms an electrostatic image on a photoreceptor (electrostatic image carrier), develops the electrostatic image with a developer to form a visible image (toner image), The visible image is transferred to a recording medium such as paper and fixed to form a fixed image (see Patent Document 1). The fixing method in the electrophotographic method is a heat roller fixing method in which a heat roller is directly pressed against a toner image on a transfer material and fixed because it is excellent in thermal efficiency and can be downsized. Is widely used.
However, in the case of the heat roller fixing method, there is a problem that a large amount of electric power is required for the fixing. For this reason, from the viewpoint of energy saving, various studies have been made to reduce the power consumption of the heating roller. For example, a layer of the heating roller that contacts the toner image transferred onto the transfer material. It has been proposed that the thermal energy efficiency is increased and the start-up time is significantly shortened by making the thickness of the as thin as possible. However, in this case, the specific heat capacity of the heating roller is reduced, and the temperature difference between the portion through which the transfer material passes and the portion through which the transfer material does not pass increases, so that the molten toner adheres to the heating roller. There is a problem that after the heating roller makes a round, a phenomenon that the molten toner is fixed to a non-image portion on the transfer material, that is, a hot offset phenomenon is likely to occur.
[0003]
In recent years, from the viewpoint of further energy saving, development of technology that enables low-temperature fixing and high-speed copying has been advanced. For example, a toner having excellent low-temperature fixing property using a resin or wax having a low softening point has been developed. It has been studied. However, since the toner having excellent low-temperature fixability is thermally weak, a phenomenon that solidifies due to heat generated from the machine being used or heat during storage, that is, a blocking phenomenon is likely to occur, and heat resistant storage stability. Is not sufficient, and there is a problem that it is difficult to secure a sufficient fixing temperature range.
[0004]
Various studies have been made from the viewpoint of achieving both the low-temperature fixability and the heat-resistant storage stability. For example, it may be possible to use a polyester resin having good low-temperature fixability and relatively good heat-resistant storage stability for the toner, but the low-temperature fixability and the heat-resistant storage stability are in a trade-off relationship. Therefore, the simple use of the polyester resin cannot achieve both the low-temperature fixability and the heat-resistant storage stability at a good level. Therefore, for the purpose of achieving both the low-temperature fixability and the heat-resistant storage stability, for example, a multi-layered toner using a resin having a glass transition temperature higher on the outer side than on the inner side of the toner particles has been proposed ( Patent Document 2).
[0005]
As a method for producing the multilayered toner, for example, an in-situ polymerization method, an interfacial polymerization method, a coacervation method, a spray / dry method, a phase inversion emulsification method (see Patent Document 3) and the like are known. . Among these, regarding the phase inversion emulsification method, a method for producing a multilayer structure toner in which fine particles having a high glass transition temperature are fixed to the particle surface of the toner has been proposed (see Patent Documents 4 and 5). In this case, although the heat-resistant storage stability of the toner can be improved to some extent, a sufficient fixing temperature range cannot be ensured, and the low-temperature fixing property and the heat-resistant storage property can be made compatible at a high level. Have difficulty.
Therefore, it has excellent properties such as anti-aggregation, charging, fluidity, transferability, and fixability, good hot offset resistance, excellent heat resistance storage and low-temperature fixability, and high image quality. At present, the obtained toner, its efficient production method, and related technology using the toner have not yet been provided.
[0006]
[Patent Document 1]
US Pat. No. 2,297,691
[Patent Document 2]
JP-A-9-258480
[Patent Document 3]
JP-A-5-66600
[Patent Document 4]
JP 2000-347455 A
[Patent Document 5]
JP 2001-022117 A
[0007]
[Problems to be solved by the invention]
An object of the present invention is to solve the conventional problems and achieve the following objects. That is, the present invention is excellent in various properties such as anti-aggregation property, charging property, fluidity, transferability, and fixability, has good hot offset resistance, and has both excellent heat-resistant storage stability and low-temperature fixability. Provided are a toner capable of obtaining high image quality, an efficient manufacturing method thereof, and a developer, a container containing toner, a process cartridge, an image forming apparatus, and an image forming method capable of achieving high image quality using the toner. With the goal.
[0008]
[Means for Solving the Problems]
  Means for solving the problems are as follows. That is,
  <1> An organic solvent phase containing an active hydrogen group-containing compound and a polymer having a site capable of reacting with the active hydrogen group-containing compound is emulsified and dispersed in an aqueous medium containing at least two kinds of resin fine particles, and the activity is obtained. A hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound are subjected to an extension reaction or a crosslinking reaction.Obtained by removing organic solventToner,
  Without the resin fine particles being fixed or fused,
  Among the resin fine particles, those having the highest glass transition temperature are the resin fine particles (A), the glass transition temperature is (TgA), the one having the lowest glass transition temperature is the resin fine particles (B), and the glass transition temperature is (TgB). ), The following equation, temperature difference (TgA−TgB) ≧ 20 ° C. is satisfied,
  The residual ratio of the resin fine particles to the toner is 4.1 to 8.0% by mass as measured by a pyrolysis chromatograph,
  A toner having a mass ratio of the resin fine particles (A) to the resin fine particles (B) (resin fine particles (A): resin fine particles (B)) of 10:90 to 50:50.
  <2> The above <1> satisfying the following formula, 8,000 ≦ (Mw) ≦ 1,500,000, where (Mw) is the weight average molecular weight in the molecular weight distribution of the tetrahydrofuran solubles in the resin fine particles. The toner is described.
  <3> The toner according to any one of <1> to <2>, wherein a toner coverage of the resin fine particles is 75 to 100%.
  <4> The toner according to any one of <1> to <3>, wherein the resin fine particles have a volume average particle diameter of 20 to 400 nm.
  <5> The BET specific surface area of the toner is 0.5 to 8.0 m.²The toner according to any one of <1> to <4>, which is / g.
  <6> The toner according to any one of <1> to <5>, wherein the toner has a volume average particle diameter of 3 to 8 μm.
  <7> The toner according to any one of <1> to <6>, wherein the toner has a volume average particle diameter / number average particle diameter of 1.00 to 1.25.
  <8> The toner according to any one of <1> to <7>, wherein the toner has an average circularity of 0.90 to 1.00.
  <9> The method for producing a toner according to any one of <1> to <8>, including an active hydrogen group-containing compound and a polymer having a site capable of reacting with the active hydrogen group-containing compound. The organic solvent phase is emulsified and dispersed in an aqueous medium containing at least two kinds of resin fine particles, and the active hydrogen group-containing compound and the polymer capable of reacting with the active hydrogen group-containing compound are subjected to an extension reaction or a crosslinking reaction. A method for producing a toner.
  <10> A developer comprising the toner according to any one of <1> to <8>.
  <11> A toner-containing container filled with the toner according to any one of <1> to <8>.
[0009]
The toner of the present invention is obtained in the form of particles while reacting an active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound to form an adhesive substrate in an aqueous medium. The resin fine particles containing the resin fine particles, the resin fine particles having the highest glass transition temperature (A), the glass transition temperature of which is (TgA), the one having the lowest glass transition temperature, the resin fine particles (B), and the glass thereof When the transition temperature is (TgB), the following equation, temperature difference (TgA−TgB) ≧ 20 ° C. is satisfied. The toner contains at least two kinds of resin fine particles, resin fine particles that impart heat-resistant storage stability to the toner and resin fine particles that impart low-temperature fixability to the toner. And excellent hot offset resistance. Further, since the toner includes the adhesive base material obtained by reacting the active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound in an aqueous medium, the aggregation resistance, charging property, Excellent properties such as fluidity, transferability and fixability. When image formation is performed using the toner, high image quality can be obtained under low-temperature fixing conditions.
[0010]
The method for producing the toner of the present invention is a method for producing the toner of the present invention, comprising an active hydrogen group-containing compound, a polymer having a site capable of reacting with the active hydrogen group-containing compound, and at least two kinds It includes at least a step of obtaining toner while dispersing and reacting resin fine particles in an aqueous medium to produce an adhesive substrate. In the toner production method of the present invention, in the step, the active hydrogen group-containing compound and the polymer having a site capable of reacting with the active hydrogen group-containing compound are present in the presence of the at least two kinds of resin fine particles. Thus, the toner is obtained in the form of particles while being dispersed and reacted in the aqueous medium to form an adhesive substrate. As a result, the toner of the present invention is excellent in various properties such as aggregation resistance, charging property, fluidity, transferability, fixing property, etc., has both excellent heat storage stability and low temperature fixing property, and has good hot offset resistance. Is efficiently manufactured.
[0011]
The developer of the present invention contains the toner of the present invention. For this reason, when an image is formed by electrophotography using the developer, a high-quality image with high image density and high sharpness is formed even under low-temperature fixing conditions.
[0012]
The toner-containing container of the present invention contains the toner of the present invention in a container. Therefore, when an image is formed by electrophotography using the toner of the present invention contained in the toner-containing container, a high-quality image having a high image density and a high sharpness is formed even under a low-temperature fixing condition.
[0013]
The process cartridge of the present invention comprises an electrostatic latent image carrier, and developing means for developing the electrostatic latent image formed on the electrostatic latent image carrier using the toner of the present invention to form a visible image. At least. The process cartridge is detachable from the image forming apparatus, is excellent in convenience, and uses the toner of the present invention. Therefore, the process cartridge has both excellent heat-resistant storage stability and low-temperature fixability, and good hot offset resistance. Yes, a high-quality image with high image density and high sharpness can be formed even under low-temperature fixing conditions.
[0014]
The image forming apparatus of the present invention includes an electrostatic latent image carrier, electrostatic latent image forming means for forming an electrostatic latent image on the electrostatic latent image carrier, and the electrostatic latent image of the present invention. The image forming apparatus includes at least a developing unit that forms a visible image by developing with toner, a transfer unit that transfers the visible image to a recording medium, and a fixing unit that fixes the transferred image transferred to the recording medium. In the image forming apparatus, the electrostatic latent image forming unit forms an electrostatic latent image on the electrostatic latent image carrier. The developing means develops the electrostatic latent image using the toner of the present invention to form a visible image. The transfer means transfers the visible image to a recording medium. The fixing unit fixes the transferred image transferred to the recording medium. As a result, a high-quality image with high image density and high sharpness is formed even under low-temperature fixing conditions.
[0015]
The image forming method of the present invention comprises an electrostatic latent image forming step of forming an electrostatic latent image on an electrostatic latent image carrier, and developing the electrostatic latent image with the toner of the present invention to make visible. It includes at least a developing step for forming an image, a transfer step for transferring the visible image to a recording medium, and a fixing step for fixing the transferred image transferred to the recording medium. In the image forming apparatus, an electrostatic latent image is formed on the electrostatic latent image carrier in the electrostatic latent image forming step. In the developing step, the electrostatic latent image is developed using the toner of the present invention to form a visible image. In the transfer step, the visible image is transferred to a recording medium. In the fixing step, the transferred image transferred to the recording medium is fixed. As a result, a high-quality image with high image density and high sharpness is formed even under low-temperature fixing conditions.
[0016]
DETAILED DESCRIPTION OF THE INVENTION
(toner)
The toner of the present invention is obtained in the form of particles while reacting an active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound to form an adhesive substrate in an aqueous medium. The resin fine particles containing the resin fine particles, the resin fine particles having the highest glass transition temperature (A), the glass transition temperature of which is (TgA), the one having the lowest glass transition temperature, the resin fine particles (B), and the glass thereof When the transition temperature is (TgB), the following formula, temperature difference (TgA−TgB) ≧ 20 ° C. is satisfied, and if necessary, a colorant, a release agent, an unmodified polyester resin, a charge control agent, etc. Contains other ingredients.
[0017]
-Resin fine particles-
The resin fine particles are used for the purpose of controlling the shape (circularity, particle size distribution, etc.) of the toner and achieving both heat-resistant storage stability and low-temperature fixability in the toner, and imparting the heat-resistant storage stability to the toner. At least one type of toner and at least one type that imparts the low-temperature fixability to the toner are used.
[0018]
As the resin fine particles, those having the highest glass transition temperature in at least two of them are the resin fine particles (A), the glass transition temperature is (TgA), the one having the lowest glass transition temperature is the resin fine particles (B), When the glass transition temperature is (TgB), it is preferable to satisfy the following formula, temperature difference (TgA−TgB) ≧ 20 ° C., and 150 ° C. ≧ temperature difference (TgA−TgB) ≧ 20 ° C. It is more preferable that 70 ° C. ≧ temperature difference (TgA−TgB) ≧ 25 ° C. is satisfied.
When the temperature difference (TgA-TgB) of the glass transition temperature is less than 20 ° C., the development of excellent properties of the resin fine particles (A) and the resin fine particles (B) is suppressed, and low temperature fixability, Either the anti-offset property or the heat-resistant storage property may not be sufficient for the toner.
[0019]
There is no restriction | limiting in particular as glass transition temperature (TgA) of the said resin fine particle (A), According to the objective, it can select suitably, For example, about 55-150 degreeC is preferable. When the glass transition temperature (TgA) is less than 55 ° C, the heat-resistant storage stability may be deteriorated, and when it exceeds 150 ° C, the low-temperature fixability may be deteriorated.
There is no restriction | limiting in particular as glass transition temperature (TgB) of the said resin fine particle (B), According to the objective, it can select suitably, For example, it is about 25-100 degreeC. When the glass transition temperature (TgB) is less than 25 ° C, the heat-resistant storage stability may be deteriorated, and when it exceeds 100 ° C, the low-temperature fixability may be deteriorated.
[0020]
The glass transition temperature can be measured by, for example, the following method using a TG-DSC system TAS-100 (manufactured by Rigaku Corporation). First, about 10 mg of toner is placed in an aluminum sample container, and the sample container is placed on a holder unit and set in an electric furnace. After heating from room temperature to 150 ° C. at a rate of temperature increase of 10 ° C./min, the sample is left at 150 ° C. for 10 minutes, and the sample is cooled to room temperature and left for 10 minutes. Then, the DSC curve is measured with a differential scanning calorimeter (DSC) after heating to 150 ° C. at a temperature rising rate of 10 ° C./min in a nitrogen atmosphere. From the obtained DSC curve, using the analysis system in the TG-DSC system TAS-100 system, the glass transition temperature (Tg) is calculated from the contact point between the tangent line of the endothermic curve near the glass transition temperature (Tg) and the baseline. can do.
[0021]
The resin fine particles preferably have a mass ratio of resin fine particles (A) to resin fine particles (B) (resin fine particles (A): resin fine particles (B)) of 10:90 to 50:50, 20 : More preferably, it is 80-40: 60.
When the mass ratio of the resin fine particles (A) is less than 10 as the mass ratio, the low-temperature fixability, the smoothness of the fixing surface, and the like may be reduced, and the mass of the resin fine particles (A) exceeds 50. Moreover, offset resistance, heat-resistant storage stability, etc. may deteriorate. On the other hand, when the mass ratio is within the numerical range, a toner having excellent low-temperature fixability and offset resistance can be obtained.
[0022]
When the weight average molecular weight in the molecular weight distribution of tetrahydrofuran-soluble matter in the resin fine particles is (Mw), it is preferable to satisfy the following formula: 8,000 ≦ (Mw) ≦ 1,500,000, More preferably, ≦ (Mw) ≦ 1,300,000 is satisfied, and it is particularly preferable that 10,000 ≦ (Mw) ≦ 1,200,000 is satisfied.
When the weight average molecular weight (Mw) is less than 8,000, heat-resistant storage stability and hot offset resistance may be deteriorated, and when it exceeds 1,500,000, low-temperature fixability cannot be obtained. There is.
[0023]
The molecular weight distribution of the resin fine particles can be measured, for example, by gel permeation chromatography (GPC) as follows. That is, the column is stabilized in a 40 ° C. heat chamber. At this temperature, tetrahydrofuran as a column solvent is allowed to flow at a flow rate of 1 ml / min, and 50 to 200 μl of a tetrahydrofuran sample solution of a resin whose sample concentration is adjusted to 0.05 to 0.6 mass% is injected and measured. In measuring the molecular weight of the sample, the molecular weight distribution of the sample is calculated from the relationship between the logarithmic value of the calibration curve created by several monodisperse polystyrene standard samples and the count number. Examples of standard polystyrene samples for preparing the calibration curve include Pressure Chemical Co. Or the molecular weight made by Toyo Soda Industry Co., Ltd. is 6 × 10²2.1 × 10²4 × 10²1.75 × 10⁴1.1 × 10⁵3.9 × 10⁵8.6 × 10⁵2 × 10⁶And 4.48 × 10⁶It is preferable to use at least about 10 standard polystyrene samples. As the detector, an RI (refractive index) detector can be used.
[0024]
The mass ratio of the resin fine particles (C) to the resin fine particles (D) (resin fine particles (C): resin fine particles (D)) is not particularly limited and may be appropriately selected depending on the intended purpose. 10: 90-50: 50 is preferable and 20: 80-40: 60 is more preferable.
When the mass ratio of the resin fine particles (C) is less than 10 as the mass ratio, the low temperature fixability, the smoothness of the fixing surface and the like may be deteriorated, and the mass of the resin fine particles (D) exceeds 50. In addition, offset resistance and heat storage stability may be deteriorated. On the other hand, when the mass ratio is within the numerical range, a toner having excellent low-temperature fixability and offset resistance can be obtained.
[0025]
There is no restriction | limiting in particular as a volume average particle diameter of the said resin fine particle, According to the objective, it can select suitably, For example, 20-400 nm is preferable and 30-350 nm is more preferable.
When the volume average particle size is less than 20 nm, the resin fine particles remaining on the surface of the toner may be formed into a film or may cover the entire surface of the toner densely. As a result, the resin fine particles May hinder the adhesion between the adhesive substrate inside the toner and the fixing paper as a transfer material, and the minimum fixing temperature may be increased. Occurrence of bleeding may be hindered, sufficient release properties may not be obtained, and offset may occur.
The volume average particle diameter of the resin fine particles can be measured using, for example, a particle size distribution measuring apparatus (“LA-920”; manufactured by Horiba, Ltd.) using a laser light scattering method.
[0026]
There is no restriction | limiting in particular as the toner coverage of the said resin fine particle, According to the objective, it can select suitably, For example, 75-100% is preferable and 80-100% is more preferable.
If the toner coverage is less than 75%, the storage stability of the toner is deteriorated, and blocking may occur during storage or use.
The toner coverage can be measured, for example, by measuring an electron micrograph of the toner surface with an image analyzer and measuring the coverage of the resin fine particles on the toner surface.
[0027]
The content (residual amount) of the resin fine particles in the toner is not particularly limited and may be appropriately selected depending on the intended purpose. For example, 0.5 to 8.0% by mass is preferable, and 0.6 -7.0 mass% is more preferable.
When the content (residual amount) is less than 0.5% by mass, the storage stability of the toner is deteriorated, and blocking may be observed during storage or use. 8.0% by mass Exceeding the above may cause the resin fine particles to inhibit the seepage of the wax, so that sufficient releasability cannot be obtained and offset may occur.
[0028]
The content (residual amount) of the resin fine particles in the toner can be measured by various methods. Substances or functional groups derived only from the resin fine particles can be measured using, for example, a pyrolysis gas chromatograph mass spectrometer. It is possible to calculate from the peak area. There is no restriction | limiting in particular as said detector, Although it can select suitably according to the objective, A mass spectrometer is suitable.
[0029]
The resin fine particle is not particularly limited as long as it is a resin that can form an aqueous dispersion in an aqueous medium, and can be appropriately selected from known resins according to the purpose, and may be a thermoplastic resin. It may be a thermosetting resin, for example, vinyl resin, polyurethane resin, epoxy resin, polyester resin, polyamide resin, polyimide resin, silicon resin, phenol resin, melamine resin, urea resin, aniline resin, ionomer resin, polycarbonate resin. , Etc.
These may be used individually by 1 type and may use 2 or more types together. Among these, at least one selected from a vinyl resin, a polyurethane resin, an epoxy resin, and a polyester resin is preferable because an aqueous dispersion of fine spherical resin resin particles can be easily obtained.
The vinyl resin is a polymer obtained by homopolymerizing or copolymerizing a vinyl monomer. For example, a styrene- (meth) acrylic acid ester resin, a styrene-butadiene copolymer, a (meth) acrylic acid-acrylic acid ester polymer. Styrene-acrylonitrile copolymer, styrene-maleic anhydride copolymer, styrene- (meth) acrylic acid copolymer, and the like.
Moreover, as the resin fine particles, a copolymer comprising a monomer having at least two unsaturated groups can be used.
The monomer having at least two unsaturated groups is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a sodium salt of ethylene oxide methacrylate adduct sulfate (“Eleminol RS-30”). "; Manufactured by Sanyo Chemical Industries Ltd.), divinylbenzene, 1,6-hexanediol acrylate and the like.
[0030]
The resin fine particles can be obtained by polymerization according to a known method appropriately selected according to the purpose, but is preferably obtained as an aqueous dispersion of the resin fine particles. The method for preparing the aqueous dispersion of the resin fine particles is, for example, (1) In the case of the vinyl resin, a vinyl monomer is used as a starting material and is selected from suspension polymerization, emulsion polymerization, seed polymerization, and dispersion polymerization. (2) In the case of polyaddition or condensation resin such as polyester resin, polyurethane resin, epoxy resin, etc., a precursor (monomer, oligomer). Or the like, or a solvent solution thereof is dispersed in an aqueous medium in the presence of an appropriate dispersant, and then heated or added with a curing agent to be cured to produce an aqueous dispersion of resin fine particles (3) ) In the case of polyaddition or condensation resin such as polyester resin, polyurethane resin, epoxy resin, etc., it may be a precursor (monomer, oligomer, etc.) or a solvent solution thereof (liquid). (4) Preliminary polymerization reaction (addition polymerization, ring-opening polymerization, polyaddition, addition) After the resin prepared by any polymerization reaction mode such as condensation and condensation polymerization is pulverized using a mechanical pulverizer or jet type pulverizer and then classified to obtain resin fine particles , A method of dispersing in water in the presence of an appropriate dispersant, (5) prepared in advance by a polymerization reaction (any polymerization reaction mode such as addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) (6) A polymerization reaction (addition polymerization) in advance, in which resin fine particles are obtained by spraying a resin solution in which the resin is dissolved in a solvent to obtain resin fine particles and then dispersing the resin fine particles in water in the presence of an appropriate dispersant. , Ring-opening polymerization, polyaddition, addition condensation The resin fine particles can be obtained by adding a poor solvent to a resin solution obtained by dissolving a resin prepared in a solvent by a polymerization reaction method such as condensation polymerization or by cooling a resin solution previously dissolved in a solvent by heating. And then removing the solvent to obtain resin particles, and then dispersing the resin particles in water in the presence of a suitable dispersant. (7) Polymerization reaction (addition polymerization, ring-opening polymerization, heavy polymerization) in advance (Any polymerization reaction mode such as addition, addition condensation, and condensation polymerization may be used.) A resin solution prepared by dissolving a resin prepared in a solvent in a solvent is dispersed in an aqueous medium and then heated or heated. (8) A resin prepared in advance by a polymerization reaction (which may be any polymerization reaction mode such as addition polymerization, ring-opening polymerization, polyaddition, addition condensation or condensation polymerization) is used as a solvent. In the dissolved resin solution A method of dissolving a suitable emulsifier and then adding water to carry out phase inversion emulsification is preferable.
[0031]
-Adhesive substrate-
The adhesive substrate is a binder obtained by reacting the active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound in the aqueous medium. It may contain at least other binders appropriately selected from known binder resins as required.
[0032]
The weight average molecular weight of the adhesive substrate is not particularly limited and may be appropriately selected depending on the purpose. For example, 1,000 or more is preferable, and 2,000 to 10,000,000 is more preferable. 3,000 to 1,000,000 is particularly preferred.
When the weight average molecular weight is less than 1,000, the hot offset resistance may be deteriorated.
[0033]
There is no restriction | limiting in particular as glass transition temperature (Tg) of the said adhesive base material, According to the objective, it can select suitably, For example, 30-70 degreeC is preferable and 40-65 degreeC is more preferable. In the toner of the present invention, the coexistence of the polyester resin subjected to the crosslinking reaction and / or the elongation reaction exhibits good storage stability even when the glass transition temperature is lower than that of the conventional polyester toner.
When the glass transition temperature (Tg) is less than 30 ° C., the heat-resistant storage stability of the toner may deteriorate, and when it exceeds 70 ° C., the low-temperature fixability may not be sufficient.
[0034]
The glass transition temperature can be measured by, for example, the following method using a TG-DSC system TAS-100 (manufactured by Rigaku Corporation). First, about 10 mg of toner is placed in an aluminum sample container, and the sample container is placed on a holder unit and set in an electric furnace. After heating from room temperature to 150 ° C. at a rate of temperature increase of 10 ° C./min, the sample is left at 150 ° C. for 10 minutes, and the sample is cooled to room temperature and left for 10 minutes. Then, the DSC curve is measured with a differential scanning calorimeter (DSC) after heating to 150 ° C. at a temperature rising rate of 10 ° C./min in a nitrogen atmosphere. From the obtained DSC curve, using the analysis system in the TG-DSC system TAS-100 system, the glass transition temperature (Tg) is calculated from the contact point between the tangent line of the endothermic curve near the glass transition temperature (Tg) and the baseline. can do.
[0035]
There is no restriction | limiting in particular as a specific example of the said adhesive base material, According to the objective, it can select suitably, A polyester resin etc. are mentioned especially suitably.
There is no restriction | limiting in particular as said polyester resin, According to the objective, it can select suitably, For example, a urea modified polyester resin etc. are mentioned especially suitably.
The urea-modified polyester resin comprises an amine (B) as the active hydrogen group-containing compound and an isocyanate group-containing polyester prepolymer (A) as a polymer that can react with the active hydrogen group-containing compound. It is obtained by reacting in a medium.
The urea-modified polyester resin may contain a urethane bond in addition to the urea bond, and in this case, the molar ratio of the urea bond to the urethane bond (urea bond / urethane bond) is particularly limited. However, 100/0 to 10/90 is preferable, 80/20 to 20/80 is more preferable, and 60/40 to 30/70 is particularly preferable.
When the urea bond is less than 10, the hot offset resistance may be deteriorated.
[0036]
Preferable specific examples of the urea-modified polyester resin include the following (1) to (10), that is, (1) a polyester pre-reacted polycondensate of bisphenol A ethylene oxide 2 mol adduct and isophthalic acid with isophorone diisocyanate. A mixture of a polymer urealated with isophoronediamine and a polycondensate of bisphenol A ethylene oxide 2 mol adduct and isophthalic acid, (2) a polycondensate of bisphenol A ethylene oxide 2 mol adduct and isophthalic acid A mixture of a polyester prepolymer reacted with diisocyanate and uread with isophoronediamine, a bicondensate of bisphenol A ethylene oxide 2 mol adduct and terephthalic acid, (3) bisphenol A ethylene oxide 2 mol Polyester prepolymer obtained by reacting an adduct / bisphenol A propylene oxide 2 mol adduct and terephthalic acid polycondensate with isophorone diisocyanate and urethanized with isophorone diamine, and bisphenol A ethylene oxide 2 mol adduct / bisphenol A propylene Mixture of oxide 2 mol adduct and terephthalic acid polycondensate, (4) Bisphenol A ethylene oxide 2 mol adduct / bisphenol A propylene oxide 2 mol adduct and terephthalic acid polycondensate were reacted with isophorone diisocyanate. A mixture of a polyester prepolymer uread with isophoronediamine, a bisphenol A propylene oxide 2-mole adduct and a polycondensate of terephthalic acid, (5) bisphenol A Polyester prepolymer obtained by reacting a polycondensate of tylene oxide 2 mol adduct and terephthalic acid with isophorone diisocyanate and ureaated with hexamethylenediamine, a polycondensate of bisphenol A ethylene oxide 2 mol adduct and terephthalic acid (6) Polyester prepolymer obtained by reacting polycondensate of bisphenol A ethylene oxide with 2 mol of bisphenol A and isophorone diisocyanate with urea and hexamethylenediamine and 2 mol of bisphenol A ethylene oxide. Product / bisphenol A propylene oxide 2 mol adduct and terephthalic acid polycondensate, (7) bisphenol A ethylene oxide 2 mol adduct and terephthalic acid polycondensate A mixture of a polyester prepolymer reacted with socyanate with urethanized with ethylenediamine and a polycondensate of bisphenol A ethylene oxide 2 mol adduct and terephthalic acid, (8) bisphenol A ethylene oxide 2 mol adduct and isophthalic acid A mixture of a polyester prepolymer obtained by reacting a polycondensate of bisphenol with diphenylmethane diisocyanate with urea and hexamethylenediamine, and a polycondensate of bisphenol A ethylene oxide 2 mol adduct and isophthalic acid, (9) bisphenol A ethylene Polyester prepolymer obtained by reacting polycondensate of oxide 2 mol adduct / bisphenol A propylene oxide 2 mol adduct and terephthalic acid / dodecenyl succinic anhydride with diphenylmethane diisocyanate Mixture of uremer urea-modified with hexamethylenediamine and bisphenol A ethylene oxide 2-mole adduct / bisphenol A propylene oxide 2-mole adduct and terephthalic acid polycondensate, (10) bisphenol A ethylene oxide 2-mole addition And a mixture of a polyester prepolymer obtained by reacting a polycondensate of isophthalic acid and isophthalic acid with toluene diisocyanate with urea methylenediamine, a 2-mole adduct of bisphenol A ethylene oxide and a polycondensate of isophthalic acid, etc. Preferably mentioned.
[0037]
-Active hydrogen group-containing compound-
The active hydrogen group-containing compound acts as an elongation agent, a crosslinking agent, or the like when a polymer capable of reacting with the active hydrogen group-containing compound undergoes an elongation reaction, a crosslinking reaction, or the like in the aqueous medium.
The active hydrogen group-containing compound is not particularly limited as long as it has an active hydrogen group, and can be appropriately selected depending on the purpose. For example, the polymer capable of reacting with the active hydrogen group-containing compound is In the case of the isocyanate group-containing polyester prepolymer (A), the amines (B) can be increased in molecular weight by a reaction such as an elongation reaction or a crosslinking reaction with the isocyanate group-containing polyester prepolymer (A). Is preferred.
There is no restriction | limiting in particular as said active hydrogen group, According to the objective, it can select suitably, For example, a hydroxyl group (alcoholic hydroxyl group or phenolic hydroxyl group), an amino group, a carboxyl group, a mercapto group etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together. Among these, an alcoholic hydroxyl group is particularly preferable.
[0038]
The amines (B) are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include diamine (B1), trivalent or higher polyamine (B2), amino alcohol (B3), and amino mercaptan. (B4), amino acid (B5), and those obtained by blocking the amino groups of B1 to B5 (B6).
These may be used individually by 1 type and may use 2 or more types together. Among these, diamine (B1), a mixture of diamine (B1) and a small amount of a trivalent or higher polyamine (B2) are particularly preferable.
[0039]
Examples of the diamine (B1) include aromatic diamines, alicyclic diamines, and aliphatic diamines. Examples of the aromatic diamine include phenylenediamine, diethyltoluenediamine, 4,4′diaminodiphenylmethane, and the like. Examples of the alicyclic diamine include 4,4′-diamino-3,3′dimethyldicyclohexylmethane, diaminecyclohexane, and isophoronediamine. Examples of the aliphatic diamine include ethylene diamine, tetramethylene diamine, and hexamethylene diamine.
Examples of the trivalent or higher polyamine (B2) include diethylenetriamine and triethylenetetramine.
Examples of the amino alcohol (B3) include ethanolamine and hydroxyethylaniline.
Examples of the amino mercaptan (B4) include aminoethyl mercaptan and aminopropyl mercaptan.
Examples of the amino acid (B5) include aminopropionic acid and aminocaproic acid.
Examples of the block (B6) obtained by blocking the amino group of B1 to B5 include ketimines obtained from any of the amines (B1) to (B5) and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.). Compounds, oxazolyzone compounds, and the like.
[0040]
In addition, a reaction terminator can be used to stop the elongation reaction, the crosslinking reaction, etc. between the active hydrogen group-containing compound and the polymer capable of reacting with the active hydrogen group-containing compound. Use of the reaction terminator is preferable in that the molecular weight and the like of the adhesive substrate can be controlled within a desired range. Examples of the reaction terminator include monoamines (diethylamine, dibutylamine, butylamine, laurylamine, etc.), or those obtained by blocking these (ketimine compounds).
[0041]
As a mixing ratio of the amines (B) and the isocyanate group-containing polyester prepolymer (A), the isocyanate group [NCO] in the isocyanate group-containing prepolymer (A) and the amines (B) The mixing equivalent ratio ([NCO] / [NHx]) of the amino group [NHx] is preferably 1/3 to 3/1, more preferably 1/2 to 2/1, It is particularly preferably 1.5 to 1.5 / 1.
When the isocyanate group [NCO] is less than 1/2 or exceeds 2/1, the molecular weight of the urea-modified polyester resin is lowered, and the hot offset resistance may be deteriorated.
[0042]
--Polymer capable of reacting with active hydrogen group-containing compound--
The polymer capable of reacting with the active hydrogen group-containing compound (hereinafter sometimes referred to as “prepolymer”) is not particularly limited as long as it has at least a site capable of reacting with the active hydrogen group-containing compound. It can be appropriately selected from known resins and the like, and examples thereof include polyol resins, polyacrylic resins, polyester resins, epoxy resins, and derivative resins thereof.
These may be used individually by 1 type and may use 2 or more types together. Among these, the polyester resin is particularly preferable in terms of good compatibility with the unmodified polyester resin.
[0043]
The site capable of reacting with the active hydrogen group-containing compound in the prepolymer is not particularly limited and may be appropriately selected from known substituents. For example, an isocyanate group, an epoxy group, a carboxylic acid, An acid chloride group, and the like.
These may be contained singly or in combination of two or more. Among these, an isocyanate group is particularly preferable.
[0044]
Among the prepolymers, it is easy to adjust the molecular weight of the polymer component, and oil-less low-temperature fixing characteristics in dry toners, in particular, good releasability and fixability even in the absence of a release oil application mechanism to a fixing heating medium. It is particularly preferable that it is a urea bond-forming group-containing polyester resin (RMPE) in that it can be secured.
As said urea bond production | generation group, an isocyanate group etc. are mentioned, for example. When the urea bond-forming group in the urea bond-forming group-containing polyester resin (RMPE) is the isocyanate group, the isocyanate group-containing polyester prepolymer (A) and the like are particularly preferable as the polyester resin (RMPE). It is done.
[0045]
The isocyanate group-containing polyester prepolymer (A) is not particularly limited and may be appropriately selected depending on the intended purpose. For example, it is a polycondensate of a polyol (PO) and a polycarboxylic acid (PC), And those obtained by reacting the active hydrogen group-containing polyester resin with polyisocyanate (PIC).
[0046]
There is no restriction | limiting in particular as said polyol (PO), According to the objective, it can select suitably, For example, diol (DIO), trihydric or more polyol (TO), diol (DIO), and trihydric or more polyol And a mixture with (TO). These may be used individually by 1 type and may use 2 or more types together. Among these, the diol (DIO) alone or a mixture of the diol (DIO) and a small amount of the trivalent or higher polyol (TO) is preferable.
[0047]
Examples of the diol (DIO) include alkylene glycol, alkylene ether glycol, alicyclic diol, alkylene oxide adduct of alicyclic diol, bisphenol, alkylene oxide adduct of bisphenol, and the like.
The alkylene glycol is preferably one having 2 to 12 carbon atoms, such as ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, and the like. Can be mentioned. Examples of the alkylene ether glycol include diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, and the like. Examples of the alicyclic diol include 1,4-cyclohexanedimethanol and hydrogenated bisphenol A. Examples of the alkylene oxide adduct of the alicyclic diol include those obtained by adding an alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide to the alicyclic diol. Examples of the bisphenols include bisphenol A, bisphenol F, and bisphenol S. Examples of the alkylene oxide adduct of the bisphenol include those obtained by adding an alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide to the bisphenol.
Among these, alkylene glycols having 2 to 12 carbon atoms, alkylene oxide adducts of bisphenols and the like are preferable, and alkylene oxide adducts of bisphenols, alkylene oxide adducts of bisphenols and alkylene glycols having 2 to 12 carbon atoms. Mixtures are particularly preferred.
[0048]
The trivalent or higher polyol (TO) is preferably 3 to 8 or higher, for example, a trivalent or higher polyhydric aliphatic alcohol, a trivalent or higher polyphenol, a trivalent or higher polyphenol. And alkylene oxide adducts.
Examples of the trihydric or higher polyhydric aliphatic alcohol include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol and the like. Examples of the trihydric or higher polyphenols include trisphenol PA, phenol novolak, cresol novolak, and the like. Examples of the alkylene oxide adducts of trihydric or higher polyphenols include those obtained by adding alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide to the trihydric or higher polyphenols.
[0049]
The mixture mass ratio (DIO: TO) of the diol (DIO) and the trivalent or higher polyol (TO) in the mixture of the diol (DIO) and the trivalent or higher polyol (TO) is 100: 0.01-10 are preferable and 100: 0.01-1 are more preferable.
[0050]
There is no restriction | limiting in particular as said polycarboxylic acid (PC), Although it can select suitably according to the objective, For example, dicarboxylic acid (DIC), trivalent or more polycarboxylic acid (TC), dicarboxylic acid (DIC) ) And a tricarboxylic or higher polycarboxylic acid.
These may be used individually by 1 type and may use 2 or more types together. Among these, dicarboxylic acid (DIC) alone or a mixture of DIC and a small amount of trivalent or higher polycarboxylic acid (TC) is preferable.
Examples of the dicarboxylic acid include alkylene dicarboxylic acid, alkenylene dicarboxylic acid, aromatic dicarboxylic acid, and the like.
Examples of the alkylene dicarboxylic acid include succinic acid, adipic acid, and sebacic acid. As said alkenylene dicarboxylic acid, a C4-C20 thing is preferable, For example, a maleic acid, a fumaric acid, etc. are mentioned. As said aromatic dicarboxylic acid, a C8-C20 thing is preferable, For example, a phthalic acid, an isophthalic acid, a terephthalic acid, naphthalene dicarboxylic acid etc. are mentioned.
Among these, alkenylene dicarboxylic acid having 4 to 20 carbon atoms and aromatic dicarboxylic acid having 8 to 20 carbon atoms are preferable.
[0051]
The trivalent or higher polycarboxylic acid (TO) is preferably 3 to 8 or higher, and examples thereof include aromatic polycarboxylic acids.
The aromatic polycarboxylic acid preferably has 9 to 20 carbon atoms, and examples thereof include trimellitic acid and pyromellitic acid.
[0052]
As the polycarboxylic acid (PC), the dicarboxylic acid (DIC), the trivalent or higher polycarboxylic acid (TC), and a mixture of the dicarboxylic acid (DIC) and the trivalent or higher polycarboxylic acid, Any acid anhydride or lower alkyl ester selected from can also be used. Examples of the lower alkyl ester include methyl ester, ethyl ester, isopropyl ester and the like.
[0053]
Mixing mass ratio (DIC: TC) of the dicarboxylic acid (DIC) and the trivalent or higher polycarboxylic acid (TC) in the mixture of the dicarboxylic acid (DIC) and the trivalent or higher polycarboxylic acid (TC) There is no restriction | limiting in particular, According to the objective, it can select suitably, For example, 100: 0.01-10 are preferable and 100: 0.01-1 are more preferable.
[0054]
The mixing ratio for the polycondensation reaction between the polyol (PO) and the polycarboxylic acid (PC) is not particularly limited and may be appropriately selected depending on the intended purpose. For example, in the polyol (PO) The equivalent ratio ([OH] / [COOH]) of the hydroxyl group [OH] to the carboxyl group [COOH] in the polycarboxylic acid (PC) is usually preferably 2/1 to 1/1. More preferably, it is 0.5 / 1 to 1/1, and particularly preferably 1.3 / 1 to 1.02 / 1. If the equivalent ratio ([OH] / [COOH]) exceeds 2/1 or is less than 1/1, the polycondensation reaction may not proceed completely.
[0055]
There is no restriction | limiting in particular as content in the said isocyanate group containing polyester prepolymer (A) of the said polyol (PO), Although it can select suitably according to the objective, For example, 0.5-40 mass% is preferable. 1-30 mass% is more preferable, and 2-20 mass% is especially preferable.
When the content is less than 0.5% by mass, the hot offset resistance deteriorates, and it may be difficult to achieve both the heat-resistant storage stability and the low-temperature fixability of the toner, and exceeds 40% by mass. In some cases, the low-temperature fixability may deteriorate.
[0056]
There is no restriction | limiting in particular as said polyisocyanate (PIC), Although it can select suitably according to the objective, For example, aliphatic polyisocyanate, alicyclic polyisocyanate, aromatic diisocyanate, araliphatic diisocyanate, isocyanurate And those blocked with phenol derivatives, oximes, caprolactams, and the like.
Examples of the aliphatic polyisocyanate include tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-diisocyanatomethylcaproate, octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, tetradecamethylene diisocyanate, trimethylhexane diisocyanate, Examples include tetramethylhexane diisocyanate. Examples of the alicyclic polyisocyanate include isophorone diisocyanate and cyclohexylmethane diisocyanate. Examples of the aromatic diisocyanate include tolylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, diphenylene-4,4′-diisocyanate, 4,4′-diisocyanato-3,3′-dimethyldiphenyl, 3- Examples thereof include methyldiphenylmethane-4,4′-diisocyanate, diphenyl ether-4,4′-diisocyanate and the like. Examples of the araliphatic diisocyanate include α, α, α ′, α′-tetramethylxylylene diisocyanate. Examples of the isocyanurates include tris-isocyanatoalkyl-isocyanurate and triisocyanatocycloalkyl-isocyanurate.
These can be used alone or in combination of two or more. Among these, isophorone diisocyanate is preferable.
[0057]
As a mixing ratio when the polyisocyanate (PIC) and the active hydrogen group-containing polyester resin (for example, a hydroxyl group-containing polyester resin) are reacted, the isocyanate group [NCO] in the polyisocyanate (PIC) and the hydroxyl group-containing component are used. The mixing equivalent ratio ([NCO] / [OH]) with the hydroxyl group [OH] in the polyester resin is usually preferably 5/1 to 1/1, and preferably 4/1 to 1.2 / 1. More preferred is 3/1 to 1.5 / 1.
If the isocyanate group [NCO] exceeds 5, the low-temperature fixability may deteriorate, and if it is less than 1, the hot offset resistance may deteriorate.
[0058]
There is no restriction | limiting in particular as content in the said isocyanate group containing polyester prepolymer (A) of the said polyisocyanate (PIC), Although it can select suitably according to the objective, For example, 0.5-40 mass% is Preferably, 1-30 mass% is more preferable, and 2-20 mass% is still more preferable.
When the content is less than 0.5% by mass, the hot offset resistance is deteriorated, and it may be difficult to achieve both heat-resistant storage stability and low-temperature fixability. When the content exceeds 40% by mass, Low temperature fixability may deteriorate.
[0059]
As an average number of the isocyanate groups contained per molecule of the isocyanate group-containing polyester prepolymer (A), 1 or more is preferable, 1.2 to 5 is more preferable, and 1.5 to 4 is more preferable.
When the average number of the isocyanate groups is less than 1, the molecular weight of the polyester resin (RMPE) modified with the urea bond-forming group is lowered, and the hot offset resistance may be deteriorated.
[0060]
--- Aqueous medium--
There is no restriction | limiting in particular as said aqueous medium, It can select suitably from well-known things, For example, water, a solvent miscible with this water, a mixture thereof, etc. are mentioned.
The solvent miscible with water is not particularly limited as long as it is miscible with water, and examples thereof include alcohol, dimethylformamide, tetrahydrofuran, cellosolves, and lower ketones.
Examples of the alcohol include methanol, isopropanol, ethylene glycol and the like. Examples of the cell solves include methyl cell solve. Examples of the lower ketones include acetone and methyl ethyl ketone.
These may be used individually by 1 type and may use 2 or more types together.
[0061]
The other components are not particularly limited and may be appropriately selected depending on the purpose. For example, a colorant, a release agent, an unmodified polyester resin, a charge control agent, inorganic fine particles, a fluidity improver, and a cleaning agent. Property improvers, magnetic materials, metal soaps, and the like.
[0062]
The colorant is not particularly limited and may be appropriately selected from known dyes and pigments according to the purpose. For example, carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G 5G, G), cadmium yellow, yellow iron oxide, ocher, yellow lead, titanium yellow, polyazo yellow, oil yellow, Hansa yellow (GR, A, RN, R), pigment yellow L, benzidine yellow (G , GR), Permanent Yellow (NCG), Vulcan Fast Yellow (5G, R), Tartrazine Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL, Isoindolinone Yellow, Bengala, Lead Red, Lead Zhu, Cadmium Red, Cadmium Mercury Red, Antimony Zhu, Permanent Red 4R Parared, Faisered, Parachlor ortho nitroaniline red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmine BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Risor Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pogment Scarlet 3B, Bordeaux 5B, Toluidine Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake, Thioindigo Red B, Thioindigo Maroon Oil Red, Quinacridone Red, Pyrazolone Red, Polyazo Red, Chrome Vermilion, Benzidine Orange, Perinone Orange, Oil Orange, Cobalt Blue, Cerulean Blue, Alkaline Blue Lake, Peacock Blue Lake, Victoria Blue Lake, Metal-Free Phthalocyanine Blue, Phthalocyanine Blue , Fast Sky Blue, Indanthrene Blue (RS, BC), Indigo, Ultramarine Blue, Bitumen, Anthraquinone Blue, Fast Violet B, Methyl Violet Lake, Cobalt Purple, Manganese Purple, Dioxane Violet, Anthraquinone Violet, Chrome Green, Zinc Green, Chrome oxide, pyridian, emerald green, pigment green B, naphthol green B, green gold, a Cid green lake, malachite green lake, phthalocyanine green, anthraquinone green, titanium oxide, zinc white, litbon, and the like.
These may be used individually by 1 type and may use 2 or more types together.
[0063]
The content of the colorant in the toner is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 1 to 15% by weight, and more preferably 3 to 10% by weight.
Even if the content is less than 1% by mass or exceeds 15% by mass, the image density may be insufficient or excessive, and good image quality may not be obtained.
[0064]
The colorant can also be used as a master batch combined with a resin.
The resin is not particularly limited and may be appropriately selected depending on the intended purpose.For example, styrene or a substituted polymer thereof, styrene copolymer, polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, Polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, polyacrylic acid resin, rosin, modified rosin, terpene resin, aliphatic hydrocarbon resin, alicyclic hydrocarbon resin, Aromatic petroleum resin, chlorinated paraffin, paraffin wax and the like can be mentioned.
These may be used individually by 1 type and may use 2 or more types together.
[0065]
Examples of the polymer of styrene or a substituted product thereof include polyester resin, polystyrene, poly p-chlorostyrene, polyvinyl toluene, and the like.
Examples of the styrene copolymer include styrene-p-chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer. Copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-methacrylic copolymer Acid butyl copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene- Acrylonitrile-indene copolymer, Len - maleic acid copolymer, styrene - maleic acid ester copolymer, and the like.
[0066]
The masterbatch can be produced by mixing or kneading the masterbatch resin and the colorant under high shear. At this time, it is preferable to add an organic solvent in order to enhance the interaction between the colorant and the resin. Also, the so-called flushing method is preferable in that the wet cake of the colorant can be used as it is, and there is no need to dry it. This flushing method is a method of mixing or kneading an aqueous paste containing water of a colorant together with a resin and an organic solvent, and transferring the colorant to the resin side to remove moisture and organic solvent components. For the mixing or kneading, for example, a high shear dispersion device such as a three-roll mill is preferably used.
[0067]
There is no restriction | limiting in particular as said mold release agent, According to the objective, it can select suitably from well-known things, For example, waxes etc. are mentioned suitably.
Examples of the waxes include carbonyl group-containing waxes, polyolefin waxes, and long-chain hydrocarbons. These may be used individually by 1 type and may use 2 or more types together. Among these, a carbonyl group-containing wax is preferable.
Examples of the carbonyl group-containing wax include polyalkanoic acid esters, polyalkanol esters, polyalkanoic acid amides, polyalkylamides, dialkyl ketones, and the like. Examples of the polyalkanoic acid ester include carnauba wax, montan wax, trimethylolpropane tribehenate, pentaerythritol tetrabehenate, pentaerythritol diacetate dibehenate, glycerin tribehenate, and 1,18-octadecane. Examples thereof include diol distearate. Examples of the polyalkanol ester include tristearyl trimellitic acid and distearyl maleate. Examples of the polyalkanoic acid amide include dibehenyl amide. Examples of the polyalkylamide include trimellitic acid tristearylamide. Examples of the dialkyl ketone include distearyl ketone. Of these carbonyl group-containing waxes, polyalkanoic acid esters are particularly preferred.
Examples of the polyolefin wax include polyethylene wax and polypropylene wax.
Examples of the long chain hydrocarbon include paraffin wax and sazol wax.
[0068]
There is no restriction | limiting in particular as melting | fusing point of the said mold release agent, Although it can select suitably according to the objective, 40-160 degreeC is preferable, 50-120 degreeC is more preferable, 60-90 degreeC is especially preferable.
When the melting point is less than 40 ° C., the wax may adversely affect the heat-resistant storage stability, and when it exceeds 160 ° C., cold offset may easily occur during fixing at a low temperature.
The melt viscosity of the release agent is preferably 5 to 1000 cps, more preferably 10 to 100 cps, as a measured value at a temperature 20 ° C. higher than the melting point of the wax.
If the melt viscosity is less than 5 cps, the releasability may be lowered, and if it exceeds 1000 cps, the effect of improving hot offset resistance and low-temperature fixability may not be obtained.
[0069]
There is no restriction | limiting in particular as content in the said toner of the said mold release agent, Although it can select suitably according to the objective, 0-40 mass% is preferable and 3-30 mass% is more preferable.
When the content exceeds 40% by mass, the fluidity of the toner may be deteriorated.
[0070]
When the unmodified polyester resin is contained in the toner, low-temperature fixability and glossiness can be improved.
Examples of the unmodified polyester resin include those similar to the urea bond-forming group-containing polyester resin, that is, a polycondensate of polyol (PO) and polycarboxylic acid (PC). The unmodified polyester resin is partially compatible with the urea bond-forming group-containing polyester resin (RMPE), that is, has a similar structure compatible with each other. It is preferable in terms of hot offset.
The weight average molecular weight of the unmodified polyester resin is preferably 1,000 to 30,000, more preferably 1,500 to 10,000, and more preferably 2,000 to 30,000, as measured by GPC (gel permeation chromatography). 8,000 is particularly preferred. When the weight average molecular weight is less than 1,000, the heat resistant storage stability may be deteriorated, and when it exceeds 30,000, the low temperature fixability may be deteriorated.
The glass transition temperature of the unmodified polyester resin is preferably 30 to 50 ° C, and more preferably 35 to 45 ° C. When the glass transition temperature is less than 30 ° C., the heat-resistant storage stability of the toner may be deteriorated, and when it exceeds 50 ° C., the low-temperature fixability may be insufficient.
The hydroxyl value of the unmodified polyester resin is preferably 5 mgKOH / g, more preferably 10 to 120 mgKOH / g, and still more preferably 20 to 80 mgKOH / g. If the hydroxyl value is less than 5, it may be difficult to achieve both heat-resistant storage stability and low-temperature fixability.
The acid value of the unmodified polyester resin is preferably 0 to 40 mgKOH / g, more preferably 0 to 30 mgKOH / g. Generally, it becomes easy to be negatively charged by giving the toner an acid value.
[0071]
When the unmodified polyester resin is contained in the toner, the mixing mass ratio (RMPE / PE) of the urea bond-forming group-containing polyester resin (RMPE) and the unmodified polyester resin (PE) is 5/95. -25/75 is preferable, and 10 / 90-25 / 75 is more preferable.
When the mixing mass ratio of the unmodified polyester resin (PE) exceeds 95, the hot offset resistance is deteriorated, and it may be difficult to achieve both heat-resistant storage stability and low-temperature fixability. Glossiness may deteriorate.
[0072]
The charge control agent is not particularly limited and may be appropriately selected from known ones according to the purpose. However, since a color tone may change when a colored material is used, a colorless or nearly white material may be used. Preferably, for example, triphenylmethane dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts (including fluorine-modified quaternary ammonium salts), alkylamides, phosphorus alone or compounds thereof, tungsten Examples thereof include a single substance or a compound thereof, a fluorine-based activator, a metal salt of salicylic acid, and a metal salt of a salicylic acid derivative. These may be used individually by 1 type and may use 2 or more types together.
Commercially available products may be used as the charge control agent. Examples of the commercially available products include quaternary ammonium salt Bontron P-51, oxynaphthoic acid metal complex E-82, and salicylic acid metal complex. E-84, E-89 of a phenol-based condensate (above, manufactured by Orient Chemical Industries), TP-302, TP-415 of a quaternary ammonium salt molybdenum complex (above, manufactured by Hodogaya Chemical Co., Ltd.), Fourth Copy charge PSY VP2038 of quaternary ammonium salt, copy blue PR of triphenylmethane derivative, copy charge of quaternary ammonium salt NEG VP2036, copy charge NX VP434 (manufactured by Hoechst), LRA-901, LR which is a boron complex -147 (Nippon Carlit), quinacridone, azo pigment, other sulfonic acid groups, cal Examples thereof include polymer compounds having a functional group such as a boxyl group and a quaternary ammonium salt.
The charge control agent may be melted and kneaded with the master batch and then dissolved or dispersed, or may be added together with each component of the toner when directly dissolving or dispersing in the organic solvent, or The toner particles may be fixed on the toner surface after production.
[0073]
The content of the charge control agent in the toner varies depending on the type of the adhesive base material, the presence or absence of additives, the dispersion method, and the like, and cannot be defined generally. 0.1-10 mass parts is preferable with respect to part, and 0.2-5 mass parts is more preferable. When the content is less than 0.1 parts by mass, the charge controllability may not be obtained. When the content exceeds 10 parts by mass, the chargeability of the toner becomes too large, and the effect of the main charge control agent is reduced. As a result, the electrostatic attractive force with the developing roller increases, which may lead to a decrease in developer fluidity and a decrease in image density.
[0074]
The inorganic fine particles are not particularly limited and may be appropriately selected from known ones according to the purpose. For example, silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, titanate Strontium, zinc oxide, tin oxide, silica sand, clay, mica, wollastonite, diatomaceous earth, chromium oxide, cerium oxide, pengala, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, carbonized Examples thereof include silicon and silicon nitride. These may be used individually by 1 type and may use 2 or more types together.
The primary particle diameter of the inorganic fine particles is preferably 5 nm to 2 μm, and more preferably 5 nm to 500 nm. The specific surface area of the inorganic fine particles by BET method is 20 to 500 m.²/ G is preferred.
The content of the inorganic fine particles in the toner is preferably 0.01 to 5.0% by mass, and more preferably 0.01 to 2.0% by mass.
[0075]
The fluidity improver means a material that can be surface treated to increase hydrophobicity and prevent deterioration of flow characteristics and charging characteristics even under high humidity. For example, a silane coupling agent, a silylating agent, Examples thereof include a silane coupling agent having a fluoroalkyl group, an organic titanate coupling agent, an aluminum coupling agent, silicone oil, and modified silicone oil.
The cleaning improver is added to the toner in order to remove the developer after transfer remaining on the photoreceptor or the primary transfer medium, and includes, for example, fatty acid metal salts such as zinc stearate, calcium stearate, stearic acid, and the like. Examples thereof include polymer fine particles produced by soap-free emulsion polymerization such as methyl methacrylate fine particles and polystyrene fine particles. The polymer fine particles preferably have a relatively narrow particle size distribution, and those having a volume average particle size of 0.01 to 1 μm are suitable.
There is no restriction | limiting in particular as said magnetic material, According to the objective, it can select suitably from well-known things, For example, iron powder, a magnetite, a ferrite etc. are mentioned. Among these, white is preferable in terms of color tone.
[0076]
The toner of the present invention is not particularly limited as to its physical properties such as shape and size, and can be appropriately selected depending on the purpose. It preferably has generation temperature, thermal characteristics, image density, average circularity, weight (mass) average particle diameter, BET specific surface area, and the like.
[0077]
As said penetration, the penetration measured by the penetration test (JIS K2235-1991) needs to be 15 mm or more, for example, and 20-30 mm is more preferable.
When the penetration is less than 15 mm, the heat resistant storage stability may be deteriorated.
The penetration can be measured according to JIS K2235-1991. Specifically, a 50 ml glass container is filled with toner and left in a thermostatic bath at 50 ° C. for 20 hours. The penetration can be measured by cooling the toner to room temperature and performing a penetration test. In addition, it has shown that the said heat-resistant preservation | save property is excellent, so that the said penetration value is large.
[0078]
As the low-temperature fixability, from the viewpoint of achieving both a reduction in fixing temperature and no occurrence of offset, the lower fixing minimum temperature is preferably lower, and the higher the offset non-reaction temperature is, the lower the fixing temperature and no occurrence of offset. As a temperature range in which both can be achieved, the minimum fixing temperature is less than 150 ° C., and the non-offset temperature is 200 ° C. or more.
The fixing minimum temperature is, for example, an image forming apparatus, a transfer sheet is set, a copy test is performed, and the obtained fixed image is rubbed with a pad. The fixing roll temperature is the lower limit fixing temperature.
The offset non-occurrence temperature is set by, for example, using an image forming apparatus, setting a transfer paper, and each color of solid images of red, blue, and green as single colors of yellow, magenta, cyan, and black, and solid colors of each color. It can be determined by adjusting the toner image to be developed, adjusting the temperature of the fixing belt to be variable, and measuring the temperature at which no offset occurs.
[0079]
The thermal characteristics are also called flow tester characteristics, and are evaluated as, for example, a softening temperature (Ts), an outflow start temperature (Tfb), a 1/2 method softening point (T1 / 2), and the like. These thermal characteristics can be measured by an appropriately selected method. For example, the thermal characteristics can be obtained from a flow curve measured using an elevated flow tester CFT500 type (manufactured by Shimadzu Corporation).
There is no restriction | limiting in particular as said softening temperature (Ts), According to the objective, it can select suitably, For example, 30 degreeC or more is preferable and 50-120 degreeC is more preferable. When the softening temperature (Ts) is less than 30 ° C., at least one of heat resistant storage stability and low temperature storage stability may be deteriorated.
There is no restriction | limiting in particular as said outflow start temperature (Tfb), According to the objective, it can select suitably, For example, 50 degreeC or more is preferable and 60-150 degreeC is more preferable. When the outflow start temperature (Tfb) is less than 50 ° C., at least one of heat resistant storage stability and low temperature storage stability may deteriorate.
The 1/2 method softening point (T1 / 2) is not particularly limited and may be appropriately selected depending on the intended purpose. For example, 60 ° C. or higher is preferable, and 80 to 170 ° C. is more preferable. If the 1/2 method softening point (T1 / 2) is less than 60 ° C., at least one of heat resistant storage stability and low temperature storage stability may be deteriorated.
[0080]
The image density is, for example, preferably 1.90 or more, more preferably 2.00 or more, and 2.10 or more, as measured by a spectrometer (X-Light, 938 Spectrodensitometer). Is particularly preferred.
If the image density is less than 1.90, the image density may be low and high image quality may not be obtained.
The image density is, for example, imagio Neo 450 (manufactured by Ricoh Co., Ltd.), and the amount of developer adhered to copy paper (TYPE 6000 <70W>; manufactured by Ricoh Co., Ltd.) is 1.00 ± 0.05 mg / cm.²The solid roller image was formed at a fixing roller surface temperature of 160 ± 2 ° C., and the image density at any six locations in the solid image obtained was measured using a spectrometer (938 Spectrodensitometer, manufactured by X-Light). It can be measured by measuring and calculating the average value.
[0081]
The average circularity is a value obtained by dividing the circumference of an equivalent circle having the same projected area as the shape of the toner by the circumference of the actual particles. For example, 0.90 to 1.00 is preferable, and 0.910 to 0 is preferable. .995 is more preferred. The particles having an average circularity of less than 0.90 are preferably 30% or less.
If the average circularity is less than 0.90, satisfactory transferability and a high-quality image free from dust may not be obtained. If the average circularity exceeds 0.995, image formation employing blade cleaning or the like is employed. In the system, defective cleaning occurs on the photoconductor and the transfer belt, and in the case of image formation with a high image area ratio such as a photographic image, an untransferred image is formed due to defective paper feeding, etc. The accumulated toner may become a transfer residual toner on the photoconductor, resulting in background smearing of the image, or it may contaminate the charging roller for charging the photoconductor in contact with the original charging ability. It may become impossible to demonstrate.
The average circularity is measured by, for example, an optical detection band method in which a suspension containing toner particles is passed through an imaging unit detection band on a flat plate, and a particle image is optically detected and analyzed by a CCD camera. For example, it can be measured using a flow type particle image analyzer FPIA-2100 (manufactured by Sysmex Corporation).
[0082]
The volume average particle diameter of the toner is preferably 3 to 8 μm, for example.
When the volume average particle size is less than 3 μm, in the case of a two-component developer, the toner may be fused to the surface of the carrier during long-term agitation in the developing device, and the charging ability of the carrier may be reduced. In the developer, toner filming on the developing roller and toner fusion to a member such as a blade are likely to occur because the toner is thinned. When the thickness exceeds 8 μm, the resolution is high and high. It becomes difficult to obtain an image of an image quality, and when the balance of the toner in the developer is performed, the variation in the particle diameter of the toner may increase.
[0083]
The ratio of the volume average particle diameter to the number average particle diameter (volume average particle diameter / number average particle diameter) in the toner is, for example, preferably 1.00 to 1.25, more preferably 1.10 to 1.25. preferable.
If the ratio of the volume average particle diameter to the number average particle diameter (volume average particle diameter / number average particle diameter) is less than 1.00, the two-component developer may cause the surface of the carrier to be agitated over a long period of time in the developing device. The toner may be fused to reduce the charging ability of the carrier. In the case of a one-component developer, the toner is applied to a member such as a blade in order to form the toner on the developing roller or to make the toner thin. Fusing tends to occur, and if it exceeds 1.25, it becomes difficult to obtain a high-resolution and high-quality image, and the toner particle size when the balance of toner in the developer is performed Fluctuations may increase.
[0084]
The volume average particle diameter and the ratio of the volume average particle diameter to the number average particle diameter (volume average particle diameter / number average particle diameter) are, for example, a particle size measuring device “Multisizer II” manufactured by Beckman Coulter, Inc. Can be measured.
[0085]
The BET specific surface area of the toner is, for example, 0.5 to 8.0 m.²/ G is preferred, 0.5 to 7.5 m²/ G is more preferable.
The BET specific surface area is 0.5 m²If it is less than / g, the organic fine particles remaining on the toner surface become a film or cover the entire surface of the toner closely, and the fine resin particles impair the adhesiveness between the binder resin component inside the toner and the fixing paper, thereby fixing the toner. While an increase in the minimum temperature may be observed, 8.0 m²When the amount exceeds / g, the resin fine particles inhibit the exudation of the wax, and the effect of releasing the wax cannot be obtained, and offset may be observed.
The specific surface area of the toner can be measured according to the BET method. For example, the specific surface area measuring device Tristar 3000 (manufactured by Shimadzu Corporation) is used to adsorb nitrogen gas on the sample surface and the BET multipoint method is used. can do.
[0086]
The coloration of the toner of the present invention is not particularly limited and can be appropriately selected according to the purpose, and can be at least one selected from black toner, cyan toner, magenta toner and yellow toner. This toner can be obtained by appropriately selecting the type of the colorant.
[0087]
The toner of the present invention contains at least two kinds of resin fine particles, resin fine particles that impart heat-resistant storage stability to the toner and resin fine particles that impart low-temperature fixability to the toner. The high-quality image can be formed even under low temperature fixing conditions. In addition, the toner of the present invention includes the adhesive base formed by reacting the active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound in an aqueous medium. Excellent properties such as properties, fluidity, transferability, and fixability. Therefore, the toner of the present invention can be suitably used in various fields, and can be more suitably used for image formation by electrophotography. The following toner-containing container, developer, and process of the present invention are described below. It can be particularly suitably used for a cartridge, an image forming apparatus, and an image forming method.
[0088]
The toner of the present invention can be produced by a known method, but can be suitably produced by the toner production method of the present invention described later.
[0089]
(Toner production method)
The method for producing the toner of the present invention is a method for producing the toner of the present invention described above, wherein the active hydrogen group-containing compound, a polymer having a site capable of reacting with the active hydrogen group-containing compound, and at least two kinds are used. At least a step of obtaining a toner while producing an adhesive substrate by dispersing and reacting the resin fine particles in an aqueous medium, and further including other steps appropriately selected as necessary.
[0090]
In the step, for example, preparation of an aqueous medium phase, preparation of an organic solvent phase, emulsification / dispersion, and others (synthesis of a polymer (prepolymer) capable of reacting with the active hydrogen group-containing compound, the active hydrogen group-containing compound) Etc.).
[0091]
The aqueous medium phase can be prepared, for example, by dispersing the at least two kinds of resin fine particles in the aqueous medium. There is no restriction | limiting in particular as the addition amount in this aqueous medium of this resin fine particle, According to the objective, it can select suitably, For example, 0.5-10 mass% is preferable.
The organic solvent phase is prepared by mixing the active hydrogen group-containing compound, the polymer capable of reacting with the active hydrogen group-containing compound, the colorant, the mold release agent, the charge control agent, The toner raw material such as a modified polyester resin can be dissolved or dispersed.
It should be noted that components other than the polymer (prepolymer) capable of reacting with the active hydrogen group-containing compound in the toner raw material are added when the resin fine particles are dispersed in the aqueous medium in the aqueous medium phase preparation. You may add and mix in an aqueous medium, or when adding the said organic solvent phase to the said aqueous medium phase, you may add to the said aqueous medium phase with this organic solvent phase.
[0092]
The organic solvent is not particularly limited as long as it is a solvent that can dissolve or disperse the toner raw material, and can be appropriately selected according to the purpose, and has a boiling point of less than 150 ° C. in terms of ease of removal. For example, toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, ethyl acetate, Examples thereof include methyl ethyl ketone and methyl isobutyl ketone. Among these, ethyl acetate, toluene, xylene, benzene, methylene chloride, 1,2-dichloroethane, chloroform, carbon tetrachloride and the like are particularly preferable. These may be used individually by 1 type and may use 2 or more types together.
There is no restriction | limiting in particular as the usage-amount of the said organic solvent, According to the objective, it can select suitably, For example, 40-300 mass parts is preferable with respect to 100 mass parts of said toner raw materials, and 60-140 mass parts is. More preferably, 80-120 mass parts is still more preferable.
[0093]
The emulsification / dispersion can be performed by emulsifying / dispersing the previously prepared organic solvent phase in the previously prepared aqueous medium phase. In the emulsification / dispersion, when the active hydrogen group-containing compound and the polymer capable of reacting with the active hydrogen group-containing compound are subjected to an extension reaction or a crosslinking reaction, the adhesive base material is generated.
The adhesive substrate (for example, the urea-modified polyester resin) includes, for example, (1) a polymer that can react with the active hydrogen group-containing compound (for example, the isocyanate group-containing polyester prepolymer (A)). The organic solvent phase is emulsified and dispersed in the aqueous medium phase together with the active hydrogen group-containing compound (for example, the amines (B)) to form a dispersion, and both are extended in the aqueous medium phase. Or (2) the organic solvent phase is emulsified and dispersed in the aqueous medium to which the active hydrogen group-containing compound has been added in advance to form a dispersion, and the aqueous medium It may be produced by extending or cross-linking both in the phase, or (3) the organic solvent phase is added and mixed in the aqueous medium and then the active hydrogen group-containing The compound was added to form a dispersion, it may be generated by elongation reaction or crosslinking reaction from particle interfaces in the aqueous medium phase. In the case of (3), a modified polyester resin is preferentially produced on the surface of the toner to be produced, and a concentration gradient can be provided in the toner particles.
[0094]
The reaction conditions for producing the adhesive base material by the emulsification / dispersion are not particularly limited, depending on the combination of the polymer capable of reacting with the active hydrogen group-containing compound and the active hydrogen group-containing compound. The reaction time is preferably 10 minutes to 40 hours, more preferably 2 hours to 24 hours, and the reaction temperature is preferably 0 to 150 ° C, more preferably 40 to 98 ° C.
[0095]
In the aqueous medium phase, as a method for stably forming the dispersion containing a polymer capable of reacting with the active hydrogen group-containing compound (for example, the isocyanate group-containing polyester prepolymer (A)), for example, Polymer capable of reacting with the active hydrogen group-containing compound dissolved or dispersed in the organic solvent in the aqueous medium phase (for example, the isocyanate group-containing polyester prepolymer (A)), the colorant, and the release agent And a method of adding the toner raw materials such as the charge control agent and the unmodified polyester resin, and dispersing them by shearing force.
The dispersion is not particularly limited as a method thereof, and can be appropriately selected using a known disperser. Examples of the disperser include a low-speed shear disperser, a high-speed shear disperser, and a friction type. Examples thereof include a disperser, a high-pressure jet disperser, and an ultrasonic disperser. Among these, a high-speed shearing disperser is preferable in that the particle size of the dispersion can be controlled to 2 to 20 μm.
When the high-speed shearing disperser is used, conditions such as the rotation speed, dispersion time, and dispersion temperature are not particularly limited and can be appropriately selected according to the purpose. For example, the rotation speed is 1000 -30000 rpm is preferable, 5000-20000 rpm is more preferable, the dispersion time is preferably 0.1-5 minutes in the case of a batch system, and the dispersion temperature is preferably 0-150 ° C. under pressure, -98 degreeC is more preferable. The dispersion temperature is generally easier when the temperature is higher.
[0096]
In the emulsification / dispersion, the usage amount of the aqueous medium is preferably 50 to 2,000 parts by mass, and more preferably 100 to 1,000 parts by mass with respect to 100 parts by mass of the toner raw material.
When the amount used is less than 50 parts by mass, the toner raw material is poorly dispersed, and toner particles having a predetermined particle size may not be obtained. When the amount exceeds 2,000 parts by mass, the production cost is high. May be.
[0097]
In the emulsification / dispersion, it is preferable to use a dispersant as necessary from the viewpoint of sharpening the particle size distribution and performing stable dispersion.
There is no restriction | limiting in particular as said dispersing agent, According to the objective, it can select suitably, For example, surfactant, a poorly water-soluble inorganic compound dispersing agent, a polymeric protective colloid, etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together. Among these, surfactants are preferable.
[0098]
Examples of the surfactant include an anionic surfactant, a cationic surfactant, a nonionic surfactant, and an amphoteric surfactant.
Examples of the anionic surfactant include alkylbenzene sulfonates, α-olefin sulfonates, phosphate esters, and the like, and those having a fluoroalkyl group are preferable. Examples of the anionic surfactant having a fluoroalkyl group include a fluoroalkylcarboxylic acid having 2 to 10 carbon atoms or a metal salt thereof, disodium perfluorooctanesulfonylglutamate, 3- [omega-fluoroalkyl (6 carbon atoms). -11) Oxy] -1-alkyl (carbon number 3-4) sodium sulfonate, 3- [omega-fluoroalkanoyl (carbon number 6-8) -N-ethylamino] -1-propanesulfonic acid sodium, fluoroalkyl (Carbon number 11-20) carboxylic acid or its metal salt, perfluoroalkyl carboxylic acid (carbon number 7-13) or its metal salt, perfluoroalkyl (carbon number 4-12) sulfonic acid or its metal salt, perfluoro Octanesulfonic acid diethanolamide, N-propyl-N- (2-hydroxy Ethyl) perfluorooctanesulfonamide, perfluoroalkyl (carbon number 6-10) sulfonamidopropyltrimethylammonium salt, perfluoroalkyl (carbon number 6-10) -N-ethylsulfonylglycine salt, monoperfluoroalkyl (carbon number) 6-16) Ethyl phosphate and the like. Examples of commercially available surfactants having a fluoroalkyl group include Surflon S-111, S-112, S-113 (manufactured by Asahi Glass Co., Ltd.); Fluorard FC-93, FC-95, FC-98, FC- 129 (manufactured by Sumitomo 3M); Unidyne DS-101, DS-102 (manufactured by Daikin Industries); Megafac F-110, F-120, F-113, F-191, F-812, F-833 (large) Nihon Ink Co., Ltd.); Xtop EF-102, 103, 104, 105, 112, 123A, 123B, 306A, 501, 201, 204 (manufactured by Tochem Products); Manufactured) and the like.
[0099]
Examples of the cationic surfactant include amine salt type surfactants and quaternary ammonium salt type cationic surfactants. Examples of the amine salt type surfactant include alkylamine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, imidazolines, and the like. Examples of the quaternary ammonium salt type cationic surfactant include alkyltrimethylammonium salt, dialkyldimethylammonium salt, alkyldimethylbenzylammonium salt, pyridinium salt, alkylisoquinolinium salt, benzethonium chloride and the like. . Among the cationic surfactants, aliphatic quaternary ammonium such as aliphatic primary, secondary or tertiary amine acids having a fluoroalkyl group, perfluoroalkyl (6 to 10 carbon atoms) sulfonamidopropyltrimethylammonium salt, etc. Salts, benzalkonium salts, benzethonium chloride, pyridinium salts, imidazolinium salts, and the like. Commercially available products of the cationic surfactant include, for example, Surflon S-121 (manufactured by Asahi Glass Co., Ltd.); Florard FC-135 (manufactured by Sumitomo 3M Co.); Unidyne DS-202 (manufactured by Daikin Industries Ltd.), MegaFuck F-150 F-824 (manufactured by Dainippon Ink Co., Ltd.); Xtop EF-132 (manufactured by Tochem Products); Footgent F-300 (manufactured by Neos).
[0100]
Examples of the nonionic surfactant include fatty acid amide derivatives and polyhydric alcohol derivatives.
Examples of the amphoteric surfactant include alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine, N-alkyl-N, N-dimethylammonium betaine and the like.
[0101]
Examples of the poorly water-soluble inorganic compound dispersant include tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, and hydroxyapatite.
Examples of the polymeric protective colloid include acids, (meth) acrylic monomers containing a hydroxyl group, vinyl alcohol or ethers of vinyl alcohol, esters of vinyl alcohol and a compound containing a carboxyl group, amides Examples thereof include homopolymers or copolymers such as compounds or their methylol compounds, chlorides, those having a nitrogen atom or a heterocyclic ring thereof, polyoxyethylenes, and celluloses.
Examples of the acids include acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid, maleic anhydride, and the like. Examples of the (meth) acrylic monomer containing a hydroxyl group include β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate, and γ-acrylate. -Hydroxypropyl, γ-hydroxypropyl methacrylate, 3-chloro-2-hydroxypropyl acrylate, 3-chloro-2-hydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerol monoacrylate Glycerin monomethacrylate, N-methylol acrylamide, N-methylol methacrylamide and the like. Examples of the vinyl alcohol or ethers with vinyl alcohol include vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, and the like. Examples of the esters of vinyl alcohol and a compound containing a carboxyl group include vinyl acetate, vinyl propionate, and vinyl butyrate. Examples of the amide compound or these methylol compounds include acrylamide, methacrylamide, diacetone acrylamide acid, or these methylol compounds. Examples of the chlorides include acrylic acid chloride and methacrylic acid chloride. Examples of the homopolymer or copolymer such as those having a nitrogen atom or a heterocyclic ring thereof include vinyl pyridine, vinyl pyrrolidone, vinyl imidazole, and ethylene imine. Examples of the polyoxyethylene are polyoxyethylene, polyoxypropylene, polyoxyethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonylphenyl ether, polyoxyethylene Examples thereof include oxyethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ester, and polyoxyethylene nonyl phenyl ester. Examples of the celluloses include methyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose.
[0102]
In the emulsification / dispersion, a dispersion stabilizer can be used as necessary.
Examples of the dispersion stabilizer include acids that are soluble in acids and alkalis such as calcium phosphate salts.
When the dispersion stabilizer is used, the calcium phosphate salt can be removed from the fine particles by a method of dissolving the calcium phosphate salt with an acid such as hydrochloric acid and then washing with water or a method of decomposing with an enzyme.
[0103]
In the emulsification / dispersion, a catalyst for the elongation reaction or the crosslinking reaction can be used. Examples of the catalyst include dibutyltin laurate and dioctyltin laurate.
[0104]
The organic solvent is removed from the emulsified slurry obtained in the emulsification / dispersion. The organic solvent is removed by (1) a method in which the entire reaction system is gradually heated to completely evaporate and remove the organic solvent in the droplets, and (2) the emulsion dispersion is sprayed in a dry atmosphere. And a method in which the water-insoluble organic solvent in the droplets is completely removed to form toner fine particles, and the aqueous dispersant is removed by evaporation.
[0105]
When the organic solvent is removed, toner particles are formed. The toner particles can be washed, dried, etc., and then classified as desired. The classification can be performed, for example, by removing fine particle portions by a cyclone, a decanter, centrifugation, or the like in a liquid, and the classification operation may be performed after obtaining a powder after drying.
[0106]
Thus, the obtained toner particles are mixed with particles of the colorant, release agent, charge control agent, etc., and further, a mechanical impact force is applied to the release agent from the surface of the toner particles. And the like can be prevented from being detached.
As a method of applying the mechanical impact force, for example, a method of applying an impact force to the mixture with a blade rotating at high speed, an appropriate collision between particles or composite particles by introducing the mixture into a high-speed air stream and accelerating the mixture is accelerated. The method of making it collide with a board etc. are mentioned. As an apparatus used for this method, for example, an ong mill (manufactured by Hosokawa Micron Co., Ltd.), an I-type mill (manufactured by Nippon Pneumatic Co., Ltd.) and a pulverization air pressure is lowered, and a hybridization system (Nara Machinery Co., Ltd.) Product), kryptron system (manufactured by Kawasaki Heavy Industries, Ltd.), automatic mortar, and the like.
[0107]
(Developer)
The developer of the present invention contains at least the toner of the present invention, and other components such as a carrier selected as appropriate. The developer may be a one-component developer or a two-component developer. However, when it is used for a high-speed printer or the like corresponding to the recent improvement in information processing speed, the life is improved. In view of the above, the two-component developer is preferable.
In the case of the one-component developer using the toner of the present invention, even if the balance of the toner is performed, there is little fluctuation in the particle diameter of the toner, and the filming of the toner on the developing roller or the toner is made thin. Therefore, the toner is not fused to a member such as a blade, and good and stable developability and image can be obtained even when the developing device is used (stirred) for a long time. Further, in the case of the two-component developer using the toner of the present invention, even if the balance of the toner over a long period of time is performed, the fluctuation of the toner particle diameter in the developer is small, and even in the long-term stirring in the developing device, Good and stable developability can be obtained.
[0108]
There is no restriction | limiting in particular as said carrier, Although it can select suitably according to the objective, What has a core material and the resin layer which coat | covers this core material is preferable.
[0109]
There is no restriction | limiting in particular as a material of the said core material, It can select suitably from well-known things, For example, 50-90 emu / g manganese-strontium (Mn-Sr) type material, manganese-magnesium (Mn-) Mg) -based materials and the like are preferable, and highly magnetized materials such as iron powder (100 emu / g or more) and magnetite (75 to 120 emu / g) are preferable in terms of securing image density. In addition, a weakly magnetized material such as a copper-zinc (Cu—Zn) -based (30 to 80 emu / g) is advantageous in that it can weaken the contact with the photoconductor in which the toner is in a spiked state and is advantageous in improving the image quality. Is preferred. These may be used alone or in combination of two or more.
[0110]
The core material has a volume average particle diameter of preferably 10 to 150 μm, more preferably 40 to 100 μm.
The average particle diameter (volume average particle diameter (D₅₀)) Is less than 10 μm, in the distribution of carrier particles, there are many fine powder systems, the magnetization per particle is lowered and carrier scattering may occur, and if it exceeds 150 μm, the specific surface area decreases, Toner scattering may occur, and in the case of a full color with many solid portions, reproduction of the solid portions may be particularly deteriorated.
[0111]
The material of the resin layer is not particularly limited and can be appropriately selected from known resins according to the purpose. For example, amino resins, polyvinyl resins, polystyrene resins, halogenated olefin resins, Polyester resin, polycarbonate resin, polyethylene resin, polyvinyl fluoride resin, polyvinylidene fluoride resin, polytrifluoroethylene resin, polyhexafluoropropylene resin, copolymer of vinylidene fluoride and acrylic monomer, vinylidene fluoride And a copolymer of vinyl fluoride, a fluoroterpolymer such as a terpolymer of tetrafluoroethylene, vinylidene fluoride, and a non-fluorinated monomer, and a silicone resin. These may be used individually by 1 type and may use 2 or more types together.
[0112]
Examples of the amino resin include urea-formaldehyde resin, melamine resin, benzoguanamine resin, urea resin, polyamide resin, and epoxy resin. Examples of the polyvinyl resin include acrylic resin, polymethyl methacrylate resin, poly Examples include acrylonitrile resin, polyvinyl acetate resin, polyvinyl alcohol resin, and polyvinyl butyral resin. Examples of the polystyrene resin include polystyrene resin and styrene acrylic copolymer resin. Examples of the halogenated olefin resin include polyvinyl chloride. Examples of the polyester resin include polyethylene terephthalate resin and polybutylene terephthalate resin.
[0113]
The resin layer may contain conductive powder or the like as necessary. Examples of the conductive powder include metal powder, carbon black, titanium oxide, tin oxide, and zinc oxide. The average particle diameter of these conductive powders is preferably 1 μm or less. When the average particle diameter exceeds 1 μm, it may be difficult to control electric resistance.
[0114]
For example, the resin layer is prepared by dissolving the silicone resin or the like in a solvent to prepare a coating solution, and then uniformly coating the coating solution on the surface of the core material by a known coating method, drying, and baking. It can be formed by doing. Examples of the application method include an immersion method, a spray method, and a brush coating method.
There is no restriction | limiting in particular as said solvent, Although it can select suitably according to the objective, For example, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cersol butyl acetate, etc. are mentioned.
The baking is not particularly limited, and may be an external heating method or an internal heating method. For example, a stationary electric furnace, a fluid electric furnace, a rotary electric furnace, a burner furnace, etc. The method of using, the method of using a microwave, etc. are mentioned.
[0115]
The amount of the resin layer in the carrier is preferably 0.01 to 5.0% by mass.
When the amount is less than 0.01% by mass, the uniform resin layer may not be formed on the surface of the core material. When the amount exceeds 5.0% by mass, the resin layer becomes thick. In some cases, granulation of carriers occurs, and uniform carrier particles may not be obtained.
[0116]
When the developer is the two-component developer, the content of the carrier in the two-component developer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, 90 to 98% by mass Is preferable, and 93-97 mass% is more preferable.
[0117]
Since the developer of the present invention contains the toner of the present invention, it is possible to achieve a balance between chargeability and fixability during image formation, and stably form high-quality images. .
The developer of the present invention can be suitably used for image formation by various known electrophotographic methods such as a magnetic one-component development method, a non-magnetic one-component development method, and a two-component development method. It can be particularly suitably used for containers, process cartridges, image forming apparatuses and image forming methods.
[0118]
(Toner container)
The toner-containing container of the present invention comprises the toner or the developer of the present invention contained in a container.
There is no restriction | limiting in particular as said container, It can select suitably from well-known things, For example, what has a container main body and a cap containing a toner etc. are mentioned suitably.
The size, shape, structure, material and the like of the container body containing toner are not particularly limited and can be appropriately selected according to the purpose. For example, the shape is preferably cylindrical. A spiral irregularity is formed on the peripheral surface, and the toner as the contents can be transferred to the discharge port side by rotating, and part or all of the spiral part has a bellows function, etc. Is particularly preferred. The material of the toner-containing container body is not particularly limited, and those having good dimensional accuracy are preferable. For example, a resin is preferably used. Among them, for example, polyester resin, polyethylene resin, polypropylene resin, polystyrene resin, Preferable examples include vinyl chloride resin, polyacrylic acid, polycarbonate resin, ABS resin, polyacetal resin, and the like.
The toner-containing container of the present invention is easy to store and transport, has excellent handleability, and is preferably used for replenishing toner by being detachably attached to the process cartridge and image forming apparatus of the present invention described later. Can do.
[0119]
(Process cartridge)
The process cartridge of the present invention develops an electrostatic latent image carrier carrying an electrostatic latent image and the electrostatic latent image carried on the electrostatic latent image carrier using a developer to form a visible image. And at least developing means for forming the film, and other means appropriately selected as necessary.
The developing means includes a developer container that contains the toner or developer of the present invention, and a developer carrier that carries and transports the toner or developer contained in the developer container. And a layer thickness regulating member for regulating the thickness of the toner layer to be carried.
The process cartridge of the present invention can be detachably provided in various electrophotographic apparatuses, and is preferably provided detachably in the electrophotographic apparatus of the present invention described later.
[0120]
(Image forming apparatus and image forming method)
The image forming apparatus of the present invention includes at least an electrostatic latent image carrier, an electrostatic latent image forming unit, a developing unit, a transfer unit, and a fixing unit, and further appropriately selected as necessary. It has other means, for example, static elimination means, cleaning means, recycling means, control means and the like.
The image forming method of the present invention includes at least an electrostatic latent image forming step, a developing step, a transfer step, and a fixing step, and further other steps appropriately selected as necessary, for example, a static elimination step, a cleaning step, Includes recycling and control processes.
[0121]
The image forming method of the present invention can be preferably carried out by the image forming apparatus of the present invention, the electrostatic latent image forming step can be performed by the electrostatic latent image forming means, and the developing step is the developing The transfer step can be performed by the transfer unit, the fixing step can be performed by the fixing unit, and the other steps can be performed by the other unit.
[0122]
-Electrostatic latent image forming step and electrostatic latent image forming means-
The electrostatic latent image forming step is a step of forming an electrostatic latent image on the electrostatic latent image carrier.
There are no particular restrictions on the material, shape, structure, size, etc. of the electrostatic latent image carrier (sometimes referred to as “photoconductive insulator” or “photoconductor”), and among the known ones The shape is preferably a drum shape, and examples of the material include inorganic photoconductors such as amorphous silicon and selenium, and organic photoconductors such as polysilane and phthalopolymethine. It is done. Among these, amorphous silicon or the like is preferable in terms of long life.
[0123]
The formation of the electrostatic latent image can be performed, for example, by uniformly charging the surface of the electrostatic latent image carrier and then performing imagewise exposure, and is performed by the electrostatic latent image forming unit. be able to.
The electrostatic latent image forming means includes, for example, at least a charger that uniformly charges the surface of the electrostatic latent image carrier and an exposure device that exposes the surface of the electrostatic latent image carrier imagewise. Prepare.
[0124]
The charging can be performed, for example, by applying a voltage to the surface of the electrostatic latent image carrier using the charger.
The charger is not particularly limited and may be appropriately selected depending on the purpose. For example, a known contact charging device including a conductive or semiconductive roll, brush, film, rubber blade, etc. And non-contact chargers using corona discharge such as corotrons and corotrons.
[0125]
The exposure can be performed, for example, by exposing the surface of the latent electrostatic image bearing member imagewise using the exposure device.
The exposure device is not particularly limited as long as it can expose the surface of the electrostatic latent image carrier charged by the charger so as to form an image to be formed, and is appropriately selected according to the purpose. For example, various exposure devices such as a copying optical system, a rod lens array system, a laser optical system, and a liquid crystal shutter optical system can be used.
In the present invention, a back light system in which imagewise exposure is performed from the back side of the electrostatic latent image carrier may be employed.
[0126]
-Development process and development means-
The developing step is a step of developing the electrostatic latent image using the toner or the developer of the present invention to form a visible image.
The visible image can be formed, for example, by developing the electrostatic latent image using the toner or the developer of the present invention, and can be performed by the developing unit.
The developing unit is not particularly limited as long as it can be developed using, for example, the toner or the developer of the present invention, and can be appropriately selected from known ones. For example, the toner of the present invention Preferred examples include a developer containing at least a developer, and at least a developing device capable of contacting or non-contacting the toner or the developer with the electrostatic latent image. More preferred is a developing device.
[0127]
The developing unit may be a dry developing type, a wet developing type, a single color developing unit, or a multi-color developing unit. For example, a toner having a stirrer for charging the toner or the developer by frictional stirring and a rotatable magnet roller is preferable.
[0128]
In the developing device, for example, the toner and the carrier are mixed and agitated, and the toner is charged by friction at that time, and held on the surface of the rotating magnet roller in a raised state to form a magnetic brush. . Since the magnet roller is disposed in the vicinity of the electrostatic latent image carrier (photoconductor), a part of the toner constituting the magnetic brush formed on the surface of the magnet roller is electrically attracted. It moves to the surface of the electrostatic latent image carrier (photoconductor) by force. As a result, the electrostatic latent image is developed with the toner, and a visible image is formed with the toner on the surface of the electrostatic latent image carrier (photoconductor).
[0129]
The developer accommodated in the developing device is a developer containing the toner of the present invention, but the developer may be a one-component developer or a two-component developer. The toner contained in the developer is the toner of the present invention.
[0130]
-Transfer process and transfer means-
The transfer step is a step of transferring the visible image onto a recording medium. After the primary transfer of the visible image onto the intermediate transfer member using an intermediate transfer member, the visible image is transferred onto the recording medium. A primary transfer step of forming a composite transfer image by transferring a visible image onto an intermediate transfer body using two or more colors, preferably full color toner as the toner, and a composite transfer image; A mode including a secondary transfer step of transferring the transfer image onto the recording medium is more preferable.
The transfer can be performed, for example, by charging the latent electrostatic image bearing member (photoconductor) of the visible image using a transfer charger, and can be performed by the transfer unit. The transfer means includes a primary transfer means for transferring a visible image onto an intermediate transfer member to form a composite transfer image, and a secondary transfer means for transferring the composite transfer image onto a recording medium. Embodiments are preferred.
The intermediate transfer member is not particularly limited and may be appropriately selected from known transfer members according to the purpose. For example, a transfer belt and the like are preferable.
[0131]
The transfer means (the primary transfer means and the secondary transfer means) is a transfer for peeling and charging the visible image formed on the electrostatic latent image carrier (photoconductor) to the recording medium side. It is preferable to have at least a vessel. There may be one transfer means or two or more transfer means.
Examples of the transfer device include a corona transfer device using corona discharge, a transfer belt, a transfer roller, a pressure transfer roller, and an adhesive transfer device.
The recording medium is not particularly limited and can be appropriately selected from known recording media (recording paper).
[0132]
The fixing step is a step of fixing the visible image transferred to the recording medium using a fixing device, and may be performed each time the toner of each color is transferred to the recording medium, or for the toner of each color. You may perform this simultaneously in the state which laminated | stacked this.
There is no restriction | limiting in particular as said fixing device, Although it can select suitably according to the objective, A well-known heating-pressing means is suitable. Examples of the heating and pressing means include a combination of a heating roller and a pressure roller, a combination of a heating roller, a pressure roller, and an endless belt.
The heating in the heating and pressing means is usually preferably 80 ° C to 200 ° C.
In the present invention, for example, a known optical fixing device may be used together with or in place of the fixing step and the fixing unit depending on the purpose.
[0133]
The neutralization step is a step of performing neutralization by applying a neutralization bias to the electrostatic latent image carrier, and can be suitably performed by a neutralization unit.
The neutralization means is not particularly limited, and may be appropriately selected from known neutralizers as long as it can apply a neutralization bias to the electrostatic latent image carrier. Preferably mentioned.
[0134]
The cleaning step is a step of removing the electrophotographic toner remaining on the electrostatic latent image carrier, and can be suitably performed by a cleaning unit.
The cleaning means is not particularly limited as long as it can remove the electrophotographic toner remaining on the electrostatic latent image carrier, and can be appropriately selected from known cleaners. Suitable examples include brush cleaners, electrostatic brush cleaners, magnetic roller cleaners, blade cleaners, brush cleaners, web cleaners, and the like.
[0135]
The recycling step is a step of recycling the electrophotographic color toner removed in the cleaning step to the developing unit, and can be suitably performed by the recycling unit.
There is no restriction | limiting in particular as said recycling means, A well-known conveyance means etc. are mentioned.
[0136]
The control means is a process for controlling the respective steps, and can be suitably performed by the control means.
The control means is not particularly limited as long as the movement of each means can be controlled, and can be appropriately selected according to the purpose. Examples thereof include devices such as a sequencer and a computer.
[0137]
One mode for carrying out the image forming method of the present invention by the image forming apparatus of the present invention will be described with reference to FIG. An image forming apparatus 100 shown in FIG. 1 includes a photosensitive drum 10 (hereinafter referred to as “photosensitive member 10”) as the electrostatic latent image carrier, a charging roller 20 as the charging unit, and exposure as the exposure unit. The apparatus 30 includes a developing device 40 as the developing means, an intermediate transfer member 50, a cleaning device 60 as the cleaning means having a cleaning blade, and a static elimination lamp 70 as the static elimination means.
[0138]
The intermediate transfer member 50 is an endless belt, and is designed to be movable in the direction of an arrow by three rollers 51 that are arranged inside and stretched. Part of the three rollers 51 also functions as a transfer bias roller that can apply a predetermined transfer bias (primary transfer bias) to the intermediate transfer member 50. The intermediate transfer body 50 is provided with a cleaning device 90 having a cleaning blade in the vicinity thereof, and for transferring (secondary transfer) a developed image (toner image) to a transfer sheet 95 as a final transfer material. A transfer roller 80 serving as a transfer unit to which a transfer bias can be applied is disposed to face the transfer roller 80. Around the intermediate transfer member 50, a corona charger 58 for applying a charge to the toner image on the intermediate transfer member 50 is arranged between the photosensitive member 10 and the intermediate transfer member 50 in the rotation direction of the intermediate transfer member 50. It is disposed between the contact portion and the contact portion between the intermediate transfer member 50 and the transfer paper 95.
[0139]
The developing device 40 includes a developing belt 41 as the developer carrying member, and a black developing unit 45K, a yellow developing unit 45Y, a magenta developing unit 45M, and a cyan developing unit 45C provided around the developing belt 41. . The black developing unit 45K includes a developer accommodating portion 42K, a developer supplying roller 43K, and a developing roller 44K. The yellow developing unit 45Y includes a developer accommodating portion 42Y, a developer supplying roller 43Y, and a developing roller 44Y. The magenta developing unit 45M includes a developer accommodating portion 42M, a developer supplying roller 43M, and a developing roller 44M, and the cyan developing unit 45C includes a developer accommodating portion 42C and a developer supplying roller 43C. And a developing roller 44C. The developing belt 41 is an endless belt, is rotatably stretched around a plurality of belt rollers, and a part thereof is in contact with the photoconductor 10.
[0140]
In the image forming apparatus 100 shown in FIG. 1, for example, the charging roller 20 charges the photosensitive drum 10 uniformly. The exposure device 30 performs imagewise exposure on the photosensitive drum 10 to form an electrostatic latent image. The electrostatic latent image formed on the photosensitive drum 10 is developed by supplying toner from the developing device 40 to form a visible image (toner image). The visible image (toner image) is transferred (primary transfer) onto the intermediate transfer member 50 by the voltage applied from the roller 51, and further transferred (secondary transfer) onto the transfer paper 95. As a result, a transfer image is formed on the transfer paper 95. The residual toner on the photoconductor 10 is removed by the cleaning device 60, and the charge on the photoconductor 10 is temporarily removed by the charge eliminating lamp 70.
[0141]
Another mode for carrying out the image forming method of the present invention by the image forming apparatus of the present invention will be described with reference to FIG. The image forming apparatus 100 shown in FIG. 2 does not include the developing belt 41 in the image forming apparatus 100 shown in FIG. 1, and a black developing unit 45K, a yellow developing unit 45Y, a magenta developing unit 45M, and Except for the fact that the cyan developing unit 45C is disposed directly opposite, it has the same configuration as the image forming apparatus 100 shown in FIG. In FIG. 2, the same components as those in FIG. 1 are denoted by the same reference numerals.
[0142]
Another mode for carrying out the image forming method of the present invention by the image forming apparatus of the present invention will be described with reference to FIG. A tandem image forming apparatus 120 shown in FIG. 3 is a tandem color image forming apparatus. The tandem image forming apparatus 120 includes a copying apparatus main body 150, a paper feed table 200, a scanner 300, and an automatic document feeder (ADF) 400.
The copying apparatus main body 150 is provided with an endless belt-like intermediate transfer member 50 at the center. The intermediate transfer member 50 is stretched around the support rollers 14, 15 and 16, and can be rotated clockwise in FIG. 3. An intermediate transfer member cleaning device 17 for removing residual toner on the intermediate transfer member 50 is disposed in the vicinity of the support roller 15. The intermediate transfer member 50 stretched between the support roller 14 and the support roller 15 is a tandem type in which four image forming units 18 of yellow, cyan, magenta, and black are arranged to face each other along the conveyance direction. A developing device 120 is disposed. An exposure device 21 is disposed in the vicinity of the tandem developing device 120. A secondary transfer device 22 is disposed on the side of the intermediate transfer member 50 opposite to the side on which the tandem developing device 120 is disposed. In the secondary transfer device 22, a secondary transfer belt 24, which is an endless belt, is stretched around a pair of rollers 23, and the transfer paper conveyed on the secondary transfer belt 24 and the intermediate transfer body 50 are in contact with each other. Is possible. A fixing device 25 is disposed in the vicinity of the secondary transfer device 22. The fixing device 25 includes a fixing belt 26 that is an endless belt, and a pressure roller 27 that is pressed against the fixing belt 26.
In the tandem image forming apparatus 120, a sheet reversing device 28 for reversing the transfer paper for image formation on both sides of the transfer paper is disposed in the vicinity of the secondary transfer device 22 and the fixing device 25. Yes.
[0143]
Next, formation of a full color image (color copy) using the tandem image forming apparatus 120 will be described. That is, first, a document is set on the document table 130 of the automatic document feeder (ADF) 400, or the automatic document feeder 400 is opened and the document is set on the contact glass 32 of the scanner 300. 400 is closed.
[0144]
When a start switch (not shown) is pressed, when the document is set on the automatic document feeder 400, the document is transported and moved onto the contact glass 32, and then the document is set on the contact glass 32. Immediately after that, the scanner 300 is driven, and the first traveling body 33 and the second traveling body 34 travel. At this time, light from the light source is irradiated by the first traveling body 33 and reflected light from the document surface is reflected by the mirror in the second traveling body 34 and is received by the reading sensor 36 through the imaging lens 35 to be color. An original (color image) is read and used as black, yellow, magenta, and cyan image information.
[0145]
Each image information of black, yellow, magenta and cyan is stored in each image forming unit 18 (black image forming unit, yellow image forming unit, magenta image forming unit and cyan image forming unit) in the tandem image forming apparatus 120. ) And black, yellow, magenta and cyan toner images are formed in the respective image forming means. That is, each image forming means 18 (black image forming means, yellow image forming means, magenta image forming means, and cyan image forming means) in the tandem image forming apparatus 120 is photosensitive as shown in FIG. On the basis of the body 10 (the black photoreceptor 10K, the yellow photoreceptor 10Y, the magenta photoreceptor 10M, and the cyan photoreceptor 10C), the charger 60 that uniformly charges the photoreceptor, and each color image information. The photosensitive member is exposed to each color image corresponding image (L in FIG. 4), and an electrostatic latent image corresponding to each color image is formed on the photosensitive member. Developing with color toner (black toner, yellow toner, magenta toner and cyan toner) to form a toner image with each color toner, and intermediate transfer of the toner image 50 includes a transfer charger 62 for transferring the toner image on the toner image 50, a photoconductor cleaning device 63, and a static eliminator 64, and each monochrome image (black image, yellow image, magenta) based on the image information of each color. Image and cyan image) can be formed. The black image, the yellow image, the magenta image, and the cyan image formed in this way are formed on the black photoconductor 10K on the intermediate transfer member 50 that is rotationally moved by the support rollers 14, 15, and 16, respectively. The black image, the yellow image formed on the yellow photoconductor 10Y, the magenta image formed on the magenta photoconductor 10M, and the cyan image formed on the cyan photoconductor 10C are sequentially transferred (primary transfer). Is done. Then, the black image, the yellow image, the magenta image, and the cyan image are superimposed on the intermediate transfer member 50 to form a composite color image (color transfer image).
[0146]
On the other hand, in the paper feed table 200, one of the paper feed rollers 142 is selectively rotated to feed out a sheet (recording paper) from one of the paper feed cassettes 144 provided in multiple stages in the paper bank 143. Each sheet is separated and sent to the paper feed path 146, transported by the transport roller 147, guided to the paper feed path 148 in the copying machine main body 150, and abutted against the registration roller 49 and stopped. Alternatively, the sheet feeding roller 150 is rotated to feed out the sheets (recording paper) on the manual feed tray 51, separated one by one by the separation roller 52, put into the manual feed path 53, and abutted against the registration roller 49 and stopped. . The registration roller 49 is generally used while being grounded, but may be used in a state where a bias is applied to remove paper dust from the sheet.
Then, the registration roller 49 is rotated in synchronization with the synthesized color image (color transfer image) synthesized on the intermediate transfer member 50, and a sheet (recording paper) is interposed between the intermediate transfer member 50 and the secondary transfer device 22. The secondary color transfer device 22 transfers the composite color image (color transfer image) onto the sheet (recording paper), thereby transferring the color image onto the sheet (recording paper). Is formed. The residual toner on the intermediate transfer member 50 after image transfer is cleaned by the intermediate transfer member cleaning device 17.
[0147]
The sheet (recording paper) on which the color image has been transferred is conveyed by the secondary transfer device 22 and sent to the fixing device 25, where the combined color image (color) is generated by heat and pressure. (Transfer image) is fixed on the sheet (recording paper). Thereafter, the sheet (recording paper) is switched by the switching claw 55 and discharged by the discharge roller 56 and stacked on the discharge tray 57, or switched by the switching claw 55 and reversed by the sheet reversing device 28 and transferred again. After being guided to the position and recording an image on the back surface, the image is discharged by the discharge roller 56 and stacked on the discharge tray 57.
[0148]
In the image forming apparatus and the image forming method of the present invention, since the toner of the present invention having both heat resistant storage stability and low temperature fixability and good hot offset resistance is used, high image quality is efficiently obtained even under low temperature fixing conditions. can get.
[0149]
【Example】
Examples of the present invention will be described below, but the present invention is not limited to these examples.
[0150]
(Production Example 1)
-Preparation of fine particle dispersion (1)-
In a reaction vessel equipped with a stirrer and a thermometer, 683 parts by weight of water, 11 parts by weight of sodium salt of ethylene oxide methacrylate adduct sulfate ("Eleminol RS-30"; manufactured by Sanyo Chemical Industries), 83 parts by weight of styrene , 83 parts by weight of methacrylic acid, 110 parts by weight of butyl acrylate, and 1 part by weight of ammonium persulfate were charged and stirred at 400 rpm for 15 minutes to obtain a white emulsion. The emulsion was heated to raise the system temperature to 75 ° C. and reacted for 5 hours. Next, 30 parts by mass of a 1% by mass ammonium persulfate aqueous solution was added, and the mixture was aged at 75 ° C. for 5 hours, and then the vinyl resin particles (styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate sodium salt co Polymer) aqueous dispersion (fine particle dispersion (1)) was prepared.
It was 100 nm when the volume average particle diameter of the fine particles contained in the obtained fine particle dispersion (1) was measured. Moreover, when a part of the fine particle dispersion (1) was dried to isolate the resin, and the glass transition temperature (Tg) of the resin was measured, it was 80 ° C. and the number average molecular weight was measured. It was 1,700 and it was 10,000 when the weight average molecular weight was measured.
[0151]
(Production Example 2)
-Preparation of fine particle dispersion (2)-
In Production Example 1, styrene was changed from 83 parts by weight to 79 parts by weight, methacrylic acid was changed from 83 parts by weight to 79 parts by weight, butyl acrylate was changed from 110 parts by weight to 105 parts by weight, and 1,6-hexanediol An aqueous solution of vinyl resin particles (a copolymer of sodium salt of styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate), except that 13 parts by mass of diacrylate was added. A dispersion (fine particle dispersion (2)) was prepared.
The volume average particle diameter of the fine particles contained in the obtained fine particle dispersion (2) was measured and found to be 105 nm. Further, when a part of the fine particle dispersion (2) was dried to isolate the resin, and the glass transition temperature (Tg) of the resin was measured, it was 105 ° C. and the number average molecular weight was measured. The weight average molecular weight was 1,000,000 as measured by weight.
[0152]
(Production Example 3)
-Preparation of fine particle dispersion (3)-
In Production Example 1, the sodium salt of ethylene oxide methacrylate adduct sulfate ("Eleminol RS-30"; manufactured by Sanyo Chemical Industries) was changed from 11 parts by mass to 21 parts by mass, and 13 parts by mass of thiocalcol 20 was added. In the same manner as in Production Example 1, an aqueous dispersion (fine particle dispersion (3)) of vinyl resin particles (a copolymer of sodium salt of styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate) Was prepared.
The volume average particle diameter of the fine particles contained in the obtained fine particle dispersion (3) was measured and found to be 15 nm. Moreover, when a part of the fine particle dispersion (3) was dried to isolate the resin component and the glass transition temperature (Tg) of the resin component was measured, it was 95 ° C. and the number average molecular weight was measured. The weight average molecular weight was 5,000 when measured.
[0153]
(Production Example 4)
-Preparation of fine particle dispersion (4)-
In Production Example 1, the sodium salt of ethylene oxide methacrylate adduct sulfate ("Eleminol RS-30"; manufactured by Sanyo Chemical Industries) was changed from 11 parts by mass to 3 parts by mass, and styrene was changed from 83 parts by mass to 71 parts by mass. Except that methacrylic acid was changed from 83 parts by weight to 71 parts by weight, butyl acrylate was changed from 110 parts by weight to 98 parts by weight, and 14 parts by weight of 1,6-hexanediol diacrylate was added. In the same manner, an aqueous dispersion (fine particle dispersion (4)) of vinyl resin particles (styrene copolymer of styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate) was prepared.
It was 600 nm when the volume average particle diameter of the fine particles contained in the obtained fine particle dispersion (4) was measured. Further, when a part of the fine particle dispersion (1) was dried to isolate the resin, and the glass transition temperature (Tg) of the resin was measured, it was 105 ° C. and the number average molecular weight was measured. It was 225,000 and it was 1,800,000 when the weight average molecular weight was measured.
[0154]
(Production Example 5)
-Preparation of fine particle dispersion (5)-
In Production Example 1, the sodium salt of methacrylic acid ethylene oxide adduct sulfate ("Eleminol RS-30"; manufactured by Sanyo Chemical Industries) was changed from 11 parts by mass to 8 parts by mass, and styrene was changed from 83 parts by mass to 82 parts by mass. In the same manner as in Production Example 1 except that methacrylic acid was changed from 83 parts by weight to 82 parts by weight and butyl acrylate was changed from 110 parts by weight to 109 parts by weight, vinyl resin particles (styrene-methacrylic acid-acrylic An aqueous dispersion (fine particle dispersion (5)) of butyl acid-ethylene methacrylate ethylene oxide adduct sulfate sodium salt copolymer) was prepared.
It was 200 nm when the volume average particle diameter of the microparticles | fine-particles contained in the obtained microparticle dispersion liquid (5) was measured. Moreover, when a part of the fine particle dispersion (5) was dried to isolate the resin, and the glass transition temperature (Tg) of the resin was measured, it was 78 ° C., and the number average molecular weight was measured. It was 15,700, and when the weight average molecular weight was measured, it was 110,000.
[0155]
(Production Example 6)
-Preparation of fine particle dispersion (6)-
In Production Example 1, 11 parts by mass of sodium salt of ethylene oxide methacrylate adduct sulfate (“Eleminol RS-30”; manufactured by Sanyo Chemical Industries) is changed to 8 parts by mass, 83 parts by mass of styrene is changed to 79 parts by mass, Except for changing 83 parts by mass of methacrylic acid to 79 parts by mass, changing 110 parts by mass of butyl acrylate to 105 parts by mass, and adding 13 parts by mass of 1,6-hexanediol diacrylate, An aqueous dispersion (fine particle dispersion (6)) of vinyl resin particles (a copolymer of styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate sodium salt) was prepared.
It was 200 nm when the volume average particle diameter of the microparticles | fine-particles contained in the obtained microparticle dispersion liquid (6) was measured. Moreover, when a part of the fine particle dispersion (6) was dried to isolate the resin, and the glass transition temperature (Tg) of the resin was measured, it was 107 ° C., and the number average molecular weight was measured. It was 210,000 and it was 1,100,000 when the weight average molecular weight was measured.
[0156]
(Production Example 7)
-Preparation of fine particle dispersion (7)-
In Production Example 1, the sodium salt of methacrylic acid ethylene oxide adduct sulfate ("Eleminol RS-30"; manufactured by Sanyo Chemical Industries) was changed from 11 parts by mass to 6 parts by mass, and styrene was changed from 83 parts by mass to 85 parts by mass. In the same manner as in Production Example 1, except that methacrylic acid was changed from 83 parts by weight to 85 parts by weight and butyl acrylate was changed from 110 parts by weight to 111 parts by weight, vinyl resin particles (styrene-methacrylic acid-acrylic An aqueous dispersion (fine particle dispersion (7)) of butyl acid-ethylene methacrylate ethylene oxide adduct sulfate sodium salt copolymer) was prepared.
It was 300 nm when the volume average particle diameter of the microparticles | fine-particles contained in the obtained microparticle dispersion liquid (7) was measured. Moreover, when a part of the fine particle dispersion (7) was dried to isolate the resin component and the glass transition temperature (Tg) of the resin component was measured, it was 78 ° C. and the number average molecular weight was measured. It was 2,100, and when the weight average molecular weight was measured, it was 9,900.
[0157]
(Production Example 8)
-Preparation of fine particle dispersion (8)-
In Production Example 1, the sodium salt of methacrylic acid ethylene oxide adduct sulfate ("Eleminol RS-30"; manufactured by Sanyo Chemical Industries) was changed from 11 parts by mass to 5 parts by mass, and styrene was changed from 83 parts by mass to 81 parts by mass. Except that the methacrylic acid was changed from 83 parts by weight to 81 parts by weight, the butyl acrylate was changed from 110 parts by weight to 107 parts by weight, and 13 parts by weight of 1,6-hexanediol diacrylate was added. Similarly, an aqueous dispersion (fine particle dispersion (8)) of vinyl resin particles (a copolymer of sodium salt of styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate) was prepared.
It was 295 nm when the volume average particle diameter of the microparticles | fine-particles contained in the obtained microparticle dispersion liquid (8) was measured. Further, when a part of the fine particle dispersion (8) was dried to isolate the resin, and the glass transition temperature (Tg) of the resin was measured, it was 105 ° C. and the number average molecular weight was measured. The weight average molecular weight was measured to be 1,000,000.
[0158]
Here, Table 1 shows the raw material blend compositions of the fine particle dispersions (1) to (8).
[Table 1]
[0159]
The volume average particle diameter (Dv), glass transition temperature (Tg), number average molecular weight (Mn), and weight average molecular weight (Mw) were measured as follows.
[0160]
<Volume average particle diameter Dv)>
The volume average particle diameter (Dv) was measured using a laser diffraction particle size distribution analyzer (“LA-920”; manufactured by Horiba, Ltd.).
[0161]
<Glass transition temperature (Tg)>
The glass transition temperature (Tg) was measured by the following method using TG-DSC system TAS-100 (manufactured by Rigaku Corporation).
First, about 10 mg of a sample was placed in an aluminum sample container, and the sample container was placed on a holder unit and set in an electric furnace. After heating from room temperature to 150 ° C. at a heating rate of 10 ° C./min, the sample was allowed to stand at 150 ° C. for 10 min, and the sample was cooled to room temperature and left for 10 min. Then, the DSC curve was measured with a differential scanning calorimeter (DSC) after heating to 150 ° C. at a heating rate of 10 ° C./min in a nitrogen atmosphere. From the obtained DSC curve, using the analysis system in the TG-DSC system TAS-100 system, the glass transition temperature (Tg) is calculated from the contact point between the tangent line of the endothermic curve near the glass transition temperature (Tg) and the baseline. did.
[0162]
<Number average molecular weight (Mn) and weight average molecular weight (Mw)>
For the number average molecular weight and the weight average molecular weight, the weight average molecular weight (Mw) and the number average molecular weight (Mn) were measured from the molecular weight distribution by gel permeation chromatography (GPC) of the tetrahydrofuran-soluble matter.
Specifically, the column was stabilized in a 40 ° C. heat chamber, tetrahydrofuran as a column solvent at this temperature was flowed at a flow rate of 1 ml / min, and the sample concentration was adjusted to 0.05 to 0.6% by mass. Measurement was performed by injecting 50 to 200 μl of a tetrahydrofuran sample solution.
In measuring the molecular weight of the sample, the molecular weight distribution of the sample was calculated from the relationship between the logarithmic value of the calibration curve prepared from several monodisperse polystyrene standard samples and the count number. The standard polystyrene sample for creating a calibration curve has a molecular weight of 6 × 10²2.1 × 10²4 × 10²1.75 × 10⁴1.1 × 10⁵3.9 × 10⁵8.6 × 10⁵2 × 10⁶And 48 × 10⁶(Made by Toyo Soda Industry Co., Ltd.) and at least about 10 standard polystyrene samples. An RI (refractive index) detector was used as the detector.
[0163]
[Table 2]
[0164]
Example 1
-Adhesive substrate production process-
Using the fine particle dispersion (1) obtained in Production Example 1 and the fine particle dispersion (2) obtained in Production Example 2, a toner was produced as follows.
[0165]
--Synthesis of unmodified polyester--
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 220 parts by mass of bisphenol A ethylene oxide 2 mol adduct, 561 parts by mass of bisphenol A propylene oxide 3 mol adduct, 218 parts by mass of terephthalic acid, 48 adipic acid 48 Part by mass and 2 parts by mass of dibutyltin oxide were charged and reacted at 230 ° C. for 8 hours under normal pressure. Next, after reacting the reaction solution under a reduced pressure of 10 to 15 mmHg for 5 hours, 45 parts by mass of trimellitic anhydride was added to the reaction vessel, and the reaction was performed at 180 ° C. for 2 hours under normal pressure. A modified polyester was synthesized.
The obtained unmodified polyester had a number average molecular weight (Mn) of 2,500, a weight average molecular weight (Mw) of 6,700, a glass transition temperature (Tg) of 43 ° C., and an acid value of 25.
[0166]
--Synthesis of prepolymer--
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 682 parts by mass of bisphenol A ethylene oxide 2 mol adduct, 81 parts by mass of bisphenol A propylene oxide 2 mol adduct, 283 parts by mass of terephthalic acid, trimellitic anhydride 22 parts by mass of acid and 2 parts by mass of dibutyltin oxide were charged and reacted at 230 ° C. for 8 hours under normal pressure. Subsequently, it was made to react under reduced pressure of 10-15mHg for 5 hours, and the intermediate polyester was synthesize | combined.
The resulting intermediate polyester has a number average molecular weight (Mn) of 2,100, a weight average molecular weight (Mw) of 9,500, a glass transition temperature (Tg) of 55 ° C., an acid value of 0.5, and a hydroxyl value of 49.
Next, 410 parts by mass of the intermediate polyester, 89 parts by mass of isophorone diisocyanate, and 500 parts by mass of ethyl acetate are charged in a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe, and reacted at 100 ° C. for 5 hours. Thus, a prepolymer (polymer capable of reacting with the active hydrogen group-containing compound) was synthesized.
The free isocyanate content of the obtained prepolymer was 1.53% by mass.
[0167]
--Synthesis of ketimine (the active hydrogen group-containing compound)-
In a reaction vessel equipped with a stir bar and a thermometer, 170 parts by mass of isophoronediamine and 75 parts by mass of methyl ethyl ketone were charged and reacted at 50 ° C. for 5 hours to synthesize a ketimine compound (the active hydrogen group-containing compound).
The amine value of the obtained ketimine compound (the active hydrogen group-containing compound) was 418.
[0168]
-Preparation of masterbatch (MB)-
40 parts by mass of carbon black (“Regal 400R”; manufactured by Cabot) as a colorant, polyester resin (“RS801”; manufactured by Sanyo Chemical Industries, Ltd., acid value = 10, weight average molecular weight (Mw) = 20,000, glass transition Temperature (Tg) = 64 ° C.) and 30 parts by mass of water were mixed with a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.). The mixture was kneaded for 45 minutes at 130 ° C. with two rolls, rolled and cooled, and pulverized to a size of 1 mm in diameter with a pulverizer (manufactured by Hosokawa Micron) to prepare a master batch.
[0169]
-Preparation of organic solvent phase-
In a reaction vessel in which a stir bar and a thermometer were set, 378 parts by mass of the unmodified polyester, 110 parts by mass of carnauba wax, 22 parts by mass of CCA (“salicylic acid metal complex E-84”; manufactured by Orient Chemical Industries), and ethyl acetate 947 parts by mass were charged, and the temperature was raised to 80 ° C. with stirring, maintained at 80 ° C. for 5 hours, and then cooled to 30 ° C. over 1 hour. Next, 500 parts by mass of the master batch and 500 parts by mass of ethyl acetate were charged into the reaction vessel and mixed for 1 hour to obtain a raw material solution.
1324 parts by mass of the obtained raw material solution was transferred to a reaction vessel, and using a bead mill (“Ultra Visco Mill”; manufactured by Imex Co., Ltd.), the liquid feeding speed was 1 kg / hr, the disk peripheral speed was 6 m / sec, and 0.5 mm zirconia. The carbon black and carnauba wax were dispersed by three passes under the condition of 80% by volume of beads. Next, 1324 parts by mass of a 65% by mass ethyl acetate solution of the unmodified polyester was added to the dispersion. One pass was performed in a bead mill under the same conditions as described above, and the mixture was dispersed to prepare an organic solvent phase.
The solid content concentration of the obtained organic solvent phase (130 ° C., 30 minutes) was 50% by mass.
[0170]
--Emulsification / Dispersion--
Into a reaction vessel, 648 parts by mass of the organic solvent phase, 154 parts by mass of the prepolymer, and 6.6 parts by mass of the ketimine compound are charged, and 5,000 rpm using a TK homomixer (manufactured by Tokushu Kika). Mixing for 1 minute gave an oil phase mixture.
Next, in a reaction vessel, 990 parts by mass of water, 72 parts by mass of the fine particle dispersion (1) (see Table 3), 8 parts by mass of the fine particle dispersion (2) (see Table 3), sodium dodecyl diphenyl ether disulfonate 4 mass% aqueous solution (“Eleminol MON-7”; Sanyo Chemical Industries, Ltd.) 40 parts by mass and ethyl acetate 90 parts by mass, and TK type homomixer (manufactured by Special Machine) for 1 minute at 3000 rpm Mixed. Next, 809 parts by mass of the oil phase mixed solution was added to the reaction vessel, and mixed with a TK homomixer at a rotation speed of 13,000 rpm for 20 minutes to prepare an emulsified slurry.
Next, the emulsified slurry was charged into a reaction vessel equipped with a stirrer and a thermometer, and after removing the solvent at 30 ° C. for 8 hours, aging was carried out at 45 ° C. for 4 hours to obtain a dispersed slurry.
The obtained dispersion slurry 1 had a volume average particle size of 4.95 μm and a number average particle size of 4.45 μm as measured by Multisizer II (manufactured by Beckman Coulter, Inc.).
[0171]
[Table 3]
[0172]
--- Washing and drying--
After filtering 100 parts by mass of the dispersion slurry under reduced pressure, adding 300 parts by mass of ion exchange water to the filter cake, mixing with a TK homomixer (at 12,000 rpm for 10 minutes), and then filtering three times. And a final filter cake was obtained.
Here, the obtained final filter cake was dried with a circulating dryer at 45 ° C. for 48 hours, and sieved with a mesh having an opening of 75 μm to obtain toner base particles of Example 1.
[0173]
--External additive treatment--
Henschel mixer (manufactured by Mitsui Mining Co., Ltd.) was added 0.7 parts by weight of hydrophobic silica as an external additive and 0.3 parts by weight of hydrophobized titanium oxide with respect to 100 parts by weight of the obtained toner base particles of Example 1. The toner of Example 1 was manufactured by using the mixture.
For the toner of Example 1, the volume average particle size, number average particle size and particle size distribution, average circularity, resin fine particle coverage, resin fine particle content (residual rate), BET specific surface area, In addition, the toner physical properties of the glass transition temperature were measured. The results are shown in Table 8.
[0174]
(Comparative Example 1)
-Preparation of toner base particles-
In Example 1, except that the fine particle dispersion (1) was changed to the fine particle dispersion (3) and the fine particle dispersion (2) was changed to the fine particle dispersion (4) (Table 4), In the same manner as in Example 1, toner base particles of Comparative Example 1 were obtained.
[0175]
-External additive treatment-
External toner was added to the obtained toner base particles of Comparative Example 1 in the same manner as the toner base particles of Example 1 to produce the toner of Comparative Example 1. The physical properties and the like of the toner of Comparative Example 1 were measured in the same manner as in Example 1. The results are shown in Table 8.
[0176]
[Table 4]
[0177]
(Example 2)
-Preparation of toner base particles-
In Example 1, except that the fine particle dispersion (1) was changed from 72 parts by weight to 40 parts by weight and the fine particle dispersion (2) was changed from 8 parts by weight to 40 parts by weight (Table 5). In the same manner as in Example 1, toner base particles of Example 2 were obtained.
[0178]
-External additive treatment-
External toner was added to the obtained toner base particles of Example 2 in the same manner as the toner base particles of Example 1, and thus the toner of Example 2 was produced. The physical properties of the toner of Example 2 were measured in the same manner as in Example 1. The results are shown in Table 8.
[0179]
[Table 5]
[0180]
(Example 3)
-Preparation of toner base particles-
In Example 1, 72 parts by mass of the fine particle dispersion (1) is changed to 48 parts by mass of the fine particle dispersion (5), and 8 parts by mass of the fine particle dispersion (2) is 32 parts by mass of the fine particle dispersion (6). The toner base particles of Example 3 were obtained in the same manner as in Example 1 except for changing to (Table 6).
[0181]
-External additive treatment-
External toner was added to the obtained toner base particles of Example 3 in the same manner as the toner base particles of Example 1 to produce the toner of Example 3. The physical properties of the toner of Example 3 were measured in the same manner as in Example 1. The results are shown in Table 8.
[0182]
[Table 6]
[0183]
(Reference example 1)
-Preparation of toner base particles-
  In Example 1, 72 parts by mass of the fine particle dispersion (1) is changed to 48 parts by mass of the fine particle dispersion (7), and 8 parts by mass of the fine particle dispersion (2) is 32 parts by mass of the fine particle dispersion (8). Except that changed to (Table 7), in the same manner as in Example 1,Reference example 1Toner base particles were obtained.
[0184]
-External additive treatment-
  ObtainedReference example 1For the toner base particles, an external additive was added in the same manner as the toner base particles of Example 1,Reference example 1Toner was produced.Reference example 1For this toner, various physical properties and the like were measured in the same manner as in Example 1. The results are shown in Table 8.
[0185]
[Table 7]
[0186]
<Toner particle size>
The volume average particle diameter (Dv) and number average particle diameter (Dn) of each toner were measured using a particle size measuring device (“Multisizer II”; manufactured by Beckman Coulter, Inc.) at an aperture diameter of 100 μm. From these results, (volume average particle diameter (Dv / number average particle diameter (Dn))) was calculated.
[0187]
<Average circularity>
The average circularity of each toner was measured using a flow type particle image analyzer (“FPIA-2100”; manufactured by Sysmex Corporation). Specifically, 0.1 to 0.5 ml of a surfactant (alkylbenzene sulfonate) as a dispersant is added to 100 to 150 ml of water from which impure solids have been removed in advance, and each toner is further added. 0.1 to 0.5 g was added and dispersed. The obtained dispersion was dispersed for about 1 to 3 minutes with an ultrasonic disperser (manufactured by Honda Electronics Co., Ltd.), and the shape and distribution of the toner were measured at a dispersion concentration of 3000 to 10,000 / μl. . The average circularity was calculated from these measurement results.
[0188]
<Measurement method of resin fine particle coverage>
The coverage of the resin fine particles was obtained by taking several fields of electron micrographs at a magnification of 50,000 times on the surface of each toner, selecting a toner surface with no tilt or crack as much as possible, and using an image analyzer (“Luzex III”). ; Nireco Co.) was used to measure the coverage of resin fine particles on the toner surface.
[0189]
<Measurement method of resin fine particle content (residual rate)>
Using the styrene monomer derived from the resin fine particles of the styrene-acrylic copolymer as a label, the toner was thermally decomposed to measure the amount of the styrene monomer in the thermal decomposition product, and the content of the resin fine particles in the toner was calculated. That is, using resin fine particles of styrene-acrylic copolymer having a known composition as a label, the content of resin fine particles of styrene-acrylic copolymer in the toner is 0.01% by mass, 0.10% by mass, It added so that it might become 1.00 mass%, 3.00 mass%, and 10.0 mass%. Each model toner having a known composition is thermally decomposed under the conditions of 590 ° C. × 12 seconds, and the thermal decomposition products are analyzed according to the following measuring equipment and measurement conditions to obtain the peak area of the styrene monomer for each toner. The content of resin fine particles in the toner was calculated.
[Measurement equipment and measurement conditions]
Analytical instrument: Pyrolysis gas chromatograph mass spectrometer
Device body: QR-5000 (manufactured by Shimadzu Corporation)
Accessory pyrolysis furnace: JHP-3S (manufactured by Nippon Analytical Industry)
Thermal decomposition temperature: 590 ° C x 12 seconds
Column: “DB-1”
(L = 30 m ID = 0.25 mm Film = 0.25 μm)
Column temperature: 40 ° C. (holding 2 minutes) to 300 ° C. (temperature raising 10 ° C./min)
Vaporization chamber temperature: 300 ° C
[0190]
<Measurement method of BET specific surface area>
According to the BET method, nitrogen gas was adsorbed on the surface of each toner base (sample) using a specific surface area measuring device (“Tristar 3000”; manufactured by Shimadzu Corporation), and measurement was performed by the BET multipoint method.
[0191]
<Method of measuring glass transition temperature (Tg)>
The glass transition temperature (Tg) was measured by the following method using TG-DSC system TAS-100 (manufactured by Rigaku Corporation).
First, about 10 mg of each toner (sample) was placed in an aluminum sample container, and the sample container was placed on a holder unit and set in an electric furnace. After heating from room temperature to 150 ° C. at a heating rate of 10 ° C./min, the sample was allowed to stand at 150 ° C. for 10 min, and the sample was cooled to room temperature and left for 10 min. Then, the DSC curve was measured with a differential scanning calorimeter (DSC) after heating to 150 ° C. at a heating rate of 10 ° C./min in a nitrogen atmosphere. From the obtained DSC curve, using the analysis system in the TG-DSC system TAS-100 system, the glass transition temperature (Tg) is calculated from the contact point between the tangent line of the endothermic curve near the glass transition temperature (Tg) and the baseline. did.
[0192]
[Table 8]
[0193]
-Preparation of developer-
  Next, Examples 1 to 6 were prepared in a conventional manner from 5% by mass of each toner treated with an external additive and 95% by mass of a copper-zinc ferrite carrier having an average particle diameter of 40 μm coated with a silicone resin.3. Reference example 1And each developer of Comparative Example 1 was produced.
[0194]
Using each developer obtained, (a) fixability (fixing lower limit temperature and offset non-occurrence temperature), (b) heat-resistant storage stability (penetration), and (c) comprehensive evaluation Was measured. The results are shown in Table 9.
[0195]
(A) Fixability (offset non-occurrence temperature and fixing lower limit temperature)
Fixability (offset non-occurrence temperature and fixing lower limit temperature) was evaluated using an image forming apparatus including the belt fixing device 110 shown in FIG.
The belt-type fixing device 110 includes a heating roller 121, a fixing roller 122, a pressure roller 124, and a fixing belt 123.
The fixing belt 123 is stretched by a heating roller 121 and a fixing roller 122 that are rotatably arranged inside, and is heated to a predetermined temperature by the heating roller 121. The heating roller 121 has a built-in heating source 125 and is designed such that the temperature can be adjusted by a temperature sensor 127 attached in the vicinity of the heating roller 121. The fixing roller 122 is rotatably disposed inside the fixing belt 123 and in contact with the inner surface of the fixing belt 123. The pressure roller 124 is in contact with the outer side of the fixing belt 123 and the outer surface of the fixing belt 123 so as to press the fixing roller 122 so as to be rotatable.
In fixing belt device 110, first, recording medium (sheet) P on which a toner image to be fixed is formed is conveyed to heating roller 121. Then, the toner T on the sheet P is heated and melted by the heating roller 121 and the fixing belt 123 heated to a predetermined temperature by the action of the built-in heating source 125. In this state, the sheet P is inserted into a nip portion formed between the fixing roller 122 and the pressure roller 124. The sheet P inserted into the nip is brought into contact with the surface of the fixing belt 123 that rotates in conjunction with the rotation of the fixing roller 122 and the pressure roller 124, and passes through the nip by the pressing force of the pressure roller 124. When pressed, the toner T is fixed on the sheet P. Next, the sheet P on which the toner T is fixed passes between the fixing roller 122 and the pressure roller 124, is peeled off from the fixing belt 123, and is conveyed to a tray (not shown) through a guide G. The fixing belt 123 is cleaned by the cleaning roller 126.
[0196]
In the belt-type fixing device shown in FIG. 5, fixing conditions of a belt tension of 1.5 kg / piece, a belt speed of 170 mm / sec, and a nip width of 10 mm are obtained by the fixing roller 122, the pressure roller 124, the heating roller 121, and the fixing belt 123. Fixing was done at
The fixing roller 122 is a roller made of silicone foam having a diameter of 38 mm and an Asker C hardness of about 30 degrees. The pressure roller 124 has a diameter of 50 mm and a Asker C hardness of about 48 mm in diameter. It is a 75 degree roller. The heating roller 121 is an aluminum roller having a diameter of 30 mm and a wall thickness of 2 mm. The fixing belt 123 has a belt diameter of 60 mm and a belt width of 310 mm, and is stretched around a roller having a release layer made of silicone rubber having a thickness of about 150 μm on the surface of a nickel belt base having a thickness of about 40 μm.
[0197]
<Temperature without offset>
The temperature at which no offset occurred was measured using an image forming apparatus equipped with the belt fixing device shown in FIG. That is, for image formation, a color copying machine ("Pretail 550"; manufactured by Ricoh Co., Ltd.) is used to transfer yellow (magenta, cyan, and black) onto transfer paper ("Type 6000-70W"; manufactured by Ricoh Co., Ltd.). Each solid color, and solid images of red, blue, and green as intermediate colors, 1.0 ± 0.1 mg / cm for each single color²The toner was adjusted so as to be developed. The obtained image was fixed using the belt fixing device shown in FIG. 5 while changing the temperature of the fixing belt (heating roller), and the fixing temperature at which no offset occurred (temperature where no offset occurred) was measured.
[0198]
<Fixing temperature limit>
Using the image forming apparatus provided with the belt fixing device shown in FIG. 5, the image is transferred to a transfer paper (“Type 6200”; manufactured by Ricoh Co., Ltd.) using a color copying machine (“Pretail 550” manufactured by Ricoh Co., Ltd.). ) Was set and a copy test was conducted. The fixing roll temperature at which the residual ratio of the image density after rubbing the obtained fixed image with a pad was 70% or more was determined as the minimum fixing temperature. A fixing lower limit temperature higher than 150 ° C. was judged as defective.
[0199]
(B) Heat resistance storage (penetration)
Each toner was filled in a 50 ml glass container and left in a constant temperature bath at 50 ° C. for 20 hours. The toner was cooled to room temperature, and the penetration was measured by a penetration test (JIS K2235-1991). In addition, it shows that heat resistance preservability is excellent, so that the value of the said penetration is large.
[0200]
(C) Overall evaluation
From the results of all the performance evaluations, comprehensive evaluation was performed based on the following criteria.
〔Evaluation criteria〕
○: Overall excellent state
△: Overall normal state
X: Overall poor condition
[0201]
[Table 9]
[0202]
  From the results of Tables 8 to 9, the following is clear. That is, Examples 1 to3With respect to, the evaluation results of the respective qualities of low-temperature fixability, hot offset resistance, and heat-resistant storage stability were good, and the overall evaluation was good (◯). On the other hand, in Comparative Example 1, although the low-temperature fixability was good, the overall evaluation was poor (x) because the hot offset resistance and the heat-resistant storage stability were poor.
[0203]
【The invention's effect】
According to the present invention, conventional problems can be solved, excellent properties such as agglomeration resistance, chargeability, fluidity, transferability, and fixability, good hot offset resistance, and excellent heat-resistant storage. That can achieve high image quality with a combination of high temperature and low temperature fixability, and an efficient manufacturing method thereof, and a developer, a container containing toner, a process cartridge, and image formation that can achieve high image quality using the toner An apparatus and an image forming method can be provided.
[Brief description of the drawings]
FIG. 1 is a schematic explanatory view showing an example in which an image forming method of the present invention is carried out by an image forming apparatus of the present invention.
FIG. 2 is a schematic explanatory view showing another example in which the image forming method of the present invention is carried out by the image forming apparatus of the present invention.
FIG. 3 is a schematic explanatory view showing an example in which the image forming method of the present invention is implemented by the image forming apparatus (tandem type color image forming apparatus) of the present invention.
FIG. 4 is a partially enlarged schematic explanatory view of the image forming apparatus shown in FIG.
FIG. 5 is a schematic explanatory view showing an example of a belt-type fixing device in the image forming apparatus of the present invention.
[Explanation of symbols]
10 Photoconductor (Photoconductor drum)
10K black photoconductor
Photosensitive body for 10Y yellow
10M photoconductor for magenta
10C Cyan photoreceptor
14 Support roller
15 Support roller
16 Support roller
17 Intermediate transfer cleaning device
18 Image forming means
20 Charging roller
21 Exposure equipment
22 Secondary transfer device
23 Laura
24 Secondary transfer belt
25 Fixing device
26 Fixing belt
27 Pressure belt
28 Sheet reversing device
30 exposure equipment
32 Contact glass
33 First traveling body
34 Second traveling body
35 Imaging lens
36 Reading sensor
40 Developer
41 Development belt
42K developer container
42Y developer container
42M developer container
42C Developer container
43K developer supply roller
43Y developer supply roller
43M Developer supply roller
43C Developer supply roller
44K development roller
44Y Development roller
44M Development roller
44C Development roller
45K black developer
45Y Yellow developer
45M Magenta developer
45C Cyan developer
49 Registration Roller
50 Intermediate transfer member
51 Laura
52 Separation roller
53 Constant current source
55 switching claw
56 Discharge roller
57 Discharge tray
58 Corona charger
60 Cleaning device
61 Developer
62 Transfer charger
63 Photoconductor cleaning device
64 Static eliminator
70 Static elimination lamp
80 Transfer roller
90 Cleaning device
95 Transfer paper
100 Image forming apparatus
110 Belt-type fixing device
120 Tandem developer
121 Heating roller
122 Fixing roller
123 Fixing belt
124 Pressure roller
125 Heat source
126 Cleaning roller
127 Temperature sensor
130 Document platen
142 Feed roller
143 Paper Bank
144 Paper cassette
145 Separation roller
146 paper feed path
147 Conveying roller
148 paper feed path
150 Copying machine body
200 Feeding table
300 scanner
400 Automatic Document Feeder (ADF)

Claims (11)

An organic solvent phase containing an active hydrogen group-containing compound and a polymer having a site capable of reacting with the active hydrogen group-containing compound is emulsified and dispersed in an aqueous medium containing at least two kinds of resin fine particles, to thereby contain the active hydrogen group A toner obtained by subjecting a compound and a polymer capable of reacting with the active hydrogen group-containing compound to an extension reaction or a crosslinking reaction , and removing an organic solvent ,
Without the resin fine particles being fixed or fused,
Among the resin fine particles, those having the highest glass transition temperature are the resin fine particles (A), the glass transition temperature is (TgA), the one having the lowest glass transition temperature is the resin fine particles (B), and the glass transition temperature is (TgB). ), The following equation, temperature difference (TgA−TgB) ≧ 20 ° C. is satisfied,
The residual ratio of the resin fine particles to the toner is 4.1 to 8.0% by mass as measured by a pyrolysis chromatograph,
A toner having a mass ratio of the resin fine particles (A) to the resin fine particles (B) (resin fine particles (A): resin fine particles (B)) of 10:90 to 50:50.   The toner according to claim 1, wherein the toner satisfies the following formula: 8,000 ≦ (Mw) ≦ 1,500,000, where (Mw) is a weight average molecular weight in the molecular weight distribution of tetrahydrofuran-soluble matter in the resin fine particles.   The toner according to claim 1, wherein the resin coverage of the resin fine particles is 75 to 100%.   The toner according to claim 1, wherein the resin fine particles have a volume average particle diameter of 20 to 400 nm. The toner according to claim 1, wherein the toner has a BET specific surface area of 0.5 to 8.0 m ² / g.   The toner according to claim 1, wherein the toner has a volume average particle diameter of 3 to 8 μm.   The toner according to claim 1, wherein the toner has a volume average particle diameter / number average particle diameter of 1.00 to 1.25.   The toner according to claim 1, wherein the toner has an average circularity of 0.90 to 1.00.   9. The method for producing a toner according to claim 1, wherein at least an organic solvent phase comprising an active hydrogen group-containing compound and a polymer having a site capable of reacting with the active hydrogen group-containing compound is contained. A toner characterized by being emulsified and dispersed in an aqueous medium containing two kinds of resin fine particles, and causing an extension reaction or a cross-linking reaction between the active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound. Production method.   A developer comprising the toner according to claim 1.   A toner-filled container filled with the toner according to claim 1.